Sustainable chlorine recycling via catalysed HCl oxidation: from fundamentals to implementation

Abstract

The heterogeneously catalysed oxidation of HCl to Cl₂ comprises a sustainable route to recover chlorine from HCl-containing streams in the chemical industry. Conceived by Henry Deacon in 1868, this process has been rejuvenated in the last decade due to increased chlorine demand and the growing excess of by-product HCl from chlorination processes. This reaction suffered from many sterile attempts in the past two centuries to obtain sufficiently active and durable catalysts. Intense research efforts have culminated in the recent industrial implementation of RuO₂-based catalysts for HCl oxidation. This paper reviews the new generation of technologies for chlorine recycling under the umbrella of Catalysis Engineering, that is, tackling the microlevel (catalyst design), mesolevel (reactor design), and macrolevel (process design). Key steps in the development are emphasised, including lab-scale catalyst screening, advanced catalyst characterisation, mechanistic and kinetic studies over model and real systems, strategies for large-scale catalyst production, mini-plant tests with a technical catalyst, and reactor design. Future perspectives, challenges, and needs in the field of catalysed Cl₂ production are discussed. Scenarios motivating the choice between catalysed HCl oxidation and HCl electrolysis or their integration for optimal chlorine recycling technology are put forward.