Quantification of NO in the post-flame region of laminar premixed ammonia/hydrogen/nitrogen-air flames using laser induced fluorescence

Abstract

Ammonia-based fuels have been identified as a promising alternative as zero-carbon energy carriers due to their high energy density and simpler logistics compared to hydrogen. As a disadvantage, the presence of fuel-bound nitrogen can lead to order of magnitude higher emissions of undesired nitric oxide (NO), nitrogen dioxide (NO₂) and nitrous oxide (N₂O) compared to more conventional fuels. Presently, chemical kinetics schemes for the combustion of ammonia and ammonia blends show large variations in the prediction of NO and there is a lack of quantitative experimental data to validate and optimize these reaction mechanisms. This paper presents measurements of NO in the product gases of laminar premixed NH₃/H₂/N₂ air flames on a flat-flame burner for 4 different ammonia decomposition ratios and over a range of equivalence ratios using laser-induced fluorescence in the NO A-X (0,1) system. A linear calibration approach based on the addition of NO to a lean premixed CH₄ flame is presented. Initial signal treatment includes the correction of laser absorption, fluorescence absorption (signal trapping) and fluctuations in laser energy. The LIF signals are corrected for changes in the Boltzmann fraction, line overlap, number density, and quenching between calibration and measurement, which requires knowledge of the local temperature and mole fractions of the main species. Temperature measurements using N₂ thermometry, where a theoretical N₂ Raman spectrum is fitted to an experimental N₂ Raman signal, excited by a 532 nm cw laser, allow characterization of the local near-adiabatic flame conditions as a function of operating conditions and adjustment of the signal corrections to the local temperature. Major species are extracted from 1-D simulations. The measured NO mole fractions are compared with five recent chemical kinetic schemes, which show good agreement for rich mixtures, however, a systematic underprediction of NO is found for stoichiometric and lean mixtures.

Novelty and significance

Emissions of NO are a major challenge for advancement of ammonia as a carbon-free fuel, yet very few measurements of NO levels in ammonia flames exist in the literature. In this paper, we present much needed quantitative experimental data on NO emissions from premixed NH₃/H₂/N₂-air flames using laser-induced fluorescence (LIF). Our diagnostic approach employs a linear calibration method based on the addition of NO to a lean CH₄ flame. Post-flame temperatures are measured by Raman spectroscopy to ensure accuracy of the local thermochemical states used in converting LIF signals to quantitative NO concentrations, accounting for variations in number density, electronic quenching, Boltzmann fraction, and the line overlap integral. Additionally, laser absorption and signal trapping are corrected using the spatial shape of the LIF signal. The presented data set can be used by modelers to refine chemical kinetic models with respect to NO emissions.