The First Study of SCR of NO x by Acetylene in Excess Oxygen

Acetylene as a reducing agent for the selective catalytic reduction (C₂H₂-SCR) of NO in the presence of excess oxygen on various Ce-exchanged zeolites was investigated for the first time. Under the conditions of 1600 ppm NO, 800 ppm C₂H₂, and 9.95 % O₂ in He, the Ce-H-ZSM-5 (Si/Al=25) catalyst shows about 83% NO conversion to N₂ at the temperatures ranged from 300 to 350 °C. It is followed by the other zeolites in the activity order of Ce-H-Y (Si/Al=2.5), Ce-H-_ (Si/A1=20∼30), and Ce-H-SAPO (Si/Al=34), Ce-H-5A (Si/Al=12). Almost no NO conversion was obtained over Ce-Na-ZSM-5 (Si/Al=25) and Na-ZSM-5 (Si/Al=25) catalyst samples. The Conversion of NO to N₂ increased with O₂ concentration in the range of 0.1 ∼ 9.95% over the CeH-ZSM-5 (Si/Al=25) catalyst. It is suggested that O₂ plays an important role in the C₂H₂-SCR of NO reaction, by oxidizing NO to NO₂ on acid sites in assistant with cerium species of the catalyst. A large amount of CO, which seems to be in proportion with the NO conversion to N₂, was produced. Long-term experiments up to 56 h combined with a excursion of the reaction temperature up to 650 °C over the Ce-H-ZSM-5 (Si/A1=25) confirmed the catalyst’s durable performance under the reaction conditions. It is found that the de-NO_x activity of Ce-H-ZSM-5 catalyst can be enhanced by the presence of 50 ppm of sulfur dioxide in the dry-feed reaction conditions.     

用于选择性催化还原法烟气脱硝的催化剂

论述了在使用不同催化剂和不同还原剂的条件下,选择性催化还原( SCR)脱除电站烟气中氮氧化物的基本原理.SCR催化剂有三种不同的类型:贵金属型、金属氧化物型和离子交换的沸石分子筛型,并讨论了三种不同催化剂在SCR反应过程中的活性特征.论述了在国外应用最广泛的V2 O5- WO3 - Mo O3 /Ti O2 类催化剂的成分组成以及各成分在反应过程中的作用.列举了在SCR催化剂的生产和使用过程中需要考虑和解决的主要问题.     

Molecular design and characterization of catalysts for NO x selective reduction by hydrocarbons in the oxygen excess based upon ultramicroporous zirconia pillared clays

Approaches to design of zirconia pillared clays via control of the properties of pillaring species in solutions were elaborated. Structural features of pillars and Pt + Cu active components fixed at these nanoparticles were shown to determine catalytic properties of pillared clays in NO_x selective reduction by hydrocarbons in the oxygen excess.     

Selective catalytic reduction of NO by ammonia using mesoporous Fe-containing HZSM-5 and HZSM-12 zeolite catalysts: An option for automotive applications

Mesoporous and conventional Fe-containing ZSM-5 and ZSM-12 catalysts (0.5–8 wt% Fe) were prepared using a simple impregnation method and tested in the selective catalytic reduction (SCR) of NO with NH₃. It was found that for both Fe/HZSM-5 and Fe/HZSM-12 catalysts with similar Fe contents, the activity of the mesoporous samples in NO SCR with NH₃ is significantly higher than for conventional samples. Such a difference in the activity is probably related with the better diffusion of reactants and products in the mesopores and better dispersion of the iron particles in the mesoporous zeolite as was confirmed by SEM analysis. Moreover, the maximum activity for the mesoporous zeolites is found at higher Fe concentrations than for the conventional zeolites. This also illustrates that the mesoporous zeolites allow a better dispersion of the metal component than the conventional zeolites. Finally, the influence of different pretreatment conditions on the catalytic activity was studied and interestingly, it was found that it is possible to increase the SCR performance significantly by preactivation of the catalysts in a 1% NH₃/N₂ mixture at 500 °C for 5 h. After preactivation, the activity of mesoporous 6 wt% Fe/HZSM-5 and 6 wt% Fe/HZSM-12 catalyst is comparable with that of traditional 3 wt% V₂O₅/TiO₂ catalyst used as a reference at temperatures below 400 °C and even more active at higher temperatures.     

Electrical properties of V2O5–WO3/TiO2 EUROCAT catalysts evidence for redox process in selective catalytic reduction (SCR) deNOx reaction

Electrical conductivity measurements on EUROCAT V₂O₅–WO₃/TiO₂ catalyst and on its precursor without vanadia were performed at 300°C under pure oxygen to characterize the samples, under NO and under NH₃ to determine the mode of reactivity of these reactants and under two reaction mixtures ((i) 2000 ppm NO + 2000 ppm NH₃ without O₂, and (ii) 2000 ppm NO + 2000 ppm NH₃ + 500 ppm O₂) to put in evidence redox processes in SCR deNO_x reaction.It was first demonstrated that titania support contains certain amounts of dissolved W⁶⁺ and V⁵⁺ ions, whose dissolution in the lattice of titania creates an n-type doping effect. Electrical conductivity revealed that the so-called reference pure titania monolith was highly doped by heterovalent cations whose valency was higher than +4. Subsequent chemical analyses revealed that so-called pure titania reference catalyst was actually the WO₃/TiO₂ precursor of V₂O₅–WO₃/TiO₂ EUROCAT catalyst. It contained an average amount of 0.37 at.% W⁶⁺dissolved in titania, i.e. 1.07 × 10²⁰ W⁶⁺ cations dissolved/cm³ of titania. For the fresh catalyst, the mean amounts of W⁶⁺ and V⁵⁺ ions dissolved in titania were found to be equal to 1.07 × 10²⁰ and 4.47 × 10²⁰ cm⁻³, respectively. For the used catalyst, the mean amounts of W⁶⁺ and V⁵⁺ ions dissolved were found to be equal to 1.07 × 10²⁰ and 7.42 × 10²⁰ cm⁻³, respectively. Since fresh and used catalysts have similar compositions and similar catalytic behaviours, the only manifestation of ageing was a supplementary progressive dissolution of 2.9 × 10²⁰ additional V⁵⁺ cations in titania.After a prompt removal of oxygen, it appeared that NO alone has an electron acceptor character, linked to its possible ionosorption as NO⁻ and to the filling of anionic vacancies, mostly present on vanadia. Ammonia had a strong reducing behaviour with the formation of singly ionized vacancies. A subsequent introduction of NO indicated a donor character of this molecule, in opposition to its first adsorption. This was ascribed to its reaction with previously adsorbed ammonia strongly bound to acidic sites. Under NO + NH₃ reaction mixture in the absence of oxygen, the increase of electrical conductivity was ascribed to the formation of anionic vacancies, mainly on vanadia, created by dehydroxylation and dehydration of the surface. These anionic vacancies were initially subsequently filled by the oxygen atom of NO. N^o atoms, resulting from the dissociation of NO and from ammonia dehydrogenation, recombined into dinitrogen molecules. The reaction corresponded to

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. In the presence of oxygen, NO did not exhibit anymore its electron acceptor character, since the filling of anionic vacancies was performed by oxygen from the gas phase. NO reacted directly with ammonia strongly bound on acidic sites. A tentative redox mechanism was proposed for both cases.     

NH3-SCR of NO at low temperatures over sulphated vanadia on carbon-coated monoliths: Effect of H2O and SO2 traces in the gas feed

The objective of this research is to asses the impact of the addition of H₂O, SO₂, and both in the SCR of NO at low temperatures over sulphated vanadia on carbon-coated monoliths. The sulphated catalyst keeps a 100% conversion and total selectivity to N₂ in the low temperature range, i.e. 473–500 K, when either H₂O or SO₂ is added to the gas feed. However, a decline of steady state conversion and selectivity occurs when both H₂O and SO₂ are added simultaneously because H₂O speeds up the deposition of ammonium sulphate salts. This decrease of catalyst performance is reversed when the reaction is carried out under dry conditions at temperatures higher than 473 K but not at lower temperature (453 K). Thus, the catalyst has demonstrated to be a good candidate for the SCR of NO at low temperatures even in stack gases containing traces of undesired components.     

Surface chemistry and kinetics of the hydrolysis of isocyanic acid on anatase

In order to meet the stricter NO_x and particulate emission limits for commercial vehicles, the selective catalytic reduction (SCR) with urea is currently seen having the highest potential. The conversion of urea into ammonia and carbon dioxide consists of two consecutive reactions, in which isocyanic acid is an intermediate that is hydrolyzed over TiO₂. The intrinsic kinetics and the surface chemistry for this reaction are explored. Up to a temperature of 132 °C the reaction was in the intrinsic kinetic regime (E_A = 73 kJ/mol), while at higher temperatures the reaction was limited by pore and external diffusion constraints, respectively. In the presence of NO, NH₃ and NO₂, the catalytic activity was negatively influenced, increasing in severity in the sequence mentioned indicating that nitrates formed from NO₂ were most effective in blocking cations and anions of TiO₂. IR spectroscopy indicates that dissociative adsorption of HNCO on TiO₂ forms Ti–NCO and hydrogen bonded OH species. In the presence of water, isocyanic acid was so rapidly hydrolyzed that only adsorbed ammonia was observed on the catalyst surface. The presence of NO, NH₃ and NO₂ retards hydrolysis leading to the appearance of isocyanate species on the surface.     

Effect of calcination temperature on the characteristics of SO<Emphasis Type="Italic">sk</Emphasis>4/2-/TiO<Subscript>2</Subscript> catalysts for the reduction of NO by NH<Subscript>3</Subscript>

The catalytic activity of sulfated titania (ST) calcined at a variety of temperatures has been investigated for selective catalytic reduction (SCR) of NO by NH₃. The NO removal activity of ST catalyst mainly depends on its sulfur content, indicating critical role of sulfur species on the surface of TiO₂. The role of sulfur is mainly the formation of acid sites on the catalyst surface. The presence of both BrØnsted and Lewis acid sites on the surface of sulfated titania has been identified by IR study with the adsorption of NH₃ and pyridine on ST. The reduction of the intensity of IR bands representing BrØsted acid sites is more pronounced than that revealing Lewis acid sites as the calcination temperature increases. It has been further clarified by IR study of ST500 catalyst evacuated at a variety of temperatures. The NO removal activity also decreases with the increase of the catalyst calcination temperature. It simply reveals that BrØnsted acid sites induced by sulfate on the catalyst surface are primarily responsible for the enhancement of catalytic activity of ST catalyst containing sulfur for NO reduction by NH₃.     

The effect of NO2 on the activity of fresh and aged zeolite catalysts in the NH3-SCR reaction

The activity of fresh and hydrothermally aged zeolite-based catalysts in the NH₃-selective catalytic reduction (SCR) reaction with excess of oxygen were studied. In addition, the effect of NO₂ in the gas feed as well as the acidity of the catalysts for the SCR activity was investigated. The studied catalysts were hydrogen, copper, iron and silver ion exchanged ZSM-5, mordenite, beta, ferrierite, and Y-zeolites. The investigation verifies that the zeolite-based catalysts are very promising for the ammonia SCR reaction. Especially, the activity at low and high temperatures was higher than the activity of commercial vanadia-based catalysts. From the studied catalysts, Fe-beta was the most potential one. The presence of NO₂ in the inlet flow enhanced significantly the catalytic activity of fresh and hydrothermally aged zeolite catalysts. This suggests that the oxidation of NO to NO₂ is probably the rate-determining step for the SCR reaction.     

3D Simulation Research on Urea-SCR DeNO<em>x Catalyst for Diesel Engine

In order to reduce oxides of nitrogen (NOx) emanated from a diesel eng ine, a comprehensive urea selective catalyst reduction (SCR) DeNOx catalys t was modeled in which numerical simulations were used as a complementary tool f or the experimental investigations to make the design decisions, and hence short en the development process. In this approach, relevant conversion reactions were studied in 1D model, and the parameters obtained in this way were transferred t o 3D simulations. According to the results ...