Synthesis gas transformations with heterogeneous iridium and homogeneous rhodium metal complexes

Thesis/Dissertation · Fri Jan 01 04:00:00 EST 1988

OSTI ID:6918984

Getty, C S

The emphasis of this work has been on the development of homogeneous and heterogeneous catalytic systems capable of the indirect transformation of H{sub 2} and CO into chemicals under mild reaction conditions. Supported iridium carbonyl and aluminum chloride were investigated in an attempt to heterogenize an analogous homogeneous catalyst. The presence of aluminum chloride was found to lead to cluster interactions resulting in a system capable of selective reduction of carbon monoxide under mild reaction conditions. When a gaseous mixture of H{sub 2}, CO, and HCl was passed over the supported cluster at 125 C, methyl chloride, methane, carbon dioxide and water were observed as major products. Unlike the homogeneous analog, only trace C{sub 2} products were detected. Infrared spectroscopy was used to investigate the preparation of the deposited clusters as well as the iridium species formed on the support during reaction. The second study involved the investigation of a rhodium carboxylate triphenylphosphine complex which was found to be an active, homogeneous hydroformylation catalyst. The system selectively produced more of the linear aldehyde than the branched. The product selectivity was found to depend upon the amount of phosphine present. Spectroscopic studies supported that a bis(triphenylphosphine)rhodium(I) trifluoroacetate carbonyl species was the active catalyst. Comparative studies with other rhodium carboxylate complexes and hydroformylation catalysts showed that the perfluorocarboxylate complexes exhibited greater activity.

• Research Organization: Florida Univ., Gainesville, FL (USA)
• OSTI ID: 6918984
• Country of Publication: United States
• Language: English

Related Subjects

01 COAL, LIGNITE, AND PEAT
010408* -- Coal
Lignite
& Peat-- C1 Processes-- (1987-)
ALDEHYDES
ALKANES
ALUMINIUM CHLORIDES
ALUMINIUM COMPOUNDS
CARBON COMPOUNDS
CARBON DIOXIDE
CARBON MONOXIDE
CARBON OXIDES
CATALYSIS
CATALYST SUPPORTS
CATALYTIC EFFECTS
CHALCOGENIDES
CHEMICAL PREPARATION
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
CHLORIDES
CHLORINATED ALIPHATIC HYDROCARBONS
CHLORINE COMPOUNDS
COMPARATIVE EVALUATIONS
COMPLEXES
DISPERSIONS
ELEMENTS
FLUIDS
GASES
HALIDES
HALOGEN COMPOUNDS
HALOGENATED ALIPHATIC HYDROCARBONS
HETEROGENEOUS CATALYSIS
HOMOGENEOUS CATALYSIS
HYDROCARBONS
HYDROCHLORIC ACID
HYDROGEN COMPOUNDS
HYDROGENATION
INFRARED SPECTRA
INORGANIC ACIDS
IRIDIUM
IRIDIUM COMPLEXES
METALS
METHANATION
METHANE
METHYL CHLORIDE
MIXTURES
ORGANIC CHLORINE COMPOUNDS
ORGANIC COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
OXIDES
OXYGEN COMPOUNDS
PLATINUM METALS
RHODIUM
RHODIUM COMPLEXES
SPECTRA
SYNTHESIS
SYNTHESIS GAS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENTS
WATER
YIELDS