Multiple paths to nanocrystalline high silica beta zeolite

Several principles from nanozeolite synthesis lore were investigated in order to prepare discrete pure silica nanocrystalline BEA zeolite. It was discovered that lowering reaction temperature to 100 °C results in a significant reduction in nano-BEA crystal size, that lowering synthesis mixture water content to the lowest possible level for a ‘pourable’ gel provides nano-BEA crystals, that tetraethylorthosilicate (TEOS) more consistently provides smaller crystals than fumed silica as a raw material, that increasing the level of structure-directing agent resulted in more discrete and smaller crystals (25–30 nm), and that ‘surfactant’ addition could generate even smaller nano-BEA crystals or nanocrystalline domains, but mild to severe aggregation was still a problem. Nearly pure silica nanocrystalline BEA zeolites were prepared from Al-containing products by a calcination followed by acid extraction procedure. The calcination step is critical for more complete Al removal. Defects generated by acid extraction could be healed by treatment of resultant powder with a hexamethyldisilazane (HMDS). Another key finding was that Al-containing synthesis mixtures could provide nanocrystalline BEA zeolite with 4,4′-trimethylenebis(N-methyl, N-benzyl-piperidinium) dihydroxide (TMP(OH)₂) as organic structure-directing agent. Interestingly, adjusting synthesis parameters in TMP and Al-containing synthesis mixtures provided some differences to pure Si BEA products. For example, stirring or lowering reaction temperature did not decrease crystal size, but did shorten crystallization time. The smallest crystals from TMP-based, Al-containing reaction mixtures were prepared when a freeze–dried colloidal silica was utilized as silica source.