Fuel Processing Technology 91 (2010) 243–248

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Fuel Processing Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / f u p r o c

Biodiesel production using alumina-supported calcium oxide: An optimization study

Masoud Zabeti, Wan Mohd Ashri Wan Daud ⁎, Mohamed Kheireddine Aroua
Chemical Engineering Department, Faculty of Engineering, University Malaya, 50603, Kuala Lumpur, Malaysia

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

Article history: This study consists of the optimization of the methyl ester yields produced via transesterification of palm oil
Received 28 May 2009 using CaO/Al2O3 solid base catalyst. Response Surface Methodology (RSM) in combination with Central
Received in revised form 9 October 2009 Composite Design (CCD) was used to optimize the operating parameters. Alcohol/oil molar ratio, catalyst
Accepted 11 October 2009
content in the reaction medium and reaction temperature were chosen as the variables and the response
selected was the amount of methyl ester yields. All the reactions were performed in a batch laboratory scale
Keywords:
reactor for 5 h; the optimum reaction conditions obtained were approximately alcohol/oil molar ratio of
Biodiesel
Calcium oxide
12:1, catalyst content of 6 wt.% and reaction temperature of 65 °C. The results from ICP-MS exhibited
Catalyst leaching insignificant leaching of the CaO active species into the reaction medium and the reusability of the catalyst
Optimization was successfully tested in two subsequent cycles. Under certain reaction conditions the glycerol obtained
Palm oil was almost colorless.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction Solid base catalysts have been proposed for transesterification

In recent years, concerns about greenhouse gas emissions, global
warming and limits of the crude oil resources have encouraged
scientist to develop an alternative fuel. Biodiesel which is defined as
mono alkyl esters of long chain fatty acids obtained from renewable
sources such as vegetable oils or animal fats has gained significant
attention as an environmentally benign substitute for petroleum-
based fuels. In comparison with conventional diesel fuels, biodiesel
offers many benefits: it is a renewable form of energy, non-toxic,
biodegradable, it has less particular matter emissions and it can be
blended with diesel at any proportion and can be used in current
diesel engines with no further engine modifications required [1–3].
However, the main disadvantage corresponding to biodiesel usage is
the high production cost which is possibly due to the price of
feedstocks or type of catalysts [4].
Biodiesel is commonly produced via transesterification reaction of
vegetable oils in which one mole of triglyceride, the major
composition of vegetable oils, reacts with three moles of a short
chain alcohol, preferably methanol, to produce one mole glycerol,
which is the most important by-product, and three moles of methyl
esters. Homogeneous base catalysts such as KOH [5], NaOH [6],
sodium methoxide and potassium methoxide [7] are the most
conventional catalysts being used in the production of biodiesel.
Although the reaction rate in the presence of homogeneous catalysts
is fast, additional step is required to remove the catalyst impurities
from the products which increase the final production costs.
⁎ Corresponding author. Tel.: +60 3 79675297; fax: +60 3 79675319.
E-mail addresses: masoud.zabeti@gmail.com (M. Zabeti), ashri@um.edu.my
(W.M.A.W. Daud), mk_aroua@um.edu.my (M.K. Aroua).
reactions as an alternative to homogeneous base catalysts [8–10].
Among metal oxides, calcium oxide has attracted many interests as a
solid base catalyst because it can be synthesized from cheap sources
such as calcium carbonate, calcium acetate and calcium nitrate; it is
non-toxic; it possess basicity as high as alkali metal oxides while it
showed less leaching of active sites into the product stream [11].
Zabeti et al. [12] reviewed different solid catalysts including calcium
oxide catalysts and found that the leaching of the CaO active species
into the reaction media can be significantly reduced by anchoring it
onto a catalyst support. Demirbas [13] used calcium oxide as a solid
base catalyst in the transesterification of sunflower oil with
supercritical methanol to produce biodiesel; after six minutes the
methyl ester yields of 98% was obtained when the reaction was
carried out at temperature of 252 °C, pressure of 24 MPa, methanol/oil
molar ratio of 41 and catalyst content of 3 wt.%. The production of
biodiesel in supercritical fluids is not a common approach since the
process needs to be carried out at high temperatures and pressures.
Granados et al. [14] used calcium oxide for methanolysis of sunflower
oil and the catalyst showed a high activity towards the conversion of
oil; a conversion of 94% was achieved when the reaction was carried
out for 100 min at temperature of 60 °C, using methanol/oil molar
ratio of 13:1 and 3 wt.% of the catalyst. However, the activity of the
catalyst was contributed to both heterogeneous sites and homoge-
neous root because of the leaching of the calcium oxide active species
into the reaction media.
On the other hand, alumina-supported calcium nitrate was applied
in the transesterification of palm kernel oil; although an insignificant
amount of the catalyst was leached into the products, a large amount
of catalyst content, 10 wt.%, and high methanol/oil molar ratio of 65:1
was required to obtained the methyl esters yields of 94% when the

0378-3820/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2009.10.004
244 M. Zabeti et al. / Fuel Processing Technology 91 (2010) 243–248
reaction was carried out for 3 h at reaction temperature of 60 °C.
Besides, the catalyst was only active at temperatures below 450 °C
because the CaO phases were completely transformed to calcium
aluminate at higher temperatures with less basicity [15]. Albuquerque
et al. [16] studied the production of biodiesel from sunflower oil using
CaO/SBA-15 as a solid base catalyst; a conversion of 95% was obtained
after 5 h using moderate operating conditions of methanol/oil molar
ratio of 12:1, catalyst content of 1 wt.% and reaction temperature of
60 °C. Moreover, the amount of the catalyst leaching into the product
measured by ICP-MS was insignificant. Nevertheless, the preparation
of SBA-15 support from Pluronic 123 polymer was expensive and can
limit the commercial applications of this catalyst.
The aim of this study is the investigation of the optimum reaction
conditions for transesterification of palm oil using CaO/Al2O3 solid
base catalyst. Palm oil was the cheapest and the most available
vegetable oil in the Malaysian market; we used palm oil as a
representative feedstock for the production of biodiesel. Central
Composite Design (CCD) was used to design the experiments and
Response Surface Methodology (RSM) was carried out for process
optimization. Leaching of the catalyst was determined using ICP-MS
analysis and the reusability of the catalyst was tested in two
subsequent cycles. Finally, the amount of the methyl ester obtained
using optimum conditions was compared with other reports in the
literature.
2. Materials and methods
2.1. Chemicals
Gamma alumina (anhydrous, specific surface area according to
BET: 120–190 m2/g), methanol (for synthesis, > 99.5%), normal
hexane (GC grade, > 99%) and other standards for GC column
calibration were purchased from Merck. Calcium acetate monohy-
drated (A.C.S reagent) was obtained from Sigma-Aldrich. Palm oil as a
sample of vegetable oil was obtained from a local market and used as
the feedstock for the transesterification reactions. The fatty acid
compositions of palm oil are given in Table 1.
2.2. Catalyst preparation
The CaO/Al2O3 catalyst was prepared using optimum conditions as
follow: calcium acetate with a mass ratio of 1:1 to the support was
dissolved in 50 ml of distilled water and then stirred with 40 g of
alumina at room temperature for 4 h. The obtained slurry was heated
up at 100 °C in an oven overnight in order to remove the water.
Finally, the catalyst was calcined in air at 718 °C for 5 h using a muffle
furnace. The catalyst was kept in a desiccator in the presence of silica
and KOH pellets in order to avoid water and CO2 contact with the
catalyst. All details pertaining to the catalyst preparation and
Table 1
Fatty acid compositions of palm oil.
Source: http://www.chempro.in/fattyacid.htm.
Fatty Acid Structure Composition (wt.%)
Lauric (sat.a) 12:0d –
Myristic (sat.) 14:0 0.5–2
Palmitic (sat.) 16:0 32–45
Stearic (sat.) 18:0 2–7
Oleic (monounsat.b) 18:1 38–52
Linoleic (polyunsat.c) 18:2 5–11
Linolenic (polyunsat.) 18:3 –
a Reaction temp. (T)
Saturated.
b Methanol/oil molar ratio (M)
Mono unsaturated.
c Catalyst content (C)
Poly unsaturated.
d
Number of carbons:double bonds.
reproducibility of the method preparation can be found in the article
by Zabeti et al. [17].
Leaching of the catalyst into the reaction medium was determined
using the Inductively Coupled Plasma Mass Spectrometry (ICP-MS)
according to an international method (EN 14538).
2.3. Transesterification reactions
Transesterification reactions were carried according to each design
points (Table 4) and the results of the methyl ester yields of palm oil
were used as the response values in order to optimize the reaction
conditions. All experiments were performed in a 150 ml glass-
jacketed reactor equipped with a water-cooled condenser and a
magnetic stirrer. Fifty grams of oil was heated up to a desired
temperature by means of a water bath; then the reaction was initiated
by adding methanol and catalyst with a desired amount. The mixture
was stirred with an optimum speed of 1000 rpm for 5 h. After the
reaction was completed, the catalyst was separated by centrifuging
and the glycerol was separated in a decanter; finally the residual
alcohol was evaporated by means of heating.
2.4. Analysis of the ester phase
Characterization of methyl ester compounds in biodiesel samples
were conducted by a HP 6890 Gas Chromatogram (GC) equipped with
a Flame Ionization Detector (FID) and capillary column DB23 (60-
m × 0.25-m × 0.15-µm) according to a methodology proposed by
Agilent [18]. Normal hexane solutions of the biodiesel samples with
a concentration of 100 mg/ml were injected by an auto injector at an
oven temperature of 50 °C, which then was heated up to 230 °C. The
injector temperature and the detector temperature were 250 °C and
280 °C, respectively; helium was used as the carrier gas. The yields
were calculated from the equation below:
ðweight of biodiesel producedÞ × total wt:% of FAME in dilluted sample
Yieldð%Þ = × 100
weight of oil
ð1Þ
Here FAME means: Fatty Acid Methyl Esters.
2.5. Statistical analysis
Design Expert software (version 7.1) was used in this study to
design the experiments and to optimize the reaction conditions. The
experimental design employed in this work was a five-level-three-
factor central composite design, including 18 experiments. Reaction
temperature, T, catalyst content, C, and methanol/oil molar ratio, M,
were selected as independent factors for the optimization study. The
response chosen was the methyl ester yields obtained from
transesterification of palm oil. Four replications of center point were
used in order to predict a good estimation of errors and experiments
were performed in a randomized order. The actual and coded levels of
each factor are shown in Table 2. The coded values were designated by
−1 (minimum), 0 (center), +1 (maximum), −α and +α. Alpha is
defined as a distance from the center point which can be either inside
or outside the range, with the maximum value of 2n/4, where n is the
Table 2
Studied range of each factor in actual and coded form.
Factor Units Low level High level
°C 55 (− 1) 65 (+ 1)
6:1 (− 1) 24:1 (+ 1)
Wt.% 1 (− 1) 8 (+ 1)
Temp., temperature.
 M. Zabeti et al. / Fuel Processing Technology 91 (2010) 243–248 245

number of factors [19]. Hereby the value of alpha is set at 0.5. It is Table 4
noteworthy to point out that the software uses the concept of the Experimental design point and the response values (experiments were performed
following run order).
coded values for the investigation of the significant terms, thus
equation in coded values (Eq. (2)) is used to study the effect of the Run Type of Factor T Factor M Factor C Yield response
variables on the response. order factor (°C) (ratio) (wt.%) (%)

Selection of levels for each factor was based on the literature 16 Fact. 55 (− 1)a 6 (− 1) 1 (− 1) 29
reports on the applications of solid base catalysts for transesterifica- 1 Fact. 65 (+ 1) 6 (− 1) 1 (− 1) 45
10 Fact. 55 (− 1) 24 (+1) 1 (− 1) 28
tion reactions. The lower level of temperature was 55 °C since below
15 Fact. 65 (+ 1) 24 (+1) 1 (− 1) 33
that the reaction rate is relatively slow. The upper level of 14 Fact. 55 (− 1) 6 (− 1) 8 (+1) 32
temperature, 65 °C, was limited by boiling point of methanol at 17 Fact. 65 (+ 1) 6 (− 1) 8 (+1) 90
which temperature the mass transfer on the three phases interface is 13 Fact. 55 (− 1) 24 (+1) 8 (+1) 45
limited by formation of the methanol bubbles [20]. The levels of 3 Fact. 65 (+ 1) 24 (+1) 8 (+1) 63
2 Axial 57.5(− α) 15 (0) 4.5 (0) 69
methanol/oil molar ratio were selected between 6:1 and 24:1 and the
9 Axial 62.5(+ α) 15 (0) 4.5 (0) 91
catalyst concentration was limited between 1 wt.% and 8 wt.% (based 12 Axial 60 (0) 10.5 (− α) 4.5 (0) 87
on the initial weight of the oil) [21]. 18 Axial 60 (0) 19.5 (+α) 4.5 (0) 66
5 Axial 60 (0) 15 (0) 2.75 (− α) 83
6 Axial 60 (0) 15 (0) 6.25 (+α) 75
3. Results and discussion 8 Center 60 (0) 15 (0) 4.5 (0) 81
11 Center 60 (0) 15 (0) 4.5 (0) 82
4 Center 60 (0) 15 (0) 4.5 (0) 90
3.1. Catalyst characterization
7 Center 60 (0) 15 (0) 4.5 (0) 73
a
The characterization results of the CaO/Al2O3 are summarized in : actual value (coded value); Fact., factorial; T, temperature; M, methanol/oil molar
ratio; C, catalyst content; α = 0.5.
Table 3. From this table it can be seen that the catalyst is a mesoporous
catalyst with a large specific surface area and high amount of active
sites concentration which can provide enough active sites and pores
removing terms of M2 and C2 was resulted in an insignificant and
where large molecules of triglycerides can react with the catalyst
negative predicted R-squared which reduce the model precision.
active species. According to our previous study [17] the CaO/Al2O3
Moreover, the insignificant term of methanol/oil molar ratio is required
catalyst with the basicity of 190 µmol/g was found as the most active
to support the model hierarchy thus cannot be removed.
catalyst for transesterification of palm oil with methanol; therefore, in
Lack of fit, which is the weighted sum of squared deviations
this study, we used it as the catalyst for the optimization studies of the
between the mean response at each factor level and the corresponding
biodiesel production.
fitted value, is not significant for the response with a P-value of 0.4139
(lack of fit p-value > 0.05 is not significant); this implies that the model
3.2. Data analysis is fitted to all data (Non-significant lack of fit is good). Predicted R-
squared, which is a measure of how good the model predicts values for
The experimental results of the methyl ester yields as well as the response, is within 0.20 of Adjusted R-squared verifying the
experimental points in coded and actual values are represented in experimental data and the model precision. Adequate precision is a
Table 4. The statistical analysis of variance (ANOVA) was performed by measure of signal to noise ratio; it compares the range of the predicted
the software in order to investigate the fitness and significance of the values at the design points to the average prediction error and as
model, the precision of the model, the effects of the individual variables prerequisite of the model, a ratio of greater than 4 is desirable. In this
and interaction effects on the response. According to the ANOVA results model, the ratio of 11.414 indicates sufficient model discrimination.
(Table 5), the model was significant with a p-value (probability of error A quadratic polynomial model was obtained based on the
value) less than 0.0001 to predict the methyl ester yields values. experimental data and the following equations were generated to
Reaction temperature, T, catalyst concentration, C, reaction tempera- predict the methyl ester yields:
ture–catalyst concentration interaction, TC, and the interaction term of Equation in the terms of coded factors
reaction temperature–molar ratio, TM, were significant model terms
with p-values less than 0.05 (model and term p-value< 0.05 indicates
Yields = −81:45 + 12:71 T−4:41 M + 10:71C−6:37TM + 6:88TC
that the model is significant for 95% confidence intervals). Additionally, 2 2
−22:89M −12:89C ð2Þ
methanol/oil molar ratio, M, quadratic term of methanol/oil molar
ratio, M2, and quadratic term of catalyst concentration, C2, were
insignificant terms (term p-value>0.100 indicates the model terms
are not significant). The elimination of the insignificant terms may
Table 5
improve the regression model. Nevertheless, in this optimization study,
ANOVA table for the model and the model terms.

Source P-value, Prob. > F

Model <0.0001 significant

Table 3 T—Reaction temperature 0.0009
Characterization results for the CaO/Al2O3 catalyst used in this study. M—Methanol/oil mol. ratio 0.1375
C—Catalyst content 0.0029
Catalyst properties Value Unit Techniquesa
TM 0.0471
2
Specific surface area 82.74 m /g BET TC 0.0348
Pore volume 0.223 cm3/g BET M^2 0.1845
Mean pore size 63.37 Å BET C^2 0.4408
Active sites concentration 190 µmol/g TPD-CO2 Lack of Fit 0.4139 not significant
Particle size D (v, 0.9)b = 216.81 µm Master sizer R-squared 0.9298
Ca content 8.84 Wt.% ICP-MS Adj. R-squared 0.8806
a Pred. R-squared 0.6966
All the characterization tests were performed by Centre for Research in
Adeq. precision 11.414
Nanotechnology and Catalysis (NANOCEN), University of Malaya, Malaysia.
b
The particle size of 90% of the particles. Adeq.: adequate; Adj.: adjusted; Pred. predicted; Prob.: probability.
246 M. Zabeti et al. / Fuel Processing Technology 91 (2010) 243–248

Equation in the terms of coded factors temperatures, the amount of methyl ester yields decline because of
the fact that the interaction term of TM is more significant with a
Yields = −183:74535 + 2:89832T + 16:48703M−11:04350C−0:14167TM negative effect on the response (Fig. 1(b) and Eq. (2)).
+ 0:39286TC−0:28257M 2 −1:05212C 2 ð3Þ
3.4. Optimization of the operating conditions

Fig. 2(a) and (b) represent contour plots for the predicted methyl
3.3. Influence of the parameters on the methyl ester yields ester yields in the studied range of each variable. As can be seen from
the figures, each contour indicates coordinates of two factors at the
Surface plots of the predicted methyl ester yields, which can be center point of the third factor, at which the same results of the
generated by either Eq. (2) or Eq. (3), are illustrated in Fig. 1(a) and biodiesel yields are obtained. For instance, when the transesterifica-
(b). The figures show that, at low reaction temperatures, the amount tion reaction is carried out at reaction temperature of 60 °C using
of methyl ester yields increase with methanol/oil molar ratio and catalyst concentration of 2.75 wt.% and methanol/oil molar ratio of
catalyst concentration. However, at higher catalyst concentrations 15:1, the methyl ester yields of 72.7% is obtained after 5 h of the
and methanol/oil molar ratios, a reduction in the amount of yields can
be observed due to the fact that the quadratic terms of the two factors
are more significant with a negative effect (Eq. (2)). At higher
temperatures, there is a considerable increase in the amount of the
biodiesel yields with the catalyst concentration as a result of a positive
significant effect of TC on the response (Fig. 1(a) and Eq. (2)). On the
other hand, by increasing methanol/oil molar ratio at higher

Fig. 1. a. Response surface of predicted yields versus catalyst content and reaction Fig. 2. a. Contour plot of the predicted yields versus reaction temperature and catalyst
temperature at methanol/oil molar ratio of 12:1. b. Response surface of predicted yields content at methanol/oil molar ratio of 12:1. b. Contour plot of predicted yields versus
versus methanol/oil molar ratio and reaction temperature at catalyst content of 4.50 wt.%. reaction temperature and methanol/oil molar ratio at catalyst content of 4.50 wt.%.
 M. Zabeti et al. / Fuel Processing Technology 91 (2010) 243–248
reaction time. When the catalyst concentration increased beyond
6.25 wt.%, a slight decrease was observed in the amount of methyl
ester yields (Fig. 2(a)) which was probably due to a mixing problem
concerning solid catalyst and reactants [11]. Moreover, Fig. 2(b)
indicates a reduction in the amount of biodiesel yields by adding more
than 15:1 alcohol/oil molar ratio because of the difficulties in glycerol
separation [20]. Based on these results, optimization of the reaction
parameters was carried out using a numerical optimization method;
the optimum operating conditions calculated were catalyst concen-
tration of 5.97 wt.%, alcohol/oil molar ratio of 12.14:1 and reaction
temperature of 64.29 °C. The amount of the methyl ester yields under
the optimum reaction conditions was predicted to be 97.88%. Fig. 3
represents the graphical optimization of the methyl ester yields in the
studied range of variables. The marked area in Fig. 3 indicates all the
possible combinations of reaction temperature and methanol/oil
molar ratio at a constant amount of catalyst concentration, 5.97 wt.%,
at which methyl ester yields of 90% to 98% are achieved.
A transesterification reaction under the obtained optimum
operating conditions was carried out in order to evaluate the precision
of the quadratic model; the experimental values and predicted values
are shown in Table 6. Comparing the experimental and predicted
results, it can be seen that the error between the experimental and
predicted values is less than 0.7%; therefore it can be concluded that
the generated model has sufficient accuracy to predict the amount of
the methyl ester yields.
3.5. Reusability test of the catalyst
The CaO/Al2O3 catalyst, which was used in the transesterification
of palm oil under operating conditions of methanol/oil 12:1, catalyst
concentration 3.5 wt.% and reaction temperature of 65 °C, was
collected after the reaction and was directly reused in the second
cycle. The amount of the biodiesel yields after the second cycle
calculated was approximately 91% which is in a good agreement with
the results from the first cycle, with 95% of the yields. Furthermore,
leaching test of the catalyst was conducted by ICP-MS technique and
the amount of calcium in the biodiesel samples, after the first and
second cycles, was measure 31 mg/kg and 12 mg/kg, respectively. The
results imply that the leaching of the catalyst active species into the
biodiesel phase is insignificant. In addition, under certain operating
conditions the glycerol, as the most important by-products of
Fig. 3. Overlay plot of the yields between 90% and 98% versus reaction temperature and
methanol/oil molar ratio; catalyst content is constant at optimum value of 5.97 wt.%.
247
Table 6
Results of the model evaluation (experiment 1 indicates the optimum reaction
conditions and yields).
Experiment Reaction temp. Methanol/ Catalyst Amount of methyl ester
(°C), T oil molar cont. yields (%)
ratio, M (wt.%), C
Experimental Predicted
1 64.29 12.14:1 5.97 98.64 97.88
biodiesel production, obtained was colorless indicating a catalyst-
free glycerol.
The activity of the CaO/Al2O3 catalyst and the optimum amount of
the yields obtained in this work were compared with the results in the
literature. Yang and Xie [11] used Sr(NO3)2/ZnO as a solid base
catalyst in the transesterification of soybean oil; after 5 h, the
conversion of oil was 94.7% when the reaction was carried out at
temperature of 65 °C, catalyst content of 5% and methanol/oil molar
ratio of 12:1. Nevertheless, the catalyst showed a weak activity in the
second cycle with a soybean conversion of 15.4%, which was due to
the leaching of the strontium oxide active species into the reaction.
Alumina-supported potassium nitrate as a solid base catalyst was
performed in the biodiesel production from soybean oil and under
reaction conditions of alcohol/oil molar ratio of 15:1, catalyst content
of 6.5 wt.% and at temperature of 65 °C the conversion of soybean oil
was 87.43% after 7 h [21]. Mg–Al hydrotalcite as a solid base catalyst
exhibited low activity towards transesterification of soybean oil;
conversion of 67% was achieved after 9 h when the reaction was
performed at temperature of 65 °C using methanol/oil molar ratio of
15:1 and catalyst content of 7.5 wt.% [22].
4. Conclusions
Optimization of the reaction parameters for biodiesel production
from palm oil was carried out using response surface methodology.
The reaction was catalyzed with a previously optimized CaO/Al2O3
base catalyst. The effects of the reaction temperature and catalyst
content on the amount of methyl ester yields were significant while
alcohol/oil molar ratio had almost insignificant influence. Moreover,
the second order model showed a significant precision to predict the
response values. The optimum values of the parameters were catalyst
content of 5.97 wt.%, alcohol/oil molar ratio of 12.14:1 and reaction
temperature of 64.29 °C; under these conditions the amount of
methyl ester yields achieved was 98.64%. According to the results
from ICP-MS analysis, the leaching of the catalyst into the reaction
was negligible and under certain reaction conditions the glycerol
obtained was colorless. The catalyst was reusable and the catalyst
activity was sustained after two cycles.
Acknowledgement
This study was carried out with the aid of a research grant from the
University Malaya Research Fund.
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