Fe- and Ru-H-Mordenites for Polyethylene Upcycling: Insights from Thermo-Catalytic Pyrolysis and DFT Studies

Catalytic pyrolysis of polyethylene (PE) was performed using Fe- and Ru-impregnated H-mordenite (HM) catalysts to produce lighter hydrocarbons. Catalyst surface areas were analyzed by N2 adsorption−desorption and acidity by NH3-TPD studies. Reducibility of metal from H2-TPR, experiments indicate multiple oxidation states of Fe due to higher H2 consumption. The catalyst activity studies monitored by GC–MS analysis highlight the importance of temperature and PE: catalyst ratio in optimizing hydrocarbon selectivity to C1–C4 alkanes and C2–C5 olefins. Studies with polymer-to-catalyst ratios of 1:1 and 1:2 at higher temperature increased PE conversion with stronger acid sites favoring conversion and moderate acid sites improving selectivity toward lighter olefins. While propane dominated at lower temperatures, propene was the main product at 500 °C. Both catalysts exhibited overall similar conversion, while Ru-HM yielded >40% propene selectivity compared to <40% for Fe-HM. Ethylene selectivity exceeded 10% in both cases. Density functional theory simulations using a C4 surrogate on Ru-HM confirmed that late-stage cracking dominates dehydrogenation, validating the proposed reaction mechanism.