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Design of highly active catalysts plays a critical role in catalytic fast pyrolysis (CFP) of lignocellulosic biomass. Advanced catalysts can improve the deoxygenation rate of pyrolysis vapors and boost the production of fuel precursors. Zeolites are suitable frameworks for catalyzing pyrolysis vapors into species of transportation fuel value. However, their nano-sized structure limits the diffusion of reactants into pores and over active sites. Consequently, the aggregation of large molecules outside micropores leads to a massive coke formation, blocking pore channels, and thus, preventing the accessibility to acid sites. This could cause quick deactivation and instability of the catalyst, necessitating frequent catalyst regeneration and replenishment. Hierarchical micro/mesopore-structured zeolites are promising candidates to cope with the mentioned challenges. In addition to their adjusted pore structure and increased accessibility of acid sites, the formation of mesoporosity in zeolites provides an adequate room for the deposition of additional active phases such as metal nanoparticles, further boosting the catalytic activity. Different strategies used for preparing hierarchical zeolites can tremendously alter their attributes, and consequently affect product selectivity during CFP of biomass. Focusing on the precursors of transportation fuels (i.e., aromatic hydrocarbons and olefins), the present paper critically reviews the impacts of methods used for synthesizing hierarchical zeolite, on CFP of bio-based feedstocks. Moreover, the role of metal addition to hierarchical zeolites in biomass catalytic pyrolysis is also discussed briefly. Among the different synthesis techniques, desilication treatment using alkaline solutions is the most promising owing to its simplicity, high productivity, and scalability. In terms of product selectivity, the addition of Ga species to hierarchical zeolites can increase aromatic hydrocarbons while Ce incorporation can increase the yield of valuable oxygenates such as furan. Despite the advantages of mono-metallic hierarchical zeolites in producing cherished chemicals, future studies should scrutinize the influence of bi-metallic hierarchical zeolites in bio-based CFP processes.

A review on the role of hierarchical zeolites in the production of transportation fuels through catalytic fast pyrolysis of biomass