Comparative pyrolysis kinetics of heavy oil and its SARA fractions using distributed activation energy model

The pyrolysis behaviors of Qingdao vacuum residue(QD-VR)and its SARA(saturates,aromatics,reins,and asphaltenes)fractions were evaluated by thermo-gravimetric with mass spectrometer(TG-MS).The pyrolysis kinetics were determined by Friedman,one-parallel and four-parallel distributed activation energy model(DAEM),respectively.The results indicated that the pyrolysis behavior of QD-VR was similar to that of aromatics.For saturates,the release of H_(2),CH_(4),CO,and CO_(2) occurred in 80-400℃,while the temperature range for QD-VR and other fractions is 200-800℃.The average activation energy(Ea)via Friedman method was 179.72 kJ/mol and increased with the conversion ratio.One-parallel Gaussian DAEM was more suitable to describe the pyrolysis process of the single SARA fractions,while four-parallel Gaussian DAEM was more suitable to describe the pyrolysis process of heavy oil.Furthermore,comparing the weighted E_(a) from one-parallel(227.64 kJ/mol)and four-parallel Gaussian DAEM(204.63 kJ/mol),the results suggested that during pyrolysis process of heavy oil,there was an interaction between the SARA fractions,which could reduce the E_(a) of heavy oil pyrolysis.Specifically,during heavy oil pyrolysis,resins and asphaltenes could increase the E_(a) of saturates and aromatics,while saturates and aromatics could decrease the E_(a) of resins and asphaltenes.