CN104039425A - 改进的NOx捕集阱 - Google Patents

改进的NOx捕集阱 Download PDF

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Publication number
CN104039425A
CN104039425A CN201280063148.9A CN201280063148A CN104039425A CN 104039425 A CN104039425 A CN 104039425A CN 201280063148 A CN201280063148 A CN 201280063148A CN 104039425 A CN104039425 A CN 104039425A
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collecting trap
layer
platinum group
storage component
group metal
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CN201280063148.9A
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CN104039425B (zh
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D·斯瓦洛
P·R·菲利普斯
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Johnson Matthey PLC
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Johnson Matthey PLC
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Abstract

公开了NOx捕集阱，及其在用于内燃机的排气系统中的用途。该NOx捕集阱包括基底和该基底上的三个层。第一层包含第一铂族金属、第一NOx储存组分和第一载体；第二层包含第二铂族金属、第二NOx储存组分和第二载体；和第三层包含铑和第三载体。第一层中的铂族金属负载量为第二层中的铂族金属负载量的1至40％。另外，第一NOx储存组分与第二NOx储存组分相同，并且第一载体与第二载体相同。该NOx捕集阱经过多次脱硫酸盐/NOx捕集阱再生循环而不易于失活。

Description

改进的NOx捕集阱
发明领域
本发明涉及用于内燃机用排气系统的NOx捕集阱，和用于处理内燃机废气的方法。
发明背景
内燃机产生含有多种污染物的废气，包括烃、一氧化碳、氮氧化物(“NOx“)、硫氧化物和颗粒物质。越来越严格的国家和地区法规已经降低了可以从这些柴油机或汽油机排放的污染物的量。已经对排气系统施用了许多不同的技术来在废气进入大气之前对其进行净化。
一种用来净化废气的这种技术是NOx捕集阱(或称“NOx吸附器催化剂”)。NOx捕集阱是在贫燃废气条件下吸附NOx，在富燃条件下释放吸附的NOx，并且还原释放的NOx形成N2的装置。NOx捕集阱通常包括用于储存NOx的NOx吸附剂和氧化/还原催化剂。
NOx吸附剂组分通常为碱土金属(如Ba、Ca、Sr和Mg)、碱金属(如K、Na、Li和Cs)、稀土金属(如La、Y、Pr和Nd)或其组合。这些金属通常以氧化物的形式存在。氧化/还原催化剂通常为一种或多种贵金属，优选铂、钯和/或铑。通常，包括铂以实现氧化功能，包括铑以实现还原功能。氧化/还原催化剂NOx吸附剂通常负载在载体材料如无机氧化物上，用于排气系统。
NOx捕集阱实现三种功能。首先，在氧化催化剂存在下一氧化氮与氧反应生成NO2。然后，NO2以无机硝酸盐的形式(例如，BaO或BaCO3在NOx吸附剂上转化为Ba(NO3)2)由NOx吸附剂吸附。最后，当发动机运行在富燃条件下时，储存的无机硝酸盐分解形成NO或NO2，其然后在还原催化剂存在下通过与一氧化碳、氢和/或烃反应而还原形成N2。通常，在废物流中的热、一氧化碳和烃存在下，氮氧化物转化为氮、二氧化碳和水。
不幸的是，柴油或汽油燃料中存在的硫化合物对NOx捕集阱有害，因为硫化合物的氧化产生废气中的硫氧化物废气。在NOx捕集阱中，二氧化硫在氧化催化剂氧化为三氧化硫，NOx吸附剂与三氧化硫反应生成表面硫酸盐(例如，氧化钡或碳酸钡与三氧化硫反应形成硫酸钡)。这些硫酸盐比硝酸盐更稳定，需要更高的温度(>650℃)脱硫酸盐。但是，脱硫酸盐和NOx捕集阱再生所需的极端条件会导致NOx捕集阱较长时间失活并可能导致NOx捕集阱寿命缩短。
美国申请公布2010/0215557描述了用于还原废气中的NOx的抗老化三效催化剂。该三效催化剂优选包含三层：(1)底部“蚀刻涂覆”层，其不含铂族金属；(2)中间(第一催化)层，其包含不含氧化铈的氧储存组分上的Pd和难熔金属氧化物上的Pt；和(3)第二催化层，其形成于第一催化层上，且包含氧储存组分上的Pt和氧化锆涂覆的或氧化钇涂覆的氧化铝上的Rh。美国申请公布2010/0215557未描述硫对该催化剂的影响。
对于任何汽车系统和过程，需要在废气处理系统中取得更进一步的改进。已经发现新的NOx捕集阱，其经过多次脱硫酸盐/NOx捕集阱再生循环而不易于失活。
发明概述
本发明是用于内燃机排气系统的NOx捕集阱。该NOx捕集阱包括基底和该基底上的三个层。第一层包含第一铂族金属、第一NOx储存组分和第一载体；第二层包含第二铂族金属、第二NOx储存组分和第二载体；和第三层包含铑和第三载体。第一层中的铂族金属负载量为第二层中的铂族金属负载量的1至40％。另外，第一NOx储存组分与第二NOx储存组分相同，并且第一载体与第二载体相同。该NOx捕集阱经过多次脱硫酸盐/NOx捕集阱再生循环而不易于失活。
发明详述
本发明的NOx捕集阱包括基底和该基底上的三个层。该基底优选为陶瓷基底或金属基底。陶瓷基底可以由任何适合的难溶材料制成，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、硅铝酸盐和金属硅铝酸盐(如堇青石和锂辉石)或者其任意两种或更多种的混合物或混合氧化物。特别优选堇青石、硅铝酸镁和碳化硅。
金属基底可以由任何适合的金属制成，特别是耐热金属和金属合金如钛和不锈钢以及含有铁、镍、铬和/或铝以及其他痕量金属的铁素体合金。
基底优选为流通式基底或过滤器基底。最优选基底为流通式基底。具体地，流通式基底为优选具有蜂窝状结构的流通式整料，该蜂窝状结构具有许多轴向穿过该基底和延伸遍及该基底的小的、平行的薄壁通道。基底的通道横截面可以为任何形状，但优选为正方形、正弦曲线形、三角形、矩形、六角形、梯形、圆形或椭圆形。
第一层包含第一铂族金属(“PGM”)、第一NOx储存组分和第一载体。第一PGM优选为铂、钯、金或其混合物；最优选地，第一PGM为铂、钯或其混合物。
第一NOx储存组分优选包括碱土金属(如钡、钙、锶和镁)、碱金属(如钾、钠、锂和铯)、稀土金属(如镧、钇、镨和钕)或其组合。最优选地，第一NOx储存组分包括钡、铈或其混合物。这些金属通常以氧化物的形式存在，但是也可以负载在载体如氧化铝或二氧化铈上。
第一载体优选为无机氧化物，更优选包括第2、3、4、5、13和14族元素的氧化物。最优选地，第一载体为氧化铝、二氧化硅、二氧化钛、氧化锆、氧化镁、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复合氧化物(例如二氧化硅-氧化铝、氧化镁-氧化铝、二氧化铈-氧化锆或氧化铝-二氧化铈-氧化锆)及其混合物。有用的无机氧化物优选表面积为10至1500m2/g，孔体积为0.1至4mL/g，和孔径为约10至1000埃。特别优选表面积大于80m2/g的高表面积载体。
NOx捕集阱的第二层包含第二铂族金属、第二NOx储存组分和第二载体。第二PGM优选为铂、钯、金或其混合物；最优选地，第二PGM为铂、钯或其混合物。
第二NOx储存组分优选包含碱土金属(如钡、钙、锶和镁)、碱金属(如钾、钠、锂和铯)、稀土金属(如镧、钇、镨和钕)或其组合。最优选地，第二NOx储存组分包括钡、铈或其混合物。这些金属通常以氧化物的形式存在，但是也可以负载在载体如氧化铝或二氧化铈上。
第二载体优选为无机氧化物，更优选包括第2、3、4、5、13和14族元素的氧化物。最优选地，第二载体为氧化铝、二氧化硅、二氧化钛、氧化锆、氧化镁、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复合氧化物(例如二氧化硅-氧化铝、氧化镁-氧化铝、二氧化铈-氧化锆或氧化铝-二氧化铈-氧化锆)及其混合物。有用的无机氧化物优选表面积为10至1500m2/g，孔体积为0.1至4mL/g，和孔径为约10至1000埃。特别优选表面积大于80m2/g的高表面积载体。
第一层的第一NOx储存组分与第二层的第二NOx储存组分相同。因此，如果氧化钡是用于第一层的NOx储存组分，则氧化钡也用于第二层。第一层的第一载体与第二层的第二载体相同。因此，如果氧化铝用作第一层中的载体，则氧化铝也用于第二层。
另外，第一层中的铂族金属负载量(按PGM的质量/第一层的体积计，例如g/L或g/ft3)为第二层中的铂族金属负载量的1至40％。更优选地，第一层中的铂族金属负载量为第二层中的铂族金属负载量的5至30％。因此，量少得多的PGM位于基底上的第一层中。优选地，第二层中的PGM负载量将为20至300g/ft3，第一层中的PGM负载量将为0.3至90g/ft3。
NOx捕集阱的第三层包含铑和第三载体。第三载体最优选为氧化铈、铈-锆混合氧化物、或者稀土金属、碱土金属或过渡金属稳定化的氧化铝。优选地，该稀土金属、碱土金属或过渡金属稳定化的氧化铝含有包含镧、钡、镨、钇、镁、铈和钴的稀土金属、碱土金属或过渡金属。优选地，该稀土金属、碱土金属或过渡金属稳定化的氧化铝包含0.5至5wt％的稀土金属、碱土金属或过渡金属。
NOx捕集阱的层可以以任何顺序布置在基底上，但是优选第一层位于基底上，第二层位于第一层上，第三层位于第二层上。
本发明的NOx捕集阱可以通过现有技术中公知的方法来制备。优选地，NOx捕集阱通过使用活化涂覆步骤将三个层沉积在基底上来制备。使用活化附图步骤制备NOx捕集阱的代表性方法如下所述。将会理解的是，根据本发明的不同实施方案，下述方法可以不同。
NOx捕集阱的第一层优选使用活化涂覆步骤来制备。优选将第一PGM添加到第一载体，然后与第一NOx吸附剂合并，再进行活化涂覆步骤。第一PGM可以通过任何已知手段负载在第一载体上，添加方式不认为是特别关键的。例如，可以通过浸渍、吸附、离子交换、初始润湿、沉淀等将铂、钯或金化合物(如硝酸铂)添加到载体，以制备负载的PGM。替代地，可以将第一载体和第一NOx吸附剂涂覆到基底上，然后将第一PGM添加到涂覆的基底。
活化涂覆优选通过以下来进行：首先将负载的PGM(或仅第一载体)的磨碎颗粒和第一NOx吸附剂在适合的溶剂(优选为水)中制浆，以形成浆料。该浆料优选含有5至70wt％的固体，更优选为10至50wt％。优选地，将该颗粒研磨或经过其他粉碎方法以确保在形成浆料之前基本上全部固体颗粒具有平均直径小于20微米的粒度。可以将另外的组分如稳定剂或促进剂掺入浆料作为水溶性或水分散性化合物或配合物的混合物。
然后可以用该浆料将基底涂覆一遍或多遍，以使基底上沉积有第一层中所需负载量的催化材料。只要第一载体和第一NOx吸附剂沉积在基底上，则可以将第一PGM通过任何已知手段添加到涂覆的基底，包括浸渍、吸附或铂化合物(如硝酸铂)的离子交换。
优选地，基底的整个长度涂覆有第一层浆料，从而第一层的活化涂层覆盖基底的整个表面。
将第一层沉积在基底上之后，通常通过在优选80至150℃的升高的温度加热来干燥第一层。基底也可以在更高的温度(如400至600℃)煅烧，但是在添加第二层之前通常不需要煅烧。
然后以与上述类似的方式将第二层添加到第一层，然后通过在优选80至150℃的升高的温度加热来干燥。基底也可以在更高的温度(如400至600℃)煅烧，但是在添加第三层之前通常不需要煅烧。优选地，基底的整个长度涂覆有第二层浆料，从而第二层的活化涂层覆盖基底的整个表面。
NOx捕集阱的第三层优选使用活化涂覆步骤来制备。在活化涂覆步骤之前，优选将铑添加到第三载体，但是替代地，可以将第三载体涂覆在第二层上，然后将铑添加到涂覆的基底。如果在活化涂覆第三层之前将铑添加到第三载体，可以通过任何已知手段将它负载在第三载体上，添加方式不认为是特别关键的。例如，可以通过浸渍、吸附、离子交换、初始润湿、沉淀等将铑化合物(如硝酸铑)添加到载体。
活化涂覆优选通过以下来进行：首先将负载的铑(或仅第三载体)的磨碎颗粒在适合的溶剂(优选为水)中制浆，以形成浆料。该浆料优选含有5至70wt％的固体，更优选为10至50wt％。优选地，将该颗粒研磨或经过其他粉碎方法以确保在形成浆料之前基本上全部固体颗粒具有平均直径小于20微米的粒度。可以将另外的组分如稳定剂或促进剂掺入浆料作为水溶性或水分散性化合物或配合物的混合物。
然后可以用该浆料将基底涂覆一遍或多遍，以使基底上沉积有第三层中所需负载量的催化材料。只要第三载体沉积在基底上，则可以将铑通过任何已知手段添加到载体涂覆的基底，包括浸渍、吸附或铑化合物(如硝酸铑)的离子交换。
优选地，基底的整个长度涂覆有第三层浆料，从而第三层的活化涂层覆盖基底的整个表面。
在第三层已经涂覆在基底上之后，通常将基底干燥，然后通过在升高的温度加热来煅烧。优选地，煅烧在400至600℃进行约1至8小时。
尽管上面示范的制备NOx捕集阱展示了优选的实施方案，其中第一层位于基底上，第二层位于第一层上，第三层位于第二层上，但是第一、第二和第三层也可以使用与上述相同的步骤以任何顺序布置在基底上。
本发明还包括内燃机的排气系统，其包括本发明的NOx捕集阱。优选地，该排气系统包括具有氧化催化剂和/或颗粒过滤器的NOx捕集阱。这些后处理装置在本领域中是公知的。颗粒过滤器是减少内燃机废气中的颗粒物的装置。颗粒过滤器包括催化烟灰过滤器(CSF)和单纯(非催化)颗粒过滤器。催化烟灰过滤器(用于柴油和汽油应用)包含金属和金属氧化物组分(如Pt、Pd、Fe、Mn、Cu和二氧化铈)以在破坏由该过滤器捕集的烟灰之外氧化烃和一氧化碳。
特别优选的排气系统包括NOx捕集阱，然后是CSF，二者均紧密连接；紧密连接的NOx捕集阱和地板下的CSF；和紧密连接的柴油机氧化催化剂/CSF和地板下的NOx捕集阱。
本发明还包括处理内燃机废气，特别是处理来自机动车贫燃内燃机(如柴油机、贫燃汽油机或由液化石油气或天然气功能的发动机)的废气。该方法包括使该废气与本发明的NOx捕集阱接触。
下面的实施例仅示例性说明本发明。本领域技术人员将会领会，许多变化处于本发明精神和权利要求书范围之内。
实施例1：制备催化基底
对比基底1A(第1、2层中50-50PGM分配)：
用三层NOx吸收器催化剂配制物涂覆400孔/平方英寸(cpsi)的流通式堇青石基底整料，该配制物包含：第一下层，其包含1g/in3的氧化铝、1g/in3的颗粒状二氧化铈、47g/ft3的Pt、9.5g/ft3的Pd和200g/ft3的Ba；第二层，其包含1g/in3的氧化铝、1g/in3的颗粒状二氧化铈、47g/ft3的Pt、9.5g/ft3的Pd和200g/ft3的Ba；和第三层，其包含0.5g/in3的85wt％的掺杂有稀土元素的氧化锆和10g/ft3的Rh。将第一和第二层使用WO99/47260中公开的方法涂覆在初始基底整料上，然后在强制通风式干燥器中于100℃干燥30分钟，然后在500℃烧制2小时，之后施涂第三层并重复相同的干燥和烧制步骤。
对比基底1B(第1、2层中0-100PGM分配)：
对比基底1B与对比基底1A相同，只是第一层中没有PGM(0g/ft3的Pt、0g/ft3的Pd)并且第二层中的PGM负载量为94g/ft3的Pt和19g/ft3的Pd。将第一层使用WO99/47260中公开的方法涂覆在初始基底整料上，然后在强制通风式干燥器中于100℃干燥30分钟，然后在500℃烧制2小时，之后施涂第二层和第三层并重复相同的干燥和烧制步骤。
本发明的基底1C(第1、2层中20-80PGM分配)：
基底1C与对比基底1A相同，只是第一层中的PGM负载量为18.8g/ft3的Pt和3.8g/ft3的Pd并且第二层中的PGM负载量为75.2g/ft3的Pt和15.2g/ft3的Pd。使用对比基底1B的步骤涂覆这三层。
实施例2：测试程序
将各实施例1基底的35mm×76.2mm的芯在炉中于800℃老化24小时，然后评价。测试在合成气装备上进行，并且全部测试于45,000h-1的GHSV进行。在评价之前，将芯在600℃预处理5分钟，并进行50秒富/10秒贫的脱硫酸盐。贫和富气体条件示于表1。然后将温度在N2下降至350℃，进行300秒贫和20秒富的5次循环以评价NOx转化效率。第5次循环的稳定化的NOx转化效率示于表2作为脱硫酸盐的(运行开始)NOx转化率。然后将90ppm的SO2引入气体进料，并完成300秒贫和20秒富的5次循环，由此将NOx捕集阱硫酸化至2g/L的S负载量。第5次硫酸化循环NOx转化率示于表2作为硫酸化的(运行结束)NOx转化率。然后将温度升至600℃，并完成50秒富和10秒贫的5分钟脱硫酸盐。脱硫酸盐之后，将温度降回至350℃，此时在没有SO2的情况下进行300秒贫和20秒富的5次循环以获得脱硫酸盐的转化效率。重复该程序七次以得到整个运行过程中的七个硫酸化的脱硫酸盐的NOx转化效率结果(见表2)。从NOx转化率结果计算运行过程中的三个基底的NOx储存容量。结果示于表3。
结果显示，与第一和第二层上PGM量相等的基底(对比基底1A)和第一层上没有PGM的基底(对比基底1B)相比，本发明基底(基底1C)在一系列硫酸化循环和再生之后保持了较高的NOx转化率和较高的NOx容量。
表1：贫和富气体条件
表2：NOx转化率结果
*对比实施例
表3：NOx储存容量结果
*对比实施例

Claims (14)

1.NOx捕集阱，其包括基底和：
(a)第一层，其包含第一铂族金属、第一NOx储存组分和第一载体；
(b)第二层，其包含第二铂族金属、第二NOx储存组分和第二载体；和
(c)第三层，其包含铑和第三载体，
其中第一层中的铂族金属负载量为第二层中的铂族金属负载量的1至40％，第一NOx储存组分与第二NOx储存组分相同，并且第一载体与第二载体相同。
2.根据权利要求1所述的NOx捕集阱，其中该基底为流通式整料。
3.根据权利要求1所述的NOx捕集阱，其中第一层位于该基底上，第二层位于第一层上，第三层位于第二层上。
4.根据权利要求1所述的NOx捕集阱，其中第一铂族金属选自钯、铂、金及其混合物。
5.根据权利要求1所述的NOx捕集阱，其中第二铂族金属选自钯、铂、金及其混合物。
6.根据权利要求1所述的NOx捕集阱，其中第一铂族金属与第二铂族金属相同。
7.根据权利要求1所述的NOx捕集阱，其中第一载体和第二载体选自氧化铝、二氧化硅、二氧化钛、氧化锆、氧化镁、二氧化铈、氧化铌、钽氧化物、钼氧化物、钨氧化物及其混合氧化物或复合氧化物。
8.根据权利要求1所述的NOx捕集阱，其中第一NOx储存组分和第二NOx储存组分包括碱土金属、碱金属、稀土金属或其混合物。
9.根据权利要求8所述的NOx捕集阱，其中第一NOx储存组分和第二NOx储存组分包括钡、铈或其混合物。
10.根据权利要求1所述的NOx捕集阱，其中第三载体选自氧化铈、铈-锆混合氧化物和稀土金属、碱土金属或过渡金属稳定化的氧化铝。
11.根据权利要求1所述的NOx捕集阱，其中第一层中的铂族金属负载量为第二层中的铂族金属负载量的5至30％。
12.用于内燃机的排气系统，其包括根据权利要求1所述的NOx捕集阱。
13.根据权利要求12所述的排气系统，其进一步包括氧化催化剂、颗粒过滤器或其组合。
14.用于处理内燃机废气的方法，其包括使该废气与根据权利要求1所述的NOx捕集阱接触。
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110075836A (zh) * 2019-05-29 2019-08-02 上海歌地催化剂有限公司 稀燃NOx捕集催化剂
CN110461444A (zh) * 2017-03-29 2019-11-15 庄信万丰股份有限公司 NOx吸附剂催化剂
CN110461443A (zh) * 2017-03-29 2019-11-15 约翰逊马西有限公司 三层NOx吸附器催化剂
CN110536740A (zh) * 2017-03-29 2019-12-03 庄信万丰股份有限公司 NOx吸附剂催化剂
CN110545913A (zh) * 2017-03-29 2019-12-06 庄信万丰股份有限公司 NOx吸附剂催化剂
CN110545901A (zh) * 2017-03-29 2019-12-06 庄信万丰股份有限公司 NOx吸附剂催化剂
CN113318736A (zh) * 2020-02-28 2021-08-31 株式会社斯巴鲁 汽油贫燃发动机用lnt层叠催化剂、及使用其的废气净化装置
CN114950424A (zh) * 2022-06-15 2022-08-30 万华化学（宁波）有限公司 一种循环气两段式脱硫催化剂、制备方法及其应用

Families Citing this family (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008140786A1 (en) 2007-05-11 2008-11-20 Sdc Materials, Inc. Method and apparatus for making uniform and ultrasmall nanoparticles
US8575059B1 (en) 2007-10-15 2013-11-05 SDCmaterials, Inc. Method and system for forming plug and play metal compound catalysts
US8652992B2 (en) 2009-12-15 2014-02-18 SDCmaterials, Inc. Pinning and affixing nano-active material
US9039916B1 (en) 2009-12-15 2015-05-26 SDCmaterials, Inc. In situ oxide removal, dispersal and drying for copper copper-oxide
US9126191B2 (en) 2009-12-15 2015-09-08 SDCmaterials, Inc. Advanced catalysts for automotive applications
US9149797B2 (en) 2009-12-15 2015-10-06 SDCmaterials, Inc. Catalyst production method and system
US8669202B2 (en) 2011-02-23 2014-03-11 SDCmaterials, Inc. Wet chemical and plasma methods of forming stable PtPd catalysts
JP2014524352A (ja) 2011-08-19 2014-09-22 エスディーシーマテリアルズ， インコーポレイテッド 触媒作用および触媒コンバータに使用するための被覆基材ならびにウォッシュコート組成物で基材を被覆する方法
US9156025B2 (en) 2012-11-21 2015-10-13 SDCmaterials, Inc. Three-way catalytic converter using nanoparticles
US9511352B2 (en) 2012-11-21 2016-12-06 SDCmaterials, Inc. Three-way catalytic converter using nanoparticles
WO2015013545A1 (en) 2013-07-25 2015-01-29 SDCmaterials, Inc. Washcoats and coated substrates for catalytic converters
EP3038746A1 (en) 2013-08-28 2016-07-06 Johnson Matthey PLC Co slip catalyst and method of using
CA2926135A1 (en) * 2013-10-22 2015-04-30 SDCmaterials, Inc. Compositions of lean nox trap
JP2016536120A (ja) 2013-10-22 2016-11-24 エスディーシーマテリアルズ， インコーポレイテッド ヘビーデューティディーゼルの燃焼機関のための触媒デザイン
WO2015143225A1 (en) 2014-03-21 2015-09-24 SDCmaterials, Inc. Compositions for passive nox adsorption (pna) systems
KR101673330B1 (ko) * 2014-06-25 2016-11-07 현대자동차 주식회사 질소산화물 저감 촉매, 이의 제조 방법, 및 질소산화물 저감 촉매 시스템
JP6389420B2 (ja) * 2014-11-12 2018-09-12 株式会社キャタラー 排ガス浄化用触媒
WO2016130566A2 (en) 2015-02-11 2016-08-18 SDCmaterials, Inc. Lean nox traps, trapping materials, washcoats, and methods of making and using the same
EP3277406B1 (en) * 2015-03-03 2023-08-02 BASF Corporation Lean nox trap with enhanced high and low temperature performance
US9616386B2 (en) * 2015-03-23 2017-04-11 Kabushiki Kaisha Toyota Chuo Kenkyusho Catalyst for purification of exhaust gas, NOx storage-reduction catalyst, and method for purifying exhaust gas
GB2553339A (en) * 2016-09-02 2018-03-07 Johnson Matthey Plc Improved NOx trap
GB201616812D0 (en) * 2016-10-04 2016-11-16 Johnson Matthey Public Limited Company NOx adsorber catalyst
GB2554859A (en) * 2016-10-04 2018-04-18 Johnson Matthey Plc NOx adsorber catalyst
GB2557673A (en) * 2016-12-15 2018-06-27 Johnson Matthey Plc NOx adsorber catalyst
JP6408062B1 (ja) * 2017-04-28 2018-10-17 株式会社キャタラー 排ガス浄化用触媒
CA3061306A1 (en) * 2017-04-28 2019-10-23 Umicore Shokubai Japan Co., Ltd. Exhaust gas purification catalyst and exhaust gas purification method using the same
EP3634623A1 (en) 2017-05-11 2020-04-15 Rhodia Operations Mixed oxide with enhanced resistance and nox storage capacity
CN111201075B (zh) 2017-10-12 2023-02-03 巴斯夫公司 组合的NOx吸收剂和SCR催化剂
US11110447B2 (en) 2017-12-08 2021-09-07 Johnson Matthey (shanghai) Chemicals Co., Ltd. Three-zone two-layer TWC catalyst in gasoline waste gas applications
US10399037B1 (en) * 2018-04-20 2019-09-03 GM Global Technology Operations LLC Nitrogen oxides storage catalyst and methods of using the same
US10953366B2 (en) 2018-04-20 2021-03-23 GM Global Technology Operations LLC Nitrogen oxides and hydrocarbon storage catalyst and methods of using the same
EP3616792A1 (de) 2018-08-28 2020-03-04 Umicore Ag & Co. Kg Stickoxid-speicherkatalysator
KR20220110760A (ko) 2019-12-13 2022-08-09 바스프 코포레이션 저온 NOx 트랩핑을 위한 희박 NOx 트랩 플러스 저온 NOx 흡착 시스템
US11642655B2 (en) * 2020-01-07 2023-05-09 Johnson Matthey Public Limited Company Multi-region TWC catalysts for gasoline engine exhaust gas treatments
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
JP2023131483A (ja) 2022-03-09 2023-09-22 株式会社キャタラー 排ガス浄化用触媒

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0992276A1 (en) * 1998-09-29 2000-04-12 Mazda Motor Corporation Exhaust gas purifying catalyst
US20030021745A1 (en) * 2001-04-13 2003-01-30 Engelhard Corporation SOx tolerant NOx trap catalysts and methods of making and using the same
CN101161337A (zh) * 2006-10-13 2008-04-16 比亚迪股份有限公司 一种三元催化剂及其制备方法
CN101528347A (zh) * 2006-08-21 2009-09-09 巴斯福催化剂公司 用于废气纯化的层式催化剂复合材料
CN101820997A (zh) * 2007-08-09 2010-09-01 巴斯夫催化剂公司 催化剂组合物
WO2010129490A2 (en) * 2009-05-04 2010-11-11 Basf Corporation Improved lean hc conversion of twc for lean burn gasoline engines

Family Cites Families (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB9805815D0 (en) 1998-03-19 1998-05-13 Johnson Matthey Plc Manufacturing process
JP2002357120A (ja) * 2001-05-30 2002-12-13 Isuzu Motors Ltd 排気ガス浄化装置
US7276212B2 (en) * 2001-10-01 2007-10-02 Engelhard Corporation Exhaust articles for internal combustion engines
US6764665B2 (en) * 2001-10-26 2004-07-20 Engelhard Corporation Layered catalyst composite
US20040001781A1 (en) * 2002-06-27 2004-01-01 Engelhard Corporation Multi-zone catalytic converter
US7329629B2 (en) * 2002-10-24 2008-02-12 Ford Global Technologies, Llc Catalyst system for lean burn engines
US7490464B2 (en) * 2003-11-04 2009-02-17 Basf Catalysts Llc Emissions treatment system with NSR and SCR catalysts
GB0422549D0 (en) * 2004-10-12 2004-11-10 Johnson Matthey Plc Method of decomposing nitrogen dioxide
US7758834B2 (en) * 2006-08-21 2010-07-20 Basf Corporation Layered catalyst composite
US7550124B2 (en) * 2006-08-21 2009-06-23 Basf Catalysts Llc Layered catalyst composite
US7517510B2 (en) * 2006-08-21 2009-04-14 Basf Catalysts Llc Layered catalyst composite
JP2008100152A (ja) * 2006-10-18 2008-05-01 Cataler Corp 排ガス浄化用触媒
JP2009248057A (ja) * 2008-04-10 2009-10-29 Toyota Motor Corp 排ガス浄化用触媒
US7981390B2 (en) * 2008-12-23 2011-07-19 Basf Corporation Small engine palladium catalyst article and method of making
US9440192B2 (en) * 2009-01-16 2016-09-13 Basf Corporation Diesel oxidation catalyst and use thereof in diesel and advanced combustion diesel engine systems
US8329607B2 (en) * 2009-01-16 2012-12-11 Basf Corporation Layered diesel oxidation catalyst composites
US10773209B2 (en) 2009-02-20 2020-09-15 Basf Corporation Aging-resistant catalyst article for internal combustion engines
US8568675B2 (en) * 2009-02-20 2013-10-29 Basf Corporation Palladium-supported catalyst composites
US9662611B2 (en) * 2009-04-03 2017-05-30 Basf Corporation Emissions treatment system with ammonia-generating and SCR catalysts
US8637426B2 (en) * 2009-04-08 2014-01-28 Basf Corporation Zoned catalysts for diesel applications
US8833064B2 (en) * 2009-11-06 2014-09-16 Basf Corporation Small engine layered catalyst article and method of making
GB0922195D0 (en) * 2009-12-21 2010-02-03 Johnson Matthey Plc Improvements in NOx traps
US8828343B2 (en) * 2010-03-05 2014-09-09 Basf Corporation Carbon monoxide conversion catalyst
US8734743B2 (en) 2010-06-10 2014-05-27 Basf Se NOx storage catalyst with improved hydrocarbon conversion activity
US8950174B2 (en) * 2010-09-02 2015-02-10 Basf Se Catalysts for gasoline lean burn engines with improved NH3-formation activity
US8323599B2 (en) * 2010-11-22 2012-12-04 Umicore Ag & Co. Kg Three-way catalyst having an upstream multi-layer catalyst
US8617496B2 (en) * 2011-01-19 2013-12-31 Basf Corporation Three way conversion catalyst with alumina-free rhodium layer
US9044734B2 (en) * 2011-09-23 2015-06-02 Basf Se Diesel oxidation catalyst with layered structure containing ceria composition as palladium support material for enhanced HC and CO gas conversion
GB2497597A (en) * 2011-12-12 2013-06-19 Johnson Matthey Plc A Catalysed Substrate Monolith with Two Wash-Coats

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0992276A1 (en) * 1998-09-29 2000-04-12 Mazda Motor Corporation Exhaust gas purifying catalyst
US20030021745A1 (en) * 2001-04-13 2003-01-30 Engelhard Corporation SOx tolerant NOx trap catalysts and methods of making and using the same
CN101528347A (zh) * 2006-08-21 2009-09-09 巴斯福催化剂公司 用于废气纯化的层式催化剂复合材料
CN101161337A (zh) * 2006-10-13 2008-04-16 比亚迪股份有限公司 一种三元催化剂及其制备方法
CN101820997A (zh) * 2007-08-09 2010-09-01 巴斯夫催化剂公司 催化剂组合物
WO2010129490A2 (en) * 2009-05-04 2010-11-11 Basf Corporation Improved lean hc conversion of twc for lean burn gasoline engines

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110461444A (zh) * 2017-03-29 2019-11-15 庄信万丰股份有限公司 NOx吸附剂催化剂
CN110461443A (zh) * 2017-03-29 2019-11-15 约翰逊马西有限公司 三层NOx吸附器催化剂
CN110536740A (zh) * 2017-03-29 2019-12-03 庄信万丰股份有限公司 NOx吸附剂催化剂
CN110545913A (zh) * 2017-03-29 2019-12-06 庄信万丰股份有限公司 NOx吸附剂催化剂
CN110545901A (zh) * 2017-03-29 2019-12-06 庄信万丰股份有限公司 NOx吸附剂催化剂
CN110075836A (zh) * 2019-05-29 2019-08-02 上海歌地催化剂有限公司 稀燃NOx捕集催化剂
CN113318736A (zh) * 2020-02-28 2021-08-31 株式会社斯巴鲁 汽油贫燃发动机用lnt层叠催化剂、及使用其的废气净化装置
CN113318736B (zh) * 2020-02-28 2024-01-09 株式会社斯巴鲁 汽油贫燃发动机用lnt层叠催化剂、及使用其的废气净化装置
CN114950424A (zh) * 2022-06-15 2022-08-30 万华化学（宁波）有限公司 一种循环气两段式脱硫催化剂、制备方法及其应用

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RU2014130019A (ru) 2016-02-20
BR112014015601A2 (pt) 2017-06-13
CN104039425B (zh) 2016-08-24
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US20150190793A1 (en) 2015-07-09
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WO2013093597A3 (en) 2013-08-22
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