Effect of synthetic antioxidants on storage
stability of Calophyllum inophyllum biodiesel
I. M. Rizwanul Fattah
*
, H. H. Masjuki, M.A. Kalam and B. M. Masum
Biofuels, especially biodiesels derived from renewable sources, are becoming increasingly
important because of environmental and energy concerns. However, biodiesels composed of
long chain unsaturated fatty acid esters are prone to oxidation. One such biodiesel is non-edible
high acid value Calophyllum inophyllum oil-based biodiesel produced through a two-stage
esterification process and one-stage transesterification process. In this study, the oxidation
stability of biodiesel treated with three prominent antioxidants, namely pyrogallol, propyl gallate
and tert-butylhydroxyquinone was evaluated. The induction period of biodiesel with or without
antioxidant was measured according to the EN14112 standard using a Rancimat instrument.
Antioxidants were added at 500 ppm, which in general improved the induction period. The
samples were kept for 70 days and different properties that change during storage, namely
induction period, density and kinematic viscosity were monitored. For all samples, oxidation
stability decreased and kinematic viscosity increased because of the formation of oxidation
products. Pyrogallol showed the best effect in retaining oxidation stability of Calophyllum
inophyllum biodiesel.
Keywords: Storage stability, Biodiesel, Antioxidants, Calophyllum inophyllum
Introduction
Biodiesel refers to the fatty acid alkyl esters (FAAEs)
derived from lipid substances originated from vegetable
oil, animal fats, waste greases, recycled cooking oils,
etc.
1–3
Vegetable oils of the edible origin are one of the
most promising feedstocks for biodiesel production.
Triglyceride molecules that are the main constituents of
these oils are transesterified with an alcohol, such as
methanol, in the presence of a catalyst to form
FAAEs.
4
However, owing to criticism on edible oil use
for fuel production, other sources e.g. non-edible oils of
plant origin and waste fats with high free fatty acid
(FFA) content are now being used for biodiesel pro-
duction.
5,6
Biodiesel production from these feedstocks
usually employs a pre-treatment step that converts the
FFAs to ester that can be used for tranesterification.
7
Biodiesels are more susceptible to degradation com-
pared to fossil diesel because of fatty acid chain unsatura-
tion (carbon double bonds C=C).
8
The mechanisms of
degradation are (a) autoxidation in the presence of atmos-
pheric oxygen; (b) thermal or thermal-oxidative degra-
dation from excess heat; (c) hydrolysis in the presence
of moisture or water during storage and in fuel lines;
and (d) microbial contamination of the fuel from
contact with dust particles or water droplets containing
fungi or bacteria. This degradation is exacerbated if two
or more carbon double bonds (polyunsaturation) are
present in the fatty acid chain.
9
Fuel instability is the sus-
ceptibility of fuel to degradation processes that form
undesirable species resulting in deterioration of fuel prop-
erties. The fatty acid profile, i.e. the chain length and the
level of unsaturation of the FAAE corresponds to that of
the parent oil.
10
The level of unsaturation is the major
factor that influences the fuel property. Although biodie-
sel is thermodynamically stable, its instability primarily
occurs from contact with oxygen, present in the
ambient air, and is referred to as oxidative instability. It
is a general term that involves oxidative degradation,
which may occur during the extended storage period,
transportation and end use.
11
Accelerated oxidation of
biodiesel results in an increase in viscosity, density and
polymer content, which initiates the formation of gums,
sediments and corrosion of engine components.
12
Biodiesel admixed in the lubricating oil during crankcase
dilution tends to be persistent within it due to less vola-
tility and begins to degrade and oxidise. This causes a sig-
nificant increase in viscosity of the sump oil and, in turn,
results in loss of performance, greater engine wear and
necessitates a premature oil change.
13
Antioxidants
(AHs) significantly slow down the biodiesel degradation
process. According to their mode of action, AHs are
classified as free radical terminators, metal ion chelators
capable of catalysing lipid oxidation, or as oxygen scaven-
gers that react with oxygen in closed systems.
14
These are
Centre for Energy Sciences, Department of Mechanical Engineering,
University of Malaya, 50603 Kuala Lumpur, Malaysia
*Corresponding author, email rizwanul.buet@gmail.com
© W. S. Maney & Son Ltd 2014
DOI 10.1179/1432891714Z.000000000936 Materials Research Innovations 2014 VOL 18 SUPPL 6 S6-90