Ammonia chemistry below 1400 K under fuel-rich conditions in a flow reactor

The oxidation of NH₃ under fuel-rich conditions and moderate temperatures has been studied in terms of a chemical kinetic model over a wide range of conditions, based on the measurements of Hasegawa and Sato. Their experiments covered the fuels hydrogen (0 to 80 vol%), carbon monoxide (0 to 95 vol%), and methane (0 to 1.5 vol%), stoichiometries ranging from slightly lean to very fuel rich, temperatures from 300 to 1330 K, and NO levels from 0 to 2500 ppm. A detailed reaction mechanism has been established, based on earlier work on ammonia oxidation in flames and on selective noncatalytic reduction of NO by NH₃. The kinetic model reproduces the experimental trends qualitatively over the full range of conditions covered, and often the predictions are in quantitative agreement with the observations. Using reaction path analysis and sensitivity studies, the major reaction paths have been identified. The comparatively low temperatures in the present study, as well as the presence of NO, promote the reaction path NH₃→NH₂→N₂ (directly or via NNH), rather than the sequence NH₃→NH₂→NH→N important in flames. The major conversion of fuel-N species to N₂ occurs by reaction of amine radicals with NO, in particular NH₂+NO. In the presence of CH₄, NO is partly converted to cyanides by reaction with CH₃. The mechanism is recommended for modeling the reduction of NO by primary measures in the combustion of biomass, since it has been validated under conditions resembling the conversion of early nitrogenous volatile species in a staged combustion process. It is also appropriate for studies of NO formation in the combustion of gas from gasifying coal.