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Emission Control Science and Technology
Erschienen in: Emission Control Science and Technology 3/2018

24.07.2018 | Special Issue: 2017 CLEERS October 3 - 5, Ann Arbor, MI, USA

Development and Validation of a Two-Site Kinetic Model for NH3-SCR over Cu-SSZ-13. Part 1. Detailed Global Kinetics Development Based on Mechanistic Considerations

verfasst von: Rohil Daya, Chintan Desai, Bruce Vernham

Erschienen in: Emission Control Science and Technology | Ausgabe 3/2018

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Abstract

In this study, we present the first of two parts in the development and validation of a two-site detailed global kinetic model for NH3 Selective Catalytic Reduction (SCR) over a well-characterized Cu-SSZ-13 catalyst. Based on fundamental literature studies and experimental data for two distinct hydrothermal aging conditions, it was observed that at least two distinct sites were necessary to describe the storage, oxidation, and SCR behavior for this catalyst. The site definitions were allocated based on analysis of simulated net desorption rates during the NH3-TPD experiment. The S1 sites were associated with extra framework copper ions stabilized by -OH ligands (ZCuOH), likely located near the eight-membered ring CHA cages, along with Brønsted acid sites, while S2 sites were associated with copper ions attached directly to the repeating units (Z2Cu) near the six-membered rings, along with physisorbed NH3 sites and low temperature transient copper dimers. The selective NH3 oxidation and NO oxidation reactions were only modeled over S1, in line with the expected catalytic sites for these reactions. Standard, fast, and NO2 SCR reactions were modeled on both sites, with different activation energies. Finally, noticeable nitrate-based hysteresis effects were observed, in both N2O concentrations and fast SCR NO conversions. These were accounted for by explicitly modeling nitrate formation, titration by NO, and thermal decomposition to N2O. The developed SCR model was validated with additional reactor data at nominal inlet NH3-to-NOx ratios (ANRs) of 0.8 and 1.2. In general, the model showed good predictability in the temperature range of 150–550 °C for both hydrothermal ageing conditions and space velocities. Further full-scale engine dynamometer validation and development of a downstream NH3 slip catalyst (ASC) reaction-diffusion model will be reported in the second part of the paper.
Vorheriger Artikel Sensitivity of Three-Way Catalyst Light-Off Temperature to Air-Fuel Ratio
Nächster Artikel Development and Validation of a Two-Site Kinetic Model for NH3-SCR over Cu-SSZ-13. Part 2. Full-Scale Model Validation, ASC Model Development, and SCR-ASC Model Application

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Fußnoten
1
It was observed that the quality of the N2 readings from the MS was relatively poor when CO2 was present in the feed gas. Ordinarily, N2 at a mass-to-charge (m/e) ratio of 28 is relatively easy to measure with the MS. However, 5% CO2 in the gas stream created a problem, as there was sizeable fragmentation from CO2 to CO+, which is picked up at m/e 28. At a typical electron filament energy of 70 ev, the CO+ from the CO2 completely overwhelmed the small signal from N2 at m/e 28. Since CO2 had absolutely no influence over any of the experiments (this was confirmed in further independent experiments).
 
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Metadaten
Titel
Development and Validation of a Two-Site Kinetic Model for NH3-SCR over Cu-SSZ-13. Part 1. Detailed Global Kinetics Development Based on Mechanistic Considerations
verfasst von
Rohil Daya
Chintan Desai
Bruce Vernham
Publikationsdatum
24.07.2018
Verlag
Springer International Publishing
Erschienen in
Emission Control Science and Technology / Ausgabe 3/2018
Print ISSN: 2199-3629
Elektronische ISSN: 2199-3637
DOI
https://doi.org/10.1007/s40825-018-0095-5

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