Stable and Reusable Hierarchical ZSM-5 Zeolite with Superior Performance for Olefin Oligomerization when Partially Coked

The character of coke is typically regarded as a "deactivator" in zeolite catalysis. We report the interdependence of coke nature and location with its true character in the mechanisms of ethylene oligomerization: a model zeolite catalyzed transformation involved in many sustainable processes. We prepared, characterized, and tested ZSM-5 zeolites of different diffusion paths and acidities, using polymeric-, organic-template, or template-free strategies and various Si/Al ratios. The results indicate that coke can improve the selectivity/yield of higher olefins and jet-fuel aliphatics, and this positive effect is better than modifying the number of acid sites. The molecular-level nature of these coke species is elucidated using high-resolution mass spectrometry. The "enhancer" character of the coke can be better exploited in polymeric templated (hierarchical) ZSM-5 zeolite because mesopores retain coke without critically affecting accessibility or causing deactivation. Furthermore, this catalyst is stable for at least 74 h on stream and in multiple reaction-regeneration cycles.