柴油机钒基与沸石基SCR催化剂对比试验研究

在柴油机台架上比较了钒基、Cu沸石、Fe沸石选择性催化还原(selective catalytic reduction,SCR)催化剂的稳态转化效率、动态反应特性、副反应产物等性能,试验中SCR喷射系统、催化剂规格和封装形式保持一致。试验结果表明:Cu沸石SCR低温转化效率高于钒基SCR和Fe沸石SCR;前置柴油机氧化催化器(diesel oxidation catalyst,DOC)能够显著提高钒基SCR和Fe沸石SCR催化剂低温转化效率;NO2/NOx摩尔比超过50%时,钒基SCR催化剂的转化效率下降,沸石SCR催化剂的转化效率不受影响;钒基SCR催化剂比沸石SCR催化剂的饱和氨存储量低,动态响应速率也较快,在低温段Cu沸石比Fe沸石SCR催化剂吸附氨气的能力更强;SCR反应中,Cu沸石SCR催化剂比钒基和Fe沸石SCR催化剂更容易生成N2O,当有前置DOC时Cu沸石SCR催化剂的N2O生成量进一步提高。     

柴油机Fe-Cu分子筛SCR催化剂的数值模拟

建立催化反应动力学模型预测和比较Fe、Cu分子筛催化剂的NOx还原性能.考虑了NH3的吸附和脱附、NH3氧化、NO氧化及NOx还原反应.结果表明:Cu分子筛催化剂低温(<400℃)时标准选择性催化还原(SCR)反应转化率较高,而Fe分子筛催化剂高温(>400℃)时催化活性较高.考虑到两种分子筛催化剂在不同温度范围内SCR反应活性的差异,将Fe、Cu分子筛催化剂进行分区及分层组合以拓宽组合催化剂的反应活性温窗.在标准SCR反应下,Fe分子筛催化剂(总长度的20%)布置在Cu分子筛催化剂上游为最佳分区组合;Fe分子筛催化剂(总涂层厚度的25%)涂覆在Cu分子筛催化剂上层为最佳分层组合,最佳分区组合布置在整个温度范围内能实现更高的NOx转化率.然而根据对Cu分子筛催化剂和最佳Fe-Cu分区组合催化剂的瞬态响应特性研究,发现Cu分子筛催化剂具有更好的低温瞬态响应特性.通过优化氨氮比,提高了最佳分区组合催化剂的NOx转化率.     

乙醇选择催化还原降低柴油机NOx排放的应用研究

以Ag/Al2O3作为催化剂、乙醇为还原剂的选择性催化还原(SCR)技术被认为是最有潜力降低稀燃NOx的技术之一。开发了基于开环控制的还原剂空气辅助喷射系统;在发动机台架上对乙醇选择性催化还原Ag/Al2O3催化剂的特性进行了性能评价试验;对与Ag/Al2O3组合使用的Cu/TiO2和Pt/TiO2氧化催化剂进行了匹配优选;对集成NOx排气后处理的整机进行了ESC工况测试试验;最后将集成的排气后处理系统装在一辆客车上,并进行了道路实车试验。台架试验结果表明:新鲜Ag/Al2O3催化剂具有很高的NOx转化效率,老化一段时间后NOx转化效率有所降低;与Ag/Al2O3 Cu/TiO2组合催化剂相比,Ag/Al2O3 Cu/TiO2 Pt/TiO2组合催化剂具有更好的NOx转化效率,并能抑制THC和CO排放升高;使用NOx集成排气后处理系统后,发动机在欧ⅢESC工况下,NOx从原机的13.06 g/(kW.h)降为4.63 g/(kW.h),整机的NOx、THC、CO排放都低于欧Ⅲ限值。道路实车试验表明,Ag/Al2O3催化剂需要进一步降低催化剂的起燃温度,以适应柴油车实际运行中低温变工况的需要。     

Cu-Fe复合沸石型SCR催化剂在重型柴油机上的应用研究

在重型柴油机台架上研究了Cu-Fe复合沸石型SCR催化剂的稳态转化效率、氨存储特性、ETC循环和WHTC循环中的瞬态反应特性,以及催化剂后副反应产物N2O的生成规律。试验表明,相同条件下该沸石型SCR催化剂饱和氨存储量明显大于钒基催化剂,温度低于250℃时NOx转化效率受到氨存储量的影响,催化剂氨存储充分时190℃温度下NOx转化效率达到74%。瞬态循环中WHTC循环的平均排气温度比ETC循环大幅降低,催化剂的NOx转化效率受到氨泄漏的限制,经过SCR控制策略优化后可以满足北京第四阶段对WHTC循环的检测要求。N2O是该SCR系统的主要副产物,在低温和高温时浓度较高,符合N2O的生成机理。     

Fe对MnO_x催化剂低温SCR脱硝性能的影响

采用共沉淀法制备一系列Fe改性的MnOx催化剂,在固定床模拟燃煤烟气气氛下考察其脱硝活性,同时借助N2吸附及XRD等研究Fe添加对MnOx催化剂低温SCR脱硝活性的促进机理。结果表明,Fe的添加显著提高了MnOx的低温NOx转化率,并将其活性温度窗口向低温段拓宽了55℃;其中,Fe0.3Mn0.7Ox催化剂在30 000h-1下具有最佳低温SCR活性,自90℃其NOx转化率均高于95%;铁、锰组分间的协同作用能提高催化剂中锰氧化物的分散度,增大催化剂的比表面积和比孔容并优化其孔径分布,进而提高MnOx催化剂的低温SCR脱硝活性。     

基于V-W/Ti基催化剂的NH3选择性催化还原NOx的试验研究

针对一使用SCR技术满足欧-Ⅳ排放标准的柴油机排气特征,在连续流动固定床反应器上利用NH3作还原剂对一纳米级V-W/Ti基催化剂的选择性催化还原NO的反应进行了试验研究,分析了在不同温度、空速、NH3/NO摩尔比的情况下对DeNOx性能的影响.试验结果表明,温度对催化还原性能的影响最大,在低温下,由于催化剂活性不高,NOx的脱除效率很低,随着反应温度的升高,催化剂活性升高,NOx脱除率随之急剧升高,在300℃～450℃范围内达到较高的NOx脱除效率;随着NH3/NO摩尔比的增加,还原效率并未明显增加,但NH3的氧化和泄漏越来越严重;另外,空速对低温下还原效率也存在一定的影响.     

利用SCR技术降低柴油机NOx的试验研究

设计了尿素水溶液还原添加装置,并使用这套装置在发动机台架上进行了稀燃NOx选择催化还原（SCR）催化剂的性能评价试验,最后分析了SCR技术目前存在的问题。试验结果表明：在30000h^-1空速、排气温度为340～420℃范围的条件下,该催化剂的NOx转化率维持在90%以上,而在低温和高温下的转化率较低;随着尿素水溶液添加量的增加,催化剂NOx转化率提高,但同时会增加CO排放;当空速为50000h^-1时,催化剂性能略有所下降。     

同时催化去除柴油机微粒和NOx的试验研究(1)

通过在γ-Al2O3小球和柴油机微粒过滤器（DPF）上涂覆复合金属氧化物催化剂Cu0.95K0.05Fe2O4和La0.9K0.1CoO3。利用程序升温反应（TPR）技术，对同时催化去除柴油机微粒（PM）和NOx反应进行了试验研究。研究结果表明，Cu0.95K0.05Fe2O4和La0.9K0.1CoO3催化剂能够明显降低NOx的浓度和PM的起燃温度和燃尽温度，具有显著的PM-NOx同时去除催化反应活性。该方法集柴油机微粒的捕集、微粒的氧化燃烧和NOx的还原等功能于一体，是一种很有发展前途的柴油机排放后处理新技术。     

同时催化去除柴油机微粒和NO_x的试验研究(2)

通过在γ Al2O3小球和柴油机微粒过滤器(DPF)上涂覆复合金属氧化物催化剂Cu0.95K0.05Fe2O4和La0.9K0.1CoO3,利用程序升温反应(TPR)技术,对同时催化去除柴油机微粒(PM)和NOx反应进行了试验研究。研究结果表明,La0.9K0.1CoO3催化剂比Cu0.95K0.05Fe2O4催化剂具有更高的同时去除PM—NOx的催化反应活性。在低负荷下,柴油机的PM由于SOF含量多而使NOx降低的幅度比高负荷下的大,其燃烧温度也比高负荷下的低。同时,NO和O2的共存促进了PM的氧化燃烧。另外,PM和催化剂之间"松接触"的催化活性要比"紧接触"低。     

乙醇选择性催化还原NOx后处理系统在重型柴油机上的应用研究

选择催化还原是解决稀燃条件下NOx排放问题的主要技术之一。在发动机台架上对以乙醇作为还原剂的Ag/Al2O3催化剂特性进行了试验研究,对Ag/Al2O3 Cu/TiO2和Ag/Al2O3 Cu/TiO2 Pt/TiO2两种还原、氧化催化剂组合进行了对比分析。分析表明,Ag/Al2O3 Cu/TiO2 Pt/TiO2催化剂组合具有较好的去除NOx并抑制THC和CO排放升高的综合性能。整个后处理系统安装在一台排量为5.12 L的柴油机上,采用开环控制策略对乙醇喷射进行控制,在ESC测试工况下,NOx转化效率为64%,THC和CO排放基本保持原机水平。最后通过对乙醇喷射控制策略的进一步改进,使THC和CO排放得到了改善。     

柴油机尿素选择催化还原技术现状及发展趋势

严格的排放法规要求进一步降低NOx排放,选择催化还原(SCR)技术是欧V和欧VI阶段去除NOx的主流技术。首先介绍降低柴油机NOx排放的尿素选择催化还原技术(Urea-SCR)的化学反应机理,然后分别从尿素存储装置、尿素供给系统、催化器及控制单元等方面指出Urea-SCR的研究现状,最终在已有研究基础上对SCR技术的发展趋势进行分析。     

A review on various after treatment techniques to reduce NOx emissions in a CI engine

NOx emissions have always been a main concern in the development of diesel engines. This paper summarizes the studies about NOx emission reduction in diesel engines. The need for meeting the stringent requirements with regard to NOx emissions in a diesel engine has led to the development of a range of after treatment techniques. After treatment methods are required to reduce NOx emissions that cannot be controlled by fuel composition and combustion phenomena. Current after treatment techniques that are being employed are Selective Catalytic Reduction (SCR), Lean NOx Trap (LNT) and SCR Filter (SCRF). The benefits and constraints of different types of SCR are discussed. Urea SCR is a prominent well proven technology. Urea SCR produces 96–99% conversion efficiency with the help of a reductant NH₃. The operating parameters such as nature of catalyst, temperature range of catalyst, flow of DEF (Diesel Exhaust fluid) to injector and mixing of NH₃ and NOx are discussed. Hybrid SCR such as Cu-SCR + Fe-SCR, SCR + LNT moderates fuel consumption and augments the catalytic activity at low temperature. SCRF has low cell density (200–300 csi vs 400–600 csi for SCR), and also has lower deNOx efficiency for a number of reasons. Pre-stored NH₃ and Preheating helps in low temperature reaction of SCRF. Technical problems in aqueous urea systems have led to the evolution of solid SCR system (SSCR). This review incorporates the study of solid ammonium salts decomposition, temperature range of the salts and infrastructure required for SSCR.     

LaCoO3钙钛矿型催化剂对柴油机NOx净化性能研究

采用柠檬酸络合法制备了LaCoO3钙钛矿型催化剂。对其理化特性及NH3-选择性催化还原催化性能的研究结果表明：纯LaCoO3颗粒具有一定的NOx催化还原能力,在250～450℃活性较高;但该催化剂对NH3具有较高的氧化活性,且催化活性随反应温度的升高而提高;在SCR反应中,在400℃以下时,该催化剂显示出一定的NOx净化能力,但当温度超过400℃以后,还原剂的加入反而恶化了NOx排放。不管反应气组成如何,LaCoO3钙钛矿型催化剂对HC和CO都具有良好的催化性能。     

含Pd双金属分子筛催化剂控制稀燃汽油机NOx排放

为实现对稀燃汽油机NOx排放的有效控制，对Pd-In-ZSM5、Cu-Pd-ZSM5催化剂在实际稀燃排气条件下进行了研究，对Pd-In-ZSM5催化剂，由于Pd、In两种金属的作用，出现了两个NOx转化效率的峰值，最高转化效率达到35．7％．Cu-Pd-ZSM5催化剂可以实现CO对NOx的还原反应，使稀燃NOx的转化效率最高达到60％，并且具有较宽的活性温度窗口；当量空燃比时，NOx的转化效率超过70％，含Pd的双金属分子筛催化剂，在不同的温度范围内，可以实现HC和CO对NOx的协同还原反应，有效拓宽较高NOx转化效率的活性温度窗口。     

NH3低温选择性催化还原NO的研究

在固定床反应器中,利用瞬态响应技术和程序升温技术研究了低温时NH3选择性催化还原(SCR)NO的瞬态动力学及V2O5-WO3/TiO2催化剂活性的影响因素,试验结果表明:O2的体积分数增大,NO转化率增大;H2O的存在抑制了NO的转化率;SO2的存在提高了NO的转化率.低温时,SCR反应遵循Eley-Rideal机理,...     

烟气脱硝装置技术介绍

催化脱硝是目前发达国家普遍采用的减少NOx排放的方法,应用较多的有选择性催化还原法(Selec-tive catalytic reduction,简称SCR)、选择性非催化还原法(Selective non-catalytic reduction,以下简称SCR)。详细介绍了SCR烟气脱硝技术的原理、工艺流程、运行控制和工业应用实例。     

Hydrogen production from the steam reforming of bioethanol over novel supported Ca/Ni-hierarchical Beta zeolite catalysts

This paper studies the H₂ production via the steam reforming of a bioresource-derived ethanol mixture over supported Ca-modified Ni-hierarchical Beta zeolite catalysts. The results showed that the hierarchical Beta zeolite with rich pore structure could be synthesized in one step by using the new quaternary ammonium gemini cationic surfactant. The zeolite had bigger BET area and pore volume than the traditional Beta zeolite. The support plays a key role for the improve of catalytic behavior. The internal structure of the catalyst can be changed by introducing calcium and nickel ions into the synthesized zeolite at the same time through ion exchange. The interaction between active metal and the support would increase, so the dispersion of the active metal can be improved. The intermediate CO₂ was efficiently absorbed by Ca in situ, which is an exothermic reaction and also help to provide the heat for the reactor. The adsorption of СО₂ in situ transmitting the reversible reforming and water gas shift reactions to the products outside their conventional thermodynamic restrictions, which enhanced H₂ production and permits high conversion to be attained. By using the method of gradient distribution of active metal in the support, the repeated catalytic effect similar to that of a hierarchical reactor was constructed, which showed excellent catalytic effect in low and medium high temperature bioethanol reforming to hydrogen. The experimental results show that when the reaction temperature is 350 °C, the 10Ni-MBeta(DI) catalyst maintains stable catalytic efficiency for continuous hydrogen production of 50 h via ESR, high hydrogen production and good stability.     

钒基催化剂NH3-SCR低温反应特性研究

利用固定床反应器及原位漫反射傅里叶变换红外光谱仪,通过稳态及瞬态反应,研究了v205-wO,rri02催化剂低温NH3选择性催化还原(SCR)机理及低温活性的影响因素.结果表明:低温时,V205-WO3l'iO2 SCR催化剂首先吸附气态NH3,形成吸附态NH3nnH4．,然后吸附态NH3vnh^和气态NO反应,生成N...     

Low-temperature flue gas denitration with transition metal oxides supported on biomass char

Several transition metals (Mn, Ce, V and Fe) were loaded on nitric acid modified biomass char (BC) using an impregnation method for the selective catalytic reduction (SCR) of NO with NH₃ at low-temperature. The series of prepared catalysts were characterized by BET, SEM, FT-IR and XRD. Results showed the sequence of NO conversion within the temperature of 125–225 °C was Mn/BC > Ce/BC > V/BC > Fe/BC > BC, and Mn/BC exhibited the highest NO conversion of 87.6% at 200 °C. BC supports provided high surface area, which could contribute to the better dispersion of transition oxides on biomass char, revealing rich oxygen containing groups. Besides, the BC worked not only as a promising support, but also provided high activity adsorption sites for NH₃ and conducted as oxidizing agent for NO due to the existence of graphite crystallite structure. Owing to the existence of “fast SCR” reaction process, the transition metal oxides supported on BC catalysts exhibited superior denitration efficiency in low temperature.