Applied Energy 108 (2013) 333339

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Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Biodiesel production by transesterication catalyzed by an efcient

choline ionic liquid catalyst
Mingming Fan, Jianglei Huang, Jing Yang, Pingbo Zhang
The Key Laboratory of Food Colloids and Biotechnology, Ministry of Education, School of Chemical and Material Engineering, Jiangnan University, Wuxi 214122, PR China

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 Basic ionic liquid choline hydroxide

shows good catalytic activity in
biodiesel synthesis.
 Technological parameters of the
transesterication reaction are
optimized.
 Choline hydroxide catalyst can
catalyze the transesterication
without soap formation.
 The mechanism has been investigated
using quasi in situ IR.

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

Article history: The catalytic synthesis of biodiesel from soybean oil by transesterication over basic ionic liquid catalysts
Received 14 January 2013 had been studied at atmospheric pressure. Choline hydroxide (ChOH) catalyst exhibited better catalytic
Received in revised form 9 March 2013 activity compared with other basic ionic liquid catalysts, and methanol is the best alcohol for biodiesel
Accepted 23 March 2013
synthesis. The suitable molar ratio of methanol and soybean oil was 9:1, and the optimum catalyst dosage
Available online 11 April 2013
existed for catalytic activity, which was about 4 wt.% (without soap formation). The study also revealed
that the appropriate reaction temperature was about 60 C, and the suitable reaction time was 2.5 h on
Keywords:
the basis of biodiesel yield. The reusability test showed that ChOH catalyst had perfect utility for repeated
Biodiesel
Soybean oil
use. By basicity test, it was found that the basic ionic liquid ChOH possessed better basicity in methanol
Basic ionic liquid solution. The catalytic reaction mechanism was illuminated by the interaction between the methoxyl
Transesterication group after activating and the carbonyl group of the triglyceride, which has been investigated using quasi
in situ infrared spectroscopy.
2013 Elsevier Ltd. All rights reserved.

1. Introduction necessary to develop alternative clean and renewable energy

Biodiesel has drawn more and more attention in recent years
because of rapidly increasing crude oil prices, limited fossil fuels,
and intensied environment pollution [1,2]. So it is increasingly
Corresponding author. Tel.: +86 510 85917090.
E-mail address: pingbozhang@126.com (P. Zhang).
sources. Biodiesel, obtained from renewable biomass feedstock
such as vegetable oil, can be used in diesel engines or blended at
various proportions with petroleum diesel as fuel [3]. Several
methods for biodiesel production have been developed so far,
e.g., direct use and blending of raw oil [4], micro-emulsication
[5], pyrolysis [6]. A particularly promising method of producing
biodiesel is transesterication route [7]. Transesterication is the

0306-2619/$ - see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.apenergy.2013.03.063
334 M. Fan et al. / Applied Energy 108 (2013) 333339
chemical reaction that involves triglycerides and alcohol in the
presence of a catalyst to form esters and glycerol. Most of hetero-
geneous catalysts are often used in transesterication reaction, be-
cause catalysts can be easily removed from the reaction mixture by
ltration and recycled in the new process. Therefore, the loss of
catalyst can be avoided [8]. Several different heterogeneous basic
catalysts have been proposed for the biodiesel synthesis by transe-
sterication reaction, such as alumina/silica supported K2CO3 cata-
lysts [9], KOH/Al2O3 and KOH/NaY catalysts [10], cinder supported
K2CO3 catalysts [11], KOH/bentonite catalysts [12], KNO3/Al2O3 so-
lid catalysts [13], Li-doped MgO catalysts [14], CaO catalysts [15
17], modied CaO catalysts [18], KF/CaO catalysts [19], KF/CaO
MgO catalysts [20], and KF/CaOFe3O4 catalysts [21]. However,
vegetable oils may contain small amounts of water and free fatty
acids (FFA). For a base-catalyzed transesterication, the basic cata-
lyst will react with the FFA to form soap which will lower the yield
of the biodiesel. The water produced during the saponication
reaction will lead to the hydrolysis of the esters to form more
FFA [7].
Recently, ionic liquids have been reported as the promising cat-
alysts for transesterication reaction for biodiesel synthesis. Acidic
ionic liquids have drawn much more attention because of their
excellent catalytic activity, but high reaction temperature is
needed [2224]. On this point, it may be interesting to explore no-
vel basic ionic liquid catalysts for biodiesel synthesis from the
transesterication route with no soap formation. A survey of liter-
ature showed that there had been little references about the use of
basic ionic liquid as catalysts for biodiesel synthesis by transeste-
rication of soybean oil and methanol. In the present paper, several
basic ionic liquid catalysts based on choline chloride were pre-
pared for biodiesel production. The purpose of this paper is to ex-
plore effective and stable ion liquid catalysts and optimum
reaction conditions for biodiesel synthesis from soybean oil.
2. Materials and methods
2.1. Catalyst preparation
Preparation of choline hydroxide (ChOH). As shown in reaction
(1), equimolar choline chloride and KOH were dissolved in ethanol.
Thereafter, the solution was kept under vigorous stirring at 60 C
for 24 h. After cooling to room temperature, KCl was removed by
ltration, and ethanol was evaporated away from the mixture to
obtain basic ionic liquid catalyst ChOH.
Preparation of choline methoxide (ChOMe). As shown in reac-
tion (2), equimolar choline chloride and NaOCH3 were dissolved
in ethanol, and then ChOMe could be prepared by the same exper-
imental steps with ChOH.
Preparation of choline imidazolium (ChIm). As shown in reac-
tion (3), iminazole was added into a vigorously stirring solution
of equimolar NaOH in methanol at room temperature and the solu-
tion was stirred for 45 min. With this solution, equimolar choline
chloride and a certain amount of ethyl ether were added, and kept
under vigorous stirring at room temperature for 24 h. After cooling
to room temperature, NaCl was removed by ltration, and the sol-
vents were evaporated away from the mixture to obtain basic ionic
liquid catalyst ChIm.
2.2. Catalytic performance
Weighed amounts of soybean oil, methanol and the prepared
catalysts were added to a ask having a reux condenser, and a
magnetic stirring apparatus. In typical experiment, a measured
amount of catalysts (from 2 wt.% to 10 wt.% based on the weight
of reactantsmethanol/oil mixture) and weighed amounts of
methanol and soybean oil (molar ratio of methanol to soybean
 M. Fan et al. / Applied Energy 108 (2013) 333339
oil = 6:1, 9:1, 12:1, 15:1, 18:1) were introduced into the reactor.
The reaction was carried out at 3065 C for 0.54.5 h. Then the
reaction mixture became biphasic, the upper phase was mainly
the desired biodiesel, and the lower phase, ionic liquid, methanol
and glycerol.
For biodiesel analysis, the upper phase was mixed with
0.05 ml methyl salicylate (internal standard) in a 2 ml tube, fol-
lowed by the addition of hexane (1.5 ml). Then, the treated sam-
ple (0.2 lL) was injected into the GC-122 gas chromatograph,
which was equipped with a SE-54 capillary column
(0.32 mm  30 m). The column temperature was kept at 160 C
for 2 min, raised to 220 C at a rate of 10 C/min, then to
260 C at a rate of 8 C/min, and nally maintained at this tem-
perature for 10 min. In our work, the mass concentration of bio-
diesel was obtained by the GC and the yield of biodiesel was
calculated by the following equation:
mactual C esters  n  V esters
Yield   100%
mtheoretical moil
C esters  n  V oil C esters  n
  100%   100%
moil qoil
where both mactual (g) and mtheoretical (g) are the actual mass and
theoretical mass of biodiesel; moil (g) is the mass of soybean oil; n
is the diluted multiple of biodiesel; Cesters (g/mL) is the mass con-
centration of biodiesel; qoil (g/mL) is the density of soybean oil;
Vesters (mL) and Voil (mL) are the volumes of biodiesel and soybean
oil, respectively [21,25,26].
To investigate the reusability of ChOH, the lower phase was rst
distilled and then separated by solvent extraction to purify the cat-
alyst. The separation procedures are explained in detail as follows.
Because the lower phase contained the ionic liquid catalyst, glyc-
erol and excess methanol, rst the excess methanol
(b.p. = 64.8 C) can be separated from the mixture by distillation.
Then the ionic liquid was separated from glycerol by solvent
extraction. 2 ml n-butanol and 4 ml water were added into the
above mixtures, which was fully mixed and placed for form two
phases. The lower phase contained glycerol and water. The desired
ionic liquid was presented in the upper 1-butanol phase. 1-Butanol
(b.p. = 117.7 C) was removed by vacuum distillation in order to
gain the desired ionic liquid. The recovery of the ionic liquid was
above 95%.
2.3. Characterization
The basicity of the catalysts in methanol solution was deter-
mined by pH meter (Sartorius PB-10).
Quasi in situ IR measurements were carried out with an ABB Bo-
mem FTLA2000-104 spectrometer with 4 cm1 resolution and
5004000 cm1 scanning ranges, using KBr pellets. Under the reac-
tion condition, the reactant and the catalyst was mixed and reacted
for 160 min. Then a drop of sample from the reaction system was
coated in KBr pellets for the observation of reaction intermediates
formed during the reaction.
2.4. Properties of soybean oil
The soybean oil (average molecular weight = 871.16 g/mol) as
analyzed before the initiation of the transesterication reaction
at the preliminary stage exhibited acid value of 0.49 mg KOH g1
of oil, and saponication index (Sv = 193.68 mg KOH g1).
335
3. Results and discussion
3.1. Choice of various basic catalysts
The inuence of various catalysts is summarized rstly in Table
1. ChOH, ChOMe, ChIm, NaOH and KOH are selected as the repre-
sentative catalysts for biodiesel synthesis. As shown in Table 1,
the biodiesel yield of ChIm catalyst is only 76.9%, and ChOMe cat-
alyst shows an increase in biodiesel production compared with
ChIm catalyst, but it is still not the best choice for the present
study. ChOH catalyst effectively enhances the biodiesel production,
the biodiesel yield reaches 95.0%, which is found to be even higher
than that of traditional basic catalysts NaOH (93.1%) and KOH
(92.2%). It is worth to mention that there is no soap formation
when ChOH catalyst dosage is 210 wt.% based on the weight of
the reactants, however, soap will appear when catalyst dosage is
over 2.5% for NaOH and KOH under same reaction conditions. Thus,
ChOH is selected as the catalyst in the following work.
3.2. Effect of n(Methanol)/n(Soybean Oil)
4
The relation between molar ratio of methanol to soybean oil
n(Methanol)/n(Soybean Oil) and the catalytic performance of
ChOH catalyst is investigated. The yield of biodiesel is shown in
Fig. 1 as a function of n(Methanol)/n(Soybean Oil). As can be seen
in Fig. 1, the yield of biodiesel steeply increases at a low n(Metha-
nol)/n(Soybean Oil), followed by a gradual decrease at n(Metha-
nol)/n(Soybean Oil) > 15:1. The increase in the amount of
methanol will produce two different effects to the reaction. On
the one hand, the increase of the reactant methanol can enhance
the conversion rate of soybean oil, hence increasing the biodiesel
yield, which is advantageous to the reaction and dominant at
Table 1
Catalytic performances of different basic catalysts.
Entry Catalyst Catalyst dosage (wt.%) Yield of biodiesel (%)
1 ChOH 4 95.0 1.7
2 ChOMe 4 88.3 1.8
3 ChIm 4 76.9 1.9
4 NaOH 2 93.1 1.1
5 KOH 2 92.4 1.2
Reaction conditions: 60 C, 2.5 h, methanol: soybean ratio of 9:1.
Fig. 1. Effect of n(Methanol)/n(Soybean Oil) on biodiesel production. (Reaction
conditions: 60 C, 2.5 h, catalyst dosage 4 wt.%.)
336 M. Fan et al. / Applied Energy 108 (2013) 333339

Fig. 2. Effect of catalyst dosage on biodiesel production. (Reaction conditions: 60 C,

2.5 h, methanol:soybean ratio of 9:1.) Fig. 3. Effect of reaction temperature on biodiesel yield. (Reaction conditions: 2.5 h,
methanol: soybean ratio of 9:1, catalyst dosage 4 wt.%.)

n(Methanol)/n(Soybean Oil) < 9:1. On the other hand, the increase

of the reactant methanol may lead to a relative decrease in the con-
centration of soybean oil and the catalyst, although the absolute
amount of catalyst increases slightly, which is disadvantageous
to the reaction and dominant at n(Methanol)/n(Soybean
Oil) > 15:1. Under the present reaction conditions, the optimum
n(Methanol)/n(Soybean Oil) for the biodiesel synthesis is about
9:1 considering both factors of biodiesel yield and reactant meth-
anol consumption.

3.3. Effect of catalyst dosage

The inuence of catalyst dosage on biodiesel synthesis is sum-

marized as shown in Fig. 2, and the catalyst dosage represents
the mass ratio of ChOH catalyst and the reactants (methanol/oil
mixture), m(catalyst):m(reactants). As can be observed from
Fig. 2, there are distinct increasing trends in biodiesel yield as
the catalyst dosage increases. The biodiesel yield was steeply in-
creased from 73.8% to 95.0% with an increase of catalyst dosage
from 1 wt.% to 4 wt.%, followed by a gradual leveling off at a cata- Fig. 4. Effect of biodiesel production with reaction time. (Reaction conditions:
lyst dosage >4 wt.%. Thus, it should be pointed out that the optimal 60 C, methanol: soybean ratio of 9:1, catalyst dosage 4 wt.%.)

catalyst dosage 4 wt.% was chosen for the production of biodiesel.

3.4. Effect of reaction temperature
Fig. 3 gives the effect of reaction temperature on the biodiesel
yield at atmospheric pressure. As can be seen, the biodiesel yield
increases with the change of reaction temperature from 30 C to
60 C and then decreases. Fig. 3 suggests that increasing reaction
temperature will improve catalytic activity in a certain extent
but higher reaction temperature may result in methanol evaporat-
ing quickly, which is an unfavorable factor for improving the con-
version of soybean oil. Thus, an optimum reaction temperature
exists for catalytic activity, which is about 60 C.
3.5. Effect of reaction time
Fig. 4 shows the effect of reaction time in the range of 0.54.5 h
on the biodiesel yield at atmospheric pressure. As expected, reac-
tion time affects the synthesis reaction for biodiesel very clearly.
Only 85.2% of biodiesel is produced at the reaction time of 0.5 h,
but its formation is increased with the increase of the reaction time
from 0.5 h to 2.5 h. When the reaction time was increased from
2.5 h to 4.5 h, the yield of biodiesel remained almost unchanged.
Conclusively, 2.5 h could be the optimal reaction time for the
reaction.
3.6. Effect of different alcohols
The biodiesel yields for the different alcohols (methanol, etha-
nol, propanol, isopropanol, butanol) are shown in Fig. 5. The type
of alcohols used affects the synthesis reaction for biodiesel very
obviously, which is perhaps because of the different dissociation
degree of the ve alcohols in oil phase. For alcohols, the more
substituted alkyl the alcohol gets, the weaker dissociation degree
the alcohol has. Therefore, the acidity decreased as the alkyl group
substitution increased [27]. Methanol can be easier to form alkox-
ide ions compared with the other four counterparts, which is help-
ful to the transesterication reaction. From Fig. 5, it is interesting
that only 10.6% of biodiesel is produced when isopropanol is em-
ployed, it is supposed that the higher steric hindrance of isopropa-
nol inhibits the ester exchange process to a great extent. In
summary, methanol is the best alcohol for biodiesel synthesis.
 M. Fan et al. / Applied Energy 108 (2013) 333339
Fig. 5. Catalytic performances of different alcohols. (Reaction conditions: 60 C,
2.5 h, alcohol: soybean ratio of 9:1, catalyst dosage 4 wt.%.)
Fig. 6. Reusability of ChOH catalyst. (Reaction conditions: 60 C, 2.5 h, methanol:
soybean ratio of 9:1, catalyst dosage 4 wt.%.)
3.7. Reusability of ChOH catalyst
The experiments were done to test the reusability of ChOH cat-
alyst, and the results were summarized as shown in Fig. 6. From
Fig. 6, the yield of biodiesel is appreciably lower than that for the
fresh catalyst. The biodiesel yield remains 90.1% when the ChOH
is employed for the second time, and the ChOH catalyst still yields
82.5% after four successive uses. Therefore, it can be concluded
from the results that ChOH catalyst not only exhibits a favorable
catalytic performance during the transesterication reaction but
also has perfect utility for repeated use.
3.8. Basicity test
The pH values for methanol solution containing different con-
centrations of basic catalysts were shown in Table 2. As seen in Ta-
ble 2, the pH values of three ionic liquids were high, which have
shown strong basicity. It was suggested that ionic liquids had ion-
ization ability in methanol solution. The basicity of ionic liquids
was near the traditional alkali. Among them, the ionic liquid ChOH
gave better ionization ability in methanol solution, which
337
Table 2
The basicity of different basic catalysts a.
C (mol/L) pH
0.1 0.3 0.6
ChOH 12.92 13.76 13.80
ChOMe 11.94 12.30 12.55
ChIM 12.47 12.74 12.94
NaOH 12.15 12.34 12.51
KOH 12.40 12.83 13.16
a
Determining conditions: solvent: methanol, T = 25 C.
facilitated the enhancement of catalytic activity. It may be as
new environment friendly catalyst to take the place of traditional
basic catalyst like NaOH, KOH and so on.
3.9. The proposed reaction mechanism
The transesterication of soybean oils with methanol to biodie-
sel is a typical nucleophilic substitution reaction. It was that nega-
tively charged nucleophiles attack the positively charged carbonyl
carbon of the original. The proposed reaction mechanism of ionic
liquids catalysts is illustrated in Scheme 1, based on the present
experimental observations. As known, the OH of basic ionic liquid
acted as active center on biodiesel synthesis through transesteri-
cation of methanol. In our case, the ionic liquids catalysts have two
OH groups. It is suggested that both OH groups as active centers
interact with isolated electron pair at O atom in methoxyl group.
Firstly, the methoxyl group from methanol is activated by the
active species OH. The methoxyl group after activating is attacked
by carbonyl group of triglyceride. The intermediate with methoxyl
group translated into diglyceride group with producing methyl es-
ter. Further, when methanol as reactants entered the catalysts sys-
tem, the intermediate products diglyceride group react rapidly
with nucleophilic reagent (CH3OH) to produce methoxyl group
and diglyceride. Finally, the other carbonyl group of diglyceride
is also attacked by methoxyl group after activating with producing
methyl ester in the same way. In the reaction system, the extrac-
tion of glycerol from the reaction intermediate facilitates the bio-
diesel production. It was supposed that the catalytic activity of
ChOH ionic liquid catalysts for the transesterication of triglycer-
ide with CH3OH depends strongly on their capability of activating
the methoxyl group by the active species OH of basic ionic liquid,
which was not only related with the basicity, but also with the
intermiscibility in the reactants.
3.10. Structure characterization
In order to prove the proposed reaction mechanism, the reac-
tion intermediates were characterized by quasi in situ IR. Infrared
spectra of the mixture of methanol and ChOH catalyst were re-
corded to aid the interpretation of the reaction intermediates pre-
sented under reaction conditions. Spectra of methanol, ChOH
catalyst and the mixture of methanol and ChOH catalyst at 60 C
are shown in Fig. 7, respectively. A strong band in the spectrum
of methanol is seen at 1026 cm1, which is attributable to metha-
nol in liquid phase. After a contact time of 30 min, bands appear at
1014 cm1, due to the CAO stretching vibrations of the methoxyl
group [28,29], which is likely due to methoxyl group formed dur-
ing the initial reaction stage. It is reasonable to suppose that the
methoxyl group from methanol is activated by the active species
OH and formed.
The infrared spectrum of the mixture at 60 C is shown in Fig. 8.
Bands are seen at 1750 cm1 due to the anti-symmetric and sym-
metric C@O stretching vibrations of carbonyl group for ester. A
338 M. Fan et al. / Applied Energy 108 (2013) 333339

Scheme 1. The proposed reaction mechanism of ChOH ionic liquids catalysts.

evidenced by the progressive increase in the intensities of the

bands at 1171, and 1198 cm1. From Fig. 8, the intensities of two
bands at 1439 and 1461 cm1 increased with the reaction from D
to F, which was related to the deformation of CH2 and CH3 groups
when the oil converted to biodiesel.

4. Conclusion

In this work, the basic ionic liquid catalysts for synthesis of bio-
diesel from soybean oil were evaluated in terms of yield of biodie-
sel. The ChOH catalyst showed better catalytic performance when
n(Methanol)/n(Soybean Oil) was 9:1 and catalyst dosage was
4 wt.%. The appropriate reaction temperature was 60 C, and the
favorable reaction time was 2.5 h. The reusability test showed that
ChOH catalyst had perfect utility for repeated use. The basic ionic
liquid ChOH possessed better basicity in methanol solution, which
promoted the catalytic performance. The reaction intermediates
methoxyl group formed has been proved using quasi in situ infra-
red spectroscopy. These pathways are supported by experiments
Fig. 7. IR of methanol, ChOH and the mixture under 60 C. (A: ChOH; B: Methanol;
involving the formation of fatty acid methyl ester.
and C: the mixture of Methanol and ChOH under 60 C for 30 min.)

Acknowledgements

The nancial supports from the Specialized Research Fund for

the Doctoral Program of Higher Education (New Teachers) (Grant
No. 20100093120003), the National Natural Science Foundation
of China (NSFC) (Grant No. 21106054) and the Fundamental Re-
search Funds for the Central Universities (JUSRP211A07) are grate-
fully acknowledged.

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