CN110191751B - 用于净化柴油发动机废气的催化剂 - Google Patents

用于净化柴油发动机废气的催化剂 Download PDF

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CN110191751B
CN110191751B CN201880007467.5A CN201880007467A CN110191751B CN 110191751 B CN110191751 B CN 110191751B CN 201880007467 A CN201880007467 A CN 201880007467A CN 110191751 B CN110191751 B CN 110191751B
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catalyst
arrangement according
material zone
platinum
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CN110191751A (zh
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C·瑞斯
B·弗雷德里希
C·亨斯特
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Umicore Corp And Lianghe Co
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Umicore Corp And Lianghe Co
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Abstract

本发明涉及一种催化剂，所述催化剂包括具有长度L的载体主体，所述载体主体在第一端面“a”和第二端面“b”之间延伸，以及布置在所述载体主体上的不同组成的催化活性材料区A、B和C，其中–材料区A包含铂或者重量比Pt:Pd≥1的铂和钯，并且从端面“a”开始或从端面“b”开始，沿着所述长度L的70％至100％延伸，并且–材料区B包含钯或者铂和钯，并且从端面“b”开始，沿着所述长度L的一部分延伸，并且–材料区C包含SCR活性材料，并且从端面“a”开始，沿着所述长度L的一部分延伸，其中材料区C被布置在材料区A上方。

Description

用于净化柴油发动机废气的催化剂
本发明涉及用于净化柴油发动机废气的催化剂，所述催化剂具有若干材料区。
除一氧化碳CO、烃HC和氮氧化物NOx之外，柴油发动机的原始废气还包含高达15体积％的相对高的氧含量。还包含了主要由烟尘残余物和可能的有机附聚物组成的并从发动机的气缸中部分地不完全的燃料燃烧产生的颗粒排放物。
虽然具有和不具有催化活性涂层的柴油微粒过滤器适用于去除颗粒排放物，但是氮氧化物可在存在氧气的情况下在SCR催化剂上通过氨转化为氮气和水。
用作还原剂的氨可通过将氨前体化合物诸如例如脲、氨基甲酸铵或甲酸铵进料到废气流中并且随后热解和水解而变得可用。
SCR催化剂在文献中有广泛的描述。它们一般是所谓的混合氧化物催化剂(其具体地包含钒、钛和钨)，或所谓的沸石催化剂(其包含金属交换的—具体地为细孔的沸石)。SCR催化活性材料可承载在流通式基底或壁流式过滤器上。
一氧化碳和烃通过在合适的氧化催化剂上氧化而变得无害。氧化催化剂在文献中也有广泛的描述。这些氧化催化剂为例如流通式基底，其将贵金属(诸如铂和钯)作为原发性的催化活性组分承载在大面积、多孔、高熔点的氧化物(诸如氧化铝)上。
还已经描述了在废气的流动方向上具有不同组成的材料区的分区氧化催化剂，废气与这些分区氧化催化剂相继地接触。
例如，US2010/257843、US2011/099975和WO2012/079598 A1描述了包含铂和钯的分区氧化催化剂。WO2011/057649 A1也描述了氧化催化剂，其中这些氧化催化剂可用于分层和分区的实施方案中。在分区的实施方案的情况下，第二区—即与流出的废气直接接触的区比前区—与流入的废气直接接触的区具有更高的贵金属含量。根据WO2011/057649 A1的氧化催化剂具体地具有为位于下游的SCR催化剂设定NO和NO2的最佳比率的目的。
在大多数情况下，各种催化剂被组合在废气净化系统中，使得氧化催化剂被布置成靠近发动机，然后微粒过滤器和SCR催化剂紧随在废气的流动方向上，其中SCR催化剂也可以承载在微粒过滤器上的方式存在。
欧盟排放法规6和6+规定下的当前和未来的柴油发动机的废气温度由于节省燃料导致的CO2排放减少而变得越来越低。因此，已在若干场合提出，废气中包含的氮氧化物的至少一部分可借助于靠近发动机布置的SCR催化剂转化，然后该废气首先被引导通过氧化催化剂、微粒过滤器，并且在适用的情况下被引导通过另一SCR催化剂。
具体地讲，在该催化剂布置中，重要的是具有产生很少的氧化亚氮但是为随后的SCR催化剂提供足够的二氧化氮的可用柴油氧化催化剂。
现已发现，下文描述并限定的柴油氧化催化剂满足这些条件。
本发明涉及催化剂，该催化剂包括具有长度L的载体主体，该载体主体在第一端面“a”和第二端面“b”之间延伸，以及
布置在载体主体上的不同组成的催化活性材料区A、B和C，其中
–材料区A包含铂或者重量比Pt:Pd≥1的铂和钯，并且从端面“a”开始或从端面“b”开始，沿着长度L的70％至100％延伸，并且
–材料区B包含钯或者铂和钯，并且从端面“b”开始，沿着长度L的一部分延伸，并且
–材料区C包含SCR活性材料，并且从端面“a”开始，沿着长度L的一部分延伸，
其中材料区C被布置在材料区A上方。
在根据本发明的催化剂的实施方案中，在一种或多种载体氧化物上的材料区A和B中施加铂或者铂和钯。这些载体氧化物有利地为高熔点的，即其熔点足够高于在根据本发明的催化剂的规定的正常操作期间出现的温度。此外，这些载体氧化物具有有利的大表面积，并且优选地具有50m2/g至200m2/g的BET表面(根据DIN 66132确定)。
材料区A和B中的载体氧化物可以相同或不同。
合适的载体氧化物选自由以下项组成的组：氧化铝、掺杂的氧化铝、氧化硅、氧化钛、氧化铈、氧化锆以及它们中一种或多种的混合的氧化物。
掺杂的氧化铝为例如掺氧化硅的氧化铝、掺氧化锆的氧化铝和/或掺氧化钛的氧化铝。有利地使用了镧系稳定的氧化铝，其中使用的镧的量为1重量％至10重量％(优选为3重量％至6重量％)，分别相对于稳定的氧化铝的重量根据La2O3计算。
如果材料区A包含铂和钯，则重量比Pt:Pd≥1，即，具体地，为20:1至1:1。示例为20:1、12:1、10:1、7:1、6:1、4:1、3:1、2:1、1.5:1和1:1。
如果材料区B包含铂和钯，则优选地重量比Pt:Pd≤3，即，具体地，为3:1至1:12。示例为2:1、1:1、1:2和1:4。
在根据本发明的催化剂的实施方案中，材料区A包含铂和过渡金属氧化物，其中具体地，在各自相对于材料区A的重量而言的情况下，铂以0.05重量％至4.0重量％的量存在，并且过渡金属氧化物以0.5重量％至15重量％的量存在。
在一个优选的实施方案中，过渡金属氧化物为CuxO，其中0<x≤2。
如果过渡金属氧化物为CuxO，则具体地，在各自相对于材料区A的重量而言的情况下，其以0.5重量％至5重量％的量存在，并且铂以0.05重量％至2重量％的量存在。
在根据本发明的催化剂的实施方案中，材料区B包含碱土金属。作为碱土金属，镁、钙、锶、钡，或这些金属中的至少两种的混合物可被使用。优选地使用锶或钡或者锶和钡。
一种或多种碱土金属通常以其氧化物、氢氧化物或碳酸盐的形式存在。这些碱土金属优选地以其氧化物的形式存在。
碱土金属以相对于材料区B的重量而言根据MeO计算的0.5重量％至5重量％的量有利地使用，其中Me表示碱土金属。
如果使用锶，则其特别优选地以相对于材料区B的重量而言的1重量％至3重量％的量存在。
然而，如果使用钡，则其特别优选地以相对于材料区A的重量而言的2.5重量％至4.5重量％的量存在。
在根据本发明的催化剂的实施方案中，材料区A和B彼此独立地以相对于载体主体的体积而言的25g/L至150g/L的量存在。
材料区C包含SCR活性材料，即SCR催化剂。
原则上可使用氮氧化物和氨的SCR反应中的所有活性催化剂(特别是诸如汽车废气催化领域的技术人员通常已知的催化剂)作为SCR催化剂。这包括混合的氧化物类型的催化剂，以及基于沸石(特别是基于过渡金属交换的沸石)的催化剂。
在本发明的实施方案中，使用SCR催化剂，该SCR催化剂包含最大环大小为八个四面体原子并且具有过渡金属的小孔沸石。这样的SCR催化剂在例如EP 2 117 707 A1和WO2008/132452 A2中有所描述。
此外，然而也可能使用大孔沸石和中孔沸石，其中尤其考虑具有BEA结构类型的那些。因此，铁BEA是特别值得关注的。
属于BEA、AEI、CHA、KFI、ERI、LEV、MER或DDR结构类型的沸石是特别优选的，并且其特别优选地与钴、铁、铜或这些金属中的两种或三种的混合物交换。
在本发明的上下文中，术语“沸石”也包括分子筛，其有时也被称为“类沸石”化合物。属于上述结构类型之一的分子筛是优选的。示例包括由术语SAPO所知的硅铝磷酸盐沸石和由术语AIPO所知的磷酸铝沸石。
当这些沸石与钴、铁、铜或这些金属中的两种或三种的混合物交换时，这些沸石也是特别优选的。
优选的沸石或分子筛也是具有2至100(特别是5至50)的SAR(硅比铝)值的那些。
这些沸石或分子筛包含根据金属氧化物(即，例如根据Fe2O3或CuO)计算为1重量％至10重量％(特别是2重量％至5重量％)的量的过渡金属。
本发明的优选实施方案包含作为SCR催化剂与铜、铁或者铜和铁交换的β型(BEA)、菱型(CHA)或插晶菱型(LEV)的沸石或分子筛。合适的沸石或分子筛为例如以名称ZSM-5、Beta、SSZ-13、SSZ-62、Nu-3、ZK-20、LZ-132、SAPO-34、SAPO-35、AlPO-34和AlPO-35所知的；还可参见例如US 6,709,644和US 8,617,474。
根据本发明，材料区A从载体主体的端面“a”开始或从载体主体的端面“b”开始沿其长度L的70％至100％延伸。在根据本发明的催化剂的实施方案中，材料区A沿载体主体的长度L的80％至100％(特别地为100％)延伸。
在一个实施方案中，材料区A从载体主体的端面“a”开始，在另一个实施方案中，从载体主体的端面“b”开始。
在根据本发明的催化剂的其他实施方案中，材料区B沿载体主体的长度L的50％至70％延伸。
在根据本发明的催化剂的其他实施方案中，材料区C沿载体主体的长度L的30％至50％延伸。
在优选的实施方案中，材料区A延伸超过载体主体的长度L的100％，并且直接定位在该载体主体上。在这种情况下，材料区B和C定位在材料区A上，其中材料区B和C的长度之和对应于载体主体的长度L。因此，以下内容适用：L＝LB+LC，其中LB是材料区B的长度，并且LC是材料区C的长度。
根据本发明的催化剂可通过以本身已知的方式使用涂层混悬剂或所谓的封闭底漆涂覆合适的载体主体来制备。为了制备用于制备材料区A或B的涂层混悬剂，将所选择的载体氧化物例如混悬在水中。然后在搅拌时按照所需量将铂和/或钯以合适的水溶性前体化合物(诸如例如硝酸钯或六羟基铂酸)的形式添加到混悬液中，并且在适当的情况下，通过设定pH值和/或通过添加辅助试剂将其附连到载体材料。
另选地，也可类似于EP 1 101 528 A2中所述的方法，将贵金属施加到载体材料。
类似于涂层混悬剂的制备，将合适的SCR催化剂(可能添加有粘结剂)混悬在水中，以便制备材料区C。
然后将以这种方式获得的混悬剂根据传统的涂覆方法中的一种进行研磨并施加到载体主体。在每个涂覆步骤后，将经涂覆的部分在热空气流中干燥并在适当的情况下煅烧。
前述前体化合物、辅助试剂和粘结剂是本领域的技术人员已知的。
具体地讲，由陶瓷(特别是堇青石)或由金属制成的所谓蜂窝主体被考虑作为载体主体。优选地使用所谓的流通式蜂窝主体。然而，也可设想其中将壁流式过滤器用作载体主体的其他实施方案。
根据本发明的催化剂适用于净化柴油发动机的废气。这些催化剂尤其能够将一氧化碳和烃氧化成二氧化碳和水。此外，这些催化剂可在SCR反应中通过氮氧化物将氨氧化，并且在适当的情况下，暂时存储氨。同时，在下流侧上的区能够将一氧化氮氧化成二氧化氮。
这些催化剂优选地集成到废气净化系统中，使得已经过靠近发动机布置的SCR催化剂的废气在端面“a”处进入催化剂并在端面“b”处再次从催化剂排出。
因此，本发明还涉及催化剂布置，其相继地包括：用于进料氨或氨前体的第一装置、第一SCR催化剂，和根据本发明的催化剂，其中根据本发明的催化剂被布置成使得其端面“a”指向第一SCR催化剂的方向。
用于进料氨或氨前体的装置具体为用于进料脲的水溶液的装置。此类装置是本领域的技术人员已知的，并且可在市场上获得。
涂覆有SCR活性材料的流通式基底尤其被考虑作为第一SCR催化剂。除上述材料区C的所有SCR催化剂之外，混合的氧化物催化剂(特别是VWT催化剂)也尤其被考虑作为SCR活性材料。VWT催化剂是基于V2O5、WO3、和TiO2的催化剂。
第一SCR催化剂优选地包括VWT催化剂，或与铜、铁或者铜和铁交换的β型(BEA)、菱型(CHA)或插晶菱型(LEV)的沸石或分子筛。
在一个实施方案中，根据本发明的催化剂布置包括被布置成使得其指向根据本发明的催化剂的端面“b”的方向的柴油微粒过滤器。该柴油微粒过滤器具体为壁流式过滤器。
与流通式基底相比，流通式基底中的通道在其两端打开并且在其两端之间平行延伸，而壁流式过滤器中的通道在第一端上或在第二端上交替地以气密的方式闭合。因此，当进入一端上的通道的气体通过通道壁进入在另一端上打开的通道时，该气体仅可再次从该壁流式过滤器排出。通道壁通常是多孔的，并且在未涂覆涂层的状态下具有例如30％至80％(具体地为50％至75％)的孔隙率。这些通道壁在未涂覆涂层的状态下的平均孔径为例如5微米至30微米。
一般来讲，壁流式过滤器的孔为所谓的开口孔，即它们与通道相连。此外，这些孔通常彼此连接。一方面，这允许容易地涂覆内孔表面，并且另一方面，允许废气容易地通过壁流式过滤器的多孔壁。
柴油微粒过滤器可以是未涂覆涂层的。然而，该柴油微粒过滤器优选地包括降低烟尘燃点并且因此有利于过滤后的烟尘颗粒的烧尽的催化活性涂层。此类涂层包括例如承载在氧化铝上的铂族金属，诸如，具体地为铂和/或钯。也可设想涂覆有SCR催化剂的微粒过滤器。在这种情况下，在柴油微粒过滤器的上游设置用于进料脲的水溶液的装置。
在另一个实施方案中，根据本发明的催化剂布置包括第二SCR催化剂，其紧随柴油微粒过滤器。
涂覆有SCR催化活性材料的流通式基底也可用作第二SCR催化剂。上述材料区C的所有SCR催化剂尤其被考虑作为SCR催化活性材料。
SCR催化剂优选地包括VWT催化剂，或与铜、铁或者铜和铁交换的β型(BEA)、菱型(CHA)或插晶菱型(LEV)的沸石或分子筛。
用于进料氨或氨前体的装置(具体地，用于进料脲的水溶液的装置)也必须定位在第二SCR催化剂的上游。
因此，根据本发明的催化剂布置的一个实施方案相继地包括：用于进料氨或氨前体的第一装置、第一SCR催化剂、根据本发明的催化剂、柴油微粒过滤器、用于进料氨或氨前体的第二装置、以及第二SCR催化剂。
根据本发明的催化剂布置的另一个实施方案相继地包括：用于进料氨或氨前体的第一装置、第一SCR催化剂、根据本发明的催化剂、用于进料氨或氨前体的第二装置、涂覆有SCR催化剂的柴油微粒过滤器、以及第二SCR催化剂。
为了提高第二SCR催化剂中的氮氧化物的转化率，可能必须以比所需量高大约10％至20％的量(即以化学计量的量)进料氨。然而，这增加了更高的二次排放的风险，具体地是由于氨滑移增加。由于氨在低浓度下已经具有刺激性气味并且在多功能车辆领域具有法律限制，因此必须将氨滑移降至最低。为此，所谓的氨滑移催化剂是已知的，其沿废气的流动方向布置在SCR催化剂的下游，以便氧化逸出的氨。各种实施方案中的氨滑移催化剂例如在US 5,120,695、EP 1 399 246 A1和EP 0 559 021 A2中有所描述。
在另一个实施方案中，根据本发明的催化剂布置因此包括氨滑移催化剂，其紧随第二SCR催化剂。
例如，氨滑移催化剂包括SCR活性材料和一种或多种铂族金属，具体地为铂或者铂和钯。上述材料区C的所有SCR催化剂尤其被考虑作为SCR催化活性材料。
因此，根据本发明的催化剂布置的一个实施方案相继地包括：用于进料氨或氨前体的第一装置、第一SCR催化剂、根据本发明的催化剂、柴油微粒过滤器、用于进料氨或氨前体的第二装置、第二SCR催化剂、以及氨滑移催化剂。
根据本发明的催化剂布置的另一个实施方案相继地包括：用于进料氨或氨前体的第一装置、第一SCR催化剂、根据本发明的催化剂、用于进料氨或氨前体的第二装置、涂覆有SCR催化剂的柴油微粒过滤器、第二SCR催化剂、以及氨滑移催化剂。
图1示意性地示出了根据本发明的催化剂布置的示例。从发动机(1)排出的废气首先被引导通过靠近发动机布置的第一SCR催化剂(3)。在第一SCR催化剂(3)的上游，在废气流中水解为氨的脲水溶液经由第一定量给料设备(2a)进料。然后，从第一SCR催化剂排出的废气流动通过根据本发明的催化剂(4)，通过微粒过滤器(5)，并且最后通过布置在更下游的第二SCR催化剂(6)。在第二SCR催化剂(6)的上游，在废气流中水解为氨的脲水溶液也经由第二定量给料设备(2a)进料。最后，废气在被释放到大气环境中之前被引导通过氨滑移催化剂(7)。箭头代表废气的流动方向。
图2示意性地示出了根据本发明的催化剂布置的另一个示例。从发动机(1)排出的废气首先被引导通过靠近发动机布置的第一SCR催化剂(3)。在第一SCR催化剂(3)的上游，在废气流中水解为氨的脲水溶液经由第一定量给料设备(2a)进料。然后，从第一SCR催化剂排出的废气流动通过根据本发明的催化剂(4)，通过涂覆有SCR催化剂的微粒过滤器(5a)，并且最后通过布置在更下游的第二SCR催化剂(6)。在这种情况下，在微粒过滤器(5a)的上游，在废气流中水解为氨的脲水溶液经由第二定量给料设备(2a)进料。最后，废气在被释放到大气环境中之前被引导通过氨滑移催化剂(7)。箭头代表废气的流动方向。
实施例1
a)从一端(对应于端面“a”)开始，将由堇青石制成的可商购获得的圆形流通式基底(其尺寸为10.5"×6.00"，单元密度为400cpsi，并且壁厚为4密尔)用包含75g/L的可商购获得的、0.67g/L的Pt和0.11g/L的Pd的封闭底漆涂覆遍及其长度的100％。重量比Pt:Pd为6:1。
b)从端面“b”开始，将根据a)获得的经涂覆的基底用包含50g/L的掺杂Si的氧化铝、0.15g/L的常规水溶性Pt化合物和0.30g/L的常规Pd化合物的封闭底漆涂覆遍及其整个长度的50％。重量比Pt:Pd为1:2。
c)从端面“a”开始，将根据b)获得的经涂覆的基底用包含200g/L的与铜交换的沸石的封闭底漆涂覆遍及其整个长度的50％。
实施例2
a)从一端(对应于端面“a”)开始，将由堇青石制成的可商购获得的圆形流通式基底(其尺寸为10.5"×6.00"，单元密度为400cpsi，并且壁厚为4密尔)用包含50g/L的可商购获得的氧化铝、0.39g/L的Pt和0.10g/L的Pd的封闭底漆涂覆遍及其长度的100％。重量比Pt:Pd为4:1。
b)从端面“b”开始，将根据a)获得的经涂覆的基底用包含70g/L的掺杂Si的氧化铝、0.37g/L的常规水溶性Pt化合物和0.37g/L的常规水溶性Pd化合物的封闭底漆涂覆遍及其整个长度的50％。重量比Pt:Pd为1:1。
c)从端面“a”开始，将根据b)获得的经涂覆的基底用包含160g/L的与铁交换的沸石的封闭底漆涂覆遍及其整个长度的50％。

Claims (19)

1.一种催化剂布置，所述催化剂布置相继地包括：用于进料氨或氨前体的第一装置、第一SCR催化剂和催化剂，所述催化剂包括具有长度L的载体主体，所述载体主体在第一端面“a”和第二端面“b”之间延伸，以及
布置在所述载体主体上的不同组成的催化活性材料区A、B和C，其中
–材料区A包含铂或者重量比Pt:Pd≥1的铂和钯，并且从端面“a”开始或从端面“b”开始，沿着所述长度L的70％至100％延伸，并且
–材料区B包含钯或者铂和钯，并且从端面“b”开始，沿着所述长度L的一部分延伸，并且
–材料区C包含SCR活性材料，并且从端面“a”开始，沿着所述长度L的一部分延伸，
其中材料区C被布置在材料区A上方，其中所述催化剂被布置成使得其端面“a”指向所述第一SCR催化剂的方向。
2.根据权利要求1所述的催化剂布置，其特征在于材料区A包含铂或者重量比为20:1至1:1的铂和钯。
3.根据权利要求1或2所述的催化剂布置，其特征在于材料区B包含钯或者重量比为3:1至1:12的铂和钯。
4.根据权利要求1或2所述的催化剂布置，其特征在于材料区A包含铂和过渡金属氧化物。
5.根据权利要求4所述的催化剂布置，其特征在于在各自相对于材料区A的重量而言的情况下，铂以0.05重量％至4.0重量％的量存在，并且所述过渡金属氧化物以0.5重量％至15重量％的量存在。
6.根据权利要求4所述的催化剂布置，其特征在于所述过渡金属氧化物为CuxO，其中0<x≤2。
7.根据权利要求6所述的催化剂布置，其特征在于在各自相对于材料区A的重量而言的情况下，CuxO以0.5重量％至5重量％的量存在，并且铂以0.05重量％至2.0重量％的量存在。
8.根据权利要求1或2所述的催化剂布置，其特征在于材料区B包含碱土金属。
9.根据权利要求8所述的催化剂布置，其特征在于材料区B中的所述碱土金属为锶或钡或者锶和钡。
10.根据权利要求1或2所述的催化剂布置，其特征在于材料区C包含作为SCR活性材料的最大环大小为八个四面体原子并且包含过渡金属的小孔沸石。
11.根据权利要求10所述的催化剂布置，其特征在于所述小孔沸石属于AEI、CHA、KFI、ERI、LEV、MER或DDR结构类型并且与钴、铁、铜或这些金属中的两种或三种的混合物交换。
12.根据权利要求1或2所述的催化剂布置，其特征在于材料区C包含作为SCR活性材料的具有结构类型BEA并且包含过渡金属的沸石。
13.根据权利要求1或2所述的催化剂布置，其特征在于材料区B沿着所述载体主体的所述长度L的30％至50％延伸。
14.根据权利要求1或2所述的催化剂布置，其特征在于材料区C沿着所述载体主体的所述长度L的50％至70％延伸。
15.根据权利要求1所述的催化剂布置，其特征在于其包括柴油微粒过滤器，所述柴油微粒过滤器被布置以便指向根据权利要求1所述的催化剂的端面“b”的方向。
16.根据权利要求15所述的催化剂布置，其特征在于其包括第二SCR催化剂，所述第二SCR催化剂紧随所述柴油微粒过滤器。
17.根据权利要求16所述的催化剂布置，其特征在于在所述第二SCR催化剂的上游的用于进料氨或氨前体的第二装置。
18.根据权利要求16或17所述的催化剂布置，其特征在于其包括氨滑移催化剂，所述氨滑移催化剂紧随所述第二SCR催化剂。
19.根据权利要求1所述的催化剂布置，其特征在于所述第一SCR催化剂是靠近发动机布置的。
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Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201616269D0 (en) * 2016-09-26 2016-11-09 Johnson Matthey Public Limited Company Oxidation catalyst for a diesel engine exhaust
US10898889B2 (en) 2018-01-23 2021-01-26 Umicore Ag & Co. Kg SCR catalyst and exhaust gas cleaning system
US11123720B2 (en) 2018-05-18 2021-09-21 Umicore Ag & Co. Kg Hydrocarbon trap catalyst
DE102019100099B4 (de) 2019-01-04 2022-09-08 Umicore Ag & Co. Kg Verfahren zur Herstellung von katalytisch aktiven Wandflussfiltern, katalytisch aktiver Wandflussfilter und dessen Verwendung
EP3815780A1 (en) * 2019-10-30 2021-05-05 Umicore Ag & Co. Kg Diesel oxidation catalyst
EP3889404A1 (en) * 2020-03-30 2021-10-06 Johnson Matthey Public Limited Company Multi-region twc catalysts for gasoline engine exhaust gas treatments with improved h2s attenuation
WO2023198570A1 (de) * 2022-04-11 2023-10-19 Umicore Ag & Co. Kg Abgassystem für überwiegend stöchiometrisch betriebene verbrennungsmotoren aufweisend einen katalysator zur verminderung der ammoniakemissionen
US20240066468A1 (en) * 2022-08-31 2024-02-29 Johnson Matthey Public Limited Company Exhaust gas treatment system

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001048466A2 (de) * 1999-12-24 2001-07-05 Robert Bosch Gmbh Sensorelement eines gassensors zur bestimmung von gaskomponenten
CN102355951A (zh) * 2009-01-16 2012-02-15 巴斯夫公司 层状柴油机氧化催化剂复合材料
CN104321506A (zh) * 2012-05-14 2015-01-28 恩亿凯嘉股份有限公司 废气净化装置
CN104588092A (zh) * 2009-11-30 2015-05-06 约翰逊马西有限公司 处理瞬时nox排放的催化剂
CN105555403A (zh) * 2013-07-30 2016-05-04 庄信万丰股份有限公司 氨逸出催化剂
GB2540484A (en) * 2013-05-17 2017-01-18 Johnson Matthey Plc Oxidation catalyst for a compression ignition engine

Family Cites Families (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5120695A (en) 1989-07-28 1992-06-09 Degusaa Aktiengesellschaft (Degussa Ag) Catalyst for purifying exhaust gases from internal combustion engines and gas turbines operated at above the stoichiometric ratio
DE4206699C2 (de) 1992-03-04 1996-02-01 Degussa NO¶x¶-Verminderung im mageren Abgas von Kraftfahrzeugmotoren
DE19955456A1 (de) 1999-11-17 2001-05-23 Degussa Verfahren zur Herstellung eines Stickoxid-Speichermaterials und damit hergestelltes Speichermaterial
EP1264628A1 (de) 2001-06-09 2002-12-11 OMG AG & Co. KG Redox-Katalysator für die selektive katalytische Reduktion der im Abgas von Dieselmotoren enthaltenen Stickoxide mittels Ammoniak sowie Verfahren zu seiner Herstellung
US6709644B2 (en) 2001-08-30 2004-03-23 Chevron U.S.A. Inc. Small crystallite zeolite CHA
EP1961933B1 (de) * 2007-02-23 2010-04-14 Umicore AG & Co. KG Katalytisch aktiviertes Dieselpartikelfilter mit Ammoniak-Sperrwirkung
ES2542510T5 (es) 2007-02-27 2019-01-16 Basf Corp Catalizadores de zeolita CHA de cobre
EP2517777A3 (en) 2007-04-26 2013-01-09 Johnson Matthey Public Limited Company Transition metal/cha-zeolite scr catalyst
US20090196812A1 (en) 2008-01-31 2009-08-06 Basf Catalysts Llc Catalysts, Systems and Methods Utilizing Non-Zeolitic Metal-Containing Molecular Sieves Having the CHA Crystal Structure
US8637426B2 (en) * 2009-04-08 2014-01-28 Basf Corporation Zoned catalysts for diesel applications
US8246923B2 (en) * 2009-05-18 2012-08-21 Umicore Ag & Co. Kg High Pd content diesel oxidation catalysts with improved hydrothermal durability
US8557203B2 (en) 2009-11-03 2013-10-15 Umicore Ag & Co. Kg Architectural diesel oxidation catalyst for enhanced NO2 generator
RU2559502C2 (ru) 2009-11-12 2015-08-10 Умикоре Аг Унд Ко. Кг Усовершенствованный каталитический нейтрализатор окислительного типа для снижения токсичности отработавших газов дизельного двигателя
US20110286900A1 (en) * 2010-05-21 2011-11-24 Basf Corporation PGM-Zoned Catalyst for Selective Oxidation of Ammonia in Diesel Systems
CN103269773B (zh) * 2010-12-14 2016-02-10 尤米科尔股份公司及两合公司 用于增强的no2发生器的构造式柴油氧化催化剂
GB2492175B (en) * 2011-06-21 2018-06-27 Johnson Matthey Plc Exhaust system for internal combustion engine comprising catalysed filter substrate
JP5938819B2 (ja) * 2011-10-06 2016-06-22 ジョンソン、マッセイ、パブリック、リミテッド、カンパニーＪｏｈｎｓｏｎ Ｍａｔｔｈｅｙ Ｐｕｂｌｉｃ Ｌｉｍｉｔｅｄ Ｃｏｍｐａｎｙ 排気ガス処理用酸化触媒
GB2497597A (en) * 2011-12-12 2013-06-19 Johnson Matthey Plc A Catalysed Substrate Monolith with Two Wash-Coats
EP2653681B2 (de) 2012-04-20 2019-12-04 Umicore AG & Co. KG Verwendung eines Beschichteten Dieselpartikelfilters zum Verhindern der Kontamination eines SCR-Katalysators
EP2674584B2 (de) * 2012-06-14 2020-04-29 Umicore AG & Co. KG Verwendung eines Oxidationskatalysators zur Verhinderung der Kontamination eines SCR-Katalysators mit Platin
US9604174B2 (en) * 2012-11-07 2017-03-28 Johnson Matthey Public Limited Company Exhaust system
GB201401115D0 (en) * 2014-01-23 2014-03-12 Johnson Matthey Plc Diesel oxidation catalyst and exhaust system
BR112017026952B1 (pt) * 2015-06-18 2022-10-11 Johnson Matthey Public Limited Company Artigo catalisador, sistema de escape, e, método para prover controle de nox de baixa temperatura

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001048466A2 (de) * 1999-12-24 2001-07-05 Robert Bosch Gmbh Sensorelement eines gassensors zur bestimmung von gaskomponenten
CN102355951A (zh) * 2009-01-16 2012-02-15 巴斯夫公司 层状柴油机氧化催化剂复合材料
CN104588092A (zh) * 2009-11-30 2015-05-06 约翰逊马西有限公司 处理瞬时nox排放的催化剂
CN104321506A (zh) * 2012-05-14 2015-01-28 恩亿凯嘉股份有限公司 废气净化装置
GB2540484A (en) * 2013-05-17 2017-01-18 Johnson Matthey Plc Oxidation catalyst for a compression ignition engine
CN105555403A (zh) * 2013-07-30 2016-05-04 庄信万丰股份有限公司 氨逸出催化剂

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EP3576865A1 (de) 2019-12-11
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