Promoting effects of Se on Rh/ZrO sub 2 catalysis for ethene hydroformylation
- Univ. of Tokyo (Japan)
The positive effects of Se added to Rh/ZrO{sub 2} catalysts in ethene hydroformylation were studied from the viewpoints of promoter effects of electronegative atoms usually regarded as poisoning atoms as well as electronic interactions with both substrate metal and adsorbed species. Se-modified Rh/ZrO{sub 2} catalysts prepared by the reactive deposition of (CH{sub 3}){sub 2}Se or coimpregnation method using SeO{sub 2} were found to be active and selective for ethene hydroformylation. The Se addition promoted the formation of propanol rather than propanal, the propanol formation being increased more than 70 times at an optimum {number sign} Se/Rh ratio. The propanoyl intermediates were observed at ca. 1770 cm{sup {minus}1} and converted reversibly to propionate species (bridge and digentate) observed at 1425-1575 cm{sup {minus}1}. The ensemble of Se{sup 2{minus}}/Rh was suggested to promote CO adsorption and the insertion of CO to ethyl species, where there is an electronic interaction between Se{sup 2{minus}} and CO or propanoyl species. The isotope effects of D{sub 2} and {sup 13}C{sup 18}O showed the switchover of the rate-determining step for hydroformylation from the CO insertion on the Rh/ZrO{sub 2} catalysts to the dissociative adsorption of H{sub 2} on the Se-Rh/ZrO{sub 2} catalysts. The role of Se is discussed in relation with the reaction mechanism.
- OSTI ID:
- 5515029
- Journal Information:
- Journal of Catalysis; (USA), Vol. 127:2; ISSN 0021-9517
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
10 SYNTHETIC FUELS
ETHYLENE
ACYLATION
PROPANOLS
SYNTHESIS
RHODIUM
CATALYTIC EFFECTS
SELENIUM
ADSORPTION
CARBON 13
CARBON MONOXIDE
CATALYST SUPPORTS
CATALYSTS
CHEMICAL REACTION KINETICS
DEPOSITION
DEUTERIUM
FORMYL RADICALS
IMPREGNATION
OXYGEN 18
POISONING
PROMOTERS
SELENIUM OXIDES
ZIRCONIUM OXIDES
ACYL RADICALS
ALCOHOLS
ALKENES
CARBON COMPOUNDS
CARBON ISOTOPES
CARBON OXIDES
CHALCOGENIDES
CHEMICAL REACTIONS
ELEMENTS
EVEN-EVEN NUCLEI
EVEN-ODD NUCLEI
HYDROCARBONS
HYDROGEN ISOTOPES
HYDROXY COMPOUNDS
ISOTOPES
KINETICS
LIGHT NUCLEI
METALS
NUCLEI
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
OXYGEN ISOTOPES
PLATINUM METALS
RADICALS
REACTION KINETICS
SELENIUM COMPOUNDS
SEMIMETALS
SORPTION
STABLE ISOTOPES
TRANSITION ELEMENT COMPOUNDS
TRANSITION ELEMENTS
ZIRCONIUM COMPOUNDS
020400* - Petroleum- Processing
100200 - Synthetic Fuels- Production- (1990-)