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.

Catalytic NOx Abatement Systems for Mobile Sources: From Three-Way to Lean Burn after-Treatment Technologies Pascal Granger* and Vasile I. Parvulescu* Unit e de Catalyse et de Chimie du Solide, UMR CNRS 8181, University of Lille 1, 59655 Villeneuve d’Ascq, France Department of Organic Chemistry, Biochemistry and Catalysis, University of Bucharest, Romania, 412 Regina Elisabeta Boulevard, Bucharest 030016, Romania

Catalytic NOx Abatement Systems for Mobile Sources: From Three-Way to Lean Burn after-Treatment Technologies

Catalysis for NOx abatement

Selective catalytic reduction (SCR) of NO with NH3 over manganese substituted iron titanate catalysts was fully studied. The low temperature SCR activity was greatly enhanced when partial Fe was substituted by Mn, although the N-2 selectivity showed some decrease to a certain extent. The Mn substitution amounts showed obvious influence on the catalyst structure, redox behavior and NH3/NOx adsorption ability of the catalysts. Among FeaMn1-aTiOx (a = 1, 0.75, 0.5, 0.2, 0) serial catalysts, Fe0.5Mn0.5TiOx with the molar ratio of Fe:Mn = 1: 1 showed the highest SCR activity, because the interaction of iron, manganese and titanium species in this catalyst led to the largest surface area and the highest porosity, the severest structural distortion and most appropriate structural disorder, the enhanced oxidative ability of manganese species, the highest mobility of lattice oxygen, the proper ratio of Bronsted acid sites and Lewis acid sites together with the enhanced NOx adsorption capacity. (C) 2009 Elsevier B.V. All rights reserved.

Effect of manganese substitution on the structure and activity of iron titanate catalyst for the selective catalytic reduction of NO with NH3

Nouveau Traité de Chimie Minérale.

We present a systematic study of the NH3-SCR reactivity over a commercial V2O5–WO3/TiO2 catalyst in a wide range of temperatures and NO/NO2 feed ratios, which cover (and exceed) those of interest for industrial applications to the aftertreatment of exhaust gases from diesel vehicles. The experiments confirm that the best deNOx efficiency is achieved with a 1/1 NO/NO2 feed ratio. The main reactions prevailing at the different operating conditions have been identified, and an overall reaction scheme is herein proposed. Particular attention has been paid to the role of ammonium nitrate, which forms rapidly at low temperatures and with excess NO2, determining a lower N2 selectivity of the deNOx process. Data are presented which show that the chemistry of the NO/NO2–NH3 reacting system can be fully interpreted according to a mechanism which involves: (i) dimerization/disproportion of NO2 and reaction with NH3 and water to give ammonium nitrite and ammonium nitrate; (ii) reduction of ammonium nitrate by NO to ammonium nitrite; (iii) decomposition of ammonium nitrite to nitrogen. Such a scheme explains the peculiar deNOx reactivity at low temperature in the presence of NO2, the optimal stoichiometry (NO/NO2 = 1/1), and the observed selectivities to all the major N-containing products (N2, NH4NO3, HNO3, N2O). It also provides the basis for the development of a mechanistic kinetic model of the NO/NO2–NH3 SCR reacting system.

Reactivity of NO/NO2–NH3 SCR system for diesel exhaust aftertreatment: Identification of the reaction network as a function of temperature and NO2 feed content

NH3–NO/NO2 chemistry over V-based catalysts and its role in the mechanism of the Fast SCR reaction

An exhaust gas aftertreatment installment and associated exhaust gas aftertreatment method utilizes a nitrogen oxide storage catalytic converter and an SCR catalytic converter. A particulate filter is provided upstream of the nitrogen oxide storage catalytic converter or between the latter and the SCR catalytic converter or downstream of the SCR catalytic converter. The time of regeneration operating phases of the nitrogen oxide storage catalytic converter can be determined as a function of the nitrogen oxide content of the exhaust gas downstream of the nitrogen oxide storage catalytic converter or of the SCR catalytic converter and/or as a function of the ammonia loading of the latter. Moreover, a desired ammonia generation quantity can be determined for a respective regeneration operating phase. The installation and method are adopted for use for motor vehicle internal combustion engines and other engines which are operated predominantly in lean-burn mode.

Exhaust Gas Aftertreatment Installation and Method

We present transient kinetic data that demonstrate an inhibiting effect of ammonia on the NH3-selective catalytic reduction (SCR) of nitric oxide (NO) at low temperatures over a V2O5-WO3/TiO2 commercial catalyst for vehicles. This effect has significant mechanistic as well as practical implications. It cannot be reproduced by conventional or modified Eley–Rideal approaches used in the past for SCR-deNOx stationary applications, but is well described by a novel dual-site redox rate expression assuming that ammonia may block the vanadium-related catalyst sites for NO + NH3 activation. The same rate model also successfully represents the kinetic influence of the oxygen concentration. It is shown that account of ammonia inhibition at low temperatures is critical for simulating the highly transient operation of onboard SCR converters for diesel exhaust aftertreatment. © 2006 American Institute of Chemical Engineers AIChE J, 2006

Brigitte Bandl-Konrad

Papers

Reactivity of NO/NO2–NH3 SCR system for diesel exhaust aftertreatment: Identification of the reaction network as a function of temperature and NO2 feed content

NH3–NO/NO2 chemistry over V-based catalysts and its role in the mechanism of the Fast SCR reaction

Exhaust Gas Aftertreatment Installation and Method

NH3‐SCR of NO over a V‐based catalyst: Low‐T redox kinetics with NH3 inhibition

Modelling of an SCR catalytic converter for diesel exhaust after treatment: Dynamic effects at low temperature