Chlorohydrination of allyl chloride with HCl and H2O2 catalyzed by hollow titanium silicate zeolite to produce dichloropropanol

Abstract

Overall, over 95% of epichlorohydrin is industrially manufactured via the chlorohydrination route with hazardous Cl₂ as a reagent, which brings serious operation and pollution problems. Herein, we describe a novel Cl₂-free process for the synthesis of dichloropropanols from allyl chloride with H₂O₂ and HCl catalyzed by hollow titanium silicate zeolite under mild conditions. A high conversion and overall dichloropropanol selectivity exceeding 95% are simultaneously achieved, and the heterogeneous catalyst is highly stable and amenable for reuse. Comprehensive experimental and spectroscopic data suggest that the Lewis acidity of the framework Ti species has a synergistic effect with the Brønsted acidity of HCl that promotes the epoxidation of allyl chloride and the ring opening of the epoxy groups.