Infrared flow cell for use at elevated temperatures and pressures

Oltay, Ernst; Penninger, J. M. L.; Alemdaroglu, N. H.; Alberigs, J. M.

doi:10.1021/ac60326a002

Cited by 13 publications

(1 citation statement)

References 5 publications

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“…Samples were taken through a capillary line, without releasing the pressure, into the high-pressure ir cell. This was of a type described previously (Oltay et al, 1973). The temperature of the liquid in the autoclave, the transfer line, and ir cell were controlled carefully at the same value within a range of 1°C.…”

Section: Methodsmentioning

confidence: 99%

Hydroformylation with Cobalt Carbonyl and Cobalt Carbonyl-Tributylphosphine Catalysts

Boven¹,

Alemdaroglu²,

Penninger³

1975

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By in situ ir spectroscopic techniques it was found that the cobalt carbonyl catalyst in hexane, after preforming at conditions of hydroformylation (temperatures of 101 and 124OC, Pc0 = 11 and 30 bars, PH2 = 20 and 49 bars, cobalt concentration = 2.0 and 4.2 mmolll.) consisted of more than 80% HCO(CO)~, the rest being C02(C0)8. Injection of octene-I, in order to start the hydroformylation, caused HCO(CO)~ to decrease (although not to zero concentration) in favor of an increasing CO~(CO)~ concentration. This reverted as the conversion of octene-1 increased. As intermediate complexes, only acyl cobalt carbonyl species were detected in very low concentrations. A catalyst composed of cobalt carbonyl and tributylphosphine in a phosphorus-to-cobalt ratio of 5, of a considerable amount of catalytically inactive CO~(CO),PBU~, while of all hydridocobalt carbonyls present only a minor part was liganded by PBu3 at the previously mentioned reaction conditions. Accordingly, in the hydroformylation of octene-I, the catalyst decreased only the octene conversion rate and left the yield of unbranched products unaffected.

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Section: Methodsmentioning

confidence: 99%

Hydroformylation with Cobalt Carbonyl and Cobalt Carbonyl-Tributylphosphine Catalysts

Boven¹,

Alemdaroglu²,

Penninger³

1975

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Heat of Adsorption of Carbon Monoxide on a Pt/Rh/CeO2/Al2O3Three-Way Catalyst Usingin-SituInfrared Spectroscopy at High Temperatures

Chafik

Dulaurent

Gass

et al. 1998

Journal of Catalysis

108

169

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Study of the mechanism of hydroformylation at industrial reaction conditions

Alemdaroglu¹,

Penninger

Oltay

1976

Monatshefte für Chemie

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With a newly developed analytical technique, i.e. high temperature/pressure IR cell coupled to the reactor, it was possible to study the mechanism of hydroformylation at reaction conditions. It has been conclusively found that the hydrogenolysis of the aeyl cobalt, complex is performed by HCo(CO)4 and not by molecular H2, as proposed by Hect~ and Breslow. Therefore the formation of HCo(CO)4 from C02(CO)s is an intermediate step in the sequence of hydroformylation reaction steps. The rate of hydroformylation of any of the olefins is smaller than the rate of formation of HCo(CO)4 from C02(CO)s. The Ig spectra reveal that always more than 30% of the cobalt is in the form of tICo(CO)4 under the reaction conditions. It is found that the formation of tICo(CO)4 from C02(CO)s is the slowest and most temperature-dependent step of the hydroformylation reaction. Also the reaction between olefin and HCo(CO)4 is slower than the hydrogenolysis of the aeyl complex. The experiments were carried out under industrial oxo conditions. The diffusional effects were eliminated.

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Infrared flow cell for use at elevated temperatures and pressures

Cited by 13 publications

References 5 publications

Hydroformylation with Cobalt Carbonyl and Cobalt Carbonyl-Tributylphosphine Catalysts

Hydroformylation with Cobalt Carbonyl and Cobalt Carbonyl-Tributylphosphine Catalysts

Heat of Adsorption of Carbon Monoxide on a Pt/Rh/CeO2/Al2O3Three-Way Catalyst Usingin-SituInfrared Spectroscopy at High Temperatures

Study of the mechanism of hydroformylation at industrial reaction conditions

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