CN104822452B - 基材整料上的区域化的催化剂 - Google Patents

基材整料上的区域化的催化剂 Download PDF

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CN104822452B
CN104822452B CN201380061005.9A CN201380061005A CN104822452B CN 104822452 B CN104822452 B CN 104822452B CN 201380061005 A CN201380061005 A CN 201380061005A CN 104822452 B CN104822452 B CN 104822452B
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oxide
substrate monolith
catalysis
area
compartmentalization
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CN104822452A (zh
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G·M·布朗
A·F·奇菲
P·R·菲利普斯
D·斯瓦洛
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Johnson Matthey PLC
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    • F01N3/10Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/18Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
    • F01N3/20Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
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    • F01N2510/068Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings
    • F01N2510/0682Surface coverings for exhaust purification, e.g. catalytic reaction characterised by the distribution of the catalytic coatings having a discontinuous, uneven or partially overlapping coating of catalytic material, e.g. higher amount of material upstream than downstream or vice versa
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02ATECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02TCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00Road transport of goods or passengers
    • Y02T10/10Internal combustion engine [ICE] based vehicles
    • Y02T10/12Improving ICE efficiencies

Abstract

一种区域化的催化的基材整料,其包含第一区和第二区,其中该第一区和该第二区是轴向串联排列的,其中该第一区包含负载于载体中的铂族金属,和选自氧化铁,氧化锰,氧化铜,氧化锌,氧化镍及其混合物的第一贱金属氧化物或者负载于无机氧化物上的选自铁,锰,铜,锌,镍及其混合物的第一贱金属,并且该第二区包含负载于沸石上的铜或者铁,和选自氧化铁,氧化锰,氧化铜,氧化锌,氧化镍及其混合物的第二贱金属氧化物或者负载于无机氧化物上的选自铁,锰,铜,锌,镍及其混合物的第二贱金属,其中该第二贱金属不同于该第一贱金属。

Description

基材整料上的区域化的催化剂
本发明涉及区域化的催化的基材整料,其用于控制在比已知的硫化氢控制机理扩展的温度范围内,在贫燃NOx捕集器脱硫酸盐过程中,在贫燃NOx捕集器中所形成的硫化氢气体。本发明还涉及用于内燃机的排气系统,其包含贫燃NOx捕集器和该区域化的催化的基材整料,并且涉及制造该区域化的催化的基材整料和处理来自于内燃机的废气的各种方法。
通常公认的车辆排放物(其是对公共健康和自然环境具有不利影响的主要污染物)是一氧化碳(CO),烃(HC),氮氧化物(NOx)和颗粒物质。
已经提出了几种解决方案来除去和/或控制这些主要污染物,它们的一些聚焦于发动机设计,并且它们的一些聚焦于控制来自排气系统的排放物。
现有的用于除去和/或控制这样的排放物的典型的排气系统包含NOx捕集器,催化转化CO和HC(其是作为燃料在发动机中不完全燃烧的结果而存在的)的氧化催化剂,和用于除去颗粒物质的过滤器基材。
贫燃NOx捕集器(LNT)(也称作NOx吸附剂催化剂;例如公开在US5473887中)使用了捕集器例如碱土金属氧化物,其在贫燃运行模式中吸附了NOx。废气通常富含NO,其在含铂族金属的氧化性催化剂(例如铂或者钌)上转化成NO2,并且该NO2被捕集和存储在碱土金属氧化物例如碳酸钡(其混入到含铂族金属的催化剂中)上。该NOx然后在当废气排放物中的氧气浓度降低时,在富含条件下从钡上释放,并且用合适的还原剂例如用于柴油机的柴油燃料还原,其使用铑催化剂作为促进剂。该铑催化剂可以混入到含铂族金属的催化剂上,或者它可以位于LNT下游。
通常给出的用于从这种配制物的贫燃废气中捕集的NOx一种机理是:
NO+0.5O2→NO2 (1);
BaO+NO2+0.5O2→Ba(NO3)2 (2),
其中在反应(1)中,NO与氧气在铂族金属催化剂的活性氧化位点上反应,来形成NO2。反应(2)包括通过无机硝酸盐形式的存储材料来吸附NO2
在较低的氧气浓度和/或在高温时,该硝酸盐物质变成热力学不稳定的并且分解,根据下面的反应(3)产生NO或者NO2。在合适的还原剂的存在下,这些氮氧化物随后由一氧化碳,氢和烃还原成N2,其可以在还原催化剂上进行(参见反应(4))。
Ba(NO3)2→BaO+2NO+1.5O2或者Ba(NO3)2→BaO+2NO2+0.5O2 (3);和
NO+CO→0.5N2+CO2(和其他反应) (4)。
在上面的反应(1)-(4)中,该反应性钡物质是作为氧化物给出的。
但是,应当理解在空气或者贫燃发动机废气存在下,大部分钡处于碳酸盐或者可能是氢氧化物的形式。本领域技术人员可以因此使上述反应方案适于非氧化物的钡物质。
将LNT用于例如柴油机和汽油应用中的一个问题是发动机燃料还包含硫,并且这在燃料燃烧过程中转化成二氧化硫(SO2)。SO2通过LNT的氧化催化剂组分被氧化成三氧化硫(SO3),并且该SO3通过与NO2类似的机理吸附到NOx吸附剂上。在用于吸附NOx的NOx捕集组分上存在着有限数目的活性位点,并且因此在NOx捕集组分上存在硫酸盐整体上降低了NOx捕集组分吸附NOx的能力。所以,为了保持足够的NOx捕集能力,必须定期从LNT上除硫。但是,在贫废气中,NOx捕集组分例如钡的硫酸盐比硝酸盐更稳定,并且相比于解吸NOx,通常需要更长时间段的更高的温度和/或更富含的条件来除去SOx
脱硫酸盐可以通过多种技术来完成,包括通过一系列短的、富含脉冲。使用比正常废气组合物更富含来对LNT脱硫酸盐的一个主要问题是硫酸盐是作为硫化氢除去的。这种化合物具有特有的和令人不快的臭鸡蛋气味,0.0047ppm是公认的阈值,其是50%的人可以察觉硫化氢的特征气味时的浓度,并且因此令人期望的是防止/限制它向大气的排放。
在近年来,对于柴油燃料来说,这个问题已经被降低到某些程度,这是因为美国现在已经使用了超低硫柴油(最大硫含量为15ppm(wt)的燃料)。在欧洲,从2010年开始已经使用最大硫限度为10ppm的柴油燃料。因此,较不经常需要LNT脱硫酸盐流程。但是硫化氢极低的气味阈值意味着甚至到大气中很小的排放也是不期望的。
颗粒过滤器已经表现出在除去全粒度范围上的颗粒物质方面是极其有效的。但是,在压力下降变得过大之前,这些过滤器具有有限的捕集颗粒物质的能力。所以必需定期再生该颗粒过滤器。被动再生可能不容易进行,因为所保留的颗粒物质在氧气存在下的燃烧需要比发动机排气所提供的典型的那些温度更高的温度,特别是在柴油机客车排气的情况中更是如此。降低颗粒过滤器上所捕集的颗粒物质的燃烧温度的一种有效的方法是在过滤器基材上添加催化的载体涂层(washcoat)。所用的催化的载体涂层的组成类似于氧化催化剂中所用的那些,并且通常包含负载在合适的载体材料上的至少一种铂族金属。合适的载体材料包括氧化铝,二氧化硅-氧化铝,二氧化铈或者二氧化铈和氧化锆的混合氧化物或者复合氧化物及其混合物。这样的过滤器通常被称作催化的烟灰过滤器(CSF)。
包含LNT和下游CSF的柴油机排气系统是已知的。例如SAE2001-01-2065,标题为“Cummins Light Truck Diesel Engine Progress Report”公开了这样的系统。这个报告的作者知道没有考虑由于硫中毒导致的劣化或污染效应,并且在任何驱动循环期间没有进行脱硫酸盐的尝试。
WO2008/075111公开了一种包含贫燃内燃机的设备,其包含用于处理来自发动机的流动废气的排气系统,其具有LNT,CSF,用于在运行期间富集该废气来提供间歇地富集废气的装置(目的是除去吸附在LNT上的硫酸盐)和位于至少一些LNT下游的化合物(其有效地除去和/或转化了在除硫酸盐方法期间所产生的硫化氢)。该硫化氢除去和/或转化材料选自镍,钙,铁和钡的氧化物。该硫化氢除去和/或转化材料可以位于排气系统的多个位点上,其包括在LNT和CSF之间,在CSF之上,在CSF和排气系统出口之间。关于为什么将该硫化氢除去和/或转化材料置于所选择的位点上的唯一的讨论涉及到任何铂族金属氧化催化剂,因为氧化镍可以使该铂族金属催化剂的烃和一氧化碳活性中毒。
US5196390公开了通过将一种或多种的镍,铁和锰的氧化物混入到位于整料基材上的底涂层中,用三效催化剂来抑制硫化氢形成的方法。叠置在该底涂层上的顶涂层包含常规的三效催化剂材料。这种结构避免了三效催化剂和硫化氢抑制性材料之间的任何相互作用。
在美国密歇根州底特律的2005Society of Automotive Engineers(SAE)WorldCongress(2005年4月11-14日)期间发表的SAE论文2005-01-1116的标题是“H2SSuppression During the Desulfation of a Lean NOx Trap with a Nickel-Containing Catalyst”。相同作者中的三个与US专利公开No.US2005/0160720的发明人姓名相同。
JP2001-070754致力于抑制来自贫燃内闭发动机的H2S排放量,而不使得NOx-遮蔽类型催化剂的处理能力劣化的问题。该公开文献公开了废气处理设备,其包含在NOx遮蔽类型催化剂下游的三效催化剂,其中该三效催化剂包含作为H2S排放抑制性催化设备安装的10-35g/1L的氧化镍,或者将氧化镍与其他H2S排放抑制剂一起,以相比于作为遮蔽剂加入NOx催化剂中的Ba为30-300%的摩尔比的量加入该三效催化剂中。
1994年6月30日的欧洲议会和理事会决议94/27/EC(随后在2004年9月27日通过委员会决议2004/96/EC来修正)限制了镍的使用,这归因于对人的致敏性,其可能导致过敏反应。欧洲医学机构的人类医学产品委员会(CHMP)在2007年1月发布了对于金属催化剂(包括镍催化剂)的残留物的规格界限的草案指南。应当理解目前存在着对于在汽车工业和它的供货商的汽车催化剂中使用镍的主动禁止。
申请人的WO2012/175948A1是在本申请之前提交,之后公开的。它公开了一种用于内燃机的排气系统和用于排气系统中的催化的基材。该排气系统包含贫燃NOx捕集器和位于该贫燃NOx捕集器下游的催化的基材。该催化的基材具有第一区和第二区,其中该第一区包含负载于载体上的铂族金属,并且该第二区包含负载于沸石上的铜或者铁。该第一区或者第二区另外包含贱金属氧化物或者负载于无机氧化物上的贱金属,其中该贱金属优选是铁,锰,铜,镍或者其混合物。该催化的基材可以在排气系统中定向,以使得该第一区在第二区上游,反之亦然。但是,优选该第一区进行定向,以使得该第一区处于上游侧上,来在第二区之前接受来自于NOx捕集器的废气。该排气系统能够存储在富燃吹扫(rich purge)中所产生的NH3,将该NH3与从NOx捕集器中逸出的NOx反应,控制从NOx捕集器脱硫酸盐中所释放的H2S,和氧化逸出的烃和一氧化碳。当该催化的基材是过滤器基材时,它还能够除去来自排气系统的烟灰。
可用于除去和/或转化硫化氢的不同的材料的每一者是在限定的温度范围内最有效地运行的。例如已知的是铁的氧化物在较低的温度是有效的,通常是400-800℃,并且已知的是锰的氧化物是在较高的温度有效的,其在一些情况中可能超过1000℃。将这些不同材料的一些混合在一起不可足够地扩展除去和/或转化硫化氢的温度范围,因为基于这样的组合可能存在不利的相互作用。
我们现在已经确定了一种系统,其能够处理从内燃机排气系统所排出的NOx和颗粒物质二者,同时还在宽的温度范围内除去和/或转化了不想要的硫化氢排放。这是通过在LNT下游提供催化的基材整料来实现的,它的脱硫酸盐方法导致形成了不期望的硫化氢,其中该催化的基材内单独的区域包含了用于除去和/或转化硫化氢排放物的不同的材料。颗粒物质可以捕集在单独的过滤器基材上,或者更优选该催化的基材整料是催化烟灰过滤器。
因此,在第一方面,本发明提供一种区域化的催化的基材整料,其包含第一区和第二区,其中该第一区和该第二区是轴向串联排列的,其中该第一区包含负载于载体中的铂族金属,和选自氧化铁,氧化锰,氧化铜,氧化锌,氧化镍及其混合物的第一贱金属氧化物或者负载于无机氧化物上的选自铁,锰,铜,锌,镍及其混合物的第一贱金属,并且该第二区包含负载于沸石上的铜或者铁,和选自氧化铁,氧化锰,氧化铜,氧化锌,氧化镍及其混合物的第二贱金属氧化物或者负载于无机氧化物上的选自铁,锰,铜,锌,镍及其混合物的第二贱金属,其中该第二贱金属不同于该第一贱金属。
优选在第二区中,负载于沸石上的铜或者铁的载体涂层负载量是0.5≤3.0gin-3,优选1.0≤2.0gin-3
优选该第一贱金属或者第二贱金属不是镍;并且该第一贱金属氧化物或者第二贱金属氧化物不是氧化镍。这是因为对于催化剂中包含镍的主动的欧洲禁令。
优选的第一贱金属或者第二贱金属是锰和锌;并且优选的第一贱金属氧化物或者第二贱金属氧化物是氧化锰和氧化锌。这是因为发明人已经发现这些贱金属和贱金属氧化物是良好的H2S抑制剂,而且与铜(或氧化铜)或者铁(或氧化铁)相比,它们对于第一区中在较低的温度下铂族金属的CO氧化具有更大的不利影响;并且与(另外的)Cu或者CuO或者(另外的)Fe或者Fe2O3相比,对于在第二区的Cu或者Fe沸石催化剂上的选择性催化NOx转化(使用NH3作为还原剂)具有更大的不利影响。可以使用氧化铜或者氧化铁作为第一区(包含铂族金属)中的H2S抑制剂,但是优选的是该Cu或者Fe是与负载于载体上的铂族金属物理分离的(参见下面)。优选的是不使用铜氧化物或者铁氧化物作为第二区中的H2S抑制剂,因为这些材料(除了用沸石骨架离子交换的Fe或者Cu之外)可能不期望的竞争性氧化NH3,由此降低了选择性催化还原反应的效率(即,4NH3+4NO+O2→4N2+6H2O(即1:1NH3:NO);4NH3+2NO+2NO2→4N2+6H2O(即1:1NH3:NOx);并且8NH3+6NO2→7N2+12H2O(即4:3NH3:NOx),优先到不期望的,非选择性副反应例如在Cu或者Fe沸石催化剂上的2NH3+2NO2→N2O+3H2O+N2)。
该第一区可以进一步包含负载于载体上的铂族金属。该铂族金属优选是铂,钯,铑或者其混合物;最优选该铂族金属是铂,钯及其混合物。该载体优选是沸石,无机氧化物或者其混合物。更优选该载体是无机氧化物例如氧化铝,二氧化硅,二氧化钛,氧化锆,二氧化铈,氧化铌,钽氧化物,钼氧化物,钨氧化物,其任意两种或更多种的混合氧化物或者复合氧化物(例如二氧化硅-氧化铝,二氧化铈-氧化锆或者氧化铝-氧化铈-氧化锆)及其混合物。氧化铝和二氧化铈-氧化锆混合氧化物是特别优选的。
当该第一区另外包含负载于载体上的铂族金属时,优选的是该第一贱金属氧化物或者负载于无机氧化物上的第一贱金属是与负载于载体上的铂族金属物理分开的。这可以通过预成形负载的铂族金属粉末来实现,包括在将该预成形的粉末引入到载体涂层中之前,将其烧结来将铂族金属固定到载体上。这是因为该第一贱金属氧化物可能使铂族金属催化剂的烃和一氧化碳氧化能力中毒。因此,将负载的铂族金属和第一贱金属氧化物或者负载于无机氧化物上的第一贱金属单独的颗粒加入到第一区中,来物理隔离该第一区内的两种催化剂。
在优选的实施方案中,其中它的目的是将根据本发明第二方面的排气系统中的第一区定向至上游侧,该第一区包含贫燃NOx捕集器组合物,其包括NOx吸附剂(用于存储/捕集NOx)和氧化/还原催化剂,如下文所述,其中该负载于载体上的铂族金属是氧化/还原催化剂。该贫燃NOx捕集器负载量可以是10≤100gft-3,优选25≤75gft-3或者35≤65gft-3。贫燃NOx捕集器载体涂层负载量可以是0.5≤3.0gin-3,优选1.0≤2.0gin-3
第二区中的沸石(即,负载了铜或者铁)优选是β沸石,八面沸石(例如X-沸石或者Y-沸石,包括NaY和USY),L-沸石,ZSM沸石(例如ZSM-5,ZSM-48),SSZ-沸石(例如SSZ-13(菱沸石),SSZ-41,SSZ-33),镁碱沸石,发光沸石,菱沸石,菱钾铝矿,毛沸石,斜发沸石,硅酸盐,磷酸铝沸石(包括金属铝磷酸盐例如SAPO-34(菱沸石)),中孔沸石(例如MCM-41,MCM-49,SBA-15)或者其混合物;更优选该沸石是β沸石,镁碱沸石或者菱沸石。
该第一区和第二区各自包含贱金属氧化物或者负载于无机氧化物上的贱金属。在该第一区和第二区的每一者中的无机氧化物可以独立地选自氧化铝,二氧化硅,二氧化钛,氧化锆,二氧化铈,氧化铌,钽氧化物,钼氧化物,钨氧化物,其任何混合氧化物或者复合氧化物及其混合物。氧化铝是特别优选的。
该区域化的催化的基材是包含催化剂组分的基材。该基材整料优选是陶瓷基材整料或者金属基材整料,更优选陶瓷基材整料。该陶瓷基材整料可以由任何合适的耐火材料制成,例如氧化铝,二氧化硅,二氧化钛,二氧化铈,氧化锆,氧化镁,沸石,氮化硅,碳化硅,硅酸锆,硅酸镁,铝硅酸盐和金属铝硅酸盐(例如堇青石和锂辉石),或者其任意两种或更多种的混合物或者混合氧化物。堇青石(其是一种铝硅酸镁)并且碳化硅是特别优选的陶瓷基材整料。
该金属基材整料可以由任何合适的金属制成,和特别是耐热金属和金属合金例如钛和不锈钢以及铁素体合金(除了其他痕量金属之外,其含有铁,镍,铬和/或铝)。
该基材整料优选是过滤器基材,但是也可以是流过式基材整料。在该基材整料是过滤器基材时,第一区中负载于载体上的铂族金属(非贫燃NOx捕集器)的载体涂层负载量优选是0.1≤1.0gin3,例如0.3≤0.7gin-3。在实施方案中,这里(非贫燃NOx捕集器)第一区定向至本发明第二方面的排气系统中的上游侧并且该基材整料是过滤器基材,该铂族金属负载量优选是10≤50gft-3;或者在第一区定向至下游侧时,该铂族金属负载量是1≤20gft-3,例如5≤15gft-3,或者1≤10gft-3
在该区域化的催化的基材整料的基材整料是过滤器基材时,为了降低本发明排气系统中的背压,优选的是将具有较低的载体涂层负载量的区域布置在下游侧上。实践上,负载于沸石上的铜或者铁将以较高的载体涂层负载量存在,并因此优选的是该第一区处于较低负载量,并且定向至下游侧。较低的载体涂层负载量通常还意味着同样较低的铂族金属负载量。出于车载诊断的目的,设计了现代的排气系统,以使得过滤器再生过程是以大约5000km的间隔来进行的,由此将该系统返回到“基线”,用于向前的诊断测试。这样的再生过程可能产生相对高的废气温度,其有益于处理在过滤器再生方法过程中来自烟灰燃烧的次要排放物,甚至在定向至下游侧的相对低的负载的第一区上也是如此,并且铜和或者铁可以用于H2S抑制剂。这是因为即使Cu或Fe可能使得例如铂族金属的CO氧化活性中毒,但是Cu中毒的铂族金属催化剂能够在较高的温度起燃,由此在过滤器再生方法期间处理次要排放物。
在本发明第一方面的优选的实施方案中,其中该第二区定向至本发明第二方面的排气系统中的上游侧和该基材整料是流过式基材整料或者过滤器基材,并且该第一区是非贫燃NOx捕集器,该铂族金属优选是处于相对较低负载量的Pt或者Pt和Pd,例如5≤15gft-3,或者1≤10gft-3或者1≤5gft-3,该第一区包含涂覆在基材整料上的第一层,并且该第一层是用第二区的负载于沸石上的铜或者铁的第二层来涂覆的。这种排列是特别优选的,这归因于氧化催化剂,其用于减少或者防止送过本发明的区域化的催化的基材整料的NH3的逸出(所谓的氨逸出催化剂或“ASC”)。
如果该基材是流过式基材整料,则该流过式基材整料是这样的流过式基材整料,其优选具有蜂窝结构,带有许多小的,平行的薄壁通道,该通道轴向穿过基材并且在整个基材中延伸。该基材的通道横截面可以是任何形状,但是优选是正方形,窦形,三角形,矩形,六边形,梯形,圆形或者椭圆形。
如果该基材整料是过滤器基材,则它优选是壁流式整料过滤器。该壁流式整料过滤器包含入口端,出口端,在该入口端和出口端之间延伸的基材轴向长度,和由该壁流式基材的内壁所限定的多个通道。该多个通道包含具有开放入口端和封闭出口端的入口通道和具有封闭入口端和开放出口端的出口通道。
因此该壁流式过滤器的通道是交替封堵的,其允许废气流从入口端进入通道,然后流过通道壁,并且从导向出口端的不同通道离开该过滤器。废气流中的颗粒因此捕集在该过滤器中。
该基材整料包含至少两个催化区,各个区含有设置在基材整料上的不同的催化剂组合物。在一种实施方案中,两个区域在基材上基本上没有重叠。例如,第一区可以覆盖基材总长度的10-90%,并且第二区将覆盖基材的其余长度(即,其余的90-10%,其没有被第一区覆盖)。优选该第一区覆盖了基材总长度的20-80%并且该第二区覆盖了基材总长度的80-20%。更优选该第一区覆盖了基材总长度的30-70%,并且该第二区覆盖了基材总长度的70-30%。更优选该第一区覆盖了基材总长度的40-60%并且该第二区覆盖了基材总长度的60-40%。
在不太优选的可选择的实施方案中,两个区在基材上可能存在一些重叠。例如可以存在最高20%或者更大的重叠。
当该基材是过滤器基材时,优选是壁流式整料过滤器。当使用这样的壁流式整料过滤器时,一个区可以设置到入口通道的内壁之中/之上,并且另一区可以设置到出口通道的内壁之中/之上,因此有效地分隔了第一和第二区。
在某些情况中,优选的是可以在基材上增加小的第三区,以使得该第三区(优选占了基材轴向长度的小于20%和更优选小于10%)位于第二区之后和基材相对于第一区的对面端上。当该基材整料是过滤器基材和该第一区位于排气系统中来在第二区之前接触废气,以使得在高温烟灰燃烧期间所形成的烃和CO可不在第二区上完全燃烧时,第三区可能是特别有用的。如果使用,则该第三区将包含负载的铂族金属,优选铂,钯和/或铑,来帮助任何烃和CO的氧化。
根据第二方面,本发明提供用于内燃机的排气系统,其包含:(a)贫燃NOx捕集器;并且(b)区域化的催化的基材整料,其中该区域化的催化的基材整料位于贫燃NOx捕集器下游。贫燃NOx捕集器(a)位于基材整料例如流过式基材整料或者过滤器基材上,例如壁流式过滤器基材。
该催化的基材整料通过在富燃气体混合物中形成硫化物化合物,并且在贫化气体混合物中将该硫化物氧化成SO2或者SO3,而除去/控制了从NOx捕集器脱硫酸盐中所释放的H2S。当存在时,该负载的铂族金属催化剂氧化了在与催化的基材接触之前没有转化的烃和一氧化碳。当该催化的基材整料是过滤器基材时,它还除去了来自废气的烟灰。
该区域化的催化的基材位于排气系统中,以使得它在贫燃NOx捕集器的下游,以使得废气在接触催化的基材之前接触该贫燃NOx捕集器。优选两区催化的基材位于该排气系统中,以使得存在上游(入口)区(其在离开贫燃NOx捕集器之后与废气接触)和在该上游区之后的下游(出口)区。该上游区(其与来自贫燃NOx捕集器的废气接触)可以是催化的基材的第一区或者第二区。因此,该第一区可以定向来在第二区之前接收来自于NOx捕集器的废气;或者该第二区可以定向来在第一区之前接收来自NOx捕集器的废气。
在一种实施方案中,该第一区定向至上游侧。
该第二区的铜或者铁负载的沸石催化剂可用于催化氮的氧化物与含氮还原剂根据下面的反应的还原:4NH3+4NO+O2→4N2+6H2O(即1:1NH3:NO);4NH3+2NO+2NO2→4N2+6H2O(即1:1NH3:NOx);并且8NH3+6NO2→7N2+12H2O(即4:3NH3:NOx),优先于不期望的,非选择性副反应例如2NH3+2NO2→N2O+3H2O+N2
在本发明第二方面的实施方案中,其中该第二区定向至上游侧,优选该排气系统包含注射器,用于将含氮还原剂例如氨或者氨前体例如尿素或者甲酸铵,优选尿素,注入到贫燃NOx捕集器和本发明第一方面的区域化的催化的基材整料之间的废气中。这样的注射器流体连接到这样的含氮还原剂前体源例如其槽上,并且通过适当编程的发动机管理手段和由监控相关废气组成的传感器所提供的闭环或者开环反馈,来调控该前体向废气流中的通过阀控制的用量。氨也可以通过加热氨基甲酸铵(固体)来产生,并且所产生的氨可以注入废气中。
氨也可以例如在用发动机来源的富燃废气富燃再生该贫燃NOx捕集器的过程中原位产生,例如其中钡是NOx吸附剂:Ba(NO3)2+8H2→BaO+2NH3+5H2O。在这种情况中,可以使用原位NH3产生来代替用于含氮还原剂的单独的注射器或者与之一起使用。将理解在其中第一区包含贫燃NOx捕集器并且定向至上游侧的实施方案中,该第一区贫燃NOx捕集器也可以对第二区的负载于沸石催化剂上的铜或者铁上游的原位氨产生做出贡献。
该贫燃NOx捕集器通常包括用于存储/捕集NOx的NOx吸附剂和氧化/还原催化剂。该氧化/还原催化剂通常包含一种或多种贵金属,优选铂,钯和/或铑。通常,包括铂来发挥氧化功能,并且包括铑来进行还原功能。该铑催化剂可以位于LNT的下游。
该NOx吸附剂优选包含至少一种碱土金属(例如钡,钙,锶和镁),至少一种碱金属(例如钾,钠,锂和铯)或者至少一种稀土金属(例如镧,钇,镨和钕)或者其组合。这些金属通常见于氧化物形式。最优选该NOx吸附剂包含氧化物形式的碱土金属。要注意的是虽然碱土金属物质是作为氧化物公开的,但是应当理解在空气或者贫燃发动机废气存在下,大部分碱土金属物质例如钡处于碳酸盐或者可能是氢氧化物的形式。
该氧化/还原催化剂和NOx吸附剂优选负载于载体材料上例如用于排气系统的无机氧化物。无机氧化物例如氧化铝,二氧化硅-氧化铝,二氧化铈,二氧化钛,氧化锆,氧化铝-氧化锆及其组合优选用作该载体材料。
该贫燃NOx捕集器起到了三个作用。第一,来自废气的NO在氧化催化剂存在下与氧反应来产生NO2。第二,该NO2被无机硝酸盐形式的NOx吸附剂所吸附(例如BaO或BaCO3在NOx吸附剂上转化成Ba(NO3)2)。最后,当该发动机在富燃条件下运行时,所存储的无机硝酸盐分解来形成NO或NO2,其然后通过与一氧化碳,氢和/或烃在还原催化剂存在下反应,还原来形成N2。通常,该氮氧化物在废气流中的热,一氧化碳和烃存在下转化成氮,二氧化碳和水。
在NOx捕集器中,该NOx吸附剂和氧化/还原催化剂优选涂覆到流过式基材整料上,优选蜂窝整料上。该流过式基材整料可以由陶瓷材料(例如堇青石)或者金属材料例如FecralloyTM制成。该贫燃NOx捕集器通常设计来提供许多通道,废气被送过该通道。该通道的表面负载有NOx吸附剂和氧化/还原催化剂。
该贫燃NOx捕集器的组分可以通过任何已知的手段来加入。例如该载体材料,氧化还原催化剂和NOx吸附剂材料可以优选施用到和结合到基材上作为载体涂层,其是结合到基材表面上的多孔高表面积层。该载体涂层通常从水基浆体施用到基材上,然后干燥和高温煅烧。该载体涂层可以可选择地包含载体和NOx吸附剂,并且氧化还原催化剂可以负载到该干燥的载体涂层载体层上(通过浸渍,离子交换等),然后干燥和煅烧。
该排气系统可以进一步包含氧化催化剂,其位于内燃机和贫燃NOx捕集器之间来氧化废气中的烃和一氧化碳。这样的氧化催化剂是本领域用于柴油和汽油发动机二者公知的。
此外,如果该催化的基材整料是流过式基材整料,则本发明的排气系统优选包括颗粒过滤器,更优选催化的烟灰过滤器。在存在时,该颗粒过滤器优选能够收集烟灰,而不引起该排气系统中过高的背压。通常,可使用陶瓷,烧结的金属或者织造或非织造丝过滤器,并且壁流式蜂窝结构是特别优选的。该颗粒过滤器的结构材料优选是多孔陶瓷,碳化硅或者烧结的金属。该颗粒过滤器可以是催化的,通常用铂族金属催化剂催化。该烟灰通常是含碳的可溶性有机级分和/或挥发性有机级分和/或重质烃。烟灰的燃烧产生了CO2和H2O。
如果使用,则该颗粒过滤器可以位于区域化的催化的基材的上游或下游。优选该颗粒过滤器在催化的基材上游和贫燃NOx捕集器的下游,以使得来自内燃机的废气送过该贫燃NOx捕集器,然后是颗粒过滤器,随后是催化的基材,然后送到大气中。
根据第三方面,本发明提供一种设备,其包含内燃机和根据本发明第二方面的排气系统。该内燃机优选是贫燃内燃机。
“贫燃”指的是在汽油和柴油(压缩点火)燃料供能的内燃机二者中使用贫燃混合物。该发动机燃料也可以包括至少一些生物柴油,生物乙醇,来源于气变油工艺的组分,液化石油气或者天然气。该发动机可以用于机动应用例如车辆中,或者用于固定应用例如发电装置中。优选将该贫燃混合物用于柴油内燃机,更优选机动应用中的柴油内燃机,特别是用于车辆中。车辆包括轻型和重型柴油机二者,例如轿车、火车和轮船,并且优选用于轻型车辆,更优选客车(这与重型车辆应用例如卡车和巴士相反的)。
根据第四方面,本发明提供一种车辆,其包含根据本发明第四方面的设备。
因此,在第五方面中,本发明提供处理来自于内燃机的废气的方法,特别是用于处理来自于车辆贫燃内燃机例如柴油发动机,贫燃汽油发动机,或者通过液化石油气或天然气供能的发动机的废气的方法,该方法包括将废气导过本发明第二方面的废气排放系统。
根据第六方面,本发明提供一种制造本发明第一方面的区域化的催化的基材整料的方法,其中该第一和第二区使用载体涂覆流程设置在基材整料上,其中在载体涂覆第二区之前,将该第一区载体涂覆到该基材整料上。
本发明的催化的基材整料可以通过本领域公知的方法来制备。区域涂覆方法公开在例如WO99/47260中。优选,该催化区域使用载体涂覆流程设置到基材上。下面阐述使用载体涂覆流程来制备催化的基材整料的代表性方法。将理解下面的方法可以根据本发明不同的实施方案来变化。同样,该第一区和第二区在基材上的添加次序不被认为是关键的。因此,在载体涂覆该第二区之前,该第一区可以载体涂覆到基材上,或者在载体涂覆第一区之前,该第二区可以载体涂覆到基材上。
该催化的基材整料的第一区优选是使用载体涂覆流程来制备的。如果使用贱金属/无机氧化物,则该贱金属优选如下来负载于无机氧化物上:例如在载体涂覆第一区之前,将贱金属化合物例如乙酸铁通过浸渍、吸附、离子交换、初始润湿、沉淀等负载到无机氧化物。首先,负载到该无机氧化物上的贱金属化合物优选进行研磨或者经历另一种粉碎方法,来确保基本上全部的固体颗粒的粒度的平均直径小于20微米。然后该载体涂覆优选是通过将负载在无机氧化物上的贱金属化合物的这些细微分散的颗粒在适当的溶剂(优选水)中制浆,来形成浆体而进行的。该浆体优选包含4-40重量%的固体,更优选6-30重量%。另外的组分例如稳定剂或者促进剂也可以作为水溶性或者水分散性化合物或者络合物的混合物而混入该浆体中。该基材然后可以用该浆体涂覆一次或多次,以使得在基材上将设置期望负载量的催化材料。
如果使用贱金属氧化物,则这可以使用上述类似的载体涂层制备技术来施用到基材上。另外的粘合剂可以用于该载体涂层浆体中来帮助将贱金属氧化物粘附到基材上。当该第一区另外包含负载的铂族金属时,则该负载的铂族金属和贱金属氧化物(或者贱金属/无机氧化物)优选负载于基材上,以使得两种催化剂在第一区内是物理分隔的。这可以通过任何已知的手段来完成,例如作为相对于铂族金属来说单独的载体涂覆步骤,将该贱金属氧化物(或贱金属/无机氧化物)加入到第一区中。
对于添加负载的铂族金属的载体涂覆步骤来说,该铂族金属可以在该载体涂覆步骤之前加入到载体中,或者可以在将载体载体涂覆到基材上之后加入到载体涂布的基材中。如果该铂族金属是在载体涂覆基材的第一区之前加入到载体的,则它可以通过任何已知的手段负载于载体,该添加方式不被认为是特别关键的。例如铂化合物(例如硝酸铂)可以通过浸渍,吸附,离子交换,初始润湿,沉淀等负载到载体上。首先在形成浆体之前,首先将该载体或者铂族金属/载体颗粒研磨或者进行另外一种粉碎方法,来确保基本上全部的固体颗粒的粒度的平均直径小于20微米。该载体涂覆优选如下来进行:首先将负载的铂族金属(或者仅仅载体)的细微分散的颗粒在适当的溶剂(优选水)中制浆,来形成浆体。该浆体优选包含4-40重量%的固体,更优选6-30重量%。优选另外的组分例如稳定剂或者促进剂也可以作为水溶性或者水分散性化合物或者络合物的混合物而混入该浆体中。
该基材然后可以用该浆体涂覆一次或多次,以使得在基材整料上将设置期望负载量的催化材料。如果仅仅载体设置在基材整料上,则该铂族金属可以通过任何已知的手段加入到载体涂布的基材整料中,包括铂化合物(例如硝酸铂)的浸渍,吸附或者离子交换。
优选涂覆该基材整料,以使得第一区仅仅占基材轴向长度的10-90%,更优选20-80%,特别的基材轴向长度的40-60%。
在基材整料的第一区已经涂覆后,将该涂覆的基材通常通过在优选80-150℃的高温加热而干燥。该基材也可以在更高温(例如400-600℃)煅烧,但是在加入第二区之前,通常不需要煅烧。
可选择地,该铂族金属和贱金属可以通过包含贱金属氧化物(或贱金属/无机氧化物)和负载的铂族金属的不同颗粒的浆体的载体涂覆而同时加入。
该催化的基材整料的第二区优选是使用载体涂覆流程,以与第一区相同的方式来制备的。在一种实施方案中,将基材整料以第二区载体涂层涂覆,以使得该第二区和第一区基本上无重叠。对于这样的实施方案,该第二区将优选仅仅占基材轴向长度的10-90%,更优选20-80,特别是占基材整料轴向长度的40-60%。在一种可选择的实施方案中,该基材以第二区载体涂层涂覆,以使得两个区存在着最高20%或更大的重叠。
在该基材整料以第二载体涂层涂覆之后,通常将该涂覆的基材干燥,然后通过在高温加热来煅烧。优选该煅烧在400-600℃进行大约1-8小时。
下面的实施例仅仅是作为说明来提供的,并且参考附图,在其中:
图1是直方图,其显示了送过本发明的催化的基材和对比的催化的基材的模拟的富燃废气的硫化氢逸出;并且
图2是第二直方图,其也显示了送过用催化剂催化的过滤器基材(对应于本发明的第一区)的模拟的富燃废气的硫化氢逸出。
实施例
实施例1
使用研磨到d90粒度<15微米的氧化铝和二氧化铈-氧化锆混合氧化物来制备了浆体。加入适量的可溶性Pt和Pd盐来给出20g/ft3的最终涂覆催化剂负载量,以及2:1的Pt:Pd重量比。将β沸石加入该浆体中,随后加入二氧化锰(d90<10微米),并且将该混合物搅拌到均匀。使用公知的颗粒过滤器涂覆技术(参见例如WO2011/080525),将该涂料浆体施用到市售的壁流式钛酸铝过滤器基材的入口通道,以使得该涂层达到基材总长的50%。将这个涂层在100℃干燥。该入口涂覆的过滤器在入口涂覆区中的锰负载量是125g/ft3
使用研磨到d90粒度<15微米的氧化铝和二氧化铈-氧化锆混合氧化物来制备了第二浆体。加入适量的可溶性Pt和Pd盐来给出20g/ft3的最终涂覆催化剂负载量,以及2:1的Pt:Pd重量比。将β沸石加入该浆体中,随后加入氧化铁(d90<5微米),并且将该混合物搅拌到均匀。使用公知的颗粒过滤器涂覆技术,将该第二涂料浆体施用到上面的壁流式钛酸铝基材的出口通道,以使得该涂层达到基材总长的50%。将这个涂层在100℃干燥并且在500℃部分煅烧。该涂覆的过滤器的铁负载量在出口区中是250g/ft3
对比例2
第一对比例
制备了与实施例1相同的涂覆的过滤器,区别在于入口区涂层不包含锰并且出口区涂层不包含铁,但是锰的负载量是125g/ft3
第二对比例
制备了与实施例1相同的涂覆的过滤器,区别在于入口区涂层不包含锰并且出口区涂层包含250g/ft3的铁和负载量为125g/ft3的锰二者。
实施例3
涂覆的过滤器的H2S控制性能是使用实验室反应器和模拟的废气来测定的。使用贫和富燃废气混合物来代表在贫燃NOx捕集器脱硫酸盐过程中所产生的那些。将全部的样品事先在800℃的水热条件下老化16小时。将该反应器加热到第一评价温度,并且将贫燃气体混合物送过该样品20秒。然后将该气体混合物切换到富燃气体混合物20秒。在测试期间,重复这种交替的贫和富燃气体混合物的循环。气体混合物浓度在表1中给出,并且余量是氮气。
表1
贫燃气体混合物 富燃气体混合物
CO2 14% 14%
HC 120ppm(C1) 2000ppm(C1)
O2 1.7% 0
H2O 5% 5%
H2 0 0.07%
CO 0 0.24%
H2S 0 500ppm
连续测量该过滤器样品下游的H2S浓度,并且确定H2S的峰值浓度。这个值称作H2S逸出。图1中显示了在5个贫燃/富燃操作循环上所测量的平均H2S逸出。
图1说明了送过本发明的催化的基材整料(根据实施例1)的模拟的富燃废气和送过对比的催化的基材(根据实施例2)的废气的H2S逸出。图1清楚地表明与在单个区域中的单个贱金属氧化物或者贱金属氧化物的混合物相比,本发明的区域化的催化的基材更有效的控制了硫化氢排放。
实施例4
使用研磨到d90粒度<15微米的氧化铝和二氧化铈-氧化锆混合氧化物来制备浆体。加入适量的可溶性Pt和Pd盐来给出10g/ft3的最终涂覆催化剂负载量,以及2:1的Pt:Pd重量比。加入氧化锌粉末,并且将该浆体搅拌到均匀。使用公知的颗粒过滤器涂覆技术(参见例如WO2011/080525),将该涂料浆体施用到市售的壁流式碳化硅过滤器基材的通道。将这个涂层在100℃干燥,然后在500℃煅烧。最终催化剂上的锌量是250g ft-3
实施例5
使用研磨到d90粒度<15微米的氧化铝和二氧化铈-氧化锆混合氧化物来制备浆体。加入适量的可溶性Pt和Pd盐来给出10g/ft3的最终涂覆催化剂负载量,以及2:1的Pt:Pd重量比。加入二氧化锰粉末,并且将该浆体搅拌到均匀。使用公知的颗粒过滤器涂覆技术(参见例如WO2011/080525),将该涂料浆体施用到市售的壁流式碳化硅过滤器基材的通道。将这个涂层在100℃干燥,然后在500℃煅烧。最终催化剂上的锰量是250g ft-3
实施例6
使用研磨到d90粒度<15微米的氧化铝和二氧化铈-氧化锆混合氧化物来制备浆体。加入适量的可溶性Pt和Pd盐来给出10g/ft3的最终涂覆催化剂负载量,以及2:1的Pt:Pd重量比。将该浆体搅拌到均匀。使用公知的颗粒过滤器涂覆技术(参见例如WO2011/080525),将该涂料浆体施用到市售的壁流式碳化硅过滤器基材的通道。将这个涂层在100℃干燥,然后在500℃煅烧。
实施例7
涂覆的过滤器的H2S控制性能是使用实验室反应器和模拟的废气来测定的。使用贫和富燃废气混合物来代表在贫燃NOx捕集器脱硫酸盐过程中所产生的那些。将全部的样品事先在800℃的水热条件下老化16小时。将该反应器加热到第一评价温度,并且将贫燃气体混合物送过该样品20秒。然后将该气体混合物切换到富燃气体混合物20秒。在测试期间,重复这种交替的贫和富燃气体混合物的循环。气体混合物浓度在表2中给出,并且余量是氮气。
表2
贫燃气体混合物 富燃气体混合物
CO2 14% 14%
HC 120ppm(C1) 2000ppm(C1)
O2 1.7% 0
H2O 5% 5%
H2 0 0.07%
CO 0 0.24%
H2S 0 500ppm
连续测量该过滤器样品下游的H2S浓度,并且确定H2S的峰值浓度。这个值称作H2S逸出。图2显示了在5个贫/富操作循环中所测量的平均H2S逸出。
图2说明了送过实施例4,实施例5和实施例6的催化的基材整料的模拟的富燃废气的H2S逸出。图1清楚地表明,与不含用于除去硫化氢的贱金属氧化物的实施例3相比,实施例4(其包含氧化锌)和实施例2(其包含氧化锰)都更有效地控制了硫化氢排放。
实施例8
测试了实施例4,实施例5和实施例6的催化的基材整料的CO氧化性能。该老化的芯是在模拟的催化剂活性测试(SCAT)气体设备中,使用表3中的入口气体混合物来测试的。在每种情况中,余量是氮气。
表3
气体组分 在入口气体混合物组合物中的量
CO 1500ppm
HC(作为C1) 430ppm
NO 100ppm
CO2 4%
H2O 4%
O2 14%
空速 55000/小时
表4显示了用于催化的基材整料的T50起燃温度。包含氧化锌的实施例4表现出与实施例6(其不包含用于控制硫化氢的贱金属氧化物)类似的起燃温度。实施例5(其包含氧化锰)表现出比实施例4和实施例6二者更高的起燃温度。表4显示了与实施例4中存在的氧化锌相比,实施例5中存在的氧化锰对于CO氧化性能具有更大的不利影响。
表4
T50温度
实施例1 219℃
实施例2 248℃
实施例3 207℃
为了避免任何疑义,此处所引用的任何和全部现有技术文献的整体内容在此引入作为参考。

Claims (21)

1.区域化的催化的基材整料,其包含第一区和第二区,其中该第一区和该第二区是轴向串联排列的,
其中该第一区包含负载于载体上的铂族金属,和选自氧化铁、氧化锰、氧化铜、氧化锌、氧化镍及其混合物的第一贱金属氧化物或者负载于无机氧化物上的选自铁、锰、铜、锌、镍及其混合物的第一贱金属,并且
该第二区包含负载于沸石上的铜或者铁,和选自氧化铁、氧化锰、氧化铜、氧化锌、氧化镍及其混合物的第二贱金属氧化物或者负载于无机氧化物上的选自铁、锰、铜、锌、镍及其混合物的第二贱金属,
其中该第二贱金属不同于该第一贱金属,并且(a)该第一区中的第一贱金属氧化物或者负载于无机氧化物上的第一贱金属是与负载于载体上的铂族金属物理隔离的,或(b)区域化的催化的基材整料还包含第三区,其轴向串联地位于第二区之后和基材的相对于第一区的对面端处,其中该第三区包含负载的铂族金属。
2.根据权利要求1的区域化的催化的基材整料,其中该第一区中的铂族金属选自钯、铂、铑及其混合物,并且该载体选自无机氧化物、沸石及其混合物。
3.根据权利要求1或2的区域化的催化的基材整料,其中该第一区包含贫燃NOx捕集器组合物,其中该负载于载体上的铂族金属是贫燃NOx捕集器组合物的组分。
4.根据权利要求1或2的区域化的催化的基材整料,其中在该第一区或第二区中,所述无机氧化物选自氧化铝、二氧化硅、二氧化钛、氧化锆、二氧化铈、氧化铌、钽氧化物、钼氧化物、钨氧化物、前述无机氧化物的混合物、包含两种或更多种来自前述无机氧化物的金属的任何混合氧化物,和前述无机氧化物和混合氧化物的混合物。
5.根据权利要求1或2的区域化的催化的基材整料,其中该基材整料是过滤器基材或者流过式基材整料。
6.根据权利要求1或2的区域化的催化的基材整料,其中该基材整料是过滤器基材,其是一种壁流式整料过滤器,包含入口端、出口端、在该入口端和出口端之间延伸的基材轴向长度、和由该壁流式基材的内壁所限定的多个通道,其中该多个通道包含具有开放入口端和封闭出口端的入口通道和具有封闭入口端和开放出口端的出口通道。
7.根据权利要求6的区域化的催化的基材整料,其中该第一区设置在该壁流式整料过滤器的入口端的入口通道之中或者之上,并且该第二区设置在该壁流式整料过滤器的出口端的出口通道之中或者之上。
8.根据权利要求1或2的区域化的催化的基材整料,其中该第一区和第二区之间基本上没有重叠。
9.根据权利要求8的区域化的催化的基材整料,其中该第一区覆盖了该基材整料总轴向长度的10-90%,并且该第二区覆盖了该基材总轴向长度的90-10%。
10.根据权利要求1或2的区域化的催化的基材整料,其中在该第一区和第二区之间存在重叠。
11.根据权利要求10的区域化的催化的基材整料,其中该第一区和第二区的每一者覆盖了基材整料总轴向长度的10-90%。
12.根据权利要求1或2的区域化的催化的基材整料,其中该第一贱金属或第二贱金属为锰和锌,或该第一贱金属氧化物或第二贱金属氧化物为氧化锰和氧化锌。
13.根据权利要求1或2的区域化的催化的基材整料,其中该第一区包含氧化铜或氧化铁。
14.用于内燃机的排气系统,其包含:
(a)贫燃NOx捕集器;并且
(b)根据权利要求1-11中任一项的区域化的催化的基材整料,
其中该区域化的催化的基材整料位于该贫燃NOx捕集器的下游。
15.根据权利要求14的排气系统,其中该第一区定向至上游侧。
16.根据权利要求14或15的排气系统,其中该区域化的催化的基材整料的基材整料是流过式基材整料,并且该排气系统还包含颗粒过滤器。
17.根据权利要求14或15的排气系统,其还包含位于贫燃NOx捕集器上游的氧化催化剂。
18.设备,其包含内燃机和根据权利要求14-17任一项的排气系统。
19.车辆,其包含权利要求18的设备。
20.处理来自于内燃机的废气的方法,该方法包括将废气导过根据权利要求14-17任一项的排气系统。
21.制造根据权利要求1-11任一项的区域化的催化的基材整料的方法,其中使用载体涂覆流程将该第一和第二区设置到基材整料上,其中在载体涂覆第二区之前,将该第一区载体涂覆到基材整料上。
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