Ethane Chlorination Toward Vinyl Chloride Synthesis: Mechanistic and Catalytic Perspectives.

Ethane chlorination has emerged as a promising alternative to conventional ethylene- and acetylene-based routes for the production of vinyl chloride monomer (VCM). Unlike conventional catalytic processes, this approach relies on chlorine radical-mediated activation to convert ethane into 1,2-dichloroethane, followed by thermal cracking to VCM. However, this route remains in its early stages, hindered by the complexity of gas-phase radical chemistry and catalyst deactivation under chlorination conditions. This review provides a critical assessment of the mechanistic foundations of ethane chlorination, highlighting the interplay between radical-mediated and surface-catalyzed pathways. Particular attention is given to advances in rare-earth oxychloride catalysts, which have shown the ability to stabilize key intermediates. We also discuss major deactivation mechanisms, including phase transformation and surface hydroxylation, that limit catalyst lifetime. Furthermore, we highlight the feasibility of ethane chlorination as a low-carbon VCM production route under future decarbonized energy scenarios. Finally, key directions in catalyst design, mechanistic understanding, and process integration are outlined to advance ethane chlorination from laboratory-scale innovation to industrial reality.