Methanol-to-olefins catalysis on window-cage type zeolites/zeotypes with syngas co-feeds: Understanding syngas-to-olefins chemistry

Zhichen Shi, Aditya Bhan

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7 Scopus citations


Catalyst lifetime and product selectivity of methanol-to-olefins (MTO) catalysis on window-cage type zeolites and zeotypes are examined and interpreted to elucidate the critical role of high-pressure H2 and CO in MTO catalysis at conditions relevant for syngas-to-olefins (STO) conversion (H2/CH3OH >100, CO/CH3OH >100). Propylene co-feed experiments elucidate that acid-catalyzed hydrogenation reactions transpire and enhance olefins-cycle propagation by intercepting formaldehyde-mediated condensation and dehydrocyclization reaction cascades to result in an increase in catalyst lifetime (>7×) and decrease ethylene-to-propylene (∼1.5×) and ethylene-to-butenes ratios (∼1.6×) during MTO with high-pressure H2 co-feeds. CO is mechanistically relevant in increasing ethylene-to-propylene (∼1.5–3.0×) and ethylene-to-butenes ratio (∼1.7×) during MTO catalysis only at high CO (3–8 bar) and syngas pressures (24 bar, H2/CO∼2–16); at these high pressures, CO participates in carbonylation reactions to enhance aromatics-cycle propagation and enable a pathway for ethylene production via methyl acetate formation. These results suggest that high-pressure syngas introduces new catalytic pathways to distinguish MTO catalysis from STO catalysis and MTO catalysis in the presence of high-pressure syngas reagents.

Original languageEnglish (US)
Pages (from-to)913-922
Number of pages10
JournalJournal of Catalysis
StatePublished - Sep 2022

Bibliographical note

Funding Information:
The authors acknowledge financial support from Dow through the University Partnership Initiative. ZS acknowledges financial support from University of Minnesota Doctoral Dissertation Fellowship.

Publisher Copyright:
© 2022 Elsevier Inc.


  • Carbonylation
  • Ethylene-to-propylene ratio
  • Hydrocarbon pool
  • Hydrogenation
  • Light olefin selectivity
  • Methanol-to-olefins
  • Small pore zeolites


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