Facile Preparation of BaClxFy for the Catalytic Dehydrochlorination of 1-Chloro-1,1-Difluoroethane to Vinylidene Fluoride

BaClxFyas well as BaF2and BaClF catalysts were prepared by solid-state reaction at room temperature with Ba(OH)2as the precursor and NH4F/NH4Cl as the F and Cl sources. The catalysts were applied for the dehydrochlorination of 1-chloro-1,1-difluoroethane to vinylidene fluoride at 350 °C. The industrial manufacture of vinylidene fluoride (VDF) is carried out at 600–700 °C, whereas the BaClxFycatalysts provided a promising pathway to produce VDF at much lower temperatures. Unfortunately, the selectivity of VDF over BaF2decreased from 94% to 84% along with the deactivation of the BaF2catalyst monotonically. In the presence of small amounts of Cl in BaF2, stabilized selectivity was achieved. Over BaCl0.05F0.95, BaCl0.1F0.9and BaCl0.25F0.75, no decrease in VDF selectivity was observed. Clearly, the presence of small amounts Cl during solid-state preparation inhibited the growth of BaF2crystalline significantly. Far smaller particles were achieved. The particle size, or more precisely, the crystal size of the barium catalyst played a major role in the catalytic performance. In addition to the crystal growth, the presence of small amounts of Cl during catalyst preparation changed the chemical state of Ba, and therefore the adsorption and activation of the C–Cl bond for HCFC-142b were altered.Keywords:barium chlorofluoride;catalytic pyrolysis;barium fluoride;dehydrochlorination;1-chloro-1,1-difluoroethane;vinylidene fluoride