Hydrodeoxygenation of Oxygen-Containing Aromatic Plastic Wastes to Liquid Organic Hydrogen Carriers

To address the global plastic pollution issues and the challenges of hydrogen storage and transportation, we report a system, based on the hydrodeoxygenation (HDO) of oxygen-containing aromatic plastic wastes, from which organic hydrogen carriers (LOHCs) can be derived. We developed a catalytic system comprised of Ru-ReO_x /SiO₂ +HZSM-5 for direct HDO of polycarbonate (PC), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyphenylene oxide (PPO), and their mixtures, to cycloalkanes as LOHCs, with high yields up to 99 %, under mild reaction conditions. The theoretical hydrogen storage capacity reaches ca. 5.74 wt%. The reaction pathway involves depolymerization of PC into C₁₅ aromatics and C₁₅ monophenols by direct hydrogenolysis of the C-O bond between the benzene ring and ester group, and subsequent parallel hydrogenation of C₁₅ aromatics and HDO of C₁₅ monophenols. HDO of cyclic alcohol is the rate-determining step. The active site is Ru metallic nanoparticles with partially covered ReO_x species. The excellent performance is attributed to the synergetic effect of oxophilic ReO_x species and Ru metallic sites for C-O hydrogenolysis and hydrogenation, and the promotion effect of HZSM-5 for dehydration of cyclic alcohol. The highly efficient and stable dehydrogenation of cycloalkanes over Pt/γ-Al₂ O₃ confirms that HDO products can act as LOHCs.