J.

of Supercritical Fluids 79 (2013) 73–75

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The Journal of Supercritical Fluids

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

Influence of impurities on biodiesel production from Jatropha curcas L. by

supercritical methyl acetate process
Noorzalila Muhammad Niza a , Kok Tat Tan b , Keat Teong Lee c,∗ , Zainal Ahmad c
a
Faculty of Chemical Engineering, UiTM Pulau Pinang, 13500 Permatang Pauh, Pulau Pinang, Malaysia
b
Department of Petrochemical Engineering, Faculty of Engineering and Green Technology, Universiti Tunku Abdul Rahman, Jalan Universiti, Bandar Barat, 31900 Kampar, Perak,
Malaysia
c
School of Chemical Engineering, Universiti Sains Malaysia, Engineering Campus, Seri Ampangan, 14300 Nibong Tebal, Pulau Pinang, Malaysia

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

Article history: Generally, water and free fatty acid (FFA) content in oils could cause a serious problem during conven-
Received 29 June 2012 tional transesterification such as saponification. Thus, without any pre-treatment, vegetable oil, especially
Received in revised form 21 February 2013 with high FFA content, will be affected. In this study, a non-catalytic supercritical methyl acetate (SCMA)
Accepted 24 February 2013
process was utilized to produce biodiesel from Jatropha curcas L. oil. The effects of water and FFA content
on the yield of biodiesel were investigated. The results obtained for the effects of water on the yield of
Keywords:
biodiesel were compared with the supercritical methanol (SCM) process and conventional catalytic reac-
Biodiesel
tion. Results revealed that the catalytic reaction suffers from low yield with the presence of high water
Supercritical methyl acetate
Supercritical methanol
content in oil. Meanwhile, the yield of both the SCM and SCMA reactions were found to increase slightly
Water with the increment of water content in the mixture. On the other hand, the results for the effect of FFA
Free fatty acids on the yield of biodiesel were compared with the SCM reaction. It was found that the presence of FFA has
Jatropha oil a negligible effect in both the SCMA and SCM reactions. These findings demonstrate that pre-treatment
procedures are not necessary in the SCMA process for Jatropha oil which normally contains a high FFA
content.
© 2013 Elsevier B.V. All rights reserved.

1. Introduction such as saponification and hydrolysis if low quality feedstock is

employed due to the presence of impurities such as free fatty acids
Biodiesel is one of the alternative fuels comprised of mono- (FFA) and water, respectively. For instance, as shown in Eq. (1),
alkyl esters of long-chain fatty acids derived from vegetable oils excessive FFA content in the base catalyzed reaction could lead
or animal fat. This fuel is obtained by a transesterification reac- to the formation of soap and water. Therefore, high FFA content
tion with an alcohol, with or without the presence of a catalyst, to present in vegetable oil must be neutralized with excess base. This
produce glycerol as a co-product [1]. The use of biodiesel in diesel could complicate the production process, and the yield obtained
engines is advantageous for its environmental friendliness over will be reduced since the FFA has been neutralized and not con-
petrol–diesel such as reducing carbon dioxide emissions, providing verted to biodiesel esters.
lubricity improvement [2,3], and having better properties in terms On the other hand, the presence of water could consume the
of biodegradability, free sulphur content, viscosity, density and catalyst and reduces catalyst efficiency [7]. As shown in Eq. (2),
flash point [4,5]. In addition, the feedstock for biodiesel production water induces the hydrolysis reaction of biodiesel esters to FFA and
can be derived from renewable sources such as edible/non-edible alcohol. The FFA can subsequently react with base-catalyst and will
oils and waste animals fats, which are abundantly available and result in the formation of more soap and water until the catalyst is
inexhaustible [6]. Therefore, production of biodiesel could ensure finally consumed and deactivated.
the sustainability of human development and an energy source in
RCOOH + NaOH ↔ RCOONa+ + H2 O (1)
the future. FFA Base catalyst Soap Water
The common method to produce biodiesel is by conventional
Base catalyst
transesterification using alkaline catalyst. Normally, conventional RCOOR + H2 O ←→ RCOOH + R OH (2)
transesterification reactions will be accompanied by side reactions Alkyl ester Water FFA Alcohol

In our previous work, we have produced biodiesel from non-

catalytic supercritical methyl acetate (SCMA), employing Jatropha
∗ Corresponding author. Tel.: +60 4 5996467; fax: +60 4 5941013. oil as feedstock [8]. In SCMA, triacetin is produced as side product
E-mail address: chktlee@eng.usm.my (K.T. Lee). rather than glycerol. In addition, triacetin is a valuable compound

0896-8446/$ – see front matter © 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.supflu.2013.02.021
74 N.M. Niza et al. / J. of Supercritical Fluids 79 (2013) 73–75
and could be utilized as a fuel additive. In the previous work, the
optimum conditions were reported to be at a reaction temperature
of 400 ◦ C, 32 min for reaction time, and 50 mol/mol molar ratio
of methyl acetate to oil. Nonetheless, the Jatropha oil used in this
study has high FFA content with a value of 10.5% (w/w). Hence, in
the present work, the feasibility of supercritical methyl acetate for
biodiesel production from Jatropha oil was investigated further by
focusing on the influence of impurities such as water and FFA con-
tent on biodiesel yield. The effect of water on the yield of biodiesel
was also compared with that from conventional transesterification.
2. Materials and methods
2.1. Raw materials and chemicals
The raw material which is Jatropha curcas L. oil was purchased
from Bionas Sdn. Bhd. For the transesterification reaction, the
chemicals used are methyl acetate (≥99) and methanol (99.8), pur-
chased from Merck. For the effect of FFA content, pure oleic acid
was used in the reaction. The internal standard which is methyl
heptadecanoate (≥99.5) and reference standards such as methyl
palmitate, methyl stearate, methyl oleate and methyl linoleate
were purchased from Fluka Chemie and utilized for gas chromatog-
raphy analysis.
2.2. Apparatus
The transesterification by SCMA process was carried out using
a supercritical reactor system, which can sustain the high temper-
ature and pressure needed in supercritical treatment. The system
mainly consists of a reaction tube of 12 mL made from stainless
steel 316, a furnace and a chilled water bath. A pressure gauge
and temperature controller were utilized to monitor the reaction
temperature and pressure, respectively.
2.3. Procedures
To simulate the effects of water on biodiesel yield, the water
content was varied with 5, 7, 10, 15 and 20 wt% of oil. The reaction
was carried out at optimum conditions of 400 ◦ C reaction temper-
ature, 32 min of reaction time and at 50:1 molar ratio of methyl
acetate to oil as obtained from our previous study [8]. Initially, a
pre-determined amount of reactants were charged into the reac-
tion tube. A pressure gauge was connected onto the tube, and the
tube was then inserted in a furnace which was heated to a pre-
determined temperature. After the desired reaction period was
reached, the reaction was stopped immediately by transferring the
tube into the chilled water bath. Subsequently, the product was col-
lected, and excess methyl acetate was removed by evaporation. The
sample was then analyzed using gas chromatography to determine
the fatty acid methyl esters (FAME) content. The effect of water
content was also investigated in the supercritical methanol reac-
tion at optimum conditions of SCM; 358 ◦ C, molar ratio of methanol
to oil at 44:1 and 27 min of reaction time [8]. Since Jatropha oil con-
sists of high FFA content, experimental results were also obtained
from reaction with the conventional acid-catalyzed method using
methanol to assess the effect and behavior of water content on
biodiesel yield through conventional transesterification at a tem-
perature of 65 ◦ C with a molar ratio of methanol to oil of 6:1 and
3 wt% of sulphuric acid [9].
Oleic acid, the highest FFA percentage in Jatropha oil, was chosen
to investigate the effect of free fatty acids content on biodiesel. The
oleic acid content was varied from 5 to 20 wt% of oil. The reaction
was carried out at optimum conditions as obtained from the opti-
mization of SCMA study [8]. For comparison, experiments were also
carried out in the SCM reaction at optimum conditions of 358 ◦ C,
Fig. 1. Effect of water addition in the SCM, SCMA and acid catalyzed reaction.
44 mol/mol of methanol to oil molar ratio and 27 min of reaction
period [8].
2.4. Analytical procedure
The FAME samples were first diluted with an internal standard.
Then 1 ␮L of each sample was injected into a gas chromatograph
(PerkinElmer, Clarus 500) equipped with a NukolTM capillary col-
umn (15 m × 0.53 mm; 0.5 ␮m film) and a flame ionization detector
(FID). n-Hexane was used as the solvent while helium gas was used
as the carrier gas. The oven temperature was set at 110 ◦ C and then
increased to 220 ◦ C at a rate of 10 ◦ C/min. The temperature of the
detector and injector were set at 250 ◦ C and 220 ◦ C, respectively.
The yield of FAME was calculated using the areas obtained in the
gas chromatographic analysis with the following Eq. (3).

Weight of fatty acid methyl esters
FAME yield (%) = × 100 (3)
Weight of Jatropha oil used (g)
3. Results and discussion
3.1. Effect of water content on FAME yield
Fig. 1 shows a direct comparison of the yield of FAME obtained
from the three methods; SCMA, SCM and conventional acid-
catalyzed reaction. In the conventional acid-catalyzed reaction, the
addition of water in the reaction led to a significant reduction of the
yield of FAME. The yield of FAME was reduced to 15% when only 5%
of water was added. The reduction in yield of biodiesel observed
at high water content was attributed to equilibrium being reached
in the reaction. At this point, the increased water concentration
causes the reverse reaction, thus hydrolysing the triglycerides into
FFA as shown in Eq. (4). Furthermore, formation of water in the
methyl esterification of FFA with methanol in the acid catalyzed
method could reduce the catalyst activity in the transesterification
[7]. Consequently, the efficiency of sulphuric acid is significantly
affected. Therefore, the conventional acid-catalyzed method may
not be suitable for Jatropha oil with high FFA content as more FFA
will be produced in the reaction resulting in a low yield of FAME.
On the other hand, the addition of water in the SCMA reaction
did not have any significant change on the yield of FAME. Similar to
the acid-catalyzed reaction, the presence of water in the reaction
mixture induces hydrolysis of triglycerides, which will produce FFA
and glycerol as shown in Eq. (4) [10]. Subsequently, the FFA will
be esterified with methyl acetate to produce FAME and acetic acid
as shown in Eq. (5) [11]. The glycerol formed in the reaction will
then react with acetic acid to produce triacetin and water (Eq. (6)).
Hence, with the presence of water in the SCMA reaction, there is no
 N.M. Niza et al. / J. of Supercritical Fluids 79 (2013) 73–75
Fig. 2. Effect of addition of free fatty acid in the SCM and SCMA reactions.
adverse effect on the yield of FAME compared to the conventional
acid-catalyzed method.
Triglyceride + Water  Freefattyacid + Glycerol
Freefattyacid + Methylacetate  Biodiesel + Aceticacid
Glycerol + Aceticacid  Triacetin + Water
Meanwhile, in the SCM reaction, the amount of water added
into the reaction system also did not have any significant effect on
the yield of FAME. Similarly in the SCMA reaction, the presence of
water could induce the hydrolysis of triglycerides, which subse-
quently produces free fatty acids and glycerol. The free fatty acid
will then react with methanol to produce FAME and water. Kusdi-
ana and Saka also have reported that the presence of water in the
SCM method could presumably act as an acid catalyst [7].
In comparing between the SCM and SCMA methods, the SCM
treatment has been shown to have higher tolerance toward water
content compared to the SCMA reaction. This observation is due to
the fact that the reaction rate of methanol in the water added for
SCM treatment is higher than in SCMA. Water has the capability of
dissolving both non-polar and polar solutes since its dielectric con-
stant can be adjusted from a room temperature value of 80–5 at its
critical point [12]. Therefore, water can solubilize most non-polar
organic compounds including most hydrocarbons at temperature
above 250 ◦ C. In addition, water at temperatures between 280 ◦ C
and 350 ◦ C is rich with ionic products. Hence, when it is mixed with
polar methanol, the mixture will have both strong hydrophilic and
hydrophobic properties [7].
3.2. Effect of FFA content on FAME yield
Fig. 2 shows the results of the influence of FFA on FAME yield
for SCMA and SCM. The results revealed that FFA contained in oils
does not affect the yield of FAME substantially in SCM and SCMA
reactions. Instead, the presence of FFA may slightly increase the
conversion of biodiesel as the oleic acid content was increased in
Jatropha oil. In the SCM reaction, the addition of FFA can be ester-
ified with methanol to produce FAME. This esterification reaction
also produces water as a side product which could help in hydroly-
sis process of triglycerides and subsequently increase the reaction
yield [6].
75
On the other hand, the addition of FFA content in SCMA also
slightly increase the yield of FAME. As reported by Saka and
Isayama, this may be due to the starting material of oleic acid
and/or the acetic acid produced that plays the role of acid catalysis
which could improve biodiesel production [13]. Although this reac-
tion produced acetic acid as the side product, this can be removed
from the reaction by employing vacuum evaporation due to the
difference in boiling points. Hence, the performance of the SCMA
method in high FFA content oils is comparable with the established
supercritical methanol (SCM) method.
4. Conclusion
Overall, the performance of SCMA and SCM in producing FAME
with the presence of impurities such as FFA and water is compara-
ble. Both processes show a high tolerance toward the presence of
impurities in the reaction medium with consistent high yield. How-
ever, SCMA has the advantage compared to SCM since the SCMA
process could produce a valuable compound, triacetin, as a side
product, instead of the unwanted glycerol. On the other hand, the
(4)
acid-catalyzed reaction suffered a substantial reduction in FAME
(5) yield even with a low percentage of water (5%).
(6)
Acknowledgments
The authors would like to acknowledge Ministry of Higher
Education, Malaysia (FRGS Grant No.: 6071233) for the financial
support given.
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