Screening of Fe–Cu-Zeolites Prepared by Different Methodology for Application in NSR–SCR Combined DeNOx Systems

The NO_x NH₃-SCR performance of several Cu and Fe catalysts supported on BETA and ZSM-5 zeolites has been studied in single SCR and double NSR–SCR configuration, and the activity related to the nature and reducibility of metal species on the catalyst surface. Intermediate ammonia formed in NSR improved greatly NO_x conversion at the exit of the double NSR–SCR configuration, which was practically totally converted to N₂.     

MnOx-WO3/TiO2NH3选择性还原NOx的催化性能与动力学

研究了Mn-W/TiO2用于NH3选择性催化还原NOx体系的催化反应性能,在很宽的温度范围和各种气体条件下,该催化剂显示了较高的催化活性.在GHSV 18900 h-1、100～350℃条件下,NOx转化率高达80.3%～99.6%,Nz选择性达98.7%～100%;当反应气体中有0.01%SO2(分压比,下同)和6%...     

Spectroscopic Evidence for a Nitrite Intermediate in the Catalytic Reduction of NOx with Ammonia on Fe/MFI

The mechanism of selective catalytic reduction (SCR) of NO_x with NH₃ over Fe/MFI was studied using in situ FTIR spectroscopy. Exposing Fe/MFI first to NH₃ then to flowing NO + O₂ or using the reversed sequence, invariably leads to the formation of ammonium nitrite, NH₄NO₂. In situ FTIR results in flowing NO + NH₃ + O₂ at different temperatures show that NH₃ is strongly adsorbed and reacts with impinging NO_x. The intensity of the NH₄NO₂ bands initially increases with temperature, but passes through a maximum at 120 °C because the nitrite decomposes to N₂ + H₂O. The mechanistic model rationalizes that the consumption ratio of NO and NH₃ is close to unity and that the effect of water vapor depends on the reaction temperature. At high temperature H_2O enhances the rate because it is needed to form NH₄NO₂. At low temperature, when adsorbed H₂O is abundant it lowers the rate because it competes with NO_x for adsorption sites.     

Selective catalytic reduction of nitrogen oxides by ammonia on iron oxide catalysts

In this study, new Fe₂O₃ based materials are developed for the selective catalytic reduction (SCR) of NO_x by NH₃ in diesel exhaust. As a result of the catalyst screening, performed in a synthetic model exhaust, ZrO₂ is considered to be the most effective carrier for Fe₂O₃. The modification of the Fe₂O₃/ZrO₂ system with tungsten leads to drastic increase of SCR performance as well as pronounced thermal stability. These results show that tungsten acts as bifunctional component. The highest catalytic activity is observed for ZrO₂ that is coated with 1.4 mol% Fe₂O₃ and 7.0 mol% WO₃ (1.4Fe/7.0W/Zr). By the use of this catalyst quantitative conversion of NO_x is obtained between 285 and 430 °C with selective formation of N₂. Here, the turnover frequency of NO_x per Fe atom is found to be 35 × 10⁻⁵ s⁻¹ that indicates a high catalytic performance. The SCR activity of the 1.4Fe/7.0W/Zr material is decreased in the presence of H₂O and CO₂, whereas it is increased by NO₂.Temperature programmed reduction by H₂ (HTPR) analyses show that the Fe sites of the 1.4Fe/7.0W/Zr catalyst are mainly in the form of crystalline Fe₂O₃, whereby relatively small oxide entities are also present. The strongly aggregated Fe₂O₃ species are associated with the presence of the promoter tungsten. Based upon stationary catalytic examinations as well as diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) studies we postulate an Eley Rideal type mechanism for SCR on 1.4Fe/7.0W/Zr catalyst. The mechanistic model includes a redox cycle of the active Fe sites. As first reaction step, we assume dissociative adsorption of NH₃ that leads to partial reduction of the iron as well as to production of very reactive amide surface species. These amide intermediates are supposed to react with gaseous NO to form N₂ and H₂O. In the final step, the reduced Fe sites be regenerated by oxidation with O₂. As a side reaction of SCR, imide species, originated from decomposition of amide, are oxidized by NO₂ or O₂ into NO.     

Selective Catalytic Reduction of NOx over H-ZSM-5 Under Lean Conditions Using Transient NH3 Supply

The selective catalytic reduction (SCR) of NO _x over zeolite H-ZSM-5 with ammonia was investigated using in situ FTIR spectroscopy and flow reactor measurements. The adsorption of ammonia and the reaction between NO _x , O₂ and either pre-adsorbed ammonia or transiently supplied ammonia were investigated for either NO or equimolar amounts of NO and NO₂. With transient ammonia supply the total NO reduction increased and the selectivity to N₂O formation decreased compared to continuous supply. The FTIR experiments revealed that NO _x reacts with ammonia adsorbed on Brønsted acid sites as NH₄ ⁺ ions. These experiments further indicated that adsorbed -NO₂ ^– is formed during the SCR reaction over H-ZSM-5.     

Manganese-enhanced porous phosphoric acid–based geopolymer templated by carbon for efficient NH3-SCR of NOx

Geopolymer-based ceramics as catalysts or catalyst supports have attracted tremendous interests in recent years owing to their low-cost and zeolite-like structure characteristics. However, most of the reported works focus on alkaline-based geopolymers, whereas the catalytic performance of acid based geopolymer has not yet been evaluated. This study aims to investigate the application potential of phosphoric acid–based geopolymer (PAG) for selective catalytic reduction (SCR) of NO_x with NH₃. To this end, the SCR reactivity of PAG and metal oxide (MnO_x)-loaded PAG were evaluated. Moreover, an activated carbon-based hard template route was proposed for further enhancing the SCR reactivity of the PAG-based catalyst. The as-prepared catalyst under the optimal condition exhibited a high NO conversion greater than 85% in a wide temperature range of 250–350°C, which is among the top literature-reported values, demonstrating its promising application prospect. A systematical X-ray diffraction, X-ray photoelectron spectroscopy, field emission scanning electron microscopy, Brunauer–Emmet–Teller, NH₃-temperature-programed desorption, and H₂-temperature-programed reduction spectroscopic analyses were also conducted to better understand the structure evolution of PAG under elevated temperature and the SCR catalytic mechanism of the acid-based geopolymer catalysts. This study would provide valuable information on the potential application prospect of PAG and its modified form for efficient NO_x removal.     

A kinetic model of the hydrogen assisted selective catalytic reduction of NO with ammonia over Ag/Al2O3

A global kinetic model which describes H₂‐assisted NH₃‐SCR over an Ag/Al₂O₃ monolith catalyst has been developed. The intention is that the model can be applied for dosing NH₃ and H₂ to an Ag/Al₂O₃ catalyst in a real automotive application as well as contribute to an increased understanding of the reaction mechanism for NH₃‐SCR. Therefore, the model needs to be simple and accurately predict the conversion of NO_x. The reduction of NO is described by a global reaction, with a molar stoichiometry between NO, NH₃ and H₂ of 1:1:2. Further reactions included in the model are the oxidation of NH₃ to N₂ and NO, oxidation of H₂, and the adsorption and desorption of NH₃. The model was fitted to the results of an NH₃‐TPD experiment, an NH₃ oxidation experiment, and a series of H₂‐assisted NH₃‐SCR steady‐state experiments. The model predicts the conversion of NO_x well even during transient experiments. © 2013 American Institute of Chemical Engineers AIChE J, 59: 4325–4333, 2013     

Selective catalytic reduction by urea in a fluidized‐bed reactor

The selective catalytic reduction (SCR) of NO_x by urea as a reducing agent was carried out over fresh and sulfated CuO/γ‐Al₂O₃ catalysts in a fluidized‐bed reactor. The optimum temperature ranges for NO reduction on the fresh and sulfated CuO/γ‐Al₂O₃ catalysts were 300–350 °C and 400–450 °C, respectively. NO reduction with the sulfated CuO/γ‐Al₂O₃ catalyst was somewhat higher than that with the fresh CuO/γ‐Al₂O₃ catalyst. N₂O formation increased with increasing reaction temperature. Ammonia (NH₃) slip increased with increasing gas velocity and decreased with increasing reaction temperature. Copyright © 2003 Society of Chemical Industry     

Lean NOx Reduction with H2 and CO in Dual-Layer LNT–SCR Monolithic Catalysts: Impact of Ceria Loading

A series of monolithic catalysts consisting of a layer of selective catalytic reduction (SCR) catalyst deposited on top of lean NO_x trap (LNT) catalyst were synthesized for lean reduction of NO_x (NO&NO₂) with H₂ and CO. The LNT catalyst exhibited a rather low NO_x conversion below 250 °C due to CO inhibition. The top SCR layer comprising Cu/ZSM5 significantly increased the NO_x conversion at low temperature by its reaction with NH₃ formed during the regeneration phase. The addition of CeO₂ to the LNT layer promoted the water gas shift reaction (CO + H₂O ? H₂ + CO₂). The WGS reaction mitigated the CO inhibition and the generated H₂ enhanced the low-temperature catalyst regeneration. The ceria addition decreased the performance at high temperatures due to increased oxidation of NH₃. The ceria loading was optimized by applying a non-uniform axial profile. A dual-layer catalyst with an increasing ceria loading axial profile improved the performance over a wide (low and high) temperature range.     

Determination of N2O Emissions Levels in the Selective Reduction of NOx by NH3 Over an On-Site-Used Commercial V2O5–WO3/TiO2 Catalyst Using a Modified Gas Cell

The formation of N₂O in NH₃–SCR deNO_x reaction over an on-site-used commercial V₂O₅–WO₃/TiO₂ catalyst has been measured using an on-line IR system with a modified gas cell. The N₂O could be formed by the SCR and NH₃ oxidation reactions. These two reactions were particularly enhanced with the on-site-used sample.     

The State of the Art in Selective Catalytic Reduction of NOx by Ammonia Using Metal‐Exchanged Zeolite Catalysts

An overview is given of the selective catalytic reduction of NO_x by ammonia (NH₃‐SCR) over metal‐exchanged zeolites. The review gives a comprehensive overview of NH₃‐SCR chemistry, including undesired side‐reactions and aspects of the reaction mechanism over zeolites and the active sites involved. The review attempts to correlate catalyst activity and stability with the preparation method, the exchange metal, the exchange degree, and the zeolite topology. A comparison of Fe‐ZSM‐5 catalysts prepared by different methods and research groups shows that the preparation method is not a decisive factor in determining catalytic activity. It seems that decreased turnover frequency (TOF) is an oft‐neglected effect of increasing Fe content, and this oversight may have led to the mistaken conclusion that certain production methods produce highly active catalysts. The available data indicate that both isolated and bridged iron species participate in the NH₃‐SCR reaction over Fe‐ZSM‐5, with isolated species being the most active.     

A new synthesis method for supported composite oxides: preparation of Ce-Cu/TiO2 catalysts by ice-melting method

In SCR denitrification technology, the conventional coprecipitation method has the disadvantages of high temperature and difficulty in controlling the precipitation rate. Various Ce_xCuTiO₂ catalysts were synthesized using ice-melting (Ce_xCuTi-Ice) and conventional coprecipitation (Ce_xCuTi-Con) methods for the selective catalytic reduction (SCR) of NO with NH₃. Ce_0.4CuTi-Ice catalyst exhibited excellent catalytic activity among the Ce_xCuTiO₂ catalysts, and 80% NO_x conversion was achieved within a temperature range of 250–375 °C, exceeding that of Ce_0.4CuTi-Con catalyst by 20%; in addition, N₂ selectivity was nearly 100%. To elucidate the release characteristics of the precursor solution during ice-melting synthesis, the changes of Cu and Ce concentrations in the solution were investigated by ICP-OES. The precursor solution was released at a slow rate via the ice-melting method, resulting in a large surface area, small crystallite sizes, and effective uniform nanoparticles with abundant active species and increased surface acidity. The promoted mechanism could be attributed to the enhanced oxidation of NO to NO₂ at low temperatures and the rapid reaction between NO species and coordinated NH₃ at high temperatures. © 2022 Society of Chemical Industry (SCI).     

High activity and wide temperature window of Fe‐Cu‐SSZ‐13 in the selective catalytic reduction of NO with ammonia

Fe‐Cu‐SSZ‐13 catalysts were prepared by aqueous solution ion‐exchange method based on the one‐pot synthesized Cu‐SSZ‐13. The catalysts were applied to the selective catalytic reduction (SCR) of NO with NH₃ and characterized by the means of XRD, UV‐Vis, EPR, XPS, NH₃‐TPD, and so on. The selected Fe‐Cu‐SSZ‐13‐1 catalyst exhibited the high NO conversion (>90%) in the wide temperature range (225–625°C), which also showed good N₂ selectivity and excellent hydrothermal stability. The results of XPS showed that the Cu and Fe species were in the internal and outer parts of the SSZ‐13 crystals, respectively. The results of UV‐Vis and EPR indicated that the monomeric Cu²⁺ ions coordinated to three oxygen atoms on the six‐ring sites and Fe monomers are the real active species in the NH₃‐SCR reaction. Furthermore, the influence of intracrystalline mass‐transfer limitations on the Fe‐Cu‐SSZ‐13 catalysts is related to the location of active species in the SSZ‐13 crystals. © 2015 American Institute of Chemical Engineers AIChE J, 61: 3825–3837, 2015     

Simulation of SCR equipped vehicles using iron-zeolite catalysts

Iron-catalysts, based on ZSM-5 (FeZSM5) and Cuban natural Mordenite (FeMORD) zeolites have been prepared by a conventional ion-exchange method and their catalytic activity in the selective catalytic reduction (SCR) of NO with ammonia was studied in the presence of H₂O and SO₂. A commercial SCR catalyst (CATCO) based on V₂O₅–WO₃–TiO₂, was also studied as a reference. This paper presents the experimental results of using these catalysts without toxic vanadium and also exploits a neural network-based approach to predict NO_x conversion efficiency of three SCR catalysts. The mathematical functions derived have been integrated into a numerical model to simulate diesel road vehicles equipped with SCR catalysts such as those studied here. The main results indicate that despite toxic vanadium and N₂O formation, CATCO shows better NO_x conversion efficiencies. However, FeMORD does not produce N₂O and performs better than the FeZSM5. The simulation results on real cycles show lower level of NO_x for heavy-duty and light-duty diesel vehicles compared with homologation load cycles.     

A kinetic model for ammonia selective catalytic reduction over Cu-ZSM-5

Kinetic modeling, in combination with flow reactor experiments, was used in this study for simulating NH₃ selective catalytic reduction (SCR) of NO_x over Cu-ZSM-5. First the mass-transfer in the wash-coat was examined experimentally, by using two monoliths: one with 11 wt.% wash-coat and the other sample with 23 wt.% wash-coat. When the ratio between the total flow rate and the wash-coat amount was kept constant similar results for NO_x conversion and NH₃ slip were obtained, indicating no significant mass-transfer limitations in the wash-coat layer. A broad range of experimental conditions was used when developing the model: ammonia temperature programmed desorption (TPD), NH₃ oxidation, NO oxidation, and NH₃ SCR experiments with different NO-to-NO₂ ratios. 5% water was used in all experiments, since water affects the amount of ammonia stored and also the activity of the catalyst. The kinetic model contains seven reaction steps including these for: ammonia adsorption and desorption, NH₃ oxidation, NO oxidation, standard SCR (NO + O₂ + NH₃), rapid SCR (NO + NO₂ + NH₃), NO₂ SCR (NO₂ + NH₃) and N₂O formation. The model describes all experiments well. The kinetic parameters and 95% linearized confidence regions are given in the paper. The model was validated with six experiments not included in the kinetic parameter estimation. The ammonia concentration was varied from 200 up to 800 ppm using NO only as a NO_x source in the first experiment and 50% NO and 50% NO₂ in the second experiment. The model was also validated with transient experiments at 175 and 350 °C where the NO and NH₃ concentrations were varied stepwise with a duration of 2 min for each step. In addition, two short transient experiments were simulated where the NO₂ and NO levels as well as NO₂-to-NO_x ratio were varied. The model could describe all validation experiments very well.     

Effect of the Presence of Ceria in the NSR Catalyst on the Hydrothermal Resistance and Global DeNOx Performance of Coupled LNT–SCR Systems

The global performance of coupled LNT–SCR systems, addressed to high NOx-to-N₂ conversion, minimal ammonia slip and null N₂O production, as well as the hydrothermal resistance of single NSR and SCR monolith catalysts and their coupling is discussed. Pt–Ba/Al₂O₃ and Pt–Ce–Ba/Al₂O₃ were washcoated on cordierite monoliths as NSR catalysts, and Cu/CHA was washcoated on similar monoliths as SCR catalysts. Both monoliths were coupled in two subsequent reactors to conform the LNT–SCR system. Previously to washcoating, the fresh powder catalysts and after severe hydrothermal aging were fully characterized by N₂ adsorption–desorption isotherms at 77 K, X-ray diffraction, NH₃ temperature-programmed desorption, and H₂ chemisorption to relate textural and chemical characteristics with the DeNO_x performance. The Cu/CHA catalyst shows an excellent hydrothermal resistance for the NH₃–SCR reaction. Incorporation of ceria to the model Pt–BaO/Al₂O₃is beneficial for the NO-to-NOx oxidation and NO₂ storage, improving NO conversion at low temperature and reducing the NH₃ slip. However, addition of ceria is detrimental for the hydrothermal resistance of the NSR catalyst. However, this detrimental effect is minimized when the NSR catalyst is coupled with the Cu/CHA monolith downstream of the NSR catalyst, achieving the coupled LNT–SCR device high NO conversion and minimal NH₃ slip with superior N₂ selectivity for an extended temperature windows, including as low as 220 °C, and maintaining performance even after severe hydrothermal aging.     

Transient reaction analysis and steady-state kinetic study of selective catalytic reduction of NO and NO + NO2 by NH3 over Fe/ZSM-5

The reaction kinetics of selective catalytic reduction (SCR) by NH₃ on NO (standard SCR) and on NO + NO₂ (fast SCR) over Fe/ZSM-5 were investigated using transient and steady-state analyses. In the standard SCR, the N₂ production rate was transiently promoted in the absence of gaseous NH₃; this enhancement can be attributed to the negative reaction order of NH₃ (between −0.21 and −0.11). The steady-state data for the standard SCR could be fit to a Langmuir–Hinshelwood-type reaction between NO_ad and O_ad to form NO₂. In the fast SCR, however, the promotion behavior in the absence of gaseous NH₃ was not observed and the apparent NH₃ order changed from positive to negative with NH₃ concentration. The steady-state rate analysis combined with elementary reaction modeling suggested that competitive adsorption between NO₂ and NH₃ was occurring due to strong NO₂ adsorption; this must be the main reason for the absence of the promotion effect.     

Selective catalytic reduction of NOx by NH3 on Fe/HBEA zeolite catalysts in oxygen-rich exhaust

This paper deals with the systematic study of Fe/HBEA zeolites for the selective catalytic reduction (SCR) of NO_x by NH₃ in diesel exhaust. The catalysts are prepared by incipient wetness impregnation of H-BEA zeolite (Si/Al = 12.5). The SCR examinations performed under stationary conditions show that the pattern with a Fe load of 0.25 wt.% (0.25Fe/HBEA) reveals pronounced performance. The turnover frequency at 200 °C indicates superior SCR activity of 0.25Fe/HBEA (8.5 × 10⁻³ s⁻¹) as compared to commercial Fe-exchanged BEA (0.99 × 10⁻³ s⁻¹) and V₂O₅/WO₃/TiO₂ (1.0 × 10⁻³ s⁻¹). Based upon powder X-ray diffraction (PXRD), temperature programmed reduction by H₂ (HTPR), diffuse reflectance UV–vis spectroscopy (DRUV–VIS) and catalytic data it is concluded that the pronounced performance of 0.25Fe/HBEA is substantiated by its high proportion of isolated Fe oxo sites. Furthermore, isotopic studies show that no association mechanism of NH₃ takes place on 0.25Fe/HBEA, i.e. N₂ is mainly formed from NO and NH₃.The evaluation of 0.25Fe/HBEA under more practical conditions shows that H₂O decreases the SCR performance, while CO and CO₂ do not affect the activity. Contrary, SCR is markedly accelerated in presence of NO₂ referring to fast SCR. Moreover, hydrothermal treatment at 550 °C does not change SCR drastically, whereas a clear decline is observed after 800 °C aging.     

Diesel Soot Catalyzes the Selective Catalytic Reduction of NOx with NH3

The catalytic activity of soot samples for the selective catalytic reduction (SCR) of NO_x with NH₃ was investigated in dependence of the NO₂, NO and NH₃ concentration in the temperature range between 200 and 350 °C. The highest NO_x reduction of up to 25 % was measured in the presence of both NO₂ and NO at a GHSV of 35,000 h^?1. Decreasing space velocities resulted in an increase of the SCR activity. In the absence of NO₂, NO_x reduction was not observed. Carbon oxidation and SCR reaction occurred in parallel due to the presence of NO₂ and O₂, but hardly influenced each other, which suggested that in the NO_x reduction on soot most probably physisorbed species were involved. The observed stoichiometries indicated the action of the fast SCR reaction in the presence of NO and the NO ₂ SCR reaction in the absence of NO, while the observed gas phase and surface species pointed at reaction steps similar to those on classical SCR catalysts.     

Cyclic Lean Reduction of NO by CO in Excess H2O on Pt–Rh/Ba/Al2O3: Elucidating Mechanistic Features and Catalyst Performance

This study provides insight into the mechanistic and performance features of the cyclic reduction of NO_x by CO in the presence and absence of excess water on a Pt–Rh/Ba/Al₂O₃ NO_x storage and reduction catalyst. At low temperatures (150–200 °C), CO is ineffective in reducing NO_x due to self-inhibition while at temperatures exceeding 200 °C, CO effectively reduces NO_x to main product N₂ (selectivity >70 %) and byproduct N₂O. The addition of H₂O at these temperatures has a significant promoting effect on NO_x conversion while leading to a slight drop in the CO conversion, indicating a more efficient and selective lean reduction process. The appearance of NH₃ as a product is attributed either to isocyanate (NCO) hydrolysis and/or reduction of NO_x by H₂ formed by the water gas shift chemistry. After the switch from the rich to lean phase, second maxima are observed in the N₂O and CO₂ concentrations versus time, in addition to the maxima observed during the rich phase. These and other product evolution trends provide evidence for the involvement of NCOs as important intermediates, formed during the CO reduction of NO on the precious metal components, followed by their spillover to the storage component. The reversible storage of the NCOs on the Al₂O₃ and BaO and their reactivity appears to be an important pathway during cyclic operation on Pt–Rh/Ba/Al₂O₃ catalyst. In the absence of water the NCOs are not completely reacted away during the rich phase, which leads to their reaction with NO and O₂ upon switching to the subsequent lean phase, as evidenced by the evolution of N₂, N₂O and CO₂. In contrast, negligible product evolution is observed during the lean phase in the presence of water. This is consistent with a rapid hydrolysis of NCOs to NH₃, which results in a deeper regeneration of the catalyst due in part to the reaction of the NH₃ with stored NO_x. The data reveal more efficient utilization of CO for reducing NO_x in the presence of water which further underscores the NCO mechanism. Phenomenological pathways based on the data are proposed that describes the cyclic reduction of NO_x by CO under dry and wet conditions.