Single-Particle Spectroscopy of Alcohol-to-Olefins over SAPO-34 at Different Reaction Stages: Crystal Accessibility and Hydrocarbons Reactivity

Abstract

Insitu synchrotron-based IR and UV/Vis micro-spectroscopy combined with isotopically labeled reactants have been used to identify the different hydrocarbon species formed as well as to assess the activity and accessibility of individual 50m-sized SAPO-34 crystals. For the methanol-to-olefins process, two reaction stages can be distinguished. The first involves the formation of methoxy species, protonated dimethyl ether, and polyalkylated benzene (PAB) carbocations, which do not affect the accessibility of the SAPO-34 crystal. In addition, methoxy species are very dynamic during this stage. The second stage is related to the formation of polyaromatic (PA) species concentrated in the outer rim of the crystal, which are bulky and interact with the acid sites and thus alter the overall accessibility of the crystal. In contrast, the ethanol-to-olefins process only consists of one major stage, as the formation of PAB and PA species cannot be separated. Furthermore, the formation of these species is more internal, and coke formation is mainly concentrated in a layer located in the inner part of the SAPO-34 crystal.