Selective catalytic reduction of NO with ammonia over Fe3+-exchanged mordenite (Fe-MOR):: Catalytic performance, characterization, and mechanistic study

Fe-exchanged zeolites, i.e., mordenite (MOR), clinoptilolite (HEU), beta, ferrierite (FER), and chabazite (CHA), are studied as catalysts for selective catalytic reduction (SCR) of NO with NH(3). It is found that SCR activity decreases in the following order: Fe-MOR>Fe-HEU>Fe-FER>Fe-beta>Fe-CHA. Fe-MOR and Fe-HEU are much more active than the commercial vanadia catalyst. For Fe-MOR, SCR activity increases with a decreasing Si/Al ratio. Moreover, SO(2) and SO(2) + H(2)O improve SCR activity. On Fe-MOR, nearly 100% NO conversion is obtained at a high space velocity (GHSV = 4.6 x 10(5) h(-1)) in the presence of SO(2). The Fe-MOR catalysts are also characterized by H(2)-TPR (temperature-programmed reduction) and Fourier transform infrared (FT-IR) spectroscopy. TPR profiles indicate that iron cations in the catalysts are present as approximately 73% Fe(3+) and 27% Fe(2+). FT-IR spectra show that NO can be oxidized by O(2) to N(2)O(3), NO(2), and nitrate adsorbed species, and that they are bonded to the iron cations. NH(3) molecules adsorb on Bronsted acid sites of the zeolite to form NH(4)(+) ions. NO + O(2) is very active in reacting with NH(4)(+) ions on Fe-MOR at 300degreesC, but it is less active with those on 4 H-MOR. This is in good agreement with their SCR activities and is probably related to the fast formation of NO(2) on Fe-MOR. A possible reaction scheme for SCR reduction is proposed. NO reduction involves the reaction between NO(2) and a pair of NH(4)(+) ions to generate an active intermediate, which then reacts with NO to produce N(2) and H(2)O. NO oxidation to NO(2) is the rate-determining step. (C) 2002 Elsevier Science (USA).