A highly catalytic bimetallic system for the low-temperature selective oxidation of methane and lower alkanes with dioxygen as the oxidant

Minren Lin, Terrence Hogan, Ayusman Sen

Research output: Contribution to journalArticle

90 Citations (Scopus)

Abstract

This report describes a highly catalytic bimetallic system for the low temperature selective oxidation of methane, ethane, and butane with dioxygen as the oxidant. The catalytic system consists of a mixture of copper chloride and metallic palladium and operates in a 3:1 mixture (v/v) of trifluoroacetic acid and water in the presence of dioxygen and carbon monoxide. Methane was selectively converted to methanol. The dependence of the reaction rate on the partial pressure of methane was measured, and saturation kinetics was observed. The dependence of the rate on the partial pressure of carbon monoxide was measured at two different pressures of methane, and a first- order dependence on the partial pressure of carbon monoxide was observed in both instances. The activation parameters for the overall reaction were obtained under the reaction conditions when the rate was first order in both methane and carbon monoxide. The values obtained were A = 2 x 104 s-1 and E(a) = 15.3 kcal mol-1. Both C-H and C-C cleavage products were observed for ethane and n-butane, resulting in the formation of methanol, ethanol, and acetic acid. The rate of formation of methanol from methane with the bimetallic system was ca. 65 x 10-4 M/min at 145-150 °C. This rate may be compared to the rate of formation of acetic acid from methanol in the benchmark Monsanto process: 380 x 10-4 M/min at 180 °C.

Original languageEnglish (US)
Pages (from-to)6048-6053
Number of pages6
JournalJournal of the American Chemical Society
Volume119
Issue number26
DOIs
StatePublished - Jan 1 1997

Fingerprint

Alkanes
Methane
Oxidants
Paraffins
Carbon Monoxide
Oxygen
Carbon monoxide
Oxidation
Temperature
Methanol
Partial Pressure
Partial pressure
Ethane
Butane
Acetic acid
Acetic Acid
Trifluoroacetic acid
Benchmarking
Trifluoroacetic Acid
Palladium

All Science Journal Classification (ASJC) codes

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

Cite this

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title = "A highly catalytic bimetallic system for the low-temperature selective oxidation of methane and lower alkanes with dioxygen as the oxidant",
abstract = "This report describes a highly catalytic bimetallic system for the low temperature selective oxidation of methane, ethane, and butane with dioxygen as the oxidant. The catalytic system consists of a mixture of copper chloride and metallic palladium and operates in a 3:1 mixture (v/v) of trifluoroacetic acid and water in the presence of dioxygen and carbon monoxide. Methane was selectively converted to methanol. The dependence of the reaction rate on the partial pressure of methane was measured, and saturation kinetics was observed. The dependence of the rate on the partial pressure of carbon monoxide was measured at two different pressures of methane, and a first- order dependence on the partial pressure of carbon monoxide was observed in both instances. The activation parameters for the overall reaction were obtained under the reaction conditions when the rate was first order in both methane and carbon monoxide. The values obtained were A = 2 x 104 s-1 and E(a) = 15.3 kcal mol-1. Both C-H and C-C cleavage products were observed for ethane and n-butane, resulting in the formation of methanol, ethanol, and acetic acid. The rate of formation of methanol from methane with the bimetallic system was ca. 65 x 10-4 M/min at 145-150 °C. This rate may be compared to the rate of formation of acetic acid from methanol in the benchmark Monsanto process: 380 x 10-4 M/min at 180 °C.",
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A highly catalytic bimetallic system for the low-temperature selective oxidation of methane and lower alkanes with dioxygen as the oxidant. / Lin, Minren; Hogan, Terrence; Sen, Ayusman.

In: Journal of the American Chemical Society, Vol. 119, No. 26, 01.01.1997, p. 6048-6053.

Research output: Contribution to journalArticle

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AB - This report describes a highly catalytic bimetallic system for the low temperature selective oxidation of methane, ethane, and butane with dioxygen as the oxidant. The catalytic system consists of a mixture of copper chloride and metallic palladium and operates in a 3:1 mixture (v/v) of trifluoroacetic acid and water in the presence of dioxygen and carbon monoxide. Methane was selectively converted to methanol. The dependence of the reaction rate on the partial pressure of methane was measured, and saturation kinetics was observed. The dependence of the rate on the partial pressure of carbon monoxide was measured at two different pressures of methane, and a first- order dependence on the partial pressure of carbon monoxide was observed in both instances. The activation parameters for the overall reaction were obtained under the reaction conditions when the rate was first order in both methane and carbon monoxide. The values obtained were A = 2 x 104 s-1 and E(a) = 15.3 kcal mol-1. Both C-H and C-C cleavage products were observed for ethane and n-butane, resulting in the formation of methanol, ethanol, and acetic acid. The rate of formation of methanol from methane with the bimetallic system was ca. 65 x 10-4 M/min at 145-150 °C. This rate may be compared to the rate of formation of acetic acid from methanol in the benchmark Monsanto process: 380 x 10-4 M/min at 180 °C.

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