Kinetics and mechanism of methanol carbonylation over Rh-Y zeolite
The carbonylation of methanol on a 4.4% rhodium(III)-exchanged Y-zeolite in the presence of methyl iodide yielded methyl acetate as only carbonylation product up to 30% conversion (and dimethyl ether as by-product) in a reaction that was zero order in carbon monoxide and methanol, proportional to the methyl iodide partial pressure, and had activation energy of 5.65 kj/mole at 428/sup 0/-473/sup 0/K. Over 95% of the methyl iodide was recoverable. These values were very similar to the known kinetic parameters of the homogeneous reaction catalyzed by rhodium complexes, and a similar mechanism was proposed and confirmed in experiments with ethyl iodide and perdeuterated methanol. The mechanism involves oxidative addition of methyl iodide to the active rhodium site, insertion of carbon monoxide into the methyl-rhodium bond, methanolysis of the acetyl-rhodium bond, reductive dissociation of hydrogen iodide from rhodium, and regeneration of methyl iodide by reaction of hydrogen iodide with methanol.
- Research Organization:
- Tokyo Inst. of Technology
- OSTI ID:
- 6313050
- Journal Information:
- J. Catal.; (United States), Journal Name: J. Catal.; (United States) Vol. 59:1; ISSN JCTLA
- Country of Publication:
- United States
- Language:
- English
Similar Records
Rhodium complx catalyzed methanol carbonylation. Effects of medium and varius additives
Catalytic features of carbon supported group VIII metal catalysts for methanol carbonylation
Related Subjects
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ACETIC ACID ESTERS
ACTIVATION ENERGY
ALCOHOLS
CARBONYLATION
CARBOXYLIC ACID ESTERS
CATALYTIC EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTION YIELD
CHEMICAL REACTIONS
COMPLEXES
DATA
ENERGY
ESTERS
EXPERIMENTAL DATA
HALOGEN COMPOUNDS
HIGH TEMPERATURE
HYDROXY COMPOUNDS
INFORMATION
INORGANIC ION EXCHANGERS
IODINE COMPOUNDS
ION EXCHANGE MATERIALS
KINETICS
MATERIALS
METHANOL
MINERALS
NUMERICAL DATA
ORGANIC COMPOUNDS
REACTION INTERMEDIATES
REACTION KINETICS
RHODIUM COMPLEXES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES
YIELDS
ZEOLITES