Combustion Chemistry of Unsaturated Hydrocarbons Mixed with NOx: A Review with a Focus on Their Interactions

Abstract

Unsaturated hydrocarbons are major components of transportation fuels, combustion intermediates, and unburnt exhaust emissions. Conversely, NOx species are minor species present in the residual and exhaust gases of gasoline-fueled engines and gas turbines. Their co-existence in transportation engines is quite common, particularly with exhaust gas recirculation, which can greatly influence engine combustion characteristics. Therefore, this paper presents a review on the combustion chemistry of unsaturated hydrocarbons and NOx mixtures, with a focus on their chemical kinetic interactions. First, a comprehensive overview of fundamental combustion experiments is provided, covering mixtures of C2–C5 unsaturated/oxygenated species (namely alkenes, alkynes, dienes, alcohols, ethers, ketones, and furans) and three major NOx species (namely NO, NO2, and N2O), as well as reactors including jet-stirred reactors, flow reactors, burners, shock tubes, and rapid compression machines. Then, two widely adopted nitrogen chemistry models are evaluated in conjunction with a core chemistry model (i.e., NUIGMech1.1) via detailed chemical kinetic modeling, and the model similarities and differences across broad temperature ranges are highlighted. Thereafter, the unique interconversions between the three major NOx species are presented. In particular, the controversy regarding the pathways governing NO and NO2 conversion is discussed. Following this, the key direct interaction reactions between unsaturated species and NOx species are overviewed. Finally, the distinguishing features of the combustion chemistry for unsaturated hydrocarbon and NOx mixtures are summarized, and recommendations for future research on this topic are highlighted.