Stabilizing the framework of SAPO-34 zeolite toward long-term methanol-to-olefins conversion

As a commercial MTO catalyst, SAPO-34 zeolite exhibits excellent recyclability probably due to its intrinsic good hydrothermal stability. However, the structural dynamic changes of SAPO-34 catalyst induced by hydrocarbon pool (HP) species and the water formed during the MTO conversion as well as its long-term stability after continuous regenerations are rarely investigated and poorly understood. Herein, the dynamic changes of SAPO-34 framework during the MTO conversion were identified by 1D (27)Al, (31)P MAS NMR, and 2D (31)P-(27)Al HETCOR NMR spectroscopy. The breakage of T-O-T bonds in SAPO-34 catalyst during long-term continuous regenerations in the MTO conversion could be efficiently suppressed by pre-coking. The combination of catalyst pre-coking and water co-feeding is established to be an efficient strategy to promote the catalytic efficiency and long-term stability of SAPO-34 catalysts in the commercial MTO processes, also sheds light on the development of other high stable zeolite catalyst in the commercial catalysis.