An experimental and kinetic modeling study of NOx sensitization on methane autoignition and oxidation

An experimental and kinetic modeling study of the influence of NOx (i.e. NO2, NO and N2O) addition on the ignition behavior of methane/‘air’ mixtures is performed. Ignition delay time measurements are taken in a rapid compression machine (RCM) and in a shock tube (ST) at temperatures and pressures ranging from 900–1500 K and 1.5–3.0 MPa, respectively for equivalence ratios of 0.5–2.0 in ‘air’. The conditions chosen are relevant to spark ignition and homogeneous charge compression ignition engine operating conditions where exhaust gas recirculation can potentially add NOx to the premixed charge. The RCM measurements show that the addition of 200 ppm NO2 to the stoichiometric CH4/oxidizer mixture results in a factor of three increase in reactivity compared to the baseline case without NOx for temperatures in the range 600–1000 K. However, adding up to 1000 ppm N2O does not show any appreciable effect on the measurements. The promoting effect of NO2 was found to increase with temperature in the range 950–1150 K, while the sensitization effect decreases at higher pressures. The experimental results measured are simulated using NUIGMech1.2 comprising an updated NOx sub-chemistry in this work. A kinetic analysis indicates that the competition between the reactions ĊH3 + NO2 ↔ CH3Ȯ + NO and ĊH3 + NO2 (+M) ↔ CH3NO2 (+M), the former being a propagation reaction and the latter being a termination reaction governs NOx sensitization on CH4 ignition. Recent calculations by Matsugi and Shiina (A. Matsugi, H. Shiina, J. Phys. Chem. A. 121 (2017) 4218–4224) for the nitromethane formation reaction CH3 + NO2 (+M) ↔ CH3NO2 (+M), together with the recently calculated rate constants for HONO/HNO2 reactions significantly improve ignition delay time predictions in the temperature range 600–1000 K. Furthermore, the experiments with NO addition reveal a non-monotonous sensitization impact on CH4 ignition at lower temperatures with NO initially acting as an inhibitor at low NO concentrations and then as a promoter as NO concentrations increase in the mixture. This non-monotonous trend is attributed to the role of the chain-termination reaction ĊH3 + NO2 (+M) ↔ CH3NO2 (+M) and the impact of NO on the transition to the chain-branching steps CH2O + HȮ2 ↔ HĊO + H2O2, H2O2 (+M) ↔ ȮH + ȮH (+M), HĊO ↔ CO + Ḣ followed by CO + O2 ↔ CO2 + Ö and Ḣ + O2 ↔ Ö + ȮH. NUIGMech1.2 is systematically validated against the new ignition delay measurements taken here together with species measurements and high temperature ignition delay time data available in the literature for CH4/oxidizer mixtures diluted with NO2/N2O/NO and is observed to accurately capture the sensitization trends.