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.

Mn-Ce-Ti mixed-oxide catalyst prepared by the hydrothermal method was investigated for the selective catalytic reduction (SCR) of NOx with NH3 in the presence of oxygen. It was found that the environmentally benign Mn-Ce-Ti catalyst exhibited excellent NH3-SCR activity and strong resistance against H2O and SO2 with a broad operation temperature window, which is very competitive for the practical application in controlling the NOx emission from diesel engines. On the basis of the catalyst characterization, the dual redox cycles (Mn4+ + Ce3+ Mn3+ + Ce4+, Mn4+ + Ti3+ Mn3+ + Ti4+) and the amorphous structure play key roles for the high catalytic deNO(x) performance. Diffuse reflectance infrared Fourier transform spectroscopy studies showed that the synergetic effect between Mn and Ce contributes to the formation of reactive intermediate species, thus promoting the NH3-SCR to proceed.

Novel Mn–Ce–Ti Mixed-Oxide Catalyst for the Selective Catalytic Reduction of NOx with NH3

Selective catalytic reduction (SCR) technology has been widely used for the removal of NOx from flue gas. However, it is still a challenge to develop novel low-temperature catalysts for SCR of NOx, especially at temperatures below 200 °C. This paper reviewed the recent progress on the Mn-based catalysts for low-temperature SCR de-NOx with NH3. Catalysts were divided into four categories, single MnOx, Mn-based multi-metal oxide, Mn-based multi-metal oxide with support, and Mn-based monolith catalyst. In the section of single MnOx, the effects of several factors, such as Mn oxidation state, crystallization state, specific surface area and morphology on catalytic activity were systematically reviewed. In the section of multi-metal oxide catalysts, the various roles played by the components of catalysts were intentionally summarized from four aspects, improving de-NOx efficiency, enhancing N2 selectivity, improving resistance to SO2 and H2O, extending operation temperature window, respectively. Moreover, the newly emerging morphology-dependent nanocatalysts were highlighted at the end of this section. In the introduction of supported metal oxide catalysts, the effects of supports were systematically analyzed according to their types, such as Al2O3, TiO2, carbon materials, etc. Considering the actual operation, Mn-based monolith catalysts were also introduced with regard to monolith supports, such as ceramics, metal wire mesh, etc. Subsequently, NH3-SCR mechanisms at low temperature, including E-R and L-H mechanisms, were discussed. At last, the perspective and the future direction of low-temperature SCR of NOx were proposed.

Manganese oxide-based catalysts for low-temperature selective catalytic reduction of NOx with NH3: A review

Promotional mechanisms of activity and SO2 tolerance of Co- or Ni-doped MnOx-CeO2 catalysts for SCR of NOx with NH3 at low temperature

Manganese oxide has been recognized as one of the most promising gaseous heterogeneous catalysts due to its low cost, environmental friendliness, and high catalytic oxidation performance. Mn-based oxides can be classified into four types: (1) single manganese oxide (MnOx), (2) supported manganese oxide (MnOx/support), (3) composite manganese oxides (MnOx-X), and (4) special crystalline manganese oxides (S-MnOx). These Mn-based oxides have been widely used as catalysts for the elimination of gaseous pollutants. This review aims to describe the environmental applications of these manganese oxides and provide perspectives. It gives detailed descriptions of environmental applications of the selective catalytic reduction of NOx with NH3, the catalytic combustion of volatile organic compounds, Hg0 oxidation and adsorption, and soot oxidation, in addition to some other environmental applications. Furthermore, this review mainly focuses on the effects of structure, morphology, and modified elements and on the rol...

Gaseous Heterogeneous Catalytic Reactions over Mn-Based Oxides for Environmental Applications: A Critical Review.

Selective catalytic reduction of NOx with NH3 over Mn-Ce mixed oxide catalyst at low temperatures

The effect of Ce on the activity and alkali resistance of V2O5/TiO2 catalyst for the selective catalytic reduction (SCR) of NOx by NH3 has been investigated It was found that the addition of Ce not only reduced the vanadium loading of V2O5/TiO2 but also enhanced its activity and alkali resistance The NOx conversion over 05%V2O5-5%CeO2/TiO2 was much higher than that over 1%V2O5/TiO2 catalyst Based on the catalyst characterization, the redox cycle (V4+ + Ce4+ V5+ + Ce3+) can account for the excellent NH3-SCR catalytic performance of 05%V2O5-5%CeO2/TiO2 catalyst In situ diffuse reflectance infrared transform spectroscopy (DRIFTS) measurements revealed that the role of Ce on the V2O5-CeO2/TiO2 catalyst was to contribute to the formation of NO2 and monodentate nitrate species, both of which were reactive intermediates for the NH3-SCR of NOx (C) 2014 Elsevier BV All rights reserved

Novel V2O5–CeO2/TiO2 catalyst with low vanadium loading for the selective catalytic reduction of NOx by NH3

The effect of Mn on the catalytic performance of V2O5/TiO2 catalyst for the selective catalytic reduction of NOx by NH3 (NH3-SCR) has been investigated in this study. It was found that the added Mn significantly enhanced the activity of V2O5/TiO2 catalyst for NH3-SCR below 400 °C. The redox cycle (V4+ + Mn4+ ↔ V5+ + Mn3+) over Mn-promoted V2O5/TiO2 catalyst plays a key role for the high catalytic deNOx performance. The redox cycle promotes the adsorption and activation of NH3 and NO, forming more reactive intermediates (NH4+, coordinated NH3, NO2, and monodentate nitrate species), thus promoting the NH3-SCR to proceed.

Junzhi Zhu

Papers

Novel Mn–Ce–Ti Mixed-Oxide Catalyst for the Selective Catalytic Reduction of NOx with NH3

Selective catalytic reduction of NOx with NH3 over Mn-Ce mixed oxide catalyst at low temperatures

Novel V2O5–CeO2/TiO2 catalyst with low vanadium loading for the selective catalytic reduction of NOx by NH3

Selective Catalytic Reduction of NOx by NH3 over Mn-Promoted V2O5/TiO2 Catalyst

Selective catalytic reduction of NOx by NH3 over MoO3-promoted CeO2/TiO2 catalyst