On reaction pathways in the conversion of methanol to hydrocarbons on HZSM-5

[Display omitted] •MTO mechanism was explored under industrially relevant conditions on ZSM-5.•Olefin- and aromatic-based cycle contribution depends on local chemical potential.•Co-feeding small concentrations of higher alcohols significantly increased catalyst lifetime.•Hydride transfer involving methanol appears to be responsible for a marked decrease in activity. The underlying mechanisms of the two distinct catalytic cycles operating during conversion of methanol to olefins (MTO) on HZSM-5 have been elucidated under industrially relevant conditions. The co-existence of olefins and aromatic molecules in the zeolite pores leads to competition between the two cycles. Therefore, their importance depends on the local chemical potential of specific carbon species and the methanol conversion. Due to a faster, “autocatalytic” reaction pathway in the olefin based cycle, olefin homologation/cracking is dominant under MTO conditions, irrespective of whether aromatic molecules or olefins are co-fed with methanol. Another hydrogen transfer pathway, faster than the usual route, has been identified, which is directly linked to methanol. In agreement with that, the co-feeding of olefins resulted in a remarkable longer lifetime of the catalyst under MTO conditions, because the high rate methylation competes with the formation of more deactivating coke – presumably oxygenates- through methanol derivatives.