Combustion of ethylamine, dimethylamine and diethylamine: Theoretical and kinetic modeling study

Abstract Aliphatic amines are an important class of nitrogen-containing compounds present in renewable fuels such as bio-oils. Conversion of this fuel-bound nitrogen can lead to the formation of HCN and NH3, as well as NOx emissions. In this work, the combustion chemistry of small aliphatic amines is investigated via a combination of quantum chemical calculations, chemical kinetic modeling and experimental validation. The influence of the degree of substitution on the nitrogen atom and the alkyl chain length on the reactivity and product distribution is studied via three model compounds, i.e. ethylamine (EA, CH3CH2NH2), dimethylamine (DMA, (CH3)2NH) and diethylamine (DEA, (CH3CH2)2NH). A detailed kinetic model containing 258 species and 2274 reactions is developed to describe their combustion over a wide range of conditions. The proposed model captures the trends in ignition delay times and species concentrations over a temperature range from 500 to 2000 K and pressures from 4 to 170 kPa. The ignition delay data are predicted with an average deviation of 10%. The difference between experimental and simulated species concentrations from laminar premixed flames is for the major species on average 50%, while the agreement for the JSR is even better, with an average deviation of 10%. The dominant decomposition pathway under all the studied conditions is a set of hydrogen abstractions from the Cα and N positions followed by β-scission of the fuel radicals. Among the unimolecular decomposition pathways, the homolytic C C and C N scissions and four-centered elimination play a minor role. HCN is the main intermediate and at temperatures above 1100 K the amines are completely converted to N2 and NO.