Professional Documents
Culture Documents
Artikel Biodiesel PDF
Artikel Biodiesel PDF
com
ScienceDirect
Energy Procedia 61 (2014) 2745 – 2749
Abstract
Perchloric acid was used as a catalyst for the treatment of free fatty acid (FFA) in acidic crude palm o il
(ACPO). Perch loric acid shows reduced the FFA content fro m 8.8% to 1% using 1% of acid to ACPO
and the conversion of FFA to fatty acid methyl ester (FAME) was 88%. The produced biodiesel from
treated ACPO meets international biod iesel standards such as EN 14214 and ASTM D6751. Perchlo ric
acid shows high catalytic activ ity for the conversion of FFA to FAME and can be used to treat a wide
range of acidic oils and fats.
© 2014 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
© 2014 The Authors. Published by Elsevier Ltd.
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Selection and/or peer-review under responsibility of ICAE
Peer-review under responsibility of the Organizing Committee of ICAE2014
Keywords: Acidic crude palm oil; biodiesel; esterification; perchloric acid; free fatty acid.
1. Introduction
Biodiesel is an alternative renewable fuel and can be produced from animal fats and vegetable oils. The
typical process to produce biodiesel fuel is trasesterification [1]. For high acidity raw materials it is
required to undergo a pre -treat ment process before trasesterification to convert the FFA to fatty acid
methyl ester (FAME) [2]. In Malaysia, at p resent, mo re than 2.8 million hectares of land are under o il
palm cult ivation. It is reported that in 1995, there were some 281 palm o il mills. Fro m these mills, non -
edible industrial o ils such as acidic crude palm oil (ACPO) are being produced [3]. Low grade palm oil,
which is usually rejected fro m palm oil refineries due to high free fatty acid (FFA) content of over 5% [4].
Pre-treat ment process for the reduction of the FFA, i.e. esterificat ion, is essential before transesterification
[5]. Sulfuric acid and p -toulenesulfonic acid (PTSA) are the co mmon ho mogenous acid used for the
1876-6102 © 2014 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Peer-review under responsibility of the Organizing Committee of ICAE2014
doi:10.1016/j.egypro.2014.12.295
2746 Adeeb Hayyan et al. / Energy Procedia 61 (2014) 2745 – 2749
esterification reaction [6,7]. While the common heterogeneous acids are ferric sulfate [8]. So lid Brønsted
acid of amorphous carbon bearing SO3 H, COOH and phenolic OH groups [9]. New types of homogenous
acids are introduced and used for biodiesel production such as ethanesulfonic acid and chromosulfuric
acid [1, 10]. A super acid such as trifluoro methanesulfonic acid was us ed for biodiesel production fro m
sludge palm oil (SPO) [11]. Perchlo ric acid is also considered as superacid and a relatively stable acid
compared to hydrochloric acid and trifluoro methanesulfonic acid. There is no reported work on the
application of perchloric acid for the reduction of FFA in an acidic raw material such as ACPO, therefore
this study aimed to study the catalytic activity of this acid as well as reporting the optimum conditions.
3. Methodol ogy
In the present work, different dosages of perchloric acid were invest igated and a single factor
optimization of the esterification experiments was observed. To facilitate ease of handling, the ACPO was
heated in an oven at a temperature 70o C for one hour. The preheated ACPO was then transferred into a
batch multi-un it reactor system with reflu x condenser for the esterification reaction using perchloric acid
catalyst after which transesterification reaction using potassium hydro xide was carried out. The
characteristics of ACPO were determined according to the Malaysian Palm O il Board (MPOB) Test
Methods [12] wh ile the FFA co mposition was determined using GC/MS (Agilent Technologies 7890A
gas chromatograph equipped with 5975C mass spectrometer).
Fig.2. Effect of perchloric dosage on the reduction of FFA and conversion of FFA to FAME
2748 Adeeb Hayyan et al. / Energy Procedia 61 (2014) 2745 – 2749
Fig.3. Effect of molar ratio on the reduction of FFA and conversion of FFA to FAME
Fig.4. Effect of reaction temperature on the reduction of FFA and conversion of FFA to FAME
Fig.5. Effect of reaction time on the reduction of FFA and conversion of FFA to FAME
Adeeb Hayyan et al. / Energy Procedia 61 (2014) 2745 – 2749 2749
5. Conclusion
The optimu m conditions for the pre -treat ment process were 1% (w/w) dosage of perchloric acid to ACPO,
10:1 M ratio, 60 o C temperature, 30 min reaction time and 300 rp m stirrer speed. The h ighest yield of
biodiesel after transesterification and purificat ion processes was 76.62%, with 0.07% FFA and 96% ester
content. The results showed that the FFA content of ACPO was reduced fro m 8.8% to 1% under the
optimu m conditions, and the final product met the biodiesel international standard specifications, such as
EN 14214 and ASTM D6751.
Acknowledgements
The authors would like exp ress their thanks to the University of Malaya HIR-M OHE (D000003-16001),
Centre fo r Ion ic Liquids (UM CiL) and the Bright Sparks Program at the University of Malaya for their
support of this research.
References
[1] Hayyan A, Mjalli FS, Hashim MA, Hayyan M, AlNashef IM. Conversion of free fatty acids in low grade crude palm oil to
methyl esters for biodiesel production using chromosulfuric acid. Bulg Chem Commun 2013; 45: 394 – 399.
[2] Hayyan A, Hashim MA, Hayyan M Mjalli FS, AlNashef IM. A novel ammonium based eutectic solvent for the treatment of free
fatty acid and synthesis of biodiesel fuel. Ind Crops Products 2013;46:392–398.
[3] Chuah, T. G., Wan Azlina A. G. K., Robiah Y., Omar R. Biomass as the renewable energy sources in Malaysia: An overview.
Int J Green Energy 2006; 3:323–46.
[4] Hayyan A, Mjalli FS, Hashim MA, Hayyan M, AlNashef IM, Al-Wahaibi T , Al-Wahaibi YM. A solid organic acid catalyst for
the pretreatment of low-grade crude palm oil and biodiesel production. Int J Green Energy; 11: 129–140.
[5] Canakci M. The potential of restaurant waste lipids as biodiesel feedstocks. Bioresour Technol 2007; 98 : 183–190.
[6] Atadashi IM, Aroua MK, Abdul Aziz AR, Sulaiman NMN. The effects of catalysts in biodiesel production: A review. J Ind Eng
Chem 2013; 19: 14-26.
[7] Di Serio M, Tesser R, Pengmei L, Santacesaria E. Heterogenous catalyst for biodiesel product ion. Energy Fuels 2008; 22: 207–
217.
[8] Mengyu GAN, Deng PAN, Li MA, En YUE, Jianbing HONG. The kinetics of the esterification of free fatty acids in waste
cooking oil using Fe2(SO4)3/C Catalyst. Chinese J Chem Eng 2009; 17: 83-87.
[9] Hara M. Biodiesel production by amorphous carbon bearing SO 3H, COOH and phenolic OH groups, a solid brønsted acid
catalyst. Top Catal 2010; 53: 805–810.
[10] Hayyan A, Mjalli FS, Hashim MA, Hayyan M, AlNashef IM, Al-Zahrani SM, Al-Saadi MA. Ethanesulfonic acid-based
esterification of industrial acidic crude palm oil for biodiesel production. Bioresour T echnol 2011; 102: 9564 –9570.
[11] Hayyan A, Hashim, MA, Mirghani MES, Hayyan M, AlNashef IM. Esterification of sludge palm oil using
trifluoromethanesulfonic acid for preparation of biodiesel fuel. Korean J Chem Eng 2013; 30:1229-1234.
[12] Kuntom A, Lin SW, Ai TY, Idris NA, Yusof M, Sue TT, Ibrahim NA. Malaysian Palm Oil Board (MPOB) Test Methods.
MPOB, Bangi, Malaysia 2005.