Recent Advances in Zeolite-Based Catalysts for Hydroisomerization of Long-Chain Alkanes

Abstract

Long-chain n-alkane hydroisomerization is a key catalytic route for upgrading wax-rich, bio-derived, and synthetic hydrocarbon feedstocks into diesel fuels, sustainable aviation fuels, and lubricant base oils with improved low-temperature properties. However, selective hydroisomerization remains challenging because mismatches in the spatial proximity and relative strength of metal and acid sites can prolong the residence time of olefin/carbenium-ion intermediates, thereby promoting over-isomerization to multibranched species, deep cracking, and coke formation. This review summarizes recent advances in zeolite-based bifunctional catalysts for long-chain n-alkane hydroisomerization. The catalytic mechanisms are first discussed, including metal-catalyzed dehydrogenation/hydrogenation, acid-catalyzed skeletal rearrangement, and shape-selective pathways governed by pore-mouth and key-lock effects. Catalyst construction strategies are then outlined, with emphasis on the preparation of zeolite supports and the introduction and localization of metal sites. Subsequently, structure–performance relationships are reviewed from the perspectives of support properties, metal site characteristics, and promoter effects, followed by a concise assessment of catalyst performance with real feedstocks under industrially relevant conditions. Finally, this review provides guidance for the precise design of metal–acid bifunctional hydroisomerization catalysts by highlighting descriptor-guided optimization, spatially regulated metal–acid–pore architectures, multiscale characterization and modeling, and scalable catalyst construction under practical reaction conditions.