Ru-Catalyzed Polyethylene Hydrogenolysis under Quasi-Supercritical Conditions

Ru/C-catalyzed polyethylene (PE) and hydrocarbon hydrogenolysis under quasi-supercritical fluid of isopentane was kinetically and mechanistically investigated. PE hydrogenolysis with C–C and C–H cleavage showed zeroth order, suggesting strong adsorption of hydrocarbons. PE yielded broad product distribution of heavy (C_21–40) and diesel-range (C_11–20) hydrocarbons in the primary step of hydrogenolysis due to stochastic C–C cleavage over Ru surface. Catalytic hydrogenolysis of n-hexadecane, squalane, and light hydrocarbons such as n-pentane, iso-pentane, and n-hexane further described C–C cleavage reactivity between primary and secondary carbons, i.e., ¹C–²C and ²C–²C, which has an order of magnitude higher hydrogenolysis rate than that involving a tertiary carbon. The PE saturated Ru surface and lower C–C cleavage reactivity of tertiary carbon in iso-pentane, therefore, imited sovlent conversion during hydrogenolysis, whereas leading to selective PE conversion. Using hexadecane, we observed comparable hydrogenolysis rates between H₂ and D₂ (k_H/k_D ∼ 1), indicating the kinetically relevant step of C–C cleavage with facilitating C–H cleavage and rehydrogenation. However, the normal kinetic isotope effect between hexadecane and deuterated hexadecane (k_C16H34/k_C16D34 ∼ 5) revealed that the dehydrogenation, i.e., C–H cleavage, can be kinetically involved in the hydrogenolysis kinetic. By considering the 8-fold lower H-D exchange rate with deuterated hexadecane compared to n-hexadecane, the lower rate for hydrogenolysis and H-D exchange with deuterated hexadecane can be attributed to the C–D bond dissociation energy being 3 kJ/mol higher than that of the C–H bond. Increasing H₂ pressure favors internal C–C bond cleavage over terminal one. This minimizes the formation of lower hydrocarbons, particularly methane. However, the increase in H₂ pressure increases the coverage of adsorbed hydrogen on the Ru particles due to competitive adsorption of H₂ and polyethylene, which, in turn, reduces the polyethylene conversion rates.