Comparative Study of SO2 and SO2/SO3 Poisoning and Regeneration of Cu/BEA and Cu/SSZ-13 for NH3 SCR

Two copper-exchanged zeolites, Cu/SSZ-13 and Cu/BEA, were studied as catalysts for the selective reduction of NOx by NH3 (NH3-SCR). Their activities for standard SCR (NOx = NO) and fast SCR (NOx = 50% NO + 50% NO2) were measured before and after sulfur poisoning at 250 °C. The effect of 30 ppm SO2 and a mixture of 24 ppm SO3 + 6 ppm SO2 was evaluated. The repetition of subsequent activity measurements served as regeneration method in SCR conditions. SO2 deactivated Cu/SSZ-13 whereas Cu/BEA was only moderately affected. SO3 led to stronger deactivation of both catalysts than SO2. However, also for this case, the Cu/BEA was significantly less affected than Cu/SSZ-13, even though Cu/BEA contained larger amount of stored sulfur. One possible reason for this could be the large pores of Cu/BEA, where the sulfur species possibly resulted in less sterical hindrance than in the small pore SSZ-13 structure. NH3 temperature-programmed desorption (NH3-TPD) showed no loss of storage sites upon sulfur treatment and subsequent regeneration. Partial activity recovery was observed after a period in SCR conditions at 400 °C and 500 °C. Temperature at 300 °C was insufficient to regenerate the catalysts. Diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) of NO adsorption suggested that SO2 interacts with the ZCuOH sites on Cu/SSZ-13, causing the strong poisoning.

Insight into the Promoting Role of Er Modification on SO2 Resistance for NH3-SCR at Low Temperature over FeMn/TiO2 Catalysts

Er-modified FeMn/TiO2 catalysts were prepared through the wet impregnation method, and their NH3-SCR activities were tested. The results showed that Er modification could obviously promote SO2 resistance of FeMn/TiO2 catalysts at a low temperature. The promoting effect and mechanism were explored in detail using various techniques, such as BET, XRD, H2-TPR, XPS, TG, and in-situ DRIFTS. The characterization results indicated that Er modification on FeMn/TiO2 catalysts could increase the Mn4+ concentration and surface chemisorbed labile oxygen ratio, which was favorable for NO oxidation to NO2, further accelerating low-temperature SCR activity through the “fast SCR” reaction. As fast SCR reaction could accelerate the consumption of adsorbed NH3 species, it would benefit to restrain the competitive adsorption of SO2 and limit the reaction between adsorbed SO2 and NH3 species. XPS results indicated that ammonium sulfates and Mn sulfates formed were found on Er-modified FeMn/TiO2 catalyst surface seemed much less than those on FeMn/TiO2 catalyst surface, suggested that Er modification was helpful for reducing the generation or deposition of sulfate salts on the catalyst surface. According to in-situ DRIFTS the results of, the presence of SO2 in feeding gas imposed a stronger impact on the NO adsorption than NH3 adsorption on Lewis acid sites of Er-modified FeMn/TiO2 catalysts, gradually making NH3-SCR reaction to proceed in E–R mechanism rather than L–H mechanism. DRIFTS.

Precursor Effect on Mn-Fe-Ce/TiO2 Catalysts for Selective Catalytic Reduction of NO with NH3 at Low Temperatures

Preparation of Mn/TiO2, Mn-Fe/TiO2, and Mn-Fe-Ce/TiO2 by the deposition-precipitation (DP) method can afford very active catalysts for low-temperature NH3-SCR (selective catalytic reduction of NO with NH3). The effect of precursor choice (nitrate vs. acetate) of Mn, Fe, and Ce on the physiochemical properties including thermal stability and the resulting SCR activity were investigated. The resulting materials were characterized by N2-Physisorption, XRD (Powder X-ray diffraction), XPS (X-ray photoelectron spectroscopy), H2-TPR (temperature-programmed reduction with hydrogen), and the oxidation of NO to NO2 measured at 300 °C. Among all the prepared catalysts 5MnAce/Ti, 25Mn0.75AceFe0.25Nit/Ti, and 25Mn0.75AceFe0.20NitCe0.05Ace/Ti showed superior SCR activity at low temperature. The superior activity of the latter two materials is likely attributable to the presence of amorphous active metal oxide phases (manganese-, iron- and cerium-oxide) and the ease of the reduction of metal oxides on TiO2. Enhanced ability to convert NO to NO2, which can promote fast-SCR like pathways, could be another reason. Cerium was found to stabilize amorphous manganese oxide phases when exposed to high temperatures.

Selective catalytic reduction of NOx with NH3: opportunities and challenges of Cu-based small-pore zeolites

Zeolites, as efficient and stable catalysts, are widely used in the environmental catalysis field. Typically, Cu-SSZ-13 with small-pore structure shows excellent catalytic activity for selective catalytic reduction of NOx with ammonia (NH3-SCR) as well as high hydrothermal stability. This review summarizes major advances in Cu-SSZ-13 applied to the NH3-SCR reaction, including the state of copper species, standard and fast SCR reaction mechanism, hydrothermal deactivation mechanism, poisoning resistance, and synthetic methodology. The review gives a valuable summary of new insights on the matching between SCR catalyst design principles and the characteristics of Cu2+-exchanged zeolitic catalysts, highlighting the significant opportunity presented by zeolite-based catalysts. Principles for designing zeolites with excellent NH3-SCR performance and hydrothermal stability are proposed. On the basis of these principles, more hydrothermally stable Cu-AEI and Cu-LTA zeolites are elaborated as well as other alternative zeolites applied to NH3-SCR. Finally, we call attention to the challenges facing Cu-based small-pore zeolites that still need to be addressed.

Ferrierite and Its Delaminated and Silica-Intercalated Forms Modified with Copper as Effective Catalysts for NH3-SCR Process

The main goal of the study was the development of effective catalysts for the low-temperature selective catalytic reduction of NO with ammonia (NH3-SCR), based on ferrierite (FER) and its delaminated (ITQ-6) and silica-intercalated (ITQ-36) forms modified with copper. The copper exchange zeolitic samples, with the intended framework Si/Al ratio of 30 and 50, were synthetized and characterized with respect to their chemical composition (ICP-OES), structure (XRD), texture (low-temperature N2 adsorption), form and aggregation of deposited copper species (UV-vis-DRS), surface acidity (NH3-TPD) and reducibility (H2-TPR). The samples of the Cu-ITQ-6 and Cu-ITQ-36 series were found to be significantly more active NH3-SCR catalysts compared to Cu-FER. The activity of these catalysts in low-temperature NH3-SCR was assigned to the significant contribution of highly dispersed copper species (monomeric cations and small oligomeric species) catalytically active in the oxidation of NO to NO2, which is necessary for fast-SCR. The zeolitic catalysts, with the higher framework alumina content, were more effective in high-temperature NH3-SCR due to their limited catalytic activity in the side reaction of ammonia oxidation.