CN106401708A - 用于包括scr催化剂的贫燃内燃机的排气*** - Google Patents
用于包括scr催化剂的贫燃内燃机的排气*** Download PDFInfo
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- CN106401708A CN106401708A CN201610788858.8A CN201610788858A CN106401708A CN 106401708 A CN106401708 A CN 106401708A CN 201610788858 A CN201610788858 A CN 201610788858A CN 106401708 A CN106401708 A CN 106401708A
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Abstract
用于内燃机的排气***(20),其包括:a)第一催化基底整料(12),其包含位于该基底整料的第一活化涂层区(16)中的第一活化涂层和位于该基底整料的第二活化涂层区(18)中的第二活化涂层,其中第一活化涂层包含催化剂组合物,该催化剂组合物包含至少一种铂族金属(PGM)和至少一种载体材料,其中当第一活化涂层暴露于包括相对高温的相对极端条件时,第一活化涂层中的至少一种PGM易于挥发,其中第二活化涂层包含用于捕集挥发的PGM的至少一种负载铜的材料,并且其中第二活化涂层经取向以接触已经接触过第一活化涂层的废气;和b)位于第一催化基底整料下游的第二催化基底整料(14),其包含用于将氮的氧化物用含氮还原剂选择性催化还原为二氮的催化剂。
Description
本申请是基于申请号为201280061157.4、申请日为2012年12月11日、发明名称为“用于包括SCR催化剂的贫燃内燃机的排气***”的中国专利申请的分案申请。
发明领域
本发明涉及用于内燃机的排气***,其包括在位于基底整料上的第一活化涂层中的含铂催化剂,该含铂催化剂在位于用于将氮的氧化物用含氮还原剂选择性催化还原为二氮的催化剂(即SCR催化剂)上游的高温中容易挥发。
发明背景
通常,有四类污染物被全世界的政府间组织立法限制:一氧化碳(CO)、未燃烧的烃(HC)、氮氧化物(NOx)和颗粒物质(PM)。
随着对来自车辆发动机的废气中污染物的可容许排放的排放标准越来越严格,提出和研发了发动机管理和多重催化剂废气后处理***的组合以满足这些排放标准。对于包括颗粒过滤器的排气***,通常定期(例如每隔500km)进行发动机管理以提高过滤器中的温度以燃烧掉保持在该过滤器上的基本上所有剩余的烟灰,由此将该***返回基线水平。这些经过发动机管理的烟灰燃烧事件经常称作“过滤器再生”。尽管过滤器再生的主要焦点是燃烧保持在该过滤器上的烟灰,但未曾预期的结果是根据该***中发动机管理的水平,排气***中存在的一个或多个催化剂涂层(例如过滤器(所谓的催化烟灰过滤器(CSF))本身的过滤涂层)、位于过滤器上游或下游的氧化催化剂(例如柴油机氧化催化剂(DOC))或NOx吸附催化剂(NAC)(例如第一DOC之后是柴油颗粒过滤器,之后又是第二DOC,最后是SCR催化剂)能够定期暴露于高废气温度。这些条件也可能经历未曾预期的偶然的发动机不正常模式(upset mode)或不受控制或控制不良的再生事件。然而,一些柴油发动机(特别是以高负荷操作的重型柴油发动机)甚至可以在正常操作条件下将催化剂暴露于高温(例如>600℃)。
因为车辆制造商研发其发动机和发动机管理***以满足排放标准,本申请人/受让人被车辆制造商要求提出催化组分和催化组分的组合,以帮助满足排放标准的目标。这些组分包括用于氧化CO、HC而且任选也氧化NO的DOC;用于氧化CO、HC、任选也氧化NO并用于捕集颗粒物质用于随后燃烧的CSF;用于氧化CO和HC并用于氧化一氧化氮(NO)和将其从贫燃废气中吸收并解吸吸附的NOx并将其在富废气中还原成N2的NAC(见下面);和用于在含氮还原剂(例如氨)存在下将NOx还原成N2的选择性催化还原(SCR)催化剂(见下面)。
在实践中,DOC和CSF中使用的催化剂组合物是非常相似的。然而,通常DOC和CSF的使用之间的主要差异是该催化剂组合物所涂覆的基底整料:在DOC的情况中,该基底整料通常是流通式基底整料,包括具有延伸贯通的细长通道阵列的金属或陶瓷蜂窝状整料,该通道在两端都开口;CSF基底整料是过滤器整料例如壁流式过滤器,例如陶瓷多孔过滤器基底,其包括与多个出口通道平行排列的多个入口通道,其中各入口通道和各出口通道部分地由多孔结构的陶瓷壁限定,其中各入口通道与出口通道通过多孔结构的陶瓷壁交替隔开,反之亦然。换言之,壁流式过滤器是蜂窝状布置,限定了多个在上游端堵塞的第一通道和多个在上游端未堵塞但在下游端堵塞的第二通道。与第一通道垂直和横向相邻的通道在下游端堵塞。当从任一端观察时,通道的交替地堵塞和开口的端呈现棋盘的外观。
在流通式基底整料上可以涂覆非常复杂的多层催化剂布置,例如DOC和NAC。尽管可以用多于一层的催化剂组合物涂覆过滤器整料的表面(例如壁流式过滤器的入口通道表面),但涂覆过滤器整料的问题是要避免在使用时通过用催化剂活化涂层过度加载该过滤器整料而不必要地提高背压,由此限制气体流通。因此,尽管用一种或多种不同的催化剂层顺序涂覆过滤器基底整料的表面并不是不可能的,但更通常地将不同的催化剂组合物分割成区,例如过滤器整料的轴向分隔的前半区和后半区,或者通过用第一催化剂组合物涂覆壁流式过滤器基底整料的入口通道,用第二催化剂组合物涂覆其出口通道。然而,在本发明的具体实施方案中,用一个或多个可以是相同或不同催化剂组合物的层涂覆过滤器入口。还提出了在过滤基底整料上涂覆NAC组合物(例如参见EP0766993)。
在包含多种催化剂组分的排气***(均包括单独的基底整料)中,通常SCR催化剂位于DOC和/或CSF和/或NAC的下游,因为已知通过将废气中的一些氧化氮(NO)氧化成二氧化氮(NO2),使得离开DOC和/或CSF和/或NAC的NO:NO2比为约1:1,促进了下游的SCR反应(见下面)。从EP341832(所谓的连续再生捕集器或)中还公知,通过将废气中的NO氧化成NO2而产生的NO2能够用于在下游过滤器上被动燃烧烟灰。在EP341832的方法重要的排气***布置中,如果SCR催化剂位于过滤器的上游,那么这将会减少或阻止捕集的烟灰在NO2中燃烧的过程,因为用于燃烧烟灰的NOx的大部分将很可能在SCR催化剂上除去。
然而,轻型柴油车辆优选的***布置是柴油机氧化催化剂(DOC)之后是含氮喷射器,然后是SCR催化剂,最后是催化烟灰过滤器(CSF)。这种布置的简称为“DOC/SCR/CSF”。这种布置优选用于轻型柴油车辆,因为重要的考虑是在车辆发动机启动之后在排气***中尽可能快地实现NOx转化,以确保(i)将含氮还原剂(例如氨)的前体喷射/分解以释放氨用于NOx转化;和(ii)尽可能高的NOx转化率。如果将大热质量过滤器放在SCR催化剂上游(即DOC和SCR催化剂之间)(“DOC/CSF/SCR”),(i)和(ii)的过程将会花费长得多的时间实现,且对于整个排放标准加州周期的NOx转化率将会降低。可以使用氧和采用发动机管理技术对过滤器的偶尔强制再生来实现颗粒物质去除。
已经提出将SCR催化剂活化涂层涂覆到过滤基底整料自身上(例如参见WO2005/016497),在这种情况中,氧化催化剂可以位于涂覆有SCR的过滤器基底上游(无论该氧化催化剂是否DOC、CSF或NAC的组分),以改进NO/NO2比用于提高SCR催化剂上的NOx还原活性。还已经提出将NAC设置在位于流通式基底整料上的SCR催化剂的上游,该NAC能够在NAC再生过程中原位产生NH3(见下面)。GB2375059中公开了一种该提议。
NAC是例如从US5,473,887已知的,且经设计以从贫废气(λ>1)中吸附NOx并在废气中氧浓度降低时解吸该NOx。解吸的NOx可以用合适的还原剂(例如发动机燃料)还原成N2,通过NAC自身或位于NAC下游的催化剂组分(例如铑)进行促进。在实践中,能够间歇地根据计算的NAC剩余的NOx吸附容量将对氧浓度的控制调节到所需的氧化还原组成,例如比正常发动机运行操作更富燃(但仍贫于化学计量的或λ=1的组成)、化学计量的或富于化学计量的(λ<1)。氧浓度可以通过多种手段调节,例如节流、将另外的烃燃料注入发动机气缸(例如在排气冲程过程中)或将烃燃料直接注入发动机集管下游的废气。
典型的NAC配方包含催化氧化组分(例如铂)、显著量(即充分大于作为助剂(例如三效催化剂中的助剂)所需的量)的NOx储存组分(例如钡)和还原催化剂(例如铑)。对于该配方来说,用于从贫废气中储存NOx通常的机理为:
NO+1/2O2→NO2 (1);和
BaO+2NO2+1/2O2→Ba(NO3)2 (2),
其中在反应(1)中,一氧化氮与氧气在铂上的活性氧化位上反应生成NO2。反应(2)包括由储存材料以无机硝酸盐的形式来吸附NO2。
在较低的氧浓度和/或升高的温度时,该硝酸盐物类变得热力学不稳定并分解,根据以下的反应(3)生成NO或NO2。在适合的还原剂存在下,这些氮氧化物随后被一氧化碳、氢和烃还原成N2,这可以在还原催化剂上发生(参见反应(4))。
Ba(NO3)2→BaO+2NO+3/2O2或Ba(NO3)2→BaO+2NO2+1/2O2(3);和
NO+CO→1/2N2+CO2 (4);
(其他反应包括Ba(NO3)2+8H2→BaO+2NH3+5H2O,然后
NH3+NOx→N2+yH2O或2NH3+2O2+CO→N2+3H2O+CO2等)。
在本文上面包括的反应(1)-(4)中,活性钡物类作为氧化物提供。然而,应当理解在空气存在下,大部分钡为碳酸盐或者可能为氢氧化物的形式。技术人员能够调整由此对于除氧化物之外的其他钡物类的上述反应方案和废气流中催化涂层的顺序。
氧化催化剂促进CO氧化为CO2和未燃烧的HC氧化为CO2和H2O。典型的氧化催化剂包括在高表面积载体上的铂和/或钯。
SCR技术用于处理车辆内燃(IC)发动机(特别是贫燃IC发动机)的NOx排放的应用是公知的。可以用于SCR反应中的含氮还原剂的实例包括化合物例如氮氢化物,例如氨(NH3)或肼或NH3前体。
NH3前体是能够例如通过水解得到NH3的一种或多种化合物。前体分解为氨和其他副产物能够通过水热或催化水解进行。NH3前体包括作为水溶液或者作为固体的尿素(CO(NH2)2)或者氨基甲酸铵(NH2COONH4)。如果使用作为水溶液的尿素,优选低共熔混合物,例如32.5%NH3(含水)。在该水溶液中可以包括添加剂以降低结晶温度。目前,尿素是用于移动应用的优选NH3源,因为它毒性比NH3低,它易于运输和处理,它廉价且通常可获得。在为满足相关的排放测试循环的测试中,尿素的不完全水解可以导致PM排放提高,因为部分水解的尿素固体或液滴将被PM的立法集管测试所用的滤纸捕集并计入PM质量。进一步地,不完全的尿素水解的某些产物(例如氰尿酸)的释放在环境上是不适宜的。
SCR具有三个主要反应(示于下面包括的反应(5)-(7)中),其将NOx还原为单质氮。
4NH3+4NO+O2→4N2+6H2O(即1:1 NH3:NO) (5)
4NH3+2NO+2NO2→4N2+6H2O(即1:1 NH3:NOx) (6)
8NH3+6NO2→7N2+12H2O(即4:3 NH3:NOx) (7)
相关不适宜的非选择性副反应为:
2NH3+2NO2→N2O+3H2O+N2 (8)
实践中,反应(7)与反应(5)相比比较慢,反应(6)是所有中最快的。因此,当技术人员设计车辆废气后处理***时,他们经常优先将氧化催化剂元件(例如DOC和/或CSF和/或NAC)设置在SCR催化剂的上游。
当某些DOC和/或NAC和/或CSF暴露于例如在过滤器再生和/或发动机不正常情况期间遇到的高温和/或(在某些重型柴油机应用中)正常的高温废气时,可以提供高温的足够时间使低含量的铂族金属组分(特别是Pt)从DOC和/或NAC和/或CSF组分中挥发出来,并随后使该铂族金属捕集在下游的SCR催化剂上。这会对SCR催化剂的性能具有高度有害的影响,因为Pt的存在导致对竞争性的非选择性氨氧化例如反应(9)中的氨氧化(其显示了NH3的完全氧化)具有高活性,由此产生二级排放和/或无谓消耗NH3。
4NH3+5O2→4NO+6H2O (9)
一个车辆制造商在SAEpaper 2009-01-0627中报道了对该现象的观察,其名称为“Impact and Prevention of Ultra-Low Contamination of Platinum Group Metals onSCR catalysts Due to DOC Design”且包括了串联位于四个供应商的含铂族金属(PGM)的DOC之后的Fe/沸石SCR催化剂在与流动模型废气在850℃接触16小时的NOx转化活性与温度的比较数据。所呈现的数据显示设置在总PGM为70gft-3的20Pt:Pd DOC之后的Fe/沸石SCR催化剂的NOx转化活性在较高的评价温度时与较低的评价温度相比有不利的变化,这是由Pt污染所导致的。还测试了总PGM为105gft-3的来自不同供应商的两种2Pt:Pd DOC。在第一种2Pt:Pd DOC中,对SCR催化剂活性的影响程度与对20Pt:Pd DOC测试的程度相似,而对于第二种测试的2Pt:Pd DOC,SCR催化剂活性污染程度较低,不过第二种2Pt:Pd DOC与空白对照样(无DOC,仅为裸露的基底)相比还是显示出降低的NOx转化活性。作者总结道,显示出更缓和的NOx转化率降低的第二种2Pt:Pd DOC的供应商在用35gft-3Pd来稳定所存在的70gft-3Pt方面更成功。150gft-3的仅含Pd的DOC证实与空白对照样相比对下游的SCR没有影响。SAE2009-01-0627作者的早期工作公开在SAEpaper no.2008-01-2488中。
US2011/0014099教导了可用于从主要在贫燃条件下运行的内燃机的废气中除去氮氧化物和颗粒的催化活性颗粒过滤器。该颗粒过滤器包括过滤器体、铂族金属氧化催化活性涂层和位于第二涂层中的铜化合物。
发明内容
车辆制造商已经开始要求申请人提供方法来解决来自SCR催化剂上游的组分的相对低含量PGM的挥发问题。非常希望研发出策略来防止这种PGM在高温向下游SCR催化剂上的移动。本发明人已经研发了多种策略来满足这种需要。
本发明人已经发现,在Pt:Pd重量比大于约2:1时,在极端温度条件下能够发生铂从包含铂和钯的含PGM的催化剂中挥发。还据信,在PGM由铂组成的情况下,也可以观察到铂的挥发。本发明人已经设计了包括含PGM催化剂组合物与下游SCR催化剂结合使用的排气***布置,其避免或减少了PGM(特别是Pt)从上游相对高负载的Pt催化剂上迁移到下游SCR催化剂的问题。
根据一个方面,本发明提供了用于内燃机的排气***,该***包括:
a)第一催化基底整料,其包含位于该基底整料的第一活化涂层区中的第一活化涂层和位于该基底整料的第二活化涂层区中的第二活化涂层,其中第一活化涂层包含催化剂组合物,该催化剂组合物包含至少一种铂族金属(PGM)和至少一种载体材料,其中当第一活化涂层暴露于包括相对高温的相对极端条件时,第一活化涂层中的至少一种PGM易于挥发,其中第二活化涂层包含用于捕集挥发的PGM的至少一种负载铜的材料,并且其中第二活化涂层经取向以接触已经接触过第一活化涂层的废气;和
b)位于第一催化基底整料下游的第二催化基底整料,其包含用于将氮的氧化物用含氮还原剂选择性催化还原为二氮的催化剂。
根据另一方面,本发明提供了包括根据本发明的排气***的内燃机,特别是用于车辆的内燃机。该贫燃内燃机可以是强制点火例如火花点火发动机,其典型地运行于用汽油燃料或汽油燃料和其他组分例如乙醇的共混物,但是优选是压缩点火例如柴油类型发动机。贫燃内燃机包括均质充量压缩点火(HCCI)发动机,其由汽油等燃料或柴油燃料提供动力。
根据另一方面,本发明提供了一种包括根据本发明的排气***的车辆。典型地,该车辆进一步包括内燃机。
根据另一方面,本发明提供了一种减少或防止贫燃内燃机的排气***中的选择性催化还原(SCR)催化剂被铂族金属(PGM)中毒的方法,当包含PGM的催化剂组合物暴露于包括相对高温的相对极端条件时,该铂族金属会从催化剂组合物挥发,该催化剂组合物包含负载在至少一种负载材料上且位于SCR催化剂上游的基底整料上的至少一种PGM,该方法包括使挥发的PGM捕集在包含至少一种负载铜的材料的活化涂层中,该活化涂层位于与包含PGM的催化剂组合物相同的基底整料上。
本发明进一步涉及活化涂层用于减少或防止选择性催化还原(SCR)催化剂被铂族金属(PGM)中毒的用途,典型地用于贫燃内燃机的排气***中,其中该活化涂层包含至少一种负载铜的材料,且该活化涂层位于包含至少一种PGM的基体整料上,优选该至少一种PGM负载在至少一种负载材料上。
本发明的另一方面涉及催化基底整料用于减少或防止选择性催化还原(SCR)催化剂被铂族金属(PGM)中毒的用途,典型地用于贫燃内燃机的排气***中,其中该催化基底整料包含位于该基底整料的第一活化涂层区中的第一活化涂层和位于该基底整料的第二活化涂层区中的第二活化涂层,其中第一活化涂层包含催化剂组合物,该催化剂组合物包含至少一种铂族金属(PGM)和至少一种载体材料,其中当第一活化涂层暴露于包括相对高温的相对极端条件时,第一活化涂层中的至少一种PGM易于挥发,其中第二活化涂层包含用于捕集挥发的PGM的至少一种负载铜的材料,并且任选地其中第二活化涂层经取向以接触已经接触过第一活化涂层的飞去。本发明优选进一步涉及该催化基底整料用于减少或防止选择性催化还原(SCR)催化剂被铂族金属(PGM)中毒并将贫燃内燃机的废气中的一氧化碳(CO)和/或烃(HC)氧化的用途。
附图说明
为了可以更充分地理解本发明,仅通过示例的方式参考以下实施例并参考附图。
图1是用于测试Fe/β沸石SCR催化剂或Cu/CHA沸石SCR催化剂上的铂污染的实验室用反应器的示意图。
图2的图比较了两个老化的SCR催化剂芯的作为温度函数的NOx转化活性,其每个已经在实验室规模的排气***构造中进行了老化,该构造含有用于本发明中的实施例3或对比例2的芯样品。将经老化的SCR活性的结果相对于新鲜的即未老化的SCR催化剂的活性进行作图。
图3的图比较了三个老化的SCR催化剂芯的作为温度函数的NOx转化活性,其每个已经在实验室规模的排气***构造中进行了老化,该构造包含位于Fe/β沸石SCR催化剂上游的催化壁流式过滤器,一个***包括在入口和出口通道上涂覆有1:1重量比的Pt:Pd的过滤器;第二***包括在入口和出口通道上涂覆有5:1重量比的Pt:Pd的过滤器;第三对比***包括在入口和出口通道上涂覆有仅Pt催化剂的过滤器。将经老化的SCR活性的结果相对于新鲜的即未老化的SCR催化剂的活性进行作图。
图4的条形图比较了两个老化的SCR催化剂芯的作为温度函数的NOx转化活性,其每个已经在图1中所示的实验室规模的排气***中进行了老化,该***包含在900℃管式炉中在流动的合成废气中加热2小时的实施例8的柴油机氧化催化剂的芯样品,并且具有位于下游的保持在300℃的Cu/CHA沸石SCR催化剂芯。
图5是根据本发明的排气实施方案的示意图。
具体实施方式
典型地,根据本发明的排气***可以包括喷射器,其用于将含氮还原剂注入到第一催化基底整料和第二催化基底整料之间的废气中。用于本发明中的含氮还原剂及其前体包括本文上面就背景技术部分所提及的那些中任一种。因此,例如含氮还原剂优选是氨或尿素。
替代地(即在第一催化基底整料和第二催化基底整料之间没有用于注入氨或其前体如尿素的装置),或者除了用于注入氨或其前体的装置之外,优选提供发动机管理装置来浓缩废气,以使得通过在位于第一基底整料上游或第一基底整料下游的第一活化涂层和/或DOC或NAC(通常是包含DOC组合物或NAC组合物的基底整料)的催化剂组合物上还原NOx来原位产生氨气。在该基底整料包含DOC组合物或NAC组合物或者NAC位于过滤器下游的情况下,优选其位于用于注入氨或其前体的装置的上游或者第一和第二催化基底整料之间。
与经适当设计和管理的柴油压缩点火发动机相组合,浓废气(即与正常贫燃运行模式相比一氧化碳和烃的量增加的废气)接触NAC。NAC或NAC组合物内的组分例如用PGM促进的二氧化铈或者二氧化铈-氧化锆可以促进水煤气变换反应,即CO(g)+H2O(v)→CO2(g)+H2(g),释放出H2。从上文所述的反应(3)和(4)脚注的副反应例如Ba(NO3)2+8H2→BaO+2NH3+5H2O可知,可以原位产生NH3和储存用于下游SCR催化剂上的NOx还原。
用于本发明中的含氮还原剂及其前体包括本文上面就背景技术部分所提及的那些中的任一种。因此,例如该含氮还原剂优选是氨或尿素。
通常,第一活化涂层包含铂。当第一活化涂层中的至少一种PGM是铂时,则当第一活化涂层暴露于包括相对高温的相对极端条件时,该PGM易于挥发。包括相对高温的相对极端条件例如是≥700℃,优选≥800℃或更优选≥900℃的温度。
典型地,第一活化涂层包含铂和钯(即该至少一种PGM是铂和钯)。当第一活化涂层暴露于包括相对高温的相对极端条件时,该铂和/或钯可以是易于挥发的PGM。但是当铂和钯均存在时,则通常当第一活化涂层暴露于包括相对高温的相对极端条件时,铂更可能是易于挥发的PGM。
在本发明的一种实施方案中,第一活化涂层不包含金,尤其是钯-金合金。
因为第一催化基底整料包括用于减少或防止挥发的铂从含铂催化剂迁移到下游SCR催化剂的措施,因此为了例如生成NO2以促进经过滤的颗粒物质的下游燃烧,在含铂催化剂中可以使用相对高的Pt:Pd重量比,例如≤10:1,例如8:1、6:1、5:1或4:1。即使PGM可能从其上挥发,也可以使用该相对高的Pt:Pd重量比,因为本发明的第一催化基底整料的设计基本上防止了挥发的PGM接触下游SCR催化剂。
然而,本发明人已经发现通过减少Pt:Pd重量比可以进一步降低PGM挥发的水平,这能够减少或防止下游SCR催化剂的PGM中毒。在第一活化涂层中的至少一种PGM包括铂和钯的情况下,优选Pt:Pd重量比≤2,例如≤1.5:1,例如约1:1。该特征的重要性显示在实施例中:本发明人发现通过经验试验,该优选的Pt:Pd重量比的挥发小于Pt:Pd重量比为4:1的类似催化剂。在层状催化剂布置中,优选外层的Pt:Pd重量比≤2,或者任选地所有层的全部Pt:Pd重量比综合≤2。
典型地,Pt:Pd重量比≥35:65(例如≥7:13)。优选Pt:Pd重量比≥40:60(例如≥2:3),更优选≥42.5:57.5(例如≥17:23),特别地≥45:55(例如≥9:11),例如≥50:50(例如≥1:1),仍然更优选≥1.25:1。Pt:Pd重量比典型地是10:1-7:13。优选Pt:Pd重量比为8:1-2:3,更优选6:1-17:23,甚至更优选5:1-9:11,例如4:1-1:1,仍然更优选2:1-1.25:1。
通常,铂族金属(PGM)的总量(例如Pt和/或Pd的总量)为1-500g ft-3。优选PGM的总量为5-400g ft-3,更优选10-300g ft-3,仍然更优选25-250g ft-3,甚至更优选为35-200gft-3。
第一活化涂层中的载体材料可以是金属氧化物(即至少一种金属氧化物)、分子筛(即至少一种分子筛)或其任意两种或更多种的混合物。优选地,载体材料包括至少一种金属氧化物。进一步优选载体材料包括至少一种金属氧化物,并且第一活化涂层包含至少一种分子筛。
典型地,第一活化涂层的至少一种金属氧化物载体可以包括选自由以下构成的组的金属氧化物:任选稳定化的氧化铝、无定形二氧化硅-氧化铝、任选稳定化的氧化锆、二氧化铈、二氧化钛、任选稳定化的二氧化铈-氧化锆混合氧化物及其任意两种或更多种的混合物。适合的稳定剂包括二氧化硅和稀土金属中的一种或多种。第一活化涂层优选包含任选稳定化的氧化铝或无定形二氧化硅-氧化铝。
典型地,第二活化涂层中的载体材料可以是金属氧化物(即至少一种金属氧化物)、分子筛(即至少一种分子筛)或其任意两种或更多种的混合物。因此,该至少一种负载铜的材料是负载在至少一种载体材料上的铜,其中该载体材料如本文所述。
第二活化涂层可以包含分子筛。可以认识到,第二活化涂层中的负载铜的分子筛可以按以下方式配制:其作为用于使用含氮还原剂还原氮的氧化物的SCR催化剂是活性的。特别优选将铜/分子筛SCR催化剂与用于浓缩废气以通过NOx在第一活化涂层的催化剂组合物上还原来原位生成氨气的发动机管理装置相结合。在一种实施方案中,第二活化涂层不包含金属氧化物,该金属氧化物例如任选稳定化的氧化铝、无定形二氧化硅-氧化铝、任选稳定化的氧化锆、二氧化铈、二氧化钛、任选稳定化的二氧化铈-氧化锆混合氧化物及其任意两种或更多种的混合物。
然而,第二活化涂层的至少一种金属氧化物载体典型地包括选自由以下构成的组的金属氧化物:任选稳定化的氧化铝、无定形二氧化硅-氧化铝、任选稳定化的氧化锆、二氧化铈、二氧化钛、任选稳定化的二氧化铈-氧化锆混合氧化物及其任意两种或更多种的混合物。适合的稳定剂包括二氧化硅和稀土金属中的一种或多种。
当第二活化涂层包含金属氧化物时,则优选该金属氧化物选自由以下构成的组:任选稳定化的氧化铝、无定形二氧化硅-氧化铝、任选稳定化的氧化锆、二氧化铈、二氧化钛、任选稳定化的二氧化铈-氧化锆混合氧化物及其任意两种或更多种的混合物。更优选地,该金属氧化物是任选稳定化的氧化铝。
在一种实施方案中,第二活化涂层不包含二氧化铈和/或分子筛。
第二活化涂层典型地包含总量为10-350g ft-3的铜。优选第二活化涂层中铜的总量为20-300g ft-3,更优选30-250g ft-3,仍然更优选45-200g ft-3,甚至更优选50-175gft-3。
第一活化涂层包含催化剂组合物,该催化剂组合物包含至少一种铂族金属(PGM)和用于该至少一种PGM的至少一种载体材料。该催化剂典型地作为活化涂层浆料施涂到基底整料上,该浆料包含在最终催化剂涂料中的至少一种PGM盐和一种或多种载体材料的,然后将经涂覆的过滤器干燥,再煅烧。该一种或多种载体材料可以称作“活化涂层组分”。还可以在制浆之前,将至少一种PGM预固定到一种或多种载体材料上,或者可以将预固定有PGM的载体材料颗粒的合并物在PGM盐的溶液中制浆。
本文用至少一种“载体材料”表示选自由任选稳定化的氧化铝、无定形二氧化硅-氧化铝、任选稳定化的氧化锆、二氧化铈、二氧化钛、任选稳定化的二氧化铈-氧化锆混合氧化物构成的组的金属氧化物或分子筛及其任意两种或更多种的混合物。
该至少一种载体材料可以包括一种或多种分子筛,例如硅铝酸盐沸石。在用于本发明的PGM催化剂中分子筛的主要任务是当相关的铂族金属催化剂组分对于HC转化来说更具活性时,通过在工作循环的冷启动后或者冷阶段过程中储存烃,并且在较高的温度释放所储存的烃,来改进工作循环上的烃转化。参见例如申请人/受让人的EP0830201。分子筛典型地用于轻型柴油车辆所用的根据本发明的催化剂组合物中,而它们很少用于重型柴油机所用的催化剂组合物中,因为重型柴油机中的废气温度意味着通常不需要烃捕集功能。
但是,分子筛例如硅铝酸盐沸石对于铂族金属来说不是特别好的载体,因为它们主要是二氧化硅,特别是相对高二氧化硅:氧化铝比的分子筛,其受益于其增加的热耐久性:它们会在老化过程中热降解,以使得该分子筛的结构可能坍塌和/或该PGM可能烧结,产生较低的分散性和因此较低的HC和/或CO转化活性。
当第一活化涂层和/或第二活化涂层均包含分子筛时,则优选第一活化涂层和/或第二活化涂层包含各自活化涂层的≤30重量%(例如≤25重量%、≤20重量%,例如≤15重量%)。第一活化涂层或第二活化涂层的剩下的至少一种载体材料可以包括选自由以下构成的组的金属氧化物:任选稳定化的氧化铝、无定形二氧化硅-氧化铝、任选稳定化的氧化锆、二氧化铈、二氧化钛和任选稳定化的二氧化铈-氧化锆混合氧化物及其任意两种或更多种的混合物。
用作载体材料/烃吸附剂的优选分子筛是中孔沸石,优选硅铝酸盐沸石,即具有八个四面体原子的最大环尺寸的那些,和大孔沸石(最多十个四面体原子),优选硅铝酸盐沸石,包括天然或者合成沸石例如八面沸石、斜发沸石、丝光沸石、硅质岩、镁碱沸石、X沸石、Y沸石、超稳定Y沸石、ZSM-5沸石、ZSM-12沸石、SSZ-3沸石、SAPO-5沸石、硅铝钾沸石或β沸石,优选ZSM-5、β和Y沸石。优选的沸石吸附剂材料具有高的二氧化硅与氧化铝比率,用于改进水热稳定性。该沸石的二氧化硅/氧化铝摩尔比可以是至少约25/1,优选至少约50/1,有用的范围为约25/1-1000/1、50/1-500/1以及约25/1-100/1、25/1-300/1、约100/1-250/1。
用于本发明的基底整料可以是陶瓷的,例如堇青石、钛酸铝、碳化硅等;或者金属的,例如由铁素体铁-铬-铝合金的薄金属箔制成。
第一基底整料可以是流通式基底整料或过滤基底整料。第二活化涂层通常经取向以接触已经接触过第一活化涂层的废气。这使得第一活化涂层首先与废气接触。来自第一活化涂层的废气和任何挥发的PGM然后与包含用于捕集挥发的PGM的铜的第二活化涂层接触。
当第一基底整料是流通式基底整料时,则典型地第一活化涂层区或第一活化涂层位于该基底整料的入口端,第二活化涂层区或第二活化涂层位于该基底整料的出口端。第一活化涂层和第二活化涂层可以重叠(例如在基底整料的中间部分)。当第一活化涂层和第二活化涂层重叠时(例如一个活化涂层在另一个之上),则优选第二活化涂层位于第一活化涂层之上(例如在重叠区域中),第一活化涂层位于基底整料上(即第一活化涂层接触基底整料的表面)。优选第一活化涂层和第二活化涂层或者第一活化涂层区和第二活化涂层区之间基本上不重叠。
典型地,过滤基底整料具有入口表面和出口表面,其中该入口表面通过多孔结构与出口表面隔开,且其中第一区的第一活化涂层施涂到该入口表面,第二区的第二活化涂层施涂到该出口表面。当第一基底整料是过滤基底整料时,则优选该过滤基底整料是壁流式过滤器,例如本文上面在背景部分中描述的,其中该壁流式过滤器的入口通道包括第一区,且其中该壁流式过滤器的出口通道包括第二区。
制备包括单层活化涂层和双层布置(一个活化涂层在另一活化涂层之上)的催化基底整料的方法是本领域已知的,包括申请人/受让人的WO99/47260,即包括以下步骤:(a)将容纳装置置于基底整料第一端上,(b)将预定量的第一活化涂层组分计量加入所述容纳装置中,以先(a)后(b)或者先(b)后(a)的顺序,和(c)通过施加压力或真空,将所述第一活化涂层组分抽取到基底整料的至少一部分中,和将所述量的基本上全部保持在该基底整料中。在第一步中,可以将从第一端施涂的涂层干燥,并且经干燥的基底整料可以翻转180度,可以对该基底整料的顶部第二端进行相同的工序,并且在从基底整料的第一和第二端的施涂之间的层中基本上没有重叠。然后将所得到的涂覆产品干燥,再煅烧。用第二活化涂层组分重复该方法,以提供根据本发明的催化(双层)基底整料。
用于本发明的过滤基底整料优选是壁流式过滤器,即包括与多个出口通道平行排列的多个入口通道的陶瓷多孔过滤基底,其中各入口通道和各出口通道部分地由多孔结构的陶瓷壁限定,其中各入口通道与出口通道通过多孔结构的陶瓷壁交替隔开,反之亦然。换言之,壁流式过滤器是蜂窝状布置,限定了多个在上游端堵塞的第一通道和多个在上游端未堵塞但在下游端堵塞的第二通道。与第一通道垂直和横向相邻的通道在下游端堵塞。当从任一端观察时,通道的交替地堵塞和开口的端部呈现棋盘的外观。
催化过滤器(优选壁流式过滤器)可以使用申请人/受让人的WO2011/080525中公开的方法涂覆。即,用包含催化剂组分的液体涂覆包括多个通道的蜂窝整料基底的方法,该方法包括以下步骤:(i)将蜂窝状整料基底基本上保持竖直;(ii)将预定体积的液体经由基底下端的通道的开口端引入该基底中;(iii)将引入的液体密封保持在该基底内;(iv)将包含所保持的液体的基底倒置;和(v)在该基底的倒置的下端对基底的通道的开口端施加真空,以沿该基底的通道抽取该液体。催化剂组合物可以从第一端涂覆到过滤器通道上,然后可以干燥经涂覆的过滤器。
第二基底整料可以是流通式基底整料或具有入口表面和出口表面的过滤基底整料,其中该入口表面通过多孔结构与该出口表面隔开,优选是壁流式过滤器。
位于第一活化涂层区中的第一活化涂层可以包括如本文上面在发明背景中描述的氧化催化剂或NOx吸附剂催化剂(即氧化或NAC组合物)。与氧化催化剂相比,NAC或NAC组合物包含显著量的碱土金属和/或碱金属。NAC或NAC组合物典型地还包含二氧化铈或者含二氧化铈的混合氧化物,例如铈和锆的混合氧化物,该混合氧化物任选地进一步包含一种或多种另外的镧系或稀土元素。在第一基底整料是过滤基底整料且第一活化涂层是氧化催化剂的情况下,该装置通常在本领域中称作“催化烟灰过滤器”或“CSF”。
第二催化基底整料包含用于将氮的氧化物用含氮还原剂选择性催化还原为二氮的催化剂(也称作选择性催化还原(SCR)催化剂)。
典型地,SCR催化剂作为涂层涂覆在基底整料上,例如本文上面所述。
替代地,SCR催化剂作为挤出物(也称作“催化剂体”)提供,即将催化剂与基底整料结构的组分混合,将二者挤出,以使得该催化剂是基底整料壁的一部分。
第二基底整料的SCR催化剂可以包含过滤基底整料或者流通式基底整料。还可以由挤出SCR催化剂来制备壁流式过滤器(参见申请人/受让人的WO2009/093071和WO2011/092521)。用于与第二催化基底整料结合使用的选择性催化还原(SCR)催化剂可以选自由以下中的至少一种构成的组:Cu、Hf、La、Au、In、V、镧系元素和第VIII族过渡金属例如Fe,其负载在难熔氧化物或者分子筛上。合适的难熔氧化物包括Al2O3、TiO2、CeO2、SiO2、ZrO2和包含其两种或更多种的混合氧化物。非沸石催化剂还可以包括氧化钨例如V2O5/WO3/TiO2。特别关注的优选金属选自由Ce、Fe和Cu构成的组。可以用上述金属对分子筛进行离子交换。
优选至少一种分子筛是硅铝酸盐沸石或SAPO。该至少一种分子筛可以是例如小孔、中孔或大孔分子筛。
本文中的“小孔分子筛”表示含有8个四面体原子的最大环尺寸的分子筛,例如CHA;本文中的“中孔分子筛”表示含有10个四面体原子的最大环尺寸的分子筛,例如ZSM-5;本文中的“大孔分子筛”表示具有12个四面体原子的最大环尺寸的分子筛,例如β。小孔分子筛对于在SCR催化剂中使用是潜在有利的,参见例如WO2008/132452。用于根据本发明的SCR催化剂中的分子筛包括掺入分子筛骨架中的一种或多种金属,例如Fe在“骨架内”的β沸石和Cu在“骨架内”的CHA。
特别可用于本发明的分子筛选自由以下构成的组:AEI、ZSM-5、ZSM-20、ERI(包括ZSM-34)、丝光沸石、镁碱沸石、BEA(包括β)、Y、CHA、LEV(包括Nu-3)、MCM-22和EU-1,目前优选CHA分子筛例如硅铝酸盐CHA,特别是与作为助剂的Cu例如通过离子交换相结合。
优选在第二催化基底整料的下游设置任选的催化过滤基底整料(即第三基底整料),即在本文上面就发明背景中所讨论的DOC/SCR/CSF布置中。该过滤基底整料优选是壁流式过滤器。在催化基底整料的情况下,用于与该过滤基底整料结合使用的催化剂是氧化催化剂,但在替代的实施方案中其可以是NAC组合物。替代地,该过滤基底整料可以是非催化的。
根据本发明的排气***示于图5中。排气***20包括从上游到下游的顺序布置的催化流通式基底整料12;氨源13,其包括用于氨前体尿素的喷射器;和涂覆有Fe/βSCR催化剂的流通式基底整料14。各基底整料12、14位于包括锥形扩散器的金属容器或“罐”中,并且它们通过一系列管道3相连,管道3的横截面积小于基底整料12、14任一个的横截面积。锥形扩散器用于散布进入“罐装”基底整料的外壳中的废气流,从而引导该废气整体越过各基底整料的基本上整个前“面”。将离开基底整料4的废气在“尾管”5排放到大气中。
催化流通式基底整料12包括:第一区16,其部分由其上游端限定,并涂覆有4:1Pt:Pd重量比的催化剂,其中Pt和Pd负载在载体材料上;和第二区18,其占该流通式基底整料总长度的约50%且与第一区16基本上不重叠,该第二区18包含负载在稳定化的颗粒状氧化铝载体材料上的铜化合物。该催化流通式基底整料经设计用于促进反应(1)并由此促进下游SCR催化剂上的反应(6)。
实施例
实施例1–制备涂覆有5重量%Fe/β沸石的基底整料
将商购的β沸石在搅拌下加入Fe(NO3)3水溶液中。混合后,加入粘合剂和流变改性剂以形成活化涂层组合物。
将400孔/平方英寸堇青石流通式基底整料用5重量%的Fe/β沸石样品的含水浆料,使用申请人/受让人的WO99/47260中公开的方法来涂覆,即包括以下步骤:(a)将容纳装置置于载体上,(b)将预定量的液体组分计量加入所述容纳装置中,以先(a)后(b)或者先(b)后(a)的顺序,和(c)通过施加压力或者真空,将所述液体组分抽取到载体的至少一部分中,和将所述量的基本上全部保持在载体中。将该涂覆产物(仅从一端涂覆)干燥和然后煅烧,从另一端重复该方法,以使得基本上整个基底整料被涂覆,并且在两个涂层之间的结合处在轴向上重叠很小。从最终制品上切下1英寸(2.54cm)直径×3英寸长的芯。
对比例2–制备仅Pt催化壁流式过滤器
制备活化涂层组合物,其包含研磨到相对高粒度分布的氧化铝颗粒、硝酸铂、粘合剂和流变改性剂在去离子水中的混合物。使用在申请人/受让人的WO2011/080525中公开的方法和设备,将钛酸铝壁流式过滤器用活化涂层负载量为0.2g/in3的催化剂组合物涂覆到最终总Pt负载量5g/ft-3,其中用包含硝酸铂和颗粒状氧化铝的活化涂层从其预定的上游端将预定取向为上游侧的第一端的通道涂覆它们总长度的75%;用与入口通道相同的活化涂层将相对端和预定取向为下游侧的通道涂覆它们总长度的25%。即该方法包括以下步骤:(i)将蜂窝状整料基底基本上保持竖直;(ii)将预定体积的液体经由基底下端的通道的开口端引入该基底中;(iii)将引入的液体密封保持在该基底内;(iv)将包含所保持的液体的基底倒置;和(v)在该基底的倒置的下端对基底的通道的开口端施加真空,以沿该基底的通道抽取该液体。催化剂组合物可以从第一端涂覆到过滤器通道上,然后可以干燥经涂覆的过滤器。然后调转从第一端涂覆的干燥过滤器,重复该方法以将相同的催化剂从第二端涂覆到过滤器通道,随后干燥和煅烧。
从最终制品上切下1英寸(2.54cm)直径×3英寸(7.62cm)长的芯。所得到的部分描述为“新鲜的”,即未老化的。
实施例3–制备含有Pt-入口/Cu-Al
2
O
3
-出口的催化壁流式过滤器
使用与对比例2相同的方法来制备经涂覆的过滤器,除了用含有硝酸钯和氧化铝的活化涂层涂覆预定取向为朝向气体接触的入口侧的通道的总通道长度的100%,然后干燥经涂覆的过滤器;和用含有氧化铝和硫酸铜的活化涂层涂覆预定取向为朝向出口侧的通道总长度的35%。然后干燥所得到的经涂覆的过滤器,然后煅烧。经涂覆的过滤器的入口通道上Pt总负载量为5gft-3。出口上的总铜负载量为66gft-3。
从最终制品上切下1英寸(2.54cm)直径×3英寸长的芯。所得到的部分描述为“新鲜的”,即未老化的。
实施例4–制备含有1:1重量%的Pt:Pd的催化壁流式过滤器
使用与对比例2相同的方法来制备经涂覆的过滤器,除了施涂到过滤器的入口通道和出口通道上的活化涂层除硝酸铂之外还包含硝酸钯。入口和出口通道中的活化涂层负载以这种方式进行,以达到在入口表面和出口表面上5g/ft3Pt、5g/ft3Pd负载量,即总PGM负载量为10g/ft3。
从最终制品上切下1英寸(2.54cm)直径×3英寸长的芯。所得到的部分描述为“新鲜的”,即未老化的。
实施例5–制备包含5:1重量%的Pt:Pd的催化壁流式过滤器
使用与对比例2相同的方法来制备经涂覆的过滤器,除了施涂到该过滤器的入口通道和出口通道的活化涂层除硝酸铂之外还包含硝酸钯。入口和出口通道中的活化涂层负载量以这种方式进行,以达到在入口表面和出口表面上5g/ft3Pt、1g/ft3Pd负载量,即总PGM负载量为6g/ft3。
从最终制品上切下1英寸(2.54cm)直径×3英寸长的芯。所得到的部分描述为“新鲜的”,即未老化的。
实施例6–***试验
在图1所示的第一合成催化剂活性试验(SCAT)实验室反应器中进行测试,其中将实施例1的经涂覆的Fe/β沸石SCR催化剂的新鲜的芯置于对比例2或者实施例3、4或5的催化壁流式过滤器的芯下游的管道中。将合成气混合物以催化剂活塞排量30,000h-1送过该管道。使用炉在过滤器入口温度900℃的稳态温度加热(或“老化”)催化壁流式过滤器样品60分钟,在此期间入口SCR催化剂温度为300℃。使用空气(热交换器)或者水冷机构进行过滤器和SCR催化剂之间的温度降低。在老化期间气体混合物为10%的O2、6%的H2O、6%的CO2、100ppm的CO、400ppm的NO、100ppm的作为C1的HC,余量为N2。
老化后,将经老化的SCR催化剂从第一SCAT反应器中移除,并且置入第二SCAT反应器中来专门测试经老化样品的NH3-SCR活性。然后使用合成气混合物(O2=14%;H2O=7%;CO2=5%;NH3=250ppm;NO=250ppm;NO2=0ppm;N2=余量)测定经老化的SCR催化剂在150、200、250、300、350、450、550和650℃的SCR活性,并且在图2中,对各温度数据点,将所得到的NOx转化率对温度作图。该图通过SCR反应(反应(5))所需的可用NH3的消耗,来基本上度量反应(9)和反应(5)之间的竞争,和因此度量反应(9)对于NOx转化率的影响程度。
结果示于图2中。从测试实施例3的结果可以看到,根据本发明的排气***中的SCR催化剂保持了比对比例2的SCR催化剂更高的活性,不过它们保持了比新鲜催化剂更低的SCR活性。本发明人将该结果解释为表明了SCR活性的损失部分是由来自上游催化壁流式过滤器的低水平的Pt沉积到下游SCR催化剂上引起的。在新鲜Fe/β催化剂和不存在任何上游催化剂在300℃老化1小时的Fe/β催化剂之间基本上没有观察到活性损失(结果未示出)。
实施例7–制备涂覆有3重量%的Cu/CHA沸石的基底整料
将商购的硅铝酸盐CHA沸石在搅拌下加入到Cu(NO3)2水溶液中。将该浆料过滤,然后清洗和干燥。可以重复该工序以实现所需的金属负载量。将最终产物煅烧。混合后,加入粘合剂和流变改性剂以形成活化涂层组合物。
将400cpsi堇青石流通式基底整料用3重量%的Cu/CHA沸石样品的含水浆料,使用上文实施例1所述的申请人/受让人的WO99/47260中公开的方法来涂覆。将经涂覆的基底整料在炉中在500℃空气中老化5小时。从最终制品上切下1英寸(2.54cm)直径×3英寸(7.62cm)长的芯。
实施例8–Pt:Pd重量比的进一步研究
如下来制备两种柴油机氧化催化剂:
柴油机氧化催化剂A
如下来制备单层DOC。将硝酸铂和硝酸钯加入二氧化硅-氧化铝浆料中。将β沸石加入该浆料中,以使得它包含<30质量%的作为沸石的固体含量。将该活化涂层浆料使用上文实施例1的方法计量加入到400cpsi流通式基底上。将计量加入的部分干燥,然后在500℃煅烧。该活化涂层中的总铂族金属负载量是60gft-3和总Pt:Pd重量比是4:1。从最终制品上切下1英寸(2.54cm)直径×3英寸(7.62cm)长的芯。所得到的部分可以描述为“新鲜的”,即未老化的。
柴油机氧化催化剂B
如下来制备单层DOC。将硝酸铂和硝酸钯加入二氧化硅-氧化铝浆料中。将β沸石加入该浆料中,以使得它包含<30质量%的作为沸石的固体含量。将该活化涂层浆料使用与用于DOC A相同的方法计量加入到400cpsi流通式基底上。将计量加入的部分干燥,然后在500℃煅烧。该单层DOC中的总PGM负载量是120g/ft3和Pt:Pd重量比是2:1。从最终制品上切下1英寸(2.54cm)直径×3英寸(7.62cm)长的芯。所得到的部分可以描述为“新鲜的”,即未老化的。
根据实施例9所述的方案来测试两种催化剂。结果示于图3中,并且参考对照样(经老化的SCR催化剂,其没有在DOC A或DOC B任一的下游进一步老化)。
实施例9–***试验
在图1所示的第一合成催化剂活性试验(SCAT)实验室反应器上进行测试,其中将实施例7的经涂覆的Cu/CHA沸石SCR催化剂的经老化的芯置于柴油机氧化催化剂(DOC)A或B(根据实施例8)任一的芯下游的管道中。将合成气混合物以6升/分钟的速率送过该管道。使用炉在催化剂出口温度900℃的稳态温度加热(或“老化”)DOC样品2小时。SCR催化剂位于DOC样品的下游,并且在老化过程中通过调整炉出口和SCR入口之间的管长来将催化剂温度保持在300℃,不过根据需要也可以使用水冷热交换器夹套。使用适合定位的热电偶来测定温度(T1和T2)。老化期间所用的气体混合物是40%的空气、50%的N2、10%的H2O。
DOC老化后,将SCR催化剂从第一SCAT反应器中移除,并且置入第二SCAT反应器中来专门测试经老化样品的NH3-SCR活性。然后使用合成气混合物(O2=10%;H2O=5%;CO2=7.5%;CO=330ppm;NH3=400ppm;NO=500ppm;NO2=0ppm;N2=余量,即使用0.8的α值(NH3:NOx之比),以使得最大可能的可用NOx转化率为80%)测试SCR催化剂在500℃的SCR活性,并且在图4中并列的条形图上将所得到的NOx转化率对温度作图。该图通过SCR反应(反应(5))所需的可用NH3的消耗,来基本上度量反应(9)和反应(5)之间的竞争,和因此度量反应(9)对于NOx转化率的影响程度。
Pt:Pd重量比研究-结论
总体而言,图3所示的实施例6关于实施例4和5和对比例2的结果表明,1:1至5:1的Pt:Pd重量比有益于减少由铂族金属(主要是铂)从含铂族金属的催化剂挥发到下游SCR催化剂而导致的NOx转化活性损失问题。
图4所示的实施例9关于柴油机氧化催化剂A和B的结果显示对于在具有总体2:1的Pt:Pd重量比的DOC下游老化的SCR催化剂,NOx转化活性损失以67%的NOx转化活性与对照的72%的NOx转化活性相比,相对轻微(在使用相同方案在1:1的Pt:Pd总体重量比的DOC(本文未描述)后面老化的SCR催化剂的NOx转化活性是69%)。但是,当总体Pt:Pd重量比增加到4:1时,SCR活性显著降低到48%。
本发明人因此得出结论,在约2:1的Pt:Pd总体重量比处存在着分界线,高于此时更可能发生Pt挥发。因此,通过整体上将DOC中的Pt:Pd总体重量比限制为2:1,和在第二活化涂层中限制为≤2:1的Pt:Pd重量比,DOC中的Pt不太可能挥发和迁移到下游SCR催化剂。
为避免任何疑义,本文引用的任何和全部文献的整体内容引入本申请作为参考。
Claims (19)
1.用于内燃机的排气***,该***包括:
a)第一催化基底整料,其包含位于该基底整料的第一活化涂层区中的第一活化涂层和位于该基底整料的第二活化涂层区中的第二活化涂层,其中第一活化涂层包含催化剂组合物,该催化剂组合物包含至少一种铂族金属(PGM)和至少一种载体材料,其中当第一活化涂层暴露于包括相对高温的相对极端条件时,第一活化涂层中的至少一种PGM易于挥发,其中第二活化涂层包含用于捕集挥发的PGM的至少一种负载铜的材料,并且其中第二活化涂层经取向以接触已经接触过第一活化涂层的废气;和
b)位于第一催化基底整料下游的第二催化基底整料,其包含用于将氮的氧化物用含氮还原剂选择性催化还原为二氮的催化剂。
2.根据权利要求1所述的排气***,其包括喷射器,其用于将含氮还原剂注入到第一催化基底整料和第二催化基底整料之间的废气中。
3.根据权利要求1或2所述的排气***,其中第一活化涂层中的该至少一种PGM包括铂。
4.根据权利要求1、2或3所述的排气***,其中第一活化涂层中的该至少一种PGM包括铂和钯。
5.根据权利要求4所述的排气***,其中Pt:Pd的重量比≤2。
6.根据前述权利要求中任一项所述的排气***,其中该载体材料是至少一种金属氧化物、分子筛或其任意两种或更多种的混合物。
7.根据权利要求6所述的排气***,其中该或各金属氧化物载体选自由以下构成的组:任选稳定化的氧化铝、无定形二氧化硅-氧化铝、任选稳定化的氧化锆、二氧化铈、二氧化钛、任选稳定化的二氧化铈-氧化锆混合氧化物及其任意两种或更多种的混合物。
8.根据权利要求6所述的排气***,其中该分子筛是硅铝酸盐沸石。
9.根据前述权利要求中任一项所述的排气***,其中第一基底整料是流通式基底整料。
10.根据权利要求1-8中任一项所述的排气***,其中第一基底整料是具有入口表面和出口表面的过滤基底整料,其中该入口表面通过多孔结构与该出口表面隔开,且其中第一区的第一活化涂层施涂到该入口表面,第二区的第二活化涂层施涂到该出口表面。
11.根据权利要求10所述的排气***,其中该过滤基底整料是壁流式过滤器,其中该壁流式过滤器的入口通道包括第一区,和其中该壁流式过滤器的出口通道包括第二区。
12.根据前述权利要求中任一项所述的排气***,其中第二基底整料是流通式基底整料。
13.根据权利要求1-11中任一项所述的排气***,其中第二基底整料是具有入口表面和出口表面的过滤基底整料,其中该入口表面通过多孔结构与该出口表面隔开。
14.根据权利要求13所述的排气***,其中该过滤基底整料是壁流式过滤器。
15.根据前述权利要求中任一项所述的排气***,其中第一活化涂层包含氧化催化剂或NOx吸附剂催化剂。
16.根据前述权利要求中任一项所述的排气***,其包括第三基底整料,其中第三基底整料是过滤基底整料,该第三基底整料位于第二催化基底整料的下游。
17.根据权利要求16所述的排气***,其中第三基底整料包含氧化催化剂。
18.一种内燃机,特别地用于车辆,其包括前述权利要求中任一项的排气***。
19.一种减少或防止贫燃内燃机的排气***中的选择性催化还原(SCR)催化剂被铂族金属(PGM)中毒的方法,当包含PGM的催化剂组合物暴露于包括相对高温的相对极端条件时,该铂族金属(PGM)会从催化剂组合物挥发,该催化剂组合物包含负载在至少一种负载材料上且位于SCR催化剂上游的基底整料上的至少一种PGM,该方法包括使挥发的PGM捕集在包含至少一种负载铜的材料的活化涂层中,该活化涂层位于与包含PGM的催化剂组合物相同的基底整料上。
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GBGB1200784.5A GB201200784D0 (en) | 2011-12-12 | 2012-01-18 | Exhaust system for a lean-burn internal combustion engine including SCR catalyst |
GB1200784.5 | 2012-01-18 | ||
CN201280061157.4A CN103987444B (zh) | 2011-12-12 | 2012-12-11 | 用于包括scr催化剂的贫燃内燃机的排气*** |
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- 2012-12-11 BR BR112014013243A patent/BR112014013243A2/pt not_active Application Discontinuation
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- 2012-12-11 GB GB201402403A patent/GB2507441B/en not_active Expired - Fee Related
- 2012-12-11 DE DE102012222807A patent/DE102012222807A1/de not_active Withdrawn
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- 2012-12-11 CN CN201610788858.8A patent/CN106401708A/zh active Pending
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- 2012-12-11 JP JP2014545363A patent/JP6182537B2/ja not_active Expired - Fee Related
- 2012-12-11 CN CN201280061157.4A patent/CN103987444B/zh not_active Expired - Fee Related
- 2012-12-11 US US13/711,138 patent/US9259684B2/en not_active Expired - Fee Related
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2015
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GB2507441B (en) | 2015-05-20 |
CN103987444B (zh) | 2016-09-14 |
BR112014013243A8 (pt) | 2017-06-13 |
JP2017214930A (ja) | 2017-12-07 |
WO2013088128A1 (en) | 2013-06-20 |
BR112014013243A2 (pt) | 2017-06-13 |
JP2015507115A (ja) | 2015-03-05 |
GB201222227D0 (en) | 2013-01-23 |
GB2497655B (en) | 2015-04-22 |
KR20140110935A (ko) | 2014-09-17 |
GB2497655A (en) | 2013-06-19 |
GB201200784D0 (en) | 2012-02-29 |
RU2014128633A (ru) | 2016-02-10 |
JP6182537B2 (ja) | 2017-08-16 |
GB2507441A (en) | 2014-04-30 |
CN103987444A (zh) | 2014-08-13 |
EP2790813B1 (en) | 2018-05-16 |
DE102012222807A1 (de) | 2013-06-27 |
US20170173530A1 (en) | 2017-06-22 |
EP2790813A1 (en) | 2014-10-22 |
US20130149223A1 (en) | 2013-06-13 |
GB201402403D0 (en) | 2014-03-26 |
RU2620421C2 (ru) | 2017-05-25 |
US9259684B2 (en) | 2016-02-16 |
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