Mass transfer in zeolite crystals can be enhanced by the introduction of a hierarchical network of auxiliary mesopores. To fully exploit pore engineering in the design of more efficient industrial catalysts, the benefit needs to be demonstrated over technically relevant forms. Here, the influence of shaping on the adsorption and diffusion properties of hierarchical ZSM-5 is assessed by studying the gravimetric uptake of 2,2-dimethylbutane over powders and millimeter-sized bodies. Formed by extrusion or granulation with clay binders, the latter display a complex trimodal network of micro-, meso-, and macropores. The enhanced intracrystalline diffusivity due to the interconnected mesopores is preserved in the macroscopic bodies, independent of the shaping method or binder applied. Furthermore the superior overall diffusivity is retained in the hierarchical bodies compared to their conventional (purely microporous) counterparts, despite the significant extracrystalline resistance to mass transfer. The connective participation of mesopores, leading to a 6 times improved effective diffusivity in hierarchical with respect to conventional zeolite powders, is revealed by the distinct dependence on the adsorbate concentration and the relationship with the mesopore surface area. Analysis of the thermodynamic parameters derived from the adsorption isotherm proves a sensitive method to detect binder-zeolite interactions induced upon shaping.
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