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Modified waste egg shell derived bifunctional catalyst for biodiesel production
from high FFA waste cooking oil. A review

Article  in  Renewable and Sustainable Energy Reviews · October 2017

DOI: 10.1016/j.rser.2017.10.0

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Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews

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

Modified waste egg shell derived bifunctional catalyst for biodiesel

production from high FFA waste cooking oil. A review
Nasar Mansira,b,d, Siow Hwa Teoa,b, Umer Rashidc, Mohd Izham Saimana,b, Yen Ping Tana,b,
⁎
G. Abdulkareem Alsultana,b, Yun Hin Taufiq-Yapa,b,
a
Catalysis Science and Technology Research Centre, Faculty of Science, Universiti Putra Malaysia, 43400 Serdang, Selangor, Malaysia
b
Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 Serdang, Selangor, Malaysia
c
Institute of advanced technology Universiti Putra Malaysia, Serdang, Selangor, Malaysia
d
Department of Chemistry, Faculty of Science, Federal University Dutse, 7156 Dutse, Jigawa State, Nigeria

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

Keywords: Global energy crisis are as a result of gradual depletion of fossil fuel reserves, coupled with population growth in
Fossil fuel developing countries. Besides, fossil fuels are not environmentally benign as they are associated with problems,
Biofuel i.e. global warming, high toxicity and non biodegradability, hence it is considered as non sustainable source of
Vegetable oil energy. Without doubt, biofuel-based energy is a promising long-term energy source that can reduce the over
High FFA waste cooking oil
dependence on fossil fuels as a result of feedstocks availability and renewability. However, biodiesel production
Homogeneous catalyst
Heterogeneous catalyst
from vegetable oil using the traditional homogeneous catalytic system is no longer defensible by industries in the
near future, particularly due to food-fuel rivalry and ecological problems related to the conventional homo-
geneous catalytic system. This review presents a comprehensive step by step process of converting waste cooking
oil (WCO) to biodiesel, using modified waste egg shell catalyst. The modified waste egg shell derived bi-func-
tional catalyst could easily be removed from the fatty acid methyl esters (FAME) with limited environmental
effects. The new modified catalytic system is able to convert the high free fatty acid (FFA) content waste cooking
oil to FAME efficiently under moderate reaction conditions. Utilization of waste cooking oil as a feedstock for
biodiesel production will reduce the food security issues that stem the biodiesel production from food-grade oil.
Moreover, it will reduce the total production cost of the FAME due to its low cost. The major objective of this
article is to demonstrate the current state of the use of heterogeneous bifunctional acid/base catalyst to produce
biodiesel from green and non-edible waste cooking oil. At the end of the article, perspectives and future de-
velopments are also presented.

1. Introduction generally considered as replaceable alternative to traditional fossil fuels

due to their feedstock availability and environmental friendly [7,8].
The global energy crises are as a result of possible future depletion Biodiesel is one of the most promising alternative sources of energy
of conventional fossil fuels and current energy demand are the major considering its biodegradability and low emission of carbon dioxide,
drivers prompted the search for alternative renewable energy sources. free sulphur and non-toxic nature [9–11]. Another interesting thing
Besides, fossil fuels are not eco-friendly as they are related to poisonous about biodiesel is that it possesses all the physico-chemical properties of
gases exhausts from automobile and industrial internal combustion traditional fossil fuel such as improved cetane number and high flash
engines, which eventually lead to global warming, acid rain and de- point [12,13].
pletion of ozone layer [1–3]. Transportation of goods and services is an As a result of rapid growth in human population, scientific and
integral part of global economy, which depends solely on petroleum technological advancements in developing countries, the biodiesel de-
based sources of energy. Apart from coal, nuclear power, natural gas mand is estimated to either doubled or tripled by the year 2020 and
and hydroelectricity that serve at different capacity in the provision of beyond. However, relevant studies have fully verified the number of
energy, transport sector alone is more than 90% dependent on fossil issues regarding biodiesel that are not convincingly addressed yet.
fuels (petroleum), consuming more than 60% of total annual global fuel Conversion of triglycerides into FAME requires a reaction of the former
consumption [4–6]. Renewable sources of energy such as bio-fuels are with monohydric alcohol (methanol). Most of the researchers

⁎
Corresponding author at: Catalysis Science and Technology Research Centre, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia.
E-mail address: taufi[email protected] (Y.H. Taufiq-Yap).

http://dx.doi.org/10.1016/j.rser.2017.10.098
Received 10 November 2016; Received in revised form 18 May 2017; Accepted 28 October 2017
1364-0321/ © 2017 Elsevier Ltd. All rights reserved.

Please cite this article as: Mansir, N., Renewable and Sustainable Energy Reviews (2017), https://doi.org/10.1016/j.rser.2017.10.098
N. Mansir et al. Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

recommended the short chain monohydric alcohol, typically methanol, Table 1

ethanol and propanol with no distinct justification of which provides Comparison of standards between biodiesel and fossil diesel, according to American
Standard for Testing and Materials (ASTM) [29].
the best viscosity requirements in line with specifications by American
Society of Testing and Materials (ASTM) and European Standard (EN) Fuel Property Diesel Biodiesel
or other related international agencies [13].
Technically, biodiesel is not yet considered as popular alternative Standard Method ASTM D975 ASTM D6751
Fuel composition Hydrocarbon(C10-C21) FAME(C12-C22)
source of energy to conventional fossil fuel worldwide due to its high
Cetane number 40–55 48–60
cost of production, which is attributed to the cost of raw materials and Density (g/cm3) 0.85 0.88
labour, hence the fundamental policy of biodiesel is not yet achieved. Cloud point (°C) −15 to 5 −3 to 12
Non availability of raw materials and effective catalytic system, are the Flash point (°C) 60–80 100–170
major problems facing commercialization of biodiesel to meet the Pour point (°C) −30 to −15 −15 to 5
Carbon content (wt%) 87 77
global demand and the united nation millennium environmental policy.
Hydrogen content (wt%) 13 12
Edible vegetable oils i.e. palm oil, soybean oil, sunflower oil, etc. are Oxygen content (wt%) 0 11
the traditional feedstocks for the production of biodiesel. However, the Sulphur content (wt%) 0.05 0.05
high cost of feedstock which account for more than 80% of total pro- Water content (vol%) 0.05 0.05
duction cost of biodiesel and possible hike in the prices of edible ve-
getable oils coupled with hunger threats as well as soil degradation
depends entirely on edible vegetable oil such as rapeseed (6.01 million
associated with large scale farming for biodiesel feedstocks have on the
ton), palm oil (6.34 million ton), soybean oil (7.08 million ton) and
other hand forced many agencies, particularly food and agricultural
some non-edible oil such as castor oil and Jatropha curcas oil as major
organizations to consider the option as non-reliable [14–17]. Non ed-
feedstocks worldwide [23,31]. The use of conventional feedstocks
ible vegetable oil such as Jatropha curcas oil, castor oil, algae oil etc.
(edible oils) for biodiesel accounts for more than 80% of total biodiesel
could be considered as reliable feedstocks for the production of bio-
production cost. Hence, making biodiesel more expensive and there-
diesel in commercial scale [18–20]. Nevertheless, most of these crops
fore, not sustainable. Moreover, continual usage of traditional edible
are perennial in nature and their plantation could cause unnecessary
oils as feedstock for biodiesel may result to future food versus fuel
deforestation in the near future which may affect the climatic condition
competition thus, violating one of the cardinal objective of FAME
of a particular region, hence un-economical and time consuming pro-
production [32]. Jatropha cucras oil is particularly remarkable feed-
cess [21]. Algae oil, even though considered as the most promising
stock for FAME production, as it possess about 40% oil content and can
feedstock for biodiesel due to its high oil content and easy cultivation,
grow on un-fertile soil thereby, avoiding competition with arable land
but is also far from biodiesel production in commercial quantity due to
for food crops, however Jatropha cucras seeds are toxic in nature, hence
the inadequate technical knowledge of cultivation and extraction of oil
the harvest requires severe labour [33]. Recent studies suggested that
to commercial scale [13,22]. Waste cooking/ frying oil is one of the
the production cost of FAME could be reduced to halve through the
feedstock having dual advantage. A part from being low cost feedstock
utilization of WCO in comparison to the high grade vegetable oils [33].
for biodiesel production, utilizing WCO as a feedstock, will further re-
About 15 million tons of waste cooking oil is annually been disposed in
duce water pollution for not been discharged into the water bodies
water or land across the globe. Such amount of low cost feedstock
[23].
noteworthy special consideration, as it could bridge significant gap in
current biodiesel demands [23]. Waste cooking oil, when properly
2. Biodiesel as a future and promising alternative renewable
utilized will produce biodiesel with less CO2 emission at relatively low
energy source
cost and thereby making it economically and socially viable as a re-
newable fuel. Besides that, converting WCO into FAME could help
Biodiesel or FAME is synthesized from renewable vegetable based
significantly in reducing the environmental pollution caused by its
oil or animal fat [23,24]. It is generally produced by the process of
disposal into water bodies and land [34]. Nevertheless, some chemical
esterification or transesterification reaction of fatty acid or vegetable oil
changes occur to chemical properties of WCO as a result of heating at
in the presence of monohydric alcohol, catalyst and temperature over
high temperature during cooking/ frying process which results to in-
the period of time [17,25]. The renewability, biodegradability and less
crease in the level of FFA and some impurities like water content. Ba-
toxicity are the most important features that made FAME globally ac-
sically fresh vegetable oil contained triglyceride, diglyceride, mono-
ceptable as viable and sustainable fuel for the universe [12,26]. Bio-
glyceride and free fatty acid (FFA) usually (< 1%). High FFA and water
diesel has the ability to work efficiently in similar way the traditional
contents in the feedstock hampers FAME production due to subsequent
fossil fuels works in internal combustion engines [27–29]. Although
soap formation when basic catalyst is used [30,35,36]. These challenges
FAME has some properties like pour point, flash point and cloud point a
must be taken into consideration before using it as a feedstock for
bit higher than the conventional fossil fuel, but still has similar cetane
biodiesel production using base catalysts [37]. Different feedstocks for
number and kinetic viscosity to that of normal diesel [30]. Conse-
FAME production have different fatty acid composition and in turn can
quently, protecting and prolonging the engine life due to its high lu-
influence the biodiesel yield. Other fuel properties such as acid value,
bricating property. The biodiesel properties (Table 1) are in agreement
cetane number, cloud point, flash point, oxidation stability, cold filter
with the ASTM and EN specifications, hence, allow the commerciali-
and plugging point, kinematic viscosity could also be influence by FFA
zation of biodiesel worldwide.
composition of the feedstock [38,39]. Basically, the vegetable based oils
comprised of five major fatty acids components as presented in Table 2,
3. Viability and socioeconomic impacts of biodiesel production
namely, palmitic (16:0), stearic (18:0), oleic (18:1), linoleic (18:2) and
from waste cooking oil
linolenic (18:3).
WCO has so far been considered as one of the cheapest feedstock for
Generally, biofuels are meant to represent a potential source of re-
biodiesel production, with dual advantage [35]. Utilizing it as feedstock
newable energy that could feasibly replace the conventional fossil fuels
for biodiesel is at the same time making the environment safe and
and provide eco-friendly fuel with less ecological problems i.e. global
cleaner for not being dispose into the water bodies that could pollute
warming and green house gas effects. Biodiesel is currently one of the
the water. Hence WCO is considered as economically and socially viable
most widely accepted alternative renewable sources of energy option to
feedstock for low cost biodiesel production on a commercial scale.
conventional fossil fuel. Nonetheless, biodiesel production cost remains
the major issue today. Current commercial production of biodiesel

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N. Mansir et al. Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

Table 2 Table 3
Common fatty acid composition of plant based oil [36]. Some globally accepted vegetable oil analysis and their standard methods [42].

No. Fatty acid Formula Structure wt% No. Analysis Method

1. Palmitic acid C16H32O2 16:0 7.3 1 Acid Value AOAC (2000) 940.28
2. Stearic acid C18H36O2 18:0 4.0 2 Carbon Residue ASTM D4530-00
3. Oleic acid C18H34O2 18:1 26.9 3 Density ASTM D4052-96
4. Linoleic acid C18H32O2 18:2 60.0 4 Fatty acid composition AOAC (2000) 963.33, 969.33
5. Linolenic acid C18H30O2 18:3 0.5 5 Iodine Value EN 14111
6 Kinematic Viscosity ASTM D 445-06
7 Oxidation Stability EN 14112
4. Preliminary investigations and pre-treatment of waste cooking 8 Saponification Value AOAS (1997)
9 Water Content AOAC (1990)
oil
10 Total Acid number ASTM D 664-01

Low grade biodiesel feedstock, like WCO will undergo some pre-
liminary investigations and preparations before subjecting it to FAME (56.1 × 1000 × 3)
MWoil =
production [11]. Prior to subsequent biodiesel reactions, the collected S. V (4)
WCO must be free from debris or other impurities through simple fil-
where MWoil is the molar weight of the oil sample and S.V is the sa-
tration technique [41]. The water content will subsequently be re-
ponification value. The detailed procedures of these analyses were de-
moved from WCO through drying with the aid of hot plate and stirrer at
scribed in the Association of Official Agricultural Chemists (AOAC)
120 °C. The FFA value greater than 1% is considered as higher FFA
method (2000). Zhang and Jiang [45] reported other globally accepted
content and therefore not suitable for transesterification using basic
methods for vegetable oil analysis in Table 3.
catalysts [42]. Further pre-treatment stages are needed to employ for
Different studies have been conducted on WCO to produce bio-
high FFA content of WCO (> 1%) in order to reduce the FFA value
diesel. Meng et al. [46] produced FAME from waste cooking oil using
to < 1% before been transesterify to FAME, otherwise a saponification
sodium hydroxide (NaOH) as a catalyst and methanol as reaction
will occur which will greatly affects the biodiesel yield [43]. However,
medium. The effects of different reaction parameters on conversion and
the pre-treatment stage previously employed to reduce the high FFA
quality of FAME were investigated. At the end of the study, 86% con-
value of the feedstock before been subjected to transesterification re-
version under the optimum reaction conditions of 6:1 methanol to oil
action process is now considered as time and material consuming,
ratio, 0.7 wt% catalyst loading, 90 min reaction time and 50 °C reaction
which will make biodiesel production difficult and expensive, and
temperature were recorded. Similarly, Arquiza et al. [47] investigated
therefore, new catalytic route of using modified heterogeneous solid
the effect of operating parameters in the production of biodiesel from
bifunctional catalysts is now adopted in order to avoid the pre-treat-
waste coconut oil using NaOH catalyst and methanol. Under the op-
ment stage [44].
timal reaction conditions of 60–65% reaction temperature, 0.5 wt%
Basically, prior to embark on FAME production reaction, the
catalyst loading and 6:1 methanol to oil ratio, FAME yield of 94% was
number of investigative analysis of WCO needs to be carried out in
achieved. There are various reports of biodiesel production from waste
order to know certain physico-chemical parameters of the feedstock
cooking oil using conventional homogeneous catalyst, typically NaOH
(WCO). Acid value, saponification value and molecular weight of the
[48–50]. Hence, waste cooking oil is now considered as a reliable
feedstock are crucial point before either transesterification or ester-
feedstock that could help in replacing the expensive edible oil for bio-
ification reaction. A simple titration method, usually in agreement with
diesel production in commercial quantity.
ASTM, EN and other scientifically accepted procedures are used to
determine the aforementioned physico-chemical parameters of the said
feedstock. 5. Catalysis of transesterification/esterification
Acid value is the acid number contained in the oil sample. It is used
to determine the FFA level in the oil sample. According to ASTM-D974 Generally a catalyst is defined as any material or substance that
acid value is calculated using the formula below; speeds up the rate of chemical reaction by lowering its activation en-
ergy [51]. It is usually added in a minute amount in comparison to the
A × M ×56.1 quantity of the reactants, which is not consumed during the chemical
A. V =
W (1) reaction; it is also known as an initiator. However, in some cases the
where A.V is the acid value in (mg KOH/g), A is the amount of po- catalyst inhibits the reaction by been consumed and regenerated, while
tassium hydroxide (KOH) consumed by the sample, M is the molar in other cases it seems not to include in the process and functions by
concentration of KOH and W is the weight of the oil in grams. Hence the high calibre of surface characteristics [52]. Catalysis generally re-
FFA value is calculated using Eq. (2). present the vital technology for accelerating essential chemical con-
version, which is a key to recognize environmentally friendly and
A. V commercially feasible reactions for transforming energy carriers to di-
FFA =
2 (2)
rectly usable energy. However, the use of heterogeneous catalysts for
Saponification value indicates the amount of KOH needed to sapo- chemical conversions not only decreases the total energy input needed
nify 1 g of oil. It can be calculated using the formula in Eq. (3) ac- for production processes, but also improves two considerable catalyst
cording to ASTM D5558-95. aspects, i.e. selectivity and thermal stability, thus leading to ecologi-
cally benign green technology.
MMKOH (B – S ) × MHCl
S. V =
W (3)
5.1. Homogeneous catalysts for biodiesel production
where S.V is the saponification value, B is the volume of hydrochloric
acid (HCl) in (ml) required by the blank, S is the volume of HCl in (ml) Commercial production of biodiesel from vegetable oil relies solely
required by the sample, MM is the molar concentration of KOH, M is the on homogeneous catalysts considering their major advantage of re-
molar concentration of HCl and W is the weight of the oil in (g). Sa- duced mass transfer resistance effect, hence faster reaction efficiency
ponification value plays an important role in determining the sample's when compared to the heterogeneous catalysts. The homogeneous
molecular weight according to the formula in Eq. (4). catalysts used in methanolysis could either be acidic or basic in nature.

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N. Mansir et al. Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

Basic homogeneous catalysts are the most frequently used catalysts to homogeneous catalysts and therefore increasing the biodiesel yield
assist the biodiesel production process at industrial scale. This is due to [53]. Biodiesel production is deemed to be promoted and sustained
the faster reaction efficiency of base-catalysed transesterification reac- economically, through proper usage of heterogeneous catalysts. Solid
tion process when compared to acid catalysts which, generally react at catalysts are in different phase with the reaction medium and therefore,
slower rate; consequently, producing high biodiesel yield at mild re- facilitate it is separation from post reaction mixture [62]. Hetero-
action conditions [53]. However, the FFA and water content of the geneous catalysts could successfully be separated from the reaction
feedstock are the fundamental consideration on choosing the type of mixture via physical process, using either filtration or centrifuging
catalyst to be used in a particular biodiesel production reaction. method. Consequently, this would enable the reutilization of these
The most commonly used homogeneous catalysts for biodiesel catalysts more than once, as in the case of homogeneous catalysts,
production are hydroxides and alkoxides of alkali metals such as KOH, hence reducing the biodiesel cost [63,64]. Additionally, the level of
NaOH, sodium methoxide (CH3ONa) and potassium methoxide dissolved metals or other elements ascending from catalyst in the pro-
(CH3OK) [54,55]. In all of the listed homogeneous catalysts, KOH and duced biodiesel or glycerol could remarkably reduced when hetero-
NaOH are the most used catalysts for biodiesel production at com- geneous catalysts are properly utilized [53].
mercial scale as a result of their ability to catalyze transesterification However, heterogeneous solid catalysts are also far from perfection
reaction at relatively low reaction temperature and high reaction rate as their counterpart homogeneous catalysts. Their major downside is
which is about 4000 times faster than acid catalyst reaction rate [56]. low or limited catalytic active centers in comparison to the conven-
High biodiesel yield could also be achieved at short reaction time, and tional homogeneous catalysts; consequently, necessitate the usage of
most importantly, these catalysts are cheap and easy to get [53]. Sev- severe reaction conditions in order to match the oil conversion related
eral studies have been conducted on different feedstocks to produce to what is obtained by homogeneous-catalysed biodiesel production
biodiesel using homogeneous catalysts. Uzun et al. [55] reported the [65]. Similarly, mass transfer resistance concerns associated to het-
biodiesel yield of 96% at a reaction temperature of 50 °C, and 30 min erogeneous catalyst owing to the presence of two or three different
reaction time when NaOH catalyst was used on soybean oil using me- phases (methanol, oil and solid catalyst) in the reaction mixture could
thanol as reaction medium. Similar studies was conducted by Fadhil be linked to slower reaction rate in the conversion of vegetable oil/lipid
and Ali [57], where KOH catalyst was used to transesterify Heckel fish to biodiesel [66]. Heterogeneous catalysts require some preparatory
oil, and 97% of biodiesel yield was recorded at 32 °C reaction tem- processes for their synthesis, which are generally time-consuming. The
perature, 60 min reaction time, 6:1 methanol to oil ratio and 5.5 wt% high price of the materials needed for the synthesis of these catalysts
catalyst loading. However, formation of soap and other unwanted would also make the biodiesel more expensive. Furthermore, poisoning
emulsions as a result of presence of FFA content (> 1%) and other of the catalytic active sites of the catalysts when exposed to the sur-
impurities from low grade feedstock is another problem that may rounding atmospheric medium could affect the stability and activity of
hinder biodiesel yield [58] The prominent homogeneous acid catalysts some catalysts. Hence detail information regarding the physical and
for methanolysis are mineral acids such as HCl and sulphuric acid chemical properties of solid material is necessary. Presently, enormous
(H2SO4) [59]. Others are nitric acid (HNO3), aluminium chloride scientific efforts are on course to develop stable and sustainable het-
(AlCl3), organic sulfonic acid and phosphoric acid (H3PO4) [53]. erogeneous catalytic system that would ensure biodiesel production
Homogeneous acid catalysts generally have a slow reaction rate, and from low grade feedstock [53]. Heterogeneous catalysts could be basic
therefore, take long reaction time to esterify feedstock to biodiesel. or acidic in nature [62]. Both classes of heterogeneous catalysts could
Marchetti and Errazu [60] reported the biodiesel yield of 96% from be utilized in alcoholysis process depending on the FFA content of the
model oil prepared using oleic acid and sunflower oil when H2SO4 was feedstock. Basic heterogeneous catalysts when properly manage could
used as a catalyst at 55 °C reaction temperature, 6.126:1 methanol to oil transesterify feedstock containing up to 3% FFA at mild reaction con-
molar ratio, 2.26 wt% catalyst loading and 240 min was the time taken ditions in a single run process [67]. Heterogeneous solid acid catalysts
to satisfactorily completes the reaction process. In a related study, could best esterify low grade oil such as palm fatty acid distillate
Soriano et al. [61] reported that 98% yield of biodiesel was achieved (PFAD), lipids containing more than 85% FFA at mild reaction condi-
when canola oil was subjected to methanolysis using AlCl3 as a catalyst tions [68]. Heterogeneous acid catalysts could transesterify low grade
under the reaction temperature of 110 °C, catalyst loading of 5 wt%, oil such as waste cooking oil containing high FFA at long reaction time
methanol to oil molar ratio of 1:1 and 1080 min as reaction time. and very high reaction temperature in a single run reaction process
However, homogeneous catalysts can only use in food grades oils [69–71]. In order to avoid severe reaction conditions on the transes-
(palm oil, soybean oil etc.) as feedstock and therefore, making biodiesel terification of low grade feedstock like waste cooking oil and jatropha
production expensive. Moreover, homogeneous catalysts are peculiar to oil, modified bifunctional heterogeneous catalysts that could perform
separation problems after the reaction process, which involves regular both transesterification and esterification reaction processes simulta-
water washing that require a substantial amount of water and conse- neously at mild conditions are highly recommended.
quently, pollute the environment due to generation of acid water.
Hence, homogeneous catalysts are not environmentally and econom- 5.3. Solid base catalysts
ically benign for the sustainable biodiesel production at industrial scale.
Heterogeneous solid base catalysts constitute of alkaline metals and
5.2. Heterogeneous catalysts for biodiesel production alkaline earth metals which made the group one and two of the periodic
table. These basic materials have been utilized as heterogeneous cata-
Heterogeneous catalysts are catalysts that are in different phase lysts for biodiesel production process. Heterogeneous base catalysts
with the reacting medium in a reaction process. In biodiesel production, could be single alkaline earth metal oxides, supported alkali metal and
the feedstock and reaction medium, usually short chain alcohol (me- alkaline earth metal oxides, mixed metal oxides, hydrotalcites and an-
thanol) are in liquid phases, and the heterogeneous catalyst for the ionic ion-exchange resins.
reaction in solid phase. With the emergence of solid heterogeneous Alkaline earth metal oxides catalysts, if properly modified have the
catalysts for biodiesel production, most of the technical problems re- capacity to assist transesterification reaction to feedstock containing
lated to conventional homogeneous catalysts would be reduced. In re- low FFA (at least 3%) for a single run process, owing to their high basic
cent years, heterogeneous catalysts are immensely receiving scientific strength. The basic strength of group II oxides and hydroxides is pro-
and industrial attention, perhaps owing to their economic and en- moted with the increase in atomic number ranging from magnesium
vironmental friendly. If properly utilized, heterogeneous catalysts (Mg) to Barium (Ba), which significantly affects their catalytic cap-
would solve the post-reaction washing problems associated with the ability to transesterify lipid feedstock [72].

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N. Mansir et al. Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

The source of basic centers in alkaline earth metal oxides could be homogeneous counterparts. Heterogeneous solid acid catalysts when
linked to the presence of M2+and O2- ion pair and surface hydroxyl properly utilized are expected to yield outstanding grade biodiesel from
group in a different coordination environment. The surface oxygen of vegetable based oils. Moreover, unlike homogeneous acid catalysts,
these oxides could be affected by the surface composition of the solid heterogeneous acid catalysts are not associated with corrosion of bio-
catalysts and calcination temperature. Moreover, the specific surface diesel production plant/equipment [82]. More importantly, hetero-
area, degree of leaching in the reaction medium, basicity and selectivity geneous acid catalysts could simultaneously accelerate both transes-
during the transesterification reaction process must be considered as terification of triglycerides (TGs) and esterification reactions of FFA.
important factors in choosing the appropriate catalyst for biodiesel The two reactions; transesterification and esterification are catalysed by
production [53]. The most commonly used basic heterogeneous catalyst bronsted acid species and lewis acid species respectively [53,83,84]. It
for transesterification process is calcium oxide (CaO) [5]. This is due to is generally assumed that biodiesel production reaction is similar for
the possession of higher basicity, low solubility, easy to handle and both homogeneous acid catalysts and heterogeneous acid catalysts,
most importantly availability of CaO at relatively low cost. Ad- except that the heterogeneous acid catalysed reaction is influenced by
ditionally, CaO derives its popularity for catalysis as a result of its the catalysts surface, which depends heavily on the interconnected
abundance in different natural resources in the form of calcium car- system of large pores, surface acid sites and hydrophobicity [53].
bonate (CaCO3). Apart from lime stone, which is natural but non-re- Heterogeneous acid catalysts can esterify waste oil like palm fatty acid
newable source of CaCO3, other renewable natural sources are egg distillate, which has over 85% FFA content and other low grade feed-
shells [73,74], crab shells [73], capiz shells [75], snail shells [76], stocks like waste cooking oil to biodiesel [30]
mussel shells [77] and oyster shells [78] among others. Proper utili- However, heterogeneous acid catalysts can only perform biodiesel
zation of waste egg shells for the synthesis of CaO will considerably production reactions under severe reaction conditions such as high
reduce the over dependency on non-renewable lime stone as a source of reaction temperature, low reaction rate and long reaction period. These
CaO. Waste egg shell is believed to have a high content of CaCO3, drawbacks may probably make biodiesel production difficult and ex-
having a composition of about 97.1%. This shell when thermally pensive. Several studies were reported on biodiesel production from
treated at 900 °C for 2 h, would result in the formation of CaO catalyst low grade feedstocks using heterogeneous solid acid catalysts under
[53]. Besides the economic advantages, the performance of CaO as a severe reaction conditions as presented in Table 4. Hence, the new
catalyst for biodiesel production could match the conventional homo- route of catalytic system that can perform biodiesel production process
geneous catalysts having achieved outstanding conversion yield over on low grade feedstock under moderate reaction conditions is needed.
some selected feedstocks. Kawashima et al. [79] reported 90% biodiesel Waste egg shell derived CaO supported by acidic transition metal oxides
yield when transesterification reaction was performed on rapeseed oil like WO3, MoO3, TiO2 when properly utilized could perform a trans-
using CaO as catalyst and methanol as reaction medium, other reaction esterification reaction process on low grade feedstock like waste
conditions used are 60 °C as reaction temperature, 0.1 g catalyst weight cooking oil at moderate reaction conditions. Most of the waste cooking
and 3 h reaction time. Similarly, Lee et al., [80] reported biodiesel yield oils are having between 2% and 15% FFA content [85,86] depending on
of 86.75% from palm oil using obtuse horn derived CaO as a catalyst how much the oil was used in frying purposes. About 85% of the waste
under the optimum reaction conditions of 5 wt% catalyst loading, 6 h cooking oil component are triglycerides, which undergo transester-
reaction time and 12:1 methanol to oil ratio. CaO material irrespective ification reaction during methanolysis, and the remaining component is
of its source, is unstable, hence, prone to poisoning effects when ex- FFA which undergoes esterification process during biodiesel produc-
posed to atmospheric medium i.e. carbon dioxide (CO2) and water tion. The CaO catalyst would transesterify the triglycerides (TGs) and
(H2O) which would results in the formation of CaCO3 and Ca(OH)2 the acidic transition metal such as WO3, MoO3, ZrO2 or TiO2 will assist
layers, respectively on the catalytic surface [81]. These effects distort in esterifying the FFA content of the oil. Mixed oxide bifunctional
and block the catalytic active sites hence lowering the activity of the catalysts could sustain biodiesel production from low grade feedstock at
catalysts and biodiesel yield [53]. moderate reaction conditions (Table 5).
Despite the encouraging results obtained using these catalysts, CaO
catalyst alone could not transesterify low grade oil such as waste 5.5. Modified waste egg shell derived bifunctional catalyst
cooking oil and Jatropha oil. This is due to the presence of high FFA
(> 3%) content and other impurities such as water in a single run Generally, separation and waste water disposal problems, corrosion
process. In order to transesterify low grade feedstock like waste cooking of biodiesel refining equipments increases concerned over the usage of
oil using CaO catalyst, two stage processes must be involved to reduce heterogeneous catalysts [87,88]. Usage of solid heterogeneous catalysts
the FFA content to (< 3%). These processes are considered as time and for biodiesel production can overcome the separation problems. Het-
resource consuming, making biodiesel production difficult and ex- erogeneous basic catalysts in which basic component comes from waste
pensive. Hence, for the CaO catalyst to work successfully on low grade material like egg shell is considered as environmentally benign due to
feedstock like waste cooking oil and Jatropha oil that have high FFA its biodegradable property hence can greatly reduce the environmental
content (> 3%), there is need for further modification that will provide problems. Over the last few years, there were greater concerns over the
some acid centers so that to esterify the high FFA present in the feed- heterogeneous catalysts whereby intensive researches were conducted
stock for efficient and sustainable biodiesel production. The modifica- for transeterification reactions over these catalysts [80,89–92]. The best
tion of basic heterogeneous catalysts like CaO for high activity on low heterogeneous catalysts should have strong basic sites, large surface
grade oil could be doping with other metal oxides from transition area, large pores, less toxicity, high stability, less corrosive effect, ease
group. Some transition metal oxides like molybdenum trioxide (MoO3), separation, high reusability, less leaching effect and low cost of pre-
tungsten trioxide (WO3), titanium dioxide (TiO2) and zirconate (ZrO3) paration [30].
possessed some acidic properties that would enhance the catalytic ac- Mixed oxides catalysts are originated from metal oxides, particu-
tivity during transesterification of low grade feedstock like waste larly alkali earth metal oxides, lanthanide metal oxides or other tran-
cooking oil. sition metal oxides. Mixed oxides catalysts could be basic, acidic or bi-
functional (having both acidic and basic properties). Bi-functional
5.4. Solid acid catalysts heterogeneous catalyst if utilized properly could perform both trans-
esterification and esterification of TGs and FFA simultaneously under
In recent years, heterogeneous solid acid catalysts are receiving moderate reaction conditions, respectively. This is due to the fact that,
greater attention from scientific and industrial point of view for bio- bi-functional catalysts are having both basic and acidic sites and
diesel production. This is due to their several advantages over their therefore can act as acid and base at the same time. Additionally, bi-

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N. Mansir et al. Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

Table 4
A literature report on biodiesel production from different feedstocks using solid acid catalysts at severe reaction condition.

Catalyst Preparation Method Reaction conditions Feedstocks Yield (%) Ref

Temperature (°C) Reaction Time Catalyst loading Methanol to oil

(h) (wt%) molar ratio

Al2O3/ZrO2/WO3 Co-precipitation 175 1 4g 40:1 Soybean 100 [77]

Zirconia supported HPA Hydrolysis 200 5 3 20:1 Sunflower mustard 97 [78]
Cs2.5H0.5PW12O40 Precipitation 260 1 3 40:1 Sesame oil 92 [22]
CsHPW Precipitation 200 10 3 20:1 Oleic acid-Soybean 90.4 [79]
mixture
WO3/ZrO2 Impregnation 75 20 Not specified 19.4:1 Not specified 85 [80]
Al2O3/TiO2/ZnO Sol-gel 200 8 5 Not specified Colza oil 93.7 [61]
Mn3.5xZr0.5yAlxO3 Co-precipitation 150 5 2.5 14:1 WCO > 93 [62]
Ar-SBA-15 Direct mixing 140 2 6 20:1 Crude palm oil 90 [81]
Sulfated ZrO2 Impregnation 180 1 3 3:1 Dodecanoic acid 96 [60]
Ar-SBA-15 Not reported 260 2.5 1 20:1 Crude palm oil 90 [81]
VOPO4.2H20 Not reported 150 1 2 1:1 Used cooking oil 80% [60]
Carbonized and Sulfated Carbonization 260 1 2.5 18.2:1 Waste cooking oil 89.9 [82]
asphalt
SO42-/TiO2-SiO2 Impregnation 200 3 4 9:1 Used cooking oil 90 [83]
2-
SO4 /SnO2-SiO2 Impregnation 150 3 4 15:1 Waste cooking oil > 92.3 [84]
ZrO2/SO42- Sulfonation 200 1 1 6:1 Palm kernel 90.3 [85]
Al2O3/TiO2/ZnO Co-mixing 200 6 8 1:1 Colza oil 93.7 [86]
TiO2/SO42- Precipitation 230 2 8 12:1 Coconut oil Cotton oil 86.3 90 [81]
ZnO Not reported 300 3 1 6:1 Soybean 80 [85]
SO42-/ZrO2/TiO2/La3+ Precipitation 200 5 2 15:1 Not reported 90 [61]
Al2O3/ZrO2/WO3 Wet impregnation 200 20 4g 4.5:1 Soybean oil > 90 [21]

functional catalysts can easily be modified to introduce the needed [69] and physical mixing/co-mixing [93] depending on the precursor of
physicochemical properties that could easily overcome the problem of the metal oxides. These preparatory methods are not only simple and
high FFA and water content present in the low grade feedstock like easy, but economically feasible as does not involve high technical
waste cooking oil during the transesterification reaction [44]. Hence, complex procedures that would make the synthesis difficult and ex-
modified waste egg shell derived bifunctional heterogeneous catalysts pensive. Biomass based bifunctional catalyst involves the use of simple
could be promising alternative catalysts to overcome the problems as- waste material (waste egg shell, palm kernel shell etc.) and few che-
sociated with other catalysts. Over the recent years, several researches micals. These catalysts are ecofriendly and therefore, reduced en-
were undertaken using modified mixed oxide catalysts with bifunc- vironmental hazards greatly through biodegradation process. The fea-
tional activity to produce biodiesel from high FFA feedstock under mild sible techniques for the synthesis of these catalysts are fully discussed
reaction conditions as presented in Table 5. In this study, similar cat- below.
alyst with bifunctional capability would be synthesized using transition
metal oxides (WO3, ZrO2, MoO3 etc.) supported on CaO from the waste
egg shell and employ for biodiesel synthesis from WCO. 6.1. Wet impregnation method

The wet impregnation method is one of the easiest methods of

6. Preparation methods of bifunctional solid catalysts catalyst preparation. During wet impregnation catalyst synthesis, the
precursors usually in salt form or salt and oxide forms are mixed to-
Mixed oxides bifunctional heterogeneous catalysts can be synthe- gether in a beaker with distilled water and stirred for at least five to six
sized through different catalyst preparatory methods such as; wet im- hours. After while the resultant slurry would be dried at 110 °C for 24 h
pregnation method [90], co-precipitation method [29], sol gel method in an oven. The dried sample would be calcine in a furnace at

Table 5
A literature report on biodiesel production from high FFA feedstocks using bifunctional catalysts under mild conditions.

Catalyst Preparation Method Reaction conditions Feedstocks Yield (%) Ref

Temperature (°C) Reaction Time Catalyst loading Methanol to oil molar

(h) (wt%) ratio

CaO/La2O3 Co-precipitation 65 6 4 24:1 Jatropha curas 86.51 [27]

oil
Bi2O3–La2O3 Impregnation 150 4 2 15:1 Jatropha curas 93 [6]
oil
Mo-Mn/ˠ-Al2O3-15 wt% Wet Impregnation 100 4 4g 27:1 Waste cooking 91.4 [40]
MgO method oil
Mn3.5xZr0.5yAlxO3 Co-precipitation 150 5 2.5 14:1 Waste cooking > 93 [66]
oil
Cs-Zr/Al2O3 Impregnation 65 3 3 20:1 Waste cooking 90 [15]
oil
CaO-ZrO2 Impregnation 65 2 10 30:1 Waste cooking 92.1 [64]
oil
SO42-/SnO2-SiO2 Impregnation 150 3 4 15:1 Waste cooking > 92.3 [87]
oil

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N. Mansir et al. Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

O Fig. 1. General equation for transesterification reaction of bio-

O
R4 O C R1 diesel synthesis from triglycerides [49].
H2 C O C R1 H2C OH
O Base O
HC O C R2 + 3R4OH R4 O C R2 + HC OH
O Catalyst O
H2 C O C R3 R4 O C R3 H2C OH
Triglycerides FAME Glycerol

appropriate temperature [90,93]. The wet impregnation method is very furnace [93].
simple and effective in synthesizing supported catalyst as it could be
able to fabricate several active sites on the surface of catalyst which are 7. Physical and chemical characterization of modified waste egg
favourable in transesterification/esterification reaction processes. shell derived CaO catalysts for biodiesel production from waste
cooking oil
6.2. Co-precipitation method
In order to ascertain the catalytic activity of the heterogeneous
Co-precipitation/precipitation method of catalyst synthesis involves mixed oxide catalysts, quite number of laboratory characterizations and
dissolution of catalyst precursors usually salt precursors into distilled other relevant analysis must be carried out. The acidic and basic
water and then stirred vigorously. To this mixture, precipitating agents properties of the catalyst could be determined using ammonia tem-
usually alkaline, such as ammonium hydroxide (NH4OH), KOH, NaOH, perature program desorption (TPD-NH3) and carbon dioxide tempera-
potassium carbonate (K2CO3) is added to precipitate the solution at ture program desorption (TPD-CO2), respectively [7]. The surface area
constant stirring for 3 h and the pH of the solution is maintained at 10. and pore size of the catalyst is measured by Brunauer-Emmett-Teller
The resultant precipitate would be dried in oven at 110 °C over night, (BET) specific surface analysis [39,94]. Crystallography, elemental
after which the dried sample would be calcine in the furnace at ap- composition and functional group analysis determinations are carried
propriate temperature [29,93]. This method could be able to facilitate out by X-ray diffraction (XRD), X-ray fluorescent (XRF), energy dis-
the development of bimetallic oxide supported CaO catalyst exhibiting persive X-ray spectrometry and Fourier transform infrared (FTIR), re-
highly acidic or basic property due to synergetic effect from the two or spectively [8,90]. It is generally known that, the calcination process of
three metal oxides involved. the solid heterogeneous catalysts in the form of carbonate or hydroxide
will maximize the active sites responsible for the catalyzation of
6.3. Sol gel method transesterification reaction. The appropriate calcination temperature of
mixed oxide catalysts is determined by thermal gravimetric analysis
Sol gel method is another technique used for catalyst synthesis, (TGA) which measures the thermal stability of the sample [58]. The
which involves the mixing of butyl titanate and anhydrous ethanol in morphology of the catalyst is obtained by scanning electron microscope
drop wise to another solution of deionized water, anhydrous ethanol, (SEM) [8,58]. With regard to catalyst leaching, which is peculiar to
nitric acid and appropriate amount of nitrate precursor at room tem- most of the metal oxides particularly alkali earth metal oxides, atomic
perature under vigorous stirring to carry out hydrolysis. A yellowish absorption spectroscopy (AAS) is used to measure the level of leached
transparent sol would form after constant stirring for 3 h. The sol would elements into biodiesel product [95].
be dried at 80 °C for 24 h to form xero-gel which would subsequently
crush and sieve to 60–100 mesh and then calcine at appropriate tem- 8. Biodiesel synthesis processes
perature in the furnace [69].
Biodiesel or FAME is generally produced by the transeterification
6.4. Physical mixing method reaction of TGs or esterification reaction of FFA. During transeter-
ification reaction process, 1 mol of triglycerides react with 3 mol of
The physical mixing method involves mixing and grinding of pure methanol in the presence of catalyst and temperature to produce 3 mol
metal oxides together using agate mortar. The oxides are usually mixed of methyl ester (biodiesel) and glycerol as presented in Fig. 1. Chan and
with distilled water in a beaker and stirred constantly for five hours. Fang [96,97] reported that the transesterification reaction can be for-
The resulting slurry would be calcine at an appropriate temperature in a mulated in three step reaction processes as depicted in Fig. 2.

Fig. 2. Three step equations for transesterification reaction pro-

cess of biodiesel production from triglycerides [49].

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N. Mansir et al. Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

Fig. 3. General equation for the esterification reaction of bio-

diesel production from a fatty acid.

Transesterification reaction is reversible reaction process and therefore 9.3. Effect of methanol to oil molar ratio
requires high amount of methanol in order to move the reaction for-
ward [53]. The excess methanol and glycerol produced together with Methanol to oil molar ratio is one of the four reaction parameters for
FAME at the end of the reaction could be separated using centrifuge the biodiesel production reaction. This parameter plays an important
[98]. Transesterification reaction rate using solid base catalyst is faster role both in transesterification and esterification reaction process.
than esterification reaction using solid acid catalyst. This is due to the During esterification of high FFA oil to biodiesel, which is reversible
slower reaction rate of solid acid catalyst resulting from lower degree of reaction process, excess methanol is necessary in order to increase the
catalyst contact with oil and methanol [96]. reaction rate and biodiesel yield [101]. Conversions of TGs to FAME
In esterification reaction 1 mol of free fatty acid reacts with 1 mol of occur when it reacts with the active site of the catalyst. At a molecular
methanol in the presence of an acid catalyst to produce 1 mol of FAME stage, TGs are protonated at the carbonyl group to form the carbonation
and water as shown in Fig. 3. Chen and Fang [96]. ion, which can undergo a reaction to form esters [30]. Nevertheless,
active sites are flooded with excess methanol which hinders the pro-
tonated TGs. Yan Li et al. (2010) reported that 90% of biodiesel yield
9. Reaction conditions and their effect on biodiesel yield
was achieved at the maximum of 15:1 methanol to oil molar ratio. No
significant increase in biodiesel yield was observed from 15:1 to 18:1
Biodiesel production reaction occurs under different reaction con-
methanol to oil molar ratio hence 15:1 was adopted in view of eco-
ditions like temperature, which has effects on calcination of the catalyst
nomics and methanol recovery after the reaction [70]. The high amount
and biodiesel reaction, methanol to oil molar ratio, reaction time and
of methanol during methanolysis was reported to be problematic during
catalyst loading, all of which have different effects on biodiesel pro-
separation process. This is due to the formation of emulsion from ester
duction process. In order to obtain a higher biodiesel yield with fulfilled
layer and glycerol layer formed. The polar nature of the methanol made
standard specification, these conditions must be optimized during the
it to act as emulsifier which enhances the formation of emulsion [101].
reaction process.
However, it is generally concluded that excess methanol increases the
production yield and also enhances the interaction between TGs mo-
9.1. Effect of calcination temperature lecules and catalyst [102,103].

Calcination temperature plays enormous role in catalyst synthesis, 10. Alternative techniques for biodiesel production
through the development of the major catalytic properties such as basic
and acidic site densities, surface area, pore volume as well as molecular Biodiesel can be produce popularly by esterification process of FFA
and crystalline structure. During calcination process, catalysts are or transesterification process of TGs using different techniques. High
subjected to high temperature which exposes the catalytic sites by renewable energy demand requires more advanced techniques such as
eliminating the loosely bound carbon dioxide and water molecules and microwave, autoclave and ultrasound reactors for the production of
also rearranges the bulk atoms on surface of the catalyst [70]. Park Y-M, biodiesel in commercial scale.
et al., [99] reported the increase in FAME yield from 62% to 90% when
the calcination temperature was varied from 250 °C to 350 °C for 4 h. 10.1. Conventional reflux method
This is due to the increase in calcination temperature to 350 °C which
enhance the catalyst performance for transesterification process. Conventional reflux method is one of the most commonly used
However, excessive increase in calcination temperature during the technique for biodiesel production, which is equipped with two or three
catalyst synthesis may results to decrease in FAME yield, signifying low neck round bottom flask placed in an oil bath on stirring hot plate and a
catalytic performance. This might be due to the gaseous diffusion out of water cool condenser; the setup is placed in a fume-cupboard during the
the pores during the thermal treatment resulting to surface pores lim- biodiesel production process. However, low or moderate reaction
itation or partial removal of the binding water molecules from catalyst temperature and lower pressure are considered as the major setback to
structure which may lead to damage of the catalyst and subsequently this technique. Hence, using reflux method for biodiesel reaction that
form unknown species [71,100]. occur at normal pressure and sufficiently high temperature could not be
achieved [30]. Slow reaction rate was also observed in conventional
9.2. Effect of catalyst loading reflux method which occurs as a result of energy transfer that depends
on conventional current and thermal conductivity of the reaction
Catalyst is generally believed to speed up the reaction process by mixture [104]. The conventional normal reflux set up is presented in
lowering the activation energy. Conversion of triglycerides or lipids to Fig. 4.
biodiesel involves the use of catalysts which speeds up the reaction
process by lowering the needed activation energy. Lower catalyst 10.2. Autoclave reactor
loading is usually applied in the initial stage of the reaction and the
conversion yield is measured. The subsequent catalyst loading will be Autoclave reactor is the general reactor for biodiesel production
increased periodically at constant reaction conditions until the best reaction processes. It could be applicable to high temperature and
biodiesel yield is achieved. Amani et al. [71] reported the high FAME pressure esterification reaction using acid catalysts. The pressure and
yield of 90% with increase in catalyst loading to 3 wt% after 3 h re- reaction temperature could be greater than the boiling point of the
action time which was considered as optimum catalyst loading for the methanol because it provides closed system reaction. More importantly,
reaction. Biodiesel yield was decreased to 83% when the catalyst the reaction temperature, pressure, feedstock or alcohol flow and stir-
loading was increased to 4 wt%. Low catalyst loading could result to ring speed could be monitored and controlled on the computer program
methanol solubility in low grade feedstock like waste cooking oil [99]. [94,98], hence, low and moderate temperature transesterification

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N. Mansir et al. Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

Conversionof FFA (%) = [1 − (FinalAcidvalue /InitialAcidvalue )] × 100%.

(6)

12. Conclusion

Conventional production of biodiesel from edible oil such as soy-

bean oil, palm oil over traditional (homogeneous) catalytic system
could no longer be sustained as an alternative source of energy, con-
sidering the future food versus fuel competition. Besides, food grade
vegetable oils are very expensive, and more than 80% of total pro-
duction cost of biodiesel is accounted for the feedstock used. Non edible
oils such as waste cooking oil, jatropha curas oil, animal fats and grease,
are considered as sustainable feedstocks for biodiesel production con-
sidering their availability and low cost. Research shows that the pro-
duction cost of FAME could be reduced to halve through the utilization
Fig. 4. Schematic diagram of conventional reflux setup for the biodiesel production [33]. of waste cooking oil as feedstock in comparison to the food grade ve-
getable oils. Hence waste cooking oil could be a viable and sustainable
feedstock for FAME production due to its low cost. Nevertheless, the
category of these feedstocks is considered as low grade oils due to the
presence of impurities such as moisture and high FFA content (> 1%).
Conventional catalytic system (homogeneous catalyst) is another pro-
blem facing the commercialization of biodiesel production due to its
separation and other environmental related problems after the reaction.
The homogeneous catalyst system forms soap on high FFA feedstock
and therefore reduces the biodiesel yield at the end of the reaction.
Heterogeneous solid base catalysts are only suitable for low grade
feedstock containing < 3% FFA, otherwise, multiple steps transester-
ification reaction process is necessary. Solid acid catalyst is also far
from perfection as it can only convert triglycerides to biodiesel under
severe reaction conditions (high temperature and long reaction time).
This study discussed new catalytic system from bio source (waste egg
shell) incorporated in transition metal oxides that could make an ex-
cellent bifunctional heterogeneous catalyst, that is renewable, biode-
Fig. 5. Schematic diagram of autoclave reactor for biodiesel production [28]. gradable with least environmental effects, and could convert waste
cooking oil to FAME under moderate reaction conditions. The step by
step processes of FAME production from waste cooking oil were also
reaction is also applicable to this reactor. However, the major setback of
discussed. FAME production from waste cooking oil over modified
this reactor is that it requires regular maintenance and consume large
waste egg shell catalyst would make a sustainable and low cost alter-
amount of electricity which could possibly make biodiesel more ex-
native renewable source of energy with less environmental effect.
pensive [30]. The schematic diagram of typical Autoclave reactor is
displayed in Fig. 5.
13. Future direction

11. Biodiesel quantitative analysis Considering the current global energy demand, there is an urgent
need to diversify into other alternative sources of energy. The over
Gas chromatography and flame ionization detector (GC-FID) is the dependent fossil fuel is no longer sustainable due to its un-renewable
combined equipment used for the determination of the composition of nature and environmental problems such as global warming.
FAME from biodiesel, which is in accordance with the EN 14103 pro- Renewable sources of energy like biofuels are now considered as the
cedure. The GC setup is made up of HP-INNOWax polar capillary best option to conventional fossil fuels due to its biodegradability, less
column with the length of 30 m and a thickness of 5 µm with the in- toxic and similar performance with fossil fuel.
ternal diameter of 0.33 mm; the carrier gas and the internal standard of Commercialization of FAME production to meet the global energy
FID is Helium gas. During the GC-FID analysis 1 µL of each sample is demand is the only solution to the current energy challenges. However,
usually mixed with methyl heptadecanoate as internal standard and current FAME production is not sustainable considering the high pro-
injected manually. The starting temperature is 50 °C, the initial rate is duction cost when high grade oil is used as a feedstock and the con-
15 °C/min up to 180 °C followed by second rate at 17 °C/min up to ventional catalytic system which is associated with separation pro-
230 °C and finally from the rate of 30 °C up to 380 °C with a holding blems. These problems could only be solved through the reduction of
time of 10 min [94,98,101]. cost of production and better catalytic systems.
Simple formulas were proposed by Wan Omar and Amin, Guo et al. The conventional feedstock for FAME production is high grade oil
[105,106] to calculate the percentage yield of methyl ester and Nasci- with low FFA (< 1%) content which can easily be converted to bio-
mento et al. [107] to calculate the percentage of FFA conversion when diesel at low reaction conditions. However, about 80% of total pro-
high FFA feedstock is used for biodiesel production. The two suggested duction cost of FAME will go to feedstock when high grade oil is used as
formulas are displayed in Eqs. (5) and (6), respectively. a feedstock. Using Waste cooking oil as a feedstock for FAME produc-
tion will reduce the production cost to halve when compared to high
%FAMEAreafromGC × weightofproduct grade vegetable oil.
Methylester (%) = ×100% The heterogeneous solid based catalyst could serve as the best op-
weightoffeedstockused (5)
tion to a homogeneous catalyst for the commercial FAME production

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N. Mansir et al. Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

considering the easy separation/removal of the catalyst after the reac- superacid catalysis in fixed bed reactor under atmospheric pressure. Catal
Commun 2004;5:721–3.
tion. Modified waste egg shell incorporated in transition metal oxides [25] Shin H, An S, Sheikh R, Park YH, Bae S. Transesterification of used vegetable oils
could serve as the best catalytic system for FAME production from with a Cs-doped heteropolyacid catalyst in supercritical methanol. Fuel
waste cooking oil under moderate reaction conditions, regardless of the 2012;96:572–8.
[26] Meher LC, Churamani CP, Ahmed Z, Naik SN. Jatropha curcas as a renewable
of high FFA and moisture content in waste cooking oil. source for bio-fuels — a review. Renew Sustain Energy Rev 2013;26:397–407.
[27] Hwa S, Goto M, Taufiq-yap YH. Biodiesel production from Jatropha curcas L. oil
Acknowledgements with Ca and La mixed oxide catalyst in near supercritical methanol conditions. J
Supercrit Fluids 2015;104:243–50.
[28] Islam A, Taufiq-yap YH, Chan E, Moniruzzaman M, Islam S. Advances in solid-
The Authors would like to extend their profound appreciation to the catalytic and non-catalytic technologies for biodiesel production. Energy Convers
Universiti Putra Malaysia, Malaysia for its funding through the research Manag 2014;88:1200–18.
[29] Taufiq-yap YH, Hwa S, Rashid U, Islam A, Zobir M. Transesterification of Jatropha
group project GP-IPD/2016/9490400.
curcas crude oil to biodiesel on calcium lanthanum mixed oxide catalyst: effect of
stoichiometric composition. Energy Convers Manag 2014;88:1290–6.
References [30] Lokman IM, Rashid U, Yunus R, Taufiq YH. Carbohydrate-derived solid acid cat-
alysts for biodiesel production from low-cost feedstocks: a review. Catal Rev Sci
Eng 2014;56:187–219.
[1] Muhammad Y, Adeniyi P, Raji-yahya AO, Aziz ARA, Mohd W, Wan A. Acidity and [31] Lee AF, Bennett JA, Manayil JC, Wilson K, Lee AF. Heterogeneous catalysis for
catalytic performance of Yb-doped SO2 for biodiesel production. J Taiwan Inst sustainable biodiesel production via esterification and transesterification. R Soc
Chem Eng 2015;000:1–10. Chem 2014:1–30.
[2] Maeda H, Hagiwara S, Nabetani H, Sagara Y, Soerawidjaya TH, Tambunan AH, [32] Sarin R, Sharma M, Sinharay S, Malhotra RK. Jatropha – palm biodiesel blends: an
et al. Biodiesel fuels from palm oil via the non-catalytic transesterification in a optimum mix for Asia. Fuel 2007;86:1365–71. http://dx.doi.org/10.1016/j.fuel.
bubble column reactor at atmospheric pressure: a kinetic study. Renew Energy 2006.11.040.
2008;33:1629–36. [33] Escobar JC, Lora ES, Venturini OJ, Yáñez EE, Castillo EF, Almazan O. Biofuels:
[3] Chouhan APS, Sarma AK. Modern heterogeneous catalysts for biodiesel produc- environment, technology and food security. Renew Sustain Energy Rev
tion: a comprehensive review. Renew Sustain Energy Rev 2011;15:4378–99. 2009;13:1275–87.
[4] Piriou B, Vaitilingoma G, Veyssiere B, Cuq B, Rouau X. Potential direct use of solid [34] Daniel C, Araújo M De, Andrade CC De, Souza E De, Dupas FA. Biodiesel pro-
biomass in internal combustion engines. Prog Energy Combust Sci duction from used cooking oil: a review. Renew Sustain Energy Rev
2013;39:169–88. 2013;27:445–52.
[5] Borges ME, Díaz L. Recent developments on heterogeneous catalysts for biodiesel [35] Tuong T, Tran V, Kaiprommarat S, Kongparakul S, Reubroycharoen P, Guan G,
production by oil esterification and transesterification reactions: a review. Renew et al. Green biodiesel production from waste cooking oil using an environmentally
Sustain Energy Rev 2012;16:2839–49. benign acid catalyst. Waste Manag 2016;52:367–74.
[6] Avhad MR, Marchetti JM. A review on recent advancement in catalytic materials [36] Atadashi IM, Aroua MK, Aziz ARA, Sulaiman NMN. The effects of water on bio-
for biodiesel production. Renew Sustain Energy Rev 2015;50:696–718. diesel production and refining technologies: a review. Renew Sustain Energy Rev
[7] Rabiah Nizah MF, Taufiq-Yap YH, Rashid U, Teo SH, Shajaratun Nur ZA, Islam A. 2012;16:3456–70.
Production of biodiesel from non-edible Jatropha curcas oil via transesterification [37] Rashid U, Ibrahim M, Yasin S, Yunus R, Taufiq-Yap YH, Knothe G. Biodiesel from
using Bi2O3-La2O3 catalyst. Energy Convers Manag 2014;88:1257–62. Citrus reticulate (Mandarin orange) seed oil, a potential non-food feedstock. Ind
[8] Shajaratun Nur ZA, Taufiq-Yap YH, Rabiah Nizah MF, Teo SH, Syazwani ON, Islam Crop Prod 2013;45:355–9.
A. Production of biodiesel from palm oil using modified Malaysian natural dolo- [38] Motasemi F, Ani FN. A review on microwave-assisted production of biodiesel.
mites. Energy Convers Manag 2014;78:738–44. Renew Sustain Energy Rev 2012;16:4719–33.
[9] Yaakob Z, Mohammad M, Alherbawi M, Alam Z, Sopian K. Overview of the pro- [39] Nakajima K, Hara M. Amorphous Carbon with SO 3H Groups as a Solid Brønsted
duction of biodiesel from waste cooking oil. Renew Sustain Energy Rev Acid Catalyst. Am Chem Soc Catal 2012;2:1296–304.
2013;18:184–93. [40] Muppaneni T, Reddy HK, Ponnusamy S, Patil PD, Sun YQ, Dailey P. SGD.
[10] Hafiidz A, Fauzi M, Aishah N, Amin S. Optimization of oleic acid esterification Optimization of biodiesel production from palm oil under supercritical ethanol
catalyzed by ionic liquid for green biodiesel synthesis. Energy Convers Manag conditions using hexane as co-solvent: a response surface methodology approach.
2013;76:818–27. Fuel 2013;107:633–40.
[11] Mardhiah HH, Chyuan H, Masjuki HH, Lim S, Lee HV. A review on latest devel- [41] Agarwal D, Agarwal AK. Performance and emissions characteristics of Jatropha oil
opments and future prospects of heterogeneous catalyst in biodiesel production (preheated and blends) in a direct injection compression ignition engine. Appl
from non-edible oils. Renew Sustain Energy Rev 2017;67:1225–36. Therm Eng 2007;27:2314–23.
[12] Nigam PS, Singh A. Production of liquid biofuels from renewable sources. Prog [42] Sherbiny SA El, Refaat AA, Elsheltawy ST. Production of biodiesel using the mi-
Energy Combust Sci 2011;37:52–68. crowave technique. J Adv Res 2010;1:309–14.
[13] Galadima A, Muraza O. Biodiesel production from algae by using heterogeneous [43] Alves CT, Oliveira A, Carneiro SAV, Silva AG, Andrade HMC, Melo SABV De, et al.
catalysts: a critical review. Energy 2014;78. (0–11). Transesterification of waste frying oil using a zinc aluminate catalyst. Fuel Process
[14] Na H, Jeong D, Jang W, Shim J. The effect of preparation method on Fe / Al / Cu Technol 2013;106:102–7.
oxide-based catalyst performance for high temperature water gas shift reaction [44] Farooq M, Ramli A, Subbarao D. Biodiesel production from waste cooking oil using
using simulated waste-derived synthesis gas. Int J Hydrog Energy bifunctional heterogeneous solid catalysts. J Clean Prod 2013;59:131–40.
2015;40:12268–74. [45] Zhang J, Jiang L. Acid catalysed esterification of Zanthoxylum bungeanum oil with
[15] Patle DS, Sharma S, Ahmad Z, Rangaiah GP. Multi-objective optimization of two high free fatty acids for biodiesel production. Bioresour Technol 2008;99:8995–8.
alkali catalyzed processes for biodiesel from waste cooking oil. Energy Convers [46] Meng X, Chen G, Wang Y. Biodiesel production from waste cooking oil via alkali
Manag 2014;85:361–72. catalyst and its engine test. Fuel Process Technol 2008;9:851–7.
[16] Amani H, Ahmad Z, Hameed BH. Highly active alumina-supported Cs – Zr mixed [47] AC A, MC B, R T. Production of biodiesel and oleochemicals from used frying oil.
oxide catalysts for low-temperature transesterification of waste cooking oil. Appl Los Banos: University of Philippines; 2000.
Catal A Gen 2014;487:16–25. [48] P F, MJN C, I R, JF M, R B, J B. Production of biodiesel from waste frying oil. Waste
[17] Yan S, Salley SO, Ng KYS. Simultaneous transesterification and esterification of Manag 2006;26:487–94.
unrefined or waste oils over ZnO-La 2 O 3 catalysts. Appl Catal A Gen [49] X Y, H M, Q Y, Z W, J C. Comparison of four different enhancing methods for
2009;353:203–12. preparing biodiesel through transesterification of sunflower oil. Appl Energy
[18] Huerga IR, Zanuttini MS, Gross MS, Querini CA. Biodiesel production from 2012;91:320–5.
Jatropha curcas: integrated process optimization. Energy Convers Manag [50] Y G, YC L, CP K. A clean biodiesel fuel produced from recycled oils and grease trap
2014;80:1–9. oils. Better air Qual. Asian Pacific rim cities. 1–6. BAQ, Hong Kong: Polytechnic
[19] Pua F, Fang Z, Zakaria S, Guo F, Chia C. Direct production of biodiesel from high- University; 2002. p. 55.
acid value Jatropha oil with solid acid catalyst derived from lignin. Biotechnol [51] Peter Atkins Fellow of Lincoln College, University of Oxford, Oxford U, Julio De
Biofuels 2011;56:2–9. Paula Professor of Chemistry, Lewis and Clark College, Portland, Oregon U.
[20] Banković-Ilić IB, Stamenković OS, Veljković VB. Biodiesel production from non- Physical Chemistry. Ninth. New York: W,H Freeman and Company New York;
edible plant oils. Renew Sustain Energy Rev 2012;16:3621–47. 2010.
[21] Supamathanon N, Wittayakun J, Prayoonpokarach S. Properties of Jatropha seed [52] Ertl G, Knözinger H, Weitkamp J. Preparation of solid catalysts. John Wiley &
oil from Northeastern Thailand and its transesterification catalyzed by potassium Sons; 2008.
supported on NaY zeolite. J Ind Eng Chem 2011;17:182–5. [53] Avhad MR, Marchetti JM. Innovation in solid heterogeneous catalysis for the
[22] Nautiyal P, Subramanian KA, Dastidar MG. Kinetic and thermodynamic studies on generation of economically viable and ecofriendly biodiesel: a review. Catal Rev
biodiesel production from Spirulina platensis algae biomass using single stage 2016;4940:1–52.
extraction – transesterification process. Fuel 2014;135:228–34. [54] Dias JM, M.C.M A-F, Almeida MF. Comparison of the performance of different
[23] Lee AF, Bennett JA, Manayil JC, Wilson K. Heterogeneous catalysis for sustainable homogeneous alkali catalysts during transesterification of waste and virgin oils
biodiesel production via esterification and transesterification. Chem Soc Rev and evaluation of biodiesel quality. Fuel 2008;87:3572–8.
2014;43:7887–916. [55] Uzun BB, Kılıç M, Özbay N, Pütün AE, Pütün E. Biodiesel production from waste
[24] Furuta Satoshi, Hiromi Matsuhashi, Kazushi A. Biodiesel fuel production with solid frying oils: optimization of reaction parameters and determination of fuel

10
N. Mansir et al. Renewable and Sustainable Energy Reviews xxx (xxxx) xxx–xxx

properties. Energy 2012;44:347–51. production: current state and perspectives. Renew Sustain Energy Rev
[56] Baskar G, Aiswarya R. Trends in catalytic production of biodiesel from various 2016;56:1387–408.
feedstocks. Renew Sustain Energy Rev 2016;57:496–504. [82] Dehkordi AM, Ghasemi M. Transesterification of waste cooking oil to biodiesel
[57] Fadhil AB, Ali LH. Alkaline-catalyzed transesterification of Silurus triostegus using Ca and Zr mixed oxides as heterogeneous base catalysts. Fuel Process
Heckel fish oil: optimization of transesterification parameters. Renew Energy Technol 2012;97:45–51.
2013;60:481–8. [83] Muhammad Y, Mohd W, Wan A, Aziz ARA. Activity of solid acid catalysts for
[58] Nur Syazwani O, Rashid U, Taufiq Yap YH. Low-cost solid catalyst derived from biodiesel production: a critical review. Appl Catal A Gen 2014;470:140–61.
waste Cyrtopleura costata (Angel Wing Shell) for biodiesel production using mi- [84] Rattanaphra D, Harvey A. Simultaneous conversion of triglyceride / free fatty acid
croalgae oil. Energy Convers Manag 2015;101:749–56. mixtures into biodiesel using sulfated zirconia. Top Catal 2010;53:773–82.
[59] Rashid U, Anwar F. Production of biodiesel through optimized alkaline-catalyzed [85] Jacobson K, Gopinath R, Meher LC, Dalai AK. Solid acid catalyzed biodiesel pro-
transesterification of rapeseed oil. Fuel 2008;87:265–73. duction from waste cooking oil. Appl Catal B Environ 2008;85:86–91.
[60] Marchetti JM, Errazu AF. Esterification of free fatty acids using sulfuric acid as [86] Sirisomboonchai S, Abuduwayiti M, Guan G, Samart C, Abliz S, Hao X, et al.
catalyst in the presence of triglycerides. Biomass Bioenergy 2008;32:892–5. Biodiesel production from waste cooking oil using calcined scallop shell as cata-
[61] Soriano NU, Venditti R, Argyropoulos DS. Biodiesel synthesis via homogeneous lyst. Energy Convers Manag 2015;95:242–7.
Lewis acid-catalyzed transesterification. Fuel 2009;88:560–5. [87] Alhassan FH, Yunus R, Rashid U, Sirat K, Islam A, Lee HV, et al. Production of
[62] Al-jammal N, Al-hamamre Z, Alnaief M. Manufacturing of zeolite based catalyst biodiesel from mixed waste vegetable oils using ferric hydrogen sulphate as an
from zeolite tuft for biodiesel production from waste sun flower oil. Renew Energy effective reusable heterogeneous solid acid catalyst. Appl Catal A Gen
2016;93:449–59. 2013;456:182–7.
[63] Tonetto GM, Marchetti JM. Transesterification of soybean oil over Me/Al2O3 (Me [88] Mansir N, Taufiq-yap YH, Rashid U, Lokman IM. Investigation of heterogeneous
= Na Ba, Ca, and K) catalysts and monolith K/Al2O3-cordierite. Top Catal solid acid catalyst performance on low grade feedstocks for biodiesel production: a
2010;53:755–62. review. Energy Convers Manag 2016.
[64] Sánchez-Cantú M, Pérez-Díaz LM, Pala-Rosas I, Cadena-Torres E, Juárez-Amador [89] Lee HV, Juan JC, Tau YH. Preparation and application of binary acid e base
L, Rubio-Rosas E, Rodríguez-Acosta M, Valente JS. Hydrated lime as an effective CaO–La2O3 catalyst for biodiesel production. Renew Energy 2015;74:124–32.
heterogeneous catalyst for the transesterification of castor oil and methanol. Fuel [90] Mahesh SE, Ramanathan A, Begum KMMS, Narayanan A. Biodiesel production
2013;110:54–62. from waste cooking oil using KBr impregnated CaO as catalyst. Energy Convers
[65] Kazemian H, Turowec B, Siddiquee MN, Rohani S. Biodiesel production using Manag 2015;91:442–50.
cesium modified mesoporous ordered silica as heterogeneous base catalyst. Fuel. [91] Wong YC, Tan YP, Ramli I, Tee HS. Biodiesel production via transesterification of
103; n.d. p. 719–24. palm oil by using CaO – CeO2 mixed oxide catalysts. Fuel 2015;162:288–93.
[66] Thitsartarn W, Kawi S. Transesterification of oil by sulfated Zr-supported meso- [92] Today C. Transesterification of vegetable oils over CaO catalysts. Catal Today
porous silica. Ind Eng Chem Res 2011;50:7857–65. 2011;167:64–70.
[67] Hua Y, Omar M, Nolasco-hipolito C, Taufiq-yap YH. Waste ostrich- and chicken- [93] Wang H, Wang M, Liu S, Zhao N, Wei W, Sun Y. Influence of preparation methods
eggshells as heterogeneous base catalyst for biodiesel production from used on the structure and performance of CaO – ZrO2 catalyst for the synthesis of di-
cooking oil: catalyst characterization and biodiesel yield performance. Appl methyl carbonate via transesterification. J Mol Catal A Chem 2006;258:308–12.
Energy 2015;160:58–70. [94] Shu Q, Jixian G, Nawaz Z, Liao Y, Wang D, Wang J. Synthesis of biodiesel from
[68] Trakarnpruk W. Biodiesel production from palm fatty acids distillate using tung- waste cooking oil with large amounts of free fatty acids using a carbon based solid
stophosphoric acid- and Cs-salt immobilized-silica. Walailak J Sci Technol acid catalyst. Appl Energy 2010;87:2589–96.
2012;9:37–47. [95] Kouzu M, Yamanaka S, Hidaka J, Tsunomori M. Heterogeneous catalysis of cal-
[69] Ardizzone S, Bianchi CL, Cappelletti G, Porta F. Liquid-phase catalytic activity of cium oxide used for transesterification of soybean oil with refluxing methanol.
sulfated zirconia from sol – gel precursors: the role of the surface features. J Catal Appl Catal A Gen 2009;355:94–9.
2004;227:470–8. [96] Chen G, Fang B. Preparation of solid acid catalyst from glucose-starch mixture for
[70] Li Y, Zhang X, Sun L, Zhang J, Xu H. Fatty acid methyl ester synthesis catalyzed by biodiesel production. Bioresour Technol 2011;102:2635–40.
solid superacid catalyst. Appl Energy 2010;87:156–9. [97] Avramovi JM, Stamenkovi OS. Biodiesel production by ultrasound-assisted trans-
[71] Amani H, Ahmad Z, Asif M, Hameed BH. Transesterification of waste cooking palm esterification: state of the art and the perspectives. Renew Sustain Energy Rev
oil by MnZr with supported alumina as a potential heterogeneous catalyst. J Ind 2012;16:1193–209.
Eng Chem 2014;20:4437–42. [98] Shu Q, Nawaz Z, Gao J, Liao Y, Zhang Q, Wang D, et al. Synthesis of biodiesel from
[72] Weckhuysen BM, Mestl G, Rosynek MP, Krawietz TR, Haw JF, Lunsford JH. a model waste oil feedstock using a carbon-based solid acid catalyst: reaction and
Destructive adsorption of carbon tetrachloride on alkaline earth metal oxides. Phys separation. Bioresour Technol 2010;101:5374–84.
Chem B 1998;102:3773–8. [99] Park Y-M, Lee D, Kim D, Lee J, Lee K. The heterogeneous catalyst system for the
[73] Correia LM, Saboya RMA, de Sousa Campelo N, Cecilia JA, Rodríguez- Castellón E, continuous conversion of free fatty acids in used vegetable oils for the production
Cavalcante Jr CL, Vieira RS. Characterization of calcium oxide catalysts from of biodiesel. Catal Today 2008;131:238–43. http://dx.doi.org/10.1016/j.cattod.
natural sources and their application in the transesterification of sun- flower oil. 2007.10.052.
Bioresour Technol 2014;151:207–13. [100] Harmer MA, Sun Q. Solid acid catalysis using ion-exchange resins. Appl Catal A
[74] Navajas A, Issariyakul T, Arzamendi G, Gandía LM, Dalai AK. Development of Gen 2001;221:45–62.
eggshell derived catalyst for transesterification of used cooking oil for biodiesel [101] Leung DYC, Guo Y. Transesterification of neat and used frying oil: optimization for
production. Asia-Pac J Chem Eng 2013;8:742–8. biodiesel production. Fuel Process Technol 2006;87:883–90.
[75] Suryaputra W, Winata I, Indraswati N, Ismadji S. Waste capiz (Amusium crista- [102] Yujaroen D, Goto M, Sasaki M, Shotipruk A. Esterification of palm fatty reaction,
tum) shell as a new heterogeneous catalyst for biodiesel production. Renew Energy acid distillate (PFAD) in supercritical methanol: effect of hydrolysis on reactivity.
2013;50:795–9. Fuel 2009;88:2011–6.
[76] Birla A, Singh B, Upadhyay SN, Sharma YC. Kinetics studies of synthesis of bio- [103] Nakpong P, Wootthikanokkhan S. High free fatty acid coconut oil as a potential
diesel from waste frying oil using a heterogeneous catalyst derived from snail shell. energy, feedstock for biodiesel production in Thailand. Renew Energy
Bioresour Technol 2012;106:95–100. 2010;35:1682–7.
[77] Rezaei R, Mohadesi M, Moradi GR. Optimization of biodiesel production using [104] Gole VL, Gogate PR. Intensification of synthesis of biodiesel from non-edible oil
waste mussel shell catalyst. Fuel 2013;109:534–41. using sequential combination of microwave and ultrasound. Fuel Process Technol
[78] Nakatani N, Takamori H, Takeda K, Sakugawa H. Transesterification of soybean oil 2013;106:62–9.
using combusted oyster shell waste as a catalyst. Bioresour Technol [105] Wan Omar WNN, Amin NAS. Biodiesel production from waste cooking oil over
2009;100:1510–3. alkaline modified zirconia catalyst. Fuel Process Technol 2011;92:2397–405.
[79] Kawashima A, Matsubara K, Honda K. Acceleration of catalytic activity of calcium [106] Guo F, Xiu ZL, Liang ZX. Synthesis of biodiesel from acidified soybean soapstock
oxide for biodiesel production. Bioresour Technol 2009;100:696–700. using a lignin-derived carbonaceous catalyst. Appl Energy 2012;98:47–52.
[80] SL L, YC W, YP T, SY Y. Transesterification of palm oil to biodiesel by using waste [107] Nascimento LAS, Angélica RS, da Costa CEF, Zamian JR, Rocha D, Filho GN.
obtuse horn shell-derived CaO. Energy Convers Manag 2015;93:282–8. Conversion of waste produced by the deodorization of palm oil as feedstock for the
[81] Marinkovi DM, Stankovi MV, Veli AV, Avramovi JM, Miladinovi MR, Stamenkovi production of biodiesel using a catalyst prepared from waste material. Bioresour
OO, et al. Calcium oxide as a promising heterogeneous catalyst for biodiesel Technol 2011;102:8314–7.

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