新型高效高稳定NO_x催化还原用分子筛催化剂的研究进展

氮氧化物选择性催化还原(SCR)是汽车尾气处理领域的研究热点,其核心问题是新型高效高稳定SCR催化剂的研制。针对分子筛催化剂的SCR过程,本文综述了分子筛催化剂上NOx在氨和碳氢化合物等还原剂作用下的选择性催化还原研究进展。以不同孔结构分子筛催化剂(如天然沸石分子筛、微孔分子筛、大孔分子筛和新兴的介孔分子筛等催化剂)为例,总结了不同孔结构分子筛催化剂与NOx催化降解的规律,系统分析了不同孔结构分子筛催化剂载体与活性组分之间的相互作用,探讨了不同孔结构分子筛催化剂与催化活性和稳定性之间的关联性,阐释了不同孔结构分子筛催化剂的催化反应机理,展望了分子筛催化剂在NOx选择性催化还原领域的前景。     

分子筛类催化剂上甲烷选择性催化还原NOx研究进展

选择性催化还原NOx是处理工业废气和稀燃汽车尾气NOx的有效方法。由于还原剂甲烷廉价易得,甲烷选择性催化还原NOx（简称CH4-SCR）已成为近年来的研究热点,而分子筛类催化剂因催化活性高而得到广泛研究。本文综述了CH4-SCR脱除NOx体系中不同金属负载的分子筛催化剂及反应机理方面的研究进展,包括Co系、Pd系、In系等分子筛催化剂在催化性能、反应机理及掺杂改性等方面的研究现状,并提出了分子筛类催化剂用于CH4-SCR的研究方向。     

金属基分子筛型NH3选择性催化还原氮氧化物催化剂的研究进展

氨气选择性催化还原(NH3-SCR)消除氮氧化物(NOx)以其高效、低成本的优势成为目前最具潜力和最广泛应用的固定源脱硝技术.传统的NH3-SCR以V2O5/WOx-TiO2为催化剂,但该类催化剂水热稳定性差,易中毒且其本身就具有毒性,因此开发金属基分子筛催化剂是当前的研究热点之一.本文介绍了分子筛型NH3-SCR催化剂的研究进展,总结了不同金属负载分子筛对选择性催化还原的影响及其反应机理,探讨了催化剂失活的影响因素.     

CO低温催化还原氮氧化物的研究进展

阐述了以金属负载型、金属氧化物型、分子筛型和活性炭负载型等不同种类催化剂CO低温催化还原NOx的研究进展,总结了各种催化剂的优势和不足之处,并指出非贵金属催化剂应作为重点研究对象和今后研究可能的发展方向,即提高催化剂的低温活性、热稳定性、抗中毒能力和提高还原产物N₂的选择性。     

在讲究环境保护的今天，减少陶瓷窑炉烟气中有害废气都有哪些方法？

减少陶瓷窑炉烟气中有害废气的方法主要有：1)还原法。目前主要有选择性非催化还原技术(SNCR)、选择性催化还原技术(SCR)，以及碳氢化合物选择性催化还原(HC—SCR)、非选择性催化还原(NSCR)等方法。其基本原理都是通过向烟气中加入还原剂(如氨、尿素等)，在有催化剂存在或在一定的温度下，将NOx还原成N2以达到脱除NOx的目的。     

贫燃条件下汽车尾气中氮氧化物的催化净化

以碳氢化合物为还原剂选择性还原汽车尾气中的NOx是研究较早且较多的一种方法。以NH3或尿素为还原剂催化还原NOx,NOx储存还原型三效催化剂以及NOx直接催化分解等净化方法也得到了广泛的研究。低温等离子体,以水滑石类化合物为前体的催化剂以及利用改性碳纤维作还原剂等是近几年新发展的净化方法。在这些方法中,钙钛矿型复合氧化物和NOx储存还原型三效催化剂是目前该领域的研究热点。指出今后应进行深入的机理研究,为催化剂的设计提供理论指导。     

正庚烷异构化催化剂研究进展

阐述了当前正庚烷异构化所用的负载型催化剂和过渡金属碳化物和氧化物催化剂的研究进展,对催化剂性能的影响因素及对策进行了分析与讨论。正庚烷异构化催化剂中,研究较多的是以SAPO、HZSM-5和Y、B型分子筛为载体的贵金属催化剂,其中SAPO分子筛载体的性能较优,Pt比Pd具有更好的催化性能,非贵金属／分子筛催化剂的活性比贵金属／分子筛催化剂相差较大。过渡金属Mo、W的碳化物和氧化物也具有较好的正庚烷异构化性能,与碳氧化物或碳化物相比,部分还原氧化物催化正庚烷异构化活性和选择性要高得多,其活性甚至高于传统的Pt/USY双功能催化剂。展望了正庚烷异构化催化剂的研究方向和意义。     

富氧条件下氢气选择性催化还原NOx催化剂研究进展

着重介绍了NOx脱除技术中的选择性催化还原技术,分析了以不同还原剂(NH3、H2、CO、HC)选择性催化还原NOx技术的优缺点,认为H2-SCR脱硝技术具有较高的研究价值和实际的应用前景。从催化剂的活性组分、助剂及载体的角度分析了不同催化剂在氢气选择性催化还原脱硝技术中的应用及其所达到的效果,得出负载贵金属Pt与Pd、添加酸性助剂以及采用复合载体的催化剂性能更佳,并对今后氢气选择性催化还原脱硝技术的研究方向进行展望。     

异丙苯催化氧化催化剂研究进展

异丙苯氧化反应是石油化学工业中重要的反应过程,传统的异丙苯氧化工艺是以少量的氧化产物过氧化氢异丙苯作为引发剂的无催化氧化工艺,存在效率低和安全性差等缺陷。几十年来,研究者对异丙苯催化氧化工艺进行了广泛研究,开发的催化剂类型主要有碱金属或碱土金属催化剂、金属氧化催化剂、过渡金属离子有机络合物催化剂、N-羟基邻苯二甲酰亚胺类催化剂、负载型催化剂、金属及合金催化剂和中孔分子筛催化剂等。其中,改性MgO催化剂、Ag及Ag-Au合金催化剂和负载过渡金属杂原子的中孔分子筛催化剂表现出较优越的催化性能,具有较好的开发前景。但迄今为止报道的各类催化体系还不能彻底解决传统氧化工艺的固有问题,开发具有高活性、高选择性和高稳定性的环境友好催化体系是今后研究的重点。     

烟气NOx低温选择性催化还原催化剂研究进展

催化剂是选择性催化还原(SCR)脱硝技术的核心,其催化性能直接关系到脱硝效果的好坏。近年来,由于低温选择性催化还原法具有良好的经济性,引起各国环保研究工作者的关注,成为近年SCR研究的热点。本文概述了贵金属、金属氧化物、分子筛和碳基材料催化剂的低温(低于250℃)选择性催化还原法脱除NOx研究进展。其中,以碳基材料为载体的催化剂显示出良好的低温选择性和稳定性,具有很好的应用前景。     

Catalytic Cracking of n-Dodecane and Diesel Fuel to Improve the Selective Catalytic Reduction of NOx in Automotive Exhaust Containing Excess Oxygen

The low exhaust gas temperatures of diesel engines and the chemical composition of diesel fuel is responsible that only a small amount of nitrogen oxides is converted into nitrogen over SCR catalysts based on Pt zeolites. In order to improve the NO_x reduction over these types of catalysts, it is investigated if a catalytic cracking process is suitable to convert the diesel fuel into more reactive molecules which should act as reducing agent in the HC-SCR process.     

低温催化脱硝技术的研究进展

面对日益严重的环境问题,燃煤烟气催化脱硝技术得到了较快发展。针对目前应用较为广泛的选择性催化还原脱硝技术,本文从催化脱硝技术的机理出发综述了低温催化脱硝方面的研究进展,将低温催化脱硝技术分成两大类:低温氨法选择性催化还原脱硝技术和低温非氨法催化脱硝技术。在低温氨法选择性催化还原脱硝技中总结了金属氧化物催化剂、分子筛催化剂以及碳基催化剂等的反应机理和反应过程,揭示了影响脱硝效率的各种因素;低温非氨法催化脱硝技术中从反应方式出发,总结了NO_x催化裂解技术、HC-SCR技术、NO_x吸附-还原技术以及CO催化脱硝技术的研究进展,并对反应影响因素进行了综述。探索了各种催化剂的优势和不足之处:低温NH₃-SCR技术具有选择性高、效率高的特点但是其还原剂价格较贵且存储运输较为困难;低温非氨法催化脱硝技术选择性差、效率低,但是还原剂价格低廉、易于制备,且在工艺方面改进时可以达到要求的效率。在此基础上本文展望了未来低温催化脱硝的研究方向:在降低脱硝成本的情况下改善催化脱硝工艺,大力发展氮氧化物吸附还原等技术。     

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.     

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.     

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.     

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.     

选择性催化还原脱硝催化剂的研究进展

选择性催化还原（SCR）是目前控制氮氧化物排放的主要技术,该技术具有选择性好、脱硝效率高、不造成二次污染等优点。本文对SCR技术及其催化剂进行了综述,重点介绍了钒钛催化剂、贵金属催化剂、金属氧化物催化剂及沸石分子筛型催化剂的研究进展,并对国内外脱硝催化剂的工业化现状及催化剂的影响因素进行了分析,最后指出我国脱硝催化剂的发展应以提高催化剂寿命、开发新型催化剂（以复合金属氧化物催化剂和新型钒基催化剂为主）及新工艺为方向进行。     

Toward improved catalytic low-temperature NOx removal in diesel-powered vehicles

The potential of different catalytic after treatment techniques to meet future diesel emission standards, which are strongly shifted toward urban driving conditions including cold start, are critically discussed in this Account and evaluated for their suitability for commercial applications. The dominating techniques in this field are NO(x) storage, urea-selective catalytic reduction (SCR), and HC-SCR. Each of these techniques have significant disadvantages such as sulfur sensitiveness and regeneration requirements of NO(x)-storage materials, infrastructure issues and formation of ammonium nitrate (at low temperatures) for urea-SCR, and low-temperature activity of HC-SCR catalysts. Ways to overcome these disadvantages in commercial applications may involve optimized regeneration strategies, reactor modifications, flow reversal, closed-loop NO(x) feedback systems, nonthermal plasma, and/or hydrogen-assisted catalyses, etc.     

A comparison study on non-thermal plasma-assisted catalytic reduction of NO by C3H6 at low temperatures between Ag/USY and Ag/Al2O3 catalysts

A comparison study was carried out on non-thermal plasma (NTP)-assisted selective catalytic reduction (SCR) of NO_x by propene over Ag/USY and Ag/Al₂O₃ catalysts. Ag/USY was almost inactive in thermal SCR while it showed obvious activities in NTP-assisted SCR at 100 °C–200 °C. Although the NO_x conversion over Ag/Al₂O₃ was also enhanced at 300 °C–400 °C by the assistance of NTP, it was ineffective below 250 °C. The intermediates over Ag/USY and Ag/Al₂O₃ were investigated using in situ DRIFTS method. It was found that key intermediates in HC-SCR, such as NCO, CN, oxygenates and some N-containing organic species were enriched after the assistance of NTP. The differences in the behaviors of above intermediates were not found between these two kinds of catalysts. However, some evidences suggested that different properties of the absorbed NO_x species resulted in the distinction of SCR reactions over Ag/USY and Ag/Al₂O₃. TPD profiles of Ag/Al₂O₃ showed that nitrates formed over the catalyst were quite stable at low temperatures, which might occupy the active sites and were unfavorable to SCR reactions. The nitrates over Ag/USY were unstable, among which the unidentate nitrate species is probably contributed to the SCR reactions at low temperatures.     

Experimental Study of the NO Oxidation to NO2 Over Metal Promoted Zeolites Aimed at the Identification of the Standard SCR Rate Determining Step

Steady state and transient kinetic runs devoted to the comparative analysis of NO oxidation and standard SCR reactions over commercial Cu- and Fe-promoted zeolite catalysts are herein presented with the aim to clarify whether NO oxidation to NO₂ is the rate determining step (rds) of the standard SCR reaction. It is found that this statement seems questionable in the light both of the herein collected experimental results and of scattered evidence from the literature.