Partial oxidation of methane and ethane in the presence of catalysts

The catalytic partial oxidation of various mixtures of methane and ethane with oxygen has been studied by the dynamic method at atmospheric pressure within the temperature range 100° to 700°C. Some experiments have also been made with a natural gas under similar conditions.

For the production of alcoholic or aldehydic intermediates, catalysts of copper and silver, oxides of these metals, activated charcoal, platinum oxide, and barium peroxide proved unsatisfactory on the basis of hydrocarbon consumed and products obtained.

Small amounts of nitrogen dioxide, when added to hydrocarbon-oxygen mixtures and passed through heated capillary tubes, were found to promote the oxidation materially. Yields of oxygenated derivatives varying from 15 to 30 per cent by volume of the amount of hydrocarbon used were obtained. As much as 38 per cent of the hydrocarbon has been decomposed in a single pass through the catalytic chamber.

Auxiliary catalysts used in conjunction with nitrogen dioxide activated the decomposition of intermediate oxidation products without materially increasing the amount of hydrocarbon decomposed.

Methyl nitrite has been shown to exert a promoting action in partial oxidation reactions of hydrocarbons.

An explanation is offered of the effect of small amounts of nitrogen dioxide and methyl nitrite on the partial oxidation of aliphatic hydrocarbons.

The hydroxylation theory of the combustion of hydrocarbons has been further confirmed by thermodynamic considerations as well as by experimental evidence.