Mechanistic studies on direct ethylene glycol synthesis from carbon monoxide and hydrogen 1. Homogeneous rhodium catalyst

Journal Article · Fri Jan 31 23:00:00 EST 1992 · Journal of Catalysis; (United States)

DOI:https://doi.org/10.1016/0021-9517(92)90243-B· OSTI ID:6984936

Ishino, M; Tamura, M; Deguchi, T; Nakamura, S ^[1]

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1. Sumitomo Chemical Co., Ltd., Osaka (Japan)

Mechanistic studies on direct syngas conversion to ethylene glycol by a homogeneous Rh catalyst combined with a trialkylphosphine were performed. High-pressure IR studies showed that when a bulky trialkylphosphine, such as P{sup i}Pr{sub 3}(L), was added to the Rh catalyst, it gave HRh(CO){sub 3}L, rather than Rh carbonyl cluster anions, whereas PPh{sub 3} and P{sup n}Bu{sub 3} tended to decompose under the reaction conditions, forming an inactive Rh phosphidocarbonyl cluster anion, (Rh{sub 9}P(CO){sub 21}){sup 2{minus}}. Kinetic studies by means of complete-mixing flow-reaction experiments revealed that the formation of formaldehyde (FAL) from CO and H{sub 2} was rate-determining, and a bulky trialkylphosphine accelerated both the formation and the hydrogenation of FAL. It was suggested that these acceleration effects were connected with enrichment of the mononuclear hydride species and improvement of the CO insertion abilities to the hydride and the hydroxymethyl complexes by the phosphine ligand. The studies on the catalyst concentration dependencies by means of batchwise reaction revealed the involvement of dinuclear mechanisms in the formation of FAL and the reductive elimination of the hydroxymethyl and the hydroxyacetyl complexes.

• OSTI ID: 6984936
• Journal Information: Journal of Catalysis; (United States), Journal Name: Journal of Catalysis; (United States) Vol. 133:2; ISSN 0021-9517; ISSN JCTLA
• Country of Publication: United States
• Language: English

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ABSORPTION SPECTROSCOPY
ALCOHOLS
ALDEHYDES
CARBON COMPOUNDS
CARBON MONOXIDE
CARBON OXIDES
CARBONYLS
CATALYTIC EFFECTS
CHALCOGENIDES
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CHEMICAL REACTIONS
ELECTROMAGNETIC RADIATION
ELEMENTS
FLUIDS
FORMALDEHYDE
GASES
GLYCOLS
HYDROGEN
HYDROGENATION
HYDROXY COMPOUNDS
INFRARED RADIATION
KINETICS
METALS
METHANATION
NONMETALS
ORGANIC COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PHASE STUDIES
PHOSPHINES
PHOSPHORUS COMPOUNDS
PLATINUM METALS
RADIATIONS
REACTION KINETICS
RHODIUM
SPECTROSCOPY
SYNTHESIS
SYNTHESIS GAS
TRANSITION ELEMENTS