Mineralogical characterization and non-isothermal pyrolysis kinetics of Moroccan Rif oil shale

The mineralogical characterization and pyrolysis kinetics of raw oil shale from Moroccan Rif region and the corresponding bitumen-free material were investigated using various analytical techniques. The structural analysis results showed the siliceous character of mineral matrix and the presence of complex organic components in both oil shales studied. Non-isothermal pyrolysis kinetic measurements indicated that bitumen-free oil shale exhibits a single behavior pyrolysis in the oil-producing stage as compared to raw oil shale. The activation energies estimated by using isoconversional methods reveal that the pyrolysis reaction occurred by one-step kinetic process. The kinetic parameters, determined from a nonlinear fitting method using various kinetic models g(alpha) and iterative Kissinger-Akahira-Sunose energy calculations, reveal that the pyrolysis mechanism is well described by the nth order kinetics (Fn), with n = 1.071, for bitumen-free oil shale, and n = 1.550, for kerogen of raw oil shale. The mechanism of the whole pyrolysis process of raw oil shale seems not to be affected by the elimination of bitumen, but only some kinetic changes have been recorded in the reaction order mechanism. The process pyrolysis is represented by independent reactions and consequently considered as parallel processes. Besides, the thermodynamic functions of activated complexes (a dagger S (not equal) , a dagger H (not equal) and a dagger G (not equal)) were also calculated and the pyrolysis is found as non-spontaneous process in agreement with the thermal analysis data.