Oxidation stability of biodiesel derived from free fatty acids associated with kinetics of antioxidants

Biodiesel derived from free fatty acids (FFAs), which has the advantage of not competing with the edible-oil market, exhibited poor oxidation stability. The induction period (IP) of the FFA-based biodiesel determined by the Rancimat method at 110 °C was 0.20 h. This study investigates the effectiveness of one natural and ten synthetic antioxidants, including α-tocopherol (α-T); butylated hydroxyanisole (BHA); butylated hydroxytoluene (BHT); 2, 5-di-tert-butylhydroquinone (DTBHQ); Ethanox 4740; Ethanox 4760E; 2,2′-methylene-bis-(4-methyl-6-tert-butylphenol) (MBMTBP); N,N′-di-sec-butyl-p-phenylenediamine (PDA); propyl gallate (PG); pyrogallol (PY); and tert-butylhydroquinone (TBHQ), at concentrations between 100 and 1000 ppm to improve the oxidation stability of the FFA-based biodiesel. The order of antioxidant effectiveness with respect to the oxidation stability of the FFA-based biodiesel was PY > Ethanox 4760E > PG > Ethanox 4740 > PDA ~ BHA > BHT > MBMTBP ~ TBHQ > DTBHQ > α-T. The IP of the FFA-based biodiesel increased as the antioxidant concentration was increased and decreased at high test temperatures. Furthermore, the relationship between the IP values associated with the consumption of antioxidants in the FFA-based biodiesel was described by first-order reaction rate kinetics. However, the natural logarithm of IP (ln IP) at various concentrations of Ethanox 4760E showed a linear relation with the test temperature. The IP at ambient temperature was predicted based on the extrapolation method of the temperature dependence relation. After long-term storage at room temperature, the IP and acid value of the original FFA-based biodiesel significantly decreased and increased, respectively, with storage time, while the addition of antioxidants ensured the oxidation stability of the FFA-based biodiesel over 6 months of storage.