The open literature concerning chemical and mechanistic aspects of the selective catalytic reduction of NO by ammonia (SCR process) on metal oxide catalysts is reviewed. Catalytic systems based on supported V2O5 (including the industrial TiO2-supported V2O5–WO3 and/or V2O5–MoO3 catalysts) and catalysts containing Fe2O3, CuO, MnOx and CrOx are considered. The results of spectroscopic studies of the adsorbed surface species, adsorption–desorption measurements, flow reactor and kinetic experiments are analyzed. The proposed reaction mechanisms are described and critically discussed. Points of convergence and of disagreement are underlined.

Chemical and mechanistic aspects of the selective catalytic reduction of NOx by ammonia over oxide catalysts: A review

The infrared spectral performance of the N x O y species observed on oxide surfaces [N2O, NO−, NO, (NO)2, N2O3, NO+, NO2 − (different nitro and nitrito anions), NO2, N2O4, N2O5, NO2, and NO3 − (bridged, bidentate, and monodentate nitrates)] is considered. The spectra of related compounds (N2, H-, and C-containing nitrogen oxo species, C─N species, NH x species) are also briefly discussed. Some guidelines for spectral identification of N x O y adspecies are proposed and the transformation of the nitrogen oxo species on catalyst surfaces are regarded.

Identification of Neutral and Charged N x O y Surface Species by IR Spectroscopy

Catalytic removal of NO

A series of manganese-cerium oxide catalysts were prepared by co-precipitation method and used for low temperature selective catalytic reduction (SCR) of NO x with ammonia in the presence of excess O 2 . These catalysts were characterized by X-ray diffraction (XRD), surface area measurement and FTIR. The experimental results showed that the best Mn-Ce mixed-oxide catalyst yielded 95% NO conversion at 150 °C at a space velocity of 42,000 h −1 . As the manganese content was increased from 0 to 40% (i.e. the molar ratio of Mn/(Mn+Ce)), NO conversion increased significantly, but decreased at higher manganese contents. The most active catalyst was obtained with a molar Mn/(Mn+Ce) ratio of 0.4. Only N 2 rather than N 2 O was found in the product when the temperature was below 150 °C. At higher temperatures, trace amounts of N 2 O were detected. A mechanistic pathway for this reaction was proposed based on earlier findings and FTIR results obtained in this work. The initial step was the adsorption of NH 3 on Lewis acid sites of catalyst, followed by reaction with nitrite species to produce N 2 and H 2 O. Possible intermediates are proposed and all the intermediates could transform into NH 2 NO, which could further react to produce N 2 and H 2 O.

MnOx-CeO2 mixed oxides prepared by co-precipitation for selective catalytic reduction of NO with NH3 at low temperatures

Selective catalytic reduction with NH3 (NH3-SCR) is the most efficient technology to reduce the emission of nitrogen oxides (NOx) from coal-fired industries, diesel engines, etc. Although V2O5-WO3(MoO3)/TiO2 and CHA structured zeolite catalysts have been utilized in commercial applications, the increasing requirements for broad working temperature window, strong SO2/alkali/heavy metal-resistance, and high hydrothermal stability have stimulated the development of new-type NH3-SCR catalysts. This review summarizes the latest SCR reaction mechanisms and emerging poison-resistant mechanisms in the beginning and subsequently gives a comprehensive overview of newly developed SCR catalysts, including metal oxide catalysts ranging from VOx, MnOx, CeO2, and Fe2O3 to CuO based catalysts; acidic compound catalysts containing vanadate, phosphate and sulfate catalysts; ion exchanged zeolite catalysts such as Fe, Cu, Mn, etc. exchanged zeolite catalysts; monolith catalysts including extruded, washcoated, and metal-mesh/foam-based monolith catalysts. The challenges and opportunities for each type of catalysts are proposed while the effective strategies are summarized for enhancing the acidity/redox circle and poison-resistance through modification, creating novel nanostructures, exposing specific crystalline planes, constructing protective/sacrificial sites, etc. Some suggestions are given about future research directions that efforts should be made in. Hopefully, this review can bridge the gap between newly developed catalysts and practical requirements to realize their commercial applications in the near future.

Selective Catalytic Reduction of NOx with NH3 by Using Novel Catalysts: State of the Art and Future Prospects.

Manganese oxides of different crystallinity, oxidation state and specific surface area have been used in the selective catalytic reduction (SCR) of nitric oxide with ammonia between 385 and 575 K. MnO2 appears to exhibit the highest activity per unit surface area, followed by Mn5O8, Mn2O3, Mn3O4 and MnO, in that order. This SCR activity correlates with the onset of reduction in temperature-programmed reduction (TPR) experiments, indicating a relation between the SCR process and active surface oxygen. Mn2O3 is preferred in SCR since its selectivity towards nitrogen formation during this process is the highest. In all cases the selectivity decreases with increasing temperature. The oxidation state of the manganese, the crystallinity and the specific surface area are decisive for the performance of the oxides. The specific surface area correlates well with the nitric oxide reduction activity. The nitrous oxide originates from a reaction between nitric oxide and ammonia below 475 K and from oxidation of ammonia at higher temperatures, proven by using 15NH3. Participation of the bulk oxygen of the manganese oxides can be excluded, since TPR reveals that the bulk oxidation state remains unchanged during SCR, except for MnO, which is transformed into Mn3O4 under the applied conditions. In the oxidation of ammonia the degree of oxidation of the nitrogen containing products (N2, N2O, NO) increases with increasing temperature and with increasing oxidation state of the manganese. A reaction model is proposed to account for the observed phenomena.

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Activity and selectivity of pure manganese oxides in the selective catalytic reduction of nitric oxide with ammonia

Alumina-Supported Manganese Oxide Catalysts: II. Surface Characterization and Adsorption of Ammonia and Nitric Oxide

Selective catalytic reduction of NO with NH3 over carbon supported copper catalysts.

Modified activated carbons for the selective catalytic reduction of NO with NH3

A kinetic study of the selective catalytic reduction (SCR) of NO with NH[sub 3] over an alumina-supported Mn[sub 2]O[sub 3]-WO[sub 3] (10.8 wt % Mn[sub 2]O[sub 3], 6.8 wt % WO[sub 3]) catalyst has been conducted between 383 and 423 K at atmospheric pressure over a broad range of concentration conditions (100-2,000 ppm NO and NH[sub 3], 0.5-10% O[sub 2]) and space times (W/F[sub NO] = 220-17,647 kg[center dot]s/mol). A kinetic model is proposed on the basis of mechanistic insights in the SCR process and data on manganese oxide catalysts, using two different types of sites: one for NH[sub 3] adsorption and the other for NO and O[sub 2] adsorption. The selected rate expression, derived from this model, can describe the entire data set within 3% conversion accuracy. A Freundlich type of NO adsorption had to be assumed. At the intermediate temperatures the rate expression reduces to a power rate expression which describes the results equally well. The apparent reaction order is over the range of conditions approximately 0.4 to NO and O[sub 2] and around 0 for NH[sub 3]. The overall activation energy amounts to 20-30 kJ/mol.

L. Singoredjo

Papers

Activity and selectivity of pure manganese oxides in the selective catalytic reduction of nitric oxide with ammonia

Alumina-Supported Manganese Oxide Catalysts: II. Surface Characterization and Adsorption of Ammonia and Nitric Oxide

Selective catalytic reduction of NO with NH3 over carbon supported copper catalysts.

Modified activated carbons for the selective catalytic reduction of NO with NH3

Kinetics of the selective catalytic reduction of nitrogen oxide (NO) with ammonia over manganese oxide (Mn2O3)-tungsten oxide (WO3)/.gamma.-alumina