Si–OH Nest and Al Distribution of Silicalite-1 Core/Al-ZSM-5 Shell Zeolites for Methane Dehydroaromatization Reaction

Silicalite-1 core/Al-ZSM-5 shell zeolite crystals were prepared in various sizes for use as catalysts in methane dehydroaromatization (MDA), and the growth kinetics and corresponding physicochemical properties of this core–shell zeolite were investigated. Al-ZSM-5 was grown on silicalite-1 seeds at various Si/Al ratios. Core–shell catalysts of all size variations exhibited similar deactivation trends in the MDA reaction, with minor changes in aromatic yields despite clear differences in reaction channel lengths and acid-site properties. This outcome was shown to originate from the unique growth kinetics of the Al-ZSM-5 layer on silicalite-1 seeds, in which the Al species in the sol used in the synthesis were consumed quickly during the early aggregative growth period. This led to an interesting spatial distribution of Al in the Al-ZSM-5 layer, in that the inner layer was relatively Al-rich. This distribution is advantageous because it can inhibit coke deactivation, which often occurs at the catalyst surface during MDA. However, a substantial quantity of Si–OH nests, which inhibit the effective loading of Mo species at the acid sites of the crystals, were detected in the microstructural analysis of large crystals. Therefore, this study shows that silicalite-1 core/Al-ZSM-5 shell zeolites can be prepared for use as coke-resistant catalysts for the MDA reaction. Further work is required, however, to design a synthesis method which reduces the number of Si–OH nests formed.

Nanostructured Catalysts for Dry-Reforming of Methane

The manuscript deals on the main progress achieved by global scientific research on the development of nanostructured catalysts for dry-reforming reaction. The importance to have a global vision on this topic is strictly related to the most currently and important challenges in the sustainable energy production. In fact, dry-reforming is one of the few known processes in which greenhouse gases are utilized as reactants (methane and carbon dioxide) to produce syngas. Syngas represents the basis for liquid fuel production by Fischer-Tropsch process. In this broad and current context, the catalyst development plays a pivotal role due to its great influence on efficiency, and therefore on the costs, of the whole process. Several are the aspects to consider during the catalyst design: role of metal, interaction between metal and support, role of promoters and resistance to the coke deactivation. These issues, as well as the thermodynamics of the process, are the main aspects of which this review speaks about.

Dehydrogenation of Propane to Propylene with Highly Stable Catalysts of Pt-Sn Supported Over Mesoporous Silica KIT-6

During several reactions, similar to dehydrogenation of propane to propylene, coke is one of the main reasons for the catalyst deactivation. The coke formation and further deactivation of the catalyst are strongly dependent to the active site in the catalyst and/or the properties of the support. KIT-6 with interconnected porous and high surface area can handle with the coke formation, and can disperse easily the deposited Pt nanoparticles. In this sense, a series of Pt-Sn/KIT-6 catalysts were synthesized with distinct Sn loadings and used in the dehydrogenation of propane. The performance of these catalysts during reaction varied with the Sn loading. The specific activities for propylene formation obtained with the catalysts were comparable to the best result reported in the literature. The nanoparticles present in the catalyst through pretreatment and reaction condition was the Pt-Sn alloy (1:1 atomic ratio), and that alloy is suggested to be the active phase. This Pt-Sn alloy was stable during the entire reaction time, that even in two catalysts containing a considerable amount of coke, deactivation was not observed. Also, the support (KIT-6) with high connectivity helped to avoid deactivation by coke.