On the mechanism of the selective catalytic reduction of NO with higher hydrocarbons over a silver/alumina catalyst

• Published in: Journal of catalysis 2004-10, Vol.227 (2), p.328-343
• Main Authors: Eränen, Kari, Klingstedt, Fredrik, Arve, Kalle, Lindfors, Lars-Eric, Murzin, Dmitry Yu
• Format: Article
• Language: English
• Subjects: Ag/alumina catalyst; Catalysis; Chemistry; Exact sciences and technology; Gas-phase reaction; GC-MS; General and physical chemistry; HC-SCR; Hydrogen effect; Reaction mechanism; Theory of reactions, general kinetics. Catalysis. Nomenclature, chemical documentation, computer chemistry
• ISSN: 0021-9517; 1090-2694
• DOI: 10.1016/j.jcat.2004.07.026

The possibility of forming nitrogen in the gas phase by reaction of activated forms of NO x with amines and ammonia as well as with other organic intermediates, which can be converted to amines and/or ammonia, was investigated. The activation of NO was carried out by passing NO together with oxygen and small amounts of hydrogen over an Ag/alumina catalyst. A special T-shaped reactor was used to produce activated forms of NO x and to feed model compounds of proposed intermediates to the gas phase after the catalyst. Nitrohexane, hexylisocyanate, heptanenitrile, hexylamine, and ammonia were used as model compounds. The T-reactor tests showed that both ammonia and hexylamine react in the gas phase with activated NO x species producing N 2. Hydrogen was shown to have at least two main functions. First, hydrogen contributed to improved oxidation of all involved species, resulting in faster production of key intermediates. Secondly, hydrogen assisted in the formation of activated NO x species for the gas-phase reactions. Nitrohexane was transformed to NH 3 in the presence of O 2 over the Ag/alumina already at 250 °C and the amounts of NH 3 produced increased in the presence of H 2O. Hexylisocyante was hydrolyzed to amine and ammonia at 250 °C over the catalyst in the presence of O 2 but only to ammonia at 400 °C. At 250 °C the conversion to amine and ammonia was almost doubled by the addition of H 2O. Heptanenitrile was quite stable and only small amounts of NH 3 were observed at 400 °C; however, nitriles may react directly with activated forms of NO x forming N 2. The importance of gas-phase reactions as a part of the HC-SCR mechanism is emphasized. R-NO 2, R-NCO, and R-CN are intermediates for the formation of amines and ammonia, which are consumed both on the surface of the catalyst and in the gas phase behind the catalyst bed by reactions with activated NO x species.