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Abstract:A hierarchical zeolite CaA with microporous, mesoporous and macroporous structure was hydrothermally synthesized by a "Bond-Blocking" method using organo-functionalized mesoporous silica (MS) as a silica source. The characterization by XRD, SEM/TEM and N 2 adsorption/desorption techniques showed that the prepared material had well-crystalline zeolite Linde Type A (LTA) topological structure, microspherical particle morphologies, and hierarchically intracrystalline micro-meso-macropores structure. With the Bond-Blocking principle, the external surface area and macro-mesoporosity of the hierarchical zeolite CaA can be adjusted by varying the organo-functionalized degree of the mesoporous silica surface. Similarly, the distribution of the micro-meso-macroporous structure in the zeolite CaA can be controlled purposely. Compared with the conventional microporous zeolite CaA, the hierarchical zeolite CaA as a catalyst in the conversion of methanol to dimethyl ether (DME), exhibited complete DME selectivity and stable catalytic activity with high methanol conversion. The catalytic performances of the hierarchical zeolite CaA results clearly from the micro-meso-macroporous structure, improving diffusion properties, favoring the access to the active surface and avoiding secondary reactions (no hydrocarbon products were detected after 3 h of reaction).