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Energy Procedia 61 (2014) 2745 2749

The 6th International Conference on Applied Energy ICAE2014

Biodiesel Production from Acidic Crude Palm Oil Using

Perchloric Acid
Adeeb Hayyana,b*,Mohd Ali Hashima,b, Maan Hayyana,c, Khor Gui Qingb
a

University of Malaya Centre for Ionic Liquids (UMCiL), University of Malaya, Kuala Lumpur 50603, Malaysia
b
Department of Chemical Engineering, University of Malaya, Kuala Lumpur 50603, Malaysia
c
Department of Civil Engineering, University of Malaya, Kuala Lumpur 50603, Malaysia

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

* Corresponding author. Tel.: +60-123002949; E-mail address: adeeb.hayyan@yahoo.com.

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

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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 Brnsted
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.
2. Materials and chemicals
ACPO was acquired fro m a local mill in the state of Selangor in Malaysia. Methanol, perch loric acid and
potassium hydroxide (KOH) pellets all of laboratory grades were purchased fro m R&M Chemicals
(Malaysia).
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).
4. Results and discussion
Figure 1 shows the fatty acid compositions of ACPO, whereb y the saturated fatty acids is higher than that
of unsaturated fatty. The fatty acid profile was almost similar to profile of crude palm o il reported by
Hashim et al., (2010). The physical p roperties of ACPO are illustrated in Table 1, indicat ing that the oil is
non-edible. The effect of the catalyst in any chemical reaction (e.g. esterificat ion reaction), is one of the
most impo rtant factors that affect the efficiency of FFA conversion to FAME. The effect of perchlo ric
acid in the reduction of the FFA content in ACPO is well illustrated in Figure 2. The acid has a good
catalytic activity, rapid ly reducing FFA to 2.92% with only 0.25% catalyst. Perch loric acid has slightly
lower catalytic act ivity co mpared to sulphuric acid and it is more stable co mpared to hydrochloric acid. In
terms of cost perchloric acid is more expensive compared to sulphuric acid and hydrochloric acid due to
limited industrial applications of perchloric acid.
Figure 2 also shows that the optimu m catalyst dosage is 1%, and at this poin t, FFA can be reduced to
1.03% wh ile the FFA conversion remains almost constant. Theoretically, methylation requires one mole
of methanol for each mole of FFA (Ding et al., 2012). Practically, mo re than 1 mo le is needed for an
esterification reaction for FFA reduction in acidic oils such as ACPO. Figure 3 shows the effect of mo lar
ratio on the reduction of FFA and conversion of FFA to FAME. Loading of 10:1 methanol to oil was
enough to reduce the FFA content to 1%. Figure 4 clearly shows that the optimu m reaction temperature
(60 o C) for the treat ment of A CPO. Figure 5 illustrated the effect of reaction time on the reduction of FFA
and conversion of FFA to FAME. Results of Figure 5 indicated that that perchloric acid has high catalytic
activity because 30 min was sufficient to reduce the FFA content to less that 1%. Hence, 30 min was
selected as optimum reaction time for esterification reaction using perchloric acid.

Fatty acid content (%)

Adeeb Hayyan et al. / Energy Procedia 61 (2014) 2745 2749

Fig.1. Fatty acid profile of ACPO

Table 1: ACPO Characterization
Parameters
Free fatty acid, FFA (%)

ACPO
8.8

Peroxide value (ml mol/kg)

7.9

Moisture content (%)

1. 4

Iodine value, IV

52.5

Impurities (%)

0.06

Saponification value (mg KOH/g oil)

191

Ash (%)

0.015

Fig.2. Effect of perchloric dosage on the reduction of FFA and conversion of FFA to FAME

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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

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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.
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