A novel method for quantifying variations in NO formation pathways using a sub-mechanism accounting and reaction tracing algorithm

Abstract

This work presents a new implementation of reaction path analysis that traces molar fluxes attributable to various sub-mechanisms from inception through to their final product. The post-processing procedure involves creating a network of these fluxes and quantifying the contributions made by the specified formation and destruction mechanisms through an iterative process starting from the individual initiation reactions. A key distinction of this approach is that the reaction fluxes are directly correlated to their initiation reaction, which is then followed throughout the entire reaction network. This allows for the distinction of contribution to the formation of a target species from an arbitrary number of sources. The effectiveness of this approach is demonstrated by examining the formation of NO in three different case studies: (1) the impact of equivalence ratio on methane/air premixed counterflow flames, (2) the effect of hydrogen addition on ultra-lean methane/air premixed counter flames, and (3) the influence of pressure elevation in partially premixed methane/air flames. The results are presented in emission indexes, NO production rates throughout the flame, and multidigraphs illustrating the allocated flows between the species. Compared to replicated analysis methods previously used for these case studies, this new approach provides a more comprehensive and detailed analysis for several reasons. Firstly, the method does not require duplicated simulations with modified kinetic mechanisms, but is applied purely post-processing. This avoids the previous problems of needing to re-simulate the flame multiple times and allows for the fully coupled chemistry set. Secondly, the method allows for an arbitrarily defined set of initiation pathways which propagate through all possible routes within the network. This allows for the identification of spatial/temporal variability in the sub-mechanisms and thereby yields more information than the integral values of previous methods.Novelty and significance statementUnderstanding reaction pathways that lead to the formation of pollutants such as NO is an essential aspect in the development of new sustainable and low-emission combustion concepts. However, evaluating the different underlying sub-mechanisms is difficult due to the high degree of interconnectedness and spatial/temporal overlap of the reaction pathways. This work, therefore, presents a new algorithm that can be used to investigate the contributions of an arbitrary number of sub-mechanisms to the formation or decomposition of a species. The results can be expressed not only as integral values, but also as spatially and/or temporally resolved production rates and reaction path figures and graphs, leading to a more comprehensive and detailed analysis. The approach is also applied as a purely post-processing technique, which does not require multiple simulations with different chemical kinetic mechanisms as has previously be applied.