Pyrolysis of algal biomass: Determination of the kinetic triplet and thermodynamic analysis

Microalgae Spirulina has good potential for bio-oil production. Therefore, kinetic and thermodynamic analysis of its pyrolysis process was performed. The activation energy values were estimated using both differential (109-340 kJ/mol) and integral (102-272 kJ/mol) isoconversional methods. Kinetic model was determined using master plot approach and the pyrolysis reaction appeared to transition between nucleation, diffusion and order-based kinetic models. Based on sigmoidal equations, a novel kinetic model equation was proposed which can define the pyrolysis process of algal biomass showing single differential thermogravimetric peak. The proposed kinetic triplet predicted the weight loss evolution quite precisely. Additionally, the thermodynamic feasibility of the reaction was examined based on enthalpy, entropy and Gibbs free energy. It was revealed that heat is consumed to make the raw sample reach a 'more orderly' state until a fractional conversion of 0.35. Moreover, bio-char and the remaining lipids at high temperature impede the reaction spontaneity towards the end.