Plasma-assisted partial oxidation of methane at low temperatures: numerical analysis of gas-phase chemical mechanism

Abstract

Methane partial oxidation was investigated using a plasma microreactor. The experiments were performed at 5 and 300 °C. Microreactor configuration allows an efficient evacuation of the heat generated by methane partial oxidation and dielectric barrier discharges, allowing at the same time a better temperature control. At 5 °C, liquid condensation of low vapour pressure compounds, such as formaldehyde and methanol, occurs. 1H-NMR analysis allowed us to demonstrate significant CH3OOH formation during plasma-assisted partial oxidation of methane. Conversion and product selectivity were discussed for both temperatures. In the second part of this work, a numerical simulation was performed and a gas-phase chemical mechanism was proposed and discussed. From the comparison between the experimental results and the simulation it was found that CH3OO· formation has a determinant role in oxygenated compound production, since its fast formation disfavoured radical recombination. At 5 °C the oxidation leads mainly towards oxygenated compound formation, and plasma dissociation was the major phenomenon responsible for CH4 conversion. At 300 °C, higher CH4 conversion resulted from oxidative reactions induced by ·OH radicals with a chemistry predominantly oxidative, producing CO, H2, CO2 and H2O.