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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.
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100
80
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12
10
Desorption
8
6
4
2
0
60
Adsorption
0.2
0.4
0.6
0.8
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
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.
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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
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(a)
100
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60
40
20
0
110
120
130
140
150
(b)
80
60
40
20
0
30
160
60
90
100
100
(c)
80
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20
0
120
150
180
210
240
80
60
40
20
0
10
12
14
16
18
10
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.
100
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.
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