Synthesis and characterization of ERI-type UZM-12 zeolites and their methanol-to-olefin performance

A wide variety of different linear, diquaternary alkylammonium ions have been used as supplementary crystallization structure-directing agents (SDAs) in the synthesis of UZM-12, a high-silica version of zeolite erionite, via a charge density mismatch (CDM) approach. When tetraethylammonium is used as a CDM SDA, the crystallization of UZM-12 was found to be critically dependent not only on the type of alkali metal cations added as another crystallization SDA to the synthesis mixture, but also on the size of the groups on the diquaternary ammonium ion employed and the length of its central polymethylene chain that are closely related to the dimensions of cylindrical 23-hedral [4(12)6(5)8(6)] eri cages in this small-pore zeolite. (27)Al MQ MAS NMR measurements reveal a preferential location of Al on the high-multiplicity site over the lower-multiplicity site of the UZM-12 framework. The catalytic results from the methanol-to-olefin reaction over a series of H-UZM-12 zeolites with similar acidic properties but different crystallite sizes (100-2500 nm in length) demonstrate that the nanocrystallinity (probably the ≤100 nm range) may have a detrimental effect on the activity and stability for this reaction, probably due to the fast buildup of large coke molecules on the external surface of zeolite crystallites that inhibits the methanol diffusion to intrazeolitic acid sites, rendering them ultimately inaccessible for catalysis.