A kinetic model was developed to describe the reactions of CO and H2 to CH4 and C2H2in a microwave plasma. The experimental system consisted of a 24 mm I.D. tubular quartz reactor which passed through a microwave cavity. A variable-incident power waveguide system could supply up to 800 watts of incident microwave power to the cavity. The reactant gas mixture of H2 and CO flowed through the reactor, where a plasma was maintained under pressures of 20 - 100 mm Hg. The reactor effluent was analyzed by IR spectroscopy for CH4 and C2H2. Conversions of up to 5.3% CO to C2H2 and 7.2% CO to CH4 were observed. A 26-reaction kinetic model was developed and fitted to the experimental data. The plasma reactor was modeled in two zones: a discharge zone where electron-impact dissociations produce H, C, and O, and a downstream recombination zone where the atomic species from the discharge recombine. The discharge zone was modeled as a well-mixed reactor, and the recombination zone was modeled as a plug-flow reactor. The model was able to explain the asymptotic shape of the observed conversion versus residence time data; the effect is due to a kinetic limitation. This also explains why the conversions obtained in the plasma cannot be predicted by thermodynamic equilibrium.
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Mertz et al. (1976) studied this question.