Ignition enhancement and NO_x formation of NH₃/air mixtures by non-equilibrium plasma discharge

This work computationally studies plasma assisted low temperature NH₃/air ignition and NO_x formation in a repetitively-pulsed nanosecond discharge at atmospheric pressure by using an experimentally-validated plasma-combustion kinetic model. The results show that plasma discharge significantly enhances low temperature NH₃ ignition. Compared with thermal ignition, the ignition delay time is shortened by 2–5 orders of magnitude due to the kinetic enhancement of excited species and radicals. The radicals (NH₂, NH, H and O) produced through electron impact dissociation and quenching of electronically excited N₂*, O(¹D) and N(²D) promote OH production and further accelerate NH₃ oxidation. The results show that there exists a non-monotonic dependence of ignition delay time on the reduced electric field strength. The optimum ignition enhancement is achieved at 250 Td at which the production of electronically excited species and radicals is most efficient. The vibrationally excited species produced at lower electric fields (<100 Td) are less effective in enhancing ignition because they only induce gas heating through the fast vibrational-translational relaxation by NH₃ and H₂O. At a higher electric field, although the efficient production of NH₂, NH, H, O and OH by plasma creates new low temperature reaction pathways in enhancing low temperature NH₃ ignition, the ignition is inhibited through NH + NO = N₂O + H and chain-termination reaction NH₂ + HO₂ = NH₃ + O₂. The ignition delay times at different equivalence ratios show that the ignition enhancement by plasma is more effective at fuel-lean conditions due to the faster generation of N₂(B), O(¹D) and O from air, leading to accelerated NH₃ oxidation via O(¹D) + NH₃ → NH₂ + OH, NH₃ + O = NH₂ + OH and NH₂ + O = NH + OH. The sensitivity analysis shows that the reactions involving O and O(¹D) production are more effective on NH₃ ignition enhancement than the fuel dissociation by electrons. Moreover, the ignition is also enhanced by NO_x formation in plasma via reactions NH₂ + NO = NNH + OH and NO + HO₂ = NO₂ + OH. This work advances the understanding of non-equilibrium excitation and NO_x formation by plasma discharge on low temperature NH₃ ignition. © 2023 The Combustion Institute