Nitrogen‐Doped Carbon‐Assisted One‐pot Tandem Reaction for Vinyl Chloride Production via Ethylene Oxychlorination

A bifunctional catalyst comprising CuCl2/Al2O3 and nitrogen‐doped carbon was developed for an efficient one‐pot ethylene oxychlorination process to produce vinyl chloride monomer (VCM) up to 76 % yield at 250 °C and under ambient pressure, which is higher than the conventional industrial two‐step process (≈50 %) in a single pass. In the second bed, active sites containing N‐functional groups on the metal‐free N‐doped carbon catalyzed both ethylene oxychlorination and ethylene dichloride (EDC) dehydrochlorination under the mild conditions. Benefitting from the bifunctionality of the N‐doped carbon, VCM formation was intensified by the surface Cl*‐looping of EDC dehydrochlorination and ethylene oxychlorination. Both reactions were enhanced by in situ consumption of surface Cl* by oxychlorination, in which Cl* was generated by EDC dehydrochlorination. This work offers a promising alternative pathway to VCM production via ethylene oxychlorination at mild conditions through a single pass reactor. Vinyl chloride monomer (VCM) is directly produced by a metal‐free nitrogen‐doped carbon catalyst in one step via the ethylene oxychlorination process at 250 °C. Ethylene oxychlorination and high‐temperature dehydrochlorination reactions are integrated into a single pass with remarkable conversion and selectivity. The efficient combination of tandem reactions produces a VCM yield as high as the current two‐step process, and under mild conditions.