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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.
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
To simulate the effects of water on biodiesel yield, the water 3. Results and discussion
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- 3.1. Effect of water content on FAME yield
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 Fig. 1 shows a direct comparison of the yield of FAME obtained
pre-determined amount of reactants were charged into the reac- from the three methods; SCMA, SCM and conventional acid-
tion tube. A pressure gauge was connected onto the tube, and the catalyzed reaction. In the conventional acid-catalyzed reaction, the
tube was then inserted in a furnace which was heated to a pre- addition of water in the reaction led to a significant reduction of the
determined temperature. After the desired reaction period was yield of FAME. The yield of FAME was reduced to 15% when only 5%
reached, the reaction was stopped immediately by transferring the of water was added. The reduction in yield of biodiesel observed
tube into the chilled water bath. Subsequently, the product was col- at high water content was attributed to equilibrium being reached
lected, and excess methyl acetate was removed by evaporation. The in the reaction. At this point, the increased water concentration
sample was then analyzed using gas chromatography to determine causes the reverse reaction, thus hydrolysing the triglycerides into
the fatty acid methyl esters (FAME) content. The effect of water FFA as shown in Eq. (4). Furthermore, formation of water in the
content was also investigated in the supercritical methanol reac- methyl esterification of FFA with methanol in the acid catalyzed
tion at optimum conditions of SCM; 358 ◦ C, molar ratio of methanol method could reduce the catalyst activity in the transesterification
to oil at 44:1 and 27 min of reaction time [8]. Since Jatropha oil con- [7]. Consequently, the efficiency of sulphuric acid is significantly
sists of high FFA content, experimental results were also obtained affected. Therefore, the conventional acid-catalyzed method may
from reaction with the conventional acid-catalyzed method using not be suitable for Jatropha oil with high FFA content as more FFA
methanol to assess the effect and behavior of water content on will be produced in the reaction resulting in a low yield of FAME.
biodiesel yield through conventional transesterification at a tem- On the other hand, the addition of water in the SCMA reaction
perature of 65 ◦ C with a molar ratio of methanol to oil of 6:1 and did not have any significant change on the yield of FAME. Similar to
3 wt% of sulphuric acid [9]. the acid-catalyzed reaction, the presence of water in the reaction
Oleic acid, the highest FFA percentage in Jatropha oil, was chosen mixture induces hydrolysis of triglycerides, which will produce FFA
to investigate the effect of free fatty acids content on biodiesel. The and glycerol as shown in Eq. (4) [10]. Subsequently, the FFA will
oleic acid content was varied from 5 to 20 wt% of oil. The reaction be esterified with methyl acetate to produce FAME and acetic acid
was carried out at optimum conditions as obtained from the opti- as shown in Eq. (5) [11]. The glycerol formed in the reaction will
mization of SCMA study [8]. For comparison, experiments were also then react with acetic acid to produce triacetin and water (Eq. (6)).
carried out in the SCM reaction at optimum conditions of 358 ◦ C, 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 75
4. Conclusion