Energy & Fuels 2009, 23, 3285–3289 3285

Effects of Oxidation during Long-term Storage on the Fuel

Properties of Palm Oil-based Biodiesel
Cherng-Yuan Lin* and Chu-Chiang Chiu
Department of Marine Engineering, National Taiwan Ocean UniVersity, Keelung 202, Taiwan, ROC

ReceiVed February 4, 2009. ReVised Manuscript ReceiVed April 10, 2009

Because palm-oil biodiesel is widely used as an alternative to petrodiesel, its long-term fuel properties have
become of great concern to the fuel industry. In this study, we investigated the dependence of the fuel properties
of palm-oil biodiesel on its oxidative degradation. We considered storage temperature, storage time, and the
addition of antioxidant as possible factors influencing oxidative instability. Palm-oil biodiesel was continuously
stored in a constant-temperature water bath at 20 or 60 °C for 3000 h to allow for variations in oxidative
degradation and fuel properties such as kinematic viscosity and acid value to be observed as the storage time
elapsed. The oxidative degradation of palm-oil biodiesel was caused by the peroxidation chain mechanism,
which started with a hydrogen-abstraction reaction in the methylene group (-CH2-) from polyunsaturated
fatty acids, leading to the formation of hydroperoxides. In turn, the fuel properties of the biodiesel became
degraded. The extent to which there was chemical reactivity in the peroxidation reaction was dominated by
the level of unsaturation of the biodiesel. Moreover, a higher storage temperature and a longer storage time
significantly accelerated the rate at which the peroxidation chain reaction proceeded in the palm-oil biodiesel.
In contrast, the addition of a chain-breaker type antioxidant was found to be effective in reducing the lipid
oxidation rate and thus retarding the fuel degradation rate of the palm-oil biodiesel. Palm-oil biodiesel to
which an antioxidant was added and which was stored at a lower temperature of 20 °C was observed to have
the highest level of oxidative stability and the lowest rate of decrease in both unsaturated fatty acids and
iodine value as storage time increased. The same sample of palm-oil biodiesel was also found to have the
lowest rates of increase in water content, kinematic viscosity, acid value, and peroxide value as storage time
increased.

1. Introduction and fuel filter of an engine being torn out or plugged, leading
to engine stalling or even breakdown. Therefore, the oxidation
The oil palm may produce the highest lipid content among stability of biodiesel is a key characteristic in determining
all land-based oleaginous plants. Palm oil, which is extracted whether the biodiesel is suitable for use as a replacement fuel
from palm fruit flesh, has been widely used to manufacture for petrodiesel in diesel engines, boilers, electricity generators,
biodiesel, primarily due to its availability in large quantities and and other combustion equipment.
its low cost in comparison with other raw renewable biolipid Palm oil contains aliphatic carbon chains, primarily in the
resources.1 Biodiesel, which is composed of monoalkyl esters ranges of C16 to C22 associated with 0-3 double bonds. A
of long-chain fatty acids, has been regarded as a promising biolipid with a larger number of double bonds in its polyun-
alternative fuel to petroleum due to its advantages in terms of saturated fatty acid chains generally has a higher level of
renewability, neutral carbon balance, low pollution and green- chemical reactivity and thus inferior oxidative stability. For
house gas (GHG) emission levels, superior lubricity, etc. example, linolenic acid (C18:3), which contains three double
However, biodiesel made from biolipids such as animal fats, bonds in the C18 carbon chain, is more prone to oxidization
vegetable oils, used cooking oil, or algae via transesterification than either linoleic acid (C18:2) or oleic acid (C18:1).3 A series
is far more susceptible to oxidization and thus has a higher level of peroxidation reactions proceeds when reactive oxygen species
of chemical reactivity than petroleum diesel. This oxidative and free radicals abstract a hydrogen atom in the methylene
instability causes deterioration in the physiochemical properties group (-CH2-) from polyunsaturated fatty acids to induce the
of the biodiesel.2 Biodiesel can suffer from oxidative degradation peroxidation chain mechanism. This chain mechanism reaction
after being stored at a high temperature for a long period of proceeds rather quickly to form hydroperoxides for a biolipid.
time and exposed to sunlight, air, water, and other contaminants. In contrast, a biolipid with a higher level of saturated fatty acids
The fuel properties of biodiesel, such as its heating value, cetane is more likely to inhibit the peroxidation chain mechanism and
number, and viscosity, etc. are subsequently affected. Moreover, has higher oxidative stability.4
sediment composed of viscous colloids, gels, and other impuri- Oil palm with rich lipid content has become one of the most
ties can form and subsequently become separated from the important raw oil sources for biodiesel production worldwide.
biodiesel. This is likely to lead to the fuel nozzle, injection pump, Although palm-oil biodiesel has been widely used as alternative
fuel to petrodiesel, the effect of oxidative degradation on its
* Corresponding author: phone/fax: +886 2 2462 2307; e-mail:
[email protected] (C.-Y.L.). fuel properties have not yet been systematically investigated,
(1) Reijnders, L.; Huijbregts, M. A. J. J. Clean Prod. 2008, 16, 477–
482. (3) Knothe, G. Fuel Process. Technol. 2005, 86, 1059–1070.
(2) Arisoy, K. Energ Sources 2008, 30, 1516–1522. (4) Browne, R. W.; Armstrong, D. Clin. Chem. 2000, 46, 829–836.

10.1021/ef900105t CCC: $40.75  2009 American Chemical Society

Published on Web 05/18/2009
3286 Energy & Fuels, Vol. 23, 2009 Lin and Chiu

in spite of the fact that there is great concern in the fuel industry closed with blue cap and ring. The closed glass bottles were then
over whether palm-oil biodiesel is suitable for use as a long- placed in a constant-temperature water bath covered with a lid for
term engine fuel. To address this gap in the research, we 3000 h (125 days). The structural body of the water bath, including
continuously observed variations in the oxidative degradation the lid, was composed of stainless steel SUS 304, which protected
and fuel properties of biodiesel produced from palm oil, which the samples from irradiation by sunlight. The daily average relative
humidity in the environment during the storage period was 82%.
was stored in a constant-temperature water bath at either 20 or At every 250 h, the lid of the water bath was lifted so the glass
60 °C. The total storage time was 3000 h (125 days) and the bottles could be temporarily removed. The cap of each bottle was
fuel properties of the biodiesel samples were analyzed every opened to pour a 60 mL biodiesel sample into a 100 mL vial (Nec
250 h. We also measured the effect of adding antioxidant. Co., Japan) with a seal of PP material. The glass bottles were
thereafter closed and placed back into the water bath, with the lid
2. Experimental Details replaced. The collected samples were used to analyze the biodiesel’s
fuel properties.
We analyzed the fuel properties of the palm-oil biodiesel samples 2.3. Fuel Property Measurements. A gas chromatography (GC)
stored in a constant-temperature water bath for 3000 h both with and analyzer (the GC-14A model by Shimadzu Inc., Japan) was used
without the addition of an antioxidant. The experimental procedures, in conjunction with a flame ionization detector (FID) and a
analytical methods, and instruments used to prepare the biodiesel chromatography data management system (by Advantech Inc.,
samples and measure their fuel properties were as follows. Taiwan) to analyze the weight proportions of the fatty acid
2.1. Production of Palm-oil Biodiesel. The palm-oil biodiesel compositions of the palm-oil biodiesel samples. The size of the
was produced via a transesterification process in which a strong fused silica capillary column (the SP-2380 model by Supelco Inc.,
alkali catalyst was used. Of all the available chemical processes, U.S.A.) used in the GC analyzer was 30 m (length) × 0.25 mm
including catalytic cracking, thermal cracking, amidation with (ID) with a 0.2 µm film thickness. A volumetric Karl Fischer
diethylamine, and transesterification in supercritical methanol, the Titration (the DL31 model by Mettler Toledo Ltd., Switzerland)
transesterification process with alkaline catalyst is the technique was used to determine the water content in the biodiesel samples.
most widely adopted in the biodiesel industry. A strong alkali A Karl Fischer solution containing iodine compound was titrated
catalyst is frequently used in the transesterification reaction, into the biodiesel samples until the first trace of excess iodine
primarily due to its significant advantages in terms of the smaller appeared, which allowed for the moisture content value to be
quantity of catalyst used and the shorter reaction time required.5 determined.7 The kinematic viscosity of the biodiesel samples was
Refined palm oil was used as the raw oil to be transesterified measured in centistokes (cSt) by a capillary viscometer (the 501
with methyl alcohol in a reacting tank at 60 °C, which is just below 23/IIc by Schott Gerate Inc., Germany) placed inside a water tube
the boiling point of methanol (63 °C), to prevent the methanol in at a constant temperature of 40 °C. The specific gravity of the
the reactant mixture from evaporating. The molar ratio of the biodiesel samples was measured on the basis of the standard ASTM
methanol and refined palm oil was set at 6:1. One percent by weight D1298-99e2 test method at a constant temperature of 15 °C using
of sodium hydroxide from the refined palm oil was stirred with a specific gravity meter.8
methyl alcohol for 10 min using an electric-magnetic stirrer to The acid value in mg KOH/g was derived by titration of 0.01 N
form sodium methoxide, which was then poured into the reacting potassium hydroxide into the mixture of the biodiesel sample and
tank and mixed with the refined palm oil. A mechanical homog- chemical reagents until the pink color appeared.9 The peroxide value
enizer operated at a speed of 6000 rpm was used to stir the reactant and iodine value were determined on the basis of the standard
mixture for 50 min until the transesterification reaction was testing methods of the American Oil Chemists’ Society10,11 by
completed. The crude product mixture was then stored in a titrating 0.01 N sodium thiosulfate into the mixture of the biodiesel
motionless or centrifuged state to enable the crude biodiesel and sample and chemical reagents until the color light blue (for the
glycerol to become separated from each other by virtue of the peroxide value) or light yellow (for the iodine value) appeared.
difference in specific gravity between these two compounds. The The peroxide and iodine values were calculated on the basis of the
crude biodiesel was heated to 70 °C to remove unreacted methanol following formulas:
and other volatile compounds. The biodiesel was then water-washed
by adding 10 wt % distilled water at 50 °C for 5 min to remove peroxide value ) (T-B) × S × 1000/G
water-soluble impurities. This was followed by a distillation process
in which the biodiesel was heated to a temperature of 110 °C for iodine value ) (B-T) × S × 0.001269/G
20 min to remove water content and other residues. This left the
palm-oil biodiesel from which the biodiesel samples analyzed in where T and B are the amounts (in mL) of sodium thiosulfate titrated
this study were taken. for the biodiesel sample being tested and the blank sample,
2.2. Preparation the Biodiesel Samples. Four samples were respectively; S is the normality of sodium thiosulfate; and G is the
prepared to enable us to study the effects of oxidative degradation weight (in g) of the biodiesel sample being tested.
on the fuel properties of biodiesel. The oxidative variables we
considered include storage time, storage temperature, and the
addition of an antioxidant, butylated hydroxytoluene (BHT). BHT, 3. Results and Discussion
which is composed of organic phenolic components, plays the role 3.1. Fuel Properties of Initially Prepared Palm-oil Biodie-
of a chain breaker and scavenger for free radicals to prevent sel. Our series of long-term experiments allowed us to assess
biolipids from spoiling. The melting point of BHT is 70-73 °C,
the dependence of palm-oil biodiesel fuel properties on oxidative
and its molecular formula is C15H24O.6 Sample 1, to which no
antioxidant was added, and sample 2, to which 0.1 wt % antioxidant
(7) Fundamentals of Volumetric Karl Fischer Titration; Mettler Toledo
BHT was added, were stored in a constant-temperature water bath Ltd.: Switzerland, 2008.
at a temperature of 20 °C. Sample 3, to which no BHT was added, (8) ASTM D1298-99e2, Standard Test Method for Density, Relative
and sample 4, to which 0.1 wt % antioxidant BHT was added, were Density (Specific Gravity), or API Gravity of Crude Petroleum and Liquid
stored in the constant-temperature water bath at a higher temperature Petroleum Products by Hydrometer Method; American Society for Testing
of 60 °C. and Materials: 2005.
(9) Official Methods and Recommended Practices - acid value, Cd 3d-
After preparation, each palm-oil biodiesel sample was stored in 63; American Oil Chemist’s Society: 1997.
a 1000 mL laboratory clear glass bottle (Scott Duran Co., Germany) (10) American Oil Chemists’ Society, Official Methods and Recom-
mended Practices - peroxide value, Cd 8-53; American Oil Chemist’s
(5) Demirbas, A. Energy ConVers. Manage. 2009, 50, 14–34. Society: 1997.
(6) Gulcin, I.; Kufrevioglu, O. I.; Oktay, M.; Buyukokuroglu, M. E. J. (11) Official Methods and Recommended Practices - iodine value, Cd
Ethnopharmacol. 2004, 90, 205–215. 1-25; American Oil Chemist’s Society: 1997.
Long-term Storage of Palm Oil-based Biodiesel Energy & Fuels, Vol. 23, 2009 3287

Table 1. Comparison of the Fuel Properties of Palm-oil respectively, as shown in Table 2. The rate of decrease in the
Biodiesel and ASTM No. 2D Diesel total quantity of unsaturated fatty acids in the sample 4 biodiesel
fuel type was significantly faster than in the sample 2 biodiesel stored at
fuel property palm-oil biodiesel ASTM No. 2D diesel a lower temperature, in which the quantity at the corresponding
specific gravity 0.871 0.834
times fell to 50.37 and 48.64 wt %, respectively. This difference
water content (wt %) 0.1054 0.0129 can be attributed to the higher storage temperature used for the
kinematic viscosity (cSt) 5.97 3.95 sample 4 biodiesel, which accelerated its oxidative degradation
heating value (MJ/kg) 40.29 46.13 through a peroxidation chain mechanism. We observed that the
carbon residue (wt %) 1.18 1.77 higher storage temperature used for the sample 4 biodiesel
flash point (°C) 182.1 75.6
cetane index 47.58 53.07 accelerated the conversion of unsaturated fatty acids into free
acid value (mg KOH/g) 2.71 fatty acids. Hence, in comparison with the sample 2 biodiesel
iodine value (g I2/100 g) 49.39 stored at a lower temperature of 20 °C, the sample 4 biodiesel
peroxide value (meq/kg) 9.33 was found to contain a significantly lower level of unsaturated
degradation according to storage time, storage temperature, and fatty acids after both 1500 h and 3000 h of storage time.
the addition of antioxidant. The fuel properties of the four 3.3. Variations in the Water Contents. The variations in
biodiesel samples were analyzed every 250 h over a continuous the water content of the four biodiesel samples as storage time
period of 3000 h. The fuel properties of the palm-oil biodiesel increased are shown in Figure 1. The daily average relative
and ASTM No. 2D diesel are shown in Table 1. The heating humidity in the environment was 82% during the storage period,
value, carbon residue, acid value, and flash point of the palm- which is somewhat high. The biodiesel may have absorbed
oil biodiesel were 40.29 MJ/kg, 1.18 wt %, 2.71 mg KOH/g, moisture from the environment when the glass bottles were
and 182.1 °C, respectively. The palm-oil biodiesel was found removed from the constant-temperature water bath and opened
to have a much higher flash point and lower heating value than to pour samples for analysis every 250 h. The samples poured
the ASTM No. 2D diesel. In addition, the palm-oil biodiesel may thus have had higher water content than their specification
had somewhat higher specific gravity and kinematic viscosity values. Some other fuel properties such as the acid value and
than the ASTM No. 2D diesel, observations consistent with carbon residue of the biodiesel samples may also have been
those made in relation to other biodiesels made from vegetable influenced by the hygroscopic characteristics of the palm oil
oils or animal fats.12 Liquid fuel with a higher flash point is biodiesel and therefore become relatively higher than their
safer during storage, transportation, and usage. respective specification values. When the biodiesel was stored
3.2. Variations in the Compositions of Fatty Acids. A at a higher temperature, the peroxidation chain reaction occurred
higher storage temperature was found to promote the chemical at a faster rate. This result in a higher hydroperoxide content,
reactivity of the olefinic carbon chains on the unsaturated fatty which is susceptible to decomposition and inter-reaction with
acids and thus accelerate the oxidative instability of the biolipids. other oxygen species and free radicals to form more secondary
Khan and Shahidi13 considered that the oxidative instability of oxidation products such as water and higher-molecular-weight
the borage and evening primrose biolipids stored at 60 °C for oligomers, which are frequently called polymers.16
4 days were equivalent to those of the same biolipids stored at The antioxidant BHT plays the role of a chain breaker and
25 °C for 4 months. The composition of the fatty acids in the scavenger for free radicals, retarding the peroxidation reaction
palm-oil biodiesel immediately after preparation and in the process in the biodiesel. In consequence, the sample 3 biodiesel
samples 2 and 4 biodiesel after 1500 and 3000 h of storage in that was stored at a higher temperature of 60 °C and to which
a constant-temperature water bath are shown in Table 2. It was no antioxidant was added was found to have the highest rate of
found that the palm-oil biodiesel was primarily composed of increase in water content. In contrast, the sample 2 biodiesel to
42.95 wt % oleic acid (C18:1), 42.08 wt % palmitic acid (C16: which the antioxidant BHT was added and that was stored at a
0), 7.03 wt % linoleic acid (C18:2), and 3.87 wt % stearic acid lower temperature of 20 °C had the lowest water content among
(C18:0). The total quantity of unsaturated fatty acid was 51.55 the four biodiesel samples. The presence of water in biodiesel
wt %, which was slightly higher than the quantity of saturated induces hydrolysis of fatty acids, leading to the formation of
fatty acids in the palm-oil biodiesel. Yung et al.14 found that acids and alcohols. The peroxidation chain reaction in the
biolipids with a higher unsaturated fatty acid content are more biodiesel can then be accelerated further and thus enhance the
prone to oxidative reaction, leading to faster degradation of fuel extent of oxidative instability.17
properties. 3.4. Variations in the Kinematic Viscosity. Figure 2 shows
The saturated palmitic acid content (C16:0) in the sample 4 the increase in the kinematic viscosity of the four biodiesel
biodiesel, to which 0.1 wt % antioxidant BHT was added and samples as storage time increased. Biodiesel sample 2, to which
which was stored at 60 °C, was observed to increase from 42.08 the antioxidant BHT was added and which was stored at a lower
to 43.13 and 43.90 wt % after 1500 and 3000 h of storage time, temperature of 20 °C, was found to have the lowest kinematic
respectively, as shown in Table 2. This implies that the saturated viscosity of the four samples. Increasing the storage temperature
fatty acid content is likely to increase with storage time at a and the absence of an antioxidant led to an increase in kinematic
higher storage temperature. This result is similar to that of viscosity. Higher kinematic viscosity implies inferior fuel
Bouaziz et al.15 for husk olive oil. After 1500 and 3000 storage fluidity, less fuel atomization, and, in turn, more incomplete
hours, the total quantity of unsaturated fatty acids in the sample burning.18
4 biodiesel decreased from 51.55 to 47.53 and 45.48 wt %, Long carbon-chain saturated fatty acids with a high molecular
weight and strong molecular bonding are formed during the
(12) Graboski, M. S.; McCormick, R. L. Prog. Energy Combust. 1998, peroxidation reaction process, particularly when the biodiesel
24, 125–164. is stored at a high temperature for a sufficient period of time.
(13) Khan, M. A.; Shahidi, F. Food Chem. 2001, 75, 431–437.
(14) Yung, C. L.; Choo, Y. M.; Cheng, S. F.; Ma, A. N.; Chuah, C. H.; (16) Williard, D. E.; Kaduce, T. L.; Harmon, S. D.; Spector, A. A. J.
Basiron, Y. Fuel 2006, 85, 867–870. Lipid Res. 1998, 39, 978–986.
(15) Bouaziz, M.; Fki, I.; Jema, H.; Ayad, M.; Sayadi, S. Food Chem. (17) Leung, D. Y. C.; Koo, B. C. P.; Guo, Y. Bioresour. Technol. 2006,
2008, 108, 253–262. 97, 250–256.
3288 Energy & Fuels, Vol. 23, 2009 Lin and Chiu

Table 2. A Comparison of the Fatty Acid Composition (wt %) of the Palm-oil Biodiesel Initially Prepared and of the Palm-oil Biodiesel
with 0.1 wt % BHT at 20 °C (Sample No. 2) and 60 °C (Sample No. 4) after 1500 h and 3000 h of Storage
biodiesel samples after 1500 h biodiesel samples after 3000 h
type of fatty acid chemical structure initial biodiesel No. 2 No. 4 No. 2 No. 4
lauric acid C12:0 1.26 1.35 1.56 1.26 1.72
myristic acid C14:0 1.10 1.01 1.05 1.45 1.12
palmitic acid C16:0 42.08 41.90 43.13 41.32 43.90
palmitoleic acid C16:1 0.15 0.09 0.23 0.17 0.24
stearic acid C18:0 3.87 4.30 3.98 4.75 4.42
oleic acid C18:1 42.95 42.46 42.10 41.27 41.43
linoleic acid C18:2 7.03 7.29 4.77 6.74 3.42
linolenic acid C18:3 0.48 0.53 0.43 0.46 0.38
arachidic acid C20:0 0.14 0.07 0.37 0.40 0.09
unsaturated fatty acids 51.55 50.37 47.53 48.64 45.48

Hence, the biodiesel became more viscous when the extent of quantity of free fatty acids in a biolipid. Biodiesel with a higher
oxidative degradation increased. For example, the saturated fatty acid value indicates a higher free fatty acid content. The peroxi-
acid content in the sample 4 biodiesel stored at a higher dation chain reaction results in the formation of hydroperoxides
temperature of 60 °C and to which 0.1% wt antioxidant BHT (LOOH) and carbon-centered lipid radicals. A series of radical
was added increased from 48.45 to 52.47 and 54.52 wt % after reactions occurs thereafter.20 This implies that the high level of
1500 and 3000 h of storage time, respectively. This increase in unsaturation in biolipids makes them more susceptible to oxidative
the formation of saturated compounds resulted in an increase reaction. More reactive radicals or free fatty acids are therefore
in kinematic viscosity as storage time elapsed, as shown in produced, resulting in a higher acid value. In addition, this
Figure 2. This increase in kinematic viscosity as storage time peroxidation chain reaction will be accelerated when biolipids are
elapsed may also have been due to the formation of trans- stored at a high temperature for a long period of time, conditions
isomers on the double bonds.19 that lead to an increase in acid value.21 In contrast, the introduction
3.5. Variations in the Acid Value. Acid value measured in of BHT made up of phenolic compounds, which is a type of chain-
mg KOH/g is one of the significant indicators of oxidative breaker antioxidant, will break the peroxidation chain reaction,
degradation in biolipids. Acid value can be used to estimate the resulting in the retardation of lipid oxidation. The acid value of a
biodiesel can thereby be reduced. As this implies, of the 4 samples,
the sample 3 biodiesel was observed to have the highest rate of
increase in acid value, as shown in Figure 3 because of its higher
storage temperature of 60 °C and the absence of an antioxidant.
Moreover, storage temperature was found to have a far bigger
influence on lipid oxidation than the presence or absence of an
antioxidant. This suggests that storing biolipids at a lower tem-
perature is an effective way of preventing them from deteriorating
quickly and suffering from further spoiling.
3.6. Variations in the Peroxide Value. Peroxide value is one
of the significant indicators of oxidative degradation and measures
the extent of lipid peroxidation. A higher peroxide value implies
greater formation of hydroperoxides through the peroxidation chain
mechanism.22 Figure 4 shows that the peroxide values of the
samples tested increased as the storage time elapsed, which implies
that hydrogen peroxide species were the primary product of the
Figure 1. Variation in the water content of palm-oil biodiesel with oxidative degradation during the storage period. Hydroperoxides
changes in storage time and storage temperature, and with the addition are prone to further decomposition and inter-reaction to form
of antioxidant. secondary products of oxidative degradation. It follows that the

Figure 2. Variation in the kinematic viscosity of palm-oil biodiesel Figure 3. Variation in the acid value of palm-oil biodiesel with changes
with changes in storage time and storage temperature, and with the in storage time and storage temperature, and with the addition of
addition of antioxidant. antioxidant.
Long-term Storage of Palm Oil-based Biodiesel Energy & Fuels, Vol. 23, 2009 3289

4 of our biodiesel samples fell with an increase in storage time.

The sample 3 biodiesel to which no antioxidant was added and
which was stored at a higher temperature of 60 °C appeared to
have the highest rate of reduction in iodine value, implying that
the largest conversion of polyunsaturated fatty acids to hydroper-
oxides took place in that sample. It followed that the fuel properties
of the sample 3 biodiesel deteriorated at the fastest rate among the
four biodiesel samples due to the occurrence of an accelerated
peroxidation chain reaction. In contrast, the sample 2 biodiesel to
which the antioxidant BHT was added and which was stored at a
lower temperature of 20 °C was observed to have the lowest rate
of decrease in iodine value, as shown in Figure 5, because it had
the lowest rate of conversion of unsaturated fatty acids.

4. Conclusions
Figure 4. Variation in the peroxide value of palm-oil biodiesel with
changes in storage time and storage temperature, and with the addition Biodiesel, which consists of monoalkyl esters of long-chain fatty
of antioxidant. acids made from biolipids, generally suffers from inferior oxidative
stability. In this study, we investigated the long-term dependence
of palm-oil biodiesel fuel properties on oxidative degradation as
influenced by changing storage conditions, including storage time,
storage temperature, and the addition of antioxidant. The results
of this study can be summarized as follows:
(1) The extent of the chemical reactivity of the peroxidation
chain mechanism is primarily dominated by the degree to which
the biodiesel is unsaturated. The peroxidation reaction starts with
the abstraction of hydrogen atoms in the methylene group from
the polyunsaturated fatty acids of the biodiesel. The unsaturated
fatty acid content is converted into hydroperoxides through the
oxidation process undergone by the biodiesel. A higher per-
oxidation reaction rate causes unsaturated fatty acids to be
converted more quickly, leading to a higher level of oxidative
degradation in the biodiesel.
(2) A higher storage temperature and a longer storage time were
Figure 5. Variation in the iodine value of palm-oil biodiesel with found to accelerate the peroxidation reaction in the palm-oil
changes in storage time and storage temperature, and with the addition biodiesel to a significant extent. A higher content of oxidation
of antioxidant. products such as hydroperoxides formed as a result of the
concentration of hydroperoxides may increase to a maximum value decomposition of unsaturated fatty acids in the biodiesel. This led
and thereafter decrease at the advanced stage of oxidative degrada- to faster deterioration in the fuel properties of the biodiesel.
tion. A higher storage temperature also enhanced the peroxidation (3) The addition of a phenolic antioxidant, BHT, which is of
reaction and increased the peroxide value. In contrast, the introduc- the chain-breaker type, played an effective role in breaking the
tion of the antioxidant BHT effectively broke the peroxidation peroxidation chain reaction, resulting in a significant reduction
reaction process and retarded the formation of hydroperoxides, in the rate at which unsaturated fatty acids were converted into
thereby reducing the peroxide value. Consequently, of the four hydroperoxides. In turn, the fuel property deterioration process
samples, sample 2, which was stored at a lower temperature and in the palm-oil biodiesel was retarded.
to which the antioxidant BHT was added, was found to have the (4) Of the four palm-oil biodiesel samples tested, the sample
lowest rate of increase in peroxide value, as shown in Figure 4. stored at a lower temperature of 20 °C and to which 0.1 wt %
Hence, the sample 2 biodiesel had the lowest rate of conversion antioxidant BHT had been added was found to have the highest
of unsaturated fatty acids into hydroperoxides, and thus the highest level of oxidative stability and the lowest rate of decrease in both
oxidative stability of all the biodiesel samples. The quantity of unsaturated fatty acids and iodine value as storage time increased.
unsaturated fatty acids in the sample 2 biodiesel fell from 51.55 to Of the samples tested, this sample also had the lowest rate of
50.37 and 48.64 wt % after 1500 h and 3000 h of storage time, reduction in the quantity of unsaturated fatty acids, with the quantity
respectively. falling from 51.55 to 50.37 and 48.64 wt % after 1500 h and 3000 h
3.7. Variations in the Iodine Value. The iodine value is a of storage time, respectively.
significant indicator of the level of unsaturation of a biolipid. A (5) Water content, kinematic viscosity, acid value, and
higher iodine value implies a higher unsaturated fatty acid content peroxide value were found to increase more quickly as storage
in biodiesel. Our experiments showed that the iodine value of all time elapsed, and there was a higher level of oxidative
degradation in the antioxidant-free biodiesel sample that was
(18) Lin, C. Y.; Lin, H. A. Fuel 2006, 85, 1743–1749. stored at a higher temperature.
(19) Tate, R. E.; Watts, K. C.; Allen, C. A. W.; Wilkie, K. I. Fuel 2006,
85, 1004–1009.
(20) Dunn, R. O. J. Am. Oil Chem. Soc. 2005, 82, 381–387. Acknowledgment. This study was financially supported by a
(21) Bondioli, P.; Gasparoli, A.; Bella, L. D.; Tagliabue, S. Eur. J. Lipid grant from the Energy Bureau and National Science Council of
Sci. Tech. 2002, 104, 777–784. Taiwan, ROC, contract No. NSC 96-ET-7-019-001.
(22) Tomasevic, A. V.; Siler-Marinkovic, S. S. Fuel Process. Technol.
2003, 81, 1–6. EF900105T