Journal of Molecular Liquids 266 (2018) 673–686

Contents lists available at ScienceDirect

Journal of Molecular Liquids

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

Review

A review on ionic liquids as perspective catalysts in transesterification of

different feedstock oil into biodiesel
Zahoor Ullah a,b,⁎, Amir Sada Khan c,d, Nawshad Muhammad e, Riaz Ullah f,g, Ali S. Alqahtani f, Syed Nasir Shah h,
Ouahid Ben Ghanem c, Mohamad Azmi Bustam c, Zakaria Man c
a
Department for Management of Science and Technology Development, Ton Duc Thang University, Ho Chi Minh City, Vietnam
b
Faculty of Applied Sciences, Ton Duc Thang University, Ho Chi Minh City, Vietnam
c
Centre of Research in Ionic Liquids, Department of Chemical Engineering, Universiti Teknologi PETRONAS, Tronoh 31750, Malaysia
d
Department of Chemistry, University of Science and Technology, Bannu 28100, Khyber Pakhtunkhwa, Pakistan
e
Interdisciplinary Research Centre in Biomedical Materials, COMSATS Institute of Information Technology, Lahore 54000, Pakistan
f
Department of Pharmacognosy (Medicinal, Aromatic and Poisonous Plants Research Center), College of Pharmacy, King Saud University Riyadh, Saudi Arabia
g
Department of Chemistry, Govt College, Ara Khel FR, Kohat, KPK, Pakistan
h
Department of Chemical Engineering, COMSATS Institute of Information Technology, Lahore, Pakistan

a r t i c l e i n f o a b s t r a c t

Article history: The past few decades had seen a rapid hike in the world's population, which has caused an excessive use of fossils
Received 20 October 2017 and, consequently, the diminution of fossil resources and the advent of global pollution problems. In this regard,
Received in revised form 4 June 2018 the renewable and eco-friendly properties of biodiesel fuel provide an alternative to petroleum fuel. Many coun-
Accepted 7 June 2018
tries are looking into the use of biodiesel, particularly countries that are more susceptible to environmental prob-
Available online 2 July 2018
lems. Biodiesel could be synthesized from different origins, including organic oils from animal fats and

Abbreviations: [Emim][BF4], ethyl-methylimidazolium tetrafluoroborate; [Omim][BF4], octyl-methylimidazolium tetrafluoroborate; [Bmim][BF4], butyl-methylimidazolium tetrafluo-
roborate; [Emim][TfO], ethyl-methylimidazolium trifluoromethanesulfonate; [Pmim][TfO], propyl-methylimidazolium trifluoromethanesulfonate; [Bmim][TfO], butyl-
methylimidazolium trifluoromethanesulfonate; [Bmpyr][MS], butyl-methylpyrrolidinium methylsulfate; [Hmim][TfO], hexyl-methylimidazolium trifluoromethanesulfonate; [Omim]
[MS], octyl-methylimidazolium methylsulfate; [Emim][MS], ethyl-methylimidazolium methylsulfate; [Bzmim][Tf2N], benzyl-methylimidazolium bis(trifluoromethylsulfonyl)imide;
[Emim][Tf2N], ethyl-methylimidazolium bis(trifluoromethylsulfonyl)imide; [Bmim][PF6], butyl-methylimidazolium hexafluorophosphate; [Pmim][Tf2N], propyl-methyl-imidazolium
bis(trifluoromethylsulfonyl)imide; [Omim][PF6], octyl-methylimidazolium hexafluorophosphate; [Bmim][Tf2N], butyl-methylimidazolium bis(trifluoromethylsulfonyl)imide; [Hmim]
[Tf2N], hexyl-methylimidazolium bis(trifluoromethylsulfonyl)imide; [Pmim][SbF6], propyl-methyl-imidazolium hexafluoroantimonate; [Edmim][Tf2N], ethyl-dimethylimidazolium bis
(trifluoromethylsulfonyl)imide; [Omim][Tf2N], octyl-methylimidazolium bis(trifluoromethylsulfonyl)imide; [Hmim][PF6], hexyl-methylimidazolium hexafluorophosphate; [Hmim]
[SbF6], hexyl-methylimidazolium hexafluoroantimonate; [Empyr][SbF6], ethyl-methylpyrrolidinium hexafluoroantimonate; [BMI][PF6], butyl-methylimidazolium hexafluorophosphate;
[Bmim][Cl], butyl-methylimidazolium chloride; [Bmim][CH3SO3], butyl-methylimidazolium methanesulfonate; [Bmim][OH], butyl-methylimidazolium hydroxide; [Emim][Cl], ethyl-
methylimidazolium chloride; [Emim][PF6], ethyl-methylimidazolium hexafluorophosphate; [Hmim][Cl], hexyl-methylimidazolium chloride; [Hmim][CH3SO3], hexyl-
methylimidazolium methanesulfonate; [Hmim][TfO], hexyl-methylimidazolium trifluoromethanesulfonate; [Omim][Cl], octyl-methylimidazolium chloride; [OmPy][BF4], octyl-
methylpyridinium tetrafluoroborate; [NMP][CH3SO3], N-methyl-pyrrolidinium methanesulfonate; [C8mim][NTf2], octyl-methylimidazolium bis(trifluoromethylsulfonyl) imide;
[C4mim][NTf2], butyl-methylimidazolium bis(trifluoromethylsulfonyl)imide; [C12mim][NTf2], dodecyl-methylimidazolium bis(trifluoromethylsulfonyl)imide; [C14mim] [NTf2],
tetradecyl-methylimidazolium bis(trifluoromethylsulfonyl)imide; [C16mim][NTf2], hexadecyl-methylimidazolium bis(trifluoromethylsulfonyl)imide; [C18mim][NTf2], octadecyl-
methylimidazolium bis(trifluoromethylsulfonyl)imide; [C12mim][PF6], dodecyl-methyl-imidazolium hexafluorophosphate; [C14mim][PF6], tetradecyl-methylimidazolium
hexafluorophosphate; [C16mim][PF6], hexadecyl-methylimidazolium hexafluorophosphate; [C18mim][PF6], octadecyl-methylimidazolium hexafluorophosphate; [C12mim] [BF4],
dodecyl-methylimidazolium tetrafluoroborate; [C14mim][BF4], tetradecyl-methylimidazolium tetrafluoroborate; [C16mim][BF4], hexadecyl-3-methylimidazolium tetrafluoroborate;
[C18mim][BF4], octadecyl-3-methylimidazolium tetrafluoroborate; [Bmp][BF4], butyl-methylpyridinium tetrafluoroborate; [Bmp][PF6], butyl-methylpyridinium hexafluorophosphate;
[Bdmim][NTf2], butyl-dimethylimidazolium bis(trifluoromethylsulfonyl)imide; [Emim][CF3SO3], ethyl-methylimidazolium trifluoromethanosulfonate; [Et3NH]Cl, triethylammonium
chloride; [BSMIM]Cl, butylsulfonic-methylimidazolium chloride; [hemim][HSO4], methyl-heptyl-imidazolium hydrogensulphate; [heemim][HSO4], (hydroxyethoxy)ethyl-methyl-
imidazolium hydrogensulphate; [BMIM][HSO4], butyl-methylimidazolium hydrogensulphate; [Et3NHSO4], triethylammonium hydrogensulphate; [BSPIM][HSO4], butyl-(sulfopropyl)-
imidazolium hydrogensulphate; [HO3S–(CH2)3–NEt3]Cl–ZnCl2, (3-sulfonic acid)-propyl-triethylammonium chlorozincinate; [BIM][HSO4], butyl-imidazolium hydrogensulphate; [MIM]
[HSO4], methyl-imidazolium hydrogensulphate; [C4SO3Hpy][HSO4], butylsulfonic-pyridinium hydrogensulphate; [NMP][HSO4], N-methyl-pyrrolidinium hydrogensulphate; [BSPy]
[CF3SO3], butylsulfonic-pyridinium trifluoromethanesulfonate; [TMEDAPS][HSO4], N,N,N0,N0-tetramethyl-N,N0-dipropanesulfonic acid ethylenediammonium hydrogensulphate;
[IMC2OH], bis-(3-methyl-1-imidazolium-)-ethylene dihydroxide; [BSPy][HSO4], butylsulfonic-pyridinium hydrogensulphate; [HO3S-pmim][HSO4], 1–(3–sulfonic acid)propyl–3–
methylimidazole hydrosulfate; [C21H20BrP], gallyltriphenyl phosphonium bromide; [PTSA] [C7H8O3S·H2O], p-toluenesulfonic acid monohydrate; [Bp][HSO4], butylpyridinium
hydrogensulphate; [BimC4SO3H][SO3CF3], 4-(3-methylimidazolium) butanesulfonic acid trifluoromethanesulfonate; [BMIM][InCl4], butyl-methylimidazolium tetrachloro-indate;
[Et3NH]Cl/AlCl3, triethylammonium chloroaluminate; [BMIM][OH], 1-butyl-3-methylimidazolium hydroxide; [IMC2OH], bis-(3-methyl-1-imidazolium)-ethylene dihydroxide; [TBP]
[OH], tetra butyl phosphonium hydroxide; [MorMeA][Br], 4-allyl-4-methylmorpholin-4-ium bromine; DAILs, dication acidic ionic liquids; FAME, fatty acid methylester; USP, U.S.
Pharmacopeia; CP, Chemically Pure; CPO, crude palm oil.
⁎ Corresponding author at: Department for Management of Science and Technology Development, Ton Duc Thang University, Ho Chi Minh City, Vietnam.
E-mail address: zahoor.ullah@tdt.edu.vn (Z. Ullah).

https://doi.org/10.1016/j.molliq.2018.06.024
0167-7322/© 2018 Elsevier B.V. All rights reserved.
674 Z. Ullah et al. / Journal of Molecular Liquids 266 (2018) 673–686

vegetables. At the same time, the production of biodiesel from vegetable edible oils can create food security prob-
Keywords: lems; hence, the selection of cheap sources, like animal fats, is a valuable feedstock, but its availability is limited.
Ionic liquids Thus, more preferable sources other than low-cost feedstocks with high free fatty acids content include unrefined
Biodiesel crude oils, discarded cooking oil and inedible oils. This paper is aimed to highlight biodiesel and its availability
Catalysis
from various feedstock for its preparation. It also discussed how the ionic liquids (ILs) can be the catalysts to pro-
Feedstock
Transesterification
duce biodiesel; these liquids are sourced by different feedstocks by transesterification method. Due to several
limitations and problems associated with traditional homogeneous and heterogeneous catalysts in recent
years, ILs are increasingly used as the catalysts or solvents for free fatty acids esterification, as well as the
transesterification of vegetable oils. This paper is focused on the transesterification of fatty acid with ILs, cost
and recycling of ILs, the effects of adding enzyme, Lewis acids and amines on ILs catalysed reaction, the use of
Brønsted acidic, basic and dicationic basic ILs as the sole solvent which supported acid/base-catalysed IL for bio-
diesel synthesis. In addition, the proper research focuses and new developments in this regard would make the
ILs as an ideal catalyst for biodiesel preparation from various feedstocks.
© 2018 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 674
2. Biodiesel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 675
2.1. Sources . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 675
2.2. High process flexibility regarding the feedstock quality . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 675
2.3. Transesterification . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 676
3. Triglyceride and ionic liquid proposed mechanism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 676
4. Ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 676
4.1. Transesterification with ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 677
4.2. Recycling of ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 677
4.3. Support of enzyme catalyst in ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 678
4.4. The effects of different Lewis acids as catalysts combine with ILs on the reaction . . . . . . . . . . . . . . . . . . . . . . . . . . . . 680
4.5. The different amines containing ILs effect on the reaction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 680
4.6. Brønsted acidic ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 680
5. Catalyst support with ionic liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 683
6. Brønsted basic ionic liquids. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 684
7. Conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 684
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 684
References. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 684

1. Introduction In the last ten years, renewable energy has been highlighted due to
its potential in replacing the decreasing amount of fossil fuel, particu-
The availability of fossil sources such as natural gas, oil, and coal in- larly in the transportation sector. Consequently, the use of renewable
fluence the present world economy as it determines the generation of energies from biomass and waste, solar energy, hydro energy, wind en-
energies such as fuel and electricity [1]. Inherently, fossil fuel can be ergy can be fruitfully expanded and utilised in different countries to re-
substituted with energy from renewable sources. For energy genera- duce dependence upon fossil fuels. However, according to the
tion, wind, water, sunlight, biomass and geothermal are renewable International Energy Agency (IEA), the energy produced from waste
sources. Among these, biomass has gained importance as it can be con- and renewable sources have more potential as fossil fuel compared to
verted into forms of energy that need to be utilised easily and efficiently. other sources (International Energy Agency I, 2008), where 10.1% of en-
Consequently, the need for the petroleum-fuel alternatives sparks ergy obtained from waste and combustible renewable sources is signif-
the demands for renewable biomass fuels sourced from corn, icantly higher than that of hydro energy (2.2%) and other sources
sugarcane, algae and switch grass, such as bio hydrogen, bioethanol combined-geothermal, solar, wind and heat (0.6%). Hence, in the near
and biodiesel [2]. future, it can be postulated that the global energy resources will be ex-
Countries across the world have penalised policies for biomass to in- panded with the intensive use of combustible renewable energies, such
crease their economic utilisation for future energy demands. In the as biodiesel.
meantime, the demands for biomass can be enormous, particularly for
transport fuels where in normal circumstances, biomass combustion
could create both heat and power [3,4].
To date, fossil fuels account for the primary energy source which ac-
counts for 80.3% for energy sources worldwide, where about 57.7% are
consumed by transportation (International Energy Agency I, 2006) [5].
In all, 934 million tonnes of diesel fuel is estimated to be consumed
per year [6]. Thus, the International Energy Forum predicted that within
a few decades fossil oil will be exhausted [7]. The rapid increase in pop-
ulation and industrialization is considered to be one of the key reasons
that leads the rapid depletion of energy resources [8]. Fig. 1 presents
the world energy projection required in the next years, and the projec-
tion indicates the dire need for more sustainable sources for energies
globally to maintain energy security [9]. Fig. 1. The future energy demand projection [5].
 Z. Ullah et al. / Journal of Molecular Liquids 266 (2018) 673–686
2. Biodiesel
The American Society for Testing and Materials (ASTM) stated that
the mono alkyl esters of long chain fatty acids, or biodiesel, could be ob-
tained from lipid feedstocks that are renewable, including animal fats
and vegetable oils. The word “bio” refers to a renewable biological
source, which is contrary to conventional diesel fuel derived from petro-
leum. Meanwhile, “diesel” indicates that this fuel is used in diesel en-
gines. In this regard, alternatives biodiesel can be used in both neat
and mixed forms with petroleum-based diesel. Furthermore, biodiesel
has nontoxic and eco-friendly qualities in comparison to petroleum-
based diesel, and it has shown a more optimistic combustion emission
profile. It has shown smaller amount of carbon monoxide, particulate
matter and unburned hydrocarbon emissions. Subsequently, compared
to petroleum-based diesel, biodiesel is less volatile and safer to handle
because it has a high flash point (150 °C). Its lubricating properties are
more enhanced, so its use can prolong an engine's life as it can minimise
engine wear. In all, biodiesel possesses characteristics that make it an
excellent alternative to petroleum-based fuel which increase its use in
many countries, particularly in areas susceptible to environmental is-
sues [10–13]. In this regard, biodiesels are mostly produced by a
transesterification reaction, as shown in Fig. 2.
2.1. Sources
A range of processes and feedstocks, including, sea mango babassu,
peanuts, coconut, castor beans, oilseed radish, polanga palm, cotton,
sunflower, algae, palm kernel, pongamia, olive, sesame, corn, linseed,
soybean, canola, jatropha, sunflower, and animal fats (lard, fish oil, but-
ter, tallow, grease and used oil etc.) can be used to synthesize biodiesel
[15–18].
2.2. High process flexibility regarding the feedstock quality
The feedstock quality was found to affect the transesterification pro-
cess; Shuit et al. [19] cited that in oil sources, free fatty acids (FFA) along
with water create serious problems, such as soap formation which
makes product separation difficult in the transesterification reaction
[20]. Consequently, the presence or moisture or water in the feedstock
could basis the methyl esters produced to be hydrolysed back to FFA,
which decreases the product yield [21]. Similarly, water can hydrolyse
triglyceride to FFA and diglyceride, especially at elevated temperatures
[20]. It was also reported that during transesterification reaction, the
presence of 0.1% H2O in the feedstock is sufficient in reducing the oil
conversion into FAME [22]. Generally, the water content is unfavourable
as it decreases the yield of FAME. During the reaction, water will react
with FFA and alkaline catalysts like KOH or NaOH, and as a result, sapon-
ification problem will occur. The saponification produces a gel-like mix-
ture, which has the issue of recovery. Consequently, the formation of a
Fig. 2. Acid or base catalysed transesterification reaction of triglycerides. The diagram
illustrates the geometry of isomers (cis and trans), in which fatty acids has cis-isomers
with double bonds located in various positions of the chains [14].
675
Fig. 3. Percentage use of different vegetable oils for biodiesel production [27].
large amount of soap like substance will affect the catalysts, in terms
of their effectiveness and consumption. This creates difficulties in sepa-
ration of glycerol and also in biodiesel purification [20]. For homoge-
neous base-catalysed transesterification, the recommended FFA level
in an oil is to be b1% [5].
One of the proposed methods to produce biodiesel by converting oil
with FFA content is the homogeneous acid and base catalyses two-step
transesterification reaction. In this method, acid esterification was con-
ducted on oil with high FFA content. For 1 h, acid esterification was con-
ducted at the temperature of 50 °C for conversion of FFA to esters
catalysed by acid (H2SO4, 1% w/w). This decreased the FFA levels to
below 2%. The subsequent step involves the transesterification process
with alkaline base catalysts at 65 °C for 2 h. This two-step method is
more suitable to obtained high yields than the alkaline base one-step
transesterification. However, the reaction mixture needs complete sep-
aration by settling the two phases for 2 h after the acid esterification;
after that, the water–methanol fraction at the top layer was decanted,
prior to the alkaline base transesterification. In a two-step process,
more NaOH/KOH is needed because it not only serves as a catalyst, but
also neutralizes the H2SO4 content that has been utilised in the first
step of acid transesterification [23]. On the other hand, in the prepara-
tion of biodiesel from high FFA oil, heterogeneous acid catalyst and su-
percritical technology are used, and this involves energy intensive
processes which will lead to the increase in the operating cost of biodie-
sel production. Therefore, lower-cost feedstocks with high FFA contents,
such as discarded cooking oil, unrefined crude and non-edible oils can
also be used in biodiesel production [19,24]. In the meantime, the use
of animal fats substrate was less likely considered, but animal fats avail-
ability is limited and has a high melting point. The animal fats also re-
quired some additional powerful freeze protectants compared to
vegetable oils, which are renewable and widely available [25]. Different
countries use different types of oils due to the availability of raw mate-
rials. For instance, soybean oil is mostly used in the U.S., but in many
European countries, sunflower and rapeseed oil are the main feedstocks
for biodiesel production. In Asian countries, palm and coconut oil are
predominantly used for the synthesis of biodiesel [26]. Figs. 3 and 4
show the world's different oil usages for biodiesel production as well
Fig. 4. Biodiesel produced from varieties of feedstocks in different countries [27].
676 Z. Ullah et al. / Journal of Molecular Liquids 266 (2018) 673–686
as feedstock production in 2007 (International Grains Council, 2007)
[27].
2.3. Transesterification
The biodiesel that we know of today is produced through
transesterification, or alcoholises. In this process, vegetable oils go
through transesterification in batch reactors – i.e., a stirred tank, either
with catalysts or under supercritical conditions, to produce glycerol
and methyl esters. Each process may require 2 to 24 h to obtain high
oil conversion and yield biodiesel in form of fatty acid methyl ester. In
this light, for the process under supercritical conditions, high pressure
N 40 MPa and high temperature of N300 °C were applied, and this pro-
cess only took several minutes to complete [29].
In the meantime, to enhance the rate of reaction and the oil yield, a
catalyst is commonly used. As the reaction is reversible, to alter the equi-
librium to the products' side, excess alcohol is used. The alcohols com-
monly used for this process are primary and secondary monohydric
aliphatic alcohols that possess 1–8 carbon atoms. For the
transesterification process, various types of alcohols are possible to be
used, including ethanol, methanol, butanol, propanol and amyl alcohol,
but methanol and ethanol are more frequently used. This is due to their
low cost. Furthermore, as the polar and the shortest chain alcohol, it pos-
sesses physical and chemical advantages compared to other alcohols [30].
It was reported that in order to stoichiometrically complete a
transesterification process, a 3:1 molar ratio of alcohol to triglycerides
is required; however, in practice, for a maximum ester yield, the ratio
needs to be higher to achieve maximum equilibrium [31,32].
Meanwhile, in comparison, biodiesel derived from VOs have closer
viscosities to that of diesel. While VO based biodiesel has higher cetane
numbers and flash points, to some extent, they have volumetric heating
values that are lower. Hence, due to these similar characteristics, biodie-
sel can potentially replace diesel. Other benefits of biodiesel use include
the following. First, it can reduce our dependency on imported fossil
fuel, which is becoming more costly as a result of the depletion of global
oil reserve [33,34]. Next, biodiesel is a renewal resource [35], which
makes it environmentally friendly. Furthermore, biodiesel can reduce
pollution as biodiesel is derived from biodegradable sources like sugar
[36], which are easily biodegradable in soil and fresh water [37]. Its
use can also prevent further depletion of the ozone layer [34], as it can
minimise the current net levels of particulate matters of carbon dioxide
(CO2), sulfur dioxide (SO2), carbon monoxide (CO), and other unburned
hydrocarbons [38]. Despite the small increase of the nitrogen oxides
(NOx) generation reported, there are many strategies undertaken to
stop biodiesel NOx emission [37,39]. Lastly, biodiesel can be blended
with petroleum diesel fuel in any proportion [35].
Glycerol, as the byproduct of the process needs to be recovered. This
is due to its industrial value, including dynamite glycerol, CP (Chemi-
cally Pure) and USP (U.S. Pharmacopeia) glycerol. Here, separation of
glycerol was done by gravitational settling or centrifuging. Fig. 5 illus-
trates the types of reaction that takes place in a transesterification pro-
cess [10].
3. Triglyceride and ionic liquid proposed mechanism
Fig. 6 shows the proposed reaction mechanism of triglyceride with
methanol and IL ([BSMIM][CF3SO3]) as a catalyst. The mechanism
shows that it involves several steps. It is suggested that after mixing
the methanol and IL, the anion of IL extracting the H+ from methanol
to generate methoxide ion. The reaction scheme proposes that in excess
of methanol, the methoxide ion is attached to the triglyceride carbonyl
group in three positions. In the first step, this methoxide ion reacts with
triglyceride to form methyl ester and diglyceride molecules. In the sec-
ond step, methoxide ion reacts with diglyceride forming monoglyceride
and methyl ester molecules. In the third step, the methoxide ion reacts
with monoglyceride molecules to form methyl ester (biodiesel) and
Fig. 5. The transesterification scheme of triglycerides (vegetable oil), with methanol to
produce methyl esters and glycerol.
side product glycerol. A similar mechanism is reported for different cat-
alysts from various researchers [29,40–42].
According to Diasakou et al. [43], the overall thermal
transesterification reaction can be categorised into three consecutive-
reversible reactions, based on the intermediate formation of diglycer-
ides (DGs) and monoglycerides (MGs). The stepwise reactions are:
TG þ MeOH⇌DG þ FAME
DG þ MeOH⇌MG þ FAME
MG þ MeOH⇌GL þ FAME
4. Ionic liquids
In general, ionic liquids (ILs) can be described as organic salts (salt-
like materials) in the liquid state at ambient temperature (melting point
below 100 °C). These liquids are entirely made out of cations and anions,
and they act as the catalysts/solvents for different reactions [44,45]. In
the meantime, as mentioned in the literature reviewed, the discovery
of ILs did not garner much interest, except for a handful of studies;
hence, this topic remained outside the focus of researcher's interest.
But in the past 10–20 years, the use of ILs have gained significant inter-
est based on the number of studies on their applications and properties,
and consequently, many papers were published in the form of and IL
patents were presented [46–48].
ILs have advantageous and unique properties, such as environmen-
tally friendly, good chemical and thermal stability, low vapour pressure,
ability to dissolve a large range of inorganic and organic compounds,
ease in separation and produced high purity of products [49–51]. ILs
are considered to be good solvents and in a variety of fields including
separation, catalysis, electrochemistry, inorganic non materials, among
others have received global attention [49,52]. ILs in some processes
can be separated by decantation and removed from the product pre-
senting the cost benefits and easiness compared to filtration [46]. The
latest development has shown an increasing interest in the use of ILs
to replace traditional catalysts, because of their outstanding properties
and features, including higher thermal stability, extremely low vapour
pressure, and simple recovery process [54,55,90]. ILs are one of the po-
tential developed catalysts that are suitable to be used in the chemical
process for esterification and transesterification [49,50,56].
In recent years, ILs are used as catalysts to develop the esterification
protocol for vegetable oil and animal fats transesterification. In fact,
through the literature review, numerous applications are provided
which are functionalised with Lewis and Brønsted acid sites [57]. Inher-
ently, if the reaction conditions are at the optimum level, ILs are capable
to give the yield up to 98.5%. This development has many benefits such
as operational simplicity, less corrosion effect, reusability, high yields,
low cost, the lack of saponification, and less waste generation [90,58].
 Z. Ullah et al. / Journal of Molecular Liquids 266 (2018) 673–686
Fig. 6. Schematic representation of triglycerides and methanol proposed reaction mechanism using the IL [BSMIM][CF3SO3] as a catalyst.
Some of the common cations and anions that are used for ILs synthesis
are given below (Fig. 7).
4.1. Transesterification with ionic liquids
It is already described in the literature how the ILs were used as cat-
alysts or support with enzymes for the transesterification reaction.
When used as catalysts, at the end of the reaction, a biphasic system
will be introduced – in which biodiesel entirely occurs in the upper
phase and in the lower phase contain the IL, a side product (glycerol)
with traces amount of methanol [59]. Thus, the two layers are separated.
Biodiesel is finally separated from the methanol and moisture content
and then subjected to dry. The glycerol phase with IL/alcohol should
be rinsed for several times with water so that the glycerol can be re-
moved. Then, it is separated for purity because it has many applications
especially in pharmaceutical and cosmetic industries. Consequently, a
number of purification steps are required to get a relative purity [60].
The used IL is again washed and dried to be used for the next
transesterification reaction.
4.2. Recycling of ionic liquids
In large scale application, ILs recyclability is the factor for its
utilisation in industries. Another factor is the cost for ILs processes
677
that blocked the applications. In comparison, this cost is higher than
the use of traditional solvents [61]. Consequently, based on the huge
cost rate gap between ILs and traditional solvents, it is suitable to com-
pensate this drawback by reclaiming and recycling the ILs for the next
process. In industrial applications, the dumping of ILs can be minimised,
which will reduce its impact on the environment. This can prevent the
discard of the homogenous catalyst used during biodiesel synthesis by
the transesterification method.
During the downstream processing, water was used to wash the
homogeneous catalyst, such as NaOH or H 2 SO 4 to separate them
from biodiesel. This process produced waste water that contains
traces of organic solvents that are destructive to the environment.
Wu et al. [62], emphasised that the recovery of ILs in which hydro-
philic one is more difficult to hydrophobic; hence, the industry has
used membrane technology for the separation of ILs. The use of hy-
drophobic ILs is an ideal for the synthesis of chemical reaction be-
cause many phases are generated after the completion of
reaction. Actually, dual phases are formed during biodiesel synthe-
sis [63]. The development of biphasic system can be induced by the
adding of potassium salt to hydrophilic IL, which further assists the
separation phase [64]. Other than that, when sucrose is added, an
aqueous biphasic system can be formed by the hydrophilic ILs,
and this enables the facile recycling of ILs after the separation
step [65].
678 Z. Ullah et al. / Journal of Molecular Liquids 266 (2018) 673–686
Fig. 7. Commonly used cations and anions in ILs.
4.3. Support of enzyme catalyst in ionic liquids
Lai et al. [66] reported that a capable reaction medium can be pro-
vided by IL [Bmim][PF6] for lipase-catalysed from corn oil to produce
biodiesel. This produced a good yield (86%), which is greater than
those obtained in tert-butanol (52%). Moreover, media PEL has shown
to be highly tolerant to methanol in these reactions. To increase the in-
terest in alteration of oils into FAMEs, the conversion of microalgal oils
by enzyme to biodiesel in ILs had been reported for the first time. In
this regard, biodiesel productivity was investigated with the use of
PEL and Novozym 435 as catalysts and compared IL ([Bmim][PF6]) and
tert-butanol as different organic solvents. Consequently, the microalgae
oil (Chlorella) was extracted and converted in to microalgal biodiesel
with this enzymatic reaction. In this light, a microalgal oil was recom-
mended as an excellent feedstock for biodiesel formation. Furthermore,
they also reported that the P. expansum lipase is also an effective catalyst
for making the microalgal biodiesel, compared to Novozym 435, which
is often used as a commercial enzyme for this application.
Meanwhile, Ha et al. [67] explained the use of 23 ILs for FAME pro-
duction, including: “[Emim][BF4], [Omim][BF4], [Bmim][BF4], [Emim]
[TfO], [Pmim][TfO], [Bmim][TfO], [Bmpyr][MS], [Hmim][TfO], [Omim]
[MS], [Emim][MS], [Bzmim][Tf2N], [Emim][Tf2N], [Bmim][PF6], [Pmim]
[Tf2N], [Omim][PF6], [Bmim][Tf2N], [Hmim][Tf2N], [Pmim][SbF6]
[Edmim][Tf2N], [Omim][Tf2N], [Hmim][PF6], [Hmim][SbF6] and
[Empyr][SbF6]”. They explained the increase of FAME with different
characteristics of these ILs. The [Emim][TfO] produced a high yield of
FAMEs that are three time higher than the solvent-free system. Fatty
acid methylester (FAME) production was also increased in the hydro-
phobic ILs that contacted [PF6] and [Tf2N] anions. In addition, they
used Novozym 435 in ILs “[Emim][TfO], [Omim][Tf2N], [Emim][MS]”,
with tert-butanol and a solvent-free system. The observed percentage
of FAMEs in tert-butanol was about 60% in 6 h, while, at 12 h, it reached
up to 65.8%, but decreased after that. The percentage decrease might be
due to product inhibition. Compared to the tert-butanol after 6 h, the
conversion in percentage of [Emim][TfO] was lesser; however at 12 h,
it reached 80%, which is 15% higher than in tert-butanol. This yield
 Z. Ullah et al. / Journal of Molecular Liquids 266 (2018) 673–686
was retained for 24 h. During the early phase of reaction, the lower con-
version might be due to the limitation of mass transfer and IL higher vis-
cosity. Consequently, [Emim][TfO] (42.7 cP) has a 10 times higher
viscosity compared to tert-butanol (4.312 cP). [Omim][Tf2N] clearly
shows the viscosity (93 cP) effect on the conversion of FAMEs. In 48 h,
the FAMEs conversion in [Omim][Tf2N] had increased, and after 60 h,
the yield of the reaction for the proposed conversion was more than
in tert-butanol. In addition, there is a high viscosity of ILs during the sep-
aration of the reaction phase (phases of oil and ILs); this can hinder
mass transfer, and their resistance can occur at the interface between
two phases. Although, it was found that there was biodiesel synthesis
by “[Emim][TfO] and [Omim][Tf2N]” ILs than in the free solvent system,
despite the high-viscous ILs and the phase separation that occurs be-
tween oil and ILs.
From the literature [68], it was found that transesterification of oil
soybean was done to generate FAME, catalysed by lipase in the presence
of ILs as a whole-cell biocatalyst producing filamentous fungi,
immobilised on support particles of biomass. Four types of whole-cell
biocatalysts were used, recombinant Aspergillus oryzae expressing Fu-
sarium Candida antarctica lipase B (r-CALB), Rhizopus oryzae wild type
producing lipase triglycerol (w-ROL), and heterosporum lipase (r-FHL),
lipase monoglycerol and diglycerol from A. oryzae (r-mdlB). The w-
ROL was put for 24 h in ILs [Emim][BF4] or [Bmim][BF4] biphase system
to produce a large amount of fatty acid methylester. Meanwhile, for the
methanolysis, w-ROL was used as the biocatalyst; it was found that
there are remnants of untreated mono-glyceride because of the
R. oryzae lipase 1,3-positional specificity. Furthermore, the combination
between the w-ROL and r-mdlB attained high FAME. The stability test
showed that W-ROL was incubated for 72 h in [Bmim][BF4], and the ef-
fect was reduced to one-third of its original value. Consequently, when
they cross-linked the biocatalyst with glutaraldehyde had significantly
improved the permanence of w-ROL in [Bmim][BF4]. The results also
demonstrated that biodiesel production using whole-cell biocatalysts
and ILs as a second solvent, is a capable candidate.
Liu et al. [69] studied the biodiesel synthesis, the conformation of
Burkholderia cepacia lipase (BCL) nineteen (19) types of room tempera-
ture ionic liquids (RTILs) and a range of cation and anion structures. In
all, compared to the choice of cation, anion selection greatly influenced
biodiesel conversion. Free lipase powder of BCL and nineteen (19) selec-
tive RTILs were with 99% purity, including, “[Bmim][Tf2N], [Bmim]Cl,
[Bmim][CH3SO3], [Bmim][OH], [Bmim][PF6], [Bmim][BF4], [Emim][TfO],
[Emim]Cl, [Emim][BF4], [Emim][PF6], [Hmim][PF6], [Hmim]Cl, [Hmim]
[CH3SO3], [Hmim][TfO], [Omim][PF6], [Omim]Cl, [OmPy][BF4], [NMP]
[CH3SO3], [Omim][BF4]”.
The study stated that the anion selection of biodiesel yield shown a
considerable influence, where yields ranged from 1.9% to 66.4%. Higher
biodiesel amounts were found in ILs with anions [PF6]− and [Tf2N]−,
rather than anions “[BF4]−, [OH]−, [Cl]−, [CH3SO3]− and [TfO]−”. Fur-
thermore, lipase activity was increased with RTILs with anions in the
order of “[PF6]− N [Tf2N]− N [TfO]− N [BF4]− N [CH3SO3]− ≈ [Cl]−”.
The RTILs with anions [PF6]− and [Tf2N]− seem to have less nucleophilic
properties than the anions [BF4]−, [Cl]−,[OH]−,[TfO]− and [CH3SO3]− as
reported by many other researchers [70,71]. Compared to anions, the
influence on the yield of biodiesel with cation was identified by compar-
ing the lipase activities of ILs “[Bmim][BF6], [Emim][BF6], [Hmim][BF6],
[Omim][BF6], [Bmim][CH3SO3], [Hmim][CH3SO3], [NMP][CH3SO3]”, had
showed smaller differences. Besides that, as observed earlier [72–74],
the length of the imidazolium ring had gradually increased the biodiesel
yields. Another study with similar biodiesel production, with different
RTILs [75], reported that CLAB (Candida antarctica lipase) in IL had
catalysed about 38% biodiesel yield with [Bmim][PF6]. According to
Devi et al. [76], the CLAB-catalysed reactions in IL [Bmim][PF6] result
in very lower yield of biodiesel (ca. 2.3%), while Gamba et al. [59] men-
tioned that the IL [Bmim][NTf2] of different types of PS (Pseudomonas
cepacia lipase) which was catalysed for the biodiesel production
achieved the utmost value of 73.9% yield using PS–C. According to Liu
679
et al. [69], after 12 h reaction, the yield of biodiesel 82.2 ± 1.2% was
achieved and catalysed in IL [Ompy][BF4] by BCL. It is also indicated
that IL [Ompy][BF4] for biodiesel synthesis is a decent medium for the
reaction.
Lozano et al. [77] mentioned the immobilised Candida antarctica li-
pase B (Novozym 435) and 99% pure ILs of “[C4mim][NTf2], [C8mim]
[NTf2], [C12mim][NTf2], [C14mim] [NTf2], [C16mim][NTf2], [C18mim]
[NTf2], [C12mim][PF6], [C14mim][PF6], [C16mim][PF6], [C18mim][PF6],
[C12mim] [BF4], [C14mim][BF4], [C16mim][BF4], and [C18mim][BF4]”.
The study showed good fitness of immobilised Candida antarctica lipase
B (Novozym 435) catalyst in the synthesis of the methyloleate (biodie-
sel) by triolein transesterification in imidazolium cations based ILs with
the bulky side alkyl chain (from C12 to C18) at 60 °C and 80 °C. At differ-
ent temperatures and concentrations, the phase mixtures performance
of methanol/IL/triolein and IL/methyloleate were examined; hence,
the IL (i.e., [C18mim][NTf2]) was provided and able to produce mono
phasic reaction systems and achieved the best results after 6 h up to a
98.6% yield. In this regard, a non-stop enzymatic reactor for biodiesel
preparation was studied based on the coated particles of biocatalysts
with hydrophobic ILs in supercritical carbon dioxide at 60 °C and 180
bars. The stability of immobilised lipase operational stability was en-
hanced by its coating with ILs, i.e., [C18mim][PF6], and based on the bio-
diesel product, which leads to two-phase systems. This showed a superb
catalytic performance (up to 82% biodiesel yield after 12 cycles of 4 h) in
progressive practice under supercritical conditions.
The lipase enzymatic methanolysis [78] for the FAME synthesis in
two hydrophobic ILs at 60 °C is also reported. The ILs were comprised
of [C16MIM][NTf2] and [C18MIM][NTf2]. The immobilised Candida
Antarctica lipase enzyme B in an IL suspension, which contained long
side alkyl-chain cations, had illustrated excellence synthetic activity
and the operational constancy in the production of biodiesel. In this
type of reaction media, the immobilised lipase is able to transform tri-
glycerides into FAME to produce 98% yield after 6 h of reaction at 60
°C. The process can recycle the biocatalyst and makes it simpler to ex-
tract biodiesel from the reaction mixture.
De los Ríos et al. [73] studied 10 different ILs based on cations alkyl-
methylimidazolium and alkyl-methylpyridinium combined with anions
bis(trifluoromethylsulfonyl) imide, trifluoromethanesulfonate,
hexafluorophosphate, tetrafluoroborate and trifluoromethanesulfonate
as the reaction media were tested for the transesterification of sun-
flower or waste cooking oils and methanol, which was catalysed by an
immobilised Candida antarctica lipase B (Novozyme 435). The reactions
were conducted in the methyl tert-butyl ether and isopropanol as the
reference solvents. The ILs with 99% purity – such as “[Bmp][BF4],
[Bmp][PF6], [Bmim][BF4], [Omim][BF4], [Emim][NTf2], [Bmim][NTf2],
[Bdmim][NTf2], [Omim][NTf2] [Bmim][TfO], and [Omim][PF6] were
tested. The ILs [Omim][PF6] and [Omim][NTf2]” – showed higher
FAME contents than obtained with solvents used as a reference. Conse-
quently, the ILs based on the outcome composition of cation and anion
were analysed on the synthetic activity of C. antarctica lipase B (CaLB);
the improved activity was caused by rising the hydrophobicity of cation
and reducing the nucleophilicity of anion. Furthermore, this study also
determined the water content and methanol/oil molar ratio, using the
IL [Omim][PF6] as the reaction media, and it found that the content
and ratio to be 1%, which is 12:1. This biphasic system allows the easy
separation of the products by decantation and centrifugation from the
phase of IL; whereas in the IL phase, the enzyme can be retained and
can be filtered for reuse. As the feedstock, the transesterification of
waste cooking oil was also conducted, and the FAMEs produced was
like that achieved from the oil of sunflower; however, the FAME coming
from waste cooking oils has reasonable cost and also reduces the raw
material costs, making it reasonable for commercialization.
Ha et al. [67] reported the soybean oil methanolysis catalysed
through enzyme lipase in twenty three ILs. The high amount (80%) of
biodiesel was obtained from the reaction after 12 h at 50 °C with the
IL [Emim][CF3SO3]. It was claimed that this was the first study about
680 Z. Ullah et al. / Journal of Molecular Liquids 266 (2018) 673–686
ILs which represents the potential for biodiesel synthesis when used as
a reaction medium and catalysed by lipase enzyme. Meanwhile, De
Diego et al. [79] produced biodiesel by utilising the long chain hydro-
phobic ILs, such as cations ([C10MIM], [C12MIM], [C14MIM], [C16MIM]
and [C18MIM]) and ([BF4], [PF6] or [NTf2]) anions with immobilised li-
pase for biodiesel production. It was mentioned that the IL [C16MIM]
[NTf2] showed the highest activity and obtained yield up to 90.29%.
Meanwhile, ILs [C16MIM][NTf2] and [C18MIM][NTf2] reported a high
yield of nearly 100 °C, for 9 days [80].
4.4. The effects of different Lewis acids as catalysts combine with ILs on the
reaction
Liang et al. [58] reported the model amine (Table 1) and chosen from
the cation part that formed the [Et3NH]Cl IL. The results illustrated the
significant effect of Lewis acids on the reactions, where Lewis acids
such as Mg2+ and Zn2+ for the reaction comparatively revealed little ac-
tivity with low yield. Meanwhile, [Et3NH]Cl–AlCl3 showed the highest
activity (98.5% yield) for the reaction.
Moreover, Yassin et al. [81] conducted a study on metal and simple
chloride anion, which contains ILs; in this study, they concluded the
metal chlorides (Fe and Al) were proved to acquire highest yield,
which is up to 97%.
The synthesis of FAME was evaluated in a variety of anion and cation,
which affected the catalytic capability of ILs. The mix of ILs and different
metal chlorides as the catalyst for soybean oil transesterification was
studied, and AlCl3 was determined the best one, which produced a
large amount of FAME. They also studied the effect of amines that
formed the ILs cation part. The ILs such as “[Et3NH][Cl]–AlCl3, [HMIM]
[Cl]–AlCl3, [C4MIM][Br]–AlCl3 and [C12MIM][Br]–AlCl3” with the yield
of N80%. Furthermore, the transesterification of Jatropha oil with
pyridinium-cation containing ILs used as catalysts, and consequently,
the experiments showed the higher conversion of biodiesel was with
stronger Brφnsted anion acidity; for instance, the higher anion acidity
in [BSPy][CF3SO3] obtained a higher (83.3%) yield compared to [BSPy]
[pTSA] as catalyst, which produced a 75.5% yield at a lower temperature
[58,82].
4.5. The different amines containing ILs effect on the reaction
The ILs (catalysts) containing the amines that form the cation part
and observed their effect on the reaction (Table 2). During the process,
the amines' catalytic properties were affected due to the long carbon
chain length, which might be due to steric hindrance. The long chain
carbon had made complicated the mass transfer in the reaction
media; hence, [Et3NH]Cl–AlCl3 composition was projected as most
effective.
4.6. Brønsted acidic ionic liquids
The literature mostly reported on the Brønsted ILs for biodiesel pro-
duction from different feedstocks. An acidic (Brønsted) IL with an al-
kane sulfonic acid group is assessed, and an optimal reaction condition
was established from a choice of parametric studies, including IL dosage,
Table 1
The different Lewis acids effect on the reaction as catalysts combine with ILs [58].
Entry Anion
1 [Et3NH]Cl–AlCl3
2 [Et3NH]Cl–FeCl3
3 [Et3NH]Cl–ZnCl2
4 [Et3NH]Cl–SnCl4
5 [Et3NH]Cl–MgCl2
The conditions of reaction: x(MCln) = 0.7, soybean oil 5 g, methanol 2.33 g, catalyst
5 mmol, 70 °C, 9 h.
The calculated yield was measure by GC using an internal standard.
Table 2
The catalyst different amines effect on the reaction [58].
Entry Cation Yield (%)
6 [Et3NH]Cl–AlCl3 98.5
7 [MimH]Cl–AlCl3 96.8
8 [C16TA]Br–AlCl3 74.5
9 [C4min]Br–AlCl3 89.4
10 [C12min]Br–AlCl3 82.3
11 [C14min]Br–AlCl3 78.6
12 [C16min]Br–AlCl3 72.5
The conditions of reaction: x(MCln) = 0.7, soybean oil 5 g, methanol 2.33 g, catalyst
5 mmol, 70 °C, 9 h.
The calculated yield was measure by GC using an internal standard.
methanol to oil molar ratio and temperature of the reaction. When the
molar ratio of methanol (oils:IL) was 12:1:0.06, the yield of the fatty
acid methyl esters can reach up to 93.5% at 170 °C for 4 h. In this light,
in biodiesel synthesis, the IL can be repeatedly reused for nine times
with slight decrease [83].
The esterification reaction of IL [Bmim][CH3SO3]–MCln was highly
active, while the Jatropha oil as a raw material (acid value =
13.8 mg KOH/g), without the pre-treatment step (or esterification),
was directly used for the FAME synthesis [44]. The produced FAME is
shown in the below (Table 3). Without adding any MCln, the [Bmim]
[CH3SO3] recorded a 12% yield at 120 °C, while when added MCln, and
FeCl3, the process achieved 99.7% yield of biodiesel. A similar trend
was found in the yields of both esterification and transesterification re-
actions for catalytic activity of MCln (99.7% and 94%). This is because of
the higher activities, caused by the stronger Lewis acidity of trivalent
metallic ions compared with bivalent metallic ions “(Cu2+, Zn2+, Co2+
and Mn2+, which resulted in the yields of 83%, 87%, 46% and 27%, re-
spectively)”. The increasing order of bivalent transition metals atomic
radius is as follows: Cu N Zn N Co N Mn in periodic table. This shows
that the metallic element of large atomic radius has its higher Lewis
acid activity. However, for transesterification, the Zn2+ salt has higher
catalytic activity compared to Cu2+ salt. This might be caused by the es-
terification reaction generated by the H2O, which caused the decline of
Cu2+ salt catalytic activity for the transesterification reaction. This indi-
cated that compared to other metallic salts Cu2+ is extra sensitive salt to
water. Consequently, the highest catalytic activities were reported for
[Bmim][CH3SO3]–FeCl3 and [Bmim][CH3SO3]–AlCl3, with the biodiesel
yields that are N94%. The relatively higher activity than Al3+ of Fe3+
(94% vs 99.7%) which varies from the work reported in the literature
[84]. One possible reason for the Jatropha oil which is highly contained
FFAs and produced H2O during the esterification reaction. At the high
temperature of 120 °C, it was able to hydrolyse the AlCl3. Inherently, it
can be concluded that the esterification and transesterification process
of commercial ILs showed weak catalytic activity. However, 97% of
methyloleate was produced from oleic acid when metal chlorides
were added in [Bmim][CH3SO3]. The [Bmim][CH3SO3]–FeCl3 mixture
was further used for biodiesel production from highly acidic non-pre-
treated Jatropha oil, where it achieved a highest product yield of
99.7%. Therefore, metal ions in ILs during reaction enable Lewis acidic
sites; particularly compared to bivalent, the Lewis acids are stronger
having metallic trivalent ions.
Table 3
Yield (%) MCln and ILs combine effect on biodiesel production from Jatropha oil [44].
98.5
Entry ILs + MCln Yield (%)
94.5
64.2 1 [Bmim][CH3SO3]–FeCl3 99.7
75.8 2 [Bmim][CH3SO3]–AlCl3 94
32.1 3 [Bmim][CH3SO3]–ZnCl2 87
4 [Bmim][CH3SO3]–CuCl2 83
5 [Bmim][CH3SO3]–CoCl2 46
6 [Bmim][CH3SO3]–MnCl2 27
 Z. Ullah et al. / Journal of Molecular Liquids 266 (2018) 673–686
Based on the high-acidic crude raw oil, metal chlorides with ILs have
shown the prospect for biodiesel production as illustrated in the below
(Table 3) [44].
Das et al. [85] reported the biodiesel from the Jatropha oil can be con-
ducted in a two-step process where IL [BSMIM]Cl was used for the ester-
ification process, which produced a 93.9% yield at 70 °C and in 6 h. Based
on Zhang et al. [86], the production of FAME from long FFAs at room
temperature and the catalytic effect of different ILs, as listed in the
below Table 4.
To compare with other catalysts, H2SO4 was the better one when
used as a model catalyst during FFAs esterification. Different anion
and cation of ILs monitor their effects and performance as catalysts.
They observed that with these ILs, the esterification process could be
conducted even at the temperature of 25 °C. The yields of these ILs at
70 °C were close or higher than the yield when using H2SO4 or
CH3SO3H as catalysts. In view of energy consumption, ILs indicate an ad-
vantage compared to the conventional catalysts. Various yields were ob-
tained even though some of the ILs cations were similar. This exhibited
that the anions of ILs had a prominent effect on the catalytic perfor-
mance. Among these, [C3SO3Hmim][CH3SO3] IL for the oleic acid esteri-
fication showed a top catalytic activity. This probably was caused by
variance in acidic strength of ILs. Hence, it is decided that the acidity
of inner salt MIM-PS increases when used a stronger acid. When these
ILs have similar anions of CH3SO− 3 , the ILs at 25 °C or 70 °C had the
higher catalytic activity than CH3SO3H. Therefore, the ILs catalytic depic-
tion was also affected due to the cations' variance.
Recently reported ammonium-based dicationic ILs with \\SO3H
group via ultrasonic technique and claim that these are the novel ILs
and catalytically more efficient compared to monocation ILs at optimum
parameters. They also determined the ILs' acidity and compared with
their results. Finally, they stated the advantages of these ILs, such as a
shorter reaction time, a clean procedure, a simple operation with good
yield, and the fact that is environmental friendly [87]. Different ILs re-
ported on the basis of cations and anions to select a better IL as a catalyst
for biodiesel production from waste cooking oil. Finally, the IL 3-methyl-
1-(4-sulfo-butyl)-benzimidazolium trifluoromethanesulfonate
[BSMBIM][CF3SO3] was selected as the best one with 96.25% yield.
They also studied the ILs acidity by UV technique and co-related their
results; the final product is according to the established standards, and
the IL was recycled for many times [88].
There is another study on [NMP][CH3SO3] IL that illustrated some
benefits. Firstly, their conversion was higher compared to other ILs. Sec-
ondly, the N-methyl-2pyrrolidone cation compared to 1-
methylpyrrolidine and 1-methylimidazole is inexpensive. Furthermore,
the IL “[NMP][CH3SO3]” preparation was relatively easy. In comparison,
ILs “[Hemim][HSO4] and [Heemim][HSO4]” as catalysts for esterification
process presented a good performance (with short-chain alcohols and
the resulted conversion was 77–90%); they were tiresomely prepared
and organic volatile solvents were also used during this process. More-
over, the [NMP][CH3SO3] with short-chain alcohol was further exam-
ined as a catalyst for the FFA esterification. The study also concluded
that the non-flammable free-halogen Brønsted IL, such as [NMP]
Table 4
Performance of different ILs on biodiesel production at room temperature from long chain
free fatty acids.
Entry ILs
1 H2SO4
2 CH3SO3H
3 [C3SO3Hmim][BF4]
4 [C3SO3Hmim][H2PO4]
5 [C3SO3Hmim][PTSA]
6 [C3SO3Hmim][CH3SO3]
7 [C3SO3HPydin][CH3SO3]
8 [C3SO3HTEA][CH3SO3]
9 [NMP][CH3SO3]
681
[CH3SO3], is thermally stable, easier to synthesize, and exhibits a negli-
gible non-volatile vapour pressure. Thus, from the esterification process
the high yield of FAME produced with good quality and can be con-
ducted at room temperatures. Thus, the use of [NMP][CH3SO3] will min-
imise the production cost and illustrated a better catalytic performance.
Consequently, esterification reaction of different free-fatty acids and al-
cohols provided satisfied yields of 93.6–95.3% with optimised condition,
and the IL [NMP][CH3SO3] is highly recyclable. Therefore, the synthesis
of competent and environmentally friendly biodiesel catalyst can be
obtained.
Ullah et al. [89] studied biodiesel production from waste palm
cooking oil where acidic IL was used as a catalyst. They performed a
two-step process, which was esterification and transesterification. It
was found that the IL [BMIM][HSO4] was effective because of its longer
side chain. The highest yield of biodiesel (95.65%) was obtained with
5 wt% of [BMIM][HSO4], methanol:oil ratio of 15:1, 60 min reaction
time at 160 °C and agitation speed of 600 rpm. Moreover, the IL
(Et3NHSO4) also used for biodiesel production from crude palm oil
and the obtained yield was 96.9% [90], and the IL (BSPIMHSO4) reported
with 95.7% yield [91]. These two ILs are also used in two steps with high
yield, and KOH was used as a catalyst in the second step.
Liu et al. [92] investigated that the dimerization of fatty acid
methylester using Brønsted–Lewis acidic ILs as catalysts. The good cata-
lytic activity of IL “[HO3S–(CH2)3–NEt3]Cl–ZnCl2 (x = 0.67)” is reported
with a yield of 96.8%. “The IL with Brønsted–Lewis acidic sites can selec-
tively catalyse the dehydrogenation, conjugation and polymerization in
the reaction, and a synergetic effect of these acid sites of ILs improved
the catalytic performance. The result from 1-butyl-3-
methylimidazolium chlorozincinate [C4mim]Cl–ZnCl2 (x = 0.67) IL
showed their catalytic effects. Among the chlorozincinate ILs, the yield
of FAME is based on the molar fraction of ZnCl2 (x). Therefore, when
the (x) value was 0.67, FAME dimerization was effectively catalysed.
However, when (x) reached 0.75, the FAME yield did not further in-
crease but showed the trimer content in the product. This is because
when the molar fraction of metal chloride (x) was higher than 0.5, the
IL would be Lewis acidic and the (x) value increase; the Lewis acidity
was also increased, which increased the IL catalytic activity. The metal
chlorides had shown significant influence on the catalytic performance
of IL. These results caused by the difference in the strength of Lewis
acidic IL. This increased the acidity of the metal chloride as the IL
shows higher Lewis acidity and a higher catalytic activity. As a result,
the [HO3S–(CH2)3–NEt3]Cl–ZnCl2 (x = 0.67) catalytic activity was
higher”.
Elsheikh et al. [93] summarised the esterification reaction of three
Brønsted acidic ILs; reported the optimised conditions as 4.0–6.0 wt%
concentrations range, at 170°, mixing degree (800 rpm) and methanol
to CPO molar ratio (21:1) for 4 h; and showed the results of the free
fatty acids conversion with different amounts of [BMIM][HSO4], [BIM]
[HSO4] and [MIM][HSO4] catalysts. The three catalysts (ILs) illustrated
free fatty acids to esters conversion with a comparable trend. The max-
imum level of conversions was achieved at 4.4, 4.8 and 5.2 wt% of the
catalyst concentration for [BMIM][HSO4], [BIM][HSO4] and [MIM]
[HSO4], respectively. The quantity of [BMIM][HSO4] used was lesser
than the others, giving conversion of fatty acids up to 91.2%. These re-
sults indicated that the acidity of the ILs is in the order of [BMIM]
[HSO4] N [BIM][HSO4] N [MIM][HSO4]. In this view, the increase of the
alkyl chains length has shown immense effect in the ILs nature. Fan
Yield (%) et al. [94] reported a range of Brønsted ILs where [C4SO3Hpy][HSO4]
66.9 was selected as the best, with 94.5% result. Qureshi et al. [95] reported
67.2 some Brønsted ILs where [NMP][HSO4] was chosen as the best on the
60.2
basis of high catalytic activity and reusability. Pyridinium based IL
65.8
68.6 ([BSPy][CF3SO3]) which is used for biodiesel synthesis from Jatropha
78.4 oil and obtained 95.1% yield at 100 °C for 6 h [96].
76.8 Ghiaci et al. [57] reported the following ILs, by coding and explaining
74.6 their effects on canola oil based biodiesel production, the ILs include:
80.2
“Synthesis of 1-benzyl-1H-benzimidazole (1A), 1-benzyl-3-hexadecyl-
682 Z. Ullah et al. / Journal of Molecular Liquids 266 (2018) 673–686

Table 5 group, which have different strengths of Brønsted acidity. The FAME
The reaction temperature effect, ILs and the transesterification of canola oil with methanol had shown the highest yield of 92%, which was recorded using “1-(4-
[57].
sulfonic acid) butylpyridinium hydrogensulphate” ILs as a catalyst.
Entry Catalyst Temperature (°C) Conversion (wt%) They reported that the ILs compared to imidazolium and
1 H2SO4 40 33.2 triethylammonium the pyridinium cation showed a stronger Brønsted
2 60 44.4 acidity because it easily dissociates H+ ion. Due to this fact, they claimed
3 80 50.0 the excellent catalytic performance of IL with pyridinium cation. Under
4 3A 40 71.6
the same reaction conditions, this IL and pure sulfuric acid catalytic per-
5 60 74.8
6 80 76.5 formance for transesterification reaction was also compared.
7 3B 40 69.5 Within three 3 h, as a catalyst the resulted FAMEs content for IL was
8 60 77.3 81%, and that of concentrated sulfuric acid was 86%. These results are
9 80 77.0 comparable, and the IL proved a good catalytic activity compared to sul-
10 4B 40 75.8
11 60 81.9
furic acid.
12 80 82.4 To evaluate the ILs catalytic performance, Fang et al. [99],used both
mono- and di-cationic ILs for FFA esterification into FAME. The increase
Reaction conditions: Methanol/oil molar ratio = 6, time = 6 h, catalyst amount = 10%
(based on the mmol of oil). of the carbon chain length between the dications had caused the slight
increase of the DAILs acidities. The transesterification conversion
95–96% was recorded from DAILs compared to the monocationic ILs
1H-benzimidazolium bromide (2A), 3-hexadecyl-6-sulfo-1-(4- with 85–87%. This proved that comparatively the Brønsted acidic inten-
sulfobenzyl)-1H-benzimidazolium hydrogensulphate (3A), 3, 3′-(bu- sity of DAILs is better. The DAIL [TMEDAPS][HSO4] shown a high cata-
tane-1,6-diyl)bis(1-benzyl-1H-benzimidazolium) bromide (1B), 3, 3′- lytic activity and achieved the high conversion of FFAs into FAME
(hexane-1,6-diyl)bis(1-benzyl-1H-benzimidazolium) bromide (2B), 3, when tested for esterification.
3′-(butane-1,6-diyl)bis(6-sulfo-1-(4-sulfobenzyl)-1H- Liang and Yang [84] used a unique IL as a catalyst with four alkane
benzimidazolium) hydrogensulphate (3B) and 3,3′-(hexane-1,6-diyl) sulfonic groups for the reaction of rapeseed oil transesterification. This
bis(6-sulfo-1-(4-sulfobenzyl)-1H-benzimidazolium) hydrogensulphate new catalyst (Brønsted acidic IL) showed unique characteristics of
(4B)”. strong acidity and high polarity; this is because of the presence of mul-
The present reported ILs, which are coded with 3A, 3B and 4B as cat- tiple alkanes' sulfonic functional groups. The strong acidity resulted the
alysts, were transesterified with oil and methanol in the temperature high conversion of rapeseed oil into FAME; consequently, the ease re-
that ranged 40–80 °C in the steps of 20 °C for 6 h, as shown in Table 5. covery of IL is also related to their higher polarity, where it was synthe-
The Brønsted acid (H2SO4) as an industrial catalyst was used to com- sized from 1,4-butane sulfonate and hexamethylenetetramine. The
pared with the synthesized catalysts (ILs). highest yield of biodiesel 98.3% was obtained with reasonable reaction
The catalytic stability of 4B was investigated by performing several temperature (70 °C) and reaction time of 7 h. Based on the experiment
runs under the optimised reaction conditions. As described, after each of catalyst performance, it is worth noting that it is highly resistance to
run, the catalyst was separated, washed and dried. The records of the water, as when increased the amount of water from 0.3 to 2.0%, the yield
catalyst recyclability (Fig. 8) shows that after eight runs the yield de- reduced from 98.3 to 95.3%. This revealed that the IL had tolerance up to
creased from 95.1% to 85.9%, thus confirming the stability of 4B during some level of water content.
the canola oil transesterification with methanol. The literature [83,98] reported that the transesterification of cotton-
Ghiaci et al. [97] mentioned “(bentonite modified with 3,3′-(butane- seed oil to biodiesel with methanol using different types of Brønsted
1,6-diyl)bis(6-sulfo-1-(4-sulfobenzyl)-1H-benzimidazolium) acidic ILs as having an alkyl chain and an alkane sulfonic functional
hydrogensulphate)” with a yield of 92% and concluded that the catalyst group. These ILs cations were composed of “butyl-methylimidazolium
was highly efficient and recyclable. Meanwhile, Wu et al. [98] studied or butyl-pyridinium” and the IL [BSPy][HSO4], was the best catalyst
Brønsted acidic ILs as catalysts for the transesterification of cotton which exhibited the stronger Brønsted acidity. Using 12 equivalents of
seed oil in to biodiesel. Before applying the transesterification experi- methanol, and achieved a yield of 92% at temperature 170 °C within
ment, synthesized five different ILs, and used cations of three different 5 h. They also assessed the performance of a catalytic system of H2SO4
types to find good IL for that process. The “pyridine, N- and IL, and after 2 h, sulfuric acid resulted 69% while the ILs resulted
methylimidazole and triethylamine”, with incorporated alkane sulfonic in a 65% yield of FAMEs, indicating close catalytic activity. Therefore,
based on the environmental friendliness, the use of ILs as a catalyst
was proposed as the better one for the transesterification reaction.
This catalyst was used again for oil containing a high content of free
fatty acids. At high temperatures, the catalyst (IL) performed better
and shows a 93.5% biodiesel yield at 170 °C for 4 h where the IL was
reused for so many times with a small decrease in the yield of FAME.
Consequently, another researcher used Jatropha oil for the conversion
to biodiesel and the best conversion was illustrated by [BSPy][CF3SO3]
IL, with a yield of 92% at the reaction conditions (temperature 100 °C,
time 5 h and 10 equivalents of alcohol). They reported that separated
the product very easily and then reused this IL for seven times and
maintained its catalytic activity. IL [HO3S-pmim]HSO4, in optimum
con1ditions, showed up to 93% yield from waste cooking oil [100].
Li et al. [82] reported that acidic IL “N-(4-sulfo)butyl) pyridinium
trifluoromethylsulfonate” for catalysing Jatropha oil transesterification
with methanol at 100 °C and the biodiesel yield obtained was up to
92%. In this light, the pyridinium based ILs are water resistant, very ac-
tive, immiscible with various organic-solvents and noncorrosive. This il-
Fig. 8. Reusability of catalyst (4B) for the transesterification of canola oil with methanol lustrates the benefits of the catalytic reaction for separating the product
[57]. from the catalyst system. The IL, “1-(4-sulfonic acid) [Bpy][HSO4]”, from
 Z. Ullah et al. / Journal of Molecular Liquids 266 (2018) 673–686
cottonseed oil produced a 92% yield of biodiesel, which confirmed its re-
usability. Furthermore, after recycling it for seven times, the [BSPy]
[CF3SO3] IL was still consistent. Meanwhile, an innovative acidic solid
IL polymer (PIL) used as a catalyst for the conversion of waste cooking
oil into biodiesel with a 99% result [101].
Aghabarari et al. [102] reported four ILs with hydrogensulphate
and bromide anion such as “1-benzyl-3-butyl-1H-imidazolium
bromide (ILB1), 3-butyl-6-sulfo-1-(4-sulfobenzyl)-1H-imidazolium
hydrogensulphate (ILB2), 1-benzyl-3-hexadecyl-1H-imidazolium bro-
mide (ILH1), 3-hexadecyl-6-sulfo-1-(4-sulfobenzyl)-1H-imidazolium
hydrogensulphate (ILH2)”, and they reported the highest yield up to
93.2% with ILH2 IL at 6 h.
In the meantime, biodiesel derived from sewage sludge lipids with
up to 90% yield by [MimC4SO3H][SO3CF3] [103], and a waste edible oil
with supercritical ethanolysis using IL [HMim][HSO4] as a catalyst ob-
tained a 97.6% yield [104].
In this light, the more acidic ILs are deemed as the more capable cat-
alysts. The acidic intensity of the ILs anions play a decisive role, and cat-
ions may significantly influence the availability of active acid sites. ILs
provides good mediums for glycerol by-product removal and for the
separation of biodiesel. However, in comparison to homogeneous
acids or alkalis catalysts, ILs need a higher reaction temperature and
compared to enzymatic process the reaction conditions are not as rigor-
ous. Consequently, acids or alkali-supported ILs possess heterogeneous
catalyst like properties and can also be considered as heterogeneous
catalysts. This helps to prevent the limitation of diffusion, which are
characteristic of heterogeneous acids and/or alkalis in the applications.
Moreover, ILs supported by immobilised lipases enzyme have good per-
formance and, at the same time, solve the deactivation problem of
methanol. Nevertheless, it is vital to mention that supported IL use in-
volves the risk of losing the catalyst [49].
5. Catalyst support with ionic liquids
Catalysts as a support can be used in ILs that provide sites for the re-
action during biodiesel production. The high surface area support, like
porous materials, results in fast reaction. In catalytic reactions, the cata-
lyst support might be active or inert. For the production of biodiesel, alu-
mina [105], silica [106] and zeolite [107] have been reported as solid
support. Some catalyst support helps in the catalyst recycling and can
be reused for many times.
Abreu [108] compared the efficiency of catalyst support (organic
solid phase) and IL ([BMIM][PF6]) for tin complexes in
transesterification reaction. A triphasic system at the end of the reaction
was produced in ILs of tin complexes, where the upper layer was of
FAME, in the middle layer water and hydroxyl compounds, and in the
bottom layer was IL. After the second recycle, the catalyst catalytic activ-
ity dropped drastically and decreased the yield from 58% to almost no
yield after being two times recycled. Meanwhile, very low yield of bio-
diesel was obtained when the tin complexes anchored to support of
acid resin which might be both a catalyst and its support active sites
deactivation.
DaSilveira [112] claimed that IL “[BMIM][InCl4]” as a catalyst was
better than “[BMIM][PF6]” for transesterification reaction in the pres-
ence of support. After optimisation, with the ILs to be supported with
catalyst, Sn(pyrone)2 was chosen as the catalyst. Conducted the exper-
iment for 10 h, reaction yield was increased, and due to the reversibility
of the reaction, yield dropped after 4 h. The catalyst was later recycled
and dropped during the first cycle; the yield of biodiesel went from
83% to 3%; in terms of catalyst retaining in ILs, “[BMIM][InCl4]” was bet-
ter than “[BMIM][PF6]” after the third cycle. They also claim that when
the alkyl chain length of alcohol was increased, then find minimisation
in the product yield. The highest yield (83%) was obtained only when
using methanol.
Lapis et al. [110] for soybean oil used ILs as support for both acidic
and basic catalysts to be converted into FAME. Various ILs were
683
evaluated, and [BMIM][NTf2] showed the highest (99%) production of
biodiesel in short interval of time (0.5 h). However, after 2–3 h the
“[BMIM][BF4] and [BMIM][PF6]” ILs were noticed to be decomposed.
The soybean oil transesterification was also booming when H2SO4 (cat-
alyst) has been used supported by IL. Similarly, 99% yield of biodiesel
was obtained while using Lewis acids. However, longer reaction time
of 13 h was required.
Liang et al. [58] reported the chlorometallate ILs for biodiesel pro-
duction from soybean oil. [Et3NH]Cl/AlCl3 results in a soybean oil con-
version up to 98.5% at 70 °C, 9 h, with a molar ratio of methanol/oil
12:1. The process reported provided ease in operation, higher yields, a
low cost of catalyst, no occurrence of saponification and recycling of cat-
alyst up to six times without affecting the yield of reaction. For compar-
ison with ILs, homogeneous acid catalysts such as (H2SO4 and H3PO4)
were evaluated for catalytic activities. In view of environmental and
economic factors, as well as feasibility of production scale, IL was con-
sidered better than the traditional catalysts. However, they did not
highlight the issue associated with the use of metal chloride catalyst,
since ILs containing metal complexes or presenting Lewis acidity causes
the metal residues. In addition, IL containing ALCl3 is unstable in alco-
holic solution and generate the HCl gas [14].
The literature [111] reported that using soybean oil
transesterification, a biphasic catalytic system was tested by liquefying
“Sn(3-hydroxy-2-methyl-4-pyrone)2(H2O)2” in ILs. The yield was
noted to increase from 55% to 83% while changing the IL from
“[BMIM][PF6] to [BMIM]InCl4”. Thus, two systems showed poor reus-
ability, and after three times, the yield of the biodiesel was negligible.
In comparison, when a Lewis acid and an organic acid/base was com-
bined with “[Et3NH]Cl-ALCl3 and H2SO4, and immobilised in [BMIM]
[NTf2]”, a high biodiesel yield (93–98.5%) was obtained from vegetable
oils, with good reusability, and after six times, there was little change
in the yield.
In general, the combination of enzymes and imidazolium ILs created
more robust and stable catalysts, as the ILs are capable to protect the li-
pase from methanol persuaded deactivation. The biodiesel production
used short-chain ILs “1,3-dialkylimidazolium cation (e.g., [BMIM][PF6]
or [BMIM][NTf2])”, and the reaction was conducted in a biphasic system.
The combination of [BMIM][NTf2] with lipase for biodiesel synthesis,
and the yield is reported 96.3% from soybean oil. The long alkyl chains
imidazolium ILs “(e.g., [C16MIM][NTf2] and [C18MIM][NTf2])” have
been used for lipase-catalysed biodiesel production in a one-phase ho-
mogeneous system; this avoids the pure methanol and enzyme direct
interactions, thus allowing the enzyme stable reuse in the ILs. It is also
stated that the ILs viscosity had increased with the [CnMIM] cations,
while the lipase-catalysed transesterification produced a negative ef-
fect. In the light of this, the anion order, based on the increase in viscos-
ity is [PF6] N [BF4] N [NTf2]. For oil esterification, certain ILs as catalysts
may also be used directly [49].
For the conversion of waste cooking oil into biodiesel, catalysts such
as “1,3-propyl sulfonic acid lactone, 1-allyl-1H-imidazole, and H2SO4”
was synthesized and immobilised on silica gel and the obtained results
at the optimum parameters is 87.58% [112].
For soybean oil, conversion used the combination of [BMI][NTf2],
K2CO3 (40 mol%) and alcohols, which result in high yields of pure bio-
diesel (N98%). In this light, sulfuric acid immobilised in “[BMI][NTf2]”
can promote the soybean oil transesterification. They also claim that
the multiphase process retained the acid in the IL phase, while the bio-
diesel was in the distinct phase. This study also found that the recycled
IL, which contains the acid, could be recycled for at least six cycles with-
out experiencing any apparent decline in the selectivity or the yield of
biodiesel. Typical ILs, such as “[BMIM][PF6] and [BMIM][BF4]”, have the
issue of de-stability in acidic or basic environments [110].
The soybean oil base-catalysed “ethanol and K2CO3” (40 mol%)
transesterification with combination of many hydrophilic and hydro-
phobic ILs at 70 °C, which produced biodiesel 2–98% [110]. The “N-
methylimidazole functionalized” anion exchange resin (R+–OH−),
684 Z. Ullah et al. / Journal of Molecular Liquids 266 (2018) 673–686
Fig. 9. Structure of “bis-(3-methyl-imidazolium)-ethylene dihydroxyl IL”.
having NaOH was synthesized in a two-step process and then applied
for the reaction of soybean oil for biodiesel production. The hydroxyl
functional groups (R+–OH− and N-methylimidazole) showed some po-
larity, and for R+OH− (Na) formation, NaOH could be absorbed in R+–
OH−. Both methanol and soybean oil fit in the partly-polar R+OH− (Na),
and the co-catalysis of R+–OH− with NaOH that enhanced the reaction.
At the optimal condition, the soybean oil conversion was up to 97.25%.
Here, the methanol and soybean oil molar ratio was 12:1 with the cata-
lyst dosage 2.5%, at 50 °C; the stirring speed was 570 rpm and at 10 h re-
action time. Furthermore, the synthesized R+–OH− (Na) have been
tested for biodiesel preparation, which shows some benefits such as
more amounts of OH−, increased surface area, homogeneous porous
structures and good stability. The N-methylimidazolium modified the
PS-DVB polarity, improves the methanol and oil solubility, as well as im-
proved the “co-catalytic activity of R+–OH− with NaOH. NaOH in R+–
OH− (Na) not only catalysed the reaction, but also polarized the anion
OH− of R+–OH−”. Quaternary ammonium-containing resin such as
Marathon (MSA) was applied for soybean oil's transesterification to bio-
diesel which was b70% yield. At optimal conditions, 97.25% was ob-
tained. The catalysis concept of “R+–OH− (Na)” has effectively been
used for biodiesel production [113].
A neutral IL like [MorMeA][Br] is used as catalytic conversion of
waste cooking oil in biodiesel using the microwave technique with tem-
perature of 70 °C and 6 min and achieved up to 98% yield [114].
6. Brønsted basic ionic liquids
In comparison to Brønsted acidic ILs, Brønsted basic ILs are rarely re-
ported in the literature. For biodiesel production, “several imidazolium
hydroxides basic ILs (such as [BMIM][OH])” were studied as catalysts
for the transesterification reaction. This resulted in a 87% biodiesel
yield for 8 h reaction time at 120 °C. The methanol and triglyceride
was used in the molar ratios of 9:1 M [41].
Liang [115], used cottonseed oil transesterification to prepare
binuclear containing imidazolium groups of five ILs that were catalyti-
cally used for biodiesel preparation. The better results were achieved
for (IMC2OH) as a catalyst (Fig. 9). They optimised the reaction param-
eters, and the biodiesel yield was 98.5%, which was found after a reac-
tion of 4 h at 55 °C, and this was equivalent to 0.4% catalyst and 12
parts of methanol. The IL was reused for many times, and there was
no prominent change in the yield (96.2%). This indicates that there is
no selective catalytic decrease.
As a catalyst for the making of biodiesel from the transesterification
of waste cooking oil, a basic IL [TBP][OH] produced an 82% yield [116].
Meanwhile, a 97% yield was reported for novel basic IL (1,1,3,3-
trimethyl-2-octyl-guanidine hydroxide) [117].
7. Conclusion
Biodiesel can replace conventional petroleum and diesel due to its
advantageous properties. It is biodegradable renewable and has a low
emission profile. As the replacement for fuel, biodiesel can be used
with petroleum-based diel, in either mixed or neat forms. Compared
to petroleum-based diesel, the emission profile of the combustion is
more optimistic. Biodiesel is derived from different sources through
the transesterification method, where the feedstock and catalyst
selection are very essential. Traditional catalysts that were used had
curbed the various problems. In this regard, this paper has shown the
potential of using ILs as a catalyst and solvent for biodiesel production.
In comparison to traditional solvents, ILs are great replacement sol-
vents; they are known as “green solvents” because they are less toxic to
the environment and human health. ILs have the most significant ad-
vantage that it can be separated from the reaction mixture by decanta-
tion and removed from the product of biodiesel, presenting the cost
benefits and easiness compared to filtration. In fact, those (ILs) have
found numerous applications which are functionalised with Lewis and
Brønsted acid sites. Under the optimum reaction conditions, ILs are ca-
pable of giving a 98.5% yield of biodiesel. The novel development
owned many benefits, including operational simplicity, high yields,
low cost, no saponification, reusability, less corrosion effect and less
waste.
Acknowledgement
I acknowledge all the co-authors cooperation and especially ac-
knowledge the continuous efforts of the Research Centre, College of
Pharmacy, and Deanship of Scientific Research at King Saud University,
Riyadh, Saudi Arabia.
References
[1] A. Uihlein, L. Schebek, Environmental impacts of a lignocellulose feedstock
biorefinery system: an assessment, Biomass Bioenergy 33 (2009) 793–802.
[2] A. Dhussa, Biogas in India, Methane to Markets Partnership, Meeting of Agriculture
Subcommittee, 2004.
[3] A. Demirbaş, Bioethanol from cellulosic materials: a renewable motor fuel from
biomass, Energy Sources 27 (2005) 327–337.
[4] S. Lewis, Fermentation alcohol, Ind. Enzymol. (1996) 11–48.
[5] M.K. Lam, K.T. Lee, A.R. Mohamed, Homogeneous, heterogeneous and enzymatic
catalysis for transesterification of high free fatty acid oil (waste cooking oil) to bio-
diesel: a review, Biotechnol. Adv. 28 (2010) 500–518 (7).
[6] M.G. Kulkarni, A.K. Dalai, Waste cooking oil an economical source for biodiesel: a
review, Ind. Eng. Chem. Res. 45 (2006) 2901–2913.
[7] Y. Sharma, B. Singh, Development of biodiesel: current scenario, Renew. Sust.
Energ. Rev. 13 (2009) 1646–1651.
[8] D. Pimentel, M. Pimentel, Global environmental resources versus world population
growth, Ecol. Econ. 59 (2006) 195–198.
[9] E. Movil, A Report in Energy Trends, Greenhouse Gas Emissions and Alternative En-
ergy, Exxon Mobile, 2004.
[10] Y.A. Zhang, M. Dube, D. McLean, M. Kates, Biodiesel production from waste cooking
oil: 1. Process design and technological assessment, Bioresour. Technol. 89 (2003)
1–16.
[11] X. Liang, Synthesis of biodiesel from waste oil under mild conditions using novel
acidic ionic liquid immobilization on poly divinylbenzene, Energy 63 (2013)
103–108.
[12] I. Atadashi, M. Aroua, A.A. Aziz, N. Sulaiman, Production of biodiesel using high free
fatty acid feedstocks, Renew. Sust. Energ. Rev. 16 (2012) 3275–3285.
[13] S.B. Lee, K.H. Han, J.D. Lee, I.K. Hong, Optimum process and energy density
analysis of canola oil biodiesel synthesis, J. Ind. Eng. Chem. 16 (2010)
1006–1010.
[14] M.J. Earle, N.V. Plechkova, K.R. Seddon, Green synthesis of biodiesel using ionic liq-
uids, Pure Appl. Chem. 81 (2009).
[15] M. Hayyan, F.S. Mjalli, M.A. Hashim, I.M. AlNashef, A novel technique for separating
glycerine from palm oil-based biodiesel using ionic liquids, Fuel Process. Technol.
91 (2010) 116–120.
[16] A.K. Endalew, Y. Kiros, R. Zanzi, Inorganic heterogeneous catalysts for bio-
diesel production from vegetable oils, Biomass Bioenergy 35 (2011)
3787–3809.
[17] M. Zabeti, W.M.A. Wan Daud, M.K. Aroua, Activity of solid catalysts for biodiesel
production: a review, Fuel Process. Technol. 90 (2009) 770–777.
[18] Z. Ullah, M.A. Bustam, Z. Man, Characterization of waste palm cooking oil for bio-
diesel production, Int. J. Chem. Eng. Appl. 5 (2014) 134.
[19] S.H. Shuit, Y.T. Ong, K.T. Lee, B. Subhash, S.H. Tan, Membrane technology as a prom-
ising alternative in biodiesel production: a review, Biotechnol. Adv. 30 (2012)
1364–1380 (11).
[20] I. Atadashi, M. Aroua, A.A. Aziz, Biodiesel separation and purification: a review,
Renew. Energy 36 (2011) 437–443.
[21] J. Van Gerpen, G. Knothe, Basics of the transesterification reaction, The Biodiesel
Handbook 2005, pp. 26–41.
[22] A. Demirbas, Progress and recent trends in biofuels, Prog. Energy Combust. Sci. 33
(2007) 1–18.
[23] H.J. Berchmans, S. Hirata, Biodiesel production from crude Jatropha curcas L. seed
oil with a high content of free fatty acids, Bioresour. Technol. 99 (2008)
1716–1721.
 Z. Ullah et al. / Journal of Molecular Liquids 266 (2018) 673–686
[24] M. Hasheminejad, M. Tabatabaei, Y. Mansourpanah, A. Javani, Upstream and
downstream strategies to economize biodiesel production, Bioresour. Technol.
102 (2011) 461–468.
[25] A. Demirbaş, H. Kara, New options for conversion of vegetable oils to alternative
fuels, Energy Sources Part A 28 (2006) 619–626.
[26] A. Demirbas, Progress and recent trends in biodiesel fuels, Energy Convers. Manag.
50 (2009) 14–34.
[27] N. Luković, Z. Knežević-Jugović, D. Bezbradica, Biodiesel fuel production by enzy-
matic transesterification of oils: recent trends, challenges and future perspectives,
Alternative Fuel, 2011.
[29] G.L. Maddikeri, A.B. Pandit, P.R. Gogate, Intensification approaches for biodiesel
synthesis from waste cooking oil: a review, Ind. Eng. Chem. Res. 51 (2012)
14610–14628.
[30] F. J. Sprules and P. Donald. Production of fatty esters. ed: US Patent 2,494,366. 1950.
[31] F. Ma, M.A. Hanna, Biodiesel production: a review, Bioresour. Technol. 70 (1999)
1–15.
[32] P. Zhang, A review on biodiesel production by transesterification catalyzed by ionic
liquid catalysts, Curr. Org. Chem. 19 (2005).
[33] J.V. Gerpen, Biodiesel processing and production, Fuel Process. Technol. 86 (2005)
1097–1107.
[34] Y. Wang, P. Liu, S. Ou, Z. Zhang, Preparation of biodiesel from waste cooking
oil via two-step catalyzed process, Energy Convers. Manag. 48 (2007)
184–188.
[35] A. Demirbaş, Biodiesel fuels from vegetable oils via catalytic and non-catalytic su-
percritical alcohol transesterifications and other methods: a survey, Energy
Convers. Manag. 44 (2003) 2093–2109.
[36] A. Demirbas, Biodiesel production from vegetable oils via catalytic and non-
catalytic supercritical methanol transesterification methods, Prog. Energy Com-
bust. Sci. 31 (2005) 466–487.
[37] Y. Sharma, B. Singh, S. Upadhyay, Advancements in development and characteriza-
tion of biodiesel: a review, Fuel 87 (2008) 2355–2373.
[38] E.-S. Song, J.-w. Lim, H.-S. Lee, Y.-W. Lee, Transesterification of RBD palm oil using
supercritical methanol, J. Supercrit. Fluids 44 (2008) 356–363.
[39] J.P. Szybist, A.L. Boehman, J.D. Taylor, R.L. McCormick, Evaluation of formulation
strategies to eliminate the biodiesel NOx effect, Fuel Process. Technol. 86 (2005)
1109–1126.
[40] L. Tao, D. Yuefeng, G. Shucai, C. Ji, Application of choline chloride· xZnCl 2 ionic liq-
uids for preparation of biodiesel, Chin. J. Chem. Eng. 18 (2010) 322–327.
[41] S. Zhou, L. Liu, B. Wang, F. Xu, R.C. Sun, Biodiesel preparation from
transesterification of glycerol trioleate catalyzed by basic ionic liquids, Chin.
Chem. Lett. 23 (2012) 379–382.
[42] M. Farooq, A. Ramli, A. Naeem, Biodiesel production from low FFA waste cooking
oil using heterogeneous catalyst derived from chicken bones, Renew. Energy 76
(2015) 362–368 (4).
[43] M. Diasakou, A. Louloudi, N. Papayannakos, Kinetics of the non-catalytic
transesterification of soybean oil, Fuel 77 (1998) 1297–1302.
[44] F. Guo, Z. Fang, X.-F. Tian, Y.-D. Long, L.-Q. Jiang, One-step production of biodiesel
from Jatropha oil with high-acid value in ionic liquids, Bioresour. Technol. 102
(2011) 6469–6472 (6).
[45] Z. Ullah, M.A. Bustam, N. Muhammad, Z. Man, A.S. Khan, Synthesis and
thermophysical properties of hydrogensulphate based acidic ionic liquids, J.
Solut. Chem. 44 (2015) 875–889.
[46] L. Andreani, J. Rocha, Use of ionic liquids in biodiesel production: a review, Braz. J.
Chem. Eng. 29 (2012) 1–13.
[47] Z. Ullah, M.A. Bustam, Z. Man, S.N. Shah, A.S. Khan, N. Muhammad, Synthesis, char-
acterization and physicochemical properties of dual-functional acidic ionic liquids,
J. Mol. Liq. 223 (2016) 81–88 (11).
[48] N. Muhammad, Z. Man, Y.A. Elsheikh, M.A. Bustam, M.A. Mutalib, Synthesis and
thermophysical properties of imidazolium-based Bronsted acidic ionic liquids, J.
Chem. Eng. Data 59 (2014) 579–584.
[49] C.-Z. Liu, F. Wang, A.R. Stiles, C. Guo, Ionic liquids for biofuel production: opportu-
nities and challenges, Appl. Energy 92 (2012) 406–414.
[50] W. Isahak, M. Ismail, J.M. Jahim, J. Salimon, M. Yarmo, Transesterification of palm
oil by using ionic liquids as a new potential catalyst, Trends Appl. Sci. Res. 6
(2011) 1055–1062.
[51] K. Ghandi, A review of ionic liquids, their limits and applications, Green Sustain.
Chem. 2014 (2014).
[52] Z. Ullah, M.A. Bustam, Z. Man, N. Muhammad, A.S. Khan, Synthesis, characteriza-
tion and the effect of temperature on different physicochemical properties of
protic ionic liquids, RSC Adv. 5 (2015) 71449–71461.
[54] M.K. Potdar, G.F. Kelso, L. Schwarz, C. Zhang, M.T. Hearn, Recent developments in
chemical synthesis with biocatalysts in ionic liquids, Molecules 20 (2015)
16788–16816.
[55] N. Muhammad, Z. Man, A.K. Ziyada, M.A. Bustam, M.A. Mutalib, C.D. Wilfred, et al.,
Thermophysical properties of dual functionalized imidazolium-based ionic liquids,
J. Chem. Eng. Data 57 (2012) 737–743.
[56] H. Zhao, G.A. Baker, Ionic liquids and deep eutectic solvents for biodiesel synthesis:
a review, J. Chem. Technol. Biotechnol. 88 (2013) 3–12.
[57] M. Ghiaci, B. Aghabarari, S. Habibollahi, A. Gil, Highly efficient Brønsted acidic ionic
liquid-based catalysts for biodiesel synthesis from vegetable oils, Bioresour.
Technol. 102 (2011) 1200–1204.
[58] X. Liang, G. Gong, H. Wu, J. Yang, Highly efficient procedure for the synthesis of bio-
diesel from soybean oil using chloroaluminate ionic liquid as catalyst, Fuel 88
(2009) 613–616.
[59] M. Gamba, A.A. Lapis, J. Dupont, Supported ionic liquid enzymatic catalysis for the
production of biodiesel, Adv. Synth. Catal. 350 (2008) 160–164.
685
[60] J. Dupont, P.A. Suarez, M.R. Meneghetti, S.M. Meneghetti, Catalytic production of
biodiesel and diesel-like hydrocarbons from triglycerides, Energy Environ. Sci. 2
(2009) 1258–1265.
[61] N.V. Plechkova, K.R. Seddon, Applications of ionic liquids in the chemical industry,
Chem. Soc. Rev. 37 (2008) 123–150.
[62] B. Wu, W. Liu, Y. Zhang, H. Wang, Do we understand the recyclability of ionic liq-
uids? Chem. Eur. J. 15 (2009) 1804–1810.
[63] N.I. Ruzich, A.S. Bassi, Investigation of enzymatic biodiesel production using ionic
liquid as a co-solvent, Can. J. Chem. Eng. 88 (2010) 277–282.
[64] K.E. Gutowski, G.A. Broker, H.D. Willauer, J.G. Huddleston, R.P. Swatloski, J.D.
Holbrey, et al., Controlling the aqueous miscibility of ionic liquids: aqueous bi-
phasic systems of water-miscible ionic liquids and water-structuring salts for recy-
cle, metathesis, and separations, J. Am. Chem. Soc. 125 (2003) 6632–6633.
[65] A.H. Mohammad Fauzi, N.A.S. Amin, An overview of ionic liquids as solvents in bio-
diesel synthesis, Renew. Sust. Energ. Rev. 16 (2012) 5770–5786 (10).
[66] J.-Q. Lai, Z.-L. Hu, P.-W. Wang, Z. Yang, Enzymatic production of microalgal biodie-
sel in ionic liquid [BMIm][PF6], Fuel 95 (2012) 329–333.
[67] S.H. Ha, M.N. Lan, S.H. Lee, S.M. Hwang, Y.-M. Koo, Lipase-catalyzed biodiesel pro-
duction from soybean oil in ionic liquids, Enzym. Microb. Technol. 41 (2007)
480–483.
[68] S. Arai, K. Nakashima, T. Tanino, C. Ogino, A. Kondo, H. Fukuda, Production of bio-
diesel fuel from soybean oil catalyzed by fungus whole-cell biocatalysts in ionic liq-
uids, Enzym. Microb. Technol. 46 (2010) 51–55.
[69] Y. Liu, D. Chen, Y. Yan, C. Peng, L. Xu, Biodiesel synthesis and conformation of lipase
from Burkholderia cepacia in room temperature ionic liquids and organic solvents,
Bioresour. Technol. 102 (2011) 10414–10418.
[70] R.A. Sheldon, R.M. Lau, M.J. Sorgedrager, F. van Rantwijk, K.R. Seddon, Biocatalysis
in ionic liquids, Green Chem. 4 (2002) 147–151.
[71] B.-M. Lue, Z. Guo, X. Xu, Effect of room temperature ionic liquid structure on the
enzymatic acylation of flavonoids, Process Biochem. 45 (2010) 1375–1382.
[72] T. De Diego, P. Lozano, S. Gmouh, M. Vaultier, J.L. Iborra, Fluorescence and CD spec-
troscopic analysis of the α-chymotrypsin stabilization by the ionic liquid, 1-ethyl-
3-methylimidazolium bis [(trifluoromethyl) sulfonyl] amide, Biotechnol. Bioeng.
88 (2004) 916–924.
[73] A. De los Ríos, F. Hernández Fernández, D. Gómez, M. Rubio, G. Víllora, Biocatalytic
transesterification of sunflower and waste cooking oils in ionic liquid media, Pro-
cess Biochem. 46 (2011) 1475–1480.
[74] W.S. Silva, A.A. Lapis, P.A. Suarez, B.A. Neto, Enzyme-mediated epoxidation of
methyl oleate supported by imidazolium-based ionic liquids, J. Mol. Catal. B
Enzym. 68 (2011) 98–103.
[75] S. Sunitha, S. Kanjilal, P. Reddy, R. Prasad, Ionic liquids as a reaction medium for
lipase-catalyzed methanolysis of sunflower oil, Biotechnol. Lett. 29 (2007)
1881–1885.
[76] B. Devi, Z. Guo, X. Xu, Characterization of ionic liquid-based biocatalytic two-phase
reaction system for production of biodiesel, AICHE J. 57 (2011) 1628–1637.
[77] P. Lozano, J.M. Bernal, M. Vaultier, Towards continuous sustainable processes for
enzymatic synthesis of biodiesel in hydrophobic ionic liquids/supercritical carbon
dioxide biphasic systems, Fuel 90 (2011) 3461–3467.
[78] N.I. Ruzich, A.S. Bassi, Investigation of lipase-catalyzed biodiesel production using
ionic liquid [BMIM][PF6] as a co-solvent in 500 mL jacketed conical and shake
flask reactors using triolein or waste canola oil as substrates, Energy Fuel 24
(2010) 3214–3222.
[79] T. De Diego, A. Manjón, P. Lozano, M. Vaultier, J.L. Iborra, An efficient activity ionic
liquid-enzyme system for biodiesel production, Green Chem. 13 (2011) 444–451.
[80] T. De Diego, A. Manjón, P. Lozano, J.L. Iborra, A recyclable enzymatic biodiesel pro-
duction process in ionic liquids, Bioresour. Technol. 102 (2011) 6336–6339.
[81] F.A. Yassin, F.Y. El Kady, H.S. Ahmed, L.K. Mohamed, S.A. Shaban, A.K. Elfadaly,
Highly effective ionic liquids for biodiesel production from waste vegetable oils,
Egypt. J. Pet. 24 (2015) 103–111 (3).
[82] K.-X. Li, L. Chen, Z.-C. Yan, H.-L. Wang, Application of pyridinium ionic liquid as a
recyclable catalyst for acid-catalyzed transesterification of Jatropha oil, Catal. Lett.
139 (2010) 151–156.
[83] M. Han, W. Yi, Q. Wu, Y. Liu, Y. Hong, D. Wang, Preparation of biodiesel from waste
oils catalyzed by a Brønsted acidic ionic liquid, Bioresour. Technol. 100 (2009)
2308–2310.
[84] X. Liang, J. Yang, Synthesis of a novel multi–SO3H functionalized ionic liquid and its
catalytic activities for biodiesel synthesis, Green Chem. 12 (2010) 201–204.
[85] S. Das, A.J. Thakur, D. Deka, Two-stage conversion of high free fatty acid Jatropha
curcas oil to biodiesel using Brønsted acidic ionic liquid and KOH as catalysts, Sci.
World J. 2014 (2014).
[86] L. Zhang, M. Xian, Y. He, L. Li, J. Yang, S. Yu, et al., A Brønsted acidic ionic liquid as an
efficient and environmentally benign catalyst for biodiesel synthesis from free fatty
acids and alcohols, Bioresour. Technol. 100 (2009) 4368–4373.
[87] A.N. Masri, M.I. Abdul Mutalib, N.F. Aminuddin, J.M. Lévêque, Novel SO3H-
functionalized dicationic ionic liquids – a comparative study for esterification reac-
tion by ultrasound cavitation and mechanical stirring for biodiesel production, Sep.
Purif. Technol. 2017 (2017) (09/01).
[88] Z. Ullah, M.A. Bustam, Z. Man, A.S. Khan, N. Muhammad, A. Sarwono, et al., A detail
description on catalytic conversion of waste palm cooking oil into biodiesel and its
derivatives: new functionalized ionic liquid process, ChemistrySelect 2 (2017)
8583–8595.
[89] Z. Ullah, M.A. Bustam, Z. Man, Biodiesel production from waste cooking oil by
acidic ionic liquid as a catalyst, Renew. Energy 77 (2015) 521–526.
[90] Z. Man, Y.A. Elsheikh, M.A. Bustam, S. Yusup, M.A. Mutalib, N. Muhammad, A
Brønsted ammonium ionic liquid-KOH two-stage catalyst for biodiesel synthesis
from crude palm oil, Ind. Crop. Prod. 41 (2013) 144–149.
686 Z. Ullah et al. / Journal of Molecular Liquids 266 (2018) 673–686
[91] Y.A. Elsheikh, Z. Man, A. Bustam, S. Yusup, F.H. Akhtar, I. Mohamed, Evaluation of
catalytic activity of two functionalized imidazolium ionic liquids for biodiesel fuel
production by a two-stage process, J. Chem. Technol. Biotechnol. 89 (2014)
998–1006.
[92] S. Liu, H. Zhou, S. Yu, C. Xie, F. Liu, Z. Song, Dimerization of fatty acid methyl ester
using Brönsted–Lewis acidic ionic liquid as catalyst, Chem. Eng. J. 174 (2011)
396–399.
[93] Y. Elsheikh, Z. Man, M.A. Bustam, S. Yusup, C. Wilfred, Brønsted imidazolium ionic
liquids: synthesis and comparison of their catalytic activities as pre-catalyst for
biodiesel production through two stage process, Energy Convers. Manag. 52
(2011) 804–809.
[94] M.M. Fan, J.J. Zhou, Q.J. Han, P.B. Zhang, Effect of various functional groups on bio-
diesel synthesis from soybean oils by acidic ionic liquids, Chin. Chem. Lett. 23
(2012) 1107–1110.
[95] Z.S. Qureshi, K.M. Deshmukh, M.D. Bhor, B.M. Bhanage, Bronsted acidic ionic liquid
as an efficient and reusable catalyst for transesterification of β-ketoesters, Catal.
Commun. 10 (2009) 833–837 (2/15).
[96] K. Li, L. Chen, Z. Yan, H. Wang, Synthesis of biodiesel from Jatropha oil using
pyridinium ionic liquid as a catalyst, Energy Sources Part A 35 (2013) 1150–1160.
[97] M. Ghiaci, B. Aghabarari, A. Gil, Production of biodiesel by esterification of natural
fatty acids over modified organoclay catalysts, Fuel 90 (2011) 3382–3389.
[98] Q. Wu, H. Chen, M. Han, D. Wang, J. Wang, Transesterification of cottonseed oil cat-
alyzed by Brønsted acidic ionic liquids, Ind. Eng. Chem. Res. 46 (2007) 7955–7960.
[99] D. Fang, J. Yang, C. Jiao, Dicationic ionic liquids as environmentally benign catalysts
for biodiesel synthesis, ACS Catal. 1 (2010) 42–47.
[100] S. Liu, Z. Wang, S. Yu, C. Xie, Transesterification of waste oil to biodiesel using
Brønsted acid ionic liquid as catalyst, Bull. Chem. Soc. Ethiop. 27 (2013) 289–294.
[101] X. Liang, Novel efficient procedure for biodiesel synthesis from waste oils using
solid acidic ionic liquid polymer as the catalyst, Ind. Eng. Chem. Res. 52 (2013)
6894–6900.
[102] B. Aghabarari, N. Dorostkar, M. Martinez-Huerta, Synthesis of biodiesel from Ni-
gella sativa seed oil using surfactant-Brønsted acidic-combined ionic liquid as cat-
alyst, Fuel Process. Technol. 118 (2014) 296–301.
[103] M. Olkiewicz, N.V. Plechkova, M.J. Earle, A. Fabregat, F. Stüber, A. Fortuny, et al., Bio-
diesel production from sewage sludge lipids catalysed by Brønsted acidic ionic liq-
uids, Appl. Catal. B Environ. 181 (2016) 738–746 (2).
[104] B.S. Caldas, C.S. Nunes, P.R. Souza, F.A. Rosa, J.V. Visentainer, S. Oscar de Olivera,
et al., Supercritical ethanolysis for biodiesel production from edible oil waste
using ionic liquid [HMim][HSO4] as catalyst, Appl. Catal. B Environ. 181 (2016)
289–297 (2).
[105] G. Arzamendi, I. Campo, E. Arguinarena, M. Sánchez, M. Montes, L. Gandia, Synthe-
sis of biodiesel with heterogeneous NaOH/alumina catalysts: comparison with ho-
mogeneous NaOH, Chem. Eng. J. 134 (2007) 123–130.
[106] C. Samart, C. Chaiya, P. Reubroycharoen, Biodiesel production by methanolysis of
soybean oil using calcium supported on mesoporous silica catalyst, Energy
Convers. Manag. 51 (2010) 1428–1431.
[107] G.J. Suppes, M.A. Dasari, E.J. Doskocil, P.J. Mankidy, M.J. Goff, Transesterification of
soybean oil with zeolite and metal catalysts, Appl. Catal. A Gen. 257 (2004)
213–223.
[108] F.R. Abreu, M.B. Alves, C. Macêdo, L.F. Zara, P.A. Suarez, New multi-phase catalytic
systems based on tin compounds active for vegetable oil transesterificaton reac-
tion, J. Mol. Catal. A Chem. 227 (2005) 263–267.
[110] A.A. Lapis, L.F. de Oliveira, B.A. Neto, J. Dupont, Ionic liquid supported acid/base-
catalyzed production of biodiesel, ChemSusChem 1 (2008) 759–762.
[111] B.A.D. Neto, M.B. Alves, A.A. Lapis, F.M. Nachtigall, M.N. Eberlin, J. Dupont, et al., 1-
n-Butyl-3-methylimidazolium tetrachloro-indate (BMI· InCl4) as a media for the
synthesis of biodiesel from vegetable oils, J. Catal. 249 (2007) 154–161.
[112] Y. Cao, H. Zhou, J. Li, Preparation of a supported acidic ionic liquid on silica-gel and
its application to the synthesis of biodiesel from waste cooking oil, Renew. Sust.
Energ. Rev. 58 (2016) 871–875 (5).
[113] T. Long, Y. Deng, G. Li, S. Gan, J. Chen, Application of N-methylimidizolium func-
tionalized anion exchange resin containing NaOH for production of biodiesel,
Fuel Process. Technol. 92 (2011) 1328–1332.
[114] Y.-C. Lin, P.-M. Yang, S.-C. Chen, J.-F. Lin, Improving biodiesel yields from waste
cooking oil using ionic liquids as catalysts with a microwave heating system,
Fuel Process. Technol. 115 (2013) 57–62.
[115] J.-H. Liang, X.-Q. Ren, J.-T. Wang, Z.-J. Li, Preparation of biodiesel by
transesterification from cottonseed oil using the basic dication ionic liquids as cat-
alysts, J. Fuel Chem. Technol. 38 (2010) 275–280.
[116] Z. Ullah, M.A. Bustam, Z. Man, Preparation of biodiesel from waste cooking oil cat-
alyzed by basic ionic liquid, Appl. Mech. Mater. (2014) 874–876.
[117] P. Zhang, Y. Liu, M. Fan, P. Jiang, Catalytic performance of a novel amphiphilic alka-
line ionic liquid for biodiesel production: Influence of basicity and conductivity,
Renew. Energy 86 (2016) 99–105 (2).