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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.

This paper presents the reaction mechanism of single-step methane partial oxidation to methanol at room temperature using non-thermal plasma microreactor. Macroscopic quantities of hydrogen peroxide (H2O2) and methyl hydroperoxide (CH3OOH) are produced when methane is partially oxidized at room temperature (about 5 °C). CH3OOH is known to be the principle intermediate of incomplete methane oxidation product such as CH3OH and HCHO, but has not been demonstrated experimentally so far. H2O2 promotes post-plasma oxidation of oxygenates in the condensed plasma-synthesized liquid. At an early stage of in-liquid oxidation, H2O2 oxidizes HCHO into HCOOH preferentially; subsequently, HCOOH is fully oxidized to CO2 and H2O. Depending upon the concentration of oxygenates and H2O2, electrical conductivity of the plasma solution dramatically increased, which detrimentally influences plasma properties. Methane partial oxidation with air was also investigated from a practical viewpoint. Generation of active nitrogen species (ANS) is the key to promoting overall methane conversion in the presence of oxygen; however, fragile oxygenates were also decomposed by ANS, thus selectivity for useful oxygenates was degraded in the presence of nitrogen. When oxygen is fully consumed, CH4 conversion is also terminated and water gas shift reaction (CO + H2O = CO2 + H2) becomes predominant.

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