Journal of Chemical Engineering of Japan, Vol. 43, No. 8, pp.

661–670, 2010 Research Paper

Kinetic Study of Methanolysis of Jatropha Curcas-Waste Food Oil Mixture

Hanny Johanes BERCHMANS, Kayoko MORISHITA
and Takayuki TAKARADA
Department of Chemical and Environmental Engineering,
Gunma University, 1-5-1, Tenjin-cho, Kiryu-shi,
Gunma 376-8515, Japan

Keywords: Kinetic, Methanolysis, Waste Food Oil, Jatropha Curcas Oil, Free Fatty Acids

Methanolysis of a Jatropha curcas-waste food oil mixture that contained 1 wt% of free fatty acids was carried
out in the presence of a KOH catalyst in a batch reactor at various methanol-to-oil molar ratios; the reaction
temperature was varied from 25 to 60°C; the catalyst concentration was varied from 0.5 to 2.0 wt% of oil; the
mixing speed was fixed at 900 rpm and the reaction time was 2 h. Samples were collected during the reaction
time and analyzed by gas chromatography (GC) to determine the weight percentages of the reaction constituents
on glycerol-free basis. The experiments revealed that the reaction conditions (mixing level, reaction temperature,
catalyst concentration, and methanol-to-oil molar ratio) have a significant effect on the hydroxide catalyzed
methanolysis reaction of the Jatropha curcas-waste food oil mixture. The conversion rate of the oil mixture and
the methyl ester production rate increased with the mixing speed, reaction temperature, catalyst concentration
and methanol-to-oil molar ratio. A second-order kinetic model with the reaction rate constants obtained in the
experiment provided a satisfactory mechanism for the methanolysis reactions. The kinetic model was able to de-
scribe the experimental data, and the average relative average difference (RAD) was 4.7%. The simulation and
experiments also indicated that although the methanolysis reaction consisted of three stepwise and reversible re-
actions, the forward reactions were the most important. Activation energy analysis showed that the methanolysis
reactions of the Jatropha curcas-waste food oil mixture were sensitive to reaction temperature changes.

available and do not compete with food oils. Some re-

Introduction
Biodiesel fuel, which is widely accepted, is an alter-
native to petroleum diesel fuel due to the technical, envi-
ronmental and strategic advantages that it offers.
However, due to the high production cost, biodiesel is
usually more expensive than petroleum diesel fuel when
it is produced from fresh vegetable oils or animal fats
(Leung and Guo, 2006). It has been reported that ap-
proximately 70 to 95% of the total cost of biodiesel is
accounted for by the cost of feedstock, that is, vegetable
oils or animal fats (Zhang et al., 2003). Therefore, it is
necessary to find ways to produce cheaper biodiesel fuel.
Reduction of biodiesel production cost through the use
of more effective and efficient production technology
and the utilization of inexpensive vegetable oils is now
becoming the main focus of biodiesel researches.
Reducing of biodiesel production cost by using in-
expensive feedstock such as inedible vegetable oils,
waste animal fats, waste food oil and mixtures of such
feedstock is more practical because inedible vegetable
oils such as Jatropha curcas (J. curcas) oil are readily
Received on February 22, 2010; accepted on April 24, 2010
Correspondence concerning this article should be addressed to
T. Takarada (E-mail address: takarada@cee.gunma-u.ac.jp).
searchers have reported that the methaholysis of J. cur-
cas oil yields a product that has characteristics similar to
those of biodiesel fuel (Gubitz et al., 1999; Berchmans
and Hirata, 2008; Tapanes et al., 2008). A report on the
methanolysis of waste food oil has also shown that the
oil can be used an effective feedstock to produce
biodiesel that meets the EN 14214 standard (Felizardo et
al., 2006). The use of a mixture of J. curcas oil and
waste food oil as a feedstock for biodiesel production
can also reduce the production cost. However, the main
problem faced in using these oils in the alkali-based cat-
alyzed alcoholysis process is their free fatty acid (FFA)
content (Achten et al., 2008; Berchmans and Hirata,
2008).
Besides identifying inexpensive feedstock, re-
searchers are focusing on minimizing the production
cost by improving the production technology. One of the
lines of research involves maximizing the yield of the al-
coholysis reaction by controlling the reaction parameters
that affect the reaction rate and mechanism. A kinetic
study of alkali-catalyzed alcoholysis can indicate the re-
action mechanism and provide the reaction parameters
that can be used to predict the compositions and concen-
tration of the reaction mixture at any time under various
reaction conditions. There are a number of kinetic stud-

Copyright © 2010 The Society of Chemical Engineers, Japan 661

ies on vegetable oil alcoholysis in the literature
(Freedman et al., 1986; Noureddini and Zhu, 1997;
Komers et al., 2002; Vicente et al., 2005; Bambase et
al., 2007). However, most of them report the kinetic
mechanism of the alcoholysis of edible vegetable oil
only. Ever since the present study started, no paper has
presented data related to second-order kinetic alcoholy-
sis of J. curcas oil, waste food oil, or their mixtures;
these oils are very important biodiesel feedstock for fu-
ture biodiesel production. Waste food oil has many un-
desirable compounds such as polymers, FFA, and many
other chemicals that are formed during frying, which are
a major concern during methanolysis. Therefore, it is
necessary to investigate the kinetic reaction mechanism
of those important oils. A kinetic study of J. curcas-
waste food oil mixtures can provide detailed information
on the behavior of these oils during hydroxide methanol-
ysis. This information is very useful for biodiesel pro-
ducers for producing biodiesel efficiently with such oils.
This paper presents a kinetic study of the methanol-
ysis of a J. curcas-waste food oil mixture, in which
potassium hydroxide is used as a catalyst. Using the re-
sults of this kinetic study, the extent to which the
methanolysis reaction has progressed at any time under
various reaction conditions can be simulated and esti-
mated accurately. The FFA content of the oil mixture
would certainly affect the reaction kinetics. Although,
FFA content can be limited to approximately 1 wt% by
fixing up the mass mixing ratio of J. curcas oil to waste
food oil, it is necessary to investigate of the effect of
this compound on the kinetics of hydroxide-catalyzed
methanolysis.
1. Experimental
1.1 Materials
J. curcas oil used in this experimental study was
supplied by B2TE-BPP Teknologi, Kawasan Puspiptek
Serpong. Waste food oil was obtained from the Gunma
Prefecture area in Japan. The FFA content of the oils was
5.53 wt% for J. curcas oil and 0.45 wt% for waste food
oil. The mass ratio of J. curcas oil to waste food oil in
the oil mixture was 1 : 9. At this mass ratio, the FFA con-
tent of the mixture was about 1 wt%. The fatty acid com-
position of the oils is given in Table 1. Methyl heptade-
canoate, which was used as an analytical internal stan-
dard for fatty acid methyl ester (FAME), was obtained
from Sigma-Aldrich Inc. FAME standards, methanol of
99.8% purity (certified), 99.0% heptane, and potassium
hydroxide were purchased from Wako Pure Chemical
Industries, Ltd. Standard test kit for glycerol and glyc-
erides was purchased from Sigma-Aldrich Inc.
1.2 Apparatus
Reactions were carried out in a 500 mL necked
batch reactor, where the total volume of reaction mixture
was 224 mL. The reactor was tightly sealed with a sili-
con rubber cap that retained any vaporized mixture and
662
Table 1 Fatty acid composition of J. curcas oil and waste
food oil
J. curcas oil Waste food oil
Fatty acid
[wt%] [wt%]
Lauric 0.14 —
Myristic 0.15 0.16
Palmitic 15.95 9.91
Palmitoleic 0.99 0.32
Stearic 4.24 2.24
Oleic 39.28 44.62
Linoleic 38.75 36.37
Linolenic 0.49 6.38
was equipped with a mechanical stirrer, digital ther-
mometer, and sampling port. The reactor was immersed
in a constant-temperature water bath. Inside the glass
water bath, there were a 100 V, 500 W electric heaters
and a shielded K-type thermocouple probe. A voltage
regulator controlled the temperature level and heat sup-
ply.
1.3 Procedures
The batch reactor was initially charged with 150 g
of a J. curcas-waste food oil mixture. It was then heated
for 2 h at atmospheric pressure, various temperatures
(25, 30, 40, 50 and 60°C), with the molar ratio of
methanol-to-oil varying from 6 : 1 to 15 : 1 and the mass
ratio of KOH to oil varying from 0.5 to 2.0 wt%. To ver-
ify the effect of mass transport on the reaction kinetics,
experiments were carried out at mixing speeds from 400
to 1200 rpm. The mechanical stirrer was started as soon
as possible as the reaction was timed. After 2 h of reac-
tion, the mixture was allowed to settle down overnight
before separating the glycerol. The top layer containing a
methyl ester fraction was removed in bottles and
weighed. The methyl ester in the bottles was washed
with hot water several times to remove impurities. For
moisture removal, the ester was heated in a furnace at
107°C under nitrogen flow at 200 mL/min for 1 h.
1.4 Sampling and analysis
To analyze the effect of the reaction time on the
methanolysis reaction products, approximately 2 mL of
the samples was withdrawn at pre-specified intervals
(0.5, 1, 2, 3, 4, 5, 6, 8, 10, 12, 15, 25, 30, 40, 90, and
120 min); at the beginning of the reaction, frequent sam-
pling was required. Each sample was collected in a
3.5 mL glass vial and was quenched immediately with
1 mL of 0.5 N hydrochloric acid. All the sample mixtures
were centrifuged at 3000 rpm for 30 min. The organic
phase of the mixture was separated, dried, and evapo-
rated. The samples were then analyzed by a gas chro-
matograph (GC-2010, Shimadzu Corp.) equipped with a
flame ionization detector and a capillary column con-
taining 95% dimethylpolysiloxane (ZB-5HT Inferno,
15 m  0.32 mm  0.10 μm). The GC oven was initially
JOURNAL OF CHEMICAL ENGINEERING OF JAPAN
heated at 50°C for 1 min; it was then heated at 15°C/min
up to 180°C, at 7°C/min up to 230°C, at 10°C/min up to
380°C, and then it was held at 380°C for 5 min. The total
analysis time was 36 min. The carrier gas was helium
(1.3 mL/min). The analysis of a sample by GC was car-
ried out by injecting 1 μL of the sample solution into the Fig. 1 Overall scheme of triglyceride methanolysis
gas chromatograph. The glycerol and glycerides formed
were identified by comparing their retention time with
the retention time of standard glycerol and glycerides
derivative. Quantitative analysis of the weight percent-
age of the glycerol and glycerides produced was carried
out by using butanetriol and tricaprin as the internal
standard. The methyl ester formed was identified by
comparing its retention time to the retention time of
standard FAME. Quantitative analysis of the weight per-
centage of the FAME produced was carried out by using
methyl heptadecanoate as the internal standard. Standard
methods (American Standards for Testing of Materials
International, 2008) were used to determine the concen-
tration of triglyceride, diglyceride, monoglyceride, glyc-
erol, and ester in the samples.
1.5 Kinetic modeling
1.5.1 Chemistry of the reaction The overall reaction
scheme for the methanolysis of triglyceride (TG) is pre-
sented in Figure 1 (Vicente et al., 2005). The stoichiom- Fig. 2 Triglyceride methanolysis reaction scheme
etry of the reaction requires 3 mol of methanol (M) and
1 mol of TG to produce 3 mol of FAME (E) and 1 mol of
glycerol (G). This reaction consists of three consecutive d[TG]
and reversible reactions (Cao et al., 2008). TG is con- k1[TG][M]  k2 [DG][E]
dt
verted stepwise to diglyceride (DG), monoglyceride
(MG), and finally G and E as shown in Figure 2. In this d[DG]
 k1[TG][M]  k2 [DG][E]  k3 [DG][M]
figure, variables k1 to k6 denote reaction constants. dt
In this study, the J. curcas-waste food oil mixture k4 [MG][E]
consisted of not only TG but also DG, MG, FFA,
and water (W). The initial oil mixture consisted of d[MG]
 k3 [DG][M]  k4 [MG][E]  k5 [MG][A]
89.9 wt% TG, 6.6 wt% DG, 2.4 wt% MG, 1.0 wt% FFA, dt
and 0.1 wt% W. The mole concentration of TG, DG, k6 [G][E]
MG, E, and G in the oil mixture was calibrated by using
d[E]
the experimental weight percentages of the reaction con-  k1[TG][M]  k2 [DG][E]  k3 [DG][M] (1)
stituents, their molecular weights, and the mechanism of dt
stepwise reactions. The calibration was based on the k4 [MG][E]  k5 [DG][M]  k6 [G][E]
conservation of mass of the reaction mixture and the d[M] d[E]
conservation of the number of moles of glycerol mole-  k1[TG][M]  k2 [DG][E]
cule. The molecular weights of TG, DG, MG, and E dt dt
were calculated from the known fatty acid composition k3 [DG][M]  k4 [MG][E]  k5 [DG][M]
of J. curcas oil and waste food oil, which is given k6 [G][E]
in Table 1, and they were 857.4, 602.3, 347.2, and
291.1 kg kmol1 respectively. d[G]
1.5.2 Initial assumptions For the purpose of reac-  k5 [MG][M]  k6 [G][E]
dt
tion kinetic modeling, the following assumptions were
made: 1.5.3 Mathematical analysis By using the assump-
(i) The effect of the FFA on the saponification reaction tions above and the mass action law, the governing set of
was insignificant because the FFA content of the J. equations for the stepwise reactions in the methanolysis
curcas-waste food oil mixture was small, limited to of TG are formulated as in Eq. (1). In the equation, vari-
1 wt%. ables k1 to k6 represent reaction rate constants
(ii) The effect of glycerides (TG, DG, and MG) and E [L mol1 min1]; [TG], [DG], [MG], [G], [M], and [E]
on saponification reaction was also neglected. denote molar concentrations of TG, DG, DG, G, M, and

VOL. 43 NO. 8 2010 663

E in the reaction mixture [molL-1]. The chemical theory
predicts that the reaction rate constant should be temper-
ature dependent. The effect of the reaction temperature
on the reaction rate is also studied from Arrhenius law,
which is given below:
k  k0 ⋅ eEa / RT
where k0 is a constant called the frequency factor, Ea
[cal mol1] is the activation energy of the reaction, T [K]
is absolute temperature, and R [cal mol K1] is the uni-
versal gas constant. The activation energy and the fre-
quency factor for each consecutive reaction can be ob-
tained by plotting the logarithm of the calculated rate
constants for the methanolysis reaction versus the recip-
rocal of absolute temperature.
The linear equation system comprising differential
kinetic equations (Eq. (1)) cannot be solved by the inte-
gration method. Thus, a differential method of analysis
must be used to directly solve the differential rate equa-
tions by evaluating all the terms in the equations, includ-
ing the derivative of concentration with respect to time.
Hence, the equations solving must be solved numerically
by using a computer. The Runge–Kutta fourth-order
method was selected. However, as is the case with all
numerical techniques, different initial guesses of the rate
constants were required and the best initial guesses pro-
vided a convergent result. The numerical solutions of
Eq. (1) provide the set of forward and reverse rate con-
stants.
1.5.4 Evaluation A computer code was written for
applying the Runge–Kutta fourth-order method to the
differential equations of the second-order kinetic model;
the code was written in Visual Basic of Excel. This code
was then applied to all obtained experimental data. To
verify the accuracy of kinetic model and the obtained
rate constants, it is necessary to compare simulation and
experimental results. The simulation result for the
species concentration in the product was compared with
the experimental result and the difference was quantified
using the relative average difference RAD, which is ex-
pressed in percentage. RAD is an objective parameter for
evaluating the correctness of the second-order kinetic
model (Komers et al., 2002). It is given by following ex-
pression.
RAD [%] 
⎛ m t ⎞
∑ ∑ y (t )
100 / n ⎜ i exp
 yi (t )cal / yi (t )exp ⎟
⎝ ⎠
i 0
In Eq. (3), n is the number of measurements in the inter-
val (0: t), m is the number of reactants, yi (t) is the con-
centration of component i at time t; exp and cal denote
the experimental and calculated values respectively.
Hence, RAD indicates the average relative difference be-
tween all experimental and relevant calculated concen-
trations of all the identified species in the given experi-
ment.
664
(2)
Fig. 3 Effect of mixing speed on oil conversion yield in the
methanolysis of the J. curcas-waste food oil mixture
at a reaction temperature of 50°C, methanol-to-oil
molar ratio of 6 : 1, and catalyst concentration of
1.0 wt%
2. Results and Discussion
2.1 Effect of mixing speed
Mixing is very important in the methanolysis reac-
tion because the J. curcas-waste food oil mixture and
potassium methoxide solution are immiscible. No reac-
tion is feasible without mixing. When potassium
methoxide solution was added to the oil mixture without
stirring, the mixture formed two layers. The top layer
was potassium methoxide solution and the bottom layer
was the oil mixture. The two layers had to be broken up
and mixed by either stirring for along time or at high
speed.
Six different mixing levels were used to investigate
the effect of mixing on the methanolysis reaction of the
J. curcas-waste food oil mixture. The mixing speeds
were set by adjusting the rotational speed of the mag-
netic stirrer, which was set at 400, 600, 700, 900, 1000,
and 1200 rpm. Figure 3 shows the effect of the mixing
speeds and reaction time on the oil conversion rate at a
reaction temperature of 50°C, a methanol-to-oil molar
ratio of 6 : 1, and a catalyst concentration of 1.0 wt%. At
the lowest stirring speed of 400 rpm, the oil conversion
yield was the lowest during the first 100 min of the reac-
tion. Upon increasing the stirring speed to 1200 rpm, the
oil conversion yield increased significantly, to more than
95 wt%, and accelerated the methanolysis reaction dur-
ing the first 10 min of the reaction. It was observed that
(3)
higher mixing speeds resulted in the formation of
smaller oil droplet in the potassium methoxide solution;
thus, high mixing speeds led to an increase the interfa-
cial area between reactants, which increased the rate of
methanolysis reaction considerably. A previous study on
methanolysis reported that the size of oil droplets at the
beginning of the rotation of the stirrer is inversely pro-
portional to the mixing speed (Ma and Hanna, 1999).
In this study, it was observed that experimental data
on the methanolysis reaction indicate a sigmoid pattern
JOURNAL OF CHEMICAL ENGINEERING OF JAPAN
Fig. 4 Effect of reaction temperature on the rate of methanolysis of the J. curcas-waste food oil mixture at a mixing speed of
900 rpm, methanol-to-oil molar ratio of 6 : 1, and catalyst concentration of 1.0 wt%: (a) TG, (b) DG, (c) MG, (d) E, (e) M
and (f) G (, 25°C; , 30°C; , 40°C; , 50°C; , 60°C). The solid lines denote simulation curves.
(S-shape) because there were three regions with different
reaction rates. These regions were clearly visible when
the mixing speed was lower than 700 rpm. The first re-
gion, where E started to form, was the low rate region.
The second region was the region where there was
a sudden surge in E production after the low rate region.
The third region was the region where the reaction pro-
ceeded towards equilibrium. A number of researchers
(Noureddini and Zhu, 1997; Stamenkovic et al., 2007)
have reported a similar sigmoid pattern for the alcoholy-
sis of vegetable oils at low mixing speeds. They have re-
vealed that the mass transfer controls the methanolysis
reaction in the initial stage of the reaction and that the
low rate region is a function of the mixing speed in the
initial stage of the reaction at a constant temperature. In
Figure 3, it can be seen that the duration of the initial
low-conversion part, which is the low-rate region, of an
imaginary curve passing through the data points for a
particular mixing speed decreased as the mixing speed
increased and that it reached a constant value of about
less than 1 min at a mixing level greater than 600 rpm.
Thus, the process of oil conversion was speeded up
when the mixing speed increase from 400 to 1200 rpm,
which indicated that the importance of mass transfer
control decreased at high mixing speeds. It was observed
hat at the mixing speed of 900 rpm, the conversion yield
was more than 90 wt% after the first 5 min of the reac-
tion time.
2.2 Effect of temperature
Figure 4 depicts experimental data points and sim-
ulation curves showing the effect of the reaction temper-
ature on the reaction rate. At the mixing speed of
900 rpm, the mass transfer control on the methanolysis
reaction became less dominant and the reaction tempera-
VOL. 43 NO. 8 2010
ture became the dominant factor influencing the rate of
reaction and oil conversion. It was observed that the
temperature affected the reaction rate and conversion of
oil into E and G. Figures 4(a) and (b) show the signifi-
cant increase in the TG and DG conversion rates as the
reaction temperature was increased from 25 to 60°C.
Figures 4(d) and (f) also show that increasing the rate
conversion of TG and DG led to an increase in the pro-
duction rate of E and G. In a previous kinetic study, it
was reported that the temperature dependence of the
overall reaction rate was similar to its dependence on the
mixing speed (Noureddini and Zhu, 1997). As shown in
Figure 4(d), the production rate of E at low temperatures
(25 and 30°C) follows a sigmoid curve. This suggests
that the mass transfer limitation becomes more impor-
tant at low reaction temperatures. This is due to the rapid
decrease in the droplet size of the dispersed phase of oil
with the progress of the methanolysis reaction and the
increase in the rate of reduction in the droplet size with
the reaction temperature, despite the mixing speed being
constant. Therefore, when the reaction temperature was
increased to 50°C, the duration of the low-rate region
decreased and the sigmoid pattern was lost. In order to
control the rate of the methanolysis reaction by varying
the solubility of the reactants, a higher temperature or
high thermal energy was required.
2.3 Change in reaction composition with time
The reaction mixture composition during the potas-
sium hydroxide-catalyzed methanolysis of the J. curcas-
waste food oil mixture at a methanol-to-oil molar ratio
of 6 : 1, a reaction temperature of 50°C, a catalyst con-
centration of 1.0 wt% of oil, and a mixing speed of
900 rpm is presented in Figure 5. In this study, a second-
order mechanism is found to provide a reasonable fit to
665

Fig. 5 Experimental data and simulation curves for the con-
centration of glycerides (TG, DG and MG), E and G
during the initial 1 h of the methanolysis of the J. cur-
cas-waste food oil mixture; methanolysis was carried
out at mixing speed of 900 rpm, methanol-to-oil
molar ratio of 6 : 1, catalyst concentration of 1 wt%,
and temperature 50°C (, TG; , DG; , MG; , E;
, G). The solid lines are simulation curves.
the experimental data for all conditions considered. The
average RAD value of all experiments is 4.7%. Figure 5
also shows that the mixing speed of 900 rpm is sufficient
to make the reaction homogeneous without the mass
transfer effect in the initial stage of the reaction. The
maximum concentration of the intermediate products
DG and MG is attained during the first minute. Their
levels then decrease and reach equilibrium in less than
20 min. At this point, TG disappears, but a small amount
of DG and MG still remains.
2.4 Effect of catalyst concentration
Figure 6 shows the effect of catalyst concentration
on the methanolysis of the J. curcas-waste food oil mix-
ture at a mixing speed of 900 rpm, methanol-to-oil molar
ratio of 6 : 1, and reaction temperature of 50°C. Under
these conditions the conversion rate of glycerides (TG,
DG and MG) and the production rate of E and G in-
crease linearly as the catalyst concentration increases
from 0.5 to 2.0 wt% of oil (see Figures 6(a), (b), (c), (d)
and (f)).
However, Figures 6(b) and (c) also show that an in-
crease in the catalyst concentration causes an increase in
the final concentration of DG and MG. The final concen-
tration is the reactant concentration at the end of the re-
action time or under equilibrium conditions. In this
study, it was assumed that all methanolysis reactions
reached equilibrium after reaction time of 2 h. For all re-
actions, under equilibrium conditions, the MG concen-
tration was typically higher than the TG and DG concen-
trations. The presence of glycerides high concentration
in the final reaction mixture must be avoided because it
causes difficulties in and increases the cost of the refin-
ing process. Moreover, the presence of high amount of
glycerides in biodiesel fuel causes serious problems in
engines using the fuel. The final concentration of glyc-
666
erides in the reaction mixture should be low for the pro-
duction of high-quality biodiesel fuel. For a catalyst con-
centration of 1.0 wt%, the final concentrations of TG,
DG and MG were 0.004, 0.006, and 0.014 mol L1
respectively. These values were fairly close to the
maximum limit for glycerides concentration in pure
biodiesel (American Standards for Testing of Materials
International, 2008). Therefore, it was not necessary to
increase the catalyst concentration to more than 1.0 wt%.
With 2.0 wt% of the catalyst, the final concentrations of
DG and MG were 1.2 and 1.4 times higher than those in
the case of 1.0 wt% of catalyst. It was reported that an
optimum KOH concentration of 1.26 wt% of oil was re-
quired to produce 93.2 % E by methanolysis of olive oil
with a methanol-to-oil molar ration of 4 : 1 and at reac-
tion temperature of 50°C (Dorado et al., 2004). Further
it was observed that increasing the KOH concentration
to a value greater than the optimum value resulted in
smaller E yield due to the presence of soaps. Soaps were
produced from the saponification of glycerides and E. A
KOH concentration of 1.0 wt% was selected as the opti-
mum catalyst concentration in the methanolysis of waste
food oil at a methanol-to-oil molar ratio of 6 : 1 and a re-
action temperature of 65°C (Encinar et al., 2005). Other
experiments on the methanolysis of other vegetable oils
have reported different optimum concentrations (Vicente
et al., 2005; Bambase et al., 2007, Berchmans and
Hirata, 2008). Thus, different vegetable oils require dif-
ferent optimum catalyst concentrations. Furthermore,
vegetable oil methanolysis depends on the reaction con-
ditions, methanol-to-oil molar ratio, and the oil composi-
tion. In this study, 1.0 wt% of oil was selected as the op-
timum catalyst concentration because it led to the pro-
duction of E with the maximum concentration and with
relatively low glycerides concentration. Figures 6(d) and
(f) show that although the catalyst concentration affected
the production rate of E and G, the final concentration of
these products did not change significantly. A high con-
centration of the catalyst accelerated the production of
only E and G. The experimental data in Figure 7 indi-
cate that E production at various reaction temperatures
was influenced by the catalyst concentration. However,
the effect was significant only at a low reaction tempera-
ture (25°C). At reaction temperatures from 50 to 60°C,
the production of E gradually decreased with an increase
in the catalyst concentration to 2.0 wt% of oil.
2.5 Effect of methanol-to-oil molar ratio
Stoichiometrically, the methanol-to-TG molar ratio
required in the methanolysis reaction is 3 : 1. However,
in practice, this molar ratio is insufficient to complete
the conversion of vegetable oils to E. A higher molar
ratio is required to shift the methanolysis reaction to-
wards the maximum production of E at a higher rate.
Thus, the amount of methanol is one of important fac-
tors that affect the yield of the methanolysis reaction,
completeness of the reaction, and production cost of
biodiesel. Figure 8 shows that while a higher methanol-
JOURNAL OF CHEMICAL ENGINEERING OF JAPAN
Fig. 6 Effect of KOH concentration (wt% of oil) on the methanolysis reaction of J. curcas-waste food oil mixture for a mixing
speed of 900 rpm, methanol-to-oil molar ratio of 6 : 1, and a reaction temperature 50°C: (a) TG, (b) DG, (c) MG, (d) E,
(e) M and (f) G (, 0.5%; , 0.7%; , 1.0%; , 1.5%; , 2.0%). Solid lines represent simulation curves.

Fig. 7 Effect of KOH concentration on the methyl ester con-
centration at various reaction temperatures in the
methanolysis of the J. curcas-waste food oil mixture;
the mixing speed was 900 rpm and the methanol-to-
oil molar ratio was 6 : 1 (, 25°C; , 30°C; , 40°C;
, 50°C; , 60°C)
Fig. 8 Effect of methanol-to-oil molar ratio on methyl ester
concentration in the methanolysis the of J. curcas-
waste food oil mixture (900 rpm, 50°C, and 1.0 wt%
KOH) (, molar ratio of 6 : 1; , molar ratio of 8 : 1;
, molar ratio of 10 : 1; , molar ratio of 15 : 1)

tages, e.g. they require a high amount of energy (long-

to-oil molar ratio increased the rate of E production sig-
nificantly, it improved the yield of E only slightly.
Increasing the molar ratio from 6 : 1 to 15 : 1 accelerated
the production of E significantly in the first min of the
reaction time from 91.4 to 97.5 wt%. At the end of the
reaction time (2 h), the yield of E slightly increased from
98.0 wt% at a molar ratio of 6 : 1 to 98.9 wt% at molar
ratio of 15 : 1. Therefore, it was clear that a higher
methanol-to-oil molar ratio shifted the methanolysis re-
action towards increased production of E and caused the
reaction mixture to reach equilibrium sooner. However,
it was undesirable to use excessive methanol because un-
reacted methanol in the reaction mixture would cause
difficulties in the biodiesel demethanolization process.
Almost all methods of demethanolization have disadvan-
term heating of the whole or ester phase of the reaction
mixture at the distillation or extraction temperature) and
relatively complicated apparatus (vacuum distillation or
extraction columns) and the demethanolization time
which accounts for a substantial part of the time taken
for the whole transesterification process is long; further,
the formation of emulsion during the extraction of the
ester phase with water poses problems (Skopal et al.,
1997). Furthermore, the high concentration of methanol
in the biodiesel tends to decrease the density, viscosity
and flash point of the biodiesel (resulting in problems
pertaining to transport, storage, and use). Other re-
searchers (Freedman et al., 1986; Vicente et al., 2005;
Bambase et al., 2007) have reported the molar ratio of
6 : 1 to be the optimum for the methanolysis of vegetable

VOL. 43 NO. 8 2010 667

 Table 2 Values the kinetic rate constants

Reaction condition Rate constant [mol1 L min1]

RAD
Temperature KOH Methanol to oil [%]
rpm k1 k2 k3 k4 k5 k6
[°C] [wt%] molar ratio

50 900 1.0 6:1 0.0730 0.0528 0.3347 0.1655 0.3869 0.0080 3.766
50 900 1.0 8:1 0.0666 0.0452 0.2064 0.1341 0.3310 0.0066 4.455
50 900 1.0 10 : 1 0.0602 0.0376 0.0780 0.1028 0.2750 0.0047 5.938
50 900 1.0 15 : 1 0.0280 0.0202 0.1283 0.0634 0.1483 0.0046 5.874
25 900 1.0 6:1 0.0051 0.0026 0.0055 0.0018 0.1888 0.0010 5.412
25 900 2.0 6:1 0.0111 0.0047 0.0100 0.0062 0.4237 0.0029 5.612
30 900 1.0 6:1 0.0135 0.0083 0.0391 0.0221 0.2373 0.0015 5.592
30 900 2.0 6:1 0.0238 0.0180 0.1037 0.0464 0.5302 0.0039 5.444
40 900 1.0 6:1 0.0245 0.0176 0.1105 0.0717 0.2781 0.0040 3.190
40 900 2.0 6:1 0.0471 0.0405 0.2411 0.1110 0.6245 0.0141 3.678
50 900 0.5 6:1 0.0361 0.0370 0.1643 0.1173 0.2336 0.0006 1.757
50 900 1.5 6:1 0.1149 0.0644 0.4754 0.2086 0.5205 0.0140 3.569
50 900 2.0 6:1 0.1567 0.0761 0.6161 0.2517 0.6541 0.0189 2.298
60 900 1.0 6:1 0.1434 0.1411 0.5199 0.4175 0.4327 0.0153 5.311
60 900 1.5 6:1 0.1891 0.1608 0.8811 0.4622 0.5845 0.0179 5.396
60 900 2.0 6:1 0.2348 0.1805 1.2423 0.5068 0.7364 0.0200 4.209

oils. In the present study, the optimum reaction condi-
tions for the methanolysis reaction of the J. curcas-waste
food oil mixture were as follows: a reaction time of
2 h, mixing speed of 900–1000 rpm, reaction tempera-
ture of 50°C, methanol-to-oil molar ratio of 6 : 1, and a
catalyst concentration of 1.0 wt%. Under these condi-
tions, the yield of the methanolysis reaction was between
97.5 wt% and 98.0 wt%.
2.6 Activation energy analysis
The reaction rate constants of the methanolysis re-
actions were calculated by the mathematical procedure
described in Section 1.5. The reaction rate constants ob-
tained for various reaction conditions at 900 rpm and the
corresponding RAD are shown in Table 2. In this table,
it can be seen that despite the methanolysis of TG with
methanol involving three stepwise and reversible reac-
tions, all the forward reaction rate constants are much
greater than those reverse reactions. It implies that the
methanolysis reaction experiments were carried out
properly because the reactions were directed towards
maximum production of E. The rate constant data also
indicate that the product formation of the methanolysis
reaction was controlled by the reaction temperature, cat-
alyst concentration, and methanol-to-oil molar ratio. The
k1 value was the lowest for the forward reaction at a low
temperature (25°C) which was the first forward reaction.
This implies that at low temperatures, the reaction from
TG to DG was the reaction that controlled the three step-
wise methanolysis reactions. This was due to the effect
of mass transfer resistance in the initial stage of the reac-
tion. The mass transfer resistance effect increased be-
cause of the increase in the oil viscosity at low tempera-
tures. Thus, a high reaction temperature was required to
increase the TG conversion. Table 2 shows that when the
reaction temperature was increased to 50°C, the forward
rate constant values (k1, k3, and k5) also increased signifi-
cantly. However, it is suggested that the maximum reac-
tion temperature should not exceed the boiling point
temperature of methanol in a batch reactor at atmos-
pheric pressure. Table 2 shows that the k1 values were
the smallest among the forward rate constant values (k3
and k5). This indicates that TG methanolysis was the
slowest step because TG has large molecular size and a
crowded molecular structure that led to steric hindrance
during the reaction (Bambase et al., 2007). On the other
hand, in all methanolysis reactions, except in the reac-
tion at the temperature of 60°C, the values of the reac-
tion rate constant k5 were the highest. This strongly indi-
cated that MG was the most unstable intermediate
species because it transformed to G rapidly. It also im-
plied that below 60°C, the rate determining reaction was
the reaction that converted MG to G. However, when the
reaction temperature was increased to 60°C, the rate de-
termining reaction changed to the reaction that con-
verted DG to MG. Figure 4(c) reveals that the final con-
centration of MG is the highest at 60°C. Therefore, it is
not necessary to increase the reaction temperature to
60°C because this only increases the final concentration
of glycerides.
The temperature dependence of the methanolysis
reaction of the J. curcas-waste food oil mixture was also
determined by considering the activation energy and re-
action temperature. Activation energy is defined as the
minimum energy that is required in order for a chemical
reaction to occur. The activation energy of the methanol-
ysis reaction was estimated by taking the logarithm of

668 JOURNAL OF CHEMICAL ENGINEERING OF JAPAN

 Table 3 Activation energy of the methanolysis reactions that yield TG, DG, MG, and G

This works* Ea [J mol1]

Reaction Freedman Noureddini Darnoko Vicente Bambase

Ea r2 et al. and Zhu and Cheryan et al. et al.
(1986) (1997) (2000) (2005) (2007)

TG → DG 16,377 0.984 16,062 13,145 14,700 25,039 14,040

DG → TG 19,202 0.991 15,843 9,932 — 16,964 10,739
DG → MG 17,867 0.979 17,247 19,860 14,200 22,092 16,049
MG → DG 19,383 0.997 13,571 14,639 — 16,887 13,907
MG → G 4,282 0.967 — 6,421 6,400 2,873 7,173
G → MG 15,302 0.994 — 9,588 — — 10,997

*At reaction temperatures from 30 to 60°C, mixing speed of 900 rpm, methanol-to-oil molar ratio of 6 : 1, and catalyst concentration
of 1.0 wt% of oil

Fig. 9 Arrhenius plot of reaction rate constants versus reac-
tion temperatures from 30 to 60°C, (mixing speed of
900 rpm, methanol-to-oil molar ratio of 6 : 1, and cat-
alyst concentration of at 1.0 wt%) (, k1; , k2; , k3;
, k4; , k5; , k6)
only 1.0 wt% of FFA, yet the FFA could reduce the cata-
lyst concentration significantly in the early stage of the
reaction by consuming it through the saponification re-
action. If the saponification reaction had occurred, then a
larger amount of more thermal energy would have been
required to produce E for a fixed final concentration and
fixed reaction conditions. Furthermore, the calculated
activation energies show that the activation energies for
the forward conversion of glycerides are lower than
those for the reverse conversion of glycerides. Therefore,
it is also possible that FFA influence the activation ener-
gies. However, further studies are necessary to confirm
this influence in the methanolysis reaction. Among the
forward reactions, the reaction converting DG to MG
was the most sensitive to the reaction temperatures. This
strongly indicates that under the reaction considered in
the present study, the oil methanolysis reactions favor
the formation of E and G.

the Arrhenius equation in Eq. (3). From the k-values ob-

tained at different temperatures, a plot of 1/T versus
ln (k) was plotted, as shown in Figure 9. The slopes
(Ea / R) are the corresponding activation energies, and
the y-intercepts are the frequency factors. The calculated
activation energies are shown in Table 3. The values are
compared to those presented in other papers. The activa-
tion energy values of the three stepwise reactions that
were obtained in the present study were slightly higher
than those obtained in other studies. This indicates that
the methanolysis reaction of the J. curcas-waste food oil
mixture was more sensitive to the temperature than the
methanolysis reaction of the Soybean oil (Noureddini
and Zhu, 1997), palm oil (Darnoko and Cheryan, 2000)
and sunflower oil (Vicente et al., 2005). If it is assumed
that most of these previous kinetic studies used fresh re-
fined vegetable oils with low FFA content, then it is pos-
sible that the higher activation energy of the methanoly-
sis the J. curcas-waste food oil mixture was because of
the concentration of FFA. Although the oil contained
Conclusions
Reaction conditions (mixing level, reaction temper-
ature, catalyst concentration, and methanol-to-oil molar
ratio) have a significant effect on the hydroxide
methanolysis reaction of the J. curcas-waste food oil
mixture. The conversion rate of the oil mixture and the
production rate of E increase with the as mixing speed,
reaction temperature, catalyst concentration, and
methanol-to-oil molar ratio. The obtained reaction rate
constants and the average RAD (4.7%) indicate that the
second-order kinetic model provides a satisfactory
mechanism for the methanolysis of the J. curcas-waste
food oil mixture under the given reaction conditions.
Values of the activation energies, which were calculated
in this study, suggest that the methanolysis reaction of
the oil mixture is highly temperature sensitive. It is pos-
sible the FFA content at 1 wt% in the oil mixture is the
cause of the high temperature sensitivity. However, fur-
ther studies are required to confirm this.

VOL. 43 NO. 8 2010 669


Acknowledgements
This work was supported by Department of Chemical and
Environmental Engineering, Gunma University, Kiryu, Japan. The au-
thors express their gratitude to Dr. Youichi Kamiishi of the Gunma
Industry Support Organization (GISO), Collaboration of Regional
Entities for the Advancement of Technology Excellence, Gunma
Prefecture, Japan, and to Dr. Markus Sumarsono of B2TE-BPP
Teknologi, Kawasan Puspiptek Serpong, Indonesia, for their support
and kind assistance.
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