András György Szanthoffer, Máté Papp, Peter Glarborg, Hamid Hashemi, István Gyula Zsély, Tamás Turányi
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引用次数: 0
Abstract
The thermal DeNOx process is a widely used NOx emission control technique, but its chemical kinetic description still lacks accuracy. In the present work, two key kinetic parameters of the thermal DeNOx process were investigated: the branching fraction (α) of the NH2 + NO reaction, and the rate coefficient of the unimolecular decomposition of NNH (inverse lifetime of NNH, τNNH). Values of these rate parameters were determined using a mechanism optimization method that utilizes both direct and indirect data and minimizes the value of an error function. Data were collected from the literature and available in data files on the ReSpecTh site (https://ReSpecTh.hu). Indirect experimental data used as optimization targets were NO mole fractions measured in tubular flow reactors. The most recent nitrogen chemistry mechanism of Glarborg and coworkers (2024) was used as the initial mechanism. Inconsistency was found between the indirect experimental data, and therefore mechanism optimization was not feasible using all the indirect data. Using a new algorithm, a consistent subset of indirect data was identified. The optimized value of τNNH (8.5 ∙ 10−11 s) is approximately an order of magnitude smaller than in the initial mechanism (10−9 s), but consistent with theoretical calculations. The posterior uncertainty of τNNH is significantly smaller than its prior uncertainty. The optimized value of the branching fraction is different from its initial value by less than 2%, but due to the very large sensitivity of the simulation results to α, this small change improves the performance of the mechanism noticeably. The width of the posterior uncertainty range of α is approximately half that of its prior uncertainty range, estimated using only direct measurements. This is a significant improvement, but more accurate indirect experimental data are needed to further increase the accuracy of the determination of α.
期刊介绍:
As the leading archival journal devoted exclusively to chemical kinetics, the International Journal of Chemical Kinetics publishes original research in gas phase, condensed phase, and polymer reaction kinetics, as well as biochemical and surface kinetics. The Journal seeks to be the primary archive for careful experimental measurements of reaction kinetics, in both simple and complex systems. The Journal also presents new developments in applied theoretical kinetics and publishes large kinetic models, and the algorithms and estimates used in these models. These include methods for handling the large reaction networks important in biochemistry, catalysis, and free radical chemistry. In addition, the Journal explores such topics as the quantitative relationships between molecular structure and chemical reactivity, organic/inorganic chemistry and reaction mechanisms, and the reactive chemistry at interfaces.