Basic approach to evaluate methane partial oxidation catalysts

Abstract

The partial oxidation of methane to formaldehyde by molecular oxygen on silica and silica-supported oxide catalysts has been investigated at a pressure of 1.7 bars in the temperature range 520-650°C by using a batch reactor with external recycle. The effects of reactor diameter recycle flow, catalyst weight, and methane-to-oxygen ratios on the catalyst activity have been outlined. By performing several blank tests with an empty and a quartz-filled reactor, it has been demonstrated that the gas-phase reaction does not affect the catalytic pathways. Reasons for controversial results reported previously are discussed. They lie in the lack of an adequate experimental approach and in the generally adopted rule to evaluate the catalytic activity at differential conditions in order to push the HCHO selectively to high values. The approach presented here allows the evaluation of the catalytic activity by performing tests at quasi-zero conversion per pass, but at a finite extent of conversion. The need to express the catalytic activity as space time yield (STY) to HCHO g.kg (cat) (-1).h-1 is presented. The reactivates of various commercial SiO2 samples obtained by precipitation, sol-gel, and pyrolysis methods have been determined. The fact that the nature and source of silica has a marked effect on STY, previously observed for reaction at 520°C, has been confirmed for operation at 550-650°C. Highest STYs are found with precipitation silica samples. In fact, at 650°C with such precipitated SiO2 a STY to HCHO of 303.kg (cat) (-1) has been obtained. Incorporation of molybdena depresses the STY value for the precipitated or fumed silica’s leads to higher STY values.