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

## TL;DR

Ethane chlorination is a potential low-carbon method to produce vinyl chloride monomer, but it requires better understanding of radical chemistry and catalyst stability.

## Contribution

This is the first focused review on ethane chlorination for vinyl chloride monomer synthesis, offering mechanistic insights and catalyst evolution pathways.

## Key findings

- Rare-earth oxychloride catalysts can stabilize key intermediates in ethane chlorination.
- Catalyst deactivation occurs via phase transformation and surface hydroxylation.
- Ethane chlorination is feasible as a low-carbon alternative for vinyl chloride monomer production.

## Abstract

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.

Ethane chlorination is emerging as a promising low‐carbon route to vinyl chloride monomer, yet it remains academically underexplored due to the complexity of radical chemistry. As the first focused Minireview on this topic, it offers forward‐looking mechanistic analysis, unveils catalyst evolution pathways, and defines research priorities to accelerate breakthroughs in this nascent but critical field.