ABSTRACT
Designing an economically viable catalyst that maintains high catalytic activity and stability is the key to unlock dry reforming of methane (DRM) as a primary strategy for biogas valorization. Ni/Al2O3 catalysts have been widely used for this purpose; however, several modifications have been reported in the last years in order to prevent coke deposition and deactivation of the samples. Modification of the acidity of the support and the addition of noble metal promoters are between the most reported strategies. Nevertheless, in the task of designing an active and stable catalyst for DRM, the selection of an appropriate noble metal promoter is turning more challenging owing to the lack of homogeneity of the different studies. Therefore, this research aims to compare Ru (0.50 and 2.0%) and Re (0.50 and 2.0%) as noble metal promoters for a Ni/MgAl2O4 catalyst under the same synthesis and reaction conditions. Catalysts were characterized by XRF, BET, XRD, TPR, hydrogen chemisorption (H2-TPD), and dry reforming reaction tests. Results show that both promoters increase Ni reducibility and dispersion. However, Ru seems a better promoter for DRM since 0.50% of Ru increases the catalytic activity in 10% and leads to less coke deposition.
ABSTRACT
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.
