Estimation and testing of single-step oxidation reactions for hydrogen and methane in low-oxygen, elevated pressure conditions

Abstract

Advanced combustion concepts, such as moderate or intense low-oxygen dilution (MILD) combustion, offer a reduction in NOx emissions and increased thermal efficiency. MILD is characterised by low-oxygen, high-temperature conditions, where finite-rate chemistry effects are significant. Modelling this regime using reduced or single-step chemistry remains a challenge in part due to the finite-rate chemistry. This work proposes a generalised method for assigning Arrhenius coefficients of a single-step reaction using the outputs of a detailed mechanism. Assigning the typical chemical conservation equation to a progress variable, activation energy and pre-exponential factor for an Arrhenius kinetics global reaction are determined for hydrogen and methane across a number of conditions, with the proposed method extended to n-heptane as well. The temperature exponent in the modified Arrhenius equation is determined by minimising the ignition delay error between detailed and single-step simulations. Functional forms of each coefficient are calculated from a multivariate regression, dependent on initial temperature, pressure, and oxidant mole fraction. The predicted mechanisms are compared against the detailed kinetics in closed homogeneous batch reactors, with comparisons for hydrogen extended to both laminar opposed flow diffusion flames, and computational fluid dynamics (CFD) simulations. Ignition delay and equilibrium temperature are both well predicted for all three fuels in the batch reactors. Notably, the negative temperature coefficient behaviour of n-heptane is successfully recreated with the single-step mechanism. Temperature and heat release of hydrogen flames are well captured in both opposed flow laminar flames, and in turbulent CFD simulations. The computational time was also significantly reduced through the single-step mechanisms, resulting in ∼100 times reduction in compute time for CFD simulations. The function form of the Arrhenius coefficients shows promise for extension outside of the ranges and fuels analysed herein, and presents interesting phenomena for exploring how initial reactant temperature and pressure influence the effective activation energy of an oxidation process.