Cooperative effects of zeolite mesoporosity and defect sites on the amount and location of coke formation and its consequence in deactivation

The cooperative effects of secondary mesoporosity and defects on the coke formation and deactivation of zeolite were investigated in n-pentane aromatization using model Ga/ZSM-5 catalysts. Mesoporosity was introduced to a commercial ZSM-5 by alkaline desilication, while the defects sites (i.e., internal silanols) in zeolites were annealed by the treatment with ammonium hexafluorosilicate. Aromatization after supporting Ga showed that the mesopore generation retarded catalyst deactivation via the suppression of internal coke formation while facilitating the external coke formation due to the enhanced diffusion of coke precursors (e.g., alkylaromatics) out of zeolite micropores. Internal coke can cause a more severe deactivation than external coke because the acid sites are mainly located in the zeolite micropores. However, the mesopore generation alone could not efficiently reduce the total amount of coke deposition (it mainly changed the location of coke). In contrast, the annealing of internal silanols could suppress the overall coke formation. This phenomenon could be explained by the fact that coke precursors are initially generated at the zeolite internal defects, and then deposited as coke at either the internal or the external surfaces of the zeolite depending on the relative kinetics of coke precursor diffusion and its polymerization. Consequently, the catalyst with mesoporosity and annealed internal silanols exhibited the slowest catalyst deactivation due to the suppression of both internal and external coke depositions.