Deactivation mechanism of catalyst in long-period experiment of 1,1,2-TCE dehydrochlorination

Abstract

ABSTRACT VDC, as an important raw material for high barrier material PVDC and lithium-ion battery binder PVDF, had an increasing demand. The catalytic dehydrochlorination of 1,1,2-TCE to generate VDC was a green process route that was expected to replace the heavily polluting sodium hydroxide saponification process in industry. There was a certain research foundation for the catalytic dehydrochlorination of 1,1,2-TCE, among which the core problem was that the catalyst was prone to deactivation. Previous studies had calculated the average molecular structure of the spent catalyst surface species when coconut shell activated carbon was used as the support. In subsequent studies, alumina support had been proven to be a better carrier for dehydrochlorination of 1,1,2-TCE, and the selected catalyst had been used in long-period laboratory experiments. The results indicated that the catalyst life had been significantly improved. In the early stage of the reaction, the activity of the catalyst decreased rapidly. In the first 20 h, the conversion of 1,1,2-TCE decreased from 49.35% to 40.36%. From 21 h to 120 h, the conversion of 1,1,2-TCE decreased from 39.96% to 36.18%, tending to stabilize. After 120 h of reaction, the catalyst was extracted and elemental analysis, FTIR, and GPC characterization were performed on the spent catalyst surface species. The average molecular formula of the carbon deposits was obtained as C96.08H50.29Cl36.53. Compared with coconut shell activated carbon support, under the action of activated alumina support, the route of catalyst carbon deposition had changed, and the sediment was more composed of polyvinylidene chloride components. Under certain conditions, sediment formed a dynamic equilibrium, which explained why the activity of the catalyst gradually stabilized. This study revealed the catalytic mechanism of active alumina supported catalyst and the pathway of carbon deposits generation, which was of great significance for improving the lifespan of improved catalyst.