Vapor phase ethanol carbonylation over Rh supported on zeolite 13X

Sara Yacob, Beata A. Kilos, David G. Barton, Justin M Notestein

Research output: Contribution to journalArticle

3 Citations (Scopus)

Abstract

While methanol carbonylation has been extensively studied, higher alcohol carbonylation has received relatively little attention, even though, for example, ethanol carbonylation could be a useful route for the production of propionates. Here we use Rh/Na13X to investigate the vapor phase carbonylation of ethanol with an ethyl iodide co-feed. In the base case, the catalyst is ∼40% selective to propionates, with the remainder forming ethylene and diethyl ether. Deposition of additional alkali can increase selectivities to ∼60%. Isotopic labeling of ethyl iodide demonstrates reversible formation of ethyl iodide from ethanol, and that preferential incorporation of ethyl iodide initiates the Rh-catalyzed carbonylation cycle. XPS and in situ X-ray absorption spectroscopy are consistent an active anionic RhI iodide species at a zeolite exchange site. This proposed structure and the attendant catalytic reaction network are directly analogous to those of classic solution-phase Rh catalysts and other supported Rh catalysts. However, important differences are noted in the reaction orders and apparent activation barrier, which suggest that the rate of ethyl iodide formation is overall rate limiting under these conditions and for this catalyst.

Original languageEnglish
Pages (from-to)122-131
Number of pages10
JournalApplied Catalysis A: General
Volume520
DOIs
Publication statusPublished - Jun 25 2016

Fingerprint

Carbonylation
Zeolites
Iodides
Ethanol
Vapors
Propionates
Catalysts
X ray absorption spectroscopy
Catalyst supports
Labeling
Alkalies
Ethers
Ethylene
Methanol
Alcohols
Ether
X ray photoelectron spectroscopy
Chemical activation

Keywords

  • Carbonylation
  • Ethanol
  • Ethyl iodide
  • Rhodium
  • Zeolite 13X

ASJC Scopus subject areas

  • Catalysis
  • Process Chemistry and Technology

Cite this

Vapor phase ethanol carbonylation over Rh supported on zeolite 13X. / Yacob, Sara; Kilos, Beata A.; Barton, David G.; Notestein, Justin M.

In: Applied Catalysis A: General, Vol. 520, 25.06.2016, p. 122-131.

Research output: Contribution to journalArticle

Yacob, Sara ; Kilos, Beata A. ; Barton, David G. ; Notestein, Justin M. / Vapor phase ethanol carbonylation over Rh supported on zeolite 13X. In: Applied Catalysis A: General. 2016 ; Vol. 520. pp. 122-131.
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