Autoignition studies of NH3/CH4 mixtures at high pressure

Autoignition delay times of NH3/CH4 mixtures with CH4 fractions of 0%, 5%, 10% and 50% were measured in a rapid compression machine at equivalence ratio phi = 0.5, pressures from 20 to 70 bar and temperatures from 930 to 1140 K. In addition, measurements were performed for NH3 mixtures with 10% CH4 at phi = 1.0 and 2.0. Methane shows a strong ignition-enhancing effect on NH3, which levels off at higher CH4 fractions, as the ignition delay time approaches that of pure methane. Autoignition delay times at 10% CH4 at phi = 0.5 and 1.0 are indistinguishable, while an increase of ignition delay times by factor of 1.5 was observed upon increasing phi to 2.0. The experimental data were used to evaluate six NH3 oxidation mechanisms capable of simulating NH3/CH4 mixtures. The mechanism previously used by the authors shows the best performance: generally, it predicts the measured ignition delay times to better than 30% for all conditions, except for 50% CH4 addition for which the differences increase up to 50% at the highest temperature. Sensitivity analysis based on the mechanism used indicates that under lean conditions the reaction CH4 + NH2 = CH3 + NH3 significantly promotes ignition for modest CH4 addition (5% and 10%), but becomes modestly ignition-inhibiting at 50% CH4. Sensitivity and rate-of-production analyses indicate that the ignition-enhancing effect of 50% CH4 addition is closely related to the formation and decomposition of H2O2. Flux analysis for NH3/CH4 mixtures indicates that CH4 + NH2 = CH3 + NH3 contributes substantially to the decomposition of methane early in the oxidation process, while CH3 + NO2 (+M) = CH3 NO2 (+M) is a significant reservoir of NO2 at low temperature. Additionally, an anomalous pre-ignition pressure rise phenomenon, which is not reproduced by the simulations, was observed with high reproducibility for the NH3 mixture with 50% CH4 addition. (C) 2020 The Combustion Institute. Published by Elsevier Inc. All rights reserved.