Energy Conversion and Management 106 (2015) 13561361

Contents lists available at ScienceDirect

Energy Conversion and Management

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

Transesterification of Jatropha oil with dimethyl carbonate to produce

fatty acid methyl ester over reusable CaLaAl mixed-oxide catalyst
Y. Syamsuddin a,b, M.N. Murat a, B.H. Hameed a,
a
b

School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Penang, Malaysia
Chemical Engineering Department, Engineering Faculty, Syiah Kuala University, Banda Aceh 23111, Indonesia

a r t i c l e

i n f o

Article history:
Received 6 July 2015
Accepted 22 October 2015
Available online 11 November 2015
Keywords:
CaLaAl catalyst
Dimethyl carbonate
Fatty acid methyl ester
Jatropha oil
Transesterification

a b s t r a c t
Jatropha oil (JO) was transesterified with dimethyl carbonate (DMC) to produce fatty acid methyl ester
(FAME) over synthesized CaLaAl mixed-oxide catalyst. The influence of different parameters on transesterification of Jatropha oil was investigated in a batch reactor. These parameters included reaction temperature (110160 C), reaction time (30240 min), DMC-to-oil molar ratio (4:118:1) and catalyst
loading amount (110 wt.%, based on the oil weight). The mixed-oxide catalyst with a molar ratio of
6:2:1 (CaLaAl) showed high catalytic activity for FAME synthesis. More than 90% of FAME was obtained
under the following reaction conditions: 150 C, reaction temperature; 180 min, reaction time; 15:1,
DMC-to-oil molar ratio; and 7 wt.% amount of catalyst loading. The catalyst also exhibited high stability
and could be reused for up to five cycles with less than 5% yield reduction per cycle.
2015 Elsevier Ltd. All rights reserved.

1. Introduction
The development of renewable energy sources, such as hydrogen and fuel cells [13], solar energy [4,5], and biofuels [6,7] has
increased worldwide because of limited energy reserves and global
warming. Biodiesel, a promising renewable energy resource, can be
used to solve the energy crisis and environmental degradation
issues. Biodiesel exhibits properties comparable with those of petroleum diesel, they are mixed for application to vehicles.
Biodiesel is a renewable, biodegradable, and environment
friendly alternative fuel because it reduces emissions of pollutants,
such as particulate matters, carbon monoxide, sulfur and polycyclic aromatic hydrocarbons [811]. Biodiesel, also known as fatty
acid methyl ester (FAME), is a mixture of methyl esters produced
from edible or non-edible vegetable oils and animal fats through
transesterification [12]. Edible and non-edible oils, such as palm
oil [8,12], sunflower oil [9], canola oil [10,13], Jatropha oil (JO)
[14,15] and karanj oil [14], have been used as raw material for biodiesel production. Jatropha oil produced in Malaysia can be a good
source for biodiesel. Malaysia has about 1.5 million ha of marginal
land and currently 1712 ha has been located for Jatropha cultivation. Also, The Ministry of plantation of industries and commodities has been allocated 300 ha for Jatropha pilot research project
together with the planning from some international leading oil
Corresponding author. Tel.: +60 45996422; fax: +60 45941013.
E-mail address: chbassim@usm.my (B.H. Hameed).
http://dx.doi.org/10.1016/j.enconman.2015.10.057
0196-8904/ 2015 Elsevier Ltd. All rights reserved.

company to develop Jatropha projects in Malaysia [16]. Jatropha

oil can be one of the promising sources for biodiesel production
in Malaysia, due to its characteristics. It is not compete with food,
agriculture land and nature. It reduces the danger of emissions
compared with the petroleum fuel. Biodiesel from Jatropha oil
has a comparable characteristics with petroleum diesel and it can
be used without any major modification in the engines [17].
Biodiesel, which exhibits high catalytic activity, is conventionally produced through homogeneous transesterification with
methanol over acid or basic catalyst. This process is not economical
and environment friendly and requires separation of the catalyst
from the reaction mixture. Moreover, large amount of glycerol
are produced during the reaction, then produced large amount of
waste water for purification of the product, thereby requiring high
purification cost. Heterogeneous catalysts are used to overcome
limitations associated with separation. Researchers have started
to produce glycerol free-biodiesel by using dimethyl carbonate
(DMC) as methylating agent to replace methanol; in this process,
the intermediate product fatty acid glycerol carbonate (FAGLC)
and the byproduct glycerol dicarbonate (GDC) are miscible in the
DMCbiodiesel phase and catalyst can be easily separated from
the reaction mixture because the polarity of the reactants are different [14]. This reaction route solves issues regarding separation
and does not require purification, thus reducing the production
cost. Transesterification reaction of vegetable oil with DMC were
reported by Kurle et al. [10], Rathore et al. [14], and Zhang et al.
[18]. The unit price of DMC is higher than methanol, but the

Y. Syamsuddin et al. / Energy Conversion and Management 106 (2015) 13561361

reaction with DMC can solve the problem in product separation

due to no glycerol produced after reaction, which make the process
more efficient. In addition, the use of DMC solve the environmental
problem comes from the purification of the product, since the
FAGLC are dissolved in the FAMEs, that can be used as fuel without
separation [19]. Thus, the substitution of methanol with DMC has a
minor impact on the overall cost of the production process.
CaO, an active and basic catalyst, is widely used for transesterification of vegetable oils but presents limitations in terms of
leaching, thereby requiring additional stages for neutralization.
The leached species reduces the catalytic activity and reusability
of the catalyst. As such, mixed-oxide are used to increase the interaction between active phases and prevent leaching. A number of
heterogeneous CaO-based mixed-oxide catalysts, such as CaMn
[20], CaZn [21], CaOSnO2 [22], and CaO/zeolite [23], have been
developed for transesterification. CaO-based mixed-oxide catalysts
may improve the performance of bulk CaO. Although these catalysts show high activity in biodiesel synthesis, the development
process and catalytic performance of mixed-oxides remains to be
investigated.
Previously, we reported that CaLa mixed-oxide catalyst was
effective for the transesterification of Jatropha oil [24]. In this
work, CaLaAl mixed-oxide catalyst was synthesized for the
transesterification of Jatropha oil in an attempt to enhance the catalyst performance. This work aims to investigate transesterification of Jatropha oil with DMC to produce glycerol free-FAME over
reusable CaLaAl mixed-oxide catalyst.
2. Materials and methods
2.1. Materials
Jatropha oil, with a free fatty acid content of 7.77% and a water
content of 0.235%, was supplied by Bionas, Sdn. Bhd., Malaysia.
Calcium nitrate tetrahydrate (Ca(NO3)2
4H2O; >99%), lanthanum
nitrate hexahydrate (La(NO3)2
6H2O; 99.9%), and aluminum nitrate
nanohydrate (Al(NO3)3
9H2O; P98.5%) were precursors used to
synthesize the catalyst and purchased from Merck company,
Malaysia. Sodium carbonate (Na2CO3; >99.5%) and sodium hydroxide (NaOH; >99%) were used as precipitant in catalyst synthesis
and purchased from R&M Chemicals, Malaysia. DMC (P99%) and
n-hexane (P96%) were used in transesterification and purchased
from Merck company, Malaysia. Pyridine (P99.5%) was used as
solvent for gas chromatography analysis and purchased from
Merck company, Malaysia.
2.2. Synthesis and characterization of catalyst
A co-precipitation method was used to prepare CaO-based alkaline catalyst from the nitrate compounds of calcium (C), lanthanum
(L) and aluminum (A). Briefly, based on 10 g of lanthanum salt,
100 mL of mixed salt solution containing 2.16 M Ca(NO3)2
4H2O,
0.72 M La(NO3)2
6H2O and 0.36 M Al(NO3)3
9H2O with a molar
ratio of 6:2:1 (C:L:A) were mixed with distilled water and stirred
at room temperature for 1 h. An aqueous solution containing 1 M
Na2CO3 and NaOH as precipitant was slowly added to the mixture
under stirring under a controlled pH of 10. The mixture was aged
with continuous stirring for 5 h at 80 C, filtered, and dried overnight at 110 C. The dried sample was calcined in a muffle furnace
at temperatures ranging from 680 C to 900 C for calcination times
of 15 h. It was found that calcination temperature of 800 C and
time of 4 h resulted in the highest FAME yield. The catalyst was
labeled as CLA621 according to the molar ratio of C:L:A, and
stored in a desicator prior to activity testing.
The BET surface area, pore diameter, and pore volume of the
prepared catalysts was determined using N2 adsorption

1357

desorption isotherms at 196 C. Analysis was conducted using a

surface area and porosity analyzer (Micromeritics ASAP 2020,
USA). X-ray diffraction (XRD) analysis was conducted to determine
the crystallinity of the compound and identify crystals present in
the sample. The diffractogram shows the diffraction intensity as
a function of diffraction angles. The powder XRD pattern was
obtained with a diffractometer (Philip PW1710) with Cu Ka radiation to generate diffraction patterns from powder crystalline samples at ambient temperature. Scanning Electron Microscopy (SEM)
analysis was performed to study surface morphology of the catalyst by using Quanta FEG 450. Fourier Transform Infrared (FTIR)
Spectroscopy analysis was carried out to determine the functional
groups on the catalyst surface. IR measurements were performed
with a Prestige-21 Shimadzu. The spectrum was recorded at room
temperature within the range of 4000400 cm 1. The IR spectra of
the samples were determined using the KBr pellet technique.
2.3. Transesterification reaction and product analysis
Transesterification was performed in 100 mL stirred pressure
reactor (Amar Equipment PVT. Ltd., India) equipped with temperature, speed and reaction time controller. Reactions were conducted under various DMC-to-oil molar ratio (4:118:1), reaction
temperature (110160 C), reaction time (30240 min), and catalyst loading amount (110 wt.%, based on the oil weight).In a typical batch run, 13 mL of Jatropha oil, 17 mL of DMC, and 0.8179 g of
the catalyst (equivalent to 7 wt.% catalyst loading from DMC-to-oil
molar ratio of 15:1) were placed inside the reactor. The reaction
was performed at 150 C for 180 min with stirring at 500 rpm.
After the reaction, the catalyst was separated from the product
through centrifugation (Thermo Scientific Pico 17, supplied by
Fischer Scientific (M) Sdn. Bhd) and supernatant was collected
for analysis.
Reaction samples were analyzed using a Shimadzu GC 2010,
equipped with a flame ionization detector and connected to ZB5HT Inferno capillary column (30 m in length, 0.25 mm inner
diameter, 0.25 lm film thickness). Helium was used as carrier
gas and supplied at a flow rate of 3 mL/min. The flow rates of air
and hydrogen gases were set at 400 and 40 mL/min, respectively.
The injector and detector temperature was set at 300 C and
370 C, respectively. The sample for analysis was diluted with pyridine before injecting into the column [25], 20 lL of sample was
diluted into 1000 lL pyridine. The retention time of the TG and
FAME was determined by running each respective standard [24].
The standard for TG was Jatropha oil and standard for FAME was
myristic acid methyl ester (C14:0), palmitic acid methyl ester
(C16:0), palmitoleic acid methyl ester (16:1), stearic acid methyl
ester (C18:0), oleic acid methyl ester (C18:1), linoleic acid methyl
ester (C18:2) and linolenic acid methyl ester (18:3).
2.4. Catalyst reusability
Reusability test was performed to investigate the stability of the
catalyst in transesterification. After each reaction, the catalyst was
separated through centrifugation (Kubota 2420) at 4000 rpm and
oil product was collected for analysis. The catalyst was washed
with hexane and dried overnight in an oven at 110 C prior to
use for another reaction.
3. Results and discussion
3.1. Screening of catalysts
Jatropha oil was transesterified with CaO-based alkaline catalysts to determine the effect of catalyst composition on FAME yield

Y. Syamsuddin et al. / Energy Conversion and Management 106 (2015) 13561361

and the interaction between metals on the synthesized catalysts.

The reactions were conducted under the following condition: agitation speed, 500 rpm; reaction temperature, 150 C; reaction time,
180 min; DMC-to-oil molar ratio, 15:1; and catalyst loading
amount, 7 wt.%. The mixed-oxide catalyst resulted in high FAME
yield, as shown in Fig. 1.
The FAME yields from the reaction between Jatropha oil and
oxides of CaO, La2O3, and Al2O3 were 50.39%, 65.78%, and 3.6%,
respectively, whereas the yield from the reaction with the CaO
La2O3 mixed-oxide catalysts was more than 70%. The combination
of CaO and La2O3, as well as CaO and Al2O3, resulted in high FAME
yields because of the acid and base properties of the catalyst,
which are essential for oils with high FFA content. Lanthanum
and aluminum, which exhibit both acid and base properties, are
responsible for the simultaneous esterification and transesterification reactions.
FAME yield minimally increased as the ratio of Ca to La
increased from 4 to 6, then decreased as the ratio increased to 8.
Excess CaO tends to block the pore of the catalyst surface, thus
reducing the active area available for the reaction. The combination of CaOLa2O3Al2O3 catalyst increased the FAME yield to
80.2%, whereas the combination of CaOLa2O3Al2O3 with the ratio
of 6:2:1 provided the highest FAME yield of 96.91% after 3 h of
reaction. The combination and the synergistic effects of the mixed
metal oxides of calcium, lanthanum and aluminum may have contributed to the high activity of the synthesized catalyst.
As the CLA621 catalyst exhibited the highest catalytic activity,
it was selected for further studies to determine the best catalyst
transesterification conditions for biodiesel production using
Jatropha oil.
3.2. Catalyst characterization
Table 1 shows the textural properties of the synthesized CLA621 catalyst. The BET surface area and pore diameter of the catalyst
were 6.81 m2/g and 7.50 nm, respectively. The catalyst was classified as mesopore and presented a pore size of 250 nm, which is
sufficient for the diffusion of triglyceride molecules with a

FAME yield (%)

100
80

diameter of 5.8 nm [26,27]. The catalyst was also classified as

mesoporous based on its Type IV N2 adsorptiondesorption isotherm (Fig. 2).
FTIR analysis was performed to investigate the functional
groups of the synthesized CLA621catalysts. Fig. 3 shows the FTIR
spectra of the fresh and used catalyst for seven reaction cycles. The
IR peak at 36003700 cm 1 is attributed to the stretching of surface hydroxyl (OH) groups attached to the surface of CaO, La2O3
and Al2O3. The IR peaks at 13001500 cm 1 are assigned to the
peaks of bending vibration of OCaO group. The peak at
800900 cm 1 is a characteristic of stretching of CO23 groups; this
peak indicates the formation of surface carbonate from the reaction of calcium oxide and carbon dioxide from the atmosphere
during sample preparation [28]. The peaks within the range of
600800 cm 1 are attributed to MO bending vibration, in which
M represents Ca, La or Al metal ions [29].The two bands within
the range of 28502950 cm 1 and peak at 1750 cm 1 on the IR
spectra of reused catalyst are ascribed to the CAH stretching of
the alkyl group and C@O stretching of the esters group, respectively. These bands occurred because the remaining organic material from the oil covered the surface of the catalyst.
The surface morphologies of the fresh and used CLA621 catalysts are shown in Fig. 4. The fresh catalyst (Fig. 4(a)) showed
various dimensions and forms, with agglomerated particles. The
morphology of used catalyst (Fig. 4(b)) showed homogeneous
surface, which could be due to material deposits that covered the
surface after seven reaction cycles. These findings were supported
by the FTIR analysis results, which showed that the bands of alkyl

Quantity adsorbed (cm3/g STP)

1358

12
10

Desorption

8
6
4
2
0

60

Adsorption

0.2

0.4

0.6

0.8

Relative pressure (P/Po)

40
Fig. 2. N2 adsorptiondesorption isothermal of the synthesized CLA621catalyst.

20
0

CaO-based catalysts
Fig. 1. Transesterification of Jatropha oil with CaO-based catalysts. Reaction
condition: 500 rpm agitation speed, 150 C reaction temperature, 180 min reaction
time, 15:1 DMC/oil molar ratio, and 7 wt.% catalyst loading.

Table 1
BET surface area, pore volume and average pore diameter of the synthesized catalysts.
Catalyst

CLA621

Single point surface area (m2/g)

BET surface area (m2/g)
Langmuir surface area (m2/g)
External surface area (m2/g)
Total pore volume (cm3/g)
Cumulative pore volume (cm3/g)
Average pore width (nm)

5.32
6.81
14.68
11.62
0.013
0.015
7.50

Fig. 3. FTIR analysis of CLA621 catalyst; (a) fresh, (b) reused after 7 cycles of
reaction.

Y. Syamsuddin et al. / Energy Conversion and Management 106 (2015) 13561361

1359

Fig. 4. SEM image of CLA621 catalyst (magnification 10,000); (a) fresh, (b) reused after 7 cycles of reaction.

and ester groups blocked the pores of the catalyst surface after
being used for seven cycles.
Fig. 5 shows the XRD pattern of synthesized CLA621 catalyst,
for fresh and seven reaction cycles reused catalysts. The XRD
phases were identified with the use of the Joint Committee of the
Powder Diffraction Standard (JCPDS) database file. The peaks
observed at 32.3, 37.5 and 53.9 correspond to CaO (JCPDS File
No. 37-1497), whereas the peaks observed at 26, 39.4 and 72
indicate the presence of a segregated La2O3 phase. The Al2O3
(JCPDS File No. 00-004-0787) peak was detected at 2h of 44.7 in
the form of c-Al2O3 phase, which was formed after dehydration
and desorption of the surface hydroxyl groups after calcination at
800 C [30]. The other peaks at 34, 48 and 60 are assigned to
the formation of Al4La1, Al3La1 and Al4Ca1 phases, respectively.
No XRD pattern was detected for the formation of CaLa2Al2O7
mixed-oxide.
3.3. Effect of reaction parameters on FAME yield
Jatropha oil was transesterified over the synthesized CLA621
catalyst at various reaction temperatures, reaction times, DMCto-oil molar ratios, and catalyst loading amounts. Reactions were
conducted to investigate the effect of these parameters on FAME
yield and determine the best reaction condition. The results are
presented in Fig. 6(a)(d).
The effect of reaction temperature was investigated, and the
results are presented in Fig. 6(a). The reaction temperature were
varied from 110 C to 160 C, while keeping the other experimental
conditions as constant. No FAME yield was obtained from the reaction at 110120 C. The FAME yield increased from 25.12% to
96.91% as the reaction temperature reached 120 C up to 150 C,
then slightly increased to 97.38% when the reaction temperature
increased to 160 C. The reaction rate increased with increasing

Fig. 5. XRD pattern of the synthesized CLA-621catalysts; (a) fresh (b) reused for
7 cycles; (1) CaO; (2) La2O3; (3) Al2O3; (4) Al3La1; (5) Al4La1; (6) Al4Ca1.

reaction temperature, which could be due to the reduction in viscosity of the oil as the temperature increase, resulting in miscible
reactants, then the reaction run and complete faster. About 0.4%
increase in FAME yield was observed when the reaction temperature increased from 150 C to 160 C, which could be due to the
vaporization of the DMC. In this process, DMC remain in the vapor
phase in the reactor and was insufficient for the reaction. Based on
the EN 14214 standard for ester content limitation, 150 C was
determined to be the best reaction temperature for subsequent
reactions.
Jatropha oil was transesterified at various reaction time ranging
from 30 min to 240 min. The yield of FAME increased with increasing reaction time, as shown in Fig. 6(b). At low reaction time, the
reaction started slowly as DMC was mixed and dispersed into the
oil [31]. The FAME yield increased up to 96.91% as the reaction
time reach 180 min and continued to increase to 99.52% as the
reaction time increased to 240 min. Hence, 180 min was selected
as the best reaction time for further reactions.
The effect of the DMC-to-oil molar ratio was assessed, and the
results are illustrated in Fig. 6(c). The reaction was conducted by
varying the ratio from 4:1 to 18:1. Stoichiometrically, 2 mol DMC
is required to transform each mole of triglyceride to produce
3 mol of FAME. As transesterification is a reversible reaction, large
amount of excess DMC are required to shift the equilibrium of the
transesterification reaction to the direction of product formation.
The FAME yield increased from 32.91% to 96.91% as the DMC-tooil molar ratio increased from 4:1 to 15:1. The yield of FAME was
poor at low DMC-to-oil molar ratios. The yield further decreased
to 87.25% as the DMC-to-oil molar ratio was increased to 18:1. It
is suggested by reduction of collision frequency of the reactants
with the catalyst that inhibit the reaction rate [15,29,32]. Thus,
the best DMC-to-oil molar ratio for the transesterification of
Jatropha oil over the CLA621 catalyst was set as 15:1.
Catalyst is an important factor that affect the biodiesel yield
during transesterification. Catalyst reduces the activation energy
required for a reaction to proceed and allows the reaction to
rapidly reach the equilibrium. Catalyst also affects the rate of the
reaction by hastening it to completion. In this work, the effect of
catalyst loading amount, which varied from 1 wt.% to 10 wt.%
(based on oil weight), was investigated at a reaction temperature
of 150 C with a reactant ratio of 15:1 (DMC:oil) for 180 min, and
the results are presented in Fig. 6(d). No FAME yield resulted from
the reaction with 1 wt.% catalyst loading, which could be due to
insufficient active area available for the collision of reactants with
the solid catalyst. The FAME yield gradually increased to higher
than 90% as the catalyst loading increased from 2 wt.% to 5 wt.%.
The transesterification reaction rate also increased with increasing
amount of catalyst loading into the reactants. The maximum FAME

1360

Y. Syamsuddin et al. / Energy Conversion and Management 106 (2015) 13561361

100

(a)

FAME yield (%)

FAME yield (%)

100
80
60
40
20

0
110

120

130

140

150

(b)

80
60
40
20
0
30

160

60

90

Reaction temperature (oC)

FAME yield (%)

FAME yield (%)

100

100

(c)

80
60
40
20
0

120

150

180

210

240

Reaction time (min)

(d)

80
60
40
20
0

10

12

14

16

18

10

Catalyst loading (wt.%)

DMC-to-oil ratio

Fig. 6. Effect of reaction parameters on FAME yield (a) Effect of reaction temperature. Reaction condition: 500 rpm agitation speed, 180 min reaction time, 15:1 DMC/oil
molar ratio, and 7 wt.% catalyst loading. (b) Effect of reaction time. Reaction condition: 500 rpm agitation speed, 150 C reaction temperature, 15:1 DMC/oil molar ratio, and
7 wt.% catalyst loading. (c) Effect of DMC/oil ratio. Reaction condition: 500 rpm agitation speed, 150 C reaction temperature, 180 min reaction time, and 7 wt.% catalyst
loading. (d) Effect of catalyst loading. Reaction condition: 500 rpm agitation speed, 150 C reaction temperature, 180 min reaction time, and 15:1 DMC/oil molar ratio.

3.4. Catalyst reusability

As heterogeneous catalyst can be recycled and reused, recyclability and reusability are important for determining the commercial viability of the catalyst. The reusability of the CLA621
catalyst was tested in transesterification of Jatropha oil under the
best reaction conditions, that is, agitation speed of 500 rpm, reaction temperature of 150 C, reaction time of 180 min, DMC-to-oil
molar ratio of 15:1 and catalyst loading amount of 7 wt.%. The
results showed that the catalyst can be easily separated from the
reaction mixture and washed to remove organic materials deposited on the surface. The catalyst was reused up to five times, with
slight yield reduction of less than 5% per cycle, as shown in Fig. 7.
Hence, the catalyst exhibited high catalytic activity and stability in
transesterification of vegetable oil containing high FFA. This finding could be attributed to the interaction and synergistic effects
of the combination of CaO, La2O3 and Al2O3.
Leaching test was also performed on the catalyst. A specific
amount of the catalyst was reacted with DMC under the best

100

FAME yield (%)

yield (96.91%) was achieved when the amount of catalyst loading

increased to 7 wt.%. However, the yield decreased with further
increase in catalyst loading, which could be due to the increasing
viscosity of the slurry that enhances the mass transfer resistance
in multiple phases (liquidliquidsolid), thereby complicating the
mixing of the reactants with the catalyst. Therefore, 7 wt.% was
selected as the best condition for catalyst loading.
The catalytic activity analysis results showed that the synthesized CLA621 catalyst exhibited high activity and stability compared with previously reported catalyst. Rathore et al. [14]
conducted transesterification of Jatropha oil with DMC by using
KOH as the catalyst. The TG conversion reached 96.91% at 3 h of
reaction time with 7 wt.% for CLA621 catalyst, whereas KOH took
8 h to obtain 94% conversion with 9 wt.% catalyst loading. The synthesized CLA621 catalyst has an acid and base properties, which
is needed for oil with high free fatty acid (FFA) content. Lanthanum
and aluminum, which present both acid and base properties, are
responsible for simultaneous triglyceride transesterification and
FFA esterification reactions, whereas calcium oxide, which has base
properties, responsible for triglyceride transesterification [33].

80
60
40
20
0

fresh
catalyst

Cycle
Fig. 7. Reusability of the catalyst. Reaction condition: 500 rpm agitation speed,
150 C reaction temperature, 180 min reaction time, 15:1 DMC/oil molar ratio and
7 wt.% catalyst loading.

reaction condition. After a certain reaction time (180 min), DMC

was filtered and used for transesterification of Jatropha oil. An
FAME yield of about 0.76% was obtained, which is almost similar
to the yield obtained from the blank run of the reaction.
After the catalyst was used for five reaction cycles, the FAME
yield decreased to 86.54% and then to 59.58%. The reduction could
be attributed to catalyst deactivation caused by the blockage of the
catalyst pores by triglycerides from the oil during the reaction,
thereby decreasing the number of active sites on the surface of
the catalyst. This result is in good agreement with the FTIR analysis
and SEM image of the used catalyst, in which the bands of alkyl and
ester groups were detected on the catalyst surface as shown on
FTIR analysis and homogeneous surface due to material deposits
shown on SEM image.
4. Conclusion
The study revealed the influence of the combination and interaction of mixed-oxide catalyst on transesterification of Jatropha oil,
as well as the effect of reaction conditions on FAME yield. The combination of calcium, lanthanum and aluminum at the ratio of
6:2:1was the best catalyst. More than 90% FAME yield was
obtained when the catalyst was calcined at 800 C for 4 h. The best

Y. Syamsuddin et al. / Energy Conversion and Management 106 (2015) 13561361

reaction condition constituted the following: agitation speed of

500 rpm, reaction temperature of 150 C, reaction time of
180 min, DMC-to-oil molar ratio of 15:1, and catalyst loading
amount of 7 wt.%. Under this condition, the FAME yield reached
96.91%. The catalyst was easily separated from the product mixture and reused for up to five reaction cycles. The stability of the
catalyst could be due to the strong synergistic interaction among
CaO, La2O3 and Al2O3. The combination of calcium, lanthanum,
and aluminum at a molar ratio of 6:2:1 is a potential catalyst for
biodiesel industry because of its high performance in transesterification of Jatropha oil.
Acknowledgments
The first author acknowledges the scholarship support from the
Directorate General of Higher Education (DGHE), Ministry of
Research, Technology and Higher Education, Indonesia. The
authors acknowledge the research grant provided by the Ministry
of Higher Education, Malaysia under the Fundamental Research
Grant Scheme (FRGS) Fasa 2/2013 (No. 203/PJKIMIA/6071273).

[13]
[14]
[15]

[16]
[17]

[18]

[19]

[20]

[21]

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