Catalytic Synergy between Lewis Acidic Alumina and Pt in Hydrodechlorination for Plastic Chemical Recycling

Pyrolysis-based plastic chemical recycling has gained significant industrial attention due to its advantage of eliminating complex plastic sorting processes. However, plastic pyrolysis oil contains various components that require stringent removal before subsequent processes. In particular, Cl compounds originating from the decomposition of poly(vinyl chloride) can cause serious corrosion of reactors and catalyst deactivation in downstream processes. While extensive research has been conducted on the removal of other heteroatoms (S, N, and O) from organic compounds via hydrotreating, studies on the removal of Cl have been scarce. In this study, hydrodechlorination over Pt catalysts on various supports is comprehensively investigated using 1,2-dichloroethane as a model reactant. Our results demonstrate that Pt on γ-Al₂O₃ can exhibit exceptionally high catalytic activity compared to those on other supports due to a distinct bifunctional mechanism. Rigorous studies reveal that the Lewis acidic pentacoordinated Al sites of γ-Al₂O₃ activate C-Cl bonds, whereas Pt activates H₂ and provides spillover H to remove Cl as HCl. The bifunctional mechanism enables the minimized use of precious Pt (<0.1 wt %) to achieve high activity. Pt/γ-Al₂O₃ also allows for efficient Cl removal (96.8%) with high stability in treating waste plastic pyrolysis oil containing 7500 ppm of Cl.