Conversion of Polyolefin Waste to Liquid Alkanes with Ru-Based Catalysts under Mild Conditions

Chemical upcycling of waste polyolefins via hydrogenolysis offers unique opportunities for selective depolymerization compared to high temperature thermal deconstruction. Here, we demonstrate the hydrogenolysis of polyethylene into liquid alkanes under mild conditions using ruthenium nanoparticles supported on carbon (Ru/C). Reactivity studies on a model n-octadecane substrate showed that Ru/C catalysts are highly active and selective for the hydrogenolysis of C(sp³)-C(sp³) bonds at temperatures ranging from 200 to 250 °C. Under optimal conditions of 200 °C in 20 bar H₂, polyethylene (average M _w ∼ 4000 Da) was converted into liquid n-alkanes with yields of up to 45% by mass after 16 h using a 5 wt % Ru/C catalyst with the remaining products comprising light alkane gases (C₁-C₆). At 250 °C, nearly stoichiometric yields of CH₄ were obtained from polyethylene over the catalyst. The hydrogenolysis of long chain, low-density polyethylene (LDPE) and a postconsumer LDPE plastic bottle to produce C₇-C₄₅ alkanes was also achieved over Ru/C, demonstrating the feasibility of this reaction for the valorization of realistic postconsumer plastic waste. By identifying Ru-based catalysts as a class of active materials for the hydrogenolysis of polyethylene, this study elucidates promising avenues for the valorization of plastic waste under mild conditions.