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Fuel 87 (2008) 216221

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Transesterication of soybean oil to biodiesel using CaO

as a solid base catalyst
Xuejun Liu, Huayang He, Yujun Wang *, Shenlin Zhu, Xianglan Piao
State Key Laboratory of Chemical Engineering, Tsinghua University, Beijing 100084, China
Received 23 October 2006; received in revised form 18 April 2007; accepted 19 April 2007
Available online 21 May 2007

Abstract
In this study, transesterication of soybean oil to biodiesel using CaO as a solid base catalyst was studied. The reaction mechanism
was proposed and the separate eects of the molar ratio of methanol to oil, reaction temperature, mass ratio of catalyst to oil and water
content were investigated. The experimental results showed that a 12:1 molar ratio of methanol to oil, addition of 8% CaO catalyst, 65 C
reaction temperature and 2.03% water content in methanol gave the best results, and the biodiesel yield exceeded 95% at 3 h. The catalyst
lifetime was longer than that of calcined K2CO3/c-Al2O3 and KF/c-Al2O3 catalysts. CaO maintained sustained activity even after being
repeatedly used for 20 cycles and the biodiesel yield at 1.5 h was not aected much in the repeated experiments.
 2007 Elsevier Ltd. All rights reserved.
Keywords: Biodiesel; Calcium oxide; Solid base catalyst; Transesterication; Soybean oil

1. Introduction
Transesterication of soybean oil to biodiesel (fatty acid
methyl ester, FAME) can be catalyzed by bases, acids and
enzymes [1,2]. Base catalysts include homogeneous base
catalysts and heterogeneous base catalysts [3]. The commonly used homogeneous catalysts are NaOH, KOH and
their alkoxides. Homogeneous alkali-catalyzed transesterication is much faster than acid-catalyzed transesterication [4]. However, a large amount of water is required to
transfer the catalysts from the organic phase to a water
phase after the reaction. Therefore, it is considerably more
costly to separate the catalyst from the produced solution
[57].
Heterogeneous base catalysts have many advantages:
they are noncorrosive, environmentally benign and present
fewer disposal problems. Meanwhile, they are much more

Corresponding author. Tel.: +86 10 62773017; fax: +86 10 62770304.

E-mail address: wangyujun@mail.tsinghua.edu.cn (Y. Wang).

0016-2361/$ - see front matter  2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2007.04.013

easily separated from the liquid products and can be

designed to give higher activity, selectivity and longer catalyst lifetimes [8,9]. Nowadays, many types of heterogeneous catalysts have been explored for transesterication
of vegetable oils to biodiesel, such as alkaline earth metal
oxides, various alkali metal compounds supported on alumina or zeolite [1013]. However, for most supported
alkali catalysts, the active ingredients are easily corroded
by methanol and they exhibit short catalyst lifetimes.
CaO has basic sites stronger than H = 26.5 and it has
been studied as a solid strong base catalyst by many
researchers [1417]. Producing biodiesel using CaO as a
solid base catalyst has many advantages, such as higher
activity, mild reaction conditions, long catalyst lifetimes,
low catalyst cost and so on. Reddy produced biodiesel
using Nanocrystalline Calcium Oxides under room-temperature. But, the reaction rate was slow and it required
624 h to obtain high conversion with their most active catalyst. He also observed deactivation after eight cycles with
soybean oil and after three cycles with poultry fat [18]. Zhu
obtained a 93% conversion of jatropha curcas oil using
CaO as a catalyst. But, the catalyst must be treated with

X. Liu et al. / Fuel 87 (2008) 216221

an ammonium carbonate solution and calcinated at high

temperature [19].
Zhang et al. found that water caused a signicant
increase in activity and selectivity of diacetone alcohol
when MgO was used as a solid base catalyst. They proposed that basic OH was an active site for aldol addition
of acetone [20,21]. Kusdiana and Saka proposed that
water could act as a stronger catalyst than methanol alone
and the presence of a certain amount of water could
enhance the methyl ester formation in the transesterication reaction with supercritical methanol [22]. In the present work, we found that the catalytic activity of CaO in the
transesterication of soybean oil to biodiesel was enhanced
with the addition of a little water into methanol. Besides,
we propose the transesterication reaction mechanism in
the presence of a little water in methanol, then, we investigate the eects of the reaction conditions and the catalyst
lifetime.
2. Experimental
2.1. Materials and catalyst preparation
Rened soybean oil was purchased from Tianjin Jiali Oil
Plant. The fatty acid composition consisted of, palmitic
acid 12.5%, stearic acid 5.2%, oleic acid 23.5%, linoleic acid
47.8%, linolenic acid 10%, and traces of other acids. CaO
was purchased from Beihua Fine Chemical Co., Beijing.
It has basic sites stronger than H = 26.5 and the BET surface area is 0.56 m2/g. Analytical reagents (e.g. standards)
were of high performance liquid chromatography (HPLC)
grade and obtained from Sigma Chemical Co. All other
chemicals were analytical reagents (AR) and were purchased from Beihua Fine Chemical Co., Beijing. For comparison with other catalysts, K2CO3 and KF loaded on
c-Al2O3 were prepared by an impregnation method from
aqueous solution. The composite catalysts were dried in
an oven at 120 C for 12 h, and then calcined in a mue
furnace at 550 C for 5 h.
2.2. Reaction procedures
Transesterication reactions were carried out in a
100 mL glass reactor with a condenser. The magnetic stirring rate was 800 rpm. The reaction procedure was as follows: First, the catalyst was dispersed in methanol under
magnetic stirring. Then, the soybean oil was added into
the mixture and heated by water circulation. Samples were
taken out from the reaction mixture every 0.5 h. Except
where otherwise stated, the amount of raw material was
50 ml soybean oil and the water mass content in methanol
was 2.03% by weight of soybean oil. In the end, the excess
methanol was distilled o under vacuum. After the products were centrifugated, it formed three phases, the upper
layer was biodiesel, the middle layer was glycerol, and
the lower layer was a mixture of solid CaO and a small

217

amount of glycerol. The biodiesel was collected for chromatographic analysis rstly. CaO and little glycerol in the
residua were separated after removal of glycerol layer.
Thereinto, more than 99.9% glycerol was removed by centrifugation. The water wash can remove all CaO basically.
The centrifugation can only remove a majority of CaO.
However, little CaO has not any eect on the GC analysis
of biodiesel yield in the experiments. Filtration is a good
method to remove all CaO in a commercial production.
The biodiesel samples were analyzed by a HP 6890
gas chromatograph equipped with a ame ionization
detector and a capillary column HP-INNOWAX
(30 m 0.15 mm). Because the capillary column cannot
endure the high temperature of 380 C, we made the suitable GC conditions for our apparatus after referred the
standards ASTM D6584. Four microliter of the upper oil
layer was dissolved in 300 ll of n-hexane and 100 ll of
internal standard solution (heptadecanoic acid methyl
ester-n-hexane solution) for GC analysis. Samples (1 ll)
were injected by a sampler at an oven temperature of
220 C. After an isothermal period of 4 min, the GC oven
was heated at 10 C/min to 230 C. Nitrogen was used as
carrier gas at a ow rate of 2 ml/min measured at 20 C
and detector made up gas at a ow rate of 30 ml/min.
The inlet pressure was 96.4 kPa. The split ratio was 10:1.
The injector temperature and detector temperatures were
300 C and 320 C, respectively. The mass concentration
of FAME was obtained by the GC, and the biodiesel yield
was calculated by the following expression:
mactual
C esters  n  V esters
 100% 
 100%
mtheoretical
moil
C esters  n  V oil
C esters  n

 100% 
 100%
qoil
moil

yield

where both mactual (g) and mtheoretical (g) are the mass of
FAME; moil (g) the mass of soybean oil; and Cester (g/ml)
is the mass concentration of FAME which was acquired
by GC; n the diluted multiple of FAME; qoil (g/ml) the
density of soybean oil; and Vesters (ml) and Voil (ml) are
the volumes of FAME layer and soybean oil, respectively
[23].
3. Results and discussion
3.1. Mechanism of transesterication reaction over CaO
in the presence of a little water
As a basic site of CaO solid base catalyst, surface O2
extracts H+ from H2O to form surface OH (Eq. (1)),
which is easily extracted by reactants in chemical reactions.
Then, the OH extracts H+ from methanol to generate
methoxide anion and H2O (Eq. (2)). Methoxide anion is
strongly basic and has high catalytic activity in transesterication reactions [3]. Also, O2 can also extract H+ from
the hydroxyl group of methanol to form surface methoxide
anions (Eq. (3))

218

X. Liu et al. / Fuel 87 (2008) 216221

2
3
The mechanism of transesterication of glyceride to biodiesel in the presence of methoxide anion is as follows: In
the rst step, the methoxide anion attaches to the carbonyl
carbon atom of the triglyceride molecule to form a tetrahedral intermediate (Eq. (4)). In the second step, the tetrahedral intermediate picks up an H+ atom from the surface of
CaO (Eq. (5)). The tetrahedral intermediate also can react
with methanol to generate methoxide anion (Eq. (6)). In
the last step, the rearrangement of the tetrahedral intermediate results in the formation of biodiesel and glycerol (Eq.
(7)) [3]. The overall reaction can be expressed by Eq. (8),
where R1, R2 and R3 represent long chain alkyl groups

little water (no more than 2.8% by weight of soybean oil),

the transesterication reaction rate can be accelerated and
the biodiesel yield is improved within a short reaction
time.
However, if too much water (more than 2.8% by weight
of soybean oil) is added to methanol, the fatty acid methyl
ester will hydrolyze under basic conditions to generate fatty
acid (Eq. (9)), which can react with CaO to form soap.
The infrared spectra of CaO (a, AR), CaO (b, which was
dried at 120 C for 30 min to remove the physically
adsorbed molecules after being dipped in methanol containing 2.03% water) and Ca(OH)2 (c) are shown in
Fig. 1. The absorption band of the OH group appeared
at 3650 cm1. The IR spectra of CaO (b) showed that there
was no band of methoxide anions and the OH group band
became broader and higher than that of CaO (a, AR). The
results indicated that the amount of CaO on the surface
OH group increased after the sample was dipped into
methanol containing a little water. The OH was more easily adsorbed on the surface of the catalyst than methoxide

9
In the presence of a little water, CaO generates more
methoxide anions, which are the real catalysts of transesterication of glyceride to biodiesel. As a result, by adding a

Fig. 1. IR analysis of dierent CaO samples. (a) Analytical reagent CaO;

(b) dried CaO after being dipped in methanol containing 2.03% water; and
(c) Ca(OH)2.

100

100

80

80

AR
0. 84%
2. 03%
2. 80%

60

40

Biodiesel Yield / %

Biodiesel Yield / %

X. Liu et al. / Fuel 87 (2008) 216221

219

60

2. 03%
AR

40

20
20

0
0.0

0.5

1.0

1.5

2.0

2.5

3.0

Time / h

anions. The IR spectra of Ca(OH)2 showed that the bands

of OH appeared at 36004000 cm1, which was dierent
than the IR spectra of CaO.
3.2. Eect of water content in methanol on biodiesel yield
In the alkaline-catalyzed transesterication of soybean
oil to biodiesel, water has important eects on the biodiesel yield. The experiments were carried out under the
conditions of 8% CaO by weight of oil, 6:1 molar ratio
of methanol to oil, 65 C and 3 h of reaction. Fig. 2 shows
the eects of the water content in methanol on the biodiesel
yield for various amounts of water in methanol. The results
show that the biodiesel yield increased with the rising water
content in methanol. It was only 80% at 3 h when analytical reagent methanol was used. In contrast, the biodiesel
yield reached 95% when the water content was in excess
of 2.03%. Water molecules were adsorbed dissociatively
on the CaO surface to form OH groups (Eq. (1)), which
accelerated the transesterication reaction rate. However,
the water content in methanol should be kept under 2.8%
to prevent soap formation.
3.3. Eect of molar ratio of methanol to oil on biodiesel yield
The biodiesel yield could be improved by introducing
excess amounts of methanol to shift the equilibrium to
the right-hand side. The experimental results, illustrated
in Fig. 3, indicate the molar ratio of methanol to oil has
a signicant impact on the biodiesel yield. The biodiesel
yields grew as the molar ratio increased, and the yield
was 75% at a 12:1 molar ratio of methanol to oil when analytical reagent methanol was used. In comparison, the biodiesel yield increased from 61% to 97% when the molar
ratio was increased from 3:1 to 12:1 at a 2.03% water content in methanol. However, the yields were slightly reduced
when the ratio of methanol to oil was higher than 12:1, and

12

15

18

Molar Ratio of Methanol to Oil

Fig. 3. Eect of molar ratio of methanol to oil on biodiesel yield. CaO/oil
mass ratio: 8%; reaction temperature: 65 C; reaction time: 1.5 h; water
content: 2.03%.

the biodiesel yield was only 90% at 18:1. The reason is that
the catalyst content decreased with increase of methanol
content. Therefore, the optimum molar ratio of methanol
to oil was 12:1.
3.4. Eect of reaction temperature on biodiesel yield
In the presence of heterogeneous catalysts, the reaction
mixture constitutes a three-phase system, oilmethanol-catalyst, in which the reaction would be slowed down because of
the diusion resistance between dierent phases. However,
the reaction rate can be accelerated at higher reaction temperatures. As shown in Fig. 4, the reaction rate was slow at
low temperatures, but the biodiesel yield rst increased and
then decreased with the increase of the reaction temperature.
Generally, a more rapid reaction rate could be obtained at
100

80

Biodiesel Yield / %

Fig. 2. Eect of water content of methanol on biodiesel yield. CaO/oil

mass ratio: 8%; reaction temperature: 65 C; methanol/oil molar ratio: 6:1.

60

2.03%
AR

40

20

0
50

55

60

65

70

75

80

Temperature/C
Fig. 4. Eect of reaction temperature on biodiesel yield. CaO/oil mass
ratio: 2%; methanol/oil molar ratio: 6:1; water content: 2.03%.

X. Liu et al. / Fuel 87 (2008) 216221

high temperatures, but at high temperatures, methanol was

vaporized and formed a large number of bubbles, which
inhibited the reaction on the three-phase interface. Therefore, the optimum reaction temperature was 65 C.
3.5. Eect of mass ratio of catalyst to oil on biodiesel yield
Fig. 5 shows the eects of the mass ratio of catalyst
to oil. The results indicate that the biodiesel yield was
signicantly improved with the increase of CaO. The biodiesel yield reached 90% after 3 h when the CaO/oil mass
ratio was 8%. However, only 55% yield was obtained at a
2% CaO/oil mass ratio. It was also recognized that the catalytic activity was extremely inuenced by alkalinity, but
the eect of CaO amount on biodiesel yield was slight when
the mass ratio of CaO to oil was above 8%. In these conditions, the intensication of mass transfer becomes more
important than increasing the amount of catalyst.
3.6. Eect of repeated experiments on biodiesel yield
CaO, K2CO3/c-Al2O3 and KF/c-Al2O3 are representative heterogeneous solid base catalysts for the transesterication of vegetable oils to biodiesel. This study investigated
and compared their stability and activity in this reaction.
CaO was activated by methanol with 2.03% water in the
rst use, and the analytical reagent methanol was used in
the repeated experiments. Fig. 6 indicates that CaO-catalyzed biodiesel yields were in excess of 86% at 65 C at
1 h every time. It maintained sustained activity even after
being used for 20 cycles and the biodiesel yield was only
slightly decreased. When K2CO3/c-Al2O3 and KF/c-Al2O3
catalysts were used, analytical reagent methanol was used
because these catalysts are sensitive to water. The results
in Table 1 indicate that the activity of K2CO3/c-Al2O3
and KF/c-Al2O3 catalysts rapidly decreased during the
repeated experiments, the biodiesel yields decreased to
30.6% from 81.1% and 17.8% from 79.9% respectively after
100

Biodiesel Yield / %

80

60

40

1%
2%
4%
8%
12%

20

100

80

Biodiesel Yield / %

220

60

40

20

0
0

10

12

14

16

18

20

Number of Repetitions (-)

Fig. 6. Eect of repeated use of CaO on biodiesel yield. CaO/oil mass

ratio: 8%; methanol/oil molar ratio: 12:1; reaction temperature: 65 C;
reaction time: 1.5 h.
Table 1
Eect of repeated use of K2CO3/c-Al2O3 and KF/c-Al2O3 catalysts on
biodiesel yield
Repeated times

K2CO3/c-Al2O3
KF/c-Al2O3

81.1%
79.9%

77.1%
75.7%

51.3%
38.6%

30.6%
17.8%

Catalyst/oil weight ratio: 8%; methanol/oil molar ratio: 6:1; reaction

temperature: 70 C; reaction time 1.5 h.

used four times. This was because alkali metal compounds

are dissolvable in methanol. Methanol corroded the active
ingredients and the biodiesel yields decreased in the
repeated experiments. For most supported alkali catalysts,
they have the same properties and exhibit short catalyst
lifetimes. Peterson also found that NaOCH3 catalyst disassociated from the SiO2 support and went into the solution
[14].
The stoichiometry of this reaction requires 0.134 volume
methanol per volume triglyceride (the molar ratio is 3:1).
The volume of methanol only increased 26.8% by volume
of oil when the ratio was increased from 6:1 to 12:1. The
amount of CaO can be decreased if a larger surface area
of catalyst is employed. Though the reaction time is relatively longer than that of the homogeneous catalysts, it
does not require too much time to dispose of the products,
for example, neutralization, washing and drying. If the catalyst can be used commercially, ltration is a possible way
to recycle the catalyst and decrease the cost. As a heterogeneous solid base catalyst, CaO has a longer catalyst lifetime
and better stability than current homogeneous catalysts. It
is cheaper, noncorrosive and environmentally benign. It
can be applied to produce biodiesel commercially.

0
0.0

0.5

1.0

1.5

2.0

2.5

3.0

4. Conclusions

Time / h
Fig. 5. Eect of mass ratio of CaO to oil on biodiesel yield. Methanol/oil
molar ratio: 6:1; reaction temperature: 65 C; water content: 2.03%.

Water has an important impact on biodiesel yield in the

transesterication of soybean oil to biodiesel using CaO as

X. Liu et al. / Fuel 87 (2008) 216221

a solid base catalyst. It was observed that a small amount

of water increased the reaction rates compared to anhydrous conditions. A 12:1 molar ratio of methanol to oil,
addition of 8% CaO catalyst, 65 C and 2.03% water content in methanol gave the best results, and the biodiesel
yield exceeded 95% at 1.5 h of reaction.
Acknowledgements
The authors thank Jie Ma and Lianyuan Wang for their
kind help.
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