Time-resolved in situ measurements and predictions of plasma-assisted methane reforming in a nanosecond-pulsed discharge

This study investigates the plasma properties and chemical kinetics of plasma-assisted methane reforming in a He diluted nanosecond-pulsed plane-to-plane dielectric barrier discharge (ns-DBD) through the combination of time-resolved in situ laser diagnostics and a 1-D numerical model. Plasma-assisted fuel reforming kinetic mechanisms have predominantly been evaluated on the basis of matching reactant conversion and syngas production to steady-state measurements, which cannot describe the full range of chemistry and physics necessary to validate the model. It was found that adding 1% CH4 to a pure He ns-DBD led to a faster breakdown along the rising edge of the applied voltage pulse, thereby lowering the reduced electric field (E/N), electron number density, and electron temperature. Further addition of CH4 did not continue to alter the E/N in the model. Laser absorption spectroscopy was used to measure gas temperature, C2H2, H2O, and CH2O in a CH4/CO2/He discharge to serve as validation targets for the predicted reaction pathways. CH2O was predicted within 25% of the measured value, while H2O and C2H2 were under-predicted by a factor of two and three, respectively. From path flux analysis, the major pathway for CH2O formation was through the reaction between CH3 and O, while C2H2 formation had multi-step pathways that relied on ions like CH3+ and C2H5+. The path flux analysis also shows that CH2 is a significant intermediate for production of both CH2O and C2H2, and increased CH2 concentration could improve model predictions. The results show that the use of reaction rate constants with lower uncertainties and inclusion of He-2(+) are needed to improve the predictions. Finally, varying the "equivalence ratio", defined by the CH4 dry reforming reaction to H-2 and CO, from 0.5 to 2 was shown to have a weak effect on measured product species and experimental trends were explained based on pathways extracted from the model. (c) 2020 The Combustion Institute. Published by Elsevier Inc. All rights reserved.