CN104582845A - 沸石助催化的V/Ti/W催化剂 - Google Patents

沸石助催化的V/Ti/W催化剂 Download PDF

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CN104582845A
CN104582845A CN201380043689.XA CN201380043689A CN104582845A CN 104582845 A CN104582845 A CN 104582845A CN 201380043689 A CN201380043689 A CN 201380043689A CN 104582845 A CN104582845 A CN 104582845A
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catalyst
component
molecular sieve
waste gas
oxide
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CN104582845B (zh
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J·鲍尔
R·道泽尔
J·约德罗克
R·勒佩尔特
J·穆恩希
I·皮拉斯
G·斯梅德勒
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Johnson Matthey PLC
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Johnson Matthey PLC
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Abstract

提供了用于处理废气的催化剂组合物,其包含第一组分和第二组分的共混物,其中该第一组分是铝硅酸盐或铁硅酸盐分子筛组分,其中该分子筛为H+形式或是用一种或多种过渡金属离子交换的,该第二组分是负载在选自下面以下的金属氧化物载体上的钒氧化物:氧化铝、二氧化钛、氧化锆、二氧化铈、二氧化硅及其组合。还提供了结合了或使用了这样的催化剂共混物的方法、系统和催化制品。

Description

沸石助催化的V/Ti/W催化剂
发明背景
A.)应用领域:
本发明涉及催化剂、系统和方法,其可用于处理烃燃料燃烧所形成的废气,和特别是含有氮氧化物的废气,例如柴油发动机所产生的废气。
B.)相关领域说明:
多数燃烧废气的最大部分包含了相对良性的氮气(N2)、水蒸汽(H2O)和二氧化碳(CO2);但是该废气也包含相对小部分的有害和/或有毒物质,例如来自不完全燃烧的一氧化碳(CO),来自未燃烧燃料的烃(HC),来自过高燃烧温度的氮氧化物(NOx),和微粒物质(主要是烟灰)。为了减轻释放到大气中的废气对于环境的冲击,需要消除或减少这些不期望的组分的量,优选通过不会再产生其他有害或有毒物质的方法。
最难以从车辆废气中除去的组分之一是NOx,其包括一氧化氮(NO)、二氧化氮(NO2)和/或一氧化二氮(N2O)。在例如通过柴油发动机产生的贫燃废气中将NOx还原成N2特别成问题,因为该废气包含足够的氧来支持氧化反应,而不是还原。但是,NOx可以在柴油机废气中通过通常称作选择性催化还原(SCR)的方法来还原。SCR方法包括在催化剂存在下和借助于还原剂,将NOx转化成单质氮(N2)和水。在SCR方法中,在使废气与SCR催化剂接触之前将气态还原剂例如氨添加到废气流中。该还原剂被吸收到催化剂上,和在气体经过催化基底之中或之上时发生NOx还原反应。
在使用NH3作为还原剂的选择性催化还原(SCR)系统中发生几种化学反应,其全部代表了令人期望的反应,这些反应将NOx还原成单质氮。主要反应机理表示在式(1)中。
4NO+4NH3+O2→4N2+6H2O    (1)
与氧的竞争性非选择性反应会产生二次排放或者会非生产性地消耗NH3。一种这样的非选择性反应是式(2)所代表的NH3的完全氧化。
4NH3+5O2→4NO+6H2O    (2)
此外,NOx中存在的NO2与NH3的反应被认为根据反应(3)进行。
3NO2+4NH3→(7/2)N2+6H2O    (3)
此外,NH3和NO和NO2之间的反应通过反应(4)来表示:
NO+NO2+2NH3→2N2+3H2O    (4)
虽然反应(1)、(3)和(4)的反应速率根据反应温度和所用催化剂的种类而发生很大的变化,但是反应(4)的反应速率通常为反应(1)和(3)的反应速率的2-10倍。
公知将SCR技术用于处理来自车辆内燃机,特别是来自贫燃内燃机的NOx排放物。所公开的用于此目的的一种典型的现有技术SCR催化剂包括负载在TiO2上的V2O5/WO3(参见WO99/39809)。但是,在一些应用中,钒基催化剂的热耐久性和性能可能是不可接受的。
已经被研究用于处理来自内燃机废气的NOx的一类SCR催化剂是过渡金属交换的沸石(参见WO99/39809和US4,961,917)。但是,在使用中,某些铝硅酸盐沸石例如ZSM-5和β沸石具有诸多缺陷。它们在高温水热老化过程中易于脱铝,导致酸度损失,特别是对于Cu/β和Cu/ZSM-5催化剂更是如此;β基催化剂和ZSM-5基催化剂还受到这样的烃的影响,烃在相对低的温度开始吸附到催化剂上,并且在催化系统温度升高时氧化,产生明显的放热,这会热损坏该催化剂。这个问题在大量烃会在冷启动过程中吸附到催化剂上的车辆柴油应用中特别尖锐。并且β和ZSM-5沸石也易于被烃焦化,这降低了催化剂性能。因此,仍然需要改进的催化剂,用于选择性催化还原方法。
发明概述
申请人已经发现,将钒基SCR或ASC催化剂与某些分子筛共混改进了催化性能,这在单独考虑这些组分中的每个时没有观察到。具体地,本发明的催化剂实现了与已知的SCR催化剂和ASC催化剂相比,改进的高温性能、改进的水热稳定性、高耐硫性和改进的NO2耐受性。这样的共混物优选包含铝硅酸盐或铁硅酸盐分子筛,其优选为H+形式或者是用过渡金属例如Fe离子交换的。优选该分子筛具有选自MFI、BEA或FER的骨架。
因此,提供了一种用于处理废气的催化剂组合物,该组合物包含第一组分和第二组分的共混物,其中该第一组分是铝硅酸盐或铁硅酸盐分子筛组分,其中该分子筛为H+形式或者是用一种或多种过渡金属离子交换的,该第二组分是负载在选自以下的金属氧化物载体上的氧化钒:氧化铝、二氧化钛、氧化锆、二氧化铈、二氧化硅及其组合。
根据本发明的另一方面,提供了一种催化洗涂层(washcoat),其包含这里所述的催化剂共混物。
根据本发明的另一方面,提供了一种催化制品,优选为挤出的流通式蜂窝体,其包含这里所述的催化剂共混物。
根据本发明的又一方面,提供了一种处理废气例如由柴油内燃机产生的废气中的NOx或NH3的方法,其中该方法包括使废气与这里所述的催化剂共混物接触,由此降低废气中NOx或NH3的浓度。
附图说明
图1的图显示了根据本发明一个实施方案的新鲜催化剂的NOx转化率数据与现有技术中已知的催化剂的对比数据。
图2的图显示了根据本发明一个实施方案的新鲜催化剂的NOx转化率数据与现有技术中已知的催化剂的对比数据。
图3的图显示了根据本发明一个实施方案的新鲜催化剂的NOx转化率数据与现有技术中已知的催化剂的对比数据。
图4的图显示了根据本发明一个实施方案的经老化催化剂的NOx转化率数据与现有技术中已知的经老化催化剂的对比数据。
图5的图显示了根据本发明一个实施方案的两种不同催化剂的NOx转化率数据与现有技术中已知的催化剂的对比数据。
本发明优选实施方案详述
在一个优选的实施方案中,本发明涉及一种催化剂,其用于改进环境空气质量,特别是用于改进柴油机和其他贫燃发动机所产生的废气排放。废气排放是至少部分通过在宽的操作温度范围上,降低贫燃废气中的NOx和/或NH3逃逸(slip)浓度来改进的。有用的催化剂是在氧化性环境中选择性还原NOx和/或氧化氨(氨逃逸)的那些(即SCR催化剂和/或ASC催化剂)。
根据一个优选的实施方案,提供了一种催化剂组合物,其包含以下的共混物:(a)分子筛组分,其包含铁助催化的铝硅酸盐分子筛或铁硅酸盐分子筛(也称作无定形铁分子筛),其具有选自MFI、BEA和FER的骨架;和(b)钒组分,其包含一种或多种钒氧化物,其负载于包含钛氧化物的金属氧化物载体上。
作为此处使用的,术语“共混物”表示两种或更多种催化组分的基本均匀的组合,其中任一种能够单独用于与共混物相同的目的。当在合并在共混物中时,单个催化组分是不易于分离的。并且至少部分由于该组合的协同性质,该构成部分的催化效果是彼此无法区分的。
在一个优选的实施方案中,该催化剂组合物包含相对于分子筛组分(包括铁)而言基于重量计主要部分的钒组分(包括金属氧化物载体)。在某些实施方案中,该催化剂组合物包含重量比为约1:1-约99:1的钒组分和分子筛组分。优选该钒组分和分子筛组分以约2:1-约4:1、约5:1-约10:1或者约10:1-约50:1的重量比存在。这里,该钒组分基于共混物中存在的钛氧化物、钒氧化物和任选的钨氧化物的氧化物的量来计算重量比,并且不包括所存在的(如果有的话)其他非催化金属氧化物。可能存在于该组合物中的非催化金属氧化物的非限定性例子包括粘合剂和其他类型添加剂例如氧化铝、氧化锆、二氧化铈、二氧化硅、氧化铝与氧化锆或二氧化铈的混合物、涂覆于氧化铝上的二氧化铈,和混合氧化物例如(非沸石)二氧化硅-氧化铝、氧化铝-氧化锆、氧化铝氧化铬和氧化铝二氧化铈。在该组合物中粘合剂不同于催化金属氧化物,因为该粘合剂不用对于SCR方法来说催化活性的金属来助催化,和/或具有远大于催化金属氧化物的粒度。本领域技术人员还将理解,该比率描述了共混物中催化活性组分的相对比例,并且不考虑其他组分例如填料、纤维性增强剂、加工助剂、水等(其会存在于不同形式的催化剂组合物中,例如浆料、洗涂层和可挤出的糊)。
在另一实施方案中,该催化剂组合物包含约60-约99wt%的钒组分和约1-约40wt%的分子筛组分,基于共混物中催化活性组分的总重量计。在某些实施方案中,该催化剂组合物包含约60-约70、约75-约85或约90-约97wt%的钒组分,和约30-约40、约15-约25或约3-约10wt%的分子筛组分。
优选的钒组分包括在载体上的钒氧化物,该载体包含钛氧化物和任选的钨氧化物。在某些实施方案中,钛氧化物和钨氧化物是以约30:1-约2:1,更优选约20:1-约5:1,和甚至更优选约15:1-约7:1的重量比存在的。在某些实施方案中,该催化剂组合物包含高到约25wt%的钨氧化物,优选约1-约25wt%,更优选约5-约20wt%,和甚至更优选约7-约15wt%,基于钒组分的总重量。
一种优选的钛氧化物是二氧化钛(TiO2),其也称作二氧化钛或氧化钛(IV),并且优选处于锐钛矿形式。在某些实施方案中,该TiO2是至少90wt%和更优选至少95wt%的锐钛矿,相对于金红石形而言。在某些实施方案中,该TiO2是化学稳定的和/或预煅烧的,例如作为硫酸盐加工的终端产物。这样的化学稳定的TiO2表现出X射线反射,其是X射线衍射法中TiO2晶格特异性的。
典型地,TiO2充当了用于钒氧化物的高表面积载体,其在一个优选的实施方案中是五氧化二钒(V2O5),也称作氧化钒(V)或钒氧化物(vanadia)。在某些实施方案中,钒氧化物是以下的一种或多种:五氧化二钒、三氧化二钒、二氧化钒或者过渡金属或稀土金属的钒酸盐例如钒酸铁。该载体也可以包括钨氧化物,优选三氧化钨(WO3),也称作氧化钨(VI)。因此,该V2O5-TiO2或V2O5-TiO2/WO3为自支撑催化剂颗粒的形式。在不同的实施方案中,该催化金属氧化物的表面积(BET)是约10-约300m2/g或更大。在某些实施方案中,TiO2或TiO2/WO3的平均粒度将是约10-约250纳米(nm),优选约10-约100nm。
优选该分子筛是铝硅酸盐,优选在骨架中没有取代的金属,或者是铁硅酸盐。优选的骨架包括FER、MFI和BEA。在某些实施方案中,该分子筛不是小孔分子筛。分子筛,特别是铝硅酸盐,为H+形式或者是用过渡金属离子交换的。优选该铝硅酸盐基本上不含碱金属和碱土金属。H+形式分子筛优选不含非骨架金属。有用的过渡金属的例子包括Fe、Cu、Ni、Co、Zn和Ni,并且优选Fe和Cu,并且特别优选Fe。在某些实施方案中,该分子筛基本上不含除了Fe之外的任何非骨架金属。优选离子交换在分子筛合成之后进行。
优选的共混物包含铁助催化的分子筛或铁硅酸盐分子筛,其具有选自MFI、BEA和FER的至少一种骨架。该分子筛可以选自沸石和非沸石材料。沸石通常被认为是铝硅酸盐,而非沸石分子筛是具有特定沸石晶体结构(例如IZA骨架类型)的分子筛,但不是铝硅酸盐,该非沸石分子筛在它的晶格中具有一种或多种非铝/非硅阳离子,例如磷、铁等。有用类型的非沸石分子筛包括硅铝磷酸盐(SAPO)和铁硅酸盐。特别优选的是含铁的铝硅酸盐沸石例如含Fe的MFI、BEA和FER,并且优选MFI。
有用的MFI同形体包括ZSM-5、[Fe-Si-O]-MFI、AMS-1B、AZ-1、Bor-C、硼硅沸石(Boralite)、Encilite、FZ-1、LZ-105、穆丁钠石(Mutinaite)、NU-4、NU-5、硅质岩、TS-1、TSZ、TSZ-III、TZ-01、USC-4、USI-108、ZBH、ZKQ-1B和ZMQ-TB,并且特别优选ZSM-5。有用的FER同形体包括镁碱沸石、[Si-O]-FER、FU-9、ISI-6、单斜晶镁碱沸石、NU-23、Sr-D和ZSM-35。有用的BEA同形体包括β、[Ti-Si-O]-*BEA、CIT-6和缺泥沸石(Tschernichite)。用于这样的材料的典型的SiO2/Al2O3摩尔比是30-100,典型的SiO2/Fe2O3摩尔比是20-300,例如20-100。
优选该BEA骨架包含交换的铁或是铁同晶形的BEA分子结构(也称作BEA型铁硅酸盐),并且特别优选铁同晶形的BEA分子结构。在某些优选的实施方案中,该BEA型铁硅酸盐分子结构是晶体硅酸盐,具有(1)含铁的BEA骨架结构,其SiO2/Fe2O3摩尔比是约20-约300,和/或(2)在新鲜状态中,至少80%所含的铁作为分离的铁离子Fe3+。可用于本发明的优选的BEA型铁硅酸盐具有下式所示的组成:
(x+y)M(2/n)O·x Fe2O3·y Al2O3·z SiO2·w H2O
其中n是阳离子M的原子值;x、y和z分别代表了Fe2O3、Al2O3和SiO2的摩尔分数;x+y+z=1;w是至少为0的数;z/x是20-300,y可以是0,和任选地z/y是至少100。
优选含铁的BEA骨架结构的SiO2/Fe2O3摩尔比是约25-约300、约20-约150、约24-约150、约25-约100或约50-约80。log(SiO2/Al2O3)摩尔的上限没有特别限制,条件是log(SiO2/Al2O3)按摩尔计是至少2(即SiO2/Al2O3摩尔比是至少100)。log(SiO2/Al2O3)按摩尔计优选是至少2.5(即SiO2/Al2O3摩尔比是至少310),更优选至少3(即SiO2/Al2O3摩尔比是至少1,000)。当log(SiO2/Al2O3)按摩尔计超过4(即SiO2/Al2O3摩尔比变成至少10,000)。
在某些实施方案中,该Fe-BEA铝硅酸盐分子筛是预老化的。预老化的Fe-BEA铝硅酸盐可以产生明显优于常规Fe-BEA的结果。因此,代替在500℃老化1小时的更常规的处理,该Fe-BEA铝硅酸盐优选在600-900℃、优选650-850℃、更优选700-800℃和甚至更优选725-775℃老化3-8小时、优选4-6小时、更优选4.5-5.5小时和甚至更优选4.75-5.25小时。使用预老化的Fe-BEA铝硅酸盐的实施方案在不希望形成N2O的应用中是有利的。
在某些实施方案中,铁在分子筛材料中的存在浓度是约0.1-约10wt%(wt%),基于分子筛总重量计,例如约0.5wt%-约5wt%、约0.5-约1wt%、约1-约5wt%、约2wt%-约4wt%和约2wt%-约3wt%。铁可以使用本领域公知的技术来掺入用于本发明的分子筛中,所述技术包括液相交换或固体-离子交换或通过初始润湿方法。这样的材料在此称作含铁的或铁助催化的分子筛。关于含铁的铝硅酸盐沸石的制造,参见Journal of Catalysis 232(2)318-334(2005);EP2072128;和WO2009/023202,其在此引入作为参考。
本发明的催化剂组合物可以通过将钒组分和分子筛组分共混来制备。共混技术的类型没有特别限制。在某些实施方案中,制备TiO2/WO3悬浮液,向其中添加V2O5粉末和铁助催化的分子筛粉末。所形成的悬浮液可以配制为洗涂层,或者可以以粉末形式干燥和煅烧,其然后用于制备洗涂层或可挤出材料。
这里所述的催化沸石能够促进还原剂、优选氨,与氮氧化物的反应,以选择性形成单质氮(N2)和水(H2O),而不是氧和氨的竞争反应。在一个实施方案中,该催化剂可以经配制以促进氮氧化物用氨(即和SCR催化剂)来还原。在另一实施方案中,该催化剂可以经配制以处理未在SCR催化剂反应中消耗的氨(即氨逃逸)。这里,氨逃逸催化剂(ASC)经配制以促进氨用氧来氧化。在又一实施方案中,SCR催化剂和ASC催化剂串联使用,其中两种催化剂都包含这里所述的催化剂共混物,其中该SCR催化剂处于ASC催化剂上游。
在某些实施方案中,该ASC催化剂作为顶层位于氧化性下层上,其中该下层包含铂族金属(PGM)催化剂或非PGM催化剂。在某些实施方案中,该ASC催化剂是挤出的蜂窝体块或者被施用到基底上,优选经设计以最小的背压提供大的接触表面的基底,例如流通式金属或堇青石蜂窝体。例如,优选的基底具有约25-约300孔/平方英寸(CPSI)来确保低背压。实现低背压对于使ASC催化剂对于低压EGR性能的影响最小化是非常重要的。该ASC催化剂可以作为洗涂层施用到基底,优选来实现约0.3-3.5g/in3的负载量。为了提供进一步的NOx转化率,该基底的前部可以仅涂覆有SCR涂层,并且后部涂覆有SCR和ASC催化剂,其可以进一步包含在氧化铝载体上的Pt或Pt/Pd。
根据本发明的另一方面,提供了一种选择性催化还原废气中的NOx化合物或氧化废气中的NH3的方法,其包括使废气与这里所述的催化剂共混物接触足以降低废气中NOx和/或NH3化合物的水平的时间。在某些实施方案中,氮氧化物在催化剂共混物存在下,用还原剂在至少约100℃的温度还原。在某些实施方案中,NOx化合物在约200℃-约650℃的温度还原。使用大于约450℃的温度的实施方案对于处理来自重型和轻型柴油发动机的废气特别有用,所述发动机装备有排气系统,该排气系统包括(任选催化的)柴油微粒过滤器,其例如通过将烃注入到该过滤器上游的排气系统中来主动再生,其中用于本发明的沸石催化剂位于该过滤器下游。在其他实施方案中,分子筛SCR催化剂掺入到过滤器基底上。本发明的方法可以包括以下步骤中的一个或多个:(a)聚集和/或燃烧与催化过滤器入口接触的烟灰;(b)在与催化过滤器接触之前,将含氮还原剂引入该废气流中,优选没有插入的催化步骤,包括处理NOx和还原剂;(c)在NOx吸附剂催化剂上产生NH3,和优选将这样的NH3作为还原剂,用于下游SCR反应中;(d)使该废气流与DOC接触,以将烃基可溶性有机成分(SOF)和/或一氧化碳氧化成CO2,和/或将NO氧化成NO2,其又可以用于氧化微粒过滤器中的微粒物质;和/或还原废气中的微粒物质(PM);(e)使该废气与一种或多种流通式SCR催化剂装置在还原剂存在下接触,以降低废气中的NOx浓度;和(f)在废气排入大气之前或者废气进入/重新进入发动机前将废气送过再循环回路之前,使该废气与ASC催化剂接触,优选在SCR催化剂下游,以氧化大部分(如果不是全部)的氨。
用于SCR方法的还原剂(也称作还原试剂)宽泛地表示了促进废气中NOx的还原的任何化合物。可用于本发明的还原剂的例子包括氨、肼或任何合适的氨前体,例如尿素((NH2)2CO)、碳酸铵、氨基甲酸铵、碳酸氢铵或甲酸铵,和烃例如柴油燃料等。特别优选的还原剂是氮基的,并且特别优选氨。在某些实施方案中,该还原剂可以是烃,例如甲烷、柴油燃料等。
在某些实施方案中,全部或至少一部分的氮基还原剂,特别是NH3,可以由NOx吸附剂催化剂(NAC)、贫NOx捕集阱(LNT)或NOx存储/还原催化剂(NSRC)来提供,其位于SCR催化剂上游,例如位于壁流式过滤器上的本发明的SCR催化剂。可用于本发明的NAC组分包括碱性材料(例如碱金属、碱土金属或稀土金属,包括碱金属氧化物、碱土金属氧化物及其组合)和贵金属(例如铂)的催化剂组合物,和任选还原催化剂组分例如铑。可用于NAC的具体类型的碱性材料包括氧化铯、氧化钾、氧化镁、氧化钠、氧化钙、氧化锶、氧化钡及其组合。贵金属优选的存在量是约10-约200g/ft3,例如20-60g/ft3。可选地,该催化剂的贵金属的特征在于平均浓度,其可以是约40-约100g/ft3
在某些条件下,在周期性富再生事件期间,NH3可以在NOx吸附剂催化剂上产生。NOx吸附剂催化剂下游的SCR催化剂可以改进整体系统NOx还原效率。在该组合系统中,SCR催化剂能够存储在再生事件期间从NAC催化剂释放的NH3,并且使用所存储的NH3以选择性还原在正常的贫运行条件期间穿过NAC催化剂逃逸的一些或全部的NOx
在其他实施方案中,将含氮还原剂或其前体引入该废气流物流中,优选在SCR催化剂的上游和柴油氧化催化剂的下游。该还原剂的引入可以通过喷射器、喷嘴或类似装置来完成。
本发明的方法可以在来源于燃烧过程的废气上进行,例如来源于内燃机(无论是移动式还是固定式)、燃气轮机和燃煤或燃油电厂。该方法也可以用于处理来自于工业过程的气体,例如炼制、来自于炼厂加热器和锅炉、炉、化学加工工业、焦化炉、市政废物处理设备和焚化炉等。在一个具体的实施方案中,该方法被用于处理来自于车辆贫燃内燃机的废气,例如柴油发动机、贫燃汽油发动机或由液化石油气或天然气供能的发动机。
根据另一方面,本发明提供一种用于车辆贫燃内燃机的排气系统,该系统包括用于运送流动废气的管道、含氮还原剂源和这里所述的催化剂共混物。该系统可以包括控制器,用于仅当确定催化剂共混物能够例如在高于100℃、高于150℃或高于175℃,以所需效率或高于该效率催化NOx还原时,将含氮还原剂计量加入流动废气中。通过控制装置的确定可以通过指示选自以下的发动机条件的一种或多种合适的传感器输入来辅助:废气温度、催化剂床温度、油门位置、系统中的废气的质量流量、集管真空度、点火时机、发动机速度、废气的λ值、注入发动机的燃料量、废气再循环(EGR)阀的位置和由此EGR的量以及推进压力。
在一个具体的实施方案中,响应于废气中氮氧化物的量来控制计量加入,该量直接测定(使用合适的NOx传感器)或者例如使用存储在控制装置中的预相关的查询表或图来间接测定,该查询表或图将上述发动机条件的输入指示中的任意一种或多种与废气的预测的NOx含量相关联。含氮还原剂的计量加入可以经布置,以使得60%-200%的理论氨在进入SCR催化剂中的废气中的存在量计算为1:1的NH3/NO和4:3的NH3/NO2。该控制装置可以包括预编程的处理器,例如电子控制单元(ECU)。
在另一实施方案中,用于将废气中的一氧化氮氧化成二氧化氮的柴油氧化催化剂可以位于含氮还原剂计量加入到废气中的位置的上游。在一个实施方案中,该柴油氧化催化剂适用于产生进入SCR沸石催化剂的气流,该气流例如在氧化催化剂入口的废气温度250℃-450℃具有约4:1-约1:3的NO与NO2体积比。在另一实施方案中,NO与NO2体积比保持在约1:2-约1:5。该柴油氧化催化剂可以包含至少一种铂族金属(或它们的某些组合),例如铂、钯或铑,其涂覆于流通式整料基底上。在一个实施方案中,该至少一种铂族金属是铂、钯或者铂和钯二者的组合。该铂族金属可以负载在高表面积洗涂层组分上,例如氧化铝、沸石例如铝硅酸盐沸石、二氧化硅、非沸石二氧化硅氧化铝、二氧化铈、氧化锆、二氧化钛或者含有二氧化铈和氧化锆二者的混合氧化物或复合氧化物。
在另一实施方案中,合适的过滤器基底位于柴油氧化催化剂和SCR催化剂之间。过滤器基底可以选自上述那些中的任一种,例如壁流式过滤器。在过滤器是催化的,例如用上面讨论的类型的氧化催化剂催化的情况中,优选含氮还原剂的计量加入位置位于过滤器和SCR催化剂共混物之间。可选地,如果该过滤器未催化的,则用于计量加入含氮还原剂的装置可以位于柴油氧化催化剂和过滤器之间。
在另一实施方案中,用于本发明的催化剂共混物被涂覆到位于氧化催化剂下游的过滤器上。在该过滤器包括催化剂共混物的情况中,含氮还原剂的计量加入位置优选位于氧化催化剂和过滤器之间。
在另一方面,提供一种车辆贫燃发动机,其包括根据本发明的排气系统。该车辆贫燃内燃机可以是柴油发动机、贫燃汽油发动机或者由液化石油气或天然气供能的发动机。
作为此处使用的,涉及催化组合物的术语“基本由……组成”表示该组合物包含所述的催化组分,但是不包含对所要求保护的发明的基本的和新颖的特性有实质性影响的另外的组分。即,该催化组合物不包含这样的另外的组分,其不然将充当用于目标反应的催化剂,或者用来增强所要求保护的催化剂的基本催化性质。
实施例
实施例1:催化剂制备
一种催化剂组合物通过将铁交换的MFI铝硅酸盐与V2O5-TiO2/WO3悬浮液共混来制备。所形成的组合物包含约20wt%的铁交换的MFI铝硅酸盐,基于铁交换的MFI铝硅酸盐和V2O5-TiO2/WO3固体的合计重量计。依照类似方法来制备含有5wt%的铁交换的MFI铝硅酸盐的催化剂;含有20wt%的铁交换的FER铝硅酸盐的催化剂;含有5wt%的铁交换的FER铝硅酸盐的催化剂;含有20wt%的BEA铁硅酸盐的催化剂;和含有10wt%的BEA铁硅酸盐的催化剂。
将这些催化剂共混物形成可挤出物体,捏合,拉伸,然后挤出来形成1英寸直径×140mm蜂窝体块。
此外,将含有20wt%的铁交换的MFI铝硅酸盐的催化剂材料形成可挤出物体,捏合,拉伸,然后挤出来形成10.5英寸直径×5.0英寸400/11蜂窝体块以及10.5英寸直径×7.0英寸400/11蜂窝体块。
实施例2:催化剂性能(改变NO2水平)
将含有铁交换的MFI铝硅酸盐和V2O5-TiO2/WO3共混物(20wt%的Fe-MFI)的挤出的1英寸直径×140mm蜂窝体块暴露于模拟的柴油发动机废气,空速是约60,000/h。该模拟的废气包含约9.3wt%的O2,约7.0wt%的H2O,约100ppm的NOx(仅NO),约100ppm的NH3和余量的N2。在180、215、250、300、400和500℃的温度测定了该催化剂对于NOx转化率的能力。
作为对比,仅使用V2O5-TiO2/WO3来制备了类似的催化块。同样在类似条件下测试了该对比样品的NOx转化率。
图1中提供了这些新鲜样品(即未老化的)的NOx转化率数据。这里,该数据显示了在0%的NO2时,基于Fe-MFI和V2O5-TiO2/WO3共混物的催化剂在高温产生了比仅含有V2O5-TiO2/WO3的催化剂更好的NOx转化率。
重复这个测试,只是调整NOx流来包含35wt%的NO2。图2中提供了用于这些新鲜样品的NOx转化率数据。这里,该数据显示了在35%的NO2时,基于Fe-MFI和V2O5-TiO2/WO3共混物的催化剂在宽的温度范围内产生了比仅含有V2O5-TiO2/WO3的催化剂更好的NOx转化率。
再次重复这个测试,只是调整NOx流来包含65wt%的NO2。图3中提供了用于这些新鲜样品的NOx转化率数据。这里,该数据显示了在65%的NO2时,基于Fe-MFI和V2O5-TiO2/WO3共混物的催化剂在宽的温度范围内产生了比仅含有V2O5-TiO2/WO3的催化剂更好的NOx转化率。
实施例3:催化剂性能(后水热老化)
将含有铁交换的MFI铝硅酸盐和V2O5-TiO2/WO3共混物(20wt%的Fe-MFI)的挤出的1英寸直径×140mm蜂窝体新鲜块在580℃老化100小时。还老化了三个另外的新鲜块,每个处于以下条件之一:在580℃和10%H2O进行100小时;在650℃进行100小时;和在650℃和10%H2O进行100小时。
作为对比,仅使用V2O5-TiO2/WO3来制备了两个类似的催化块。每个对比样品在以下条件之一老化:在580℃进行100小时,和在650℃进行100小时。
将全部块暴露于模拟的柴油发动机废气中,空速是约60,000/h。该模拟的废气包含约9.3wt%的O2,约7.0wt%的H2O,约100ppm的NOx(仅NO),约100ppm的NH3和余量的N2。在180、215、250、300、400和500℃的温度测定了该催化剂对于NOx转化率的能力。
图4提供了这些老化样品的NOx转化率数据。这里,该数据显示了基于Fe-MFI和V2O5-TiO2/WO3共混物的催化剂与仅含有V2O5-TiO2/WO3的催化剂相比具有明显更大的水热稳定性,特别在苛刻的老化条件下更是如此。
实施例4:对比催化剂性能
将含有铁交换的MFI铝硅酸盐和V2O5-TiO2/WO3共混物(20wt%的Fe-MFI)的挤出的1英寸直径×140mm蜂窝体块暴露于模拟的柴油发动机废气,空速是约60,000/h。该模拟的废气包含约9.3wt%的O2,约7.0wt%的H2O,约100ppm的NOx(65wt%的NO2),约100ppm的NH3和余量的N2。在180、215、250、300、400和500℃的温度测定了该催化剂对于NOx转化率的能力。
将另一挤出的1英寸直径×140mm蜂窝体块,但是含有铁交换的FER铝硅酸盐和V2O5-TiO2/WO3(20wt%的Fe-FER),暴露于模拟的柴油发动机废气,空速是约60,000/h。该模拟的废气包含约9.3wt%的O2,约7.0wt%的H2O,约100ppm的NOx(65wt%的NO2),约100ppm的NH3和余量的N2。在180、215、250、300、400和500℃的温度测定了该催化剂对于NOx转化率的能力。
作为对比,仅使用V2O5-TiO2/WO3来制备了类似的催化块。同样在类似条件下测试了该对比样品的NOx转化率。
图5提供了这些样品的NOx转化率数据。这里,该数据显示在65%的NO2时,基于Fe-MFI和V2O5-TiO2/WO3共混物的催化剂在高温产生了与含有Fe-FER和V2O5-TiO2/WO3共混物的催化剂相比更好的NOx转化率,并且基于Fe-MFI和V2O5-TiO2/WO3共混物的催化剂在高温与仅含有V2O5-TiO2/WO3的催化剂相比产生了更好的NOx转化率。

Claims (20)

1.用于处理废气的催化剂组合物,其包含第一组分和第二组分的共混物,其中该第一组分是铝硅酸盐或铁硅酸盐分子筛组分,其中该分子筛为H+形式或是用一种或多种过渡金属离子交换的,该第二组分是负载在选自以下的金属氧化物载体上的钒氧化物:氧化铝、二氧化钛、氧化锆、二氧化铈、二氧化硅及其组合。
2.根据权利要求1所述的催化剂,其中该分子筛具有选自MFI、BEA和FER的骨架。
3.根据权利要求2所述的催化剂,其中该分子筛是H+/MFI铝硅酸盐。
4.根据权利要求1所述的催化剂,其中该分子筛是Fe离子交换的MFI、BEA或FER铝硅酸盐。
5.根据权利要求4所述的催化剂,其中分子筛包含约1-约10wt%的离子交换的Fe。
6.根据权利要求1所述的催化剂,其中该分子筛是BEA铁硅酸盐。
7.根据权利要求1所述的催化剂,其中该金属氧化物载体是钛氧化物。
8.根据权利要求1所述的催化剂组合物,其中该第二组分进一步包含钨氧化物。
9.根据权利要求1所述的催化剂组合物,其中该第二组分进一步包含钒酸铁。
10.根据权利要求1所述的催化剂组合物,其中该第一组分和第二组分在该共混物中分别以重量比约5:95-约40:60存在。
11.根据权利要求1所述的催化剂组合物,其中该共混物包含约0.5-约5wt%的钒氧化物,基于该第一和第二组分的重量计。
12.催化洗涂层,其包含根据权利要求1所述的催化剂,进一步包含一种或多种填料、粘合剂、加工助剂、水和掺杂剂。
13.催化制品,其包含涂覆有或结合了根据权利要求1所述的催化剂的基底,其中该基底选自金属流通式基底、陶瓷流通式基底、壁流式过滤器、烧结的金属过滤器、部分过滤器和挤出的催化剂蜂窝体。
14.根据权利要求13所述的催化制品,其进一步包含具有第二催化剂组合物的洗涂层,用于选择性还原NOx和/或用于氧化NH3
15.根据权利要求14所述的催化制品,其中所述第二催化剂组合物选自(a)根据权利要求1所述的催化剂共混物,(b)过渡金属助催化的分子筛,(c)铂族金属催化剂,或(d)钒基催化剂。
16.根据权利要求13所述的催化剂制品,其中该基底包含:用于氧化氨的含有铂族金属的第一层,和包含根据权利要求1所述的催化剂的第二层,其中该第一层直接位于该基底之上或之内,该第二层覆盖该第一层。
17.处理废气的系统,其包括氨逃逸催化剂(ASC)上游的选择性催化还原(SCR)催化剂,其中在所述SCR和ASC催化剂的至少一个中包含根据权利要求1所述的催化剂。
18.根据权利要求17所述的系统,其进一步包括具有铂族金属的柴油氧化催化剂,该催化剂位于所述选择性催化还原催化剂的上游。
19.处理废气的方法,其包括步骤:
a.在根据权利要求1所述的催化剂存在下,接触含有NOx和/或NH3的废气流;和
b.将至少一部分所述NOx转化成N2,和/或将至少一部分NH3转化成N2和NO2中的至少一种。
20.根据权利要求19所述的方法,其中所述废气包含的NO与NO2的体积比是约4:1-约1:3。
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