Effect of the aging temperature on soybean biodiesel oxidation, quantifying the formed gums and sediments by thermogravimetry

• Published in: Journal of thermal analysis and calorimetry 2020-12, Vol.142 (5), p.2049-2059
• Main Authors: Leonardo, R. S., Dweck, J., Murta Valle, M. L.
• Format: Article
• Language: English
• Subjects: Aging; Alternative fuels; Analytical Chemistry; Biodiesel fuels; Bubbling; Carbonyls; Chemistry; Chemistry and Materials Science; Degradation; Diesel engines; Diesel fuels; Diesel motor; Esters; Fatty acids; Flow velocity; Fourier transforms; Functional groups; Gums; Infrared analysis; Infrared spectroscopy; Inorganic Chemistry; Internal combustion engine industry; Ketones; Measurement Science and Instrumentation; Molecular weight; Oxidation; Oxidation-reduction reaction; Physical Chemistry; Polymer Sciences; Reaction products; Sediments; Sediments (Geology); Size exclusion chromatography; Soybean; Soybeans; Spectrum analysis; Temperature dependence; Thermogravimetric analysis; Thermogravimetry
• ISSN: 1388-6150; 1588-2926
• DOI: 10.1007/s10973-020-09900-8

Biodiesel has been widely used as an alternative fuel in diesel engines. However, although its physicochemical properties make it a substitute for traditional diesel fuel, biodiesel is more susceptible to oxidation and degradation during storage than diesel. The high content of unsaturated fatty acid methyl (or ethyl) esters in biodiesel causes its fast oxidative degradation when in contact with precursor agents as oxygen. These reaction products are highly unstable, resulting in a mixture of different species, some of them of high molecular weight, producing sediments and undesirable polymeric compounds. In this study, a sample of commercial soybean biodiesel (BS100) was aged at 50 °C, 110 °C, 150 °C and 200 °C in a Rancimat apparatus. This was performed bubbling air into the sample at 10 L h −1 flow rate for 5 h. The original biodiesel and the aged samples were analyzed by thermogravimetry (TG/DTG), in dynamic mode, under nitrogen atmosphere. Data were compared with those obtained from the analyses performed by size-exclusion chromatography (SEC). Fourier transform infrared spectroscopy (FTIR) analyses were also performed. The objective of this work was to evaluate the effect of the aging temperature on the oxidation of biodiesel and on the degraded product composition, as well as to quantify the formed gums and sediments. The thermogravimetric analysis shows that biodiesel samples aged at 150 °C and 200 °C have a higher content of heavier products (gum), 33.4% and 44.9%, respectively, than the non-aged biodiesel (2.8%). The SEC analysis indicates molecular weight value of 283, 1241 and 1380 g mol −1 for samples aged at 150 °C, 200 °C and for the non-aged sample, respectively, which confirms the results of the TG/DTG analysis. The widening of ester carbonyl stretching band (C=O, 1740 cm −1 ) in the FTIR spectra, as the aging temperature rises, confirms the degradation of biodiesel into acids, ketones and other compounds containing this functional group. The decrease in percentage transmittance in the region corresponding to the fingerprint (1500–500 cm −1 ) indicates that heavy products (gums and sediments) are produced. These results indicate that the degradation product content in the aged biodiesel is strongly dependent on the temperature of the aging process.