Modeling the thermal DENOx process in flow reactors. Surface effects and Nitrous Oxide formation

We have investigated the impact of surface reactions such as NH₃ decomposition and radical adsorption on quartz flow reactor data for Thermal DeNO_x using a model that accounts for surface chemistry as well as molecular transport. Our calculations support experimental observations that surface effects are not important for experiments carried out in low surface to volume quartz reactors. The reaction mechanism for Thermal DeNO_x has been revised in order to reflect recent experimental results. Among the important changes are a smaller chain branching ratio for the NH₂ + NO reaction and a shorter NNH lifetime than previously used in modeling. The revised mechanism has been tested against a range of experimental flow reactor data for Thermal DeNO_x with reasonable results. The formation of N₂O in Thermal DeNO_x has been modelled and calculations show good agreement with experimental data. The important reactions in formation and destruction of N₂O have been identified. Our calculations indicate that N₂O is formed primarily from the reaction between NH and NO, even though the NH₂ + NO₂ reaction possibly contributes at lower temperatures. At higher temperatures N₂O concentrations are limited by thermal dissociation of N₂O and by reaction with radicals, primarily OH. © 1994 John Wiley & Sons, Inc.