The Selective Catalytic Reduction of NO by Hydrocarbons over Pt- and Ir-Based Catalysts

Platinum- and iridium-based catalysts are the most active ones among noble metals for the selective catalytic reduction of NO by hydrocarbons (HC-SCR). Yet, the level of our understanding of the behavior of these two metals varies greatly. From the early stages of the research efforts in the HC-SCR field Pt-based catalysts were identified as “promising” and have been studied extensively for this application. Subsequently, there is a substantial body of literature focusing on the catalytic performance of such systems, as well as on the fundamental chemistry taking place on their surface under HC-SCR conditions. A fairly good understanding of the behavior of such catalysts has been developed and different reaction mechanisms have been proposed and debated extensively. In contrast, limited information is available regarding the properties and HC-SCR behavior of Ir-based catalysts. Recent reports have demonstrated advantages in the HC-SCR performance of such catalysts and have documented substantial iridium particle size, support and promoter effects.     

Co-ZSM-5催化剂上烃类选择性催化还原NOx机理研究进展

烃类选择性催化还原氮氧化物可能是富氧条件下脱除汽车尾气中氮氧化物污染的有效途径。以Co-ZSM-5催化剂为例,综述了国内外有关Co-ZSM-5催化剂及其在富氧条件下烃类选择还原氮氧化物的机理研究,并将烃类选择还原氮氧化物的过程概括为以下三个步骤：(1) (NO)ad + (O₂)ad (NOy)ad ( y ≥2 );(2) (NOy)ad + (CxHy)ad …… (NCaObHc )ad;(3) (NCaObHc )ad + NO + O₂ …… N₂ + CO₂ + CO + H₂O。     

Silver/Alumina Catalyst for Selective Catalytic Reduction of NO x to N2 by Hydrocarbons in Diesel Powered Vehicles

Ag/alumina has been found to be a promising catalyst for the selective catalytic reduction of NO _x to N₂ by hydrocarbons (HC-SCR) in laboratory tests as well as in full-scale diesel engine operation. The steps in developing an active silver catalyst for practical applications involve knowledge of the mechanism, choice of the right metal content and correct support, adjustment of the concentration of the hydrocarbon to be used for reduction reactions etc. As gas phase reactions seem to play a significant role in obtaining high NO to N₂ conversion, also reactor aspects have to be included in the optimisation procedure of a full size Ag/alumina catalytic converter.     

The Zeolite Micropore as a Unique Reaction Field for the Selective Catalytic Reduction of NO by Hydrocarbon

Zeolite micropores offer unique reaction fields for catalytic reactions based on narrow pores, a wide variety of channel structure, ion exchangeability and strong solid acids. As a negative effect, narrow pore and channels may suppress the diffusivity of reactant molecules and reduce the catalyst effectiveness factor. This article focuses on the influence of the intracrystalline unique reaction fields of zeolite on the selective catalytic reduction of NO by hydrocarbons (HC-SCR) under extreme conditions, i.e. high space-velocity ratio and low content of reactants in exhausts. Zeolite diffusivity in the HC-SCR is affected by two types of diffusion: geometry-limited diffusion, which is determined by the relative size of diffusing molecule and zeolite pore-opening, and adsorption-controlled diffusion, which is determined by the strong interaction between diffusing molecule and intracrystalline cation.     

On the activation of Pt/Al2O3 catalysts in HC-SCR by sintering: determination of redox-active sites using Multitrack

A highly dispersed Pt/Al₂O₃ catalyst was used for the selective catalytic reduction of NO_x using propene (HC-SCR). Contact with the reaction gas mixture led to a significant activation of the catalyst at temperatures above 523 K. According to CO chemisorption data and HRTEM analysis, Pt particles on the activated catalyst had sintered. The redox behavior of the fresh and sintered catalysts was investigated using Multitrack, a TAP-like pulse reactor. If Pt particles on the catalyst are highly dispersed (average size below 2 nm), only a small part (10%) of the total number of Pt surface sites as determined by CO chemisorption (Pt_surf) participates in H₂/O₂ redox cycles (Pt_surf,redox) in Multitrack conditions. For a sintered catalyst, with an average particle size of 2.7 nm, the number of Pt_surf and Pt_surf,redox sites are in good agreement. Similar results were obtained for both catalysts using NO as the oxidant. The low number of Pt_surf,redox sites on highly dispersed Pt/Al₂O₃ is explained by the presence of a kinetically more stable—probably ionic—form of Pt---O bonds on all surface sites of the smaller Pt particles, including corner, edge and terrace sites. When the average particle size shifts to 2.7 nm, the kinetic stability of all Pt---O bonds is collectively decreased, enabling the participation of all Pt surface sites in the redox cycles.

A linear correlation between the NO_x conversion in HC-SCR, and the amount of Pt_surf,redox was found. This suggests that redox-active Pt sites are necessary for catalytic activity. In addition, the correlation could be significantly improved by assuming that Pt_surf,terrace sites of the particles larger than 2.7 nm are mainly responsible for HC-SCR activity in steady state conditions. Implications of these results for the pathway of HC-SCR over Pt catalysts are discussed.     

Use of Double Wash-Coatings of Platinum and Zeolite Catalysts to Improve Selective Reduction of NOx by Hydrocarbons

The selective catalytic reduction by hydrocarbons (HC-SCR) of NO _x under lean conditions has been improved by the use of double-layered catalysts with a lower layer of Pt/SiO₂ and an upper layer of a zeolite such as H-, Ce-, and Cu-ferrierite (-FER). H-FER wash-coated over Pt/SiO₂ (H-FER//Pt/SiO₂) performed best among the samples examined. The promotional effect was attributed to the synergy of the oxidation catalyst (Pt/SiO₂) in converting NO into NO₂, which is more reactive to C₃H₆, and the HC-SCR catalyst (H-FER). Cu-FER//Pt/SiO₂ was also effective at widening the temperature window, but with this combination the performance was attributed to a simple summation of the activity of two HC-SCR catalysts that were active at different temperatures.     

固体吸附/再生法同时脱硫脱硝技术的研究进展

在静态污染源的排放物中，SOx和NOx是导致光化学烟雾和酸雨的主要污染物，又较难净化处理，因此针对它们的控制技术受到了广泛的重视，本文综述了用固体吸附法同时脱除硫氧化物和氮氧化物的研究现状和进展。包括炭质材料吸附法，氧化铜吸附法，NOXSO，以及当今国外广泛研究的储存还原技术。     

The selective catalytic reduction of NO by propylene over Pt supported on dealuminated Y zeolite

The reactivity of Pt supported on a stable dealuminated Y zeolite (Pt/DeY) for the Selective Catalytic Reduction of NO by hydrocarbons (HC-SCR) has been investigated with a monolith sample. The results show that the Pt/DeY catalyst has substantial activity for this reaction at temperatures between 200 and 300°C. Furthermore, the presence of water and sulfur dioxide, at levels similar to the ones expected in vehicle exhaust gas, does not significantly affect the performance of the catalyst, which makes it a promising candidate for further commercial development. In the same temperature range, oxygen promotes the rate of the NO reduction by assisting in the activation of the hydrocarbon. NO₂ is also formed under the conditions studied as a result of the oxidation of NO. In the presence of the hydrocarbon however, it is preferentially reacting with the hydrocarbon, and reduces primarily back to NO. High selectivities were observed toward the formation of N₂O, which is a primary product of the hydrocarbon-SCR reaction.     

Molecule sieving catalysts for NO reduction with hydrocarbons in exhaust of lean burn gasoline and diesel engines

NO oxidation catalysts with small pores and low hydrocarbon oxidation activity owing to molecular sieving were prepared by dispersing platinum in the pores of ferrierite and chabazite zeolites. These small pore platinum zeolite crystals were physically mixed with large pore silver mordenite zeolite crystals and evaluated as HC-SCR catalysts for selective catalytic reduction of NO in a synthetic gas mixture doped with octane or isooctane, mimicking exhaust from lean burning engines with unburned hydrocarbons. A synergetic effect on N₂ formation and hydrocarbon efficiency was obtained in these physical zeolite mixtures. In the pores of the small pore zeolite where the diffusion of NO, O₂ and NO₂ molecules with small kinetic diameters was rapid, NO was effectively oxidized by the platinum into NO₂, while the small window apertures suppressed the diffusion and reaction of the hydrocarbon. The silver plated large pore zeolite catalyzed the reaction between the NO₂ formed in the small pore zeolite and the hydrocarbon. The importance of molecular sieving was demonstrated in experiments with permutation of pore sizes and catalytic functions.     

选择性催化还原法脱硝研究进展

催化脱硝是目前研究较多的脱除氧化物的方法 ,分为催化分解法和催化还原法 .后者又分为选择性催化还原法 ( SCR)和非选择性催化还原法 ( NSCR) .概述了 NH3 作还原剂的SCR法 .介绍了选择性催化还原降低氮氧化物排放技术 ( SCR)的机理、SCR技术催化剂使用情况、SCR反应的吸附机理、反应化学关系式以及化学动力学研究 .同时展望了这一技术领域的重点研究方向     

贫燃条件下净化汽车尾气中NOx的还原催化剂研究现状

本文对贫燃条件下NOx的催化净化进行了综述与探讨,着重评述各种催化剂的优缺点及国内外相关领域的科研开发与进展,提出开发贫燃条件下汽车尾气净化催化剂尚需解决的问题和今后的研究方向,并指出了以后可能应用于实际的催化剂.     

Adsorption of Propene in the Presence and Absence of Oxygen or Nitric Oxide on Pt-Loaded ZSM-5, Beta, Y, and Ferrierite Zeolites

Adsorption and desorption of NO and propene on pure and platinum-loaded ZSM-5, Beta, Y and Ferrierite zeolites have been studied by FTIR and temperature programmed desorption (TPD). Platinum-loaded ZSM-5 and Beta are found to have a good adsorption capacity for hydrocarbons and NO at low temperatures. HC-SCR on Pt-zeolites is a promising NO abatement method.     

NOX removal in excess oxygen by plasma-enhanced selective catalytic reduction

In the off-gases of internal combustion engines running with oxygen excess, non-thermal plasmas (NTPs) have an oxidative potential, which results in an effective conversion of NO to NO₂. In combination with appropriate catalysts and ammonia (NH₃-SCR) or hydrocarbons (HC-SCR) as a reducing agent, this can be utilized to reduce nitric oxides (NO and NO₂) synergistically to molecular nitrogen.

The combination of SCR and cold plasma enhanced the overall reaction rate and allowed an effective removal of NO_X at low temperatures. Using NH₃ as a reducing agent, NO_X was converted to N₂ on zeolites or NH₃-SCR catalysts like V₂O₅–WO₃/TiO₂ at temperatures as low as 100–200 °C. Significant synergetic effects of plasma and catalyst treatment were observed both for NH₃ stored by ion exchange on the zeolite and for continuous NH₃ supply.

Certain modifications of Al₂O₃ and ZrO₂ have been found to be effective as catalysts in the plasma-assisted HC-SCR in oxygen excess. With an energy supply of about 30 eV/NO-molecule, 500 ppm NO was reduced by more than half at a temperature of 300 °C and a space velocity of 20 000 h⁻¹ at the catalyst. The synergistic combinations of NTP and both NH₃- and HC-SCR have been verified under real diesel engine exhaust conditions.     

A study of the mechanisms of NO reduction over vanadium loaded activated carbon catalysts

The kinetics of the selective catalytic reduction of NO in the presence of vanadium loaded carbon-based catalysts has been studied, by means of different techniques, such as transient response analysis, temperature programmed desorption and DRIFT spectrometry. The results point out to a reaction mechanism involving adsorbed species of ammonia, which react with the NO from the gas phase. The role of oxygen will be the regeneration of the spent catalytic sites. Finally, the Mars van Krevelen kinetic model was successfully used to fit the experimental data.     

Catalytic effect of platinum on the kinetics of carbon oxidation by NO2 and O2

The effect of a commercial Pt/Al₂O₃ catalyst on the oxidation by NO₂ and O₂ of a model soot (carbon black) in conditions close to automotive exhaust gas aftertreatment is investigated. Isothermal oxidations of a physical mixture of carbon black and catalyst in a fixed bed reactor were performed in the temperature range 300–450 °C. The experimental results indicate that no significant effect of the Pt catalyst on the direct oxidation of carbon by O₂ and NO₂ is observed. However, in presence of NO₂–O₂ mixture, it is found that besides the well established catalytic reoxidation of NO into NO₂, Pt also exerts a catalytic effect on the cooperative carbon–NO₂–O₂ oxidation reaction. An overall mechanism involving the formation of atomic oxygen over Pt sites followed by its transfer to the carbon surface is established. Thus, the presence of Pt catalyst increases the surface concentration of –C(O) complexes which then react with NO₂ leading to an enhanced carbon consumption. The resulting kinetic equation allows to model more precisely the catalytic regeneration of soot traps for automotive applications.     

Microreactor technology and process miniaturization for catalytic reactions—A perspective on recent developments and emerging technologies

Recent developments in microreactor technology (MRT) are reviewed within the context of discovery, development and commercialization of catalytic systems. Emerging trends and drivers for development of pilot plants and scale-up methods for the next generation of multiphase catalytic processes are presented. Developments in microreactor scale-out, materials of construction, fabrication techniques, and the potential effect of materials of construction on performance are highlighted. Key issues that impact the adoption and implementation of MRT for research, development, and small-scale commercial applications, including safety, potential performance enhancement, environmental impact, distributed production, scale-up, and computer-aided design tools are also analyzed. The role of MRT in portable power systems is given as an example of a potential commercial application.     

Characterization of an S-nitroso-N-acetylpenicillamine–based nitric oxide releasing polymer from a translational perspective

Due to the role of nitric oxide (NO) in regulating a variety of biological functions in humans, numerous studies on different NO releasing/generating materials have been published over the past two decades. Although NO has been demonstrated to be a strong antimicrobial and potent antithrombotic agent, NO-releasing (NOrel) polymers have not reached the clinical setting. While increasing the concentration of the NO donor in the polymer is a common method to prolong the NO release, this should not be at the cost of mechanical strength or biocompatibility of the original material. In this work, it was shown that the incorporation of S-nitroso-penicillamine (SNAP), an NO donor molecule, into Elast-eon E2As (a copolymer of mixed soft segments of polydimethylsiloxane and poly(hexamethylene oxide)), does not adversely impact the physical and biological attributes of the base polymer. Incorporating 10 wt% of SNAP into E2As reduces the ultimate tensile strength by only 20%. The inclusion of SNAP did not significantly affect the surface chemistry or roughness of E2As polymer. Ultraviolet radiation, ethylene oxide, and hydrogen peroxide vapor sterilization techniques retained approximately 90% of the active SNAP content and did not affect the NO-release profile over an 18-day period. Furthermore, these NOrel materials were shown to be biocompatible with the host tissues as observed through hemocompatibility and cytotoxicity analysis. In addition, the stability of SNAP in E2As was studied under a variety of storage conditions, as they pertain to translational potential of these materials. SNAP-incorporated E2As stored at room temperature for over six months retained 87% of its initial SNAP content. Stored and fresh films exhibited similar NO release kinetics over an 18-day period. Combined, the results from this study suggest that SNAP-doped E2As polymer is suitable for commercial biomedical applications due to the reported physical and biological characteristics that are important for commercial and clinical success.     

合成己二酸工艺研究进展

己二酸是一种极其重要的石油化工原料和有机合成中间体,近年来全球的消费量呈现出稳定的增长趋势。由于传统生产工艺存在环境污染等问题,其绿色合成方法备受研究者的关注。本文主要综述了近年来国内外采取不同的原料及催化体系清洁合成己二酸的最新研究进展,重点介绍了以环己烷、环己醇、环己烯及丁二烯等为原料,以分子氧、过氧化氢或臭氧为氧源,采用不同的催化体系合成己二酸的工艺路线,并分析了各种方法的优缺点。研究结果表明,在这些方法中,采用环己烷为原料,一步绿色催化合成己二酸的工艺路线具有很好的应用前景,是未来工业化的最佳方法和思路。     

稀土Cu/HZSM-5催化剂NH_3选择性催化还原法低温脱硝性能

采用浸渍法制备Re(x)Cu/HZSM-5(Re=La,Ce,Pr,Nd;x=0.5,1,2)系列催化剂。采用XRD和H_2-TPR等对催化剂进行表征,在微型固定床反应器中评价催化剂低温NH_3选择还原NO的催化活性。结果表明,Re(x)Cu/HZSM-5(Re=La,Ce,Pr,Nd;x=0.5,1,2)催化剂具有较好的低温NH_3选择还原NO催化活性,以La为助剂和添加质量分数1%的La(1)Cu/HZSM-5催化剂低温脱硝活性较好,T85和T95分别为153℃和164℃,活性温度窗口宽,(153~362)℃时,NO转化率超过95%。     

Engineering HC-SCR: Improved Low Temperature Performance through a Cascade Concept

A catalytic after treatment system for lean HC-SCR was constructed of two different catalyst beds, e.g. of a Ag/alumina and Cu-ZSM-5 catalyst (cascade concept). The improved activity especially at low temperature range was found to be due to the synergetic effect of the two catalysts, which combines the transformation of the feed gas over Ag/alumina to such compounds that are highly reactive towards N₂ over Cu-ZSM-5. The effluent coming from the Ag/alumina bed was analysed by GC–MS along with the NO to N₂ conversion over the whole system by GC. The results obtained from the GC–MS measurements revealed that hydrocarbon used as a reducing agent is oxidised and that besides oxygenates also various N-containing hydrocarbons are formed over the Ag/Al₂O₃.