TEAOH-Templated SAPO-34 Zeolite with Different Crystallization Processes and Silicon Sources: Crystallization Mechanism and MTO Performance

摘要

SAPO-34 zeolites were synthesized by one-, two-, and three-stage crystallization processes with fumed silica (FS), acidic silica sol (AS), basic silica sol (BS) and tetraethoxysilane (TEOS) as silicon sources. Properties of samples were characterized by XRD, SEM, EDX, N-2-adsorption/desorption, NH3-TPD and Si-29 NMR. In contrast with one- and two-stage processes, the three-stage one favors the formation of SAPO-34s with higher purity, higher Si/Al ratio, smaller crystallite/crystal size, better dispersion and more acidic sites. Crystallization mechanism was proposed. It is supposed that three-stage process favors the formation of high supersaturated SBUs (secondary building units) and CBUs (composite building units) before nucleation. Thus massive nuclei are formed during nucleation and well-dispersed small size SAPO-34 crystals are formed in three-stage process. Three-stage SAPO-34s are longer catalytic lifetime and better olefin selectivity in MTO process. TEOS-3 has the best MTO performance. It was found that acidity of sample and mesopores in 2-4 nm range have little effect on the MTO performance of SAPO-34. Catalytic lifetime and olefin selectivity are mainly depending on the size of crystallites, the dispersity of crystallites, and the purity of SAPO-34.