Identification of the Reaction Sequence of the MTO Initiation Mechanism Using Ab Initio-Based Kinetics.

The initiation of the methanol-to-olefins (MTO) process is investigated using a multiscale modeling approach where more than 100 ab initio computed (MP2:DFT) rate constants for H-SSZ-13 are used in a batch reactor model. The investigated reaction network includes the mechanism for initiation (42 steps) and a representative part of the autocatalytic olefin cycle (63 steps). The simulations unravel the dominant initiation pathway for H-SSZ-13: dehydrogenation of methanol to CO is followed by CO-methylation leading to the formation of the first C-C bond in methyl acetate despite high barriers of >200 kJ/mol. Our multiscale approach is able to shed light on the reaction sequence that ultimately leads to olefin formation and strikingly demonstrates that only with a full reactor model that includes autocatalysis with olefins as cocatalysts is one able to understand the initiation mechanism on the atomic scale. Importantly, the model also shows that autocatalysis takes over long before significant amounts of olefins are formed, thus guiding the interpretation of experimental results.