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Fuel 87 (2008) 1807–1813

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Oxidation stability of biodiesel fuel as prepared

by supercritical methanol
Jiayu Xin, Hiroaki Imahara, Shiro Saka *
Department of Socio-Environmental Energy Science, Graduate School of Energy Science, Kyoto University, Yoshida-honmachi,
Sakyo-ku, Kyoto 606-8501, Japan

Received 19 September 2007; received in revised form 18 December 2007; accepted 19 December 2007
Available online 14 January 2008

Abstract

A non-catalytic supercritical methanol method is an attractive process to convert various oils/fats efficiently into biodiesel. To eval-
uate oxidation stability of biodiesel, biodiesel produced by alkali-catalyzed method was exposed to supercritical methanol at several tem-
peratures for 30 min. As a result, it was found that the tocopherol in biodiesel is not stable at a temperature higher than 300 °C. After the
supercritical methanol treatment, hydroperoxides were greatly reduced for biodiesel with initially high in peroxide value, while the
tocopherol slightly decreased in its content. As a result, the biodiesel prepared by the supercritical methanol method was enhanced
for oxidation stability when compared with that prepared by alkali-catalyzed method from waste oil. Therefore, supercritical methanol
method is useful especially for oils/fats having higher peroxide values.
Ó 2007 Elsevier Ltd. All rights reserved.

Keywords: Biodiesel; Oxidation stability; Supercritical methanol; Antioxidant; Peroxide value

1. Introduction To overcome these drawbacks, non-catalytic conversion

Biodiesel fuel, which is defined as mono alkyl esters
derived from vegetable oils or animal fats through transe-
sterification, is an alternative for diesel engines. Being
derived from biomass resources, biodiesel is regarded as a
renewable and carbon-neutral fuel. For sustainable devel-
opment of society and energy, biodiesel has been recently
given more attentions [1] and commercially used in many
countries.
Current commercial production for biodiesel involves
the use of alkali-catalyzed method [2]. In this method, how-
ever, oils/fats that are high in free fatty acid and water con-
tents are difficult to be utilized since the former reacts with
alkaline catalyst to form undesirable saponified product
and the latter hinders the complete conversion. Further-
more, purification process is necessary to remove catalyst
and saponified products.
*
Corresponding author. Tel./fax: +81 75 753 4738.
E-mail address: saka@energy.kyoto-u.ac.jp (S. Saka).
method has been developed as supercritical methanol
method: one-step supercritical methanol method (Saka
process) [3–5] has been developed by our research group.
The shortcoming of this one-step supercritical methanol
method is that it requires a severe reaction condition com-
pared with the conventional commercial method. Conse-
quently, the special alloy must be used for the biodiesel
production system. Therefore, an alternative method for
biodiesel production that has milder reaction condition
than the one-step supercritical methanol method, two-step
supercritical methanol method (Saka–Dadan process) [6,7]
has been developed, the reaction temperature and pressure
of which can be decreased down to 270 °C and 20 MPa.
In a previous study, thermal stability of biodiesel in
supercritical methanol was investigated and it was found
that biodiesel could be stable without decomposition or
cis–trans isomerization under the condition of 300 °C/
19 MPa or lower in temperature [8]. For high-quality bio-
diesel production, on the other hand, oxidation stability
of biodiesel is also one of the most important issues.

0016-2361/$ - see front matter Ó 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2007.12.014
1808 J. Xin et al. / Fuel 87 (2008) 1807–1813
As is well known, in general, biodiesel has relatively
poorer oxidation stability compared with fossil diesel [9–
11]. Many reports have appeared on the oxidation stability
of various biodiesel fuels. Factors affecting the stability of
biodiesel fuels have been studied by Knothe [12], Falk
and Meyer-Pittroff [13] and McCormick et al. [14]. The
changes of key fuel properties of biodiesel during oxidation
have been reported by Lacoste and Lagardere [15] and
Bondioli et al. [16]. From these literatures, it is clear that
oxidation stability of biodiesel fuels are highly related with
its fatty acid composition, storage condition (temperature,
light, etc.), materials of the container, water and metal
content.
To enhance the oxidation stability, antioxidants were
employed to prolong the stabilized time of biodiesel. The
effect of various synthetic and natural antioxidants on the
oxidation stability of biodiesel fuels has been reported by
Mittelbach and Gangl [17,18], Liang et al. [19] and Dunn
[20]. Biodiesel is usually prepared from vegetable oil, vari-
ous natural antioxidants originally in oils are important for
oxidation stability of biodiesel. Main natural antioxidants
in vegetable oils are tocopherols (a-tocopherol, b-tocoph-
erol and c-tocopherol). However, these natural antioxi-
dants may be denatured and/or decomposed when they
are placed for a long time under air or high temperature.
Since high temperature and high pressure are inevitable
in supercritical methanol method, stability of natural anti-
oxidant during supercritical methanol treatments is an
important issue that should be studied.
In this work, therefore, stability of tocopherol in biodie-
sel was studied in supercritical methanol. Effect of super-
critical methanol treatment on oxidation stability of
various biodiesels was evaluated with an addition of phe-
nol-type and amine-type antioxidants at different concen-
trations. Comparison was then made between oxidation
stability of biodiesel prepared by supercritical methanol
method and alkali-catalyzed method.
2. Materials and methods
The vegetable oils used in this study were safflower,
rapeseed and palm oils; the chemical compositions of fatty
acids in their triglycerides were shown in Table 1. As repre-
sentative synthetic antioxidants, 3,4,5-trihydroxybenzoic
acid propyl ester(Propyl gallate, PG, P99%) and N,N0 -
diphenyl-p-phenylenediamine (DPD, P99%) bought from
Aldrich–Sigma were chosen and their chemical structures
are shown in Fig. 1. Anhydrous methanol (P99.7%), dis-
Table 1
Various vegetable oils used in this study and their chemical compositions of fatty acids in triglycerides
Vegetable oil Fatty acid composition (wt%)
C16:0 C18:0 C18:1 C18:2
Safflower 6.4 2.2 13.9 76.0
Rapeseed 4.3 1.9 61.5 20.6
Palm 39.5 4.1 43.2 10.6
O O(CH2)2 CH3
HO OH
OH
3,4,5-trihydroxybenzoic acid propyl ester (Propyl gallate, PG)
H H
N N
N,N -diphenyl-p-phenylenediamine (DPD)
Fig. 1. Chemical structures of antioxidants used in this study.
tilled water (HPLC grade), potassium hydroxide (reagent
grade), potassium iodide (reagent grade) and sodium thio-
sulfate solution were purchased from Nacalai Tesque Inc.
Japan. Waste oil samples were collected from several res-
taurants in Kyoto city, their chemical compositions of fatty
acids in triglycerides and tocopherol content were shown in
Table 2.
The vegetable oils were converted to fatty acid methyl
esters (biodiesel) by alkali-catalyzed method with potas-
sium hydroxide as a catalyst. The reaction conditions
adopted were as follows: 30 g oil and 8.25 ml methanol
were mixed with 0.15 g potassium hydroxide. Transesterifi-
cation reaction was carried out at 69 °C in an oil bath
under continuous mixing with a magnetic stirrer for
60 min. The obtained esters were subjected to supercritical
methanol exposure; biodiesel was mixed with methanol
(biodiesel/methanol = 1/1 (v/v)) in a 5 ml batch-type reac-
tion vessel made of Inconel-625 and exposed to supercriti-
cal methanol at 270 °C/17 MPa for 30 min. After the
exposure, methanol was evaporated with a rotary evapora-
tor at 75 °C for 15 min to get ‘‘exposed biodiesel” to super-
critical methanol.
Chemical composition of biodiesel was analyzed by
high-performance liquid chromatography (HPLC) (Shima-
dzu, LC-10AT) which consists of the column (Cadenza
CD-C18, 25 cm in length  4.6 mm in inner diameter,
Imtakt Co.) and refractive index detector (Shimadzu,
RID-10A) operated at 40 °C with 1.0 ml/min flow rate of
methanol as a carrier solvent. Tocopherol, as one of the
main natural antioxidant in vegetable oils [21–23], was also
studied by the HPLC consisting of the column (Asahipak
ODP-50, 25 cm in length  4.6 mm in inner diameter, Sho-
Saturated fatty acid Unsaturated fatty acid
(wt%) (wt%)
C18:3 Others
0.2 1.3 8.6 89.1
8.3 3.4 6.2 85.5
0.2 2.4 43.6 54.0
 J. Xin et al. / Fuel 87 (2008) 1807–1813 1809

Table 2
Waste oils used in this study, their chemical compositions of fatty acids in triglycerides and tocopherol content
Waste oil Fatty acid composition (wt%) Saturated fatty acid Unsaturated fatty acid Tocopherol content
(wt%) (wt%) (ppm)
C16:0 C18:0 C18:1 C18:2 C18:3 Others
Sample 1 8.3 2.7 44.4 36.8 6.3 1.5 11.0 87.5 83
Sample 2 4.3 1.5 61.5 21.6 6.3 4.8 6.8 89.4 <5
Sample 3 5.8 2.3 60.1 21.8 7.3 2.7 9.1 89.2 <5
Sample 4 8.8 2.3 53.7 30.7 1.8 2.7 11.1 86.2 <5
Sample 5 12.3 3.4 32.0 47.6 1.6 3.1 15.7 81.2 <5

dex Co.) and fluorescence detector (RF-10AXL, Shima-
dzu) operated under the same condition above. The struc-
tural changes of biodiesels were analyzed by a Fourier-
transform infrared spectrometry (Shimadzu, FT-IR
8300). Tocopherol content and peroxide value were mea-
sured according to Standard Methods for the Analysis of
Fats, Oils and Related Materials 2.4.10 [24] and 2.5.21
[25], respectively. In the work, ‘‘induction period” was used
to determine oxidation stability of biodiesel. In the proce-
dure, biodiesel is aged at 110 °C by passing air through
at constant rate. The effluent gases are collected in a cell
filled with distilled water of which the conductivity is
recorded. Once hydrogen peroxides as primary oxidation
products are decomposed into volatile acids, conductivity
values steeply increase. The period of time up to this point
is called induction period and is expressed in hours. Oxida-
tion stability of biodiesel before and after supercritical
methanol exposure and their blends with different antioxi-
dants were studied in accordance with EN14112 [26] on
Rancimat equipment model 743 (Methrom, Herisau,
Switzerland).
3. Results and discussion
of biodiesel. To study the effect of temperature on the
tocopherol content in biodiesel, rapeseed biodiesel was
chosen as a representative biodiesel. Rapeseed biodiesel
in Table 3 was exposed to supercritical methanol at
270 °C/17 MPa, 300 °C/20 MPa, 330 °C/37 MPa, and
360 °C/47 MPa for 30 min, the remaining tocopherol con-
tent in rapeseed biodiesel is presented in Fig. 2. At the tem-
perature lower than 300 °C, the remaining tocopherol
slightly decreased with an increase in temperature. With
the increase in temperature, the tocopherol content was sig-
nificantly decreased. When the temperature reached
360 °C, only about 1/3 tocopherol remained in rapeseed
biodiesel.
The significant decrease in the tocopherol content results
in inevitably poor oxidation stability of biodiesel. Further-
more, it has been already confirmed that the poly-unsatu-
rated fatty acid methyl esters are decomposed in
supercritical methanol at the temperature higher than
300 °C [8]. Therefore, reaction temperature adopted in
supercritical methanol method lower than 300 °C is favor-
able. For this reason and the proposed two-step supercrit-
ical methanol method, oxidation stability of biodiesel was
thus studied at 270 °C.

3.1. Effect of temperature on the natural antioxidant in
biodiesel
As a main natural antioxidant in vegetable oils, toc-
opherols play an important role in preventing oxidation
3.2. Oxidation stability of various biodiesel fuels
Three biodiesel samples, from safflower, palm and rape-
seed oils, with different fatty acid compositions were suc-
cessfully prepared by alkali-catalyzed method, and the

Table 3
Key properties of biodiesel fuels used in this study and European specification standard (EN14214)
Properties Method Unit EN14214 Biodiesel
Safflower Rapeseed Palm
Density at 15 °C EN ISO 3675 g/cm3 0.86–0.90 0.89 0.88 0.87
Viscosity at 40 °C EN ISO 3104 mm2/s 3.5–5.0 4.11 4.29 4.01
Pour point ISO 3016 °C – 7.5 13 10
Cloud point ISO 3105 °C – 5 5 10
Ester content EN 14103 wt% >96.5 97.75 97.39 98.46
Monoglyceride EN 14105 wt% <0.8 0.53 0.23 0.27
Diglyceride EN 14105 wt% <0.2 0.50 0.09 0.25
Triglyceride EN 14105 wt% <0.20 n.d. n.d. n.d.
Total glycerol content EN 14105 wt% <0.25 0.21 0.07 0.11
Water content EN ISO 12937 ppm <500 288 284 197
Acid number EN 14104 mg(KOH)/g <0.5 0.33 0.30 0.09
Iodine value EN 14111 g(I2)/100 g <120 141 114 50
Oxidation stability at 110 °C EN 14112 h >6 0.9 6.5 14.7
n.d., not detectable.
1810 J. Xin et al. / Fuel 87 (2008) 1807–1813

a 50
Safflower biodiesel, exposed
Safflower biodiesel, unexposed
40

Induction period (hour)

Rapeseed biodiesel, exposed
Rapeseed biodiesel, unexposed
Palm biodiesel, exposed
30 Palm biodiesel, unexposed

20

10

0
0 1,000 2,000 3,000 4,000 5,000
Fig. 2. Effect of temperature on the tocopherol content in rapeseed PG concentration (ppm)
biodiesel as treated in supercritical methanol at 270 °C/17 MPa, 300 °C/
20 MPa, 330 °C/37 MPa, and 360 °C/47 MPa for 30 min.
b 50
Safflower biodiesel, exposed
fuel properties of the obtained biodiesels are shown in Safflower biodiesel, unexposed
40 Rapeseed biodiesel, exposed

Induction period (hour)

Table 3. Rapeseed biodiesel, unexposed
Taking into account the fatty acid composition in Table Palm biodiesel, exposed
1 and oxidation stability in Table 3, it is apparent that oxi- 30 Palm biodiesel, unexposed

dation stability gets better with decrease in the degree of

unsaturation in biodiesel. Safflower biodiesel, which is high
in content in poly-unsaturated fatty acids, has the shortest
induction period (0.9 h), whereas palm biodiesel, which is
high in saturated fatty acid content, has the longest one
(14.7 h). This tendency is consistent with the literatures
[27]. Since the induction period longer than 6 h determined
by Rancimat Method is required to satisfy the biodiesel
specification EN14112, an addition of the antioxidant is
inevitable for safflower biodiesel.
These biodiesels were subjected to supercritical metha-
nol exposure at 270 °C/17 MPa for 30 min. From HPLC
chromatograms and FT-IR spectra, it was observed that
there exists no decomposition or structural change such
as cis–trans isomerization. Fig. 3 shows oxidation stability
of biodiesels before and after supercritical methanol expo-
sure at 270 °C/17 MPa for 30 min as a function of various
PG and DPD concentrations. Induction period increased
monotonously with increasing PG concentration. How-
ever, the increment at higher PG concentration was not
so obvious as that at lower PG concentration. With regard
to safflower biodiesel, 5000 ppm of the PG was required to
guarantee an induction period of 25 h. For palm biodiesel,
on the other hand, less than 100 ppm of the PG was
enough to guarantee an induction period of 50 h.
In a similar manner, oxidation stability test was con-
ducted by using DPD. As shown in Fig. 3b, basically the
same results were observed. From these results, it can be
emphasized that DPD antioxidant can offer better oxida-
tion stability over palm biodiesel than safflower biodiesel,
indicating that more antioxidant is needed for the latter
to ensure an induction period more than 6 h.
From Fig. 3a and b, it is seen that at the same concen-
tration of the antioxidant, PG provides longer induction
period than DPD. Oxidation of biodiesel is a chain reac-
20
10
0
0 1,000 2,000 3,000 4,000 5,000
DPD concentration (ppm)
Fig. 3. Oxidation stability of biodiesels before and after supercritical
methanol exposure at 270 °C/17 MPa for 30 min as a function of various
antioxidant concentrations (shadowed area is a range unsatisfactory in
specification standard) (a) PG and (b) DPD.
tion process; free radicals produced in this process are elec-
tron acceptor and can be readily reduced by hydrogen
donors. As shown in Fig. 1, PG molecule has three hydro-
gens can be given from OH bond, while DPD has two
hydrogens can be given from NH bond. Moreover, the
molecular weight of PG (212 g/mol) is smaller than that
of DPD (260 g/mol); as a result, the effect of enhancing
the oxidation stability is better in the former than the
latter.
In Fig. 3, two opposite tendencies were found in oxida-
tion stability of biodiesels before and after supercritical
methanol exposure; oxidation stability of exposed biodiesel
is better than unexposed one for safflower biodiesel,
whereas slightly worse for rapeseed and palm biodiesel
for both cases of (a) and (b). To clarify these tendencies,
peroxide value and tocopherol content were analyzed for
both exposed and unexposed biodiesels. Peroxide value
indicates the content of hydroperoxide, which triggers oxi-
dation process and reacts with antioxidant [28], thus low
peroxide value is favorable for high oxidation stability in
biodiesel.
 J. Xin et al. / Fuel 87 (2008) 1807–1813 1811

25 250
Unexposed Unexposed
Exposed

Tocopherol content (ppm)

Exposed
Peroxide value (meq/kg)

20 200

15 150

10 100

5 50

0 0
Safflower Rapeseed Palm Safflower Rapeseed Palm
Fig. 4. Changes in peroxide value of various biodiesels as exposed to Fig. 5. Changes in tocopherol content of various biodiesels as exposed to
supercritical methanol at 270 °C/17 MPa for 30 min. supercritical methanol at 270 °C/17 MPa for 30 min.

Fig. 4 shows changes in peroxide value of various bio-
diesels as exposed to supercritical methanol at 270 °C/
17 MPa for 30 min. With regard to safflower biodiesel,
the initial peroxide value was rather high, about 23 meq/
kg; after supercritical methanol exposure, it decreased to
about 2 meq/kg, while for peroxide value of rapeseed bio-
diesel, only a slight decrease was observed. For palm bio-
diesel, however, peroxide value increased slightly after
exposure in supercritical methanol. These results indicate
that both decomposition and formation of hydroperoxide
might occur at the same time under the supercritical meth-
anol condition. In addition, hydroperoxide is reported to
be unstable at a temperature higher than 180 °C [29].
Therefore, peroxide value could be reduced the biodiesel
with high peroxide value as observed under supercritical
methanol exposure.
For safflower biodiesel, exposed biodiesel shows supe-
rior oxidation stability to unexposed one, since the decom-
position of hydroperoxide is so significant during the
supercritical methanol exposure. For palm biodiesel, on
the contrary, exposed biodiesel shows slightly lower oxida-
tion stability due to the slight formation of hydroperoxide
and deformation of tocopherol during the supercritical
methanol exposure.
Fig. 5 shows changes in tocopherol content of various
biodiesels as exposed to supercritical methanol at 270 °C/
oxyl radicals. As a result, less tocopherols are left in less
unsaturated methyl esters (palm biodiesel). This result
could explain the above tendencies in Fig. 3.
3.3. Comparison of conversion methods for oxidation
stability
Due to the repeated use of the waste oils and long term
storage, waste oils are usually high in peroxide value and
low in tocopherol content. To verify the effect of conver-
sion methods on peroxide value and tocopherol content
of biodiesel, five samples of waste oils were collected from
restaurants in Kyoto city and converted into biodiesels by
both alkali-catalyzed method and supercritical methanol
method. Peroxide value and tocopherol content of waste
oils and their biodiesels are shown in Figs. 6 and 7. Since
the samples with high peroxide value leads to side reaction
between hydroperoxides and antioxidant, that with low
peroxide value is favorable for oxidation stability of biodie-
sel. As shown in Fig. 6, peroxide values of biodiesel pre-
pared by alkali-catalyzed method were reduced,
50
Waste oil, no treatment
Alkali-catalyst method
Peroxide value (meq/kg)

40 Supercritical methanol method

17 MPa for 30 min. For only palm biodiesel, a noticeable
decrease can be observed in tocopherol content after super-
30
critical methanol exposure. These results were consistent
with the literature, where decreasing rate of tocopherol is
proportional to the degree of saturation in vegetable oil 20
[30,31].
Yamauchi proposed a mechanism to explain this phe- 10
nomenon [32]. At high temperature, the peroxyl radicals
react with esters and form hydroxyl radicals, by rearrange- 0
ment and further oxidation, epoxyalkoxyl radicals are 1 2 3 4 5
formed. Because the epoxyalkoxyl radicals are less selective Sample number
in the reactions with tocopherols and fatty acid esters than Fig. 6. Peroxide value of waste oils and biodiesels prepared from the
peroxyl radicals, some of the unsaturated esters will be able waste oils by alkali-catalyzed method and supercritical methanol method
to compete with tocopherol in the reaction with epoxyalk- (270 °C/17 MPa for 60 min).
1812 J. Xin et al. / Fuel 87 (2008) 1807–1813

100 method were longer than those prepared by alkali-cata-

Waste oil, no treatment lyzed method. As mentioned before in Fig. 7, the tocoph-
Alkali-catalyzed method erol content of waste oil sample 1 is higher than sample
Tocopherol content (ppm)

80 Supercritical methanol method

3. As a result, the induction period of biodiesel prepared
from sample 1 can be expected to be longer than sample
60
3. In addition, supercritical methanol exposure can reduce
the peroxide value by efficient decomposition of hydroper-
40 oxide. Consequently, it can be clarified that supercritical
methanol method is superior to alkali-catalyzed method
20 for biodiesel production from oils/fats having high perox-
ide value.
0
1 2 3 4 5
4. Conclusions
Sample number

Fig. 7. Tocopherol content of waste oils and biodiesels prepared by alkali-
catalyzed method and supercritical methanol method (270 °C/17 MPa for
60 min).
compared with waste oil itself, but around 7 meq/kg of the
peroxide is remaining. When the biodiesel prepared by
supercritical methanol method, in contrast, there exists
almost no peroxide value detected.
In terms of tocopherol content, as shown in Fig. 7, there
is almost no difference between biodiesel prepared by
alkali-catalyzed and supercritical methanol methods from
waste oil sample 1. The initial tocopherol contents in waste
oil samples 2–5 are very low, the significant difference
between them and sample 1 may be because of reservation
and utilization in the restaurants. For example, the tocoph-
erol at frying temperature is unstable and quickly con-
sumed by oxidation. If the oil is repeatedly used at high
temperature, the tocopherol in the oil will be destroyed.
Fig. 8 shows a comparison of oxidation stability of bio-
diesels prepared by alkali-catalyzed and supercritical meth-
anol methods from waste oils. It is apparent that induction
periods of biodiesels prepared by supercritical methanol
50
45
40
Induction period (hour)
Oxidation stability of biodiesel prepared by supercritical
methanol method was evaluated through the exposure of
biodiesels to supercritical methanol at 270 °C/17 MPa for
30 min. As a result, it was found that oxidation stability
became better after the exposure for biodiesel initially high
in peroxide value, while it was slightly decreased for that
initially low in peroxide value, compared with unexposed
biodiesel prepared by alkali-catalyzed method. During
supercritical methanol exposure, most hydroperoxides
was decomposed due to high temperature and high pres-
sure, while tocopherol remained almost unchanged in its
content for high unsaturated biodiesel (safflower and rape-
seed biodiesel) but slightly decreased for low unsaturated
biodiesel (palm biodiesel). Therefore, it was clarified that
supercritical methanol method is useful especially for
oils/fats that have higher peroxide values.
Acknowledgements
This work has been done as in part of the Kyoto Univer-
sity 21 COE program ‘‘Establishment of COE on Sustain-
able-Energy system” (2002.9-2007.3), and in part of NEDO
‘‘High Efficiency Bioenergy Conversion Projects” (2003.9–
2006.3), for all of which the authors are highly
acknowledged.
Sample 1, Supercritical methanol method
Sample 1, Alkali-catalyzed method
Sample 3, Supercritical methanol method
References

Sample 3, Alkali-catalyzed method

35 [1] Ma F, Hanna M. Biodiesel production: a review. Biores Technol
1999;70:1–15.
30
[2] Leung D, Guo Y. Transesterification of neat and used frying oil:
25 Optimization for biodiesel production. Fuel Process Technol
20 2006;87:883–90.
[3] Saka S, Kusdiana D. Biodiesel fuel from rapeseed oil as prepared in
15 supercritical methanol. Fuel 2001;80:225–31.
10 [4] Kusdiana D, Saka S. Kinetics of transesterification in rapeseed oil to
biodiesel as treated in supercritical methanol. Fuel 2001;80:693–8.
5 [5] Kusdiana D, Saka S. Methyl esterification of free fatty acids of
0 rapeseed oil as treated in supercritical methanol. J Chem Eng Jpn
0 1,000 2,000 3,000 2001;34:384–7.
PG concentration (ppm) [6] Kusdiana D, Saka S. Two-step preparation for catalyst-free biodiesel
fuel production: hydrolysis and methyl esterification. Appl Biochem
Fig. 8. Comparison of oxidation stability of biodiesels prepared by alkali- Biotechnol 2004;115:781–91.
catalyzed method and supercritical methanol method (Shadowed area is a [7] Kusdiana D, Saka S. Development of the batch-type and flow-type
range unsatisfactory in specification standard). supercritical fluid biomass conversion systems. In: 12th European
 J. Xin et al. / Fuel 87 (2008) 1807–1813
conference on biomass for energy, Ind. Climate Protec., 2002,
Amsterdam, The Netherlands; 2002, p. 789–92.
[8] Imahara H, Minami E, Hari S, Saka S. Thermal stability of biodiesel
in supercritical methanol. Fuel 2008;87:1–6.
[9] Clark S, Wagner L, Schrock MD, Piennaar P. Methyl and ethyl
soybean esters as renewable fuels for diesel engines. JAOCS
1984;61:1632–8.
[10] Ali Y, Hanna M, Cuppett SL. Fuel properties of tallow and soybean
oil esters. JAOCS 1995;72:1557–64.
[11] Monyem A, Van Gerpen JH. The effect of biodiesel oxidation on
engine performance and emissions. Biomass Bioenergy
2001;20:317–25.
[12] Knothe G. Dependence of biodiesel fuel properties on the structure of
fatty acid alkyl esters. Fuel Process Technol 2005;86:1059–70.
[13] Falk O, Meyer-Pittroff R. The effect of fatty acid composition on
biodiesel oxidative stability. Euro J Lipid Sci Technol 2004;106:837–43.
[14] McCormick RL, Ratcliff M, Moens L, Lawrence R. Several factors
affecting the stability of biodiesel in standard accelerated tests. Fuel
Process Technol 2007;88:651–7.
[15] Lacoste F, Lagardere L. Quality parameters evolution during
biodiesel oxidation using Rancimat test. Euro J Lipid Sci Technol
2003;105:149–55.
[16] Bondioli P, Gasparoli A, Della Bella L, Silvia T. Evaluation of
biodiesel sorage stability using reference methods. Euro J Lipid Sci
Technol 2002;104:777–84.
[17] Mittelbach M, Gangl S. The influence of antioxidants on the
oxidation stability of biodiesel. JAOCS 2003;80:817–23.
[18] Gangl S, Mittelbach M. The impact of antioxidants on biodiesel
oxidation stability. Euro J Lipid Sci Technol 2004;106:382–9.
[19] Chee Liang Y, Yuen May C, Sit Foon C, Ah Ngan M, Cheng Hock
C, Basiron Y. The effect of natural and synthetic antioxidants on the
oxidative stability of palm diesel. Fuel 2006;85:867–70.
[20] Dunn RO. Effect of oxidation under accelerated conditions on fuel
properties of methyl soyate (biodiesel). JAOCS 2002;79:910–5.
[21] Kalogeropoulos N, Mylona A, Chiou A, Ioannou MS, Andrikopo-
ulos NK. Retention and distribution of natural antioxidants
1813
(a-tocopherol, polyphenols and terpenic acids) after shallow frying
of vegetables in virgin olive oil. LWT – Food Sci Technol
2007;40:1008–17.
[22] Frankel EN. Antioxidants in lipid food and their impact on food
quality. Food Chem 1996;57:51–5.
[23] Barrera-Arellano D, Ruiz-Mendez V, Velasco J, Márquez-Ruiz M,
Dobarganes C. Loss of tocopherols and formation of degradation
compounds at frying temperatures in oils differing in degree of
unsaturation and natural antioxidant content. J Sci Food Agric
2002;82:1696–702.
[24] Standard Methods for the Analysis of Fats, Oils and Related
Materials, 2.4.10-1996, Tocopherol content (acetic acid–isooctane
method), Japan Oil Chemists’ Society, Tokyo, 1996.
[25] Standard Methods for the Analysis of Fats, Oils and Related
Materials, 2.5.21-1996, Peroxide value (acetic acid–isooctane
method), Japan Oil Chemists’ Society, Tokyo, 1996.
[26] EN14112, Determination of oxidation stability (accelerated oxidation
test), Euro. Committ. for Standardization, Berlin, 2003.
[27] Knothe G, Dunn RO. Dependence of oil stability index of fatty
compounds on their structure and concentration and presence of
metals. JAOCS 2003;80:1021–6.
[28] Denisov ET, Khudyakov IV. Mechanisms of action and reactivities of
the freeradicals of inhibitors. Chem Rev 1987;87:1313–57.
[29] Edwards T. Supercritical fuel deposition mechanisms. Ind Eng Chem
Res 1983;32:3117–22.
[30] Verleyen T, Revilija K, Afaf M, Revilija M, Roland V, Koen D, et al.
Oxidation at elevated temperatures: competition between a-tocoph-
erol and unsaturated triacylglycerols. Euro J Lipid Sci Technol
2002;104:228–33.
[31] Yamauchi R, Kato K, Ueno Y. Free-radical scavenging reactions of
a-tocopherol during the autoxidation of methyl linoleate in bulk
phase. J Agric Food Chem 1995;43:1455–61.
[32] Neff WE, Selke E, Mounts TL, Rinsch W, Frankel EN, Zeitoun
MAM. Effect of triacylglycerol composition and structures on
oxidative stability of oils from selected soybean germplasm. JAOCS
1992;69:111–8.