Fuel 162 (2015) 288–293

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Fuel
journal homepage: www.elsevier.com/locate/fuel

Biodiesel production via transesterification of palm oil by using

CaO–CeO2 mixed oxide catalysts
Y.C. Wong, Y.P. Tan ⇑, Y.H. Taufiq-Yap, I. Ramli, H.S. Tee
Centre of Excellence for Catalysis Science and Technology, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor Darul Ehsan, Malaysia
Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 UPM Serdang, Selangor Darul Ehsan, Malaysia

h i g h l i g h t s

 Optimum biodiesel yield of 95% was achieved by 50Ca–Ce mixed oxide catalyst.
 Biodiesel yield increased with increasing basicity and BET surface area.
 The catalyst can be reused 6 times without significant loss of catalytic activity.
 Stability of 50Ca–Ce was enhanced by synergic effect between CaO and CeO2.
 Deactivation of catalyst was mainly due to leaching of CaO and pores filling.

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

Article history: Solid base CaO–CeO2 mixed oxide catalysts have been synthesized via wet impregnation method and
Received 24 July 2014 characterized by X-ray diffraction (XRD), Brunauer–Emmett–Teller (BET) surface area analysis,
Received in revised form 2 August 2015 temperature-programmed desorption of CO2 (TPD-CO2) and scanning electron microscopy (SEM). The
Accepted 7 September 2015
catalytic activity was determined by transesterification of palm oil. Optimum biodiesel yield, 95%, was
Available online 21 September 2015
achieved by 50Ca–Ce catalyst under the reaction conditions of 5 wt.% of catalyst, methanol to oil molar
ratio of 12:1, reaction temperature of 65 °C and reaction time of 4 h. The high catalytic activity (95%)
Keywords:
of 50Ca–Ce catalyst may be due to strong basicity and high BET surface area, which indicate more number
Biodiesel
Calcium oxide
of active sites on the catalyst surface for transesterification process. Besides, 50Ca–Ce catalyst showed
Cerium oxide better reusability than the bulk CaO where it can be reused up to 6 times without a significant loss of
Palm oil catalytic activity (>80%). The lixiviation of CaO active phase was greatly reduced with the presence of
Transesterification strong synergic interaction between CaO and CeO2. Deactivation of the catalyst was mainly due to the
leaching of CaO active phase into the methanolic solution and pore-filling by fatty acid or glycerol.
Ó 2015 Elsevier Ltd. All rights reserved.

1. Introduction
In recent studies, researches have shown great interests in the
field of biodiesel. Biodiesel is believed to serve as an alternative
for petroleum, to overcome the scarcity of petroleum-based
resources and the price fluctuation related to these resources.
Biodiesel is a mixture of methyl esters produced via transesterifica-
tion of animal fats or vegetable oils [1]. Since it is derived from
biomass, it is known as renewable energy source.
Calcium oxide, CaO, is the most commonly utilized heteroge-
neous catalyst in transesterification reactions [2–4]. Although
CaO is a promising catalyst in transesterification reactions, the
⇑ Corresponding author at: Department of Chemistry, Faculty of Science,
Universiti Putra Malaysia, 43400 UPM Serdang, Selangor Darul Ehsan, Malaysia.
E-mail address: typ@upm.edu.my (Y.P. Tan).
active phase CaO component tends to leach into the methanolic
solution [5,6]. The soluble Ca2+ was generated from the dissocia-
tion of CaO during the reaction with methanol [7]. The leached
CaO active phase will react with the free fatty acid and result in
soap formation and deactivation of the catalyst. Hence, the
stability of bulk CaO can be further improved by supporting CaO
onto carriers such as transition metals oxides.
Cerium (IV) oxide, CeO2, is a basic catalyst [8]. Although it is not
very reactive in transesterification reactions, it is a good candidate
to improve the properties of bulk CaO. However, the studies on
transesterification process using CaO–CeO2 mixed oxide catalyst
are scarce. Yu et al. [8] reported the use of CaO–CeO2 mixed oxide
catalyst with Ce/Ca molar ratio of 0.15 for transesterification of
Pistacia chinensis oil with methanol. The optimum yield of 91%
was achieved under reaction conditions of methanol to oil molar
ratio of 30:1, catalyst amount of 9%, reaction time of 6 h and

http://dx.doi.org/10.1016/j.fuel.2015.09.012
0016-2361/Ó 2015 Elsevier Ltd. All rights reserved.
 Y.C. Wong et al. / Fuel 162 (2015) 288–293 289

reaction temperature of 110 °C. The catalyst can be reused 5 times

Δ ∗ CaO
with biodiesel yield of more than 70%. Kawashima et al. [9] carried Δ CeO2
out transesterification reaction on rapeseed oil with the aid of
CaO–CeO2 catalyst. The optimum biodiesel yield obtained was * Δ
Δ Δ
89% at 60 °C with a 6:1 molar ratio of methanol to oil and a (i) 70Ca-Ce * Δ
*

Intensity (Arbritary unit)

reaction time of 10 h. It was relatively durable with reusability of
(h) 60Ca-Ce
7 times with biodiesel yield more than 80%.
(g) 50Ca-Ce
In this study, CaO–CeO2mixed oxide catalysts were prepared in
order to improve the physico-chemical properties, catalytic activ- (f) 40Ca-Ce
ity and reusability of the bulk CaO in transesterification of palm (e) 30Ca-Ce
oil. CaO–CeO2 mixed oxide catalysts with various CaO composi- (d) 20Ca-Ce
tions were prepared via wet impregnation method. Effects of vari-
(c) 10Ca-Ce
ous CaO loadings, the correlation between basicity and BET surface
area with biodiesel yield were studied. Deactivation of catalyst in (b) CeO2
transesterification reaction was also investigated. (a) CaO

2. Experimental
10 20 30 40 50 60
ο
2.1. Preparation and characterization of catalysts 2Θ ( )

The catalysts with composition 10–70 wt.% CaO, were prepared
via wet impregnation method and labeled as xCa–Ce, where x = 10,
20, 30, 40, 50, 60 and 70 wt.% CaO. An appropriate amount of cal-
cium nitrate tetrahydrate, Ca(NO3)2
4H2O (Sigma–Aldrich, 99%)
was dissolved in 100 ml distilled water. Next, a complementary
amount of cerium (IV) oxide, CeO2 (Sigma–Aldrich, 99.9%) was
added slowly into the solution and continuously stirred to obtain
homogenous solution. The solution was gently heated to evaporate
the excess water and then the mixture was further dried in an oven
at 100 °C. After drying, the sample was calcined in a furnace at
600 °C.
X-ray diffraction (Shimadzu diffractometer model XRD-6000)
was employed to determine the phase identity of the synthesized
samples. The diffractometer generated the diffraction pattern by
irradiating Cu Ka radiation on the powder crystalline samples.
The elemental compositions of the samples were determined by
using energy dispersive X-ray fluorescence spectrometer (XRF
model EDX-720).
Brunauer–Emmett–Teller (BET) surface area analysis was
performed to determine the total surface area of the prepared
samples. Analysis was conducted using a Quantachrome Autosorb
1 with nitrogen adsorption–desorption at – 196 °C. Thermo
Finnigan TPDRO 1100 was performed to evaluate the basicity of
the catalysts. Analysis was carried out by using CO2 as probe mole-
cule and the amount of CO2 desorbed in the temperature range of
50–1000 °C was detected by thermal conductivity detector. The
morphology of the samples was studied by using scanning electron
microscopy (SEM). Morphological studies of the catalysts were
performed by using JEOL JSM-6400 SEM. Prior to the analysis, the
samples were coated with gold by Sputter Coater.
2.2. Transesterification process
Fig. 1. XRD patterns of CaO, CeO2 and various compositions of CaO–CeO2 mixed
oxide catalysts.
equipped with a flame ionization detector (FID) and a capillary
column (RTX-65, 30 m  id 0.25 mm) was used in determination
of biodiesel yield. During measurements, a series of standards
(methyl myristate, methyl palmitate, methyl stearate, methyl
oleate and methyl linoleate) were used as reference while methyl
heptadecanoate was added as internal standard. The amount of
leached metal (Ca and Ce) in biodiesel was evaluated by using
atomic absorption spectroscopy (SOLAAR S Series, Thermo Scien-
tific). Before measurement, a calibration curve was established
from a series of known concentration standards.
3. Results and discussion
3.1. Characterization of catalyst
The phase identity of the prepared catalysts was studied by
using XRD. The XRD patterns for various compositions CaO–CeO2
mixed oxide catalysts are depicted in Fig. 1. All catalysts showed
similar patterns where two distinct metal oxide crystalline phases,
calcium oxide (CaO) and cerium (IV) oxide (CeO2) were identified,
without formation of new binary phases (CaCeO solid solutions).
CaO peaks were observed at 2h = 32.3°, 37.3°, and 53.8° (JCPDS file
No. 37-1497) whereas CeO2 peaks at 2h = 28.5°, 33.1°, 47.5°, 56.3°
and 59.1° (JCPDS file No. 34-0394). The elemental compositions of
the prepared catalysts were confirmed by using X-ray fluorescence
(XRF) spectroscopy (Table 1). The predicted and experimental
compositions were in good agreement with each other with no
significant deviation (less than 3%) observed.

Batch-type transesterification process was carried out, where Table 1

0.50 g of catalyst was added into the reaction mixture of 10.00 g Elemental compositions of various CaO–CeO2 mixed oxide catalysts.
of palm oil (provided by IOI Corporation Berhad) and 3.75 g of Samples Predicted weight Experimental weight
methanol (Merck). The mixture was refluxed at 65 °C in an oil bath percent (wt.%) percent (wt.%)
with constant magnetic stirring for 4 h. Upon the completion of the CaO CeO₂ CaO CeO₂
reaction, the mixture was cooled and centrifuged at 3000 rpm for
10Ca–Ce 10.0 90.0 9.3 90.6
3 min. The glycerol and methyl esters phases were separated from 20Ca–Ce 20.0 80.0 21.6 78.3
the catalyst and loaded into rotary evaporator to recover the excess 30Ca–Ce 30.0 70.0 31.4 68.3
methanol. Then, the phase containing methyl esters was separated 40Ca–Ce 40.0 60.0 38.7 61.3
from glycerol phase by using separating funnel. 50Ca–Ce 50.0 50.0 50.3 49.6
60Ca–Ce 60.0 40.0 59.6 40.3
The biodiesel yield was determined by using gas chromatogra- 70Ca–Ce 70.0 30.0 70.2 29.8
phy (GC). Gas chromatograph model Shimadzu GC-14B which was
290 Y.C. Wong et al. / Fuel 162 (2015) 288–293

66 Crystalline size of the catalysts was calculated by using

Debye–Scherrer’s equation [10]. Crystalline sizes of CaO in the
64
mixed oxide catalysts were in the range of 59–64 nm, whilst
62 CeO2 was in the range of 57–63 nm (Fig. 2). The calculated crys-
Average crystallite size (nm)

talline sizes decreased gradually with CaO loading (from 10 to

60 50 wt.%) in CaO–CeO2 mixed oxide catalysts. Reduction in crys-
talline sizes may be due to the homogeneous dispersion of CaO
58
and CeO2 in the mixed oxide catalysts [11,12]. The crystallite sizes
56 increased with further CaO increment (60 and 70 wt.%). BET sur-
face area of the CaO–CeO2 mixed oxide catalysts was in the range
54 3.4–8.6 m2/g. It is conspicuously shown in Fig. 3 that the BET sur-
CeO2
face area increased with CaO (from 10 to 50 wt.%) in the CaO–CeO2
52
CaO mixed oxide catalysts. Increase in surface area of the CaO–CeO2
50 mixed oxide catalysts was closely related to the crystalline sizes.
CeO2 10 20 30 40 50 60 70 CaO BET surface area of the CaO–CeO2 mixed oxide catalysts agreed
Fracon of CaO (wt. %) well with their respective crystalline sizes where small crystalline
sizes will result in larger surface area.
Fig. 2. Crystallite sizes of CaO and CeO2 in various compositions of CaO–CeO2 mixed
oxide catalysts.
However, excessive CaO phases (from 60 to 70 wt.%) caused sat-
uration or filling of pores in catalyst composite, which contribute
to the reduction in surface area [7].
The total basicity of the CaO–CeO2 mixed oxide catalysts was
10 evaluated by TPD-CO2. The TPD-CO2 profiles are displayed in
Fig. 4, while the total amount of CO2 desorbed is shown in Table 2.
9 8.6
8.1 CeO2 showed a desorption peak at the temperature range of 600–
7.8
8 7.5 700 °C, with 58 lmol/g of CO2 desorbed, indicating the number of
BET surface area (m2/g)

7 basic site in CeO2 is small, hence CeO2 is not very active in transes-
6 terification process. On the other hand, a desorption peak with
5.4
larger amount of CO2 desorbed (795 lmol/g) was observed from
5 4.4 CaO at the temperature range of 520–750 °C. The strong basic site
4 3.4 can be related to the existence of oxygen in Ca–O, Ce–O2 ion pairs
3.0
3 2.6 and isolated O2 anions [13]. In general, the CaO–CeO2 mixed oxide
2
catalysts showed higher basicity than the bulk CaO and CeO2. The
basicity was found to increase (from 864 to 1783 lmol/g) in the
1
order: 10Ca–Ce < 20Ca–Ce < 30Ca–Ce < 40Ca–Ce < 50Ca–Ce, then
0 slightly decreased (from 1783 to 1692 lmol/g) in the order
CeO2 10 20 30 40 50 60 70 CaO
50Ca–Ce > 60Ca–Ce > 70Ca–Ce. The improved basicity may be
Fracon of CaO (wt. %) due to the synergic effect between CaO and CeO2, in which the
vacancies created by the substitution of Ca2+ in CeO2 [14]. In fact,
Fig. 3. BET surface area of various compositions of CaO–CeO2 mixed oxide catalysts.
the Ce ion has a valence of 3 or 4 while the Ca ion has only a

Fig. 4. TPD-CO2 profiles of CeO2, CaO, various compositions of CaO–CeO2 mixed oxide catalysts.
 Y.C. Wong et al. / Fuel 162 (2015) 288–293 291

Table 2
Total basicity of CeO2, CaO and various compositions of CaO–CeO2 mixed oxide catalysts, expressed in lmol CO2/g desorbed.

Catalyst CO2 desorbed (lmol/g) Temperature range (°C) Peak temperature (°C)
CeO2 58 600–700 653
CaO 795 520–750 639
10Ca–Ce 864 600–825 769
20Ca–Ce 1061 560–825 789
30Ca–Ce 1367 600–800 756
40Ca–Ce 1455 560–800 753
50Ca–Ce 1783 600–800 760
60Ca–Ce 1758 600–800 754
70Ca–Ce 1692 600–800 758

valence of 2, therefore, some vacancies are created during Table 3

substitution to maintain charge neutrality in the ionic crystal. Dissolution of CaO and CeO2 from the catalysts into the products.
Subsequently, these vacancies induce the lattice distortion to form Catalysts Concentration of Normalized CaO Concentration of
defects that are favorable for heterogeneous catalysis [15]. Besides, CaO leaching (ppm) leaching content CeO2 leaching
the increase in basicity may be due to the larger BET surface area (%) (ppm)
(from 3.4 to 8.6 m2/g) at higher CaO loading, where more active CaO 190.5 3.8 ND
sites are available on the surface for CO2 desorption. 10Ca–Ce 4.1 0.4 ND
20Ca–Ce 6.8 0.5 ND
30Ca–Ce 7.8 0.4 ND
3.2. Catalytic activity 40Ca–Ce 18.0 0.7 ND
50Ca–Ce 32.3 1.3 ND
60Ca–Ce 58.4 1.9 ND
Catalytic activity of various compositions CaO–CeO2 mixed 70Ca–Ce 97.5 2.8 ND
oxide catalysts on the transesterification of palm oil was evaluated
under conditions of 5 wt.% of catalyst, methanol to oil molar ratio Note: ND = Not Detected (limit of detection = 2 ppm).

of 12:1, reaction temperature of 65 °C and reaction time of 4 h

(Fig. 5). It is noteworthy that the biodiesel yield increased gradu-
ally from 6% to 95% as calcium oxide loading in CaO–CeO2 mixed 100 2000
yield
oxide catalysts increased from 10 to 50 wt.%. Beyond 50 wt.% 90 1800

Total amount of CO₂ desorbed (μmol/g)

CaO, the catalytic activity reached a plateau. However, 60Ca–Ce Total amount of CO2
80 desorbed 1600
and 70Ca–Ce catalysts showed higher CaO leaching compared to
50Ca–Ce (Table 3). Hence, 50Ca–Ce was chosen as the optimum 70 1400
Conversion (%)

catalyst with the highest catalytic activity of 95%. High catalytic 60 1200
activity of 50Ca–Ce catalyst can be related to its basicity and BET
50 1000
surface area. The correlation between the basicity and biodiesel
yield is displayed in Fig. 6, while the correlation between the BET 40 800
surface area and biodiesel yield is depicted in Fig. 7. 30 600
It is conspicuously shown in Figs. 6 and 7 that the biodiesel 20 400
yield increased (from 6% to 95%) with the total basicity (from
864 to 1783 lmol/g) and the BET surface area (from 3.4 to 10 200

8.6 m2/g) as calcium oxide loading in CaO–CeO2 mixed oxide cata- 0 0

CeO2 10 20 30 40 50 60 70 CaO
lysts increased from 10 to 50 wt.%. Weaker basicity and lower BET Fracon of CaO (wt. %)
surface area at lower calcium oxide loadings (less than 50 wt.%)
suggested that there is a significantly lower amount of active sites. Fig. 6. Correlation between total basicity and biodiesel yield of CaO–CeO2 mixed
Consequently, these lower number of active sites limited the oxide series.
extent of the reaction [14], resulting in lower biodiesel yield (less
100 10
100 90 yield 9
90 BET surface area
80 8
80
BET surface area (m²/g)

70 7
Conversion (%)

70
Conversion (%)

60 6
60
50 5
50
40 4
40
30 30 3

20 20 2

10 10 1

0 0 0
CeO2 10 20 30 40 50 60 70 CaO CeO2 10 20 30 40 50 60 70 CaO
Fracon of CaO (wt. %) Fracon of CaO (wt. %)

Fig. 5. Catalytic activity of CeO2, CaO and various compositions of CaO–CeO2 mixed Fig. 7. Correlation between surface area and biodiesel yield of CaO–CeO2 mixed
oxide catalysts. oxide series.
292
100
90
80
70
Conversion (%)
60
50
40
30
20
10
0
1 2 3 4
Run
Fig. 8. Reusability of CaO and 50Ca–Ce mixed oxide catalyst.
Table 4
Durability studies of 50Ca–Ce mixed oxide catalyst.
Number of runa Concentration of CaO in biodieselb (ppm)
1 32.3
2 35.5
3 32.8
4 36.7
5 35.6
6 30.5
7 11.0
a
Transesterification conditions: reaction temperature, 65 °C; reaction time, 4 h;
catalyst dosage, 5 wt.%; and methanol to oil molar ratio, 12:1.
b
Concentration of CaO in biodiesel determined by AAS analysis.
than 80%). On the other hand, a combination of stronger basicity
(1783 lmol/g) and larger BET surface area (8.6 m2/g) of 50Ca–Ce
mixed oxide catalyst, resulting more number of base sites, which
will facilitate the transesterification of triglycerides and
subsequently higher yield. As CaO loading increased, the biodiesel
yield of 60Ca–Ce and 70Ca–Ce slightly decreased due to a slight
reduction in basicity and BET surface area.
Leaching of calcium and cerium phases from the catalysts were
studied by using atomic absorption spectroscopy (AAS) and the
data is presented in Table 3. The bulk CaO showed the highest
concentration of soluble CaO in the biodiesel layer with
190.5 ppm detected. Conversely, the residual CaO content in the
biodiesel samples catalysed by 10–70Ca–Ce mixed oxide catalysts
was in the range of 4.1–97.5 ppm. It is at least two folds lower than
Fig. 9. SEM images of (a) fresh 50Ca–Ce and (b) 50Ca–Ce after seventh run.
Y.C. Wong et al. / Fuel 162 (2015) 288–293
that of bulk CaO. This result clearly showed that the enhancement
50 % CaO/CeO2
CaO
of interaction between CaO and CeO2 greatly stabilized the active
phases of the catalysts to reduce the lixiviation of CaO into
methanolic solution [15]. In this case, 50Ca–Ce was chosen as an
optimum catalyst as it showed the highest catalytic activity but
with lower CaO leaching property.
3.3. Reusability
Although bulk CaO is a promising solid base catalyst in biodiesel
production, its poor reusability remains a major disadvantage in
biodiesel production. Thus, the reusability of 50Ca–Ce mixed oxide
catalyst was evaluated in order to determine its potential applica-
5 6 7 tion in biodiesel industry. Reusability of bulk CaO and 50Ca–Ce
mixed oxide catalyst in transesterification reaction are depicted
in Fig. 8. The catalysts were reused after filtration without any fur-
ther post-treatment. In general, catalytic activity of CaO decreased
sharply from runs 1 to 7, which may be due to the dissolution of a
fraction of the bulk CaO in the reaction medium [16–18]. However,
the biodiesel yield of 50Ca–Ce mixed oxide catalyst decreased more
gradually (biodiesel yield remains more than 80% within six runs).
There are two possible factors that contribute to the deactivation of
50Ca–Ce mixed oxide catalyst, which are (a) leaching of CaO into
reaction medium, and (b) adsorption of fatty acid, glycerol or
glycerides (triglycerides, diglycerides and monoglycerides) on the
active sites.
AAS analysis was carried out to investigate the leaching active
species (Table 4) while SEM was performed to investigate the deac-
tivation of the 50Ca–Ce mixed oxide catalyst (Fig. 9). AAS results
revealed that CeO2 was not detected in the biodiesel products. This
may due to the content of CeO2 was below the detection limit.
However, the loss of Ca2+ in the biodiesel was in the range of
11.0–32.3 ppm, which was relatively small. This clearly shows that
the 50Ca–Ce mixed oxide catalyst is more durable than the bulk
CaO oxide. The enhanced stability of the 50Ca–Ce mixed oxide cat-
alyst was due to the enhanced interaction between CaO and CeO2
metal oxides [15]. Meanwhile, SEM image of 50Ca–Ce catalyst after
seven runs (Fig. 9) showed that the catalyst coagulated into gum-
like cluster. This may be due to the adsorption of fatty acid or glyc-
erol on the pores [19], which inhibit the further transesterification
between the reactants and the active sites inside the pores.
4. Conclusion
The CaO–CeO2 mixed oxide catalysts prepared via wet impreg-
nation method was successfully applied in transesterification of
 Y.C. Wong et al. / Fuel 162 (2015) 288–293
palm oil. Among these catalysts, 50Ca–Ce showed the highest cat-
alytic activity with biodiesel yield, 95%, under the reaction condi-
tions of 5 wt.% of catalyst, methanol to oil molar ratio of 12:1,
reaction temperature of 65 °C and reaction time of 4 h. The high
catalytic activity of the 50Ca–Ce catalyst was governed by both
basicity and high BET surface area, in which more base sites on
the catalyst surface for transesterification process. In addition,
the reusability of 50Ca–Ce catalyst was better than the bulk CaO.
It can be reused up to six times without significant loss of catalytic
activity (with biodiesel yield >80%). The enhanced stability of
50Ca–Ce catalyst was due to the synergic interaction between
CaO and CeO2. Hence, 50Ca–Ce mixed oxide catalyst is a very
promising heterogeneous solid base catalyst for biodiesel produc-
tion due to its high catalytic activity, reasonably high stability,
and comparatively low leaching into the biodiesel product.
Acknowledgement
The authors acknowledge the financial supports of the National
Science Fund (NSF) from the Ministry of Science, Technology and
Innovation (MOSTI), and University Putra Malaysia (UPM), as well
as the palm oil provided by IOI Corporation Berhad.
References
[1] Meher LC, Vidya Sagar D, Naik SN. Technical aspects of biodiesel production by
transesterification – a review. Renew Sustain Energy Rev 2006;10:248–68.
[2] Lim BP, Maniam GP, Hamid SA. Biodiesel from adsorbed waste oil on spent
bleaching clay using CaO as a heterogeneous catalyst. Eur J Sci Res
2009;33:347–57.
[3] Vujicic D, Comic D, Zarubica A, Micic R, Boskovic G. Kinetics of biodiesel
synthesis from sunflower oil over CaO heterogeneous catalyst. Fuel
2010;89:2054–61.
293
[4] Zhu HP, Wu ZB, Chen YX, Zhang P, Duan SJ, Liu XH, et al. Preparation of
biodiesel catalysed by solid super base of calcium oxide and its refining
process. Chin J Catal 2006;27:391–6.
[5] Granados ML, Poves MDZ, Alonso DM, Mariscal R, Galisteo FC, Moreno-Tost R,
et al. Biodiesel from sunflower oil by using activated calcium oxide. Appl Catal
B 2007;73:249–53.
[6] Kouzu M, Kasuno T, Tajika M, Yamanaka S, Hidaka J. Active phase of calcium
oxide used as solid base catalyst for transesterification of soybean oil with
refluxing methanol. Appl Catal A 2008;334:357–65.
[7] Taufiq-Yap YH, Lee HV, Yunus R, Juan JC. Transesterification of non-edible
Jatropha curcas oil to biodiesel using binary Ca–Mg mixed oxide catalyst:
effect of stoichiometric composition. Chem Eng J 2011;178:342–7.
[8] Yu X, Wen Z, Li H, Tu S-T, Yan J. Transesterification of Pistacia chinensis oil for
biodiesel catalyzed by CaO–CeO2 mixed oxides. Fuel 2011;90:1868–74.
[9] Kawashima A, Matsubara K, Honda K. Development of heterogeneous catalysts
for biodiesel production. Bioresour Technol 2008;99:3439–43.
[10] Patterson AL. The Scherrer formula for X-ray particle size determination. Phys
Rev 1939;56:978–82.
[11] Emin SU, Mert T, Erol S. Transesterification of Nannochloropsis oculata
microalga’s lipid to biodiesel on Al2O3 supported CaO and MgO catalysts.
Bioresour Technol 2009;100:2828–31.
[12] Cinibulk MK. Effect of precursors and dopants on the synthesis and grain
growth of calcium hexaaluminate. J Am Ceram Soc 1998;81:3157–68.
[13] Sohn J, Park E. Acidic properties of CaO–SiO2 binary oxide catalyst and activity
for acid catalysis. Korean J Chem Eng 1997;14:192–7.
[14] Taufiq-Yap YH, Teo SH, Rashid U, Islam A, Hussien MZ. Transesterification of
Jatropha curcas crude oil to biodiesel on calcium lanthanum mixed oxide
catalyst: effect of stoichiometric composition. Energy Convers Manage 2014.
http://dx.doi.org/10.1016/j.enconman.2013.12.075.
[15] Thitsartarn W, Kawi S. An active and stable CaO–CeO2 catalyst for
transesterification of oil to biodiesel. Green Chem 2011;13:3423–30.
[16] Kotwal MS, Niphadkar PS, Deshpande SS, Bokade VV, Joshi PN.
Transesterification of sunflower oil catalyzed by flyash-based solid catalysts.
Fuel 2009;88:1773–8.
[17] Mootabadi H, Salamatinia B, Bhatia S, Abdullah AZ. Ultrasonic-assisted
biodiesel production process from palm oil using alkaline earth metal oxides
as the heterogeneous catalysts. Fuel 2010;89:1818–25.
[18] Gryglewicz S. Rapeseed oil methyl esters preparation using heterogeneous
catalysts. Bioresour Technol 1999;70:249–53.
[19] Wen ZZ, Yu XH, Tu ST, Yan YJ, Dahlquist E. Synthesis of biodiesel from
vegetable oil with methanol catalyzed by Li-doped magnesium oxide catalysts.
Appl Energy 2010;87:743–8.