Increased productivity in ethylene carbonylation by zeolite-supported molybdenum carbonyls

Chieh Chao Yang, Sara Yacob, Beata A. Kilos, David G. Barton, Eric Weitz, Justin M. Notestein*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

15 Scopus citations

Abstract

Ethylene carbonylation to propionic acid is a powerful route to the synthesis of oxygenates. Mo(CO)6 is a known homogenous catalyst for this reaction. When supported on HY zeolite, prepared by incipient wetness impregnation from pentane or by vapor deposition, turnover numbers dramatically increase to over 40,000 in 5 h of reaction, particularly for the supports with lower Si/Al ratios. Diffuse reflectance UV-visible spectra and thermogravimetric analysis indicate that lower Si/Al ratios promote more and stronger interactions between Mo(CO)6 and the support, leading to higher reactivity under liquid-phase reaction conditions. Although some leaching occurs under these conditions, the active catalyst is the supported Mo(CO)x/HY, and the recovered catalysts are still stable and active for ethylene carbonylation with turnover numbers exceeding 30,000 mol propionic acid/mol of Mo over 5 h at 190 °C. FTIR provides evidence for the formation and stabilization of under-coordinated carbonyl species during heat treatment, and such sub-carbonyls are known to be relevant in previously-established catalytic mechanisms.

Original languageEnglish (US)
Pages (from-to)313-320
Number of pages8
JournalJournal of Catalysis
Volume338
DOIs
StatePublished - Jun 1 2016

Funding

The authors acknowledge the financial support of The Dow Chemical Company . The CleanCat Core facility acknowledges funding from the Department of Energy ( DE-AC02-06CH11357 ) used for the purchase of the gas chromatography equipment and NH 3 -TPD. XRD characterization was done at the J.B. Cohen X-Ray Diffraction Facility supported by the MRSEC program of the National Science Foundation ( DMR-1121262 ) at Northwestern University. ICP-OES and Solid State NMR were performed at the Northwestern University Integrated Molecular Structure Education and Research Center with funding provided by NSF ( DMR-0521267 ). The authors thank Yuyang Wu at IMSERC for his technical assistance for solid state 27 Al NMR.

Keywords

  • Carbonylation
  • Ethylene
  • Heterogeneous catalysis
  • Impregnation
  • Metal carbonyl
  • Molybdenum
  • Promotion
  • Y-type zeolite

ASJC Scopus subject areas

  • Catalysis
  • Physical and Theoretical Chemistry

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