Abstract
The catalytic mechanism and activation energies of metal chlorides RuCl3, AuCl3, and BaCl2 for 1,2-dichloroethane (DCE)-acetylene exchange reaction were studied with a combination of density functional theory (DFT) calculations and experiments. Two reported reaction pathways were discussed and acetylene-DCE complex pathway was supported through adsorption energy analysis. The formation of the second vinyl chloride monomer (VCM) was proven to be the rate-determining step, according to energy profile analysis. Activity sequence of BaCl2 > RuCl3 > AuCl3 was predicted and experimentally verified. Furthermore, reversed activity sequences of this reaction and commercialized acetylene hydrochlorination reaction were explained: the adsorption abilities of reactants are important for the former reaction, but chlorine transfer is important for the latter.
Highlights
Vinyl chloride (PVC) is one of the most versatile plastics synthesized by radical polymerization of vinyl chloride monomer (VCM)
All metal chlorides were loaded on activated carbon support with a 10% weight content through impregnation in order to facilitate the dispersion of active metal chlorides and produce comparable in order to facilitate the dispersion of active metal chlorides and produce comparable results
Decomposition pathway and the acetylene-DCE complex pathway, were proposed and the second pathway was proved to be more favourable through adsorption energy calculation
Summary
Vinyl chloride (PVC) is one of the most versatile plastics synthesized by radical polymerization of vinyl chloride monomer (VCM). New reaction routes and non-mercury catalysts for VCM production is urgently needed for future green PVC industry. To the best of our knowledge, no DFT study has been reported for the new Jiang-Zhong VCM process, and the experimental exploration is in the early stage. It is highly useful for guiding the rational development of novel DCE-acetylene exchange catalysts with the assistance of computational chemistry. The work provided guidance for the deep understanding and screening methodology of catalysts for DCE-acetylene exchange reaction, which can accelerate the development of this green and highly efficient route for VCM production
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