Bioresource Technology 100 (2009) 696700

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Bioresource Technology
journal homepage: www.elsevier.com/locate/biortech

Acceleration of catalytic activity of calcium oxide for biodiesel production

Ayato Kawashima *, Koh Matsubara, Katsuhisa Honda
Environmental Science for Industry, Faculty of Agriculture, Ehime University, 3-5-7 Tarumi, Matsuyama, Ehime 790-8566, Japan

a r t i c l e

i n f o

Article history:
Received 24 April 2008
Received in revised form 25 June 2008
Accepted 26 June 2008
Available online 5 August 2008
Keywords:
Biodiesel
Heterogeneous catalyst
Transesterification
Calcium oxide
Activation

a b s t r a c t
This research was aimed at studying the acceleration of the catalytic activity of calcium oxide (CaO) for
developing an effective heterogeneous catalyst for biodiesel production by the transesterification of plant
oil with methanol. CaO was activated by pretreatment with methanol and was used for the transesterification reaction. The activation and transesterification reaction conditions were examined. The obtained
optimal reaction conditions were 0.1-g CaO, 3.9-g methanol, 15-g rapeseed oil, and 1.5-h activation time
at room temperature that provided methyl ester in approximately 90% yield within a reaction time of 3 h
at 60 !C. The activation mechanism was also investigated, and the proposed mechanism is as follows. By
pretreatment with methanol, a small amount of CaO gets converted into Ca(OCH3)2 that acts as an initiating reagent for the transesterification reaction and produces glycerin as a by-product. Subsequently, a
calciumglycerin complex, formed due to the reaction of CaO with glycerin, functions as the main catalyst and accelerates the transesterification reaction.
" 2008 Elsevier Ltd. All rights reserved.

1. Introduction
In recent years, global warming, environmental pollution, and
depletion of fossil resources due to heavy consumption have become major issues of global dimensions. Biomass energy is expected to resolve these issues and has gained international
attention as a source of renewable and environment-friendly energy. Biodiesel fuel, fatty acid methyl ester (FAME), produced by
the transesterification of vegetable oils and animal fats with methanol has the following characteristics: it is a biomass-derived fuel
and is free from aromatic compounds, and it has high biodegradability and low SOx and particulate matter content in diesel fumes
(Graboski and McCormick, 1998; Schuchardt et al., 1998; Ma and
Hanna, 1999). Therefore, FAME is expected to be one of the
biomass-derived alternatives to petroleum-derived diesel fuels.
Currently, FAME is commonly produced by performing a transesterification reaction with homogeneous base catalysts such as KOH
or NaOH dissolved in methanol. This production process can provide high FAME yields under mild conditions atmospheric pressure, a temperature of 60 !C, and a reaction time of
approximately 1 h (Vicente et al., 2004; Meher et al., 2006a). However, for its safe and practical application as diesel fuel in the market, the produced FAME is required to be purified by removing
impurities such as base catalyst and glycerin using a water washing process that is cumbersome and requires the disposal of a large
amount of basic water. Moreover, the total cost of this process is

* Corresponding author. Tel.: +81 89 946 9970; fax: +81 89 946 9980.
E-mail address: a-kawa@agr.ehime-u.ac.jp (A. Kawashima).
0960-8524/$ - see front matter " 2008 Elsevier Ltd. All rights reserved.
doi:10.1016/j.biortech.2008.06.049

not sufficiently competitive as compared to the cost of petroleum-derived diesel fuels.

In order to solve these problems, several types of FAME production processes have been studied: homogeneous acid-catalyzed
process (Freedman et al., 1984; Edgar et al., 2005), supercritical
process (Demirbas, 2006; Minami and Saka, 2006), enzymatic process (Shimada et al., 2002; Nie et al., 2006; Akoh et al., 2007), and
heterogeneous catalyst process. In particular, the heterogeneous
catalyst process has been extensively researched from the viewpoint of simplifying the production and purification processes,
decreasing the amount of basic waste water, downsizing the process equipment, and, in consequence, reducing the environmental
impact and process cost. Heterogeneous catalysts are of two types
acids and bases. The advantage of using acid heterogeneous catalysts is that they are capable of esterifying the fatty acids in rapeseed oil; many acid heterogeneous catalysts have been reported,
such as sulfated metal oxide (Furuta et al., 2004; Jitputti et al.,
2006), heteropolyacid (Narasimharao et al., 2007), sulphonated
amorphous carbon (Toda et al., 2005), acid ion exchange resin
(Lpez et al., 2007; Kiss et al., 2006), etc. However, acid catalysts
generally exhibit weak catalytic activities and require high reaction
temperatures and long reaction times. On the other hand, base catalysts exhibit high catalytic activities, and a number of basic heterogeneous catalysts have been developed, e.g., metal oxides (Xie et
al., 2006; Meher et al., 2006b), zeolites (Suppes et al., 2004), hydrotalcites (Cantrell et al., 2005), and anion exchange resins (Shibasaki-Kitakawa et al., 2007). Among these base catalysts, CaO is one of
the well-researched heterogeneous catalysts as it has a higher basicity, lower solubility, lower price, and is easier to handle than
KOH. However, its transesterification reaction rate is insufficient

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A. Kawashima et al. / Bioresource Technology 100 (2009) 696700

2. Experimental
2.1. Chemicals
Commercial edible-grade rapeseed oil was purchased from the
market and used without further purification. Other chemicals
such as CaO, FAME that was used as the standard substance, and
solvents were obtained from Wako Pure Chemical Industries (Osaka, Japan), Kanto Chemical Co. Inc., (Tokyo, Japan), and Sigma-Aldrich Corporation (Missouri, USA), respectively. The purchased
CaO (up to 99.9% purity) was used without further treatment.
2.2. Catalytic activation and activity measurements
The catalytic activities for the transesterification of oil were
measured by performing a batch-type reaction. The standard activation and reaction conditions were as follows. A given amount of
CaO and 3.9 g of methanol were placed in a 50-ml two-necked flask
equipped with a reflux condenser and stirred for 1 h at 25 !C for
activation. Next, 15 g of rapeseed oil was added to the mixture;
the mixture was stirred using a magnetic stirrer and subsequently
heated at 60 !C in an oil bath for 10 h. Small aliquots of this reaction mixture were sampled for studying the progress of the reaction. As for the activation by glycerin, CaO was mixed with
glycerin for a few minutes at 60 !C; subsequently, the solid phase
of the reaction mixture was separated. The transesterification reaction with methanol and rapeseed oil was then performed in a similar manner.
Quantitative determinations of the FAME yield were performed
as follows. The liquid phase of the reaction mixture was collected
and was evaporated under vacuum in order to remove the excess
methanol; then, the oil phase was separated from the reaction
mixture by centrifugation at 9170 g for 5 min. A methyl heptadecanoate solution was added as an internal standard to 100 mg of
the oil phase; this mixture was diluted to 5 ml with isooctane,
and 2 ll of the resulting solution was subjected to a high-performance liquid chromatography (HPLC) analysis for the quantitative
determination of the FAME yield. The HPLC system consisted of a
JASCO PU-2089 pump, JASCO AS-2057 auto injector, and JASCO
RI-2031 differential refractive index (RI) detector (JASCO Corp., To-

kyo, Japan). Data was collected and analyzed using JASCO Borwin
software. The mobile phase was methanol at a flow rate of
1.0 ml/min. The columns were 250 mm ! 4.6 mm Intersil ODS-3
(GL Science Inc. Japan, Tokyo, Japan) and were protected using a
10 mm ! 4 mm Intersil ODS-3 guard column. The sample injection
volume was 2 ll, and the RI analyses were conducted at 35 !C. The
HPLC analysis was carried out two times for each sample and
methyl ester yield was calculated using the average value. The
yield was defined as the ratio of the weight of methyl esters determined by HPLC to the weight of the oil phase.
2.3. Catalyst characterization
X-ray powder diffraction (XRD) patterns were recorded on a
MiniFlex X-ray diffractometer using monochromatic CuKa radiation (Rigaku Corp., Tokyo, Japan). Data were collected over a 2h
range of 390! with a step size of 0.02! at a scanning speed of
4!/min.
The basic strengths of the catalysts (H_) were determined by
using Hammett indicators. Approximately 25 mg of the catalyst
was shaken with 5 ml of a solution of Hammett indicators diluted
with methanol and was left to equilibrate for 2 h. After the equilibration, the color of the catalyst was noted. The following Hammett indicators were used: neutral red (H_ = 6.8), bromthymol
blue (H_ = 7.2), phenolphthalein (H_ = 9.3), Nile blue (H_ = 10.1),
Tropaeolin O (H_ = 11.1), 2,4-dinitroaniline (H_ = 15.0), and 4nitroaniline (H_ = 18.4).
3. Results and discussion
3.1. Activation of CaO
First, we investigated the catalytic activity of nonactivated CaO
for the transesterification reaction. The reactions were performed
with the addition of (0.01 or 0.05 g) CaO to 15 g of rapeseed oil
and 3.9 g of methanol at 60 !C. As shown in Fig. 1, the reaction rate
for the initial few hours was very low, but it increased gradually;
the ester yields obtained after 10 h for 0.01 and 0.05 g of CaO were
64% and 87%, respectively. This acceleration of the reaction rate in
the middle of the reaction pathway indicated that the catalyst was
somehow activated during the initial part of the reaction. Since the
catalyst coexisted only with oil and methanol in this reaction system, it was considered that it was activated by a reaction with

100

KOH 0.05 g

80

FAME yield (%)

for practical applications (Peterson and Scarrah, 1984). Recently, it

has been reported that its catalytic activity can be improved by
employing thermal activation treatment such as calcination
(973 K) in order to remove the surface carbonate and hydroxyl
groups (Granados et al., 2007). It has also been demonstrated that
nanocrystallized CaO is an efficient catalyst for a transesterification
reaction due to the high surface area associated with the small
crystallite sizes and defects (Reddy et al., 2006). In addition to
these reports, there have been several other reports on heterogeneous catalysts. Some of these reported catalysts exhibit high catalytic activities for a transesterification reaction. However, there is
little information regarding their practical applicability.
Thus far, we have studied heterogeneous base catalysts containing CaO for FAME production and have found that the initial reaction rate of the transesterification reaction using these catalysts
was very low, but it increased subsequently. The cause for this increase in the reaction rate was that the catalyst was somehow activated during the initial part of the reaction (Kawashima et al.,
2008). On the basis of these observations, we studied a simple
and practical activation method of CaO for the development of
an effective catalyst for FAME production. CaO was activated by
pretreatment with methanol and was used for the transesterification reaction. The activation conditions and the mechanism were
also investigated.

Activated
CaO, 0.05 g

60

Nonactivated
CaO, 0.05 g

Activated
CaO, 0.01 g

40

20

Nonactivated
CaO, 0.01 g
0

Reaction time (h)

10

Fig. 1. Catalytic activity of nonactivated CaO (0.01 and 0.05 g), activated CaO (0.01
and 0.05 g), and KOH (0.05 g) in transesterification reaction of rapeseed oil with
methanol at 60 !C. CaO was activated with 3.9 g of methanol by stirring for 1 h at
25 !C.

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A. Kawashima et al. / Bioresource Technology 100 (2009) 696700

methanol. Therefore, we subsequently investigated the effect of

methanol pretreatment on CaO before the transesterification reaction. A 0.01 g and 0.05 g of CaO were pretreated with 3.9 g of methanol by stirring for 1 h at 25 !C; then, rapeseed oil was added and
the reaction was initiated at 60 !C. Fig. 1 illustrates that the reaction rate for the initial few hours with activated CaO was considerably higher than that with nonactivated CaO. For example, the
FAME yield at 3 h with 0.05 g of activated CaO was significantly
higher (88%) than that with 0.05 g of nonactivated CaO (5%). The
catalytic activities of an equimolar amount of KOH, which is commonly used as a homogeneous catalyst for FAME production, under
the same reaction conditions are also illustrated in Fig. 1. Activated
CaO exhibited a high catalytic activity as compared to KOH. The
yield with 0.05 g of activated CaO reached 80% after 2 h and
approximately 88% after 3 h. The reaction rate with activated
CaO was slightly slow, but the FAME yield with activated CaO
was equal to that with KOH. On the basis of these results, it is estimated that the activated CaO catalyst will be practically applicable
for FAME production as the KOH catalyst.
In order to evaluate the optimal reaction conditions for the
above-mentioned transesterification process with activated CaO,
we examined the effect of the following reaction parameters by
conducting a batch-type reaction: activation temperature, activation time, catalytic amount, and methanol quantity. In order to
investigate the effect of the activation temperature of CaO, 0.01 g
of CaO was activated with 3.9 g of methanol for 1 h at three temperatures, i.e., 25, 40, and 60 !C. Subsequently, oil was added to
the mixture, and the transesterification reaction was initiated at
60 !C. The observed reaction rates for all the activation temperatures were approximately equal. However, the final FAME yield
was the maximum for the activation temperature of 25 !C. Therefore, the optimal temperature determined for the activation of
CaO was 25 !C.
The effect of the activation time of CaO was then studied. 0.01 g
of CaO was activated with 3.9 g of methanol for 024 h at 25 !C;
then, oil was added to the mixture, and the transesterification reaction was initiated at 60 !C. Fig. 2 presents a plot of FAME yield versus reaction time for different activation times. The FAME yields at
3 h using CaO activated for 0.5 h and 1.0 h were approximately
60%, i.e., slightly lower than those, 7080%, using CaO activated
for longer time periods; the optimal activation time was considered to be 1.5 h. However, all the activated CaO samples exhibited

a higher catalytic activity for the transesterification reaction than

the nonactivated CaO samples.
The effect of the catalytic amount on the transesterification
reaction rate was studied using three different amounts, 0.01,
0.05, and 0.1 g, of CaO that were activated with 3.9 g of methanol
for 1.5 h at 25 !C. Fig. 3 indicates that 0.05 and 0.1 g of CaO exhibited almost the same catalytic activity and could produce nearly
90% FAME yields.
Finally, the influence of the amount of methanol was examined.
0.1 g of CaO was activated for 1.5 h at 25 !C with four different
amounts of methanol, 1.95 (13 wt% of oil), 3.9 (26 wt% of oil), 6
(40 wt% of oil), and 9 g (60 wt% of oil), which were equivalent to
3.6, 7.2, 10.8, and 16.5 molar ratios of methanol/oil, respectively.
Fig. 4 presents a plot of FAME yield versus reaction time for different amounts of methanol. The FAME yield with 13 wt% of methanol
was slightly low, but with more than 26 wt% of methanol, approximately 90% and equivalent FAME yields were obtained. Since a
transesterification reaction is reversible, the excess amount of
methanol was expected to increase the yield by shifting the equilibrium. Therefore, the transesterification reaction using the CaO
catalyst activated with more than 26 wt% of methanol was preferred. From these results, the optimized reaction conditions for
the transesterification reaction with activated CaO were as follows:
0.0033 g of CaO per gram of oil (0.05 g of CaO was added to 15 g of
oil), 26 wt% of methanol, an activation time of 1.5 h at 25 !C, and a
reaction temperature of 60 !C. Under these conditions, approximately 90% methyl ester yield can be obtained from a 3-h reaction.
A FAME production process using KOH as a homogeneous basic
catalyst is commonly performed by using a two-step reaction in order to obtain high FAME yields. Since the produced FAME is required to comply with the relevant quality standards, it is
necessary to minimize the amount of unreacted triglycerides and
byproducts such as monoglycerides and diglycerides for the effective refining of crude FAME. Therefore, we investigated the transesterification reaction by performing a two-step reaction using
activated CaO. The first step of the reaction was performed at
60 !C with 15 g of oil and 0.1 g of CaO, which was previously stirred
with 3.9 g of methanol for 0.5 h. As a result, 91% yield of methyl ester was obtained in 4 h. The ester phase was separated from the
reaction mixture. The second step was then performed in the same
manner as above using 0.05 g of CaO. The obtained methyl ester
yield reached up to 97% after 1 h from the start of the reaction.

80

80

FAME yield (%)

100

FAME yield (%)

100

60
24 h

40

6h
1.5 h

20
0

1h
0.5 h

60
40

0.01 g

20

0.1 g

0.05 g

Nonactivated

10

Reaction time (h)

Fig. 2. Influence of activation time on FAME yield of transesterification reaction
with methanol at 60 !C. 0.01 g of CaO was activated with 3.9 g of methanol for 0
24 h at 25 !C.

Reaction time (h)

10

Fig. 3. Influence of catalytic amount on reaction rate of transesterification reaction

with methanol at 60 !C. 0.01, 0.05, and 0.1 g of CaO were activated with 3.9 g of
methanol for 1.5 h at 25 !C.

A. Kawashima et al. / Bioresource Technology 100 (2009) 696700

100

FAME yield (%)

80

60

13 wt%

40

26 wt%
40 wt%

20

60 wt%
0

Reaction time (h)

10

Fig. 4. Influence of amount of methanol on transesterification reaction with

methanol at 60 !C. 0.1 g of CaO was activated for 1.5 h with four different amounts
of methanol at 25 !C.

These results indicated the possibility of the activated CaO catalyst

being used as an effective heterogeneous base catalyst for the
FAME production process.
3.2. Mechanism of activation
The mechanism behind the enhancement in the reaction rate as
a result of using the activated CaO catalyst was also investigated.
The XRD measurement of activated CaO, nonactivated CaO,
Ca(OH)2, and Ca(OCH3)2 was performed. CaO was activated by stirring with methanol for 1 h at 25 !C and was subsequently dried.
The XRD spectrum of activated CaO was similar to that of nonactivated CaO but exhibited small diffraction peaks, attributable to
Ca(OCH3)2 (2h = 10.8!) and Ca(OH)2 (2h = 18.0! and 34.1!). This implies that a small amount of activated CaO reacted with methanol
and was transformed to Ca(OCH3)2 and Ca(OH)2, but most of CaO
remained as is, i.e., a small amount of activated CaO reacted with
methanol and formed Ca(OCH3)2, and subsequently, H2O generated
during the formation of Ca(OCH3)2 reacted with the remaining CaO
and formed Ca(OH)2.
The basic strengths of the catalysts were then determined by
using the Hammett indicators. The measured basic strengths of
nonactivated CaO, Ca(OH)2, and activated CaO ranged from 10.1
to 11.1. On the other hand, Ca(OCH3)2 had a high basic strength
that ranged from11.1 to 15.0. These results suggest that Ca(OCH3)2
exhibited a higher catalytic activity for the transesterification reaction than CaO and Ca(OH)2.
As mentioned above, a small amount of activated CaO was converted to Ca(OCH3)2 that exhibited a higher catalytic activity than
CaO. However, the basic strength of activated CaO was nearly equal
to that of nonactivated CaO, and it appeared less probable that the
high catalytic activity of activated CaO resulted only from the formation of Ca(OCH3)2. Therefore, the presence of an activated species other than Ca(OCH3)2 was conceivable.
In the transesterification reaction of oil (triglycerides) and
methanol, glycerin is obtained as a by-product. Since glycerin is a
trihydric alcohol, it can react with CaO to form a CaO-glycerin complex, and there is a possibility that the obtained complex exhibits a
catalytic activity for the transesterification reaction. Therefore, we
performed a catalytic activity test on a CaO-glycerin complex that
was synthesized under conditions similar to those of the transesterification reaction: CaO was mixed with glycerin at 60 !C. An equimolar amount of CaO-glycerin complex to 0.1 g of CaO was stirred
with 15 g of oil and 3.9 g of methanol at 60 !C. As a result, it was
found that the catalytic activity of CaO activated with glycerin

699

was equivalent to that activated with methanol. We also compared

the XRD patterns of this CaO-glycerin complex to that of CaO used
in the transesterification reaction after activation with methanol at
the optimal condition mentioned above. As a result, the XRD pattern of the catalyst used in the transesterification reaction is almost the same as that of the CaO-glycerin complex. These results
revealed that CaO was converted into a CaO-glycerin complex during the transesterification reaction.
From these results, it is evident that the probable activation
mechanism of the transesterification reaction with methanol is
as follows. First, CaO is activated with methanol and a small
amount of CaO is converted into Ca(OCH3)2, which exhibits a higher catalytic activity than nonactivated CaO. Next, oil is transesterified by Ca(OCH3)2 to produce FAME and glycerin as by-products.
The produced glycerin reacts with CaO, and a CaO-glycerin complex is formed. Since this CaO-glycerin complex also exhibits a high
catalyst activity, the reaction advances further and generates more
glycerin. This process repeats itself and further accelerates the
transesterification reaction. Thus, the CaO catalyst activated with
methanol acts as an initiating reagent for the reaction to produce
glycerin; then, the CaO-glycerin complex, which is formed from
the generated glycerin and CaO, functions as the main catalyst
for the transesterification reaction.
4. Conclusions
In this study, we intended to examine the activated CaO catalyst
in order to develop an effective catalyst for the FAME production
process. We found that CaO activated with methanol was an efficient catalyst for a high-yield transesterification reaction. The optimal reaction conditions were 0.1 g of CaO and 3.9 g of methanol
added to 15 g of rapeseed oil and activation at 25 !C for 1.5 h,
which resulted in approximately 90% yield of methyl ester within
a reaction time of 3 h at 60 !C. We also investigated the activation
mechanism and demonstrated a probable scheme: Ca(OCH3)2 generated by the activation of CaO with methanol acts as an initiating
reagent for the transesterification reaction to produce glycerin;
then, the CaO-glycerin complex, which is formed from the generated glycerin and CaO, functions as the main catalyst and accelerates the transesterification reaction.
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