2. Material and methods
The Rancimat 743 equipment, from the company Metrohm AG,
was used for carrying out the experimental tests. Its working principle consists in continuously passing an air flow through a biodiesel 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 monitored. 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 wasvaried to study its effect on the induction period. While EN 14112
is valid for testing only pure biodiesel fuel samples, EN 15751
enlarges its applicability to diesel–biodiesel blends whose biodiesel content is above 2% (V/V).
The induction period was evaluated manually through the
so-called ‘‘tangent method’’. This was not arbitrary, since the other
alternative evaluation method (‘‘second derivative method’’) presented some difficulties. First, the second derivative of the conductivity-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 ‘‘second derivative reaching a maximum’’, the automatic evaluation
performed by the software is then wrong. Second, when moderate/high BHT concentrations [BHT] are tested at high temperature,
the conductivity usually exceeds 200 lS/cm (the maximum limit
proposed by the equipment manufacturer and specified by standard EN 15751) without showing any change in the conductivity
increasing rate. In this case, manual evaluation after a first examination of the resulting curve is a more secure method than the
automatic evaluation.
The composition of the biodiesel fuels tested was obtained by
gas chromatography, following the method described in standard
EN 14103 [33]. Biodiesel samples were weighed using an electronic
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)
was allowed in all the experiments. Graduated pipettes were used
to manipulate the samples when weighing, and they were cleaned
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
most important chemical and physical properties listed in Table
3. The first one (B100_UO) was provided by Bionet Corporation
(Spain) and elaborated from used cooking oil. The second one
(B100_SO), supplied by Bio-Oils Corporation (Spain), was derived
from the transesterification of soybean oil. The last sample
(B100_AF) was produced from animal fats by Stocks del Vallés Corporation (Spain). This range of oils and fats is representative of
both current raw materials for biodiesel production and those
which offer better future perspectives. At the same time the unsaturation degree is very different among the samples, since this is
one of the variables that most affect the oxidation stability.