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.

Low-temperature selective catalytic reduction of NOx with NH3 over metal oxide and zeolite catalysts—A review

An overview is given of the selective catalytic reduction of NOx by ammonia (NH3‐SCR) over metal‐exchanged zeolites. The review gives a comprehensive overview of NH3‐SCR chemistry, including undesired side‐reactions and aspects of the reaction mechanism over zeolites and the active sites involved. The review attempts to correlate catalyst activity and stability with the preparation method, the exchange metal, the exchange degree, and the zeolite topology. A comparison of Fe‐ZSM‐5 catalysts prepared by different methods and research groups shows that the preparation method is not a decisive factor in determining catalytic activity. It seems that decreased turnover frequency (TOF) is an oft‐neglected effect of increasing Fe content, and this oversight may have led to the mistaken conclusion that certain production methods produce highly active catalysts. The available data indicate that both isolated and bridged iron species participate in the NH3‐SCR reaction over Fe‐ZSM‐5, with isolated species being the ...

https://www.tandfonline.com/doi/pdf/10.1080/01614940802480122

The State of the Art in Selective Catalytic Reduction of NOx by Ammonia Using Metal‐Exchanged Zeolite Catalysts

This paper surveys the present status and the perspective of de-NO x SCR catalysis for stationary sources, that is based on the reduction of NO x by NH 3 to form water and nitrogen. After a brief description of the SCR chemistry the characteristics of commercial SCR catalysts, their physico-chemical properties and reactivity, and their performances in both NO x reduction and SO 2 oxidation are presented. The mechanism of the SCR reactions, the mathematical modeling of the reactor and the arrangements of the reactor and process are then described. Finally the emerging technologies for NO x removal and the future perspectives of the SCR catalysis are outlined.

Present status and perspectives in de-NOx SCR catalysis

The low-temperature behavior of the selective catalytic reduction (SCR) process with feed gases containing both NO and NO2 was investigated. The two main reactions are 4NH3 + 2NO + 2NO2 → 4N2 + 6H2O and 2NH3 + 2NO2 → NH4NO3 + N2 + H2O. The “fast SCR reaction” exhibits a reaction rate at least 10 times higher than that of the well-known standard SCR reaction with pure NO and dominates at temperatures above 200 °C. At lower temperatures, the “ammonium nitrate route” becomes increasingly important. Under extreme conditions, e.g., a powder catalyst at T ≈ 140 °C, the ammonium nitrate route may be responsible for the whole NOx conversion observed. This reaction leads to the formation of ammonium nitrate within the pores of the catalyst and a temporary deactivation. For a typical monolithic sample, the lower threshold temperature at which no degradation of catalyst activity with time is observed is around 180 °C. The ammonium nitrate route is interesting from a standpoint of general DeNOx mechanisms:  This reac...

Reaction Pathways in the Selective Catalytic Reduction Process with NO and NO2 at Low Temperatures

Selective catalytic reduction of NO and NO2 at low temperatures

Enhanced reoxidation of vanadia by NO2 in the fast SCR reaction

The thermal behaviour of TiO 2 -WO 3 -V 2 O 5 catalysts with various vanadia contents (1, 2 and 3 wt.% V 2 O 5 ) was investigated using X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and BET surface area determination. The activity and selectivity of the new and thermally treated catalysts were tested in the SCR reaction. Both structural and catalytic investigations have shown that the vanadia content has a strong effect on the thermal behaviour of the SCR catalysts. The structural investigations evidenced anatase sintering, increase of polymeric vanadyl surface species and three-dimensional growth of supported vanadia upon ageing. The catalytic tests have shown that the SCR activity of catalysts containing 1 or 2% V 2 O 5 increased upon ageing, whereas the SCR performance of the catalyst with 3% V 2 O 5 decreased. The observed improvement of the SCR performance is attributed to an increase of the amount of polymeric vanadyl surface species upon ageing. The decrease of the SCR performance of the catalyst with 3% V 2 O 5 is due to the extensive loss of surface area and to the three-dimensional growth of supported vanadia upon ageing. The catalyst containing 2% V 2 O 5 represents the best compromise between high SCR activity and good thermal stability.

Thermal stability of vanadia-tungsta-titania catalysts in the SCR process

The main and side reactions of the three selective catalytic reduction (SCR) reactions with ammonia over TiO2−WO3−V2O5 catalysts have been investigated using synthetic gas mixtures matching the composition of diesel exhaust. The three SCR reactions are standard SCR with pure NO, fast SCR with an equimolar mixture of NO and NO2, and NO2 SCR with pure NO2. At high temperatures the selective catalytic oxidation (SCO) of ammonia and the formation of nitrous oxide compete with the SCR reactions. Water strongly inhibits the SCO of ammonia and the formation of nitrous oxide, thus increasing the selectivity of the SCR reactions. However, water also inhibits SCR activity, most pronounced at low temperatures. NO2 fractions exceeding 50% enhance the formation of nitrous oxide at low temperatures. If the feed of NOx consists of pure NO2, the formation of nitrous oxide may occur by two different reactions having different temperature regimes. The reaction responsible for N2O formation at low temperatures probably invo...

Giuseppe Madia

Papers

Reaction Pathways in the Selective Catalytic Reduction Process with NO and NO2 at Low Temperatures

Selective catalytic reduction of NO and NO2 at low temperatures

Enhanced reoxidation of vanadia by NO2 in the fast SCR reaction

Thermal stability of vanadia-tungsta-titania catalysts in the SCR process

Side Reactions in the Selective Catalytic Reduction of NOx with Various NO2 Fractions