Predicting the effect of framework and hydrocarbon structure on the zeolite-catalyzed beta-scission

Developing improved zeolites is essential in novel sustainable processes such as the catalytic pyrolysis of plastic waste. This study used density functional theory to investigate how alkyl chain length, unsaturated bonds, and branching affect β-scission kinetics in four zeolite frameworks, a key reaction in hydrocarbon cracking. The activation enthalpy was evaluated for a wide variety of 23 hydrocarbons, with 6 to 12 carbon atoms, in FAU, MFI, MOR, and TON. The consideration of both branched and linear olefin and diolefin reactants for the β-scission indicates how the reactant structure influences the intrinsic cracking kinetics, which is especially relevant for the catalytic cracking of plastic waste feedstocks. Intrinsic chemical effects, such as resonance stabilization, the inductive effect, and pore stabilization were found to provide an essential contribution to the activation enthalpy. Additionally, a predictive group additive model incorporating a novel so-called "pore confinement descriptor" was developed for fast prediction of the β-scission activation barrier of a wide range of molecules in the four zeolites. The obtained model can serve as an input for detailed kinetic models in zeolite-catalyzed cracking reactions. The acquired fundamental insights in the cracking of hydrocarbons, relevant for renewable feedstocks, correspond well with experimental observations and will facilitate an improved rational zeolite design.