Incorporation of Aluminum and Iron Into the ZSM-12 Zeolite: Synthesis and Characterization of Acid Sites

Abstract

Zeolite ZSM-12 with aluminum and iron in the framework was synthesized in a broad range of Si/Al (Si/Fe) ratios using triethylmethylammonium bromide as structure-directing agent with the aim to characterize the type and concentration of acid sites in dependence on the Si/Al (Si/Fe) ratio and calcination procedure. It was shown that the minimum Si/Al ratio achieved for (Al)ZSM-12 is around 35, which is very close to the minimum Si/Fe ratio ca 37 for (Fe)ZSM-12. The rate of crystallization of (Al)ZSM-12 and (Fe)ZSM-12 depends on the concentration of Al and Fe in the reaction mixture. The higher was the concentration of these trivalent cations, the slower was the apparent crystallization rate. It is suggested that the crystallization rate is controlled by the number of nucleation centers, which depends on the amount of trivalent cations (Al, Fe) in the reaction mixture. Zeolites (Al)ZSM-12 and (Fe)ZSM-12 were calcined under a variety of carefully controlled conditions to investigate the resulting concentration of Brønsted and Lewis acid sites. FTIR spectroscopy used to study the adsorption of acetonitrile-d3 and pyridine on Brønsted and Lewis acid sites revealed that both sites are present in significant concentrations in all calcined (Al)ZSM-12 and (Fe)ZSM-12 zeolites. The highest concentrations of Brønsted sites especially at low Si/Al or Si/Fe ratios were achieved via calcination of the zeolites in a stream of ammonia followed by a repeated sodium ion exchange and further calcination in a stream of air.