Polystyrene Hydrogenolysis to High-Quality Lubricants Using Ni/SiO2

Pyrolytic and light-activated oxidation processes are leading technologies for utilizing polystyrene (PS) wastes. These approaches exhibit poor selectivities, use complex reactors, and require solvents. Hydrogenolysis is effective for deconstructing polyolefins, but its application to PS feedstocks has been limited. Herein, we demonstrate Ni/SiO2 catalysts to facilitate PS (Mw ≈ 97 kDa) hydrogenolysis to produce lubricant base oils possessing group IV properties, achieving maximum yields of 70% within 6 h at 300 °C and 70 bar of H2. Gas, liquid, and oil product yields are stable across reaction conditions, whereas hydrogenation of the PS aromaticity and reduction of the molecular weight benefit from higher temperatures and H2 pressures. Time-dependent experiments underscore the importance of elevated H2 pressure, revealing that PS hydrogenolysis occurs sequentially, with aromatic ring hydrogenation preceding degradation of the C–C backbone. Kinetic measurements with 1,2-diphenylethane as a probe molecule demonstrate that ring hydrogenation pis 3 orders of magnitude faster than internal C–C bond cleavage over Ni/SiO2. Ni/SiO2 proves to be effective in the hydrogenolysis of heavier PS polymers and rigid commercial PS products. Conversely, flexibility and foam PS feeds result in Ni/SiO2 deactivation, attributed to performance additives. Unlike polyolefins, the process produces very little methane and other light hydrocarbons. These findings expand the applicability of hydrogenolysis to PS feedstocks, offering a versatile solution and broadening the range of high-value products from PS to include lubricant base oils.