Vapor-Phase Chlorination of Chlorobenzene over Solid-Acid Catalysts

Catalytic chlorination of chlorobenzene was studied in vapor phase using various solid-acid catalysts such as silica-alumina, alumina, zeolite and a modified clay prepared by impregnating bentonite with ferric chloride. The conversions of both chlorine gas and chlorobenzene showed high over silica-alumina, alumina and modified clay catalysts. However relatively large amounts of polychlorinated benzene derivatives were also observed. The active species of catalytic activity in chlorination of chlorobenzene in vapor phase were proved to be as Lewis acid sites by in-situ IR experiments. The strength of Lewis acid sites which were effective for the vapor-phase chlorination seemed to be having Hammett acidity Ho >-3.0. The selectivity to dichlorobenzenes was proved to be high over the zeolite catalyst due to their shape-selective properties. p-Dichlorobenzene or dichlorobenzene selectivities were improved more or less by changing the reaction conditions.