| Abstract
| - This report describes a highly catalytic bimetallic system for thelow temperature selective oxidation ofmethane, ethane, and butane with dioxygen as the oxidant. Thecatalytic system consists of a mixture of copperchloride and metallic palladium and operates in a 3:1 mixture (v/v) oftrifluoroacetic acid and water in the presenceof dioxygen and carbon monoxide. Methane was selectively convertedto methanol. The dependence of the reactionrate on the partial pressure of methane was measured, and saturationkinetics was observed. The dependence of therate on the partial pressure of carbon monoxide was measured at twodifferent pressures of methane, and a first-order dependence on the partial pressure of carbon monoxide was observedin both instances. The activation parametersfor the overall reaction were obtained under the reaction conditionswhen the rate was first order in both methaneand carbon monoxide. The values obtained were A = 2× 104 s-1 andEa = 15.3 kcalmol-1. Both C−H and C−Ccleavage products were observed for ethane and n-butane,resulting in the formation of methanol, ethanol, andaceticacid. The rate of formation of methanol from methane with thebimetallic system was ca. 65 × 10-4 M/minat145−150 °C. This rate may be compared to the rate of formationof acetic acid from methanol in the benchmarkMonsanto process: 380 × 10-4 M/min at 180°C.
|
