Clean Energy, 2019, Vol. 3, No.

1, 2–23

doi: 10.1093/ce/zky020
Advance Access Publication Date: 17 December 2018
Homepage: https://academic.oup.com/ce

Review Article
Catalysis in biodiesel production—a review
Baskar Thangaraj1*, Pravin Raj Solomon2, Bagavathi Muniyandi3,
Srinivasan Ranganathan4 and Lin Lin1

Downloaded from https://academic.oup.com/ce/article/3/1/2/5250541 by guest on 03 July 2022

1
School of Food and Biological Engineering, Jiangsu University, Zhenjiang-212013, Jiangsu Province, P.R.China
2
School of Chemical and Biotechnology, SASTRA-Deemed University, Thanjavur-613 402, Tamil Nadu, India
3
Department of Materials Science, School of Chemistry, Madurai Kamaraj University, Madurai-625021, Tamil Nadu,
India
4
Department of Physics, Thiagarajar College, Madurai-625009, Tamil Nadu, India
For Permissions, please email: journals.permissions@oxfordjournals.org

*Corresponding author. E-mail: biodieselbaskar@yahoo.co.in

Abstract
Catalysts play a significant role in transesterification of vegetable oils. Currently, chemical and biological
catalysts are being investigated, and both have their inherent merits and demerits. In large-scale applications,
these catalysts are expected to be cost effective and environmentally friendly. If the catalyst is homogeneous
in its physical form it is more effective than is the heterogeneous catalyst, but its separation from the mixture
is a major issue. Some of the heterogeneous catalysts suffer leaching in harsh reaction conditions. Of late,
nanocatalysts that demonstrate high efficiency are being studed. Nanoparticles are used in biological catalysts
as solid carriers for lipase immobilization. Lipase immobilized on magnetic nanoparticles has proved to be a
versatile biocatalyst for biodiesel production. This article reviews the role of various catalytic systems commonly
used in the transesterification reaction of oils in biodiesel generation.

Key words:  transesterification; chemical catalysts; biological catalysts; biodiesel; renewable energy

Introduction diesel must be technically feasible, economically competi-

tive, environmentally benign and adequately available at
Worldwide, primary energy demand is expected to grow by
an affordable cost. In this context, vegetable oils, bio-alco-
1.6% per year from now through the next decade. Much of
hols, biogas and biodiesel are considered as fitting options
the primary energy used today is from fossil fuel resources
[1, 2]. Among these alternative fuels, biodiesel is promoted
such as crude oil (35%), coal (29%) and natural gas (24%),
as a supplementary fuel for diesel engines. Biodiesel is
whereas nuclear and renewable energy resources account
formed from mono-alkyl esters of long-chain fatty acids
for 7 and 5% of global energy consumption, respectively [1].
derived from vegetable oil [3]. It is renewable, non-toxic,
Fossil fuel resources are therefore the single largest energy
biodegradable and environmentally friendly—and can be
source, representing 88% of total world energy consump-
used in compression-ignition (diesel) engines with lit-
tion. Large-scale combustion of fossil fuels causes air pol-
tle or no modification due to its adjustable physical and
lution, which has stimulated research efforts in identifying
chemical properties. It also has favourable combustion
alternatives. A  substitute fuel to conventional petroleum
emission profile, producing much less carbon monoxide,

Received: 9 July, 2018; Accepted: 18 October, 2018

© The Author(s) 2018. Published by Oxford University Press on behalf of National Institute of Clean-and-Low-Carbon Energy
This is an Open Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License (http://
creativecommons.org/licenses/by-nc/4.0/), which permits non-commercial re-use, distribution, and reproduction in any medium, 2
provided the original work is properly cited. For commercial re-use, please contact journals.permissions@oup.com

sulphur dioxide and unburned hydrocarbons compared to
petroleum-based diesel fuel [3, 4]. One of the major issues
confronting the biodiesel production path is the use of a
suitable catalyst in accordance with the nature of the oil.
The functional efficiencies and side effects of catalysts
during transesterification have become a matter for dis-
cussion and thus attracted comprehensive analysis.
Biodiesel is now receiving attention as a fluid fuel devel-
oped as a modified vegetable oil. Biodiesel produced from
edible oils is currently more expensive than the conven-
tional petroleum-based fuels; in addition, it competes
with cooking oil. Hence the focus has shifted to the use of
non-edible oils as a raw material for biodiesel [5]. Popular
non-edible oils being considered for biodiesel production
include jatropha or seemaikattamankku (Jatropha curcas)
[5], karanja or honge (Pongamia pinnata) [6], candlenut
(Aleurites moluccana) [7], French peanut (Pachira glabra) [8],
Alexandrian laurel balltree (Calophyllum inophyllum) [9],
rubber seed (Hevea brasiliensis) [10], desert date (Balanites
aegyptiaca) [11], sea mango (Cerbera odollam) [12], Kenya cro-
ton (Croton megalocarpus) [13], bedda nut (Terminalia belerica)
[14], neem (Azadirachta indica) [15], mahua (Madhuca indica
and Madhuca longifolia) [16], tobacco seed (Nicotiana tabacum
L.) [17], Chinese tallow (Sapium sebiferum L.) [18], silk cot-
ton (Ceiba pentandra) [19], jojoba (Simmondsia chinensis) [20],
babassu (Attalea speciosa) [21], Sichuan pepper (Zanthoxylum
bungeanum) [22], cotton (Gossypium herbaceum) [23] and
Euphorbia tirucalli [24]. Some edible-oil resources, such as
coconut (Cocos nucifera) [25], soybean (Glycine max) [26],
palm (Elaeis guineensis) [27] and canola (Brassica napus) [28],
have also been in use for biodiesel production due to their
ready availability and lower free fatty acid (FFA) content
than non-edible oils.
There are many options in making the vegetable oil
amenable, such as blending the oil with conventional
diesel, micro-emulsion, thermal cracking (pyrolysis) or
catalytic cracking and transesterification. Among these,
transesterification has become popular [29]. In transesteri-
fication, vegetable oil (triglycerides) is made to react with
primary alcohol in the presence of a catalyst to produce
biodiesel (fatty acid alkyl esters). In this process glycerol
emerges as a by-product [30]. Transesterification consists
of sequent reversible steps. The first step is the conversion
of triglycerides to diglycerides, followed by the conversion
of diglycerides to monoglycerides and glycerol, producing
one methyl ester molecule at each step. The transesterifi-
cation reaction is primarily aided by an external catalytic
system.
1  Catalysis in transesterification
Either chemical or biological catalysts are employed to acti-
vate the transesterification process. The chemical catalyst
comprises homogeneous agents (alkali or acid), heteroge-
neous agents (solid acid or solid alkali catalysts), heteroge-
neous nanocatalysts and supercritical fluids (SCFs). These
Thangaraj et al.  |  3
catalysts are effective in bringing the process to complete-
ness, although the reaction demands high energy and a
cumbersome purification process to obtain the purified
end product [31, 32]. Among the biological catalysts, immo-
bilized lipases are much preferred. The different catalytic
processes of transesterification used to produce biodiesel
are presented in Fig.  1. Enzymatic transesterification has
an environmental advantage over the other methods
[33–37]. Its major disadvantage is its prohibitive cost [35].
Table 1 explains the merits and demerits of using enzymes
in the transesterification process.
1.1  Chemical catalysts
1.1.1  Homogeneous catalysts
Downloaded from https://academic.oup.com/ce/article/3/1/2/5250541 by guest on 03 July 2022
Generally, homogeneous chemical catalysts have several
advantages, including high selectivity, turnover frequency,
reaction rate and effortless optimization of activity
[42, 43]. In earlier research acid or alkali was employed
as a homogeneous catalyst. The common alkali catalysts
being employed are sodium hydroxide (NaOH), sodium
methoxide (CH3ONa) and potassium hydroxide (KOH).
NaOH is preferred over KOH because it dissolves quickly
in methanol. NaOH is considered in transesterification due
to its high purity and low cost; in addition, a relatively low
quantity is needed as compared to KOH [44–46]. Strong
alkali catalysts such as NaOH, KOH, CH3ONa and CH3OK
(potassium methoxide) are used for biodiesel produc-
tion. However, alkali metal alkoxides are found to be more
active than hydroxides [26]. In alkali-catalyzed transesteri-
fication, even if water-free vegetable oils and alcohol are
used, a certain amount of water is formed by the CH3ONa
solution because of the interaction between NaOH and
methanol. The presence of water and FFA leads to soap
formation by hydrolysis of the triglycerides, which reduces
the biodiesel yield and affects the quality of the product
[17, 43–46]. Product recovery becomes complicated in an
alkali-catalyzed transesterification reaction if the oil has
>1% FFA; in such an event, part of the process may take the
saponification route, thereby forming soap. The soap thus
formed inhibits the separation of biodiesel and glycerine.
Because of this, two-step transesterification—acid first
and alkali next—is recommended [15, 16]. The initial acid-
based esterification effectively reduces the FFA content
of the oil and presents the amended oil ready for alkali
catalysis. In the esterification of candlenut oil, as a first
step, sulfuric acid and acetonitrile were used as catalyst
and co-solvent, respectively. The FFA level was reduced
to 0.8 wt% and the esterification process continued sub-
sequently as alkaline transesterification using acetone as
the co-solvent and KOH as the alkali catalyst. The two-step
processes achieved 99.3% biodiesel yield under optimum
conditions [7].
Sulphuric, phosphoric, hydrochloric and sulphonic
acids are used in such esterification as well as transes-
terification reactions; however, sulphonic acid is preferred
4 | Clean Energy, 2019, Vol. 3, No. 1

Catalytic systems

Chemical Biological

Traditional Lipase immobilized on

Homogeneous Heterogeneous/ SCFs Free lipase
immobilized lipase magnetic nanoparticles

Downloaded from https://academic.oup.com/ce/article/3/1/2/5250541 by guest on 03 July 2022

Nano

Fig. 1  The different catalytic systems for transesterification

Table 1  Advantages and disadvantages of free, traditionally immobilized lipase and lipase immobilized on magnetic nanoparti-
cles [37–41]

Lipase-based
catalyst Advantages Disadvantages

Free lipase More efficient catalytic activity, highly selective,
involves less energy consumption (mild reaction
conditions). Environmentally favorable.
Traditional immo- Improved lipase stability and reusability; eco-
bilized lipase nomical. Provides operational flexibility, in-
creased thermal stability and chemical stability.
Eliminates downstream operations like separ-
ation and recycling.
Lipase immobil- High activity and selectivity. Less energy consump-
ized on magnetic tion, green catalysts, improved thermal stability,
nanoparticles high operational stability, easily recovered from
reaction mixture by an external magnetic field.
Lipase inactivation by methanol, lipase stability, re-
covery and reusability
High mass-transfer resistance, lower reaction rate,
surface to volume ratio moderate. Centrifugation
and filtration required for separation. Decreased
enzyme activity during immobilization process.
Costly fabrication.
Increased magnetic nanoparticle size by agglomer-
ation among particles. Decreased enzyme activity
during immobilization process. Costly fabrication
process.

[45]. Sulphuric acid catalyzed the transesterification
reaction of Zanthoxylum bungeanum seed oil with metha-
nol recovered >94% in 12  h [22]. Tin tetrachloride (SnCl4)
catalyzed the esterification of Z.  bungeanum seed oil and
achieved >96% output in optimum reaction conditions [47].
The acid catalyst offers high yield but the reaction rate is
too slow, requires a higher oil/alcohol molar ratio and and
an extended reaction duration (>1 day) [48, 49].
If the oil has a high FFA content, it is treated first
with p-toluene-4-sulphonic acid and then with potas-
sium hydroxide (KOH) [50]. The biodiesel thus obtained
is refined by washing repeatedly with hot distilled water
and neutralized using sulphuric acid. This product is again
washed and freed from moisture by a suitable dehydrant
[6]. To extract the ester from vegetable refinery waste, the
heterogeneous acid catalyst Amberlyst-35 sulphonic resin
and homogeneous catalyst p-toluenesulphonic acid were
used at the 5% level in series. This esterification reaction
gave a biodiesel yield of >90% with different alcohols such
as methanol, ethanol and butanol [51]. The double-stage
process has become a successful practice in different oils
having high FFA content. Crude rubber seed oil has ~17%
FFA, which was reduced to <2% by a sulphuric acid (H2SO4)
esterification process and was followed by an alkali (NaOH)
transesterification process [10]. Two-step methods were
also followed for transesterification of crude rubber seed
oil, which brought a recovery of 96.8% [10, 15, 16, 52–54].
H2SO4 was found to reduce the FFA by 88.8% in waste oil,
and subsequently with alkali (KOH) catalysis a 94% bio-
diesel yield was obtained at 50°C [55].
The effect of the type of alcohol being used on the
transesterification process indicated that methanol is best
suited, with a faster reaction and good ester isolation. The
reaction speed is relatively low in ethanol use, and the

ester recovery also is low [56]. The effect of different alco-
hols on biodiesel production from different vegetable oils
has also been investigated. Methanol is a better reactant
with vegetable oils than other alcohols (ethanol, 2-pro-
panol and 1-butanol). Biodiesel production using metha-
nol as compared with ethanol is recommended because
the ethanol purity is less than that of methanol. Ethanol
procurement is relatively difficult and expensive. Long-
chain alcohols such as 2-propanol and 1-butanol are also
recommended for biodiesel production, especially when a
high oil/alcohol (1:70) ratio is employed. 2-Propanol may
not give a high yield of biodiesel in a shorter reaction time
because of its branched chain and it also needs a high tem-
perature to dissolve the alkaline catalyst. 1-Butanol also
requires heat energy to dissolve the alkaline catalyst. The
reactivity of 1-butanol is lower than that of 2-propanol.
Long-chain alcohols need a higher reaction temperature
than methanol. In addition, 2-propanol and 1-butanol tend
to retain the washwater. This phenomenon may increase
the production cost and time [57]. An increased stirring
speed enhances the yield of biodiesel because uniform
mixing of oil and alcohol is ensured. In the mixing process,
a turbine impeller performs better than paddles [58].
1.1.2  Heterogeneous catalysts
Heterogeneous catalysts are known to improve the trans-
esterification process by eliminating the extra process-
ing costs involved in homogeneous catalysis, as well as
reducing the generation of pollutants [59]. Heterogeneous
catalysts promote easy recovery, reusability and a cost-
effective green process [60]. These catalysts tolerate high
FFA and moisture content. Efficient and inexpensive het-
erogeneous catalysts help to minimize the overall cost
of biodiesel production [61]. Heterogeneous catalysts are
considered integral in certain harsh conditions such as
high temperature and pressure. These catalysts are easy
to recover from the reaction mixture, are capable of with-
standing aqueous treatment steps and are amenable to
modification to obtain high activity, selectivity and longer
catalyst lifetimes.
Heterogeneous catalysts can be designed to bring out
grafting and entrapment of the active molecules on the
surface of or inside the pores of a solid support such as
silica, alumina or ceria. Alkali earth metal oxides [62],
transition metal oxides [63], mixed metal oxides [64], ion
exchange resins [65, 66] and alkali metal compounds sup-
ported on alumina or zeolite [67] are used in various chem-
ical reactions such as isomerization, aldol condensation,
Knoevenagel condensation, Michael condensation, oxida-
tion and transesterification [60, 68]. Alkaline earth metal
oxides are successfully used as catalysts which include
BeO, MgO, CaO, SrO, BaO and RaO.MgO and SrO [69]. SrO
(strontium oxide) has high basicity and is not lost in meth-
anol due to solubility. It maintains its efficiency for up to 10
cycles [68]. Modified zeolites, anionic clays (hydrotalcite),
calcium carbonate rock, EST-4 (Eni Slurry Technology), Li/
Thangaraj et al.  |  5
CaO, MgO/KOH and Na/NaOH/λ–Al2O3 are efficient hetero-
geneous catalysts for transesterification reaction [4, 67].
Solid acid catalysts favour both esterification and transes-
terification simultaneously for biodiesel production from
oils with high FFA content [61]. NaY zeolite-supported
La2O3 catalysts prepared by a physical mixing method for
the transesterification of castor oil achieved a biodiesel
yield of 84.6% under optimized reaction conditions [70].
Air-stable and water-tolerant zirconocene perfluorooc-
tanesulphonate Lewis acid catalyst was used in the direct
esterification of FFAs and transesterification of triglyc-
erides. In addition, this catalyst behaves as a reaction-
induced self-separating agent, because during the course
of reaction it transforms from homogeneous to heteroge-
neous. Finally the catalyst precipitates as a white solid,
Downloaded from https://academic.oup.com/ce/article/3/1/2/5250541 by guest on 03 July 2022
which is favourable for recycling [71].
Solid base catalysts have higher catalytic activity than
solid acid catalysts [46]. Different solid-base catalysts used
in transesterification include CaO, MgO, SrO, KNO3/Al2O3,
K2CO3/Al2O3 [72, 73], KF/Al2O3, Li/CaO, KF/ZnO, basic hydro-
talcite of Mg/Al, Li/Al, anion exchange resins and base zeo-
lites [74, 75]. Calcined Li/Al hydrotalcites are more active
in the glycerolysis of fatty acid than Mg/Al material due to
high Lewis basicity [76]. Different molar ratios of Mg/Al cat-
alysts within the 1.5–5 range have been used in biodiesel
production. The high ratios of Mg/Al catalyst have demon-
strated excellent characteristics despite a low surface area.
The above catalyst has well-defined flakelike crystals hav-
ing strong basic sites with H_ values > 11. These catalysts
produce >92% yield of biodiesel under optimum reaction
conditions [77].
The purpose of impregnating the mixed metal oxides is
to enhance the base or acid strength, increase the surface
area and strengthen the stability more than that of the
sole metal oxides [78]. Li-doped MgO catalyst at a 9% level
gives a fatty acid methyl ester (FAME) yield of 93.9% at 60°C
in a 12:1 methanol/oil molar ratio. This catalyst expresses
a strong base site formed by the addition of Li, resulting in
an increasing biodiesel yield [79]. Li-doped BaO has shown
high activity as compared to Na/BaO and K/BaO in a trans-
esterification reaction [80]. Lithium-doped ZnO catalysts
(Li/ZnO) exhibit good catalytic activities, although their
performance greatly depends on the amount of Li loading
and temperature [81]. The catalyst KF/λ–Al2O3 has a strong
base site that promotes the transesterification reaction
at low temperature, whereas the medium base strength
requires high temperature [82].
Calcium oxide (CaO), a solid base catalyst, is favoured
as an eco-friendly material that promotes long catalyst
life, high activity and moderate reaction conditions [3].
Generally, calcium nitrate and calcium hydroxide are the
raw materials for the production of CaO. As well, several
calcium-rich waste materials are available in nature, such
as chicken eggshells, mollusk shells and bone, which can be
used as raw materials for catalyst synthesis, thereby mini-
mizing the problem of waste disposal and simultaneously
6 | Clean Energy, 2019, Vol. 3, No. 1
producing highly cost-effective catalysts [83]. A solid base
catalyst of CaO nanocatalyst achieved 93% biodiesel con-
version in jatropha oil [84]. A CaO/KF (or KF/CaU) solid-base
catalyst is prepared by loading CaO on KF, which exhibits
high catalytic activity [85]. Even though CaO showed high
catalytic activity in transesterification, this catalyst leached
out the calcium (Ca2+) ions that influence the quality of the
product. The leaching of Ca2+ ions is due to the presence of
moisture that hydrolyzes the calcium diglyceride (derived
by the instability of CaO with the by-product glycerol). The
formation of soluble Ca2+ also directly dissociates CaO dur-
ing the reaction with methanol. The leached calcium ions
react with FFA of oil, which leads to saponification and
deactivates the effective function of the catalyst. Therefore
use of suitable supporting materials may avoid leaching of
Ca active species [86–90]. Another major inconvenience in
using CaO is that it requires thermal activation to remove
the adsorbed CO2 and moisture. Then it is necessary to
carry out the process in a vacuum or a nitrogen atmos-
phere to avoid carbonization [3]. The mixed metal oxide
catalysts have shown an excellent tolerance to FFA and
water content of the crude oil in transesterification. Several
mixed metal oxide catalysts—including CaTiO3, CaMnO3,
Ca2Fe2O5, CaZrO3 and CaO–CeO2—are involved in biodiesel
production. Among these, CaZrO3 and CaO–CeO2 catalysts
have high stability and yield [61, 91]. The CaO–MgO catalyst
was evaluated by transesterification of jatropha oil under
optimum reaction conditions and obtained a 75–90% yield
of FAME [90]. Acid-base bifunctional mixed-metal oxide
catalysts of Mn0.5Ce0.5OX were highly effective for biodiesel
production, achieving ~100% conversion under suitable
reaction conditions. This catalytic system was observed to
have acid sites, whereas Mn offered basic sites. K incorpo-
rated into the catalyst structure during the synthesis pro-
cedure could enhance the MnCeOX catalytic performance
[92]. Several mixed metal oxide catalysts such as CaO–MgO,
CaO–ZnO, CaO–La2O3 and MgO–ZnO are used in the transes-
terification reaction with a catalyst amount of 3 wt%, an oil/
methanol molar ratio of 1:25, a temperature of 120°C and
a working duration of <3 h. Among them, CaO–ZnO offers
the highest catalytic activity [93]. The mixed metal oxides
of CaO–MgO loaded on Al2O3 catalysts gave 97.62% yield in
transesterification of cottonseed oil [23]. Li-impregnated
CaO–La2O3 mixed metal oxide was used in transesterifi-
cation of canola oil. This catalyst has a strong interaction
among lithium, calcium and lanthanum in the structure.
The above material showed that Li-doping improved the
basic strength and the presence of La2O3 in the support
structure maintained the BET (Brunauer–Emmett–Teller)
surface area as well as the stability of the catalyst even after
Li impregnation. The catalyst achieved a biodiesel conver-
sion of 96.3% at 65°C in 2.5 h of reaction duration [94].
Mesostructured materials have been developed to
improve the catalytic performance of the solid catalysts.
Mesoporous materials offer versatile support to a vari-
ety of catalytically active functional groups. Nafion and
Amberlyst are solid-acid catalysts for esterification reac-
tion of fatty acids through its organosulfonic groups [95–
97]. MCM-41 (Mobil Composition of Matter No. 41) coated
with different organic and inorganic compounds shapes
the properties of catalysts by its nanostructured surface
with flexible pore sizes [97]. The Fe3O4/MCM-41 composite
catalyst has extraordinary catalytic activities in transester-
ification of soybean oil, with a biodiesel yield of 99.2%. The
solid catalyst showed a strong magnetic response as Fe3O4
is a superparamagnetic material [98].
The sulphonic-acid–modified mesostructured cata-
lyst is used in the transesterification reaction, achieving
a conversion as high as 100%. However, the high concen-
tration of methanol has been found to be detrimental to
the catalytic activity [99]. Synthesized catalyst ZnO/SBA-15
Downloaded from https://academic.oup.com/ce/article/3/1/2/5250541 by guest on 03 July 2022
(Santa Barbara Amorphous) and MgO/SBA-15 with butanol
were used in the esterification of lauric acid. Both catalysts
enhanced the lauric acid conversion. MgO/SBA-15 achieved
a conversion of 81% in 6 h, better than that of ZnO/SBA-15
because the basicity of MgO is higher than that of ZnO [100].
Mesoporous SBA-15 is widely used in catalytic applications
with metal oxides because of its outstanding characteris-
tics: high surface area, large uniform pore sizes, resistance
to leaching of supporting materials and enhanced catalyst
reusability. CaO supported on a SBA-15 catalyst along with
methanol provides better catalytic activity than NaOH in
transesterification of ethyl butyrate [101, 102]. CaO–MoO3–
SBA-15 catalyst at a 6% level when used in transesterifica-
tion of soybean oil/methanol at a 1:50 molar ratio gave an
83.2% biodiesel yield. The acid base interaction between
the basic CaO and the acidic MoO3 could promote a high,
stable dispersion of catalytically active sites, thus eventu-
ally improving the stability of a catalyst [103].
When employed on Cerbera odollam (sea mango), sul-
phated zirconia catalyst gave a FAME yield of 83.8% [12].
A  superacid catalyst of sulphated tin oxide with silica
(SO42−/SnO2–SiO2) has been observed to achieve 95% bio-
diesel from Croton megalocarpus oil without any pretreat-
ment [13]. Various solid-acid catalysts along with inorganic
and organic materials—including ion-exchange resins
having sulphonic acid groups, metal-containing molecular
sieves, sulphated or mixed oxides, heteropoly acids, metal-
organic framework–based solid acids, and acid functional-
ized mesoporous silica—are used in the esterification and
transesterification of fatty acids with alcohols [104].
Niobia supported on silica is used as a heterogeneous
catalyst for biodiesel production from waste oil. This cata-
lyst has been observed to be active in both esterification
and transesterification, due to the acidic nature of nio-
bia, and it maintains its ability for >100 h without loss of
activity [105]. Analysis of the activity of niobium catalysts
such as niobic acid and niobium phosphate with butanol
in the esterification of lauric acid indicated that niobium
phosphate has higher catalytic activity than niobic acid
due to the greater number of active surface sites, balanced
acid characteristics even in highly polar solvents and also
 Thangaraj et al.  |  7

its strong Brønsted acidity. Niobium phosphate catalyst

achieved a 97% yield at normal atmospheric pressure and
reflux conditions. It could maintain the catalytic activity up
to three cycles without loss of activity [106]. Synthesized
sulphonated polydivinylbenzene gave a biodiesel conver-
sion of more than 90%, higher than that of the commer-
cial ion-exchange resins Amberlyst 35 and Amberlyst 36.
All catalysts expressed good conversions (76–93%) for fatty
acid residue of palm and soybean oil [107].
Understandably, the water content of ethanol brings
a negative influence on the biodiesel production process,
which leads to a saponification reaction. The MnGly cata-
lyst could solve the above issue of bioethanol-based trans-
esterification reaction, having demonstrated excellent
Cut pieces with small sizes
water tolerance that can resist the presence of 80% water

Downloaded from https://academic.oup.com/ce/article/3/1/2/5250541 by guest on 03 July 2022

in ethanol causing 90% conversion with an elongated reac-
tion time. The catalyst achieved a maximum 99.7% conver-
sion within 6 h when 95% aqueous ethanol was used [108].
Recently, waste materials have been used as catalysts Washed with double distilled water
for chemical reactions. Low-cost solid-waste materials (three times)
have demonstrated a promising scope for sustainable bio-
diesel production process. Cement waste from concrete
and mortar containing quartz, calcite, sodium/calcium
aluminosilicates, albite and portlandite are the dominant
Dried in oven at 80°C for 48 h
mineral wastes used. Cement has an alkaline nature due
to its inherent mineral matrix [109]. Eggshell has a large
amount of calcium carbonate that can be converted into
CaO through calcination at 900°C. It exhibited high catalytic
activity in the transesterification process and achieved up
Calcination at 700°C for 4 h
to 93.5% biodiesel yield. Using waste materials for catalyst
preparation may partially solve waste disposal issues and
the value-added materials are a boon for different indus-
trial processes [110]. Organic waste–based solid catalysts
have been developed and used successfully, including Heterogeneous catalyst
plantain peels [111], wood [112], coconut shells [25], palm
trunks and sugarcane bagasse [113]. Banana peels contain
potassium and sodium oxides, which have been converted
to corresponding oxides. A banana peel catalyst was pro-
duced by drying the peel in a hot-air oven at 80°C for 48 h Biodiesel production
and calcining it at 700°C for 4 h [114] (Fig. 2). It was used in a
two-step transesterification of neem oil [111]. The calcined
(800°C) peels of tucumã palm, containing a rich quantity of Fig. 2  Preparation of heterogeneous catalyst from banana peels for bio-
K, P, Ca and Mg ions, showed a good catalytic performance diesel production
[115]. The waste shells of Cyrtopleura costata (angelwing
clam) yielded 84.11% biodiesel under optimum reaction a sulphonated carbon-based catalyst for the esterification
conditions and could also be reused in three cycles with of caprylic acid and gave a 71.5% conversion in 4 h [120].
>65% biodiesel yield [116]. Calcined animal bone was used Wood ash from birch bark and fly ash from a biomass-
as a catalyst to produce biodiesel from jatropha oil, giving based power plant calcinated at 800°C have been used as
a yield of 96.1% at 70°C in a single-step process [117]. CaO heterogeneous catalysts [112]. Sulphonated coconut shelsl
supported on waste fly ash achieved a conversion of 94.5% used as a solid-acid catalyst gave a yield of 88.03% [25]. Oil
biodiesel from palm oil under suitable reaction conditions palm trunks and sugarcane bagasse–derived heterogene-
[118]. Cinder, a solid-waste material obtained from the ous acid catalysts have been used for biodiesel production,
coal-burning industry, served as a support for CaO/KF to achieving 88.8 and 96% yields, respectively [113].
synthesize a solid base catalyst for transesterification soy- Active molecules in heterogeneous catalysts are gen-
bean oil [87]. A catalyst derived from rice husks gave a high erally not accessible in a homogeneous system and, as a
yield of biodiesel (>90%) due to the strong acid sites and result, catalytic activity may be diminished. Additionally,
high surface area [119]. Coffee residue was used to make external-surface active sites of a porous solid support are
8 | Clean Energy, 2019, Vol. 3, No. 1
actively involved in diminishing the overall activity of the
catalysts. In such situation, researchers are required to
develop a catalyst system that not only shows high cata-
lytic activity and selectivity but also retains the catalyst
separation and regeneration. This may be achieved by
grafting through covalent binding and adsorption [36] and
also by the use of nanostructured catalysts. A nanocatalyst
acts as a junction between homogeneous and heterogene-
ous catalysts so as to have the desirable characteristic of
both systems.
1.1.3  Heterogeneous nanocatalysts
Research on nanocatalysts to produce a catalyst with
exceedingly high activity, selectivity and high stability
with a high yield of the reaction product is possible by
changing the surface functionality, elemental composition
or the number of atoms in the particle [36, 121, 122]. These
characteristics enable a heterogeneous catalytic system to
bring out reaction rates equal to its homogeneous catalytic
system [36].
Nanosphere catalysts offer a low ratio of methanol/oil
separation and renovate the large accessible surface area
of the mesoporous silica nanosphere by providing high
catalytic loading to improve transesterification efficiency.
The nanoscale metal oxides have a good catalytic activity
for methanolysis of vegetable oils through a large num-
ber of active sites situated at the edge of the crystals [123].
Nanocrystalline CaO brings a conversion efficiency of 100%
in a reaction duration of 6  h at room temperature using
methanol on vegetable oil and poultry fat [124]. Nanosized
CaO is an effective catalyst for transesterification of jat-
ropha oil by a two-step process and has been observed to
enhance biodiesel yield up to 98.54%. Catalyst reusability
is about nine cycles, maintaining stable activity up to six
cycles with a yield of ~95.8% [125]. Nanostructured CaO
derived from calcium nitrate (CaO/CaN) and snail shells
(CaO/ss) have been evaluated for their catalytic activity
in transesterification; the biodiesel yield was 93 and 96%,
respectively [126].
Li-doped CaO nanocatalyst gave a high yield of bio-
diesel at a methanol/oil molar ratio of 12:1 and reaction
temperature of 65°C at a reaction duration of 2 h using 5
wt% catalyst [127]. Nanostructured mixed-metal oxides
of CaO–MgO produced a yield of 98.95% biodiesel as the
mixed-metal oxides catalyst demonstrated better activ-
ity than nano CaO alone [128]. KF/CaO prepared by the
impregnation method produced biodiesel from Chinese
tallow oil with a yield of 96% [18]. Another CaO-based
nanocatalyst of Ca/Fe3O4@SiO2 has become popular for bio-
diesel production. A catalyst supported on magnetic mate-
rial can be easily separated by an external magnetic field
due to Fe3O4 and maintained its catalytic activity in sev-
eral cycles [129]. Cadmium oxide and tin oxide nanocata-
lysts supported by magnetic material have been used in
esterification, transesterification and hydrolysis reaction.
These catalysts are obviously more active in esterification
than transesterification and hydrolysis reactions [130].
Guanidine-functionalized Fe3O4 and Fe3O4@SiO2 magnetic
nanoparticles (MNPs) have been used as basic recyclable
catalysts for biodiesel production. Fe3O4–TBD (1,5,7-tri-
azabicyclo[4,4,0]dec-5-ene) also exhibited high catalytic
performance in the first cycle and achieved 96% biodiesel
conversion [131]. A  nano-solid base catalyst, K2O/γ–Al2O3,
achieved 94% conversion in rapeseed oil [132]. KOH impreg-
nated with alumina and calcium aluminate has also been
used in the transesterification reaction [133]. The solid
base nanocatalyst of zirconia-loaded potassium bitartrate
was also used in biodiesel production [134].
Transesterification was carried out in microwave, auto-
clave or ultrasound using nanostructured MgO. A  higher
conversion was obtained in the microwave than in auto-
Downloaded from https://academic.oup.com/ce/article/3/1/2/5250541 by guest on 03 July 2022
clave or under ultrasound [135]. Transesterification of
Madhuca indica oil was carried out by heteropoly acid
(HPW)–coated ZnO catalyst and the FAME recovery was
>95% in 5 h [136]. Iron (II)-doped ZnO nanocatalyst provided
a conversion of 91% from castor oil [137]. Ni-doped ZnO
nanocomposite yielded 92.5% biodiesel [138]. Mn-doped
ZnO nanocatalyst achieved 97% biodiesel from mahua
oil [139]. Zn1.2H0.6PW12O40 nanotubes are known to exhibit
higher catalytic activities for the simultaneous esterifica-
tion and transesterification of palmitic acid than the par-
ent acid catalyst of HPW (H3PW12O40) [140]. The solid acid
of an aluminum dodecatungstophosphate (Al0.9H0.3PW12O40,
AlPW) nanotube catalyst showed higher catalytic activ-
ity and stability toward biodiesel production under mild
reaction conditions than other catalysts such as AIPW salt
with non-nanotube structure, Cs2.5H0.5PW12O40 (CsPW) and
HPW. The higher activity is credited to the combined effect
of Lewis acid sites, Brønsted acid sites and the nanotube
structure [141]. The acid-base bifunctional HPA nanocata-
lyst (C6H15O2N2)2HPW12O40 (abbreviated as ly2 HPW) was
highly efficient in esterification of FFA and transesterifi-
cation of triglycerides [142]. The catalytic performance
of Cs–MgO and nano MgO-500 benchmark was assessed
successively toward transesterification of tricaprylin (C8),
trilaurin (C12) and olive oil at 60°C. Cs–MgO has superior
catalytic activity to nano MgO-500 for all three heavier oils
[143]. The spinel-structured catalyst of urea, labelled MgO/
MgAl2O4, achieved 95% conversion, and the activity was
seen to have been retained after six reaction cycles [144].
Ionic liquids (ILs) have attracted significant interest as
green materials, alternative reaction media and a promis-
ing catalyst. Poly ionic liquids are ionic polymers having
a polymeric backbone and IL units that can simultane-
ously act as IL and polymer with high thermal stability
and corrosion resistance. Magnetically recoverable acidic
polymeric ILs decorated with hydrophobic regulators have
been used as catalysts for biodiesel production. These
catalysts had good activity and recyclability in the produc-
tion of biodiesel via acid transesterification processes. The
catalyst achieved a yield of 95.3% under mild reaction con-
ditions (1:17 oil/methanol molar ratio, 4% catalyst dosage

at 75°C for 3  h) in which a 91.7% yield was obtained via
concurrent esterification and transesterification in crude
Euphorbia lathyris seed oil [145]. The magnetically recov-
erable catalyst of MgO-supported MgFe2O4 was used as a
heterogeneous nanocatalyst in transesterification of sun-
flower oil. The spinel ferrite catalyst of MgFe2O4 has unique
and tunable magnetic, electronic and structural properties.
The catalyst produced a biodiesel yield of 91.2% and main-
tained its catalytic activity up to five cycles with a steady
conversion [146]. Ni0.5Zn0.5Fe2O4 was an effective nanocata-
lyst in methyl and ethyl esterification with 99.54% recov-
ery [147]. In situ decorated TiO2 on reduced graphene oxide
nanocomposite via the hydrothermal route on transesteri-
fication of waste cooking oil gave a yield of 98% [148].
Tungsten-impregnated TiO2/SiO2 nanocatalyst has been
used in transesterification of vegetable oils. The pore size
of W/Ti/SiO2 was larger than the pores of support material
as the tungstate ions immersed the pores of support mate-
rial (Ti/SiO2). Thus the surface area and pore volume are
related to tungsten impregnation. The catalyst produced
>98% biodiesel [149]. Sulphonic acid–supported graphene
catalysts could eliminate the problems of limited robust-
ness and extensive leaching in the aqueous phase due to
their partial solubility in methanol. Sulphonated graphene
catalysts consisting of highly accessible active acidic sites
strongly anchored to a stable, insoluble platform would
constitute an efficient strategy, and have achieved >98%
biodiesel yield with a high purity [27]. A  comparison of
the biodiesel synthesis performance using heterogeneous
nanocatalysts is presented in Table 2.
1.1.4  Supercritical fluids (SCF)
The supercritical fluid (SCF) technique could be used to
produce biodiesel through transesterification of vegetable
oils in the absence of catalysts. Saka and Kusdiana pro-
posed that biodiesel fuels could be prepared from vegetable
oil via noncatalytic transesterification with supercritical
methanol [151]. Compared to the conventional catalytic
processes, the SCF technique offers a number of notable
advantages: easy separation of the products, fast reaction,
and it is also environmentally benign. The SCF technique
was also credited with solving problems associated with
the two-phase nature of methanol and oil mixtures by
forming a single phase as a result of the low dielectric con-
stant of methanol in the supercritical state. This process
gives a maximum yield of ester in the absence of a catalyst
at a higher reaction temperature (>400°C) [152]. The effi-
ciency of transesterification can be increased by using cal-
cium oxide catalysts in the SCF system [45, 152, 153].
The effect of added water on the yield of biodiesel in
transesterification of triglycerides and methyl esterifi-
cation of FFAs under supercritical methanol has been
explored. The water-added supercritical methanol features
easy separation of products, because glycerol, a by-product
of transesterification, is more soluble in water than meth-
anol [154]. It is a novel process of biodiesel production
Thangaraj et al.  |  9
developed by a noncatalytic supercritical method in which
the yield was 96% in 10 min [30]. A co-solvent-supported
supercritical methanol system can improve the yield of
biodiesel. Hexane and supercritical CO2 act as excellent
solvents for vegetable oil [155]. Transesterification of soy-
bean oil in supercritical methanol has been carried out in
the presence of propane and achieved a FAME efficiency of
98% with optimum reaction conditions such as tempera-
ture, methanol to oil molar ratio, duration and reaction
pressure (280°C, 24:1, 10  min and 12.8  MPa). Supercritical
CO2 is applied in enzymatic reactions because the enzyme
can be separated easily by reducing the pressure. As the
enzyme and the product cannot dissolve in carbon dioxide
at atmospheric conditions, they can be easily regenerated.
The yield of biodiesel is found to increase as the tem-
Downloaded from https://academic.oup.com/ce/article/3/1/2/5250541 by guest on 03 July 2022
perature, methanol-to-oil molar ratio, concentration and
stirring rate (>850  rpm) increase [156, 157]. Supercritical
dimethyl carbonate is used to produce biodiesel at 350°C
at a pressure of 20 MPa [158].
Wet spent coffee grounds, a waste product of coffee-
brewing industries, have gained attention for use in bio-
diesel. The study demonstrated the elimination of both
biomass drying and catalyst usage by integrating the extrac-
tion and conversion processes to produce biodiesel [159].
Methanol and ethanol, which are being used in the
supercritical process, are hygroscopic and corrosive. This
problem can be overcome by involving higher-carbon alco-
hol such as 1-propanol. 1-Propanol is advantageous over
ethanol as it is derived from glucose without CO2 formation,
whereas the biosynthetic track in ethanol production has
CO2 emission steps. Therefore the use of 1-propanol as a
reactant for biodiesel production offers promise. The reac-
tion parameters of biodiesel production involving super-
critical 1-propanol showed that significant conversion of
oil into biodiesel can be obtained at 350°C and 20 MPa after
30-min residence time, with a resulting biodiesel yield of
93.8% [160]. This process needs many safety precautions
given the involvement of high temperature and pressure.
1.2 Biocatalysts
Biocatalysts can overcome the demerits of the chemical
catalytic system. Biocatalysts consist of free lipase, tradi-
tionally immobilized lipase (lipase immobilized on non-
magnetic material) and lipase immobilized on MNPs.
1.2.1 Free lipase
Enzymes are better than homogeneous catalysts because
of their biocompatibility, biodegradability and environ-
mental acceptability [51, 161]. Lipases have excellent
catalytic activity and stability in nonaqueous media. The
specificity, regioselectivity and enantioselectivity of lipases
favour many applications in organic synthesis, including
kinetic resolution and symmetric synthesis, which also
facilitate the esterification and transesterification of car-
boxylic esters during biodiesel production and aminolysis
Table 2  Comparison of the performance of heterogeneous nanocatalysts in biodiesel production as reported

Transesterification reaction Biodiesel effi-

Catalyst Method of synthesis conditions ciency (%) Cycles Reference

CaO Calcination−hydration dehy- Catalyst ratio 0.02:1 (w/w); reaction time 95.8 9 [125]
dration of Polymesoda erosa 133.1 min; oil/ methanol molar ratio 1:5.15;
shells temperature 65°C; stirring rate 500 rpm
CaO (Nanocrystalline-1) Commercial CaO Catalyst amount 1 mmol; time 6 h; temperature 100 3 [124]
25°C; methanol 10 ml
CaO/CaN, CaO/ss Sol–gel method Catalyst 8 wt%; temperature 65°C; oil/methanol 93 (CaO/CaN) 96 5 [126]
ratio 1:12; time 6 h (CaO/ss)
Li–CaO Wet impregnation method Oil/methanol molar ratio 1:12; catalyst 5 wt%; >99 NA [127]
10 | Clean Energy, 2019, Vol. 3, No. 1

temperature 65°C; time 2 h

CaO–MgO
KF/CaO
ZrO2–C4H4O6HK
(Zirconia-loaded potassium
bitartrate)
CaO/Fe3O4@SiO2
Mixed iron/tin oxide (ISnO)
Guanidine-functionalized
Fe3O4 (MNP–TBD) and Fe3O4@
SiO2 (MNP@SiO2-TBD)
K2O/γ–Al2O3)
KOH/Ca12Al14O33
MgO
Heteropoly acid (HPW)–coated
ZnO
Iron (II)-doped ZnO
Zinc dodecatungstophosphate
(Zn1.2H0.6PW12O40; ZnPW)
nanotubes
Aluminum dodeca-
tungstophosphate
(Al0.9H0.3PW12O40) (AIPW)
Nano CaO (sol–gel method),
nano MgO (sol–gel
self-combustion)
Wet impregnation method
Incipient wetness impregna-
tion method
Sol–gel and wetness impreg-
nation methods
Co-precipitation method
Co-precipitation and
functionalization
Grinding-calcination method
Microwave and wetness im-
pregnation method
Sol–gel, supercritical drying
and calcination
Co-precipitation method
Co-precipitation method
Sol–gel method
Sol–gel method
Oil/methanol molar ratio 1:7; catalyst 1.2 g (CaO, 98.95 6 [128]
0.7 g; Mgo, 0.5 g); time 6 h; temperature 75°C
Oil/methanol molar ratio 1:12; catalyst 4 wt%; 96.8 16 [48]
temperature 65°C; time 2.5 h
Oil/methanol ratio 16:1; catalyst 6wt%%, tem- 98.03 5 [134]
perature 60°C, time 2 h
Catalyst 6 wt%; oil to methanol molar ratio 97 Several batches [129]
1:15; temperature 65°C; mechanical stirring
500 rpm; time 5 h
Catalyst 1 g; methanol 6 g; temperature 200°C; 90 4 [130]
time 3 h
Oil/methanol molar ratio 1:30; temperature 96 (MNP-TBD), 2 (MNP-TBD), [131]
120°C; time 24 h 80 (MNP@SiO2 4 (MNP@SiO2
–TBD) –TBD)
Catalyst 3%; oil/methanol ratio 12:1; tempera- 94 NA [132]
ture 70°C; time 3 h
Methanol/oil molar ratio 18; catalyst 4 wt%; time 93.4 5 [133]
60-min microwave power 450 W
Oil/methanol molar ratio 1:4; catalyst 300 mg; 99 6 [140]
temperature 70°C; time 40 min
Methanol 30 ml; catalyst 2 g; temperature 55°C; 98 NA [136]
time 5 h
Oil/methanol molar ratio 1:12, catalyst 14 wt%, 91 7 [141]
temperature 55°C; time 50 min
Oil/methanol molar ratio 1:28; catalyst 2.3 wt%; 97.2 5 [143]
temperature 65 ºC; stirring 300 rpm; time 12 h
Oil/methanol molar ratio 1:34; catalyst 3 wt%; 96 6 [144]
temperature 65 ºC; time 14 h

Downloaded from https://academic.oup.com/ce/article/3/1/2/5250541 by guest on 03 July 2022

 Thangaraj et al.  |  11

[161–165]. Microbial lipases are drawn from Aspergillus niger,

Reference
Bacillus thermoleovorans, Candida cylindracea, Candida rugosa,

[145]

[146]

[147]

[148]

[138]
[139]

[150]
Chromobacterium viscosum, Geotrichum candidum, Fusarium
heterosporum, Fusarium oxysporum, Humicola lanuginose,
Mucor miehei, Oospora lactis, Penicillium cyclopium, Penicillium
roqueforti, Pseudomonas aeruginosa, Pseudomonas cepacia,
Pseudomonas fluorescens, Pseudomonas putida, Rhizopus arrhi-
zus, Rhizopus boreas, Rhizopus thermosus, Rhizopus usamii,
Rhizopus stolonifer, Rhizopus fusiformis, Rhizopus circinans,
Cycles

Rhizopus delemar, Rhizopus chinensis, Rhizopus japonicus

5

3
6

4
NR 400, Rhizopus microsporus, Rhizopus nigricans, Rhizopus
niveus, Rhizopus oryzae, Rhizopus rhizopodiformis, Rhizopus
stolonifer NRRL 1478, Rhodotorula rubra and Staphylococcus
hyicus [166] for esterification of FFA or transesterification
Biodiesel effi-

of triglyceride molecules [46, 163, 165, 167]. Intracellular

ciency (%)

Downloaded from https://academic.oup.com/ce/article/3/1/2/5250541 by guest on 03 July 2022

lipase from microbial cells is considered to be inexpensive
and works well as a biocatalyst. However, whole cell–based
91.2

95.7

84.2
93

98

98
97

catalysts are used in transesterification, which has rela-

tively low efficiency on an oily substrate and hence gives a
Catalyst 3 wt%; oil/methanol ratio 1:12; tempera-
Oil/methanol molar ratio 1:30; 18.5 wt% butanol;

Catalyst 8% (w/v); oil/methanol molar ratio 1.7%

Methanol 374.4 mmol; catalyst 9 wt%; tempera-

low yield of biodiesel [168]. In selected situations the con-

Catalyst 1.5 wt%; oil/methanol molar ratio 1:12;
Catalyst 10 wt%; oil/methanol molar ratio 1:20;

Catalyst 10 wt%; oil/methanol molar ratio 1:12;

catalyst 2.8 wt% (50 mg); temperature 90°C;

version is high (95–97%) but the reaction duration is long.

Theoretically, the use of an isolated enzyme can increase
the catalytic activity [169]. Enzymatic transesterification
(v/v); temperature 50°C; time 50 min

is not yet implemented in large-scale production due to

the high cost of the enzyme, difficulty in enzyme recov-
temperature 100°C; time 14 h

ery from the products, non-reusability and exhaustion of

temperature 65°C; time 3 h

temperature 70°C; time 8 h

Transesterification reaction

enzyme activity [46, 170]. Although the technology of the

enzymatic mode of biodiesel production is still not com-
ture 65°C; time 12 h

ture 110°C; time 3 h

mercially ventured in full, many researchers have reported

the commercial scope of enzymes in the field of biodiesel.
The enzymatic transesterification system mainly rests on
time 24 h

reaction parameters such as temperature, oil-to-alcohol

conditions

molar ratio and the type of microorganism that generates

the enzyme, enzyme amount and duration of the process
[171]. The methanolysis activities of lipases from several
lipases such as Candida rugosa, P. cepacia and P. fluorescens
and the effects of the water and methanol contents in the
Modified Hummers’ method,
Supercritical sol–gel method

reaction mixture were investigated for biodiesel produc-

Chemical exfoliation and

hydrothermal method

tion. Among them, P. cepacia was found to be more desir-

Combustion method
Method of synthesis

able for methanolysis reaction of vegetable oil [172].

functionalization

sono-dispersion
Impregnation and
Co-precipitation
Sol–gel method

1.2.2  Traditional immobilized lipase

In recent years, a new immobilization technique has been
reported as a powerful tool to improve almost all enzyme
properties such as stability, activity, specificity and selec-
tivity coupled with the reduction of inhibition that may
positively influence the operating conditions, with a sig-
nificant increase in turnover [37]. Several methods are
available in lipase immobilization such as physical adsorp-
tion, covalent bonding, entrapment, encapsulation and
Acid-base HPA catalyst

Sulfonated graphene

cross-linking [173, 174]. Nonmagnetic materials are often

Ca(30%)/Al-MCM-41
Table 2 Continued

used as carriers for lipase immobilization. These immobi-

Mn-doped ZnO

lization techniques have already been reported briefly by

(Urea labelled)
MgO/MgAl2O4
(C6H15O2N2)2

many researchers [38, 175–180]. A generalized comparison

HPW12O40

TiO2/RGO
(ly2HPW)

of different kinds of enzyme immobilization techniques is

Catalyst

Cs–MgO

presented in Table 3. The activity of the enzyme is affected

mainly by two factors: pH and temperature [175, 181]. The
 12 | Clean Energy, 2019, Vol. 3, No. 1

immobilized lipase has advantage over a broader range

molecules by adding the salt

mers, non-covalent bonding

Physical aggregates of protein
of temperature and pH than that of free lipase [181, 182].

solvents or non-ionic poly-

or water miscible organic
The effect of pH on immobilization was investigated at
various levels. The immobilization of enzymes is nega-
tively influenced by unfavourable pH because the enzymes
are liable to be irrevocably denatured [183]. The immobi-
lized lipase may function at up to 8.0 pH whereas the free
Cross-linking

Entrapment

lipase has an action boundary of 7.5 pH. The immobilized

enzyme has an anion support of Mg–Al hydrotalcite [182,
Simple

Wide
184]. The effect of temperature on lipase immobilization
Low has been examined by many researchers.
At 50 and 60°C the relative activity of free lipase
achieved a turnover of 88.46 and 75.38% , whereas the
immobilized lipase achieved 95.86 and 81.26%, respec-
Encapsulation

confinement)

tively. Immobilized lipase is more stable than free lipase

(membrane

Downloaded from https://academic.oup.com/ce/article/3/1/2/5250541 by guest on 03 July 2022

Very wide

[181]. Free lipase easily undergoes denaturation at a higher

Simple
Strong

temperature whereas immobilized lipase is well protected

Low

due to its rigid conformation [185].

The effect of enzyme dosage, the impact of methanol/
oil molar ratio, water content, reaction duration, stirring
rate and the influence of temperature are well documented
Physical entrap-

[186–188]. The catalyst dosage ranges from 1.5 to 3.5% at a

Some amount
ment, weak
Entrapment

methanol/oil molar ratio of 4:1, water 7% (w/w), tempera-

ture 40°C, stirring speed 200  rpm for 12  h for a biodiesel
Difficult

yield varying from 73 to 90% [186]. High concentration of

Wide

the enzyme is not favourable [189].

Generally, the higher molar ratio of oil to methanol
than the stoichiometric dose in transesterification favours
Chemical bonding, strong (diazo-
tation, peptic bond, alkylation,
bonding with poly-functional

the reaction. If the methanol is added stepwise, transes-

terification is relatively faster. As methanol is soluble in
oil and water, there will be loss of methanol if it is added
Simple and reversible
Table 3  Comparison of different kinds of immobilization of enzymes [179, 180]

in bulk [190].
The activity of an enzyme in a nonaqueous medium is
Covalent bonding

Very low amount

disturbed by water content [191]. Water strongly influences

the catalytic activity and stability of lipase. Lipase activ-
agents)

Selective

ity depends on the interfacial area existing between the

aqueous and organic phases. Water increases the interfa-
cial area, helping to sustain the lipase activity. An excess
amount of water kindles hydrolysis because lipase is more
flexible in the aqueous phase [163]. The stability of lipase is
ionic strength may detach
Variable, reversible, changes
in pH, temperature and

high at an optimum level of water content [191].

The optimum reaction temperature on transesteri-
fication of vegetable oil using an immobilized lipase is
reported to be 37°C and an increase in temperature desta-
Some amount
the enzyme

bilizes the function of the enzyme [188, 190]. Free lipase

Adsorption

(P. fluorescens) and immobilized lipase were used in a pro-

Simple

pyl oleate reaction. The conversion ratio of propyl oleate

Wide

is high at 60°C, whereas the activity of free lipase is low

at 70°C. The reaction rate of immobilized lipase increased
at 70°C, which revealed the stability of immobilized lipase
[191]. The activity of lipase immobilized on hydrotalcite at
30 and 60°C are 89.6 and 86.8%, respectively [192].
Enzyme leakage
Characteristics

The optimum conditions for canola oil biodiesel syn-

Binding force

Applicability
Preparation

thesis by Novozym 435 are as follows: reaction time 12.4 h,

temperature 38°C, enzyme concentration 42.3%, alcohol/
substrate molar ratio 3.5:1 and water content 7.2% [182].
The maximum conversion of 95% biodiesel was obtained
 Thangaraj et al.  |  13

in 10–20% (v/v) water content [188]. A  low-cost biocata-

Catalyst recovery easy

Continuous process
lyst microporous polymer matrix-supported enzyme was

Immobilized lipase
catalysts [190–193]
used to produce biodiesel from sunflower, soybean and
waste cooking oils; their yields were 97, 90.2 and 93.9%,

Not sensitive
respectively. This catalyst has retained its activity up to

Moderate
Possible
10 repeated cycles at 25°C with a reaction duration of 24 h

Higher
Easy

Easy
[39].

Low
Silica gel as a solid support for Lipozyme TL accelerates
the acyl migration and >90% biodiesel recovery is achieved

[45, 49, 167–169, 171]

Continuous process
when 6% silica gel is combined with 4% lipase [193]. A high

Catalyst recovery
Lipase catalysts
yield (91.5%) of biodiesel was obtained from refined cot-

Not sensitive

Not possible
tonseed oil with 30% enzyme based on oil weight, 1:4 oil/

difficult
alcohol molar ratio, 50°C temperature and 7  h reaction

Difficult

Higher
duration. But the primary alcohol gave only a 72% yield

High

Easy
Low
[194]. Thermomyces languinosus lipase immobilized on

Downloaded from https://academic.oup.com/ce/article/3/1/2/5250541 by guest on 03 July 2022

hydrophilic polyurethane foams gave 90% recovery and

Continuous process
the enzymatic activity continued after 10 cycles when
tertiary butanol was used [28]. The recombinant R. oryzae

Not applicable
Not sensitive
lipases (ROL) was immobilized on a macroporous resin and

[30, 152–158]

Ill-favoured

Ill-favoured
Absence of
anion exchange resin, namely MI-ROL and AI-ROL, respec-

catalysts

Medium

Higher
tively, and were used as biocatalysts for Pistacia chinensis

High

Easy
Bge seed oil biodiesel production with methanol. A  yield
as high as 92 and 94% by MI-ROL and AI-ROL, respectively,

Catalyst recovery easy

was obtained [190]. Biocatalyst formulated by encapsulat- Table 4  Comparison of the different catalytic processes of transesterification for biodiesel production

Continuous process
ing lipase in a microporous zeolite imidazolate framework,

[42, 79, 122, 124]

ZIF-67, using a ship-in-a-bottle method lipase@ZIF-67 cat-
Heterogeneous

Much cheaper
nanocatalysts

Not sensitive
alyzed the transesterification of soybean oil to biodiesel
(78.5%) in a solvent-free medium. The catalyst maintained

Possible

Higher
the catalytic activity up to six cycles with marginal loss in High

Easy

Easy
activity (78.5 to 56.0%) [195].
Cationic lignin nanosphere was used as a carrier for

Easy by filtration method

enzyme immobilization. Four consecutive steps were fol-

bed operation possible

Catalyst recovery easy

lowed in the synthesis of biocatalysts: cationic lignin

Potentially cheaper
adsorption, enzyme adsorption, entrapment and evapora-
Continuous fixed-

tion. Calcium alginate was used to entrap the enzyme-c-

Heterogeneous

[45, 59, 67, 74]

Not sensitive

CLP complexes. It did not require covalent cross-linking to

the support or synthetic polymers to stabilize the lipases.
Moderate

Moderate
catalysts

Possible

The immobilized biocatalyst (immob.Hic) yielded 91%

Easy
butyl butyrate under the biphasic state (50% water), in a
4-fold enzyme dosage with a reaction duration of 24 h [28].
must be neutralized leading to

Multipoint attachment of C.  rugosa (Amano AY-30) lipase

Catalyst recovery not possible,

onto a polyvinylidene fluoride membrane, formed as a bio-

catalyst for biodiesel production from soybean oil, gave a
Limited use of continuous
Homogeneous catalysts

yield of 95%. The catalyst maintained a good reusability in

Comparatively costly

transesterification reactions, enabling five cycles with no

waste of chemical

Repeated washing

significant loss of activity [196]. A summary of the different

methodology

catalytic processes of transesterification used to produce

[42, 43, 45, 49]

Not possible

biodiesel is presented in Table 4.

Sensitive

Difficult

Normal

1.2.3  Lipase immobilized on MNPs

Fast

MNPs are widely used in the immobilization of proteins,

peptides, drugs and enzymes [197]. As a solid carrier for
After treatment

methodology

immobilization of enzymes, magnetic nanoparticles have

Biodiesel yield
Catalyst reuse

Purification of
Reaction rate

some advantages: higher specific surface area/volume

Recovery of
presence

biodiesel
Processing

Water/FFA

glycerol

ratio for binding the high amount of enzyme, low mass-

Factor

transfer resistance and less fouling for selective separa-

Cost

tion of immobilized enzymes by an external magnetic field

14 | Clean Energy, 2019, Vol. 3, No. 1
from the products [198]. In addition, the physical charac-
teristics of nanoparticles such as increased diffusion and
particle mobility can affect the intrinsic catalytic activity
of immobilized enzymes [197]. Other advantages of using
nanoparticles are thermal stability, increased surface area
and irradiation resistance for their potential applications
in photodetectors, solar cells, biosensor, nanogenera-
tors and ceramics [199]. MNPs residing on an iron oxide
core and silica shell have unique magnetic reactivity, low
toxicity and a chemically modified surface. Silica-coated
nanoparticles (Fe3O4@SiO2) are well adapted solid carriers
for enzyme immobilization [35]. Many studies have been
carried out for the production of biodiesel by lipase immo-
bilized on MNPs as biocatalysts.
Thermomyces lanuginosa lipase was immobilized on
3-aminopropyltriethyloxysilane (APTES)–Fe3O4 by the
covalent binding method for transesterification of vegeta-
ble oil [200]. C. rugosa lipase immobilized on ionic liquids
Fe3O4@SiO2 MNPs was used as a catalyst for the esterifi-
cation reaction; the activity was 118.3% higher than that
of the crude lipase. The ionic liquid acts as an enzymatic
resistance [201]. Burkholderia lipase immobilized on an
alkyl-functionalized Fe3O4@SiO2 catalyst achieved 90%
biodiesel recovery from olive oil by employing 11 wt% of
a catalyst for 30 h in a batch reaction [202]. P. cepacia lipase
immobilized on MNPs achieved a high conversion (79%) of
biodiesel [40]. The thermal stability of P. cepacia lipase was
significantly amended through immobilization, thereby
attracting its use in the production of biodiesel [40, 41].
Thermomyces lanuginosus lipase immobilized on Fe3O4 was
used as a catalyst for transesterification of palm oil, which
achieved 97.2% biodiesel yield. The biocatalyst showed
high operational stability and could be separated easily by
an external magnetic field and the catalyst reusability was
maintained up to five cycles with the biodiesel yield above
80% [203]. The effect of reaction temperature was investi-
gated in lipase NS18006 immobilized on APTES and mer-
captopropyltriethoxysilane (MPTMS) functionalized-Fe3O4
MNPs. The maximum biodiesel conversion was obtained
at 45°C by both catalysts [36]. A  study on the effect of
methanol addition on hydrophobic magnetic nanoparti-
cle (HMP)–lipase catalyzed transesterification by one-step
addition (whole dosing) or stepwise addition of methanol
with a 4:1molar ratio indicated that one-step addition per-
formed better in transesterification of olive oil than the
stepwise addition of methanol. High conversion of FAME
(70%) was obtained within 12  h by Burkholderia lipase
immobilized onto hydrophobic magnetic particles) [204].
Reactive extraction is a process that involves reaction
and separation of liquid phases in the same unit. Phase
separation can occur naturally or with the assistance of a
solvent. Lipase immobilized on MNPs is used as a catalyst
for biodiesel production in a reactive extraction process.
A  reactive extraction process can directly produce 77%
ethyl oleate (biodiesel) using lower ethanol/triolein ratios
compared to 35–40% purity obtained in a normal stirred
reaction with higher ethanol/triolein ratios [205]. The mix-
ing efficiency is an important factor influencing the effi-
ciency of lipase for biodiesel production. An optimum
stirring rate was 500–600  rpm for the transesterification
process. Burkholderia lipase immobilized on MNPs achieved
90% conversion with low-dosage biocatalyst loading and
better catalyst reusability [206]. Lipase NS81006 immobi-
lized on Fe3O4@SiO2 MNPs at a ratio of 1:0.25 used in trans-
esterification provided a higher yield of methyl esters than
that of Fe3O4@SiO2 MNPs developed with a high level (1:0.5,
1:1 and 1:2) of TEOS (tetraethyl orthosilicate) [207]. C. rugosa
lipase immobilized onto Fe3O4-decorated graphene oxide
yielded 92.8% biodiesel at 40°C by three-step addition of
methanol. The catalyst maintained the catalytic activity
up to five cycles without significant loss of its activity [101].
Downloaded from https://academic.oup.com/ce/article/3/1/2/5250541 by guest on 03 July 2022
Table 5 provides a summary of biodiesel synthesis perfor-
mance using different immobilized biocatalysts (lipase
immobilized on MNPs).
A packed-bed reactor was used in the transesterifica-
tion reaction with lipase immobilized on Fe3O4 MNPs. The
FAME conversion rate and catalyst stability were much
higher in the four-packed-bed reactor than that of the
single-packed-bed reactor. The biodiesel conversion was
more than 88% in 192 h [220]. Transesterification was car-
ried out in a magnetically stabilized fluidized-bed reac-
tor by immobilized R.  oryzae lipase on magnetic chitosan
microspheres. This reactor is observed to be efficient when
coupled with magnetically immobilized cells and enzymes
[221]. It offers many advantages over conventional fluid-
ized-bed reactors because it can protect the structure of
the magnetic catalyst particles, eliminate the need for
solid mixing, decrease the pressure drop through the bed,
ease solid transportation and can work at increased fluid
velocities even at countercurrent. The conversion was
91.3% (w/v) by the reactor at a fluid rate of 25 ml/min [222].
A new approach of electrolysis process was used for
biodiesel production from used cooking oils (Fig.  3). This
process has a few advantages such as high tolerance with
water content (>2%) and high FFA content. The reaction
can be carried out at room temperature. The chitosan gels
(i.e. hydrogel and xerogel phase) were used as catalysts for
electrolysis of vegetable oils for biodiesel production. The
electro-catalytic process achieved a biodiesel yield of 90.3%
in chitosan hydrogel and 93.1% in chitosan xerogel [223].
2.  Conclusion and prospects
Transesterification is the better choice for biodiesel
production compared with other existing methods.
Transesterification reaction mainly depends on catalytic
systems. There are two kinds of major catalytic systems,
chemical and biological. In the chemical-based catalytic
system, homogeneous catalysts are effective but the pro-
cess involves high energy consumption as well as wastewa-
ter treatment due to unreacted chemicals. In heterogeneous
catalysts, external-surface active species of porous solid
Table 5  Comparison of the biodiesel production process using immobilized lipases as reported

Activity Biodiesel
Method of Immobilization recovery conversion
Catalyst immobilization efficiency (%) w(%) Reaction conditions efficiency (%) Cycles Reference

Lipase (NS81006) immobilized on Covalent binding 97.73 (APTES); 86.08 (APTES); Temperature 45°C; 3-step add- 89 (APTES) 3 [36]
APTES and MPTMS-Fe3O4 95.39 (MPTMS) 83.7 (MPTMS) ition of methanol 1:3; catalyst 81 (MPTMS)
0.5 g; stirring rate 600 rpm;
(mechanical blender); time 12 h
Burkholeria sp. lipase Physisorption alkyl- 97 96 Oil/methanol molar ratio 1:4; stir- 92 10 [206]
immobilized on Fe3O4–SiO2 functionalized ring rate 600 rpm; water con-
magnetic tent 10 wt%; temperature 40°C;
nanoparticles time 30 h; stirring rate 600 rpm
Pseudomonas cepacia lipase Covalent binding 92.3 60 Methanol/oil ratio 5.2; water 79 3 [208]
immobilized on Fe3O4 content 12.5 wt%; catalyst 40%
(w/w oil); temperature 44.2°C;
time 24 h
Candida rugosa lipase immobilized Covalent binding 84 63 Oil/methanol ratio 1:4; 3-step 86 4 [209]
on polymer [poly(styrene-meth- addition of methanol; catalyst
acrylic acid])–coated Fe3O4 40% (w/w oil); temperature
35°C, time 24 h
Thermomyces Covalent binding NA NA Methanol/ oil ratio 7.6:1; catalyst 97 (CA) 11 [210]
lanuginosus lipase (TLL) & Candida 3.3% (w/w oil); temperature 98 (TL)
antarctica lipase B (CALB) immo- 30°C; time 12 h; shaking rate
bilized on Fe3O4 30 rpm
Candida antarctica (Novozym Physisorption NA NA Temperature 30°C; 98.4 50 [211]
435) immobilized on acrylic MeOH/oil 3:1; stepwise adding
resin solvent-free water <1%;
pH not controlled; catalyst 4.2%;
72 h; shaker
(Pseudomonas fluorescens & P. cepa- Physical adsorption NA NA Temperature 40°C; MeOH/oil 8:1; 58, 22 h NA [212]
cia) lipase immobilized on solvent-free water 0%; pH not 37, 51.5 h
macroporous polypropylene controlled; catalyst 6.25%;
shaker
Novozym 435 C. antarctica lipase Not available NA NA Temperature 40 °C; MeOH/oil 3:1; 85 5 [213]
immobilized on acrylic resin t-butanol 78.09%; water 0.35–
0.45%[ pH not controlled, cata-
lyst 4%; 30 h, shaker
Themomyces Covalent binding 90.4 70 Temperature 45 °C; 90 3 [214]
lanuginose(Novozymes) immobi- stepwise MeOH addition (MeOH/
lized on Fe3O4 oil, 1:1 each step); pH 7.0; 35 h;
shaker
Thangaraj et al.  |  15

Downloaded from https://academic.oup.com/ce/article/3/1/2/5250541 by guest on 03 July 2022

Table 5 Continued
Activity Biodiesel
Method of Immobilization recovery conversion
Catalyst immobilization efficiency (%) w(%) Reaction conditions efficiency (%) Cycles Reference

C. antarctica lipase B Encapsulation NA NA Fatty acid (oleic acid)/geraniol 95 8 [215]

immobilized on magnetic ratio 3:1; catalyst 10 wt%;
poly(urea-urethane) temperature 50°C; shaking
150 rpm; time 6 h
Lipase immobilized on APTES– Covalent binding 96 (1:0.25); 83 (1:0.25); Temperature 45°C; 3-step add- 92 (1:0.25); 3 [207]
Fe3O4@SiO2 (1:X, X-0.25, 0.5, 1, 87 (1:0.5); 81 (1:0.5); ition of methanol; 1:3; catalyst 88 (1:0.5); 3
1.2) 86 (1:1); 77 (1:1); 0.5 g; stirring rate 600 rpm; 86 (1:1); 3
82 (1:2); 76 (1:2) (mechanical blender); 12 h 78 (1:2) 4
16 | Clean Energy, 2019, Vol. 3, No. 1

Lipase immobilized on MPTMS- Covalent binding 94 (1:0.25); 83 (1:0.25); Temperature 45°C, 3-step add- 91 (1:0.25) 3 [207]
Fe3O4@SiO2 (1:X, X–0.25, 0.5, 1, 86 (1:0.5); 79 (1:0.5); ition of methanol 1:3; catalyst 75 (1:0.5) 3
1.2) 85 (1:1); 76 (1:1); 0.5 g; stirring rate 600 rpm; 78 (1:1) 3
82 (1:2); 68 (1:2) (mechanical blender); 12 h 71 (1:2) 4
T. lanuginosa immobilized on Fe3O4 Covalent binding 84 70 Oil/methanol ratio 1:1 (each 90 4 [216]
step); 3-step addition of
methanol (1.05 g); catalyst 40%
(w/w oil); temperature 50°C;
time 12 h; shaker
Burkholderia lipase immobilized on Physisorption NA NA Oil/methanol ratio 1:4; catalyst 70% 6 [204]
hydrophobic Fe3O4@SiO2 300 U/ml; room temperature;
10% water content; agitation
200 rpm; time 12 h
Porcine pancreas lipase (lipase Physisorption & covalent 85.2 (L1); 95.7 (L1); Catalyst 5 mg; temperature 100% (L3) 9 [217]
L1), C. rugosa lipase (lipase L2) & binding 82.4 (L2); 70.1 (L2); 40°C; shaking 120 rpm; 1.5 ml
P. cepacia lipase (lipase L3) im- 80.3 (L3); 82.6 (L30 distilled water; oil/methanol
mobilized on Fe3O4 molar ratio 1:6
Rhizopus oryzae lipase immo- Covalent binding NA NA Oil/methanol molar ratio 1:4; 91.3 6 [218]
bilized on magnetic chitosan catalyst 25 g; temperature 35°C;
microspheres reactant flow rate 20 ml/min;
magnetic field intensity 225 Oe;
time 72 h
Lipase immobilized on APTES- Covalent Binding 79 54 Temperature 45°C; 3-step add- 76 5 [219]
Fe3O4@SiO2 (1:3) ition of methanol 1:3; catalyst
0.5 g; stirring rate 600 rpm;
time 12 h
Lipase immobilized on MPTMS- Covalent binding 77 50 Temperature 45°C; 3-step add- 72 5 [220]
Fe3O4@SiO2 (1:3) ition of methanol 1:3; catalyst
0.5 g; stirring rate 600 rpm;
time 12 h
Lipase immobilized on graphene Covalent binding 85.5 64.9 Oil 48.5 g; methanol/ oil ratio 1:4; 92.8 5 [98]
oxide–Fe3O4 biocatalyst amount 20 wt%;
temperature 40°C; time 60 h

Downloaded from https://academic.oup.com/ce/article/3/1/2/5250541 by guest on 03 July 2022


DC power supply
+ –
Cathode
Anode
Catalyst
Vegetable oil
+
Methanol
Magnetic stirrer
Fig. 3  Electro-catalytic reactor for biodiesel production
support only is involved. In some catalysts, particularly CaO,
leaching takes place that adversely influences the reaction.
Nanotechnological synthetic protocols can help to design
and modify the catalyst’s surface to meet the requirements
of specific applications and solve the issues of the homo-
geneous as well as heterogeneous catalysts. Nanocatalysts
act as a junction between homogeneous and heterogeneous
catalysts, which can make potential solid-acid or solid-base
catalysts. Conventional filtration and centrifuge are not suf-
ficient to recover the materials after synthesis due to the
tiny particles. Magnetic nanoparticle-supported catalysts
could be recovered easily by a magnetic field.
In biological catalyst systems, free enzyme cata-
lysts have many advantages over chemical catalysts,
but the production cost of biodiesel is still high because
of the high cost of the enzymes and the lack of reus-
ability. Immobilized enzymes can be reused and hence
should be considered favourably. Silica-coated magnetic
nanoparticles are used as the best carrier for enzyme
immobilization due to effective aggregation. The immo-
bilization technique is considered important because
it would prevent the leaching of the enzymes during
the reaction. Covalent binding is the best technique for
enzyme immobilization, especially when solid materi-
als are used as carriers. Information on the interaction
between lipase and carrier is not available; this is an
important area worth exploring. Progress has been made
on the electro-catalytic mode of biodiesel production.
Electrodes made of biomass-derived carbon quantum
dots (CQD) undertake electrolysis-based transesterifica-
tion reaction for biodiesel production. CQD-based elec-
trodes can perform well in electro-catalytic reactors due
Thangaraj et al.  |  17
to the physical and chemical properties of CQD. Novel
methods will take centre stage in the near future to pro-
duce biodiesel through environmentally and economi-
cally acceptable processes.
Development of effective and inexpensive catalysts
with an environmentally benign process is essential to
overcome the present issues. Even if the biodiesel produc-
tion procedure is perfected, the problem may not reach a
tangible end because the oil production rate per unit area
of derelict land needs to be improved. This will be a great
challenge at the planning level. Genetic evolution of high-
yielding varieties must be promoted so as to enhance
low-FFA oil availability. One concept worth attention is
the use of CO2 contained in stack emissions from indus-
trial processes as a means of growing algae for oil produc-
Downloaded from https://academic.oup.com/ce/article/3/1/2/5250541 by guest on 03 July 2022
tion, thereby achieving the dual benefit of greenhouse gas
reduction and resource recovery. An appropriate catalyst, if
identified for effective transesterification, will represent a
milestone in the fuel sector.
Conflict of interest statement. None declared.
References
[1] Jahirul MI, Brown RJ, Senadeera W, et al. The use of artificial
neural networks for identifying sustainable biodiesel feed-
stocks. Energies 2013; 6:3764–806.
[2] Patel R, Patel S. Renewable hydrogen production from butanol:
a review. Clean Energy 2017; 1:90–101.
[3] Borges  ME, Díaz  L. Recent developments on heterogeneous
catalysts for biodiesel production by oil esterification and
transesterification reactions: a review. Renew Sust Energy Rev
2012; 16:2839–49.
[4] Xie W, Li H. Alumina-supported potassium iodide as a hetero-
geneous catalyst for biodiesel production from soybean oil. J
Mol Catal A: Chem 2006; 255:1–9.
[5] Pramanik K. Properties and use of Jatropha curcas oil and diesel
fuel blends in compression ignition engine. Renewable Energy
2003; 28:239–48.
[6] Meher LC, Dharmagadda VSS, Naik SN. Optimization of alkali-
catalyzed transesterification of Pongamia pinnata oil for pro-
duction of biodiesel. Bioresour Technol 2006; 97:1392–7.
[7] Pham  LG, Luu  BV, Phuoc  HD, et  al. Production of biodiesel
from candlenut oil using a two-step co-solvent method
and evaluation of its gaseous emissions. J Oleo Sci 2018;
67:617–26.
[8] Kibazohi  O, Sangwan  RS. Vegetable oil production potential
from Jatropha curcas, Croton megalocarpus, Aleurites moluccana,
Moringa oleifera and Pachira glabra: assessment of renewable
energy resources for bio-energy production in Africa. Biomass
Bioenergy 2011; 35:1352–6.
[9] Ashok  B, Nanthagopal  K, Vignesh  DS. Calophyllum inophyl-
lum methyl ester biodiesel blend as an alternate fuel for die-
sel engine applications. Alexandria Eng J 2017; doi: 10.1016/j.
aej.2017.03.042.
[10] Ramadhas AS, Jayaraj S, Muraleedharan C. Biodiesel produc-
tion from high FFA rubber seed oil. Fuel 2005; 84:335–40.
[11] Nitièma-Yefanova S, Conigilo L, Schneider R, et al. Ethyl bio-
diesel production from non-edible oils of Balanites aegyptiaca,
Azadirachta indica, and Jatropha curcas seeds – laboratory scale
development. Renewable Energy 2016; 96:881–90.
18 | Clean Energy, 2019, Vol. 3, No. 1
[12] Kansedo  J, Lee  KT, Bhatia  S. Cerbera odollam (sea mango) oil
as a promising non-edible feedstock for biodiesel production.
Fuel 2009; 88:1148–50.
[13] Kafuku  G, Lam  MK, Kansedo  J, et  al. Croton megalocarpus oil:
a feasible non-edible oil source for biodiesel production.
Bioresour Technol 2010; 101:7000–4.
[14] Omkaresh  BR, Suresh  R, Shivashankar  M, et  al. Production
optimization of methyl esters from Terminalia billerica mate-
rial using RSM. Mater Today: Proc 2017; 4:10690–5.
[15] Thangaraj  B, Ramachandran  KB, Raj  SP. Homogeneous cata-
lytic transesterification of renewable Azadirachta indica (Neem)
oil and its derivatives to biodiesel fuel via acid/alkaline esteri-
fication processes. Int J Renew Energy Biofuels 2014; 2014:1–11.
[16] Ghadge  SV, Raheman  H. Biodiesel production from mahua
(Madhuca indica) oil having high free fatty acids. Biomass
Bioenergy 2005; 28:601–5.
[17] Velijkovic  VB, Lakicevic  SH, Stamenkovic  OS, et  al. Biodiesel
production from tobacco (Nicotiana tabacum L.) seed oil with a
high content of free fatty acids. Fuel 2006; 85:2671–5.
[18] Wen L, Wang Y, Lu D, et al. Preparation of KF/CaO nanocatalyst
and its application in biodiesel production from Chinese tal-
low seed oil. Fuel 2010; 89:2267–71.
[19] Norjannah  B, Ong  HC, Masjuki  HH. Effects of methanol and
enzyme pretreatment to Ceiba pentandra biodiesel production.
Energy Sources Part A 2017; 39:1548–55.
[20] Sandouqa  A, Al-Hamamre  Z. Energy analysis of biodiesel
production from jojaba seed oil. Renewable Energy 2019;
130:831–42.
[21] Bouald  A, Martinez  M, Aracil  J. Biodiesel production from
babassu oil: a statistical approach. J Chem Eng Process Technol
2015; 6:1–4.
[22] Zhang L, Wu HT, Yang FX, et al. Evaluation of Soxhlet extrac-
tor for one-step biodiesel production from Zanthoxylum
bungeanum seeds. Fuel Process Technol 2015; 131:452–7.
[23] Mahdavi  V, Monajemi  A. Optimization of operational condi-
tions for biodiesel production from cottonseed oil on CaO–
MgO/Al2O3 solid base catalysts. J Taiwan Inst Chem Eng 2014;
45:2286–92.
[24] Atabani  AE, Silitonga  AS, Badruddin  IA, et  al. A comprehen-
sive review on biodiesel as an alternative energy resource and
its characteristics. Renew Sust Energy Rev 2012; 16:2070–3.
[25] Endut A, Abdullah SHYS, Hanapi NHM, et al. Optimization of
biodiesel production by solid acid catalyst derived from coco-
nut shell via response surface methodology. Int Biodeterior
Biodegrad 2017; 124:250–7.
[26] Saydut A, Kafadar AB, Aydin F, et al. Effect of homogeneous
alkaline catalyst type on biodiesel production from soybean
[Glycine max (L.) Merrill] oil. Indian J Biotechnol 2016; 15:596–600.
[27] Nongbe MC, Ekou T, Ekou L, et al. Biodiesel production from
palm oil using sulfonated graphene catalyst. Renewable Energy
2017; 106:135–41. [same as 157]
[28] Dizge N, Keskinler B. Enzymatic production of biodiesel from
canola oil using immobilized lipase. Biomass Bioenergy 2008;
32:1274–8.
[29] Juan  JC, Kartika  DA, Wu  TY, et  al. Biodiesel production from
jatropha oil by catalytic and non-catalytic approaches: an
overview. Bioresour Technol 2011; 102:452–60.
[30] Demirbas A. Biodiesel production from vegetable oils via cat-
alytic and non-catalytic supercritical methanol transesterifi-
cation methods. Prog Energy Combust Sci 2005; 31:466–487.
[31] Shah S, Sharma S, Gupta MN. Biodiesel preparation by lipase-
catalyzed transesterification of jatropha oil. Energy Fuels 2004;
18:154–9.
[32] Bajaj  A, Lohan  P, Jha  PN, et  al. Biodiesel production through
lipase catalyzed transesterification: an overview. J Mol Catal B:
Enzym 2010; 62:9–14.
[33] Luque R, Clark JH. Biodiesel-like biofuels from simultaneous
transesterification/esterification of waste oils with a biomass-
derived solid acid catalyst. ChemCatChem 2011; 3:594–7.
[34] Huang D, Han S, Han Z, et al. Biodiesel production catalyzed
by Rhizomucor miehei lipase-displaying Pichia pastoris whole
cells in an isooctane system. Biochem Eng J 2012; 63:10–4.
[35] Kalantari  M, Kazemeini  M, Arpanaei  A. Evaluation of bio-
diesel production using lipase immobilized silica nanocom-
posite particles of various structures. Biochem Eng J 2013;
79:267–73.
[36] Thangaraj  B, Jia  Z, Dai  L, et  al. Lipase NS81006 immobilized
on Fe3O4 magnetic nanoparticles for biodiesel production.
Ovidius Univ An Chem 2016; 27:13–21.
[37] Yiu HHP, Keane MA. Enzyme-magnetic nanoparticles hybrids:
Downloaded from https://academic.oup.com/ce/article/3/1/2/5250541 by guest on 03 July 2022
new effective catalysts for the production of high value chem-
icals. J Chem Technol Biotechnol 2012; 87:583–94.
[38] Sheldon RA, Pelt SV. Enzyme immobilization in biocatalysis:
why, what and how. Chem Soc Rev 2013; 42:6223–35.
[39] Dizge N, Aydiner C, Imer DY, et al. Biodiesel production from
sunflower, soybean and waste cooking oils by transesterifica-
tion using lipase immobilized onto a novel microporous poly-
mer. Bioresour Technol 2009; 100:1983–91.
[40] Ahmad R, Sardar M. Enzyme immobilization: an overview on
nanoparticles as immobilization matrix. Biochem Anal Biochem
2015; 4:1–8.
[41] Yi S, Dai F, Zhao C, et al. A reverse micelle strategy for fabricat-
ing magnetic lipase-immobilized nanoparticles with robust
enzymatic activity. Sci Rep 2017; 7:1–9.
[42] Vivek P, Rafael L, Aziz F, et al. Magnetically recoverable nano-
catalysts. Chem Rev 2011; 111:3036–75.
[43] Ma  F, Hanna  MA. Biodiesel production: a review. Bioresour
Technol 1999; 70:1–15.
[44] Jitputti J, Kitiyanan B, Rangsunvigit P, et al. Transesterification
of crude palm kernel oil and crude coconut oil by different
solid catalysts. Chem Eng J 2006; 116:61–6.
[45] Fukuda  H, Kondo  A, Noda  H. Biodiesel fuel production by
transesterification of oils. J Biosci Bioeng 2001; 92:405–16.
[46] Renganathan SV, Narashimhan SL, Muthukumar K. An over-
view of enzymatic production of biodiesel. Bioresour Technol
2008; 99:3975–81.
[47] Zhang  J, Liu  J, Ma  H. Esterification of free fatty acids in
Zanthoxylum bungeanum seed oil for biodiesel production by
stannic chloride. J Am Oil Chem Soc 2012; 89:1647–53.
[48] Zheng  S, Kates  M, Dube  MA, et  al. Acid-catalyzed produc-
tion of biodiesel from waste frying oil. Biomass Bioenergy 2006;
30:267–72.
[49] Marchetti JM, Miguel VU, Errazu AF. Possible methods for bio-
diesel production. Renew Sust Energy Rev 2007; 11:1300–11.
[50] Hayyan A, Alam MZ, Mirghani MES, et al. Sludge palm oil as a
renewable raw material for biodiesel production by two-step
processes. Bioresour Technol 2010; 101:7804–11.
[51] Reis MC, Freitas FA, Lachter ER, et al. Biodiesel production from
fatty acids of refined vegetable oils by heterogeneous acid catal-
ysis and microwave irradiation. Quim Nova 2015; 38:1307–12.
[52] Ahmad J, Yusup S, Bokhari A, et al. Study of fuel properties of
rubber seed oil based biodiesel. Energy Convers Manage 2014;
78:266–75.
[53] Awolu OO, Layokun K. Optimization of two-step transesterifi-
cation production of biodiesel from neem (Azadirachta indica)
oil. Int J Energy Environ Eng 2013; 39:1–9.

[54] Betiku  E, Omilakin  OR, Ajala  SO, et  al. Mathematical model-
ling and process parameters optimization studies by artificial
neural network and response surface methodology: a case of
non-edible neem (Azadirachta indica) seed oil biodiesel syn-
thesis. Energy 2014; 72:266–73.
[55] Sahar, Sadaf  S, Iqbal  J, et  al. Biodiesel production from
waste cooking oil: an efficient technique to convert waste
into biodiesel. Sustain Cities Soc 2018; 41:220–6. doi:10.1016/j.
scs.2018.05.037.
[56] Sanli  H, Canakci  M. Effects of different alcohol and catalyst
usage on biodiesel production from different vegetable oils.
Energy Fuels 2008; 22:2713–9.
[57] Freedman  B, Pryde  EH, Mounts  TL. Variable affecting the
yields of fatty esters from transesterified vegetable oils. J Am
Oil Chem Soc 1984; 61:1643–83.
[58] Peiter AS, Lins PVS, Meili L, et al. Stirring and mixing in ethylic
biodiesel production. J King Saud Univ Sci 2018. doi:10.1016/j.
jksus.2018.01.010.
[59] Xie W, Huang X, Li H, et al. Soybean oil methyl esters prepara-
tion using NaX zeolites loaded with KOH as a heterogeneous
catalyst. Bioresour Technol 2007; 98:936–9.
[60] Refaat  AA. Different techniques for the production of bio-
diesel from waste vegetable oil. Int J Environ Sci Technol 2010;
7:183–213.
[61] Endalew AK, Kiros Y, Zanzi R. Inorganic heterogeneous cata-
lysts for biodiesel production from vegetable oils. Biomass
Bioenergy 2011; 35:3787–809.
[62] Corma A, Iborra S. Optimization of alkaline earth metal oxide
and hydroxide catalysts for base-catalyzed reactions. Adv
Catal 2006; 49:239–302.
[63] Jørgensen KA. Transition-metal-catalyzed epoxidations. Chem
Rev 1989; 89:431–58.
[64] Gawande  MB, Pandey  RK, Jayaram  RV. Role of mixed metal
oxides in catalysis science—versatile applications in organic
synthesis. Catal Sci Technol 2012; 2:1113–25.
[65] Dos  Reis  SCM, Lachter  ER, Nascimento  RSV, et  al.
Transesterification of Brazilian vegetable oils with methanol
over ion-exchange resins. J Am Chem Soc 2005; 82:661–5.
[66] Harmer  MA, Sun  Q. Solid acid catalysis using ion-exchange
resins. Appl Catal A 2001; 221:45–62.
[67] İlgen  O, Akin  AN. Development of alumina supported alka-
line catalysts used for biodiesel production. Turk J Chem 2009;
33:281–7.
[68] Liu X, Piao X, Wang Y, et al. Calcium ethoxide as a solid base
catalyst for the transesterification of soybean oil to biodiesel.
Energy Fuels 2008; 22:1313–7.
[69] Chouhan  APS, Sarma  AK. Modern heterogeneous catalysts
for biodiesel production: a comprehensive review. Renew Sust
Energy Rev 2011; 15:4378–99.
[70] Du  L, Ding  S, Li  Z, et  al. Transesterification of castor oil to
biodiesel using NaY zeolite-supported La2O3 catalysts. Energy
Convers Manage 2018; 173:728–34.
[71] Deng Y, Hu X, Cheng L, et al. Zirconocene-catalysed biodiesel
synthesis from vegetable oil with high free fatty acid con-
tents. J Organomet Chem 2018; 870:116–20.
[72] Gama PE, Gil RASS, Lachter ER. Biodiesel production by in situ
transesterification of sunflower seeds by homogeneous and
heterogeneous catalysis. Quim Nova 2010; 33:1859–62.
[73] Gama  PE, Lachter  ER, Gil  RASS, et  al. Characterization and
catalytic activity of K2CO3/Al2O3 in the transesterification of
sunflower oil in conventional and microwave heating. Quim
Nova 2015; 38:185–90.
[74] Wan T, Yu P, Wang S, et al. Application of sodium aluminate as
a heterogeneous base catalyst for biodiesel production from
soybean oil. Energy Fuels 2009; 23:1089–92.
Thangaraj et al.  |  19
[75] Vyas AP, Verma JL, Subrahmanyan N. A review on FAME pro-
duction processes. Fuel 2010; 89:1–9.
[76] Di Serio M, Cozzolino M, Giordano M, et al. From homogene-
ous to heterogeneous catalysts in biodiesel production. Ind
Eng Chem Res 2007; 46:6379–84.
[77] Navajas A, Campo I, Moral A, et al. Outstanding performance
of rehydrated Mg-Al hydrotalcites as heterogeneous metha-
nolysis catalysts for the synthesis of biodiesel. Fuel 2018;
211:173–81.
[78] Chang F, Zhou Q, Pan H, et al. Solid mixed-metal-oxide cata-
lysts for biodiesel production: a review. Energy Technol 2014;
2:865–73.
[79] Wen Z, Yu X, Tu ST, et al. Synthesis of biodiesel from vegetable
oil with methanol catalyzed by Li-doped magnesium oxide
catalysts. Appl Energy 2010; 87:743–8.
[80] D’Cruz A, Kulkarni MG, Meher LC, et al. Synthesis of biodiesel
from canola oil using heterogeneous base catalyst. J Am Oil
Downloaded from https://academic.oup.com/ce/article/3/1/2/5250541 by guest on 03 July 2022
Chem Soc 2007; 84:937–43.
[81] Xie W, Yang Z, Chun H. Catalytic properties of lithium-doped
ZnO catalysts used for biodiesel preparations. Ind Eng Chem
Res 2007; 46:7942–9.
[82] Melero  JA, Bautista  LF, Morales  G. Biodiesel production with
heterogeneous sulfonic acid functionalized mesostructured
catalysts. Energy Fuels 2008; 23:539–47.
[83] Viriya-empikul  N, Krasae  P, Puttasawat  B, et  al. Waste shells
of mollusk and egg as biodiesel production catalysts. Bioresour
Technol 2010; 101:3765–7.
[84] Zhu H, Wu Z, Chen Y, et al. Preparation of biodiesel catalyzed
by solid super base of calcium oxide and its refining process.
Chin J Catal 2006; 27:391–6.
[85] Liu  H, Su  L, Shao  Y, et  al. Biodiesel production catalyzed by
cinder supported CaO/KF particle catalyst. Fuel 2012; 97:651–7.
[86] Hattori  H, Shima  M, Kabashima  H. Alcoholysis of ester and
epoxide catalyzed by solid base. Stud Surf Sci Catal 2000;
130:3507–12.
[87] Granados ML, Alonso DM, Sádaba I, et al. Leaching and homo-
geneous contribution in liquid phase reaction catalysed by
solids: the case of triglycerides methanolysis using CaO. Appl
Catal B 2009; 89:265–72.
[88] Kouzu M, Kasuno T, Tajika M, et al. Calcium oxide as a solid
base catalyst for transesterification of soybean oil and its
application to biodiesel production. Fuel 2008; 87:2798–806.
[89] Kouzu M, Yamanaka SY, Hidaka JS, et al. Heterogeneous catal-
ysis of calcium oxide used for transesterification of soybean
oil with refluxing methanol. Appl Catal A 2009; 355:94–9.
[90] Taufiq-Yap  YH, Lee  HV, Yunus  R, et  al. Transesterification of
non-edible Jatropha curcas oil to biodiesel using binary Ca–Mg
mixed oxide catalyst: effect of stoichiometric composition.
Chem Eng J 2011; 178:342–7.
[91] Kawashima  A, Matsubara  K, Honda  K. Development of het-
erogeneous base catalysts for biodiesel production. Bioresour
Technol 2008; 99:3439–43.
[92] Cannilla C, Bonura G, Rombi E, et al. Highly effective MnCeOX
catalysts for biodiesel production by transesterification of
vegetable oils with methanol. Appl Catal A 2010; 383: 158–166.
[93] Lee HV, Juan JC, Hin TYY, et al. Environment-friendly hetero-
geneous alkaline-based mixed metal oxide catalysts for bio-
diesel production. Energies 2016; 9:1–12.
[94] Maleki H, Kazemeini M, Larimi AS, et al. Transesterification of
canola oil and methanol by lithium impregnated CaO–La2O3
mixed oxide for biodiesel synthesis. J Ind Eng Chem 2017;
47:399–404.
[95] Liu R, Wang X, Zhao X, et al. Sulfonated ordered mesoporous
carbon for catalytic preparation of biodiesel. Carbon 2008;
46:1664–9.
20 | Clean Energy, 2019, Vol. 3, No. 1
[96] Mbaraka  IK, Shanks  BH. Design of multifunctionalized
mesoporous silicas for esterification of fatty acid. J Catal 2005;
229:365–73.
[97] Mbaraka  IK, Shanks  BH. Conversion of oils and fats using
advanced mesoporous heterogeneous catalysts. J Am Oil Chem
Soc 2006; 83:79–91.
[98] Xie W, Huang M. Immobilization of Candida rugosa lipase onto
graphene oxide Fe3O4 nanocomposite: Characterization and
application for biodiesel production. Energy Convers Manage
2018; 159:42–53.
[99] Heidekum  A, Harmer  MA, Hoelderich  WF. Addition of car-
boxylic acids to cyclic olefins catalyzed by strong acidic ion-
exchange resins. J Catal 1999; 181:217–22.
[100] Barros SDT, Coelho AV, Lachter ER, et al. Esterification of lau-
ric acid with butanol over mesoporous materials. Renewable
Energy 2013; 50:585–589.
[101] Albuquerque  MCG, Jiménez-Urbistondo  I, Santamaría-
González  J, et  al. CaO supported on mesoporous silicas as
basic catalysts for transesterification reactions. Appl Catal A
2008; 334:35–43.
[102] Thitsartarn W, Maneerung T, Kawi S, et al. Highly active and
durable Ca-doped Ce-SBA-15 catalyst for biodiesel produc-
tion. Energy 2015; 89:946–56.
[103] Xie WL, Zhao LL. Heterogeneous CaO-MoO3-SBA-15 catalysts
for biodiesel production from soybean oil. Energy Convers
Manage 2014; 79:34–42.
[104] Shagufta, Ahmad  I, Dhar  R. Sulfonic acid-functionalized
solid acid catalyst in esterification and transesterification
reactions. Catal Surv Asia 2017; 21:53–69.
[105] Tesser R, Vitiello R, Carotenuto G. Niobia supported on silica
as a catalyst for biodiesel production from waste oil. Catal
Sustain Energy 2015; 2:33–42.
[106] Bassan IAL, Nascimento DR, San Gil RAS, et al. Esterification
of fatty acids with alcohols over niobium phosphate. Fuel
Process Technol 2013; 106:619–24.
[107] Aguiar VM, de Souza ALF, Galdino FS, et al. Sulfonated poly
(divinylbenzene) and poly (styrene-divinylbenzene) as
catalyst for esterification of fatty acids. Renewable Energy
2017;114:725–32.
[108] Lau PC, Kwong TL, Yung KF. Effective heterogeneous transi-
tion metal glycerolates catalysts for one-step biodiesel pro-
duction from low grade non-refined Jatropha oil and crude
aqueous bioethanol. Sci Rep 2016; 6:23822–32.
[109] Kumar D, Singh B, Banerjee A, et al. Cement wastes as trans-
esterification catalysts for the production of biodiesel from
Karanja oil. J Cleaner Prod 2018; 183:26–34.
[110] Farooq M, Ramli A, Naeem A. Biodiesel production from date
seed oil (Phoenix dactylifera L.) via egg shell derived heteroge-
neous catalyst. Chem Eng Res Des 2018; 132:644–51.
[111] Etim OA, Betiku E, Ajala SO, et al. Potential of ripe plantain
fruit peels as an ecofriendly catalyst for biodiesel synthe-
sis: optimization by artificial neural network integrated with
genetic algorithm. Sustainability 2018; 10:1–15.
[112] Uprety BK, Chaiwong W, Ewelike C, et al. Biodiesel produc-
tion using heterogeneous catalysts including wood ash and
the importance of enhancing by-product glycerol purity.
Energy Convers Manage 2016; 115:191–9.
[113] Ezebor F, Khairuddean M, Abdullah AZ, et al. Oil palm trunk
and sugarcane bagasse derived heterogeneous acid cata-
lysts for production of fatty acid methyl esters. Energy 2014;
70:493–503.
[114] Gohain  M, Devi  A, Deka  D. Musa balbisiana Colla peel as
highly effective renewable heterogeneous base catalyst for
biodiesel production. Ind Crops Prod 2017; 109:8–18.
[115] Mendonça IM, Paes OARL, Maia PJS, et al. New heterogeneous
catalyst for biodiesel production from waste tucumã peels
(Astrocaryum aculeatum Meyer): parameters optimization
study. Renewable Energy 2018; 130:103–10.
[116] Nur  Syazwani  O, Rashid  U, Taufiq  Yap  YH, et  al. Low-cost
solid catalyst derived from waste Cyrtopleura costata (Angel
Wing Shell) for biodiesel production using microalgae oil.
Energy Convers Manage 2015; 101:749–56.
[117] Nisar J, Razaq R, Farooq M, et al. Enhanced biodiesel produc-
tion from Jatropha oil using calcined waste animal bones as
catalyst. Renewable Energy 2017; 101:111–9.
[118] Ho WWS, Ng HK, Gan S, et al. Development and characterisa-
tion of novel heterogeneous palm oil mill boiler ash-based
catalysts for biodiesel production. Bioresour Technol 2012;
125:158–64.
[119] Zeng DL, Zhang Q, Chen SY, et al. Synthesis porous carbon-
based solid acid from rice husk for esterification of fatty
Downloaded from https://academic.oup.com/ce/article/3/1/2/5250541 by guest on 03 July 2022
acids. Microporous Mesoporous Mater 2016; 219:54–8.
[120] Ngaosuwan  K, Goodwin  JG Jr, Prasertdham  P, et  al. A green
sulfonated carbon-based catalyst derived from coffee resi-
due for esterification. Renewable Energy 2016; 86:262–9.
[121] Uddin M, Chowdhury R. Environmental Impact of Nanotechnology.
AC 2007–387. American Society for Engineering Education.
https://peer.asee.org/environmental-impact-of-nanotech-
nology.pdf
[122] Thangaraj  B, Muniyandi  B, Ranganathan  S, et  al.
Functionalized magnetic nanoparticles for catalytic applica-
tion—a review. Rev Adv Sci Eng 2015; 4:106–19.
[123] Wagner  GW, Koper  OB, Lucas  E, et  al. Reactions of VX, GD
and HD with nanosize CaO: autocatalytic dehydrogenation
of HD. J Phys Chem B 2000; 104:5118–23.
[124] Venkat Reddy CR, Oshel R, Verkade JG. Room-temperature con-
version of soybean oil and poultry fat to biodiesel catalyzed by
nanocrystalline calcium oxides. Energy Fuels 2006; 20:1310–4.
[125] Reddy ANR, Saleh AA, Isalm MS, et al. Biodiesel production
from crude Jatropha oil using a highly active heterogene-
ous nanocatalyst by optimizing transesterification reaction
parameters. Energy Fuels 2016; 30:334–43.
[126] Gupta J, Agarwal M. Preparation and characterization of CaO
nanoparticle for biodiesel production. In: 2nd International
Conference on Emerging Technologies: Micro to Nano 2015 (ETMN-
2015), AIP Conference Proceedings, 2016; 1724:1–10.
[127] Kaur  M, Ali  A. Lithium ion impregnated calcium oxide as
nano catalyst for the biodiesel production from karanja and
jatropha oils. Renewable Energy 2011; 36:2866–71.
[128] Tahvildari K, Anaraki YN, Fazaeil R, et al. The study of CaO
and MgO heterogenic nano-catalyst coupling on transesteri-
fication reaction efficacy in the production of biodiesel from
recycled cooking oil. J Environ Health Sci Eng 2015; 73:1–9.
[129] Feyzi  M, Norouzi  L. Preparation and kinetic study of mag-
netic Ca/Fe3O4@SiO2 nanocatalysts for biodiesel production.
Renewable Energy 2016; 94:579–86.
[130] Alves BM, Medeiros FCM, Sousa MH, et al. Cadmium and tin
magnetic nanocatalysts useful for biodiesel production. J
Braz Chem Soc 2014; 25: 2304–13.
[131] Santos  ECS, Santos  TCD, Guimarães  RB, et  al. Guanidine-
functionalized Fe3O4 magnetic nanoparticles as basic recy-
clable catalysts for biodiesel production. RSC Adv 2015;
5:48031–8.
[132] Heyou H, Yanping G. Synthesis of biodiesel from rapeseed oil
using K2O/γ-Al2O3 as nano-solid-base catalyst. J Wuhan Univ
Natur 2009; 14:75–9.
[133] Nayebzadeh  H, Saghatoleslami  N, Tabasizadeh  M.
Optimization of the activity of KOH/calcium aluminate

nanocatalyst for biodiesel production using response surface
methodology. J Taiwan Inst Chem Eng (DNLM) 2016; 68:379–86.
[134] Qiu F, Li Y, Yang D, et al. Heterogeneous solid base nanocata-
lyst: preparation, characterization and application in bio-
diesel production. Bioresour Technol 2011; 102:4150–6.
[135] Verziu M, Cojocaru B, Hu J, et al. Sunflower and rapeseed oil
transesterification to biodiesel over different nanocrystal-
line MgO catalysts. Green Chem 2008; 10:373–81.
[136] Thangaraj B, Piraman S. Heteropoly acid coated ZnO nano-
catalyst for Madhuca indica biodiesel synthesis. Biofuels 2016;
7:13–20.
[137] Baskar  G, Soumiya  S. Production of biodiesel from castor
oil using iron (II) doped zinc oxide nanocatalysts. Renewable
Energy 2016; 98:101–7.
[138] Baskar G, Selvakumari IAE, Aiswarya R, et al. Biodiesel pro-
duction from castor oil using heterogeneous Ni doped ZnO
nanocatalyst. Bioresour Technol 2018; 250:793–8.
[139] Baskar G, Gurugulladevi A, Nishanthini T, et al. Optimization
and kinetics of biodiesel production from Mahua oil using
manganese doped zinc oxide nanocatalyst. Renewable Energy
2017; 103:641–6.
[140] Li  J, Wang  X, Zhu  W, et  al. Zn1.2H0.6PW12O40 nanotubes with
double acid sites as heterogeneous catalysts for the produc-
tion of biodiesel from waste cooking oil. ChemSusChem 2009;
2:177–83.
[141] Wang J,Chen Y,Wang X,et al.Aluminumdodecatungstophosphate
(Al0.9H0.3PW12O40) nanotube as a solid acid catalyst one-pot pro-
duction of biodiesel from waste cooking oil. Bioresources 2009;
4:1477–86.
[142] Zhao Q, Wang H, Zheng H, et al. Acid-base bifunctional HPA
nanocatalysts promoting heterogeneous transesterifica-
tion and esterification reactions. Catal Sci Technol 2013; 3:
2204–2209.
[143] Woodford  JJ, Parlett  CMA, Dacquin  JP, et  al. Identifying the
active phase in Cs-promoted MgO nanocatalysts for tri-
glyceride transesterification. J Chem Technol Biotechnol 2013;
89:73–80.
[144] Vahid BR, Haghighi M. Biodiesel production from sunflower
oil over MgO/MgAl2O4 nanocatalyst: effect of fuel type on
catalyst nanostructure and performance. Energy Convers
Manage 2017; 134:290–300.
[145] Zhang H, Li H, Hu P, et al. Magnetically recyclable acidic poly-
meric ionic liquids decorated with hydrophobic regulators
as highly efficient and stable catalysts for biodiesel produc-
tion. Appl Energy 2018; 223:416–29.
[146] Alaei S, Haghighi M, Toghiani J, et al. Magnetic and reusable
MgO/MgFe2O4 nanocatalyst for biodiesel production from
sunflower oil: influence of fuel ratio in combustion synthesis
on catalytic properties and performance. Ind Crops Prod 2018;
117:322–32.
[147] Dantas  J, Leal  E, Cornejo  DR, et  al. Biodiesel produc-
tion evaluating the use and reuse of magnetic nanocata-
lysts Ni0.5Zn0.5Fe2O4. Arabian J Chem 2018; doi: 10.1016/j.
arabjc.2018.08.012.
[148] Borah  MJ, Devi  A, Saikia  RA, et  al. Biodiesel production
from waste cooking oil catalyzed by in-situ decorated TiO2
on reduced graphene oxide nanocomposite. Energy 2018;
158:881–9.
[149] Kaur M, Malhotra R, Ali A. Tungsten supported Ti/SiO2 nano-
flowers as reusable heterogeneous catalyst for biodiesel pro-
duction. Renewable Energy 2018; 116:109–19.
[150] Vardast N, Haghighi M, Dehghani S, et al. Sono-dispersion of
calcium over Al-MCM-41used as a nanocatalyst for biodiesel
production from sunflower oil: influence of ultrasound
Thangaraj et al.  |  21
irradiation and calcium content on catalytic properties and
performance. Renewable Energy 2019; 132:979–88.
[151] Saka S, Kusdiana D. Biodiesel fuel from rapeseed oil as pre-
pared in supercritical methanol. Fuel 2001; 43:2349–56.
[152] Demirbas A. Biodiesel from vegetable oils via transesterifica-
tion in supercritical methanol. Energy Convers Manage 2002;
43:2349–56.
[153] Deslandes  N, Bellenger  V, Jaffiol  F, et  al. Solubility parame-
ters of a polyester composite material. J Appl Polym Sci 1998;
69:2663–71.
[154] Kusdiana D, Saka S. Effects of water on biodiesel fuel produc-
tion by supercritical methanol treatment. Bioresour Technol
2004; 91:289–95.
[155] Yin JZ, Xiao M, Song JB. Biodiesel from soybean oil in super-
critical methanol with co-solvent. Energy Convers Manage
2008; 49:908–12.
[156] Han  H, Cao  W, Zhang  J. Preparation of biodiesel from soy-
Downloaded from https://academic.oup.com/ce/article/3/1/2/5250541 by guest on 03 July 2022
bean oil using supercritical methanol and CO2 as co-solvent.
Process Biochem 2005; 40:3148–51.
[157] Alenezi R, Leeke GA, Winterbottom JM, et al. Esterification
kinetics of free fatty acids with supercritical methanol
for biodiesel production. Energy Convers Manage 2010;
51:1055–9.
[158] Ilham Z, Saka S. Dimethyl carbonate as potential reactant in
non-catalytic biodiesel production by supercritical method.
Bioresour Technol 2009; 100:1793–6.
[159] Son  J, Kim  B, Park  J, et  al. Wet in situ transesterification of
spent coffee grounds with supercritical methanol for the
production of biodiesel. Bioresour Technol 2018; 259:465–8.
[160] Farobie O, Leow ZYM, Samanmulya T, et al. New insights in
biodiesel production using supercritical 1-propanol. Energy
Convers Manage 2016; 124:212–8.
[161] Fjerbaek L, Christensen KV, Norddahl B, et al. A review of the
current state of biodiesel production using enzymatic trans-
esterification. Biotechnol Bioeng 2008; 102:1298–315.
[162] Villeneuve  P, Muderhwa  JM, Graille  J, et  al. Customizing
lipases for biocatalysis: a survey of chemical, physical and
molecular biological approaches. J Mol Catal B: Enzym 2000;
9:113–8.
[163] Tan T, Lu J, Nie K, et al. Biodiesel production with immobi-
lized lipase: a review. Biotechnol Adv 2010; 28:628–34.
[164] Belafi-Bako K, Kovacs F, Gubicza L, et al. Enzymatic biodiesel
production from sunflower oil by Candida antarctica lipase in
a solvent-free system. Biocatal Biotransform 2002; 20:437–9.
[165] Adriana  G, Roman  M, Tosa  M, et  al. Biodiesel production
using enzymatic transesterification – current state and per-
spectives. Renewable Energy 2012; 39:10–6.
[166] Akoh CC, Chang SW, Lee G, et al. Enzymatic approach to bio-
diesel production. J Agric Food Chem 2007; 55:8995–9005.
[167] Zhang B, Weng Y, Xu H, et al. Enzyme immobilization for bio-
diesel production. Appl Microbiol Biotechnol 2012; 93:61–70.
[168] Li W, Du W, Liu D. Rhizopus oryzae IFO 4697 whole cell cata-
lyzed methanolysis of crude and acidified rapeseed oils for
biodiesel production in tert-butanol system. Process Biochem
2007; 42:1481–5.
[169] Li Q, Xu J, Du W, et al. Ethanol as the acyl acceptor for bio-
diesel production. Renew Sust Energ Rev 2013; 25:742–8.
[170] Xu Y, Du W, Liu D, et al. A novel enzymatic route for biodiesel
production from renewable oils in a solvent-free medium.
Biotechnol Lett 2003; 25:1239–41.
[171] Naranjo JC, Córdoba A, Giraldo L, et al. Lipase supported on
granular activated carbon and activated carbon cloth as cat-
alyst in the synthesis of biodiesel fuel. J Mol Catal B: Enzym
2010; 66:166–71.
22 | Clean Energy, 2019, Vol. 3, No. 1
[172] Kaieda  M, Samukawa  T, Kondo  A, et  al. Effect of methanol
and water contents on production of biodiesel fuel from
plant oil catalyzed by various lipases in a solvent-free sys-
tem. J Biosci Bioeng 2001; 91:12–5.
[173] Subramanian  A, Kennel  SJ, Oden  PI, et  al. Comparison of
techniques for enzyme immobilization on silicon supports.
Enzyme Microb Technol 1999; 24:26–34.
[174] Franssen  MCR, Steunenberg  P, Scott  EL, et  al. Immobilized
enzymes in biorenewables production. Chem Soc Rev 2013;
42:6491–533.
[175] Tischer W, Wedekind F. Immobilized enzymes: methods and
applications. Top Curr Chem 1999; 200:95–126.
[176] Datta S, Christena LR, Rajaram YRS. Enzyme immobilization:
an overview on techniques and support materials. 3 Biotech
2013; 3:1–9.
[177] Ghaly AE, Dave D, Brooks MS, et al. Production of biodiesel by
enzymatic transesterification: review. Am J Biochem Biotechnol
2010; 6:54–76.
[178] Homaei  AA, Sariri  R, Vianello  F, et  al. Enzyme immobiliza-
tion: an update. J Biol Chem 2013; 6:185–205.
[179] Guisan  JM. Immobilization of Enzymes and Cells. Methods in
Biotechnology. Humana Press, 2006;22:1–439.
[180] Sheldon  RA. Characteristic features and biotechnological
applications of cross-linked enzyme aggregates (CLEAs).
Appl Microbiol Biotechnol 2011; 92:467–77.
[181] Zheng Y, Quan J, Ning X, et al. Lipase-catalyzed transesteri-
fication of soybean oil for biodiesel production in tert-amyl
alcohol. World J Microbiol Biotechnol 2009; 25:41–6.
[182] Chang  MY, Juang  RS. Activities, stabilities, and reaction
kinetics of three free and chitosan-clay composite immobi-
lized enzymes. Enzyme Microb Technol 2005; 36:75–82.
[183] Yücel  Y. Biodiesel production from pomace oil by using
lipase immobilized onto olive pomace. Bioresour Technol 2011;
102:3977–80.
[184] Ulibarri MA, Pavlovic I, Barriga C, et al. Adsorption of anionic
species on hydrotalcite-like compounds: effect of interlayer
anion and crystallinity. Appl Clay Sci 2001; 18:17–27.
[185] Tutar  H, Yilmaza  E, Pehlivan  E, et  al. Immobilization of
Candida rugosa lipase on sporopollenin from Lycopodium
clavatum. Int J Biol Macromol 2009; 45:315–20.
[186] Li  Q, Yan  Y. Production of biodiesel catalysed by immobi-
lized Pseudomonas cepacia lipase from Sapium sebiferum oil in
micro-aqueous phase. Appl Energy 2010; 87:3148–3154.
[187] Chang  HM, Liao  HF, Lee  CC, et  al. Optimized synthesis of
lipase-catalyzed biodiesel by Novozym 435. J Chem Technol
Biotechnol 2005; 80:307–12.
[188] Tan  T, Nie  K, Wang  F. Production of biodiesel by immobi-
lized Candida sp. lipase at high water content. Appl Biochem
Biotechnol 2006; 128:109–16.
[189] Noureddini  H, Gao  X, Philkana  RS, et  al. Immobilized
Pseudomonas cepacia lipase for biodiesel fuel production from
soybean oil. Bioresour Technol 2005; 96:769–77.
[190] Li  X, He  XY, Li  ZL, et  al. Enzymatic production of biodiesel
from Pistacia chinensis bge seed oil using immobilized lipase.
Fuel 2012; 92:89–93.
[191] Iso  M, Chen  B, Eguchi  M, et  al. Production of biodiesel fuel
from triglycerides and alcohol using immobilized lipase. J
Mol Catal B: Enzym 2001; 16:53–8.
[192] Yagiz  F, Kazan  D, Akin  AN, et  al. Biodiesel production from
waste oils by using lipase immobilized on hydrotalcite and
zeolites. Chem Eng J 2007; 134:262–7.
[193] Du W, Xu YY, Liu DH, et al. Study on acyl migration in immobi-
lized lipozyme TL-catalyzed transesterification of soybean oil
for biodiesel production. J Mol Catal B: Enzym 2005; 37:68–71.
[194] Köse  O, Tüter  M, Aksoy  HA. Immobilized Candida antarctica
lipase-catalyzed alcoholysis of cotton seed oil in a solvent-
free medium. Bioresour Technol 2002; 83:125–9.
[195] Rafiei  S, Tangestaninejad  S, Horcajada  P, et  al. Efficient bio-
diesel production using a lipase@ZIF-67 nanobioreactor. Chem
Eng J 2018; 334:1233–41.
[196] Kuo CH, Peng LT, Kan SC, et al. Lipase-immobilized biocata-
lytic membranes for biodiesel production. Bioresour Technol
2013; 145:229–32.
[197] Yu CY, Huang LY, Kuan IC, et al. Optimized production of bio-
diesel from waste cooking oil by lipase immobilized on mag-
netic nanoparticles. Int J Mol Sci 2013; 14:24074–86.
[198] Huang SH, Liao MH, Chen DH, et al. Direct binding and char-
acterization of lipase onto magnetic nanoparticles. Biotechnol
Downloaded from https://academic.oup.com/ce/article/3/1/2/5250541 by guest on 03 July 2022
Progr 2003; 19:1095–100.
[199] Moghaddam AB, Nazari T, Badraghi J, et al. Synthesis of ZnO
nanoparticles and electrodeposition of polypyrrole/ZnO
nanocomposite film. Int J Electrochem Sci 2009; 4: 247–257.
[200] Jia  H, Zhu  G, Wang  P, et  al. Catalytic behaviors associated
with enzymes attached to nanoparticles: the effect of parti-
cle mobility. Biotechnol Bioeng 2003; 84:406–14.
[201] Mak KH, Yu CY, Kuan IC, et al. Immobilization of Pseudomonas
cepacia lipase onto magnetic nanoparticles for biodiesel pro-
duction. ISESCO J Sci Technol Vision 2009; 5:19–23.
[202] Ansari SA, Husain Q. Potential applications of enzymes on/in
nanomaterials: a review. Biotechnology Adv 2012; 30:512–23.
[203] Raita M, Arnthong J, Champreda V, et al. Modification of mag-
netic nanoparticle lipase designs for biodiesel production
from palm oil. Fuel Process Technol 2015; 134:189–97.
[204] Liu  CH, Huang  CC, Wang  YW, et  al. Biodiesel production
by enzymatic transesterification catalyzed by Burkholderia
lipase immobilized on hydrophobic magnetic particles. Appl
Energy 2012; 100:41–6.
[205] Dussan KJ, Cardona CA, Giraldo OH, et al. Analysis of a reac-
tive extraction process for biodiesel production using a
lipase immobilized on magnetic nanostructures. Bioresour
Technol 2010; 101:9542–9.
[206] Tran  DT, Chen  CL, Chang  JS. Immobilization of Burkholderia
sp. lipase on a ferric silica nanocomposite for biodiesel pro-
duction. J Biotechnol 2012; 158:112–9.
[207] Thangaraj B, Jia Z, Dai L, et al. Effect of silica coating on Fe3O4
magnetic nanoparticles for lipase immobilization and their
application for biodiesel production. Arabian J Chem 2016;
doi: 10.1016/j.arabjc.2016.09.004.
[208] Sipponen MH, Farooq M, Koivisto J, et al. Spatially confined
lignin nanospheres for biocatalytic ester synthesis in aque-
ous media. Nature Commun 2018; 9:art2300. doi:10.1038/
s41467-018-04715-6.
[209] Xie W, Wang J. Enzymatic production of biodiesel from soy-
bean oil by using immobilized lipase on Fe3O4/poly (styrene-
methacrylic acid) magnetic microsphere as a biocatalyst.
Energy Fuels 2014; 28:2624–31.
[210] Ngo TPN, Li A, Tiew KW, et al. Efficient transformation of grease
to biodiesel using highly active and easily recyclable magnetic
nanobiocatalyst aggregates. Bioresour Technol 2013; 145:233–9.
[211] Shimada  Y, Watanabe  Y, Samukawa  T, et  al. Conversion of
vegetable oil to biodiesel using immobilized Candida antarc-
tica lipase. J Am Oil Chem Soc 1999; 76:789–93.

[212] Salis  A, Pinna  M, Monduzzi  M, et  al. Comparison among
[218] Chen G, Liu J, Yao J, et al. Biodiesel production from waste cook-
immobilised lipases on macroporous polypropylene toward
biodiesel synthesis. J Mol Catal B: Enzym 2008; 54:19–26.
[213] Talukder  MMR, Wu  JC, Nguyen  TBV, et  al. Novozym 435
[219] Thangaraj  B, Jia  Z, Dai  L, et  al. Lipase NS81006 immobi-
for production of biodiesel from unrefined palm oil:
Comparison of methanolysis methods. J Mol Catal B: Enzym
2009; 60:106–12.
[214] Xie  W, Ma  N. Enzymatic transesterification of soybean oil
by using immobilized lipase on magnetic nano-particles.
Biomass Bioenergy 2010; 34:890–896.
[215] Chiaradia  V, Soares  NP, Valério  A, et  al. Immobilization
of Candida antarctica lipase B on magnetic poly(urea-
urethane) nanoparticles. Appl Biochem Biotechnol 2016;
180:558–75.
[216] Xie  W, Ma  N. Immobilized lipase on Fe3O4 nanoparticles
as biocatalyst for biodiesel production. Energy Fuels 2009;
23:1347–53.
[217] Wang X, Dou P, Zhao P, et al. Immobilization of lipases onto
magnetic Fe3O4 nanoparticles for application in biodiesel
production. ChemSusChem 2009; 2:947–50.
Thangaraj et al.  |  23
ing oil in a magnetically fluidized bed reactor using whole-cell
biocatalysts. Energy Convers Manage 2017; 138:556–64.
lized on functionalized ferric-silica magnetic nanoparti-
cles for biodiesel production. Biofuels 2017; doi: 10.1016/j.
arabjc.2016.09.004.
[220] Wang X, Liu X, Zhao C, et al. Biodiesel production in packed-
bed reactors using lipase-nanoparticle composite. Bioresour
Technol 2011; 102:6352–5.
[221] Tong  XD, Sun  Y. Application of magnetic agarose support
in liquid magnetically stabilized fluidized bed for protein
adsorption. Biotechnol Progr 2003; 19:1721–7.
[222] Zhou  GX, Chen  GY, Yan  BB, et  al. Biodiesel production in a
magnetically-stabilized, fluidized bed reactor with an immo-
bilized lipase in magnetic chitosan microspheres. Biotechnol
Lett 2014; 36:63–8.
Downloaded from https://academic.oup.com/ce/article/3/1/2/5250541 by guest on 03 July 2022
[223] Putra RS, Pratama K, Antono Y, et al. Enhanced electrocata-
lytic biodiesel production with chitosan gel (hydrogel and
xerogel). Procedia Eng 2016; 148:609–14.