Fuel 93 (2012) 391–396

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Fuel
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Effect of the test temperature and anti-oxidant addition on the oxidation stability
of commercial biodiesel fuels
M. Lapuerta a,⇑, J. Rodríguez-Fernández a, Á. Ramos a, B. Álvarez b
a
Escuela Técnica Superior de Ingenieros Industriales, University of Castilla – La Mancha, Edificio Politécnico, Avda., Camilo José Cela, s/n, 13071 Ciudad Real, Spain
b
APPA Biocarburantes, C/Muntaner 269, 1°1ª, 08021 Barcelona, Spain

a r t i c l e i n f o a b s t r a c t

Article history: The oxidation stability of biodiesel fuels is a property specified in the European and American biodiesel
Received 14 October 2010 quality standards. It is measured by the Rancimat test, whose parameters and final result (an induction
Received in revised form 2 September 2011 period) are subjected to a continuous discussion among different committees, associations, distributors
Accepted 5 September 2011
and final users. This study evaluates the stability of three biodiesel fuels derived from different feed-
Available online 17 September 2011
stocks, assessing the effect of the test temperature and the concentration of a commercial oxidation sta-
bility enhancing additive. The results showed a drastic decrease (in the range of one order of magnitude)
Keywords:
in the induction period when the test temperature increases from 110 °C to 130 °C. This finding makes
Oxidation stability
Biodiesel
impossible to achieve the threshold currently imposed in the standards at 130 °C, even after a massive
Anti-oxidant additive addition. The effect of the unsaturation degree and the previous use of the feedstock in cooking
Rancimat processes are also addressed. An experimental model, adjusted with statistical tools, is proposed to esti-
mate the induction period as a function of the test temperature, the additive concentration and the origin
of the biodiesel, the last considering the unsaturation degree and the previous use of the raw material.
Ó 2011 Elsevier Ltd. All rights reserved.

1. Introduction flow properties at the expense of higher tendency to lose stability

Biodiesel (saturated and unsaturated alkyl esters produced from
the transesterification reaction of vegetable oils or animal fats) is a
recognized alternative fuel for diesel engines. By partially substi-
tuting the consumption of fossil fuels, biodiesel contributes to
slowing up the depletion of fossil resources and reducing the
GHG emissions from the transport sector. In the European Union,
the successive directives [1,2] for the promotion of renewable
energies, the mandatory consumption of biodiesel and bio-ethanol
that has been imposed by many member states [3,4] and the devel-
opment of fuel quality standards for regulating the specifications of
the final product [5,6] have all contributed to the consolidation of
biodiesel fuels as a reality.
However, biodiesel growth has not been free of obstacles. These
have been related to the biodiesel effect on the engine (mainly a
slight but well-documented [7] increase in NOx emissions and
some experiences [8,9] reporting deposits in the combustion
chamber and injection system), and to the quality of the final fuel
along the entire supply chain [10,11]. Two properties emerge as
the most critical in guaranteeing biodiesel quality, namely the cold
flow properties and the fuel stability [12–14]. Managing both is not
an easy task as a consequence of the biodiesel composition itself:
fuels with a higher unsaturated esters content show better cold
⇑ Corresponding author. Tel.: +34 926295431; fax: +34 926295361.
E-mail address: Magin.Lapuerta@uclm.es (M. Lapuerta).
through degradation [15–17].
The two reasons behind the biodiesel degradation process are
(i) its exposure to high temperatures (usually above 250–300 °C)
or (ii) the presence of an oxidant agent (usually air oxygen, but also
dissolved oxygen) in contact with the fuel during a sufficiently long
period of time. The first case is commonly referred to as thermal
stability, and it is not considered in detail in this work. The second
is named as oxidative stability [18–20], although the term storage
stability is commonly used as well [21,22] to refer to it, since when
stored during months the fuel is highly likely to become in contact
with air oxygen. To make it worse, other agents such as the light,
the presence of metals, water or dissolved oxygen in the fuel and
a relatively high storage temperature may speed up the oxidation
process [12,23].
Biodiesel oxidation can proceed through two mechanisms,
namely auto-oxidation and photo-oxidation [24–26]. However,
the second mechanism, which requires the exposure to ultraviolet
light and the presence of a photo-sensitizer, is unlikely to take part
in biodiesel degradation. Thus, many authors [27–29] use indi-
stinctively the terms oxidation and auto-oxidation. This mecha-
nism is free-radical chain reaction which initiates when the
oxygen in the atmosphere reacts with unsaturated methyl esters,
especially those with two or more double-bonds in its molecule
[20,30]. The primary products are hydro-peroxides and free radi-
cals, these being subsequently used for self-sustain the process.
Later, other reactions are triggered to form acids, polymers, etc.

0016-2361/$ - see front matter Ó 2011 Elsevier Ltd. All rights reserved.
doi:10.1016/j.fuel.2011.09.011
392 M. Lapuerta et al. / Fuel 93 (2012) 391–396
Nomenclature
A, Ai, B, Bi experimentally-adjusted coefficients for the single-
fuel models
Ci experimentally-adjusted coefficients for the integrated
model
B100_AF biodiesel (methyl esters) derived from animal fats
B100_SO biodiesel (methyl esters) derived from soybean oil
B100_UO biodiesel (methyl esters) derived from used cooking oil
BHT butyl hydroxyl toluene
which adversely affect some fuel properties (acid and peroxide
value, ester content, viscosity) and even the injection process in
the engine (polymers may block injector nozzles). The use of oxida-
tion stability enhancing additives [23] is almost imperative in
order to fulfil the stability requirements established in the fuel
quality standards.
For testing the oxidation stability of biodiesel fuel, an acceler-
ated method run at 110 °C, Rancimat test, is specified in the stan-
dards (EN 14112 in the European Union and ASTM D7462 in the
United States, although EN 15751 is also valid in Europe), being
the apparatus and the test procedure detailed later. The final result
is an induction period (IP), which has to be higher than the mini-
mum prescribed value in the biodiesel quality standard (currently
6 h in the European EN 14214:2009 [5] and a more relaxed mini-
mum limit of 3 h in the American ASTM D6751-09 [6]). This limit
and other test parameters (such as the temperature test) are being
questioned, and some modifications are expected in the near fu-
ture. For instance, in Europe it is already approved an increase of
the IP up to 8 h for the next version of the EN 14214. In addition
some voices have suggested a test temperature of 130 °C, since
current injection systems work at higher pressure (and conse-
quently higher temperature) than older ones. Nevertheless, such
a change is not well justified since this test is intended to predict
the storage stability of biodiesel fuels under an accelerated method
and the oxygen availability in the injection system is limited. On
the contrary, some authors recommended after their tests that a
lower test temperature would be necessary for some esters, espe-
cially for those with high unsaturation degree [22,31]. Another
drawback of increasing the test temperature is the high vapour
pressure of some synthetic antioxidants, which could be lost by
evaporation during the test [32].
Fig. 1. Experimental apparatus Rancimat 743, Metrohm AG.
[BHT] butyl hydroxyl toluene concentration (ppm)
IN iodine number (gI2/100 gsample)
IP induction period (h)
P dichotomous binary-coded variable (P = 0 or P = 1)
SPSS Statistical Package for Social Sciences
T temperature (°C)
U diameter (mm)
The present work is aimed to determine the effect that the test
temperature in the Rancimat method shows when samples of real
biodiesel fuels are evaluated, and the required concentration of a
reference oxidation stability enhancing additive to assure an
induction period higher than the threshold imposed in the stan-
dards. For each biodiesel sample, a mathematical model to esti-
mate IP as a function of the test temperature and the additive
concentration is proposed. These results and the conclusions de-
rived will help biodiesel manufacturers in deciding the amount
of additive and the raw material to choose. All the sectors involved
in the standards development will benefit of this study as well.
2. Material and methods
The Rancimat 743 equipment, from the company Metrohm AG,
was used for carrying out the experimental tests. Its working prin-
ciple consists in continuously passing an air flow through a biodie-
sel sample located in a sealed, heated vessel. The effluent flow
which contains the oxidation products (acids, among others) is
conducted to a second vessel with distilled water (Fig. 1). Here
the electrical conductivity is continuously measured and moni-
tored. The induction period (IP) is defined as the elapsed time
between the start of the test and the moment at which a sudden
increase in the conductivity is detected. The lower the induction
period, the lower the oxidation stability.
Although both EN 14112 and EN 15751 are allowed for testing
the oxidation stability of biodiesel samples, and the first one was
the original, EN 15751 will be used in case of dispute. Thus, all
the parameters specified in EN 15751 (see Table 1) were selected
for the tests with the exception of the temperature, which was
 M. Lapuerta et al. / Fuel 93 (2012) 391–396 393

Table 1 Table 2
Testing parameters specified in the oxidation stability standards. Methy ester composition of tested biofuels.

EN 14112 EN 15751 B100_UO B100_SO B100_AF

Sample mass (g) 3 7.5 C8:0 0.08
Reaction vessel dimensions (mm) 150  U24 250  U24 C10:0 0.08
Distilled water volume (ml) 50 60 C12:0 0.07 0.17
Air flow (l/h) 10 10 C14:0 0.22 0.07 2.09
Test temperature (°C) 110 110 C16:0 10.24 11.13 24.92
C16:1 0.37 0.09 3.45
C17:0 0.56
varied to study its effect on the induction period. While EN 14112 C18:0 3.82 3.80 12.02
C18:1 38.05 23.91 33.50
is valid for testing only pure biodiesel fuel samples, EN 15751
C18:2 44.43 53.55 20.73
enlarges its applicability to diesel–biodiesel blends whose biodie- C18:3 1.20 5.95 1.95
sel content is above 2% (V/V). C20:0 0.36 0.40 0.10
The induction period was evaluated manually through the C20:1 0.23 0.25 0.33
so-called ‘‘tangent method’’. This was not arbitrary, since the other C22:0 0.59 0.53 0.03
C22:1 0.17
alternative evaluation method (‘‘second derivative method’’) pre- C24:0 0.14 0.13 0.02
sented some difficulties. First, the second derivative of the conduc-
tivity-time curve did not always show a single relative maximum,
this being more likely at higher temperature (Fig. 2 shows an
example of this). When the test-stop criterion is selected as ‘‘sec- Table 3
Fuels properties.
ond derivative reaching a maximum’’, the automatic evaluation
performed by the software is then wrong. Second, when moder- B100_UO B100_SO B100_AF
ate/high BHT concentrations [BHT] are tested at high temperature, Density (kg/m ) 3 a
886 885 880
the conductivity usually exceeds 200 lS/cm (the maximum limit Kinematic viscosity (cSt)b 4.46 4.09 4.25
proposed by the equipment manufacturer and specified by stan- Higher heating value (MJ/kg) 39.65 39.42 39.11
dard EN 15751) without showing any change in the conductivity % C (wt.) 77.04 77.14 76.57
% H (wt.) 12.03 11.93 12.27
increasing rate. In this case, manual evaluation after a first exami- % O (wt.) 10.93 10.93 11.16
nation of the resulting curve is a more secure method than the Molecular weight 292.72 292.63 286.73
automatic evaluation. Iodine number (g/100g) 113.6 129.3 73.5
The composition of the biodiesel fuels tested was obtained by Water content (mg/kg) 636 272 124
gas chromatography, following the method described in standard a
Measured at 15 °C.
EN 14103 [33]. Biodiesel samples were weighed using an electronic b
Measured at 40 °C.
balance Sartorius Mechatronics AG, with a stated accuracy of
0.01 g, although a deviation of 0.03 g from the set point (7.50 g) An oxidation stability enhancing additive (BHT) was added in
was allowed in all the experiments. Graduated pipettes were used different concentrations to the former biodiesel samples in order
to manipulate the samples when weighing, and they were cleaned to increase the oxidation stability of the additivated fuel.
with a proper solvent to avoid contamination.
Three pure biodiesel fuels from different raw materials have
been tested, being their ester profiles depicted in Table 2 and the 3. Test matrix
most important chemical and physical properties listed in Table
3. The first one (B100_UO) was provided by Bionet Corporation An experimental matrix (Fig. 3) was designed for each of the
(Spain) and elaborated from used cooking oil. The second one three biodiesel fuels tested, consisting in five test temperatures
(B100_SO), supplied by Bio-Oils Corporation (Spain), was derived (from 110 °C to 130 °C in 5 °C steps) and different BHT concentra-
from the transesterification of soybean oil. The last sample tions. These concentrations were not set the same for all fuels and
(B100_AF) was produced from animal fats by Stocks del Vallés Cor- temperatures, since the additive presence is not equally effective
poration (Spain). This range of oils and fats is representative of depending on the other parameters. In the case of B100_AF, rela-
both current raw materials for biodiesel production and those tively low BHT concentrations proved to be enough to reach an
which offer better future perspectives. At the same time the unsat- induction period over 8 h (the limit expected to come into force
uration degree is very different among the samples, since this is soon). The other fuels needed much higher BHT concentrations,
one of the variables that most affect the oxidation stability. especially at the highest test temperatures.

conductivity
2nd derivative
200 200
conductivity (µS/cm)

conductivity (µS/cm)

160 110 ºC 160

130 ºC
120 120

80 80

40 40

0 0
0 4 8 12 0 1 2 3 4
time (h) time (h)

Fig. 2. Evaluation of the induction period through the second derivative method at 110 °C (left) and 130 °C (right).
394 M. Lapuerta et al. / Fuel 93 (2012) 391–396

30000 10 R2=0.999

20000 8
0 ppm BHT

IP (h)
[BHT] (ppm)

10000 6 3070 ppm BHT

B100_UO R2=0.999
5000 3570 ppm BHT
2
R =0.999
4000
B100_SO 4 4070 ppm BHT
B100_AF
3000 2
R2=0.921
2000 0
1000 110 115 120 125 130
0 T (ºC)
110 115 120 125 130
Fig. 5. Induction period vs. temperature (B100_UO).
T (ºC)

Fig. 3. Experimental matrix.

Table 5
Values for the coefficients in Eq. (3).
Table 4 B100_UO B100_SO B100_AF
Rancimat test results.
A1 (h) 1.0482e0 2.6266e1 8.2142e4
B100_UO B100_SO B100_AF A2 (1/°C) 2.4174e3 1.7760e2 7.6527e2
B1 (h/ppm) 9.8450e2 2.2247e4 5.9800e0
T [BHT] IP (h) T [BHT] IP (h) T [BHT] IP (h)
B2 (1/°C) 1.1801e1 1.4157e1 5.8494e2
(°C) (ppm) (°C) (ppm) (°C) (ppm)
R2 0.975 0.904 0.952
110 0 0.77 110 0 3.61 110 0 15.88
110 3070 8.67 110 800 7.95 110 1000 33.00
110 3570 9.67 110 1300 7.43 110 2000 33.32
110 4070 10.57 110 1800 12.06 adversely affect other fuel properties, such as the ester content, the
115 0 0.76 115 800 4.32 115 0 11.68 carbon residue or the total contamination).
115 3070 5.69 115 1800 6.01 115 1000 19.98
115 3570 6.63 115 2873 8.27 115 2000 28.78
115 4070 7.11 4. Results and discussion
115 8000 10.83
120 0 0.51 120 1300 4.68 120 0 7.75 The results obtained after performing the Rancimat tests are
120 3070 3.91 120 1800 5.51 120 1000 15.39 shown in Table 4, along with the testing temperature and the addi-
120 3570 4.24 120 4681 8.00 120 2000 18.85 tive concentration. The process followed for adjusting a mathemat-
120 4070 4.61 120 7534 9.90
120 10,122 8.44
ical model was identical for each biodiesel sample, therefore it is
120 14,883 11.07 explained here only for one of them (B100_UO).
125 3570 2.90 125 7797 5.44 125 0 5.04
The effect of the BHT concentration on the induction period is
125 4070 3.20 125 10,637 7.86 125 1000 10.81 illustrated in Fig. 4. It is observed that the induction period in-
125 8000 5.01 125 17,327 9.68 125 2000 12.98 creased linearly with the anti-oxidant concentration at all testing
125 32,664 12.98 temperatures. For all the temperatures tested, the R2 coefficient
130 0 0.39 130 1300 2.37 130 0 3.65 of the linear regression was higher than 0.96, as seen in Fig. 4. Thus
130 3070 1.80 130 1800 2.59 130 1000 7.40 the mathematical model here proposed for the induction period as
130 3570 1.91 130 3765 2.87 130 2000 8.04
a function of the BHT concentration follows the form of Eq. (1),
130 4070 2.16 130 7534 4.78
130 10,122 3.96 130 10,975 5.80 where the coefficients A and B depend on the temperature.
130 14,883 5.16 130 17,044 7.40
130 32,805 9.66 130 20,105 8.10 IP ¼ A þ B  ½BHT ð1Þ
While 2000–3000 ppm of BHT in the biodiesel fuel were enough
to achieve the threshold of 8 h for the induction period at 110 °C
R2=0.965
(the currently prescribed temperature in the fuel quality norma-
14 R2=0.997
R2=0.997 tive), a much higher additive concentration (>25,000 ppm) turned
12 R2=0.978
R2=0.992 out to be necessary when the temperature was raised up to 130 °C.
10
The effect of the testing temperature on the oxidation stability
IP (h)

8 is observed in Fig. 5, where each of the series plotted correspond

110 ºC
6 115 ºC
4 120 ºC
125 ºC
2 130 ºC
0 exponential Arrhenius-type fittings are here proposed and their
0 10000 20000 30000
[BHT] (ppm)
Fig. 4. Induction period vs. BHT concentration (B100_UO).
In order to improve the significance of the models fitted, a few
experiments with BHT concentrations above 15,000 ppm (1.5% V/
V) were performed although this is neither economically nor tech-
nically feasible for the biodiesel industry (such additivation levels
to a specific BHT concentration. It is obvious from this figure that
the induction period decreases non-linearly when the temperature
is increased, especially for the additivated samples. Therefore,
R2 coefficients are shown in the figure.
It is worth noticing that coefficient A in Eq. (1) represents the
induction period when no oxidation stability enhancing additive
is added to the fuel sample, and this corresponds to the exponen-
tial curve ‘‘0 ppm BHT’’ adjusted in Fig. 5. With respect to coeffi-
cient B, the oxidation stability is much more sensitive to the BHT
presence at the lowest temperature (110 °C) than at higher ones.
Thus, an exponential fitting is proposed for coefficient B as well,
Eq. (2). By substituting (2) into (1), the ultimate form of the model
to be adjusted is presented in Eq. (3).
 M. Lapuerta et al. / Fuel 93 (2012) 391–396 395

20
20000 30000
10000 15000
16 8000

12 6000

IP (h)
8
4000

2000
4
0 ppm

0
110 115 120 125 130
T (ºC)

Fig. 6. Model proposed for estimating the induction period of B100_UO.

20
10000
15000 30000
6000 20000
8000
16
4000
12

IP (h)
8 2000

4 0 ppm

0
110 115 120 125 130
T (ºC)

Fig. 7. Model proposed for estimating the induction period of B100_SO.

20 400
200 600 1000
1500 3000
800 2000
16
0 ppm

12
IP (h)

0
110 115 120 125 130
T (ºC)

Fig. 8. Model proposed for estimating the induction period of B100_AF.

A ¼ A1  expðA2  TÞ; B ¼ B1  expðB2  TÞ ð2Þ

Table 6
Values for the coefficients in Eq. (4).
IP ¼ A1  expðA2  TÞ þ B1  expðB2  TÞ  ½BHT ð3Þ C1 (h) 2.1365e4
C2 (h) 1.3560e2
The values of the coefficients A1, A2, B1 and B2 where found by
C3 (h) 4.0408e3
adjusting the model to the experimental data (see Table 4) using C4 (1/°C) 5.9129e2
a minimum square method implemented in the commercial, statis- C5 (h/ppm) 5.7431e2
tical package SPSS [34]. The values resulting from this process for C6 (h/ppm) 4.0283e0
the three biodiesel fuels are shown in Table 5, and the graphical C7 (h/ppm) 7.3325e1
C8 (1/°C) 9.2405e2
representations of the models are in Fig. 6 (B100_UO), Fig. 7
R2 0.960
(B100_SO) and Fig. 8 (B100_AF).
It is manifest from the observation of the model graphs the strong
effect that both the test temperature and the anti-oxidant concen- 8 h if the test temperature is 110 °C. On the contrary, such concen-
tration present on the oxidation stability of the fuels. The higher tration, or even a much higher one, increases the induction period
the temperature, the lower the induction period. Similarly, the lower only marginally at 130 °C, far below the current and the future limits
the anti-oxidant concentration, the lower the induction period. For in the biodiesel European standard. This result shows clearly the
the biodiesel fuel that showed the worst results (B100_UO), just dramatic effect that increasing the test temperature has on the
3000 ppm of BHT are required to raise up the induction period above induction period.
396 M. Lapuerta et al. / Fuel 93 (2012) 391–396
With regard to the biodiesel origin, it is also evident from the
same graphs that it plays a significant role. As expected,
B100_AF, which is the most saturated fuel tested, was found to
have the highest induction period, making the addition of anti-
oxidant unnecessary in order to fulfil the oxidation stability
requirements at 110 °C. At 130 °C, around 1400 ppm of BHT was
enough to increase the induction period up to 8 h. Among the other
two biodiesel fuels, both being more unsaturated than the former,
B100_SO showed better results. However, the higher unsaturation
degree of B100_SO with respect to B100_UO proves that the unsat-
uration degree is not the only variable affecting the oxidation sta-
bility. The presence of water and other compounds derived either
from external contamination or from thermal degradation (the last
two being more likely in the case of oils that have been used for
cooking) may act promoting oxidation reactions, and this could
explain the lower induction periods obtained with B100_UO. Also
the documented reduction in the natural anti-oxidants when the
oil is subjected to a frying process contributes to the lower oxida-
tion stability of B100_UO [35].
Thus, a combination of the unsaturation degree (represented
through the Iodine Number, IN) and the previous use of the biodie-
sel raw material, represented through a dichotomous binary-coded
variable P (P = 1 if the original oil was used for cooking and P = 0 if
it was not) is here used to find a single correlation for the three bio-
diesel fuels tested. The parameters of the integrated model, Eq. (4),
were adjusted to the experimental data with SPSS, and the values
found are listed in Table 6. It should be noted that C2, C3, C6 and C7
are negative in sign, meaning that the induction period is reduced
when the unsaturation degree is increased and/or when the raw
material suffered other uses previously.
IP ¼ðC 1 þ C 2  IN þ C 3  PÞ  expðC 4  TÞ
þ ðC 5 þ C 6  IN þ C 7  PÞ  expðC 8  TÞ  ½BHT
5. Conclusion
The oxidation stability of three biodiesel fuels additivated with
varied concentrations of a commercial anti-oxidant has been eval-
uated through the Rancimat test. In order to assess the effect of the
biodiesel origin and the test temperature on this property, an
experimental model was adjusted to the experimental data. The
results revealed that increasing the test temperature prescribed
in standards for the biodiesel quality, currently set at 110 °C, while
maintaining the same requirement for the induction period, is
unfeasible. This statement is supported on the methodological
and technical implications of such modification. Methodologically,
at higher temperatures the accuracy of the evaluation of the induc-
tion period is adversely affected and part of the additive could be
lost by evaporation as a consequence of its high vapour pressure.
Technically, achieving the current limits for the induction period
would imply the use of huge amounts of oxidation stability
enhancing additives. Apart from its obvious economical conse-
quences to the biodiesel industry, this would be detrimental to
other fuel properties.
More saturated biodiesel fuels showed better stability, but the
unsaturation degree alone was insufficient to explain the effect
of the raw material. The previous use of the oil for frying processes
reduced the stability of the final fuel, probably through the appear-
ance of contaminants and other compounds and the loss of natural
anti-oxidants.
Acknowledgments
The companies Bionet Corporation, Bio-Oils Corporation and
Stocks del Vallés Corporation are gratefully acknowledged for the
donation of the biodiesel fuels tested in this work. The Spanish
Renewable Energy Association (APPA) is also acknowledged for
their support and participation in the discussions.
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