Catalytic performance and reaction mechanisms of NO removal with NH3 at low and medium temperatures on Mn-W-Sb modified siderite catalysts.

Iron-based catalysts have been explored for selective catalytic reduction (SCR) of NO due to environmentally benign characters and good SCR activity. Mn-W-Sb modified siderite catalysts were prepared by impregnation method based on siderite ore, and SCR performance of the catalysts was investigated. The catalysts were analyzed by X-ray diffraction, H2-temperature-programmed reduction, Brunauer-Emmett-Teller, Thermogravimetry-derivative thermogravimetry and in-situ diffused reflectance infrared Fourier transform spectroscopy (DRIFTS). The modified siderite catalysts calcined at 450°C mainly consist of Fe2O3, and added Mn, W and Sb species are amorphous. 3Mn-5W-1.5Sb-siderite catalyst has a wide temperature window of 180-360°C and good N2 selectivity at low temperatures. In-situ DRIFTS results show NH4+, coordinated NH3, NH2, NO3- species (bidentate), NO2- species (nitro, nitro-nitrito, monodentate), and adsorbed NO2 can be discovered on the surface of Mn-W-Sb modified siderite catalysts, and doping of Mn will enhance adsorbed NO2 formation by synergistic catalysis with Fe3+. In addition, the addition of Sb can inhibit sulfates formation on the surface of the catalyst in the presence of SO2 and H2O. Time-dependent in-situ DRIFTS studies also indicate that both of Lewis and Brønsted acid sites play a role in SCR of NO by ammonia at low temperatures. The mechanism of NO removal on the 3Mn-5W-1.5Sb-siderite catalyst can be discovered as a combination of Eley-Rideal and Langmuir-Hinshelwood mechanisms with three reaction pathways. The mechanism of NO, oxidized by synergistic catalysis of Fe3+ and Mn4+/3+ to form NO2 among three pathways, reveals the reason of high NOx conversion of the catalyst at medium and low temperatures.

[Experimental studies on low-temperature selective catalytic reduction of NO on magnetic iron-based catalysts].

Low-temperature selective catalytic reduction (SCR) of NO is a new technique needing urgent development in flue gas cleaning. Elementary studies were done about selective catalytic reduction of NO from flue gas on magnetic iron oxides with ammonia at low and medium temperatures in a fluidized bed, such as Fe3O4 and gamma-Fe2O3. Magnetic field effects for NO removal on gamma-Fe2O3 were also researched with low assisted magnetic fileds. X-ray diffraction spectroscopy was used to identify and characterize the iron oxides catalysts. Results show that gamma-Fe2O3 is active in SCR at low temperatures, and Fe3O4 is apparently less active in SCR than gamma-Fe2O3, but Fe2O3 is also active in ammonia oxidation by O2 above 25 degrees C. Therefore, the optimal catalytic temperature zone in SCR on gamma-Fe2O3 includes 250 degrees C and adjacent temperature zone below it. Furthermore, a better NO conversion, which is 90%, is obtained at 250 degrees C on the gamma-Fe2O3 particle catalyst. In addition, chemisorption of NO on gamma-Fe2O3 is accelerated by assisted magnetic fields at 150-290 degrees C, thus the NO conversion is improved and higher NO removal efficiency of 95% is obtained at 250 degrees C. But the efficiency of NO removal decreases above 290 degrees C with the magnetic field. It is concluded that gamma-FeO3 catalyst is fit to be used in low-temperature SCR of NO with ammonia at 200-250 degrees C, which may suppress oxidation of ammonia and take advantage of positive effects by external magnetic fields.