Novel catalytic materials for carbon dioxide reforming of methane under severely deactivating conditions.

摘要

In recent years, the utilization of carbon dioxide for the reforming of methane (dry reforming) has attracted significant interest due to the industrial advantages over conventional steam reforming. The major obstacle preventing commercialization of this process is the lack of a catalyst capable of operating at the high temperatures and pressures required by industry.; This thesis reports the study of the dry reforming reaction over SiO 2 and ZrO2 supported Pt catalysts. It was found that the Pt/ZrO2 catalyst had much higher activity and stability than the Pt/SiO2 catalyst due to the ability of the ZrO2 to adsorb CO2 near the metal particle, facilitating its dissociation. The decomposition of CH4 and the dissociation of CO2 occur via two independent pathways. CH4 decomposition occurs on the metal particle resulting in the formation of H2 and carbon deposition. When Pt is supported on ZrO2, the carbon formed during the decomposition of CH4 can reduce the support to form CO2 creating oxygen vacancies in the support lattice near the metal particle. The adsorption and dissociation of CO2 occurs at the vacancies, forming CO and replenishing the oxygen in the support lattice. This redox mechanism results in a cleaning of the metal particle by oxygen provided by the support. Promoters were added to both the metallic phase and to the support to improve the stability of the catalyst by decreasing carbon deposition. The co-impregnation of Sn and Pt on the ZrO2 resulted in lower activity and stability than the monometallic catalysts. Under oxidizing conditions, segregation of the Pt-Sn alloys occurred, resulting in the formation of tin oxide inhibiting the role of the ZrO2. Catalysts prepared by methods that allow for the controlled placement of Sn on the Pt particle, exhibited high activity and stability under severely deactivating conditions.; Promotion of the ZrO2 support with cerium and lanthanum resulted in increased activity and stability of the catalyst. The improved performance of the promoted catalyst can be attributed stabilizing the surface area for high temperature operation, increasing the density of CO2 adsorption sites near the metal particle, and retarding particle growth under reaction conditions.