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.

Effects of Si/Al ratio on Cu/SSZ-13 NH3-SCR catalysts: Implications for the active Cu species and the roles of Brønsted acidity

Cu-SSZ-13 has been characterized by different spectroscopic techniques and compared with Cu-ZSM-5 and Cu-β with similar Si/Al and Cu/Al ratios and prepared by the same ion exchange procedure. On vacuum activated samples, low temperature FTIR spectroscopy allowed us to appreciate a high concentration of reduced copper centres, i.e. isolated Cu+ ions located in different environments, able to form Cu+(N2), Cu+(CO)n (n = 1, 2, 3), and Cu+(NO)n (n = 1, 2) upon interaction with N2, CO and NO probe molecules, respectively. Low temperature FTIR, DRUV-Vis and EPR analysis on O2 activated samples revealed the presence of different Cu2+ species. New data and discussion are devoted to (i) [Cu–OH]+ species likely balanced by one framework Al atom; (ii) mono(μ-oxo)dicopper [Cu2(μ-O)]2+ dimers observed in Cu-ZSM-5 and Cu-β, but not in Cu-SSZ-13. UV-Vis-NIR spectra of O2 activated samples reveal an intense and finely structured d–d quadruplet, unique to Cu-SSZ-13, which is persistent under SCR conditions. This differs from the 22 700 cm−1 band of the mono(μ-oxo)dicopper species of the O2 activated Cu-ZSM-5, which disappears under SCR conditions. The EPR signal intensity sets Cu-β apart from the others.

Characterization of Cu-exchanged SSZ-13: a comparative FTIR, UV-Vis, and EPR study with Cu-ZSM-5 and Cu-β with similar Si/Al and Cu/Al ratios

Cu-exchanged zeolites have demonstrated widespread use as catalyst materials in the abatement of NOx, especially from mobile sources. Recent studies focusing on Cu-exchanged zeolites with the CHA structure have demonstrated them to be excellent catalysts in the ammonia-assisted selective catalytic reduction (NH3-SCR) of NOx. Thorough characterization of these materials using state-of-the-art techniques has led to a significant improvement in the understanding of active sites present, which contributes toward a fundamental understanding of the catalytic processes and the rational design of new materials; however, the availability of multiple techniques at our disposal has led to various observations and conclusions on the nature of the active sites. This article begins with a brief introduction to exhaust emission control in the mobile sector, followed by an overview of hydrocarbon-SCR and NH3-SCR; the former technology having found common use in light duty passenger vehicles, whereas the latter are applie...

Local Environment and Nature of Cu Active Sites in Zeolite-Based Catalysts for the Selective Catalytic Reduction of NOx

The development of Cu-chabazite (CHA) catalysts, i.e. Cu-SSZ-13 and Cu-SAPO-34, represents a significant technology breakthrough for the removal of NOx by selective catalytic reduction (SCR) with ammonia. Cu-CHA catalysts show an excellent hydrothermal stability towards high temperature aging and wide active temperature windows for the ammonia SCR reaction. This work summarizes the recent progress in the development of the Cu-CHA catalysts for the NH3-SCR reaction. The state of Cu in the reaction and the preparation methods on the catalytic performance are discussed. The advances in the understanding of the reaction mechanism are reviewed. The hydrothermal stability of the typical Cu-CHA catalysts are compared.

Recent advances in the selective catalytic reduction of NOx with NH3 on Cu-Chabazite catalysts

An investigation into the impact of sulfur oxide on the activity of Cu-SAPO-34 towards selective catalytic reduction of NOx by NH3 has been conducted to clarify the possible mechanism of deactivation induced by sulfur. Several reactions including NH3 storage/TPD, NO/NH3 oxidations, standard and fast SCR, as well as SCR with an NO2/NOx ratio of 75% were performed at temperature range of 150-500 degrees C over the fresh Cu-SAPO-34 after it had been sulfated at 300 degrees C with 30 ppm SO2 in the presence of 8% O-2 and 5% H2O for 90 min. The catalyst is characterized by using XRD, BET, ICP-AES, H-2-TPR and micro-calorimetry. The BET surface area as well as the pore volume decreased after sulfur poisoning, hence some pores in the zeolite were blocked by sulfur. The standard SCR reaction was significantly influenced by the sulfur poisoning. The H-2-TPR data showed that there is less available copper that could undergo the redox cycle for the sulfated sample compared to the fresh sample and this could be the main reason for the deactivation seen. The conversion for NO during standard SCR showed a more pronounced decrease in activity compared to that of fast SCR and the smallest effect of the sulfur poisoning was observed for SCR with the 75% NO2/NOx. Hence, the SCR reactions in the presence of NO2 are less influenced by the sulfur on the surface and it is likely that the mechanism is different for SCR in the presence of NO2. Cu-SAPO-34 produced very small amounts of N2O and its production correlated with the amount of NO2 in the feed. From the calorimeter experiment, it was observed that the binding of SO2 is very strong on the catalyst sites, most likely the copper sites, and the heat of adsorption of SO2 was higher in the presence of O-2.

Impact of sulfur oxide on NH3-SCR over Cu-SAPO-34

In this study, we have developed a kinetic model for ammonia-SCR over a well-characterized Cu/SSZ-13 catalyst. It was found that a three-site model was needed in order to describe the ammonia temperature programmed desorption (TPD) with adsorption at 50 and 150 degrees C as well as ammonia oxidation, and NH3-SCR up to 600 degrees C. Based on literature studies, where detailed characterization of Cu/SSZ-13 have been conducted using several experimental techniques', we suggest the following physical interpretation of the S1 and S2 sites in the model. The S1 sites are associated with copper located in a six-membered ring, possibly slightly distorted due to interactions with-water and ammonia while, the S2 sites represent copper in the large cages or CuxOy species. In addition, ammonia is also stored on Bronsted acid sites, but in order not to complicate the model further, it was lumped together in the S1 and S2 sites. Finally, S3 sites have been added in order to describe the large amount of physisorbed ammonia at low temperature. This three-site model was capable of adequately describing the ammonia TPD experiments with the initial temperature of 50 and 150 degrees C. The heats of adsorption of ammonia on the Si and S2 sites were determined using micro-calorimeter experiments. Further, the main SCR reaction in the model occurs on S1 sites and the main ammonia oxidation reaction on S2 sites. However, due to the complex behavior associated with ammonia oxidation, where the conversion slightly decreased when the temperature was increased from 350 to 400 degrees C, an ammonia oxidation reaction occurring at low temperature with low rate needed to be introduced on S1. In a similar way, an added step was needed for ammonia-SCR on S2, which occurred at high temperature where the ammonia coverage on Si was low resulting in low conversion. To summarize, the-three-site model developed was capable of well describing the ammonia storage and release, ammonia oxidation as well as SCR and N2O formation across a broad temperature interval (100-600 degrees C).

A multi-site kinetic model for NH3-SCR over Cu/SSZ-13

Comparison of Cu/BEA, Cu/SSZ-13 and Cu/SAPO-34 for ammonia-SCR reactions

Deactivation of Cu-SSZ-13 by SO2 exposure under SCR conditions

This study focuses on the effect of gas composition during SO2 poisoning over Cu/SSZ-13 for NH3-SCR application and was performed by conducting SO2-TPD experiments in a variety of lean gas compositions. In addition, the poisoned monoliths were characterized in detail using ICP-SFMS, UV–vis and XPS. During SO2 poisoning under dry and lean conditions, two different sulfur species were found, which were assigned to weakly bound SO2 and copper sulfate like species. Moreover, a significantly larger amount of copper sulfates was present in humid environment. The presence of NH3 during the poisoning resulted in the formation of ammonium sulfate species which were decomposed at the same temperature independently if the poisoning with SO2 was conducted in ammonia oxidation conditions or under standard or fast SCR conditions. Moreover, if the temperature ramp was conducted with O2 and H2O compared to Ar alone, more stable sulfate species were formed. In addition, SO2 poisoning under standard SCR conditions resulted in mostly ammonium sulfate formation at 200 °C, whereas copper sulfates were predominant after poisoning at 400 °C. After hydrothermal aging at 800 °C, more reducible copper species were noticeable and UV–vis showed that copper oxides had been formed. Sulfur poisoning of the hydrothermally aged sample resulted in the additional formation of copper sulfates during poisoning at 200 °C, which was not the case for poisoning of the fresh catalyst. Thus, the copper oxide species enhanced the copper sulfate formation.

Kurnia Wijayanti

Papers

Impact of sulfur oxide on NH3-SCR over Cu-SAPO-34

A multi-site kinetic model for NH3-SCR over Cu/SSZ-13

Comparison of Cu/BEA, Cu/SSZ-13 and Cu/SAPO-34 for ammonia-SCR reactions

Deactivation of Cu-SSZ-13 by SO2 exposure under SCR conditions

Effect of gas compositions on SO2 poisoning over Cu/SSZ-13 used for NH3-SCR