Numerical Modeling of Hydroperoxyl-Mediated Oxidative Dehydrogenation of Formic Acid under SCR-Relevant Conditions
| Autor: | John Mantzaras, Jeroen A. van Bokhoven, Oliver Kröcher, Manasa Sridhar |
|---|---|
| Rok vydání: | 2018 |
| Předmět: |
010405 organic chemistry
Formic acid General Chemical Engineering Selective catalytic reduction General Chemistry 010402 general chemistry Photochemistry 01 natural sciences Decomposition Industrial and Manufacturing Engineering 0104 chemical sciences Catalysis chemistry.chemical_compound chemistry Hydroperoxyl 13. Climate action Ammonium formate Formate Dehydrogenation |
| Zdroj: | Industrial & Engineering Chemistry Research. 57:10206-10215 |
| ISSN: | 1520-5045 0888-5885 |
| DOI: | 10.1021/acs.iecr.8b01592 |
| Popis: | Formic acid decomposition to carbon dioxide is an important step during the decomposition of alternative formate-based ammonia precursor compounds, such as ammonium formate, guanidinium formate, and methanamide, in the selective catalytic reduction (SCR) process. At oxygen and water concentrations prevalent in a typical SCR feed, an oxidative dehydrogenation (ODH) type pathway of formic acid decomposition proceeds on titania-supported gold catalysts. Using the surface perfectly stirred reactor (SPSR) model, the ODH mechanism is demonstrated to satisfactorily predict the experimentally observed conversions. The single-site mechanistic model captured the negative trend in conversion with increasing formic acid concentrations, stemming from an extensive coverage of the active sites by formates. This in turn rendered the active sites unavailable for the formation of the active hydroperoxyls required for the rate-determining step of C–H bond scission of formates. The positive order dependency on oxygen concent... |
| Databáze: | OpenAIRE |
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