Biogas Conversion to Syngas Using Advanced Ni-Promoted Pyrochlore Catalysts: Effect of the CH₄/CO₂ Ratio

Biogas is defined as the mixture of CH₄ and CO₂ produced by the anaerobic digestion of biomass. This particular mixture can be transformed in high valuable intermediates such as syngas through a process known as dry reforming (DRM). The reaction involved is highly endothermic, and catalysts capable to endure carbon deposition and metal particle sintering are required. Ni-pyrochlore catalysts have shown outstanding results in the DRM. However, most reported data deals with CH₄/CO₂ stoichiometric ratios resulting is a very narrow picture of the overall biogas upgrading via DRM. Therefore, this study explores the performance of an optimized Ni-doped pyrochlore, and Ni-impregnated pyrochlore catalysts in the dry reforming of methane, under different CH₄/CO₂ ratios, in order to simulate various representatives waste biomass feedstocks. Long-term stability tests showed that the ratio CH₄/CO₂ in the feed gas stream has an important influence in the catalysts' deactivation. Ni doped pyrochlore catalyst, presents less deactivation than the Ni-impregnated pyrochlore. However, biogas mixtures with a CH₄ content higher than 60%, lead to a stronger deactivation in both Ni-catalysts. These results were in agreement with the thermogravimetric analysis (TGA) of the post reacted samples that showed a very limited carbon formation when using biogas mixtures with CH₄ content <60%, but CH₄/CO₂ ratios higher than 1.25 lead to an evident carbon deposition. TGA analysis of the post reacted Ni impregnated pyrochlore, showed the highest amount of carbon deposited, even with lower stoichiometric CH₄/CO₂ ratios. The later result indicates that stabilization of Ni in the pyrochlore structure is vital, in order to enhance the coke resistance of this type of catalysts.