Fuel 190 (2017) 104–112

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Fuel
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Full Length Article

Prediction of biodiesel yield during transesterification process using

response surface methodology
M. Mohamad, N. Ngadi ⇑, S.L. Wong, M. Jusoh, N.Y. Yahya
Department of Chemical Engineering, Faculty of Chemical and Energy Engineering, Universiti Teknologi Malaysia, 81310 Skudai, Johor, Malaysia

h i g h l i g h t s

Transesterification of vegetable palm oil (VPO) to biodiesel was performed over CaO-TiO2 under UV light.

Effects of reaction time, VPO:methanol ratio and catalyst dosage on biodiesel yield was studied.

The catalyst was reusable up to four cycles at optimized conditions with >80% biodiesel yield.

The fatty methyl ester (FAME) in the biodiesel was analyzed using GC-MS.

The biodiesel produced meets the ASTM D6751 specifications.

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

Article history: This study examines the production of biodiesel from vegetable palm oil (VPO) via transesterification cat-
Received 14 May 2016 alyzed by calcium oxide modified with titanium dioxide (CaO-TiO2) under UV light. Response surface
Received in revised form 17 October 2016 methodology (RSM) with central composite design (CCD) was used to optimize the biodiesel yield. The
Accepted 31 October 2016
optimized conditions for transesterification were 2.52 wt.% for catalyst dosage, 3:4 for volumetric ratio
Available online 17 November 2016
of VPO to methanol, 65 °C for reaction temperature, and 145.51 min for reaction time. VPO transesterifi-
cation under optimum conditions produced 96.67% biodiesel yield. In addition, regeneration of CaO-TiO2
Keywords:
catalyst was studied under optimum conditions. This catalyst can be reused for four times with biodiesel
Biodiesel
Vegetable palm oil (VPO)
yields beyond 80%. GC-MS analysis revealed the main methyl ester components in the biodiesel product
Transesterification including 9-octadecenoic acid, methyl ester (E)-(oleic acid) and hexadecanoic acid methyl ester (palmitic
CaO-TiO2 acid). Kinetic viscosity and higher heating value of the biodiesel were found to be in agreement with the
Ultraviolet (UV) light ASTM D 6751 standard. This study demonstrated a practical method to produce biodiesel from VPO with
Optimization less corrosion, less toxicity, and less environmental problems using an effective, stable and economic
heterogeneous basic catalyst, CaO-TiO2.
Ó 2016 Elsevier Ltd. All rights reserved.

1. Introduction and co-workers [3] on CaO-SiO2 in palm oil transesterification

Biodiesel has been widely used as an alternative to fossil fuels.
However, there are several challenges and issues associated with
this technology, especially in process cost which depends on
numerous factors such as the types of feedstock, technologies used,
types of catalyst and the operational cost. In order to tackle the
issue on the catalyst, various attempts have been made by
researchers to develop a stable and effective catalyst for industrial
biodiesel production [1]. Such catalyst must have high mechanical
strength which translates to easy handling, separation and
reusability. Hence, the material cost associated with the catalyst
can be reduced [2]. A reusability study was performed by Chen
⇑ Corresponding author.
E-mail address: norzita@cheme.utm.my (N. Ngadi).
under optimum conditions for 12 cycles. Along with the increase
of the amount of Si compounds in the CaO–SiO2 catalysts, they
found that the catalytic activity was gradually decreased, while
the reusability was significantly improved [3].
There are also other works on improvement of CaO activity
since catalytic transesterification over CaO suffers slower rate than
other homogeneous catalytic reaction. Witoon et al. [4] studied on
biodiesel production from transesterification of palm oil with
methanol over CaO supported on bimodal meso-macroporous sil-
ica catalyst. The use of such support enhanced the accessibility of
CaO dispersed inside the pores. The catalyst with the smallest pel-
let size (50CaO/B-82.5) produced 95.16% biodiesel yield under the
conditions of 5 wt.% for catalyst amounts, 12:1 for molar ratio of
methanol to oil, and reaction temperature of 60 °C for 6 h. Mean-
while, another study on calcium-based mixed oxide catalysts for

http://dx.doi.org/10.1016/j.fuel.2016.10.123
0016-2361/Ó 2016 Elsevier Ltd. All rights reserved.
 M. Mohamad et al. / Fuel 190 (2017) 104–112
methanolysis of Jatropha curcas oil to biodiesel by Taufiq-Yap et al.
[5] revealed that more than 80% biodiesel yield can be achieved
with CaMgO and CaZnO catalysts at temperature of 338 K, 6 h for
reaction time, 4 wt.% for catalyst dosage and 15:1 for ratio of
methanol to oil. These catalysts maintained their activity even
after being reused up to 3 and 4 times respectively. Moreover,
Liu et al. [6] found that 99.9% biodiesel yield can be achieved in
soybean oil transesterification catalyzed by 2.1 wt.% cinder sup-
ported CaO/KF particle catalyst with 12:1 for ratio of methanol to
oil, 20 min for reaction time and 65 °C for reaction temperature.
In addition to abovementioned studies, there are efforts on
modification of CaO to increase its catalytic activity, including
the use of alkali metal doping, wet impregnation, sol-gel method,
nano-sizing, combination of CaO with other metal oxide, as well
as pasting biodiesel on CaO surface to protect the basic sites and
surface regeneration by fouled surface reaction with methanol
[7]. Among these methods, wet impregnation is commonly used
to combine CaO with other compounds. A promising catalyst, tita-
nium dioxide (TiO2) is useful in many applications due to low
material cost, resource availability and non-toxicity. Many
researchers claim that TiO2 is very efficient in the presence of UV
light due to fast response and high responsivity [8–11]. Thus,
TiO2 becomes an ideal candidate for various commercial and
industrial applications. However, studies on effect of ultraviolet
(UV) light on TiO2 catalytic activity in transesterification process
are still limited.
Basic catalysts are commonly used in transesterification due to
their higher reactivity and lower process temperature require-
ment. The biodiesel yield increases with catalyst concentration.
However, when the basic catalysts are added above their optimum
concentration, the biodiesel yield reduces due to soap formation.
Boro et al. [12] studied on transesterification of waste cooking oil
(WCO) over heterogeneous catalyst (Ba-doped CaO) derived from
waste shells of Turbonilla Striatula. They also investigated on the
effect of catalyst amount (0.1–1.5 wt.%) on biodiesel conversion
at 60 °C, 6 h of reaction time and 6:1 for ratio of methanol to oil.
From their observation, the optimum catalyst amount was
1.0 wt.% and they concluded that the catalytic activity is highly
affected by basicity [12].
Generally, palm oil conversion and biodiesel yield increase with
reaction time. The reaction is initially slow due to mixing and dis-
persion of alcohol in the oil. The reaction proceeds faster after
some time until maximum yield is reached. The maximum biodie-
sel yield for transesterification over homogenous basic catalysts
can be achieved at reaction time of 1–3 h depending on types of
vegetable oil. However, researchers also state that excess reaction
time leads to reduction in the product yield due to soaps formation
from fatty acids [13,14]. Li et al. [15] studied on the influence of
reaction time (15–120 min) on biodiesel yield from soybean oil
over a solid basic catalyst prepared from waste carbide slag. It
was found that 91.3% biodiesel yield was achieved (30 min for
reaction time, 65 °C for temperature, 9:1 for ratio of methanol to
oil, and 1 wt.% for catalyst concentration). They stated that calcined
carbide slag catalyst is one of the best CaO catalysts in reducing the
reaction time [15].
Among numerous experimental designs, Response Surface
Methodology (RSM) is widely used by researchers due to its versa-
tility for various processes. RSM is defined as a statistical method
that uses quantitative data from properly designed experiments
to solve multivarient equations. RSM is commonly used to design
experiments, build optimization models, evaluate the variable
effects and determine the optimum conditions that produce tar-
geted responses [16]. Besides that, RSM is used to quantify the
relationship between measurable responses and experimental fac-
tors presumed to affect the response.
105
In studies on transesterification of vegetable oils to biodiesel,
there are many methods to determine the content of biodiesel
glycerides and esters, such as spectroscopy and chromatography.
Gas chromatography (GC) is commonly used to determine methyl
esters, monoglycerides, diglycerides and triglycerides in pure bio-
diesel products [3]. Yusuf et al. [17] stated that biodiesel is a clear
amber-yellow liquid with a viscosity similar to petroleum diesel.
Generally, biodiesel should meet the respective limits in the afore-
mentioned standards. There are two major biodiesel standards,
namely European Standard for Biodiesel (EN 14214: 2012) and
American Standard Specifications for Biodiesel Fuel (B100) Blend
Stock for Distillate Fuels (ASTM D 6751: 2012). These standards
are important to avoid the operational problems when using bio-
diesel in diesel engines.
According to the summarized literature, it is vital to search for
an effective catalyst that leads to high biodiesel yield in transester-
ification of vegetable palm oil (VPO) upon repeated usage. Thus,
the aim of this study is to investigate on the catalytic activity of
CaO-TiO2 during reflux transesterification of VPO under UV light.
The effects of process variables, namely catalyst dosage, ratio of
VPO to methanol and reaction time on the biodiesel production
were also explored based on preliminary study. Finally, the cat-
alytic effect of CaO-TiO2 upon repeated usage was examined.
2. Materials and methods
2.1. Materials
Seri Murni vegetable palm oil (VPO) was obtained from a local
manufacturer company in Johor, Malaysia. Catalysts (CaO and
TiO2) were purchased from Sigma-Aldrich while methanol with
purity of 99.8% was purchased from Fluka.
2.2. Catalyst preparation
CaO-TiO2 catalyst was prepared via wet impregnation method.
3 g of CaO was mixed with 3 g of TiO2 with 10 mL of distilled water.
Then, the mixture was dried in an oven at 100 °C for 2 h, followed
by calcination for 5 h in a furnace at 600 °C for activation. Then, all
the catalysts were cooled down and kept in the desiccator prior to
the experiment.
2.3. Transesterification of VPO
The performance of the modified catalyst, CaO-TiO2, on the bio-
diesel production via the transesterification of VPO under reflux
was tested under UV light (4 W). The experiment was also repeated
using CaO catalyst to compare its performance with that of the
modified catalyst. The reaction was conducted in a round bottom
flask equipped with a reflux condenser, UV light source, magnetic
stirrer and heater (Fig. 1). Selected amount of VPO, methanol and
catalyst were poured into a 250 mL round bottom flask. The reac-
tion was carried out at atmospheric pressure with stirring speed
of ±250 rpm and reaction temperature of 65 °C for specific reaction
time. A thermometer was attached to the round bottom flask to
monitor the reaction temperature. After the reaction was com-
pleted, solid catalyst was filtered off the filtrate mixture, which
was then transferred to a separating funnel and was allowed to
stand overnight. The bottom layer was drained off, while the top
layer was collected and rinsed with hot distilled water until clear
wash water was observed. The final volume of the top layer (bio-
diesel) was measured and the percentage yield was calculated
using Eq. (1) [3,18].
Weight of biodiesel produced ðgÞ
Yield ð%Þ ¼  100% ð1Þ
Weight of oil used ðgÞ
106 M. Mohamad et al. / Fuel 190 (2017) 104–112

2.5. Parametric study and optimization with RSM

Based on the result from the preliminary study, parametric

Fig. 1. Schematic diagram of reflux transesterification of VPO under UV light.
2.4. Preliminary study on transesterification of VPO
Preliminary study was conducted to observe the effect of cata-
lyst dosage on the performance of biodiesel production from VPO.
The range of catalyst dosage (0.1–2.0 wt.%) was selected based on
works by other researchers on biodiesel production [12,19]. Other
parameters were kept constant (3:5 for ratio of VPO to methanol,
60 min for reaction time, 65 °C for reaction temperature and
±500 rpm for stirring speed). Each experiment was repeated for
three times, and good reproducibility was observed.
Similar study was also conducted to observe the effect of reac-
tion time on the transesterification process. The range of reaction
time used in this study (30–150 min) was selected based on others
works in catalytic transesterification of oils [19–22]. The experi-
mental data were analyzed by Tukey’s range test (P 6 0.05) (Origin
9.0, OriginLab).
study on biodiesel production from VPO under UV light was carried
out using RSM. STATISTICA 8.0 software was utilized to generate
the experiment design and to perform data analysis. The variables
studied included catalyst dosage (wt.%) (X1), ratio of VPO to metha-
nol (X2) and reaction time (X3), while the response was biodiesel
yield (Y). The selected variables were considered as the most influ-
ential variables on biodiesel yield [23].
Central composite design (CCD) was used to study the effects of
the process variables and to predict the optimum process condi-
tions. The range and coded level of the studied variables are listed
in Table 1. Zero (0) value represents the center point for the vari-
able while +1 and 1 represent the upper and lower values studied
for the three variables [23,24]. A total of sixteen experimental runs
were carried out as listed in Table 2, and additional runs were per-
formed to ensure validity of the data. The full quadratic model of
biodiesel yields (Eq. (2)) was established using the method of least
squares. Y is referred to as the response (biodiesel yield) while b0 is
the intercept coefficient (offset); b1, b2 and b3 are the linear terms,
b11, b22 and b33 are the quadratic terms and b12, b13 and b23 are the
interaction terms.
Y ¼ b0 þ b1 X1 þ b2 X2 þ b3 X3 þ b11 X21 þ b22 X22 þ b33 X23
þ b12 X1 X2 þ b13 X1 X3 þ b23 X2 X3 ð2Þ
2.6. Catalyst reusability
It is important to test the stability of the synthesized catalyst
over repeated usage in the reaction. The setup for the reusability
study was the same as the transesterification reaction process
described in Section 2.3. The experiment was studied under opti-
mum conditions obtained from RSM study. The solid catalyst was
filtered off by a funnel with a filter paper and then was washed

Table 1
Coded variables of experimental design layout in optimization study.

Standard run Symbol Range and levels

1 0 +1
Catalyst dosage (wt.%) X1 0.1 1.62 2.0
Volumetric ratio of oil to methanol X2 1:15 1:2 3:5
Reaction time (min) X3 30 110 150

Table 2
CCD matrix with response values.

Standard run X1 X2 X3 Y
Catalyst dosage (wt.%) Coded Volumetric ratio of oil to methanol Coded Reaction time (min) Coded Biodiesel Yield (%)
1 0.1 1 0.07 1 30 1 65
2 0.1 1 0.07 1 150 +1 75
3 0.1 1 0.6 +1 30 1 76.67
4 0.1 1 0.6 +1 150 +1 75
5 2 +1 0.07 1 30 1 60
6 2 +1 0.07 1 150 +1 76.67
7 2 +1 0.6 +1 30 1 83.33
8 2 +1 0.6 +1 150 +1 86.67
9 0.02 a 0.5 0 110 0 76.67
10 3.22 +a 0.5 0 110 0 86.67
11 1.62 0 0.05 a 110 0 83.33
12 1.62 0 0.95 +a 110 0 90
13 1.62 0 0.5 0 9.09 a 65
14 1.62 0 0.5 0 210.91 +a 90
15 1.62 0 0.5 0 110 0 93.33
16 1.62 0 0.5 0 110 0 96.67
 M. Mohamad et al. / Fuel 190 (2017) 104–112
with methanol to remove the impurities. Then, the catalyst was
calcined for 5 h in an air furnace at 600 °C before being used for
the next cycle. This step was repeated for 5 cycles.
2.7. Determination of Fatty Methyl Ester (FAME) using GC-MS
Agilent Technologies 6890N Gas Chromatography-Mass Spec-
trometer (GC-MS) was used to analyze the fatty acid methyl ester
(FAME) contents in the product samples. For each analysis, the
sample was analyzed with an inert mass selectivity detector
5975. The capillary column was Agilent 19091S-433 HP-5MS
(30 mm  250 lm  0.25 lm) and helium was used as a carrier
gas. The oven temperature was held at initial temperature of
80 °C for 0.5 min, then ramped to a final temperature of 250 °C at
a rate of 10 °C min1, held for 5 min, with a total run time of
42 min. The injector temperature was 325 °C and that of the detec-
tor was 250 °C. The helium gas was flowed at 2 mL min1.
2.8. Determination of FAME properties
The physical properties of biodiesel produced were determined
accordingly using the ASTM method to compare the quality of the
product with the biodiesel standard specification ASTM D 6751-02
and ASTM DEN. Kinematic viscosity of the biodiesel was character-
ized using test method ASTM D445. For each test, 50 mL of sample
was heated on Cole-Parmer Viscometer for 30 min from 40 °C until
100 °C at 100 rpm. Higher heating value (HHV) of the biodiesel was
determined using test method ASTM D2015. 1.5 g of the sample
was analyzed using an oxygen bomb calorimeter at 30 atm. All
the analysis was carried out for three times for each sample.
3. Results and discussions
3.1. Preliminary study on biodiesel production
Fig. 2 illustrates the effect of catalyst dosage on percentage yield
of the biodiesel. Ideally, the use of catalyst reduces the activation
energy of the reaction, hence increases the effective collisions that
lead to reactions. The total number of active sites available for
reaction increases with the amount of catalyst, thus more reactant
molecules can collide with the active sites and react to form bio-
diesel. However, it has to be noted that excessive catalyst amount
Fig. 2. Effect of catalyst dosage on percentage yield. (Conditions: calcined catalyst
temperature for all catalysts at 600 °C, ratio of VPO to methanol 3:5, reaction time
60 min, reaction temperature 65 °C, stirring speed ±500 rpm).
107
also results in saponification reaction. Therefore, it is important to
determine the appropriate amount of catalyst that increases the
formation of biodiesel while reducing the chance of saponification.
Fig. 2 shows that biodiesel yields increased with catalysts dosage.
However, catalysts dosage above 0.5 wt.% decreased the biodiesel
yield due to soaps and emulsions formation. As shown in Fig. 2,
all catalysts produced higher biodiesel yield at 0.5 wt.% for catalyst
dosage. This amount is important to minimize the production cost
[23]. From the result, the range of catalyst dosage was suitable to
be used in the parametric study.
The result from Tukey’s range test (Fig. S1 in Supplementary
Material) indicates no significant difference between the yields
when CaO and CaO-TiO2 were used in transesterification. However,
significant difference in liquid yield was observed for transesterifi-
cation over CaO-TiO2 under UV light. This result shows that UV
light is essential to promote the catalytic activity of TiO2. Com-
pared to VPO transesterification over CaO and CaO-TiO2 without
UV light, the process over 0.5 wt.%, CaO-TiO2 under UV light pro-
duced higher biodiesel yield, which was 95%. The possible reason
for this observation is the ease of cations generation from CaO cat-
alyst which were easily inserted into vacant sites on the surface of
TiO2 [25]. After the substitution of CaO atoms in the crystal lattice
of TiO2, new impurity is introduced between the conduction band
and valence band of TiO2. Then the electrons of the modified cata-
lyst can be promoted to the conduction band from the impurity
level, producing a narrower band gap than pure CaO and increase
the absorption in the visible-light region [26]. Therefore, higher
catalytic activity of CaO-TiO2 transesterification under UV light
results in higher biodiesel yield. This trend is supported by Tang
et al. [27], who found that the rate of soybean transesterification
increased with CaO loading up to 30 mg CaO/1.3 mL mixture, as
more catalytic sites are available at higher CaO loading. However,
decrement in the reactions rate was observed at higher CaO load-
ing due to unfavorable substrate absorption on the surface of
excess CaO. Catalyst dosage of 0.5 wt.% was selected as the opti-
mum dosage for the parametric study.
Fig. 3 shows the effect of reaction time on percentage yield of
biodiesel. As illustrated in Fig. 3, the yield gradually increased with
reaction time. Transesterification over CaO and CaO-TiO2 under UV
light produced the highest biodiesel yield after 150 min, which
were 90% and 96.67% respectively. It is also noticed that transester-
ification of VPO over CaO-TiO2 under UV light is always higher than
Fig. 3. Effect of reaction time on percentage yield. (Conditions: catalyst dosage
0.5 wt.%, calcined catalyst temperature CaO and CaO-TiO2 under UV light at 600 °C,
ratio of palm oil to methanol 3:5, reaction temperature 65 °C, stirring speed
±500 rpm).
108 M. Mohamad et al. / Fuel 190 (2017) 104–112
the reaction over CaO. The difference in the percentage yield is pro-
ven by the Tukey’s range test result (Fig. S2 in Supplementary
Material). This again shows the superior performance of
CaO-TiO2 compared to CaO.
Modification of catalytic transesterification under UV light
enhanced the photocatalytic performance TiO2 by exhibiting faster
reaction rate than pure CaO catalyst. The TiO2 photocatalytic activ-
ity appeared to be attributable to properties such as large surface
area of the CaO-TiO2 catalyst and its activity under UV light [28].
Photogenerated holes and electrons of TiO2 appear under UV light
irradiation, and then the electrons migrate into the reaction mix-
ture while the holes remained on the catalyst surface. The elec-
trons also migrate to the catalyst surfaces which induced the
reduction of the CaO catalyst, resulting in increase of catalytic
activity [8]. Hence, transesterification of CaO-TiO2 catalyst exhib-
ited higher biodiesel yield under UV light. Based on Fig. 3, the addi-
tion of TiO2 improves the ability of the CaO-TiO2 catalyst to be
stable and increases the biodiesel yield at longer reaction time.
Such finding is supported by result from Viriya-Empikul et al.
[29] on performance of eggshell, golden apple snail shell, and
meretrix venus shell on palm olein oil transesterification. All the
catalysts produced high biodiesel yield (more than 90%) after 2 h
reaction time. This finding shows that basic site of CaO catalyst
produce higher biodiesel yield over long reaction time. However,
a study by Lu et al. [30] concluded that reaction time longer than
3 h is unfavorable on transesterification because it is an exother-
mal reversible reaction. Therefore, the same range of reaction time
was used in the parametric study.
3.2. Statistical analysis in parametric study
3.2.1. Parity Plot and Analysis of Variance (ANOVA)
Table 2 tabulates the CCD matrix with coded units together
with the response values. An empirical model was tested with
the ANOVA at confidence level of 95%. Based on the central com-
posite design, the predicted model for biodiesel yield in this study
is shown in Eq. (3).
Y ¼ 54:285 þ 2:120X1 þ 42:704X2 þ 0:313X3  3:841X21
 37:946X22  0:001X23 þ 11:791X1 X2 þ 0:058X1 X3
 0:109X2 X3
Fig. 4 illustrates the Parity plot, which graphically shows the
relationship between predicted values and observed (experimen-
tal) values for biodiesel yield in this study. In such experimental
design, the R2 value in the Parity plot should be more than 0.75
to validate the empirical model [24]. The R2 value for predicted
Fig. 4. Parity plot for biodiesel yield.
biodiesel yield is 0.862; in which 86.2% of the variability in the data
is accounted to the model. Thus, Eq. (3) is a valid model that
expresses the effect of the factors on the response.
In statistical analysis, it is necessary to test the model equation
with the null hypothesis, which states that all the regression coef-
ficients in the equation are zero. F-value is a common indicator
used to determine the significance of model in ANOVA analysis.
In order to reject the null hypothesis, the calculated F-value related
to the model must be greater than the tabulated F-value. The cal-
culated F-value is defined as the ratio between the mean of square
regression (MSSSR) and the mean of square residual (MSSSE). The
MSSSR and MSSSE are obtained by dividing sum of squares (SSR)
and sum of residual (SSE) over degree of freedom (DF), respec-
tively. Meanwhile, the tabulated F-value is defined as an value
which can be obtained from the F distribution table at specified
level of significance with degree of freedom of regression and
residual, respectively. Alpha (a) is defined as the distance from
the center point which can be either inside or outside the range
of the variables. The maximum value of the a- value can be calcu-
lated by formula 2n/4, where n is the number of factors [3,31]. The
p-values and F-values for each term in Eq. (3) are tabulated in
Table S1 (Supplementary Material), while Table 3 summarizes
the important figures in ANOVA analysis. Based on the F-test eval-
uation, this model is statistically significant at 95% confidence
level. The calculated F-value of 4.17 for this model is slightly higher
than the tabulated F-value (F0.05, 9, 6 = 4.1). Therefore, the empirical
model in this study gives a good prediction on biodiesel
production.
Fig. 5 represents a Pareto chart, which graphically shows the
significance of each coefficient in Eq. (3). The coefficient with
greater t-value contributes more to the significance of the model.
As demonstrated in the figure, linear term for reaction time (X3)
is the most significant term that contributes to biodiesel yield
with t-value = 3.385, followed by the linear term of volume ratio
(X2) (t-value = 2.888) and the quadratic term of reaction time
(X2) (t-value = 2.471). These variables are regarded as the
significant variables on biodiesel yield.
3.2.2. Interaction effects of variables on biodiesel yield
The interaction effects of the variables used in this study on the
response are graphically shown in Fig. 3. Each three-dimensional
ð3Þ
surface plot represents the effects of two variables on the biodiesel
yield as a response, while another variable is held constant.
Fig. 6(a) demonstrates the effect of interaction X1X2 on the bio-
diesel yield (Y) at constant reaction time (X3) of 110 min. Based on
the surface plot, the combined effect of the increased catalyst
dosage and ratio of VPO to methanol leads to the increment in bio-
diesel yield up to an optimum point. The biodiesel yield increases
with catalyst dosage at lower ratio of VPO to methanol. It is also
observed the increase has less effect on biodiesel yield. Such effect
was also observed by Zhang et al. [32]. However, since transester-
ification is a reversible reaction, low ratio of VPO to methanol
would dilute the catalyst and reverse the reaction. The same pat-
tern has been reported by Omar and Amin [23]. In short, Fig. 6(a)
indicates significant interaction of catalyst dosage and ratio of
VPO to methanol on biodiesel yield.
Fig. 6(b) illustrates the surface plot for the interaction X1X3 on
the biodiesel yield (Y) at constant X2 of 0.5 (1:2). The interaction
of catalyst dosage and reaction time is almost identical as the
interaction reported in Fig. 6(a). This finding is also similar to the
pattern reported by Omar and Amin [23]. The biodiesel yield is
lower at low catalyst dosage with shorter reaction time, as well
as at a higher catalyst dosage with longer reaction time. However,
the reaction is considered incomplete at shorter reaction time even
at higher catalyst dosage. On the other hand, longer reaction time
than necessary promotes the reverse reaction as suggested by Lee
 M. Mohamad et al. / Fuel 190 (2017) 104–112 109

Table 3
Analysis of variance (ANOVA) for biodiesel yield.

Sources Sum of Squares (SS) Degree of Freedom (DF) Mean Squares (MS) F-value F0.05
Regression (SSR) 1465.80 9 162.87 4.17 >4.1
Residual 234.201 6 39.03
Total (SST) 1700.00 15

Fig. 5. Pareto chart of biodiesel yield.

et al. [33]. Thus, the biodiesel yield would decrease. Moreover, the
three phase system (oil-methanol-catalyst) would slow down the
reaction when the amount of catalyst dosage is high. Therefore,
biodiesel yield is influenced by the interaction of catalyst dosage
and reaction time.
The interaction X2X3 on biodiesel yield (Y) at constant X1
(1.62 wt.%) is shown in Fig. 6(c). Based on the figure, interaction
of the mentioned variables produced significant effect on biodiesel
yield, which is supported by finding from Omar and Amin [23]. The
biodiesel yield increased as the ratio of VPO to methanol and reac-
tion time increased up to the optimum point. Therefore, all vari-
ables in this optimization model are significant on the biodiesel
yield.

3.2.3. Optimization of biodiesel yield

Optimized reaction conditions determined from the experimen-
tal data using Statistica software is tabulated in Table 4. The pre-
dicted optimum conditions for the biodiesel production were
suggested as follows: 2.52 wt.% for catalyst dosage, 0.75 (3:4) for
ratio of VPO to methanol and 145.51 min reaction time. Transester-
fication of VPO was carried out for three times at optimized condi-
tions, and the average value on biodiesel was calculated. The
predicted and experimental biodiesel yields are reported as
95.67% and 96.72%, respectively, with 1.05% error. Thus, the opti-
mized conditions for the process is verified.

3.3. Catalyst reusability

The catalyst reusability study was repeated for five times at

optimized conditions (Fig. 7). Small difference was observed in bio-
diesel yield for the first two cycles (within 3% deviation). However,
the biodiesel yield started to decrease slightly after three cycles.
The yield decreased to about 77% after five cycles. The experimen- Fig. 6. Response surface plot of biodiesel yield as function of (a) catalyst dosage and
tal error calculated using data from repeated experiments was ratio of VPO to methanol; (b) catalyst dosage and reaction time, and (c) ratio of VPO
small when compared to the difference in biodiesel yield upon to methanol and reaction time.
110 M. Mohamad et al. / Fuel 190 (2017) 104–112

Table 4 study is considered stable and can be reused for more than five
Analysis of optimum conditions for biodiesel yield. cycles. In contrast, Dias et al. [34] stated that heterogeneous cata-
Variable Observed Critical Observed lyst can be reused without significant loss of its activity, regardless
minimum values maximum of the experimental conditions used.
Catalyst dosage (wt.%) 0.022 2.523 3.218
Volumetric ratio oil to 0.054 0.745 0.946
methanol
3.4. Determination of FAME in biodiesel using GC-MS
Reaction time (min) 9.092 145.511 210.908
The methyl esters present in the biodiesel product detected in
GC-MS (Fig. 8) is tabulated in Table 5. The main methyl esters pro-
duced in this study are 9-octadecenoic acid, methyl ester, (E)-(oleic
acid) and hexadecanoic acid, methyl ester (palmitic acid). In addi-
tion, dodecanoic acid, methyl ester (lauric acid); tridecanoic acid,
12-methyl-, methyl ester; 9-hexadecenoic acid, methyl ester,
(Z)-; 7-hexadecenoic acid, methyl ester, (Z)-; 9,12-
octadecadienoic acid (Z,Z)-, methyl ester (linoleic acid); 7-
octadecenoic acid, methyl ester; octadecanoic acid, methyl ester
(stearic acid); cis-11-eicosenoic acid, methyl ester; cis-13-
eicosenoic acid, methyl ester; 11-eicosenoic acid, methyl ester;
and eicosanoic acid, methyl ester (arachidonic acid) were formed
as well. The methyl esters with area (%) less than 0.10 were not
listed.

3.5. Physico-chemical properties of biodiesel

The physico-chemical properties of the biodiesel determined

Fig. 7. Percentage yield of biodiesel for catalyst reusability study. (Conditions:
catalyst dosage of 2.52 wt.%, 3:4 for ratio of VPO to methanol, reaction time of
145.51 min, reaction temperature 24 of 65 °C).
repeated usage of catalyst. Thus, the comparison of the catalyst
performance is adequate. The decrement in catalytic activity was
probably due to the loss of catalyst during filtration and washing
process [18]. The same trend was observed by Dias et al. [34],
where the biodiesel yield gradually decreased from 93.61% to
52.89% after Sr/ZrO2 catalyst being used for 6 times, due to catalyst
loss during the experiment. Hu et al. [35] also reported the slight
drop of biodiesel yield after two cycles from 96% to 60% when
using freshwater mussel shell (FMS) as catalyst for 16 cycles. In
another study, after the modified TiO2 doped with C4H4O6HK was
reused for 5 cycles, the percentages of biodiesel yield slightly
decreased from 90.1% to 80% [36]. Thus, CaO-TiO2 catalyst in this
using ASTM 6751 method are listed in Table 6. It is clear that the
biodiesel produced meets all the ASTM D 6751 specifications.
Kinetic viscosity is the most important property of diesel fuel as
it influences the wear rate of engine components. Besides that,
the main objective of the transesterification or esterification pro-
cess is to reduce the viscosity in vegetable oil. The viscosity value
obtained is similar to the result from Hossain and Boyce [36] (5.8
cSt) on production of biodiesel from pure sunflower cooking oil
(PSCO). The obtained viscosity value shows that the biodiesel can
be used in cold climate areas without any problem because it has
a good flow characteristic at low temperature [25]. Therefore, the
biodiesel in this study can be used in diesel engines without fur-
ther modification on the injection pump.
Generally, the higher heating value or calorific value for biodie-
sel lies in the range of 37–40 MJ/kg, which is lower than diesel
(above 41 MJ/kg). The biodiesel obtained in this study has compar-
atively low heating value which is 37.84 MJ/kg. However, it is still
in the range of ASTM standard. The lower heating value is due to
the lower elemental carbon and higher elemental oxygen contents

Fig. 8. GC chromatograph analysis of biodiesel product/methyl ester (ME).

 M. Mohamad et al. / Fuel 190 (2017) 104–112 111

Table 5 References
The methyl ester component from GC-MS analysis.
[1] Islam A, Taufiq-Yap YH, Chu CM, Chan ES, Ravindra P. Studies on design of
Retention time Area Compound
heterogeneous catalysts for biodiesel production. Process Saf Environ Prot
(min) (%)
2013;91(131):44.
9.363 0.31 Dodecanoic acid, methyl ester [2] Sani YM, Daud WMAW, Aziz ARA. Activity of solid acid catalysts for biodiesel
11.657 0.92 Tridecanoic acid, 12-methyl-, methyl ester production: a critical review. Appl Catal A – Gen 2014;470:140–61.
13.540 0.19 9-Hexadecenoic acid, methyl ester, (Z)- [3] Chen G, Shan R, Li S, Shi J. A biomimetic silicification approach to synthesize
13.906 30.70 Hexadecanoic acid, methyl ester CaO–SiO2 catalyst for the transesterification of palm oil into biodiesel. Fuel
2015;153:48–55.
15.405 2.16 9,12-Octadecadienoic acid (Z,Z)-, methyl
[4] Witoon T, Bumrungsalee S, Vathavanichkul P, Palitsakun S, Saisriyoot M,
ester
Faungnawakij K. Biodiesel production from transesterification of palm oil with
15.629 42.40 9-Octadecenoic acid, methyl ester, (E)-
methanol over CaO supported on bimodal meso-macroporous silica catalyst.
15.743 3.65 Octadecanoic acid, methyl ester Bioresour Technol 2014;156:329–34.
17.214 0.27 cis-11-Eicosenoic acid, methyl ester [5] Taufiq-Yap YH, Lee HV, Hussein MZ, Yunus R. Calcium-based mixed oxide
17.419 0.50 Eicosanoic acid, methyl ester catalysts for methanolysis of Jatropha curcas oil to biodiesel. Biomass
Bioenergy 2011;35:827–34.
[6] Liu H, Su LY, Shao Y, Zou LB. Biodiesel production catalyzed by cinder
supported CaO/KF particle catalyst. Fuel 2012;97:651–7.
Table 6 [7] Kouzu M, Hidaka J. Transesterification of vegetable oil into biodiesel catalyzed
The physico-chemical properties of biodiesel. by CaO: a review. Fuel 2012;93:1–12.
[8] Ren CJ, Qiu W, Zhang HL, He ZJ, Chen YQ. Degradation of benzene on TiO2/SiO2/
Physico-chemical properties ASTM D 6751 Biodiesel Bi2O3 photocatalysts under UV and visible light. J Mol Catal A – Chem
2015;398:215–22.
Kinetic viscosity at 40 °C, cSt 1.9–6.0 mm2/s 5.94
[9] Rodríguez D, Perillo P. TiO2 nanopores with high sensitivity to ultraviolet light.
Higher heating value 37.37–40.168 MJ/kg 37.84
Opt Mater 2015;42:52–5.
[10] Madhuvilakku R, Piraman S. Biodiesel synthesis by 1 TiO2–ZnO mixed oxide
nanocatalyst catalyzed palm oil transesterification process. Bioresour Technol
2013;150:55–9.
in biodiesel product [37]. The oxygen contents increased after the [11] Mukenga M, Muzenda E, Jalama K, Meijboom R. Biodiesel production from
peroxidation process and consequently produced less carbon resi- soybean oil over supported nano-ZnO. World Acad Sci Eng Technol Int J Chem
due. Therefore, the biodiesel in this study can produce the least Mol Nucl Mater Metall Eng 2012;6:348–52.
[12] Boro J, Konwar LJ, Thakur AJ, Deka D. Ba doped CaO derived from waste shells
amount of black smoke emitted from the diesel engine and also of Tstriatula (TS-CaO) as heterogeneous catalyst for biodiesel production. Fuel
will reduce the emission of particulate matter. 2014;129:182–7.
[13] Brunschwig C, Moussavou W, Blin J. Use of bioethanol for biodiesel production.
Prog Energy Combust Sci 2012;38:283–301.
4. Conclusions [14] Issariyakul T, Dalai AK. Biodiesel from vegetable oils. Renew Sust Energy Rev
2014;31:446–71.
[15] Li FJ, Li HQ, Wang LG, Cao Y. Waste carbide slag as a solid base catalyst for
Wet impregnation of TiO2 on CaO produced significant effective synthesis of biodiesel via transesterification of soybean oil with
improvement on the palm oil transesterification compared to the methanol. Fuel Process Technol 2015;131:421–9.
transesterification over pure CaO. Thus, CaO-TiO2 can be regarded [16] Yahya NY, Ngadi N, Muhamad I, Alias H. Application of cellulose from Pandan
leaves as grafted flocculant for dyes treatment. J Eng Sci Technol 2015:19–28.
as another potential catalyst in biodiesel transesterification from [17] Yusuf NNAN, Kamarudin SK, Yaakub Z. Overview on the current trends in
palm oil under UV light using reflux method. Optimization of bio- biodiesel production. Energy Convers Manage 2011;52:2741–51.
diesel production from VPO was carried out to estimate the effects [18] Boro J, Thakur AJ, Deka D. Solid oxide derived from waste shells of Turbonilla
striatula as a renewable catalyst for biodiesel production. Fuel Process Technol
of the process variables (i.e. catalyst dosage, ratio of VPO to metha-
2011;92:2061–7.
nol, and reaction time) on biodiesel yield. Reaction time (X3) pro- [19] Yusup S, Khan MA. Base catalyzed transesterification of acid treated vegetable
duced the most significant effect on biodiesel production oil blend for biodiesel production. Biomass Bioenergy 2010;34:1500–4.
[20] Sirisomboonchai S, Abuduwayiti M, Guan GQ, Samart C, Abliz S, Hao XG, et al.
followed by ratio of VPO to methanol (X2), while the catalyst
Biodiesel production from waste cooking oil using calcined scallop shell as
dosage (X1) exhibited the least significant effect. VPO transesterifi- catalyst. Energy Convers Manage 2015;95:242–7.
cation under optimum conditions produced 96.67% biodiesel yield, [21] Zhang PB, Han QJ, Fan MM, Jiang PP. A novel waste water scale-derived solid
which was 1.05% more than the predicted value (95.67%). The cat- base catalyst for biodiesel production. Fuel 2014;124:66–72.
[22] Hu S, Guan Y, Wang Y, Han H. Nano-magnetic catalyst KF/CaO–Fe3O4 for
alyst can be reused up to four times with biodiesel yields beyond biodiesel production. Appl Energy 2011;88:2685–90.
80%. Thus, CaO-TiO2 catalyst was found to be an effective, stable [23] Omar WNNW, Amin NAS. Biodiesel production from waste cooking oil over
and economic heterogeneous basic catalyst for biodiesel produc- alkaline modified zirconia catalyst. Fuel Process Technol 2011;92:2397–405.
[24] Haaland PD. Experimental design in biotechnology. CRC Press; 1989.
tion from palm oil. Physical properties of the biodiesel are within [25] Takase M, Chen Y, Liu H, Zhao T, Yang L, Wu X. Biodiesel production from non-
the acceptable ranges corresponding to the ASTM D 6751 standard. edible Silybum marianum oil using heterogeneous solid base catalyst under
This study provides a practical method for biodiesel production ultrasonication. Ultrason Sonochem 2014;21:1752–62.
[26] Zhang Y, Zhao Z, Chen J, Cheng L, Chang J, Sheng W, et al. C-doped hollow TiO2
from VPO with less corrosion, less toxicity, and less environmental spheres: in situ synthesis, controlled shell thickness, and superior visible-light
problems. photocatalytic activity. Appl Catal B 2015;165:715–22.
[27] Tang SK, Zhao H, Song ZY, Olubajo O. Glymes as benign co-solvents for CaO-
catalyzed transesterification of soybean oil to biodiesel. Bioresour Technol
Acknowledgement 2013;139:107–12.
[28] Lee HU, Lee Y-C, Lee SC, Park SY, Son B, Lee JW, et al. Visible-light-responsive
bicrystalline (anatase/brookite) nanoporous nitrogen-doped TiO2
The authors are grateful to MyBrain15 (MyMaster) and Univer-
photocatalysts by plasma treatment. Chem Eng J 2014;254:268–75.
siti Teknologi Malaysia (UTM) Zamalah Scholarship. The authors [29] Viriya-Empikul N, Krasae P, Puttasawat B, Yoosuk 1 B, Chollacoop N,
also extend their sincere gratitude to Universiti Teknologi Malaysia Faungnawakij K. Waste shells of mollusk and egg as biodiesel production
and Ministry of Higher Education, Malaysia (MOHE) for the finan- catalysts. Bioresour Technol 2010;101:3765–7.
[30] Lu HF, Liu YY, Zhou H, Yang Y, Chen MY, Liang B. Production of biodiesel from
cial supports received under University Grant (Vot no. Q. Jatropha curcas L. oil. Comput Chem Eng 2009;33:1091–6.
J130000.2544.04H95). [31] Atadashi IM, Aroua MK, Aziz ARA, Sulaiman NMN. The effects of water on
biodiesel production and refining technologies: a review. Renew Sust Energy
Rev 2012;16:3456–70.
Appendix A. Supplementary material [32] Zhang JH, Chen SX, Yang R, Yan YY. Biodiesel production from vegetable oil
using heterogenous acid and alkali catalyst. Fuel 2010;89:2939–44.
[33] Lee HV, Yunus R, Juan JC, Taufiq-Yap YH. Process optimization design for
Supplementary data associated with this article can be found, in jatropha-based biodiesel production using response surface methodology. Fuel
the online version, at http://dx.doi.org/10.1016/j.fuel.2016.10.123. Process Technol 2011;92:2420–8.
112 M. Mohamad et al. / Fuel 190 (2017) 104–112

[34] Dias JM, Alvim-Ferraz MCM, Almeida MF, Diaz JDM, Polo MS, Utrilla JR. [36] Hossain ABMS, Boyce AN. Biodiesel production from waste sunflower cooking
Selection of heterogeneous catalysts for biodiesel production from animal fat. oil as an environmental recycling process and renewable energy. Bulgarian J
Fuel 2012;94:418–25. Agric Sci 2009;15:313–8.
[35] Hu SY, Wang Y, Han HY. Utilization of waste freshwater mussel shell as an [37] Lin CY, Lin HA, Hung LB. Fuel structure and properties of biodiesel produced by
economic catalyst for biodiesel production. Biomass Bioenergy the peroxidation process. Fuel 2006;85:1743–9.
2011;35:3627–35.