Competitive and sequence reactions of typical hydrocarbon molecules in diesel fraction hydrocracking – a theoretical study by DFT calculations

The molecular structures of hydrocarbon molecules determine the competitive and sequence reactions in the diesel hydrocracking process. In this study, the hydrocracking reactions of typical hydrocarbons with various saturation degrees and molecular weights in diesel fractions synergistically catalyzed by the Ni–Mo–S nanocluster and Al–Si FAU zeolite are investigated. The results show that the two major rate-controlling steps in saturated hydrocarbon hydrocracking are dehydrogenation on the Ni–Mo–S active sites and the cracking of the C–C bonds on the FAU zeolite acid center. Moreover, the major rate-controlling step in cracking the cycloalkyl aromatic hydrocarbons is the protonation of the aromatic ring. Moreover, the aromatic hydrocarbons presented an apparent advantage in competitive adsorption on the Ni–Mo–S active sites, whereas hydrocarbons with higher molecular weights demonstrated a moderate adsorption advantage on both Ni–Mo–S active sites and FAU zeolite acid centers.