Rodolfo Lopes Coppo

Kinetic and thermodynamic parameters of biodiesel oxidation with synthetic antioxidants: simplex centroid mixture design

Temperatures influence on biodiesel oxidation was evaluated by kinetic and thermodynamic data in biofuel from soybean oil and lard with synthetic antioxidants: butylatedhydroxyanisol (BHA), butylatedhydroxytoluene (BHT), tert-butylhydroquinone (TBHQ), and propylgallate (PG) by simplex centroid mixture design. The kinetic parameters ware obtained by Arrhenius equation and showed that addition of antioxidants in all tests increased activation energy (Ea) and that TBHQ and PG were more efficient and presented synergistic effect. BHT and BHA were the least efficient, as well as their mixtures. The thermodynamic activation parameters of the reactions, evaluated by the Eyring equation and based on the theory of the activated complex (ACT), indicated no spontaneous processes (∆G‡ > 0) with positive ∆H‡ values and positive and negative ∆S‡ values. The application of simplex centroid mixture design, using Ea as response, showed the optimised value of 174.46 kJ mol-1 for a mixture containing 33.33 and 66.67% of TBHQ and PG, respectively.

Study of oxidation kinetics of b100 biodiesel from soybean and pig fat: activation energy determination.

The quality of biodiesel is extremely important for its commercialization and use; oxidation of biodiesel is a critical factor because it decreases the fuel storage time. A commercial biodiesel was mixed with synthetic antioxidants, according to a simplex-centroid experimental mixture design, and its stability was evaluated through induction period and activation energy. In all trials, addition of antioxidants increased activation energy in the mixtures containing tertiary butylhydroquinone (TBHQ). When a mixture containing 50% TBHQ and 50% butylated hydroxyanisole was used, synergistic effect was observed, and the major activation energy obtained was 104.43 kJ mol-1.

FAME Storage Time in an Optimized Natural Antioxidant Mixture

The study of B100 biodiesel oxidation stability, and its conservation, is extremely important to control its quality, especially regarding storage. Many spices have shown antioxidant effect and are the targets of study. Knowing the oxidation process in greater detail allows a reliable storage period to be stipulated for the biodiesel without its degradation until the time of use. Results have shown that according to the accelerated stove method, the optimal mixture, composed of 100% of oregano extract, can confer a 535-day shelf life to biodiesel without evident oxidation. According to the results obtained by the Rancimat method, the ideal mixture consists of 100% rosemary, resulting in 483 days of storage. The application of the process variable showed that the accelerated stove method was more suitable to determine oxidative stability of biodiesel.