Energy Conversion and Management 51 (2010) 1428–1431

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Energy Conversion and Management

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

Biodiesel production by methanolysis of soybean oil using calcium supported on

mesoporous silica catalyst
Chanatip Samart a,*, Chaiyan Chaiya b, Prasert Reubroycharoen c,d
a
Department of Chemistry, Faculty of Science and Technology, Thammasat University, Klongluang, Pathumtani 12121, Thailand
b
Chemical Engineering Division, Faculty of Engineering, Rajamangala University of Technology Krungthep, Sathorn, Bangkok 10120, Thailand
c
Department of Chemical Technology, Faculty of Science, Chulalongkorn University, Phatumwan, Bangkok 10330, Thailand
d
Center for Petroleum, Petrochemicals and Advanced Materials, Chulalongkorn University, Phatumwan, Bangkok 10330, Thailand

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

Article history: The transesterification of soybean oil with a CaO/mesoporous silica catalyst was achieved. The effects of
Received 18 June 2009 CaO loading levels in the mesoporous silica catalyst, the amount of catalyst to substrate level and the
Accepted 29 January 2010 reaction temperature and time on the conversion of soybean oil were investigated. Increasing the tem-
Available online 24 February 2010
perature and reaction time raised the total conversion of soybean oil attained. The optimized condition,
found to be 15 wt.% of Ca loading on the mesoporous silica catalyst, a 5% (w/w) catalyst to oil level and a
Keywords: reaction temperature of 60 °C for 8 h, provided the highest yield of 95.2%. The fuel properties of the bio-
Biodiesel
diesel obtained under these optimized conditions were acceptable under the biodiesel standards of
Calcium
Heterogeneous catalyst
Thailand.
Soybean oil Ó 2010 Elsevier Ltd. All rights reserved.

1. Introduction

Biodiesel is an alternative, renewable, ecologically low polluting

on combustion and potentially sustainable energy resource for
supplementation and eventual replacement of the non-renewable
petroleum diesel, and is of growing interest as the world energy
crisis approaches. Biodiesel is produced by transesterification of
vegetable oils or animal fats with methanol (or ethanol) to obtain
the mono-alkyl ester [1], as shown (for methanol) in Eq. (1). Be-
cause it is derived from renewable biological sources, such as veg-
etable oils and animal fats [1], it is potentially more suitable for
agricultural countries, since although spent (waste) oils and fats
can be utilized as the substrates, which is an economically, ethi-
cally and environmentally important factor, the future demand
for biodiesel will outstrip the supply of spent oils and fats [1,3–
6]. In Thailand, the government has promoted 5% (v/v) biodiesel
(B5) in transport section since 2005 and it plans on implementing
the use of 100% biodiesel (B100) in 2011.
* Corresponding author. Tel./fax: +66 2 5644483.
E-mail address: chanatip@tu.ac.th (C. Samart).
ð1Þ
The conventional biodiesel production system is a homoge-
neous base catalyst system, using sodium hydroxide or potassium
hydroxide solution, to reduce the reaction temperature. The draw-
back of this system is that firstly it gives a saponified product,
especially in the presence of oils or fats with a free fatty acid level
of more than 0.5% (w/w) or a water content above 2% (v/v), as is
common in spent oils and fats as well as some plant oils. Pretreat-
ment with sulphuric acid and alcohol to prevent this saponification
is possible but is slow expensive and adds considerable environ-
mental and economic costs through additional wastewater produc-
tion. Secondly, this conventional process produces a lot of
environmentally unfriendly water, that is for every 5 l biodiesel
produced 1 l of raw biodiesel wastewater is discharged [7],
assuming no prior acid pretreatment to remove free fatty acids
which otherwise will increase this. Currently, greater than
350,000 l/day of biodiesel is produced in Thailand causing the for-
mation of at least 70,000 l/day biodiesel contaminated wastewater
of high pH and diesel content, that requires expensive treatment
prior to environmental discharge.

0196-8904/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.enconman.2010.01.017
 C. Samart et al. / Energy Conversion and Management 51 (2010) 1428–1431 1429

The supercritical fluid method is an alternative method that
solves the saponification problem in biodiesel production, but re-
quires a high temperature [2,8–10] and, therefore, the economic
and environmental costs of a high production energy requirement
[2,11].
A heterogeneous system is considered as a possible solution to
overcome these problems and, as such, heterogeneous catalysts
suitable for transesterification are divided into two types: a solid
alkali catalyst and an alkali support catalyst. Calcium oxide, used
as solid alkali catalyst in the transesterification of soybean oil,
showed a lower conversion yield of 85% when compared with
the homogeneous system that gave a conversion yield of over
95% in the otherwise same system [12]. The use of zinc oxide
and alkali metal-doped zinc oxide improved the conversion and
methyl ester selectivity [13,14], but the solid alkali catalyst had a
low catalytic activity per unit mass because the active surface area
is the only contact area between the oil substrate and catalyst. Sup-
porting of the alkali metal compound on a large surface area is an
interesting option for decreasing the amount of catalyst required to
still obtain a similar level of catalytic activity. Accordingly, the
transesterification of triolein using alkali loaded on alumina
achieved a conversion yield of nearly 100%, making it of interest
to apply in biodiesel production [15]. In contrast, the superbase
catalyst of Eu2O3/Al2O3 converted soybean oil to biodiesel at a con-
version yield of only 63% [16]. Although the use of alumina loaded
with potassium halide improved the soybean oil conversion to bio-
diesel to nearly 90% [17], the catalyst needed a high content of cal-
cined potassium halide, up to 35% (w/w) because the low surface
area of alumina results in a low dispersion of potassium salt. Pre-
vious work has suggested that calcined potassium iodide sup-
ported on mesoporous silica as the catalyst for transesterification
of soybean oil to biodiesel gave the highest conversion yield,
attaining nearly 95% [18], whilst mesoporous silica also showed
good catalytic support ability for 15% (w/v) calcium oxide on
SBA-15 in the transesterification of ethylbutylate [19]. Therefore,
this research work investigated the calcium oxide supported on
mesoporous silica to enhance the catalytic activity, as determined
by conversion yield and rate, of soybean oil transesterification.
2. Experiment
2.1. Catalyst preparation
Two grams of pluronic P123 (Aldrich, USA) were dissolved in
72 ml of 2 M HCl and stirred for 4 h. Pluronic P123 in tetraethoxy-
silane (Fluka, Italy) solution at a 3:1 ratio was added to the previ-
ous solution, stirred for 4 h and then hydrothermal treatment was
applied. The mixture was filtered, dried at 100 °C for 6 h, and cal-
cined at 600 °C for 3 h to obtain the silica powder. The mesoporous
silica was evacuated and the water adsorption volume determined
and the required volume of calcium acetate solution (15%, 20% or
25% (w/v)) was loaded on the mesoporous silica and left to impreg-
nate for 24 h, then dried at 100 °C for 12 h and calcined under sta-
tic conditions for 3 h at 800 °C. The catalysts so obtained were
characterized for their surface area, pore size and pore volume
by the N2 adsorption technique (Autosorb 1C, Quantrachome
Instruments Co. Ltd.). The X-ray powder diffraction pattern of cat-
alysts was recorded to study the crystal structure by Siemens: D8
Advance using Cu Ka radiation in the range of 5–80° with a step
size of 0.02°.
2.2. Transesterification of soybean oil
The transesterification of soybean oil was carried out in a
250 ml one-necked round-bottom flask equipped with a magnetic
stirrer and water-cooled condenser. The reaction of commercial
edible grade soybean oil (Thai Vegetable Oil Public Company Lim-
ited, Thailand) and methanol, at a methanol: oil molar ratio of 16:1
was studied at various reaction temperatures (50 °C, 60 °C and
70 °C) and times (6 h, 8 h and 10 h) with catalysts of different lev-
els of calcium loading (5–15 wt.%) and catalyst amounts (2.5–
7.5 wt.% by oil weight). The mixtures were vigorously stirred and
refluxed for the required reaction time. To determine the methyl
ester conversion yield, the product from the transesterification
was washed by saturated NaCl solution to remove the glycerol.
The organic phase was then dehydrated by anhydrous Na2SO4,
and the treated product analyzed by Nuclear Magnetic Resonance
(NMR) (Bruker, DPX-400). The conversion of the soybean oil to
Table 1
The physical properties of mesoporous silica supported CaO/CaCO3 catalysts derived
from different amounts of impregnating calcium acetate and calcinations.
The percentage of Ca in BET surface area Pore volume Pore
mesoporous silica (m2/g) (cm3/g) diameter (Å)
0.0 801.0 1.046 52.52
10.0 168.9 0.4342 102.8
15.0 175.6 0.4389 99.97
20.0 162.4 0.3176 78.23
25.0 139.4 0.3798 109.0

Fig. 1. Determination of methyl ester yields from Nuclear Magnetic Resonance (NMR) Spectroscopy analysis.
1430 C. Samart et al. / Energy Conversion and Management 51 (2010) 1428–1431

methyl esters was determined by the ratio of the signals at
3.68 ppm (hydrogen of the methoxy groups in the methyl esters)
and 2.30 ppm (hydrogen of the methylene groups of all fatty acid
derivatives) [17,20], as illustrated in Fig. 1.
The suitable condition was considered as that which gave the
highest yield of acceptable quality biodiesel with economic viabil-
ity as a secondary factor. To ascertain the acceptability of the bio-
diesel, it was tested for standard fuel properties, which are
viscosity, flash point, pour point and copper strip, by the American
Society for Testing and Material (ASTM) methods.
3. Results and discussion
3.1. Characterization of catalysts
The physical properties of mesoporous silica loaded with differ-
ent amounts of calcium acetate are presented in Table 1. The mes-
oporous silica had a large surface area and pore volume and
presented a uniform pore size (Fig. 2). The calcium acetate impreg-
nated into the mesoporous silica was also distributed on all the
surfaces of the silica and filled in the pores, resulting in blocked
up pores of the silica and, therefore, a lower surface area and pore
volume (Table 1). The diffraction patterns of the impregnated mes-
oporous silica presented as mainly calcium oxide with some cal-
cium carbonate, and showed increasing peak intensities as the
concentration of calcium acetate was increased (Fig. 3), supporting
that the calcined catalyst was mostly calcium oxide (CaO) with
some calcium carbonate, presumably as a subsequent product
from water and carbon dioxide absorption. Thus the calcined com-
pounds are refereed to as CaO hereafter.
3.2. Catalytic activity testing by transesterification of soybean oil
The reaction temperature affected the biodiesel conversion
yield (Fig. 4), with the highest conversion of soybean oil (>90%)
being obtained at 60 °C for all three catalysts although the highest
conversion was attained with the 15 wt.% CaO impregnated meso-
porous silica catalyst (95%). Running the reaction at below (50 °C)
or above (70 °C) the optimal temperature of 60 °C resulted in a sig-
nificant decrease in the conversion of soybean oil. This is expected
due to the temperature-dependent kinetics and also, in the latter
case since methanol has a boiling point that is lower (64.5 °C) than
the 70 °C reaction temperature, due to methanol evaporation
reducing the effective methanol to oil molar ratio around the cat-
alyst. The conversion of soybean oil was also affected by the reac-
tion time and this effect interacted with the level of Ca loading of
the catalyst (Fig. 5). With the relatively short reaction time (6 h),
100
90
80 15%Ca
% Conversion of soybean oil
70 20%Ca
60 25%Ca
50

40

30

20

10

0
50 60 70
o
Temprerature ( C)

Fig. 4. The conversion of soybean oil at various reaction temperatures and

concentrations of calcium acetate impregnated and calcined mesoporous silica
catalysts.

15%Ca
100 20%Ca
Fig. 2. The pore size distribution of CaO/CaCO3 supported on mesoporous silica
90 25%Ca
catalysts at various percentages of calcium loading.
80
% conversion of soybean oil

70

60

50

40

30

20

10

0
6 8 10
Reaction time (hrs)

Fig. 3. Representative X-ray diffraction patterns of CaO/CaCO3 supported on Fig. 5. The conversion of soybean oil at 60 °C for various reaction times and
mesoporous silica catalysts, impregnated with different concentrations of calcium concentrations of calcium acetate impregnated and calcined mesoporous silica
acetate prior to calcining. catalysts.
 C. Samart et al. / Energy Conversion and Management 51 (2010) 1428–1431 1431

100 4. Conclusion
15%Ca
90 20%Ca
Transesterification of soybean oil can be achieved by heteroge-
80 25%Ca
% Conversion of soybean oil

neous catalysis with calcium oxide supported on mesoporous sil-

70 ica. The optimum condition, which yielded a conversion of
soybean oil of nearly 95%, was a reaction temperature of 60 °C
60
for 8 h with a 15 wt.% Ca loaded mesoporous silica catalyst at
50 5 wt.% by oil weight. The fuel properties of the biodiesel so ob-
tained meet all biodiesel standards.
40

30 Acknowledgements
20
This research was granted by Thailand Research Fund (TRF) and
10
Targeted Research Initiative Funding, Thammasat University. The
0 authors would like to thank Mr. Jatuporn, Chemistry Dept.,
2.5 5.0 7.5 Thammasat University for H-NMR service.
Catalyst amount (%wt of oil)

Fig. 6. The conversion of soybean oil at 60 °C for 8 h with different amounts of

catalyst, each formed from different concentrations of calcium acetate impregnated
and calcined mesoporous silica catalysts.
Table 2
Fuel properties of biodiesel obtained from the transesterification of soybean oil at
60 °C for 8 h by 15% calcium oxide/carbonate supported on mesoporous silica at 5%
(w/w) to oil.
Properties This work
Viscosity (cst) 2.16
Pour point (°C) 13
Flash point (°C) 280
Copper strip corrosion 1B
the conversion rate was related to the Ca loading, being highest
with the highest Ca loaded catalyst (calcined from 25 wt.% calcium
acetate). However, although increasing the reaction time to 8 h sig-
nificantly increased the conversion yield for all three CaO loaded
catalysts, this was almost to the same level (90–95%) with a
slight numerical inverse dependence upon the Ca loading level of
the mesoporous silica. The apparent loss of Ca loading dependence
at the longer reaction times (8 h and see also 10 h) is due to the
condensation of methanol yielding a lower conversion. Thus, under
these laboratory scale based conditions, a reaction time of 8 h at
60 °C was the optimal conversion time and temperature, yielding
95% oil conversion. Increasing the amount of Ca-mesoporous sil-
ica catalyst relative to the oil substrate level enhanced the methyl
ester conversion with the highest conversion of over 90% when the
amount of catalyst was 5 wt.% by oil weight (Fig. 6). However, the
conversion efficiency decreased significantly as the catalyst level
increased to 7.5 wt.% by oil weight, especially for the catalysts with
a lower level of loaded Ca, because the excess catalyst disturbed
the mixing of methanol, oil and catalyst causing a phase separation
[21].
From these results, mesoporous silica as a Ca loading support
improved the transesterification efficiency of this alkali-supported
catalyst. The most suitable condition was a reaction temperature of
60 °C for 8 h, with a 15 wt.% Ca loaded mesoporous silica catalyst at
5 wt.% by oil weight. Under these conditions, the obtained biodie-
sel was in the acceptable range of the biodiesel standards for all
specified and measured parameters (Table 2).
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