CN105682792B - 包含含银挤出沸石基材的三元催化剂及其在排气系统中的用途 - Google Patents

包含含银挤出沸石基材的三元催化剂及其在排气系统中的用途 Download PDF

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CN105682792B
CN105682792B CN201480059569.3A CN201480059569A CN105682792B CN 105682792 B CN105682792 B CN 105682792B CN 201480059569 A CN201480059569 A CN 201480059569A CN 105682792 B CN105682792 B CN 105682792B
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zeolite
way catalyst
catalyst
argentiferous
oxide
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CN105682792A (zh
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H-I·张
H-Y·陈
K·顾
J·S·瑞克
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Johnson Matthey PLC
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Johnson Matthey PLC
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Abstract

公开了三元催化剂。三元催化剂包含含银挤出沸石基材和布置在含银挤出沸石基材上的催化剂层。催化剂层包含负载的铂族金属催化剂，所述负载的铂族金属催化剂包含一种或多种铂族金属和一种或多种无机氧化物载体。本发明还包括排气系统，其包括三元催化剂。三元催化剂带来改善的烃储存和转化，特别是在冷启动时期期间。

Description

包含含银挤出沸石基材的三元催化剂及其在排气系统中的 用途
发明领域
本发明涉及三元催化剂及其在用于内燃机的排气系统中的用途。
发明背景
内燃机产生排气气体，其包含各种污染物，包括烃、一氧化碳、和氮氧化物(“NOx”)。包括排气气体催化剂的排放控制系统广泛用于减少这些排放到大气中的污染物的量。用于汽油发动机应用的常用催化剂为“三元催化剂”(TWC)。TWC表现出三种主要功能：(1)氧化CO；(2)氧化未燃烃；和(3)将NOx还原成N2。
TWC，例如其它排气气体催化剂，通常一旦它们达到其操作温度(通常，200℃以上)就实现非常高效率。然而，在低于其操作温度(“冷启动”时期)时，这些系统相对低效。随着越发严格的政府和地区立法降低了可以从柴油或汽油发动机排放的污染物的量，在冷启动时期期间减少排放物变成主要的挑战。因此，用于减少冷启动条件期间排放的NOx和烃的水平的方法被持续探索。
对于冷启动烃控制，已经研究了烃(HC)阱，其包括沸石作为烃捕集组分。在这些系统中，沸石组分在启动时期期间吸附并且储存烃并且在排气温度足够高以解吸烃时释放储存的烃。解吸的烃随后通过并入至HC阱中的TWC组分或通过放置在HC阱下游的单独的TWC转化。
例如，US Pat.No.5,772,972公开了烃捕集材料和钯系三元催化剂材料的混合系统。US Pat.No.6,617,276教导了催化剂结构件，其包含：第一层，其基本上由烃吸附沸石和浸渍至沸石上的K、Rb或Cs活性金属组成；至少一个另外的层，其基本上由至少一种铂族金属组成；和催化剂基材，其上布置第一层和一个或多个另外层。在EP1129774中，教导了烃吸附构件包括这样的沸石，其SiO2:Al2O3摩尔比为100或更大并且平均主粒径(primaryparticle diameter)为1μm或更小，并且不含一价金属元素。US Pat.No.6,074,973教导了催化的烃阱材料，其包含分散在高表面积金属氧化物载体和沸石材料(例如ZSM-5、β、Y及其它适合的沸石中的一种或多种)上的钯和银。
U.S.Appl.Pub.No.2012/0117953A1教导了三元催化剂，其包含挤出固体主体，所述固体主体包含10-100wt％的至少一种粘合剂/基体组分、5-90wt％的沸石分子筛、非沸石分子筛或其任何两种或更多种的混合物，和0-80wt％的任选的稳定化二氧化铈。催化剂包含至少一种贵金属和任选至少一种非贵金属，其中：(i)至少一种贵金属负载在挤出固体主体表面上的一个或多个涂覆层中；(ii)至少一种金属存在于整个挤出固体主体中并且至少一种贵金属也负载在挤出固体主体表面上的一个或多个涂覆层中；或(iii)至少一种金属存在于整个挤出固体主体中，以更高浓度存在于挤出固体主体表面处并且至少一种贵金属也负载在挤出固体主体表面上的一个或多个涂覆层中。此外，U.S.Appl.Pub.No.2012/0308439A1教导冷启动催化剂，其包含(1)沸石催化剂，所述沸石催化剂包含贱金属、贵金属和沸石，和(2)负载的铂族金属催化剂，所述负载的铂族金属催化剂包含一种或多种铂族金属和一种或多种无机氧化物载体。
针对任何汽车系统和方法，期望的是获得排气气体处理系统的进一步的改善，特别是在冷启动条件下。我们已经发现了新型三元催化剂，其提供了对来自内燃机的排气气体的改善的清洁。
发明概述
本发明为用于排气系统的三元催化剂。三元催化剂包含含银挤出沸石基材。三元催化剂还包含布置在含银挤出沸石基材上的催化剂层。催化剂层包含负载的铂族金属催化剂，所述负载的铂族金属催化剂包含一种或多种铂族金属和一种或多种无机氧化物载体。本发明还包括包含三元催化剂的排气系统。
发明具体实施方式
本发明的三元催化剂包含含银挤出沸石基材。
含银挤出沸石基材的沸石可以为任何天然或合成沸石，包括分子筛，并且优选包含铝、硅和/或磷。沸石通常具有SiO4、AlO4和/或PO4的三维排布，其通过共享氧原子结合。沸石骨架通常为阴离子，其由电荷补偿阳离子平衡，通常为碱金属元素和碱土金属元素(例如，Na、K、Mg、Ca、Sr和Ba)以及质子。
沸石优选为β沸石、八面沸石(例如X-沸石或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、SSZ-41、SSZ-33)、AEI骨架沸石、丝光沸石、菱沸石、菱钾沸石、毛沸石、斜发沸石、硅质岩、铝磷酸盐沸石(包括金属铝磷酸盐例如SAPO-34)、中孔沸石(例如，MCM-41、MCM-49、SBA-15)或其混合物；更优选的是沸石为β沸石、ZSM-5沸石或SSZ-33，或Y-沸石。沸石最优选为β沸石、ZSM-5沸石或SSZ-33。
挤出沸石基材可以通过任何已知的方式形成。通常，挤出沸石以形成流通式或过滤式基材，并且优选挤出以形成蜂窝状流通式整料。挤出沸石基材和蜂窝状体和用于制备它们的方法在本领域中是已知的。参见，例如，U.S.Pat.Nos.5,492,883、5,565,394和5,633,217和U.S.Pat.No.Re.34,804。通常，沸石材料与永久粘合剂(例如有机硅树脂)和临时粘合剂(例如甲基纤维素)混合，并且将混合物挤出以形成生坯蜂窝状体，然后将其煅烧并且烧结以形成最终挤出沸石基材。
挤出沸石基材可以形成为流通式或过滤式基材。如果形成为流通式基材，优选为这样的流通式整料，其具有轴向穿过基材并且从基材入口或出口延伸贯穿的多个小的、平行薄壁通道的蜂窝状结构。基材的通道横截面可以为任何形状，但是优选为方形、正弦形、三角形、矩形、六边形、梯形、圆形或椭圆形。
如果形成为过滤式基材，含银挤出沸石基材优选为壁流式整料过滤器。壁流式过滤器的通道交替地封阻，其允许排气气体物流从入口进入通道，然后流动穿过通道壁，并且从不同的导向出口的通道离开过滤器。因此，排气气体物流中的颗粒捕集在过滤器中。
沸石可以在挤出之前包含银，使得通过挤出流程产生含银挤出沸石基材。如果沸石在挤出之前包含银，则可以通过任何已知的方式将银添加至沸石以形成含银沸石，不认为添加的方式是特别关键的。例如，可以通过浸渍、吸附、离子交换、初湿含浸法或沉淀等将银化合物(例如硝酸银)添加至沸石。
如果首先在没有银的情况下形成挤出沸石基材，则然后用银负载挤出沸石整料以产生含银挤出沸石基材。优选的是挤出沸石整料经受浸渍流程来将银负载至沸石整料上。
优选的是含银挤出沸石基材包含1-700g/ft3的银，更优选10-200g/ft3的银。
三元催化剂还包含布置在含银挤出沸石基材上的催化剂层。催化剂层包含负载的铂族金属催化剂。负载的铂族金属催化剂包含一种或多种铂族金属(“PGM”)和一种或多种无机氧化物载体。PGM可以为铂、钯、铑或其组合，并且最优选钯和铑。无机氧化物载体最通常地包括第2、3、4、5、13和14族元素的氧化物。有用的无机氧化物载体优选地具有10-700m2/g的表面积、0.1-4mL/g的孔体积和约10-1000埃的孔径。无机氧化物载体优选为氧化铝、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、钨氧化物或其任何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、二氧化铈-氧化锆或氧化铝-二氧化铈-氧化锆。氧化铝和二氧化铈-氧化锆是特别优选的。
负载的铂族金属催化剂可以通过任何已知的方式制备。优选的是通过任何已知的方式将一种或多种铂族金属负载至一种或多种无机氧化物上以形成负载的PGM催化剂，不认为添加的方式是特别关键的。例如，可以通过浸渍、吸附、离子交换、初湿含浸法或沉淀等将钯化合物(例如硝酸钯)负载在无机氧化物上。也可以将其它金属添加至负载的PGM催化剂。
将负载的PGM催化剂层布置在含银挤出沸石基材上。可以通过现有技术中公知的方法将负载的PGM催化剂层布置在含银挤出沸石基材上。优选的是使用载体涂覆流程将负载的铂族金属催化剂涂覆至含银挤出沸石基材上以产生本发明的三元催化剂。
在以下描述用于使用载体涂覆流程制备三元催化剂的代表性方法。应该理解以下方法可以根据本发明的不同实施方案而改变。
载体涂覆流程优选通过以下进行：首先将负载的铂族催化剂的细碎颗粒在恰当的溶剂(优选水)中制浆，以形成浆料。也可以将另外的组分，例如过渡金属氧化物、粘合剂、稳定剂或促进剂并入浆料中，作为水溶性或水分散性化合物的混合物。浆料优选包含10-70wt％，更优选30-50wt％的固体。在形成浆料之前，负载的铂族催化剂颗粒优选经受减尺寸处理(例如，研磨)使得固体颗粒的平均粒度为直径小于20微米。
然后可以将含银挤出沸石基材浸入浆料中一次或多次或可以将浆料涂覆在基材上，使得在含银挤出沸石基材上沉积了期望的负载量的催化材料。替代地，可以首先将仅包含无机氧化物(一种或多种)的浆料沉积在涂覆沸石催化剂的基材上以形成涂覆无机氧化物的基材，随后是干燥和煅烧步骤。然后可以通过任何已知的方式(包括铂族金属化合物(例如硝酸铂)的浸渍、吸附或离子交换)将铂族金属(一种或多种)添加至涂覆无机氧化物的基材。
优选的是用浆料涂覆含银挤出沸石基材的整个长度，以使得负载的铂族催化剂的载体图层覆盖基材的整个表面。
在用负载的铂族催化剂浆料涂覆含银挤出沸石基材之后，优选将涂覆的基材干燥并且然后通过在升高的温度下加热来煅烧以形成三元催化剂。优选的是煅烧在400-600℃下进行大约1-8小时。
本发明还包括用于内燃机的包括三元催化剂的排气系统。排气系统优选包括一种或多种另外的后处理装置，其能够从内燃机排气气体中除去污染物。
优选的是排气系统包括紧联式(close-coupled)催化剂和本发明的三元催化剂。紧联式催化剂位于三元催化剂的上游。优选的是也可以将颗粒过滤器添加至该系统。颗粒过滤器可以位于紧联式催化剂和上游三元催化剂的下游，或颗粒过滤器可以位于三元催化剂的下游。
紧联式催化剂在本领域中是公知的。紧联式催化剂通常用于在发动机发动后的冷启动时期期间在三元催化剂处测量的温度低于约150-220℃的温度时减少烃排放。紧联式催化剂位于发动机室内，通常与排气歧管相邻并且在罩下，以便使其暴露于发动机暖机之后立即离开发动机的高温排气气体。
紧联式催化剂优选包含用包含选自Pt、Pd和Rh的至少一种贵金属的耐热无机氧化物的催化剂层涂覆的基材结构件。耐热基材通常为整料基材，并且优选陶瓷基材或金属基材。陶瓷基材可以由任何适合的耐热耐火材料制备，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、锆硅酸盐、镁硅酸盐、铝硅酸盐和金属铝硅酸盐(例如堇青石和锂辉石)，或其任何两种或更多种的混合物或混合氧化物。金属基材可以由任何适合的金属制备，并且特别是耐热金属和金属合金例如钛和不锈钢以及除其它痕量金属(通常，稀土金属)之外包含铁、镍、铬和/或铝的铁素体合金。
基材优选为流通式基材，但是也可以为过滤式基材。流通式基材优选地具有蜂窝状结构，所述蜂窝状结构具有轴向穿过基材和延伸贯穿基材的多个小的、平行薄壁通道。如果基材是过滤式基材，优选的是壁流式整料过滤器。壁流式过滤器的通道交替地封阻，其允许排气气体物流从入口进入通道，并且然后流动穿过通道壁，并且从不同的导向出口的通道离开过滤器。因此，排气气体物流中的颗粒捕集在过滤器中。
通常将紧联式催化剂的催化剂层添加至基材作为载体涂层，所述载体涂层优选包含一种或多种无机氧化物和一种或多种铂族金属。无机氧化物最通常包括第2、3、4、5、13和14族元素的氧化物。有用的无机氧化物优选地具有10-700m2/g的表面积、0.1-4mL/g的孔体积和约10-1000埃的孔径。无机氧化物优选为氧化铝、二氧化硅、二氧化钛、氧化锆、氧化铌、钽氧化物、钼氧化物、钨氧化物、稀土氧化物(特别是二氧化铈或钕氧化物)，或其任何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、二氧化铈-氧化锆或氧化铝-二氧化铈-氧化锆，并且也可以为沸石。PGM包括铂、钯和铑的一种或多种。紧联式催化剂也可以包含其它金属或金属氧化物。
在另一个有用的实施方案中，排气系统也可以优选包括常规氧化催化剂组分和本发明的三元催化剂。在该配置中，排气系统优选包含阀门或其它气体-引导装置，使得在冷启动时期期间(低于约150-220℃的温度，如在三元催化剂处测量的)引导排气气体来在流动至常规氧化催化剂组分之前接触三元催化剂。一旦后处理装置(一种或多种)达到操作温度(约150-220℃，如在三元催化剂处测量的)，然后重新引导排气气体流来在接触三元催化剂之前接触常规氧化催化剂组分。也可以将颗粒过滤器添加至该旁通系统。例如，U.S.Pat.No.5,656,244(其教导通过引用方式并入本文)教导了用于在冷启动和常规操作条件期间控制排气气体的流动的方式。
常规氧化催化剂组分优选为常规TWC催化剂，其包含用TWC层涂覆的基材。基材通常为整料基材，并且优选陶瓷基材或金属基材，并且优选为流通式基材，但是也可以为过滤式基材。TWC催化剂层优选包含负载的铂族金属催化剂，所述负载的铂族金属催化剂包含一种或多种铂族金属(“PGM”)和一种或多种无机氧化物载体，如以上描述的。
以下实施例仅展示了本发明。本领域技术人员将认识到本发明的精神和权利要求的范围之内的多种变体。
实施例1：制备本发明催化剂
催化剂1A：挤出β沸石上的Ag+Pd-Rh层
用硝酸银水溶液浸渍β沸石整料(通过将β沸石挤出成蜂窝状整料形成，并且包含55％的β沸石；参见，例如，U.S.Pat.Nos.5,492,883、5,565,394和5,633,217)，随后干燥并且通过在500℃下加热4小时来煅烧以实现150g/ft3的Ag负载量。
然后用常规TWC层涂覆Ag/β沸石整料，所述常规TWC层由氧化铝和二氧化铈-氧化锆混合氧化物组成，作为用于Pd和Rh的载体。Pd负载量为76.5g/ft3并且Rh负载量为8.5g/ft3。干燥负载的涂覆基材，并且通过在500℃下加热4小时来煅烧。
实施例2：对比催化剂制备
对比催化剂2A：挤出β沸石+Pd-Rh层
根据与催化剂1A相同的流程制备对比催化剂2A，除了用银浸渍挤出β沸石。
对比催化剂2B：堇青石基材+Pd-Rh层
根据与催化剂1A相同的流程制备对比催化剂2B，除了使用Ag/β沸石整料替代堇青石基材整料。
实施例3：实验室测试流程和结果
对流通式催化剂涂覆基材的芯样品(2.54cm x 8.4cm)测试所有催化剂。测试了新鲜催化剂和老化催化剂两者。将催化剂芯在流通条件下在炉中在水热条件(5％的H2O，余量空气)下在800℃下老化80小时。然后测试芯的实验室反应器中的烃吸附，所述测试使用通过调整个体排气气体组分的质量流制备的进料气体物流。气体流速维持在21.2L min-1下，使得气时空速为30,000h-1(GHSV＝30,000h-1)。
在650℃下在2250ppm的O2、10％的CO2、10％的H2O和余量氮的气体流中在冷却至室温之前预处理催化剂。在预处理之后，催化剂经历HC吸附步骤，其中使催化剂与含HC气体接触30秒，所述含HC气体由以下组成：1500ppm(C1基)的HC(17体积％的甲苯、24体积％的异戊烷和59体积％的丙烯)、1000ppm的NO、1000ppm的CO、2250ppm的O2、10％的H2O、10％的CO2和余量氮。然后，HC吸附步骤之后是HC解吸时期，其中催化剂经受由200ppm的(C1基)HC、300ppm的O2、10％的H2O、10％的CO2和余量氮组成的解吸气体。
对新鲜和老化催化剂来说的吸附时期和氧化时期期间的HC排放的结果以及除去的总HC显示在表1中。
实施例4：发动机测试流程
对2.4L汽油车辆评估实施例1A和对比实施例2A和2B的完全尺寸的催化剂。在各个测试中，将商业Pd-Rh TWC催化剂以紧联式位置放置在实施例催化剂的上游。CCC TWC催化剂在前区中包含405g/ft3的Pd和15g/ft3的Rh，并且在后区中包含105g/ft3的Pd和15g/ft3的Rh。使用峰值在800℃的实施例催化剂床温度将各个系统老化150小时。FTP 75测试方案下，系统的尾管总HC(THC)排放显示在表2中。相比于两个对比实施例，催化剂1A除去了额外4mg/英里的THC。
结果显示在表2中。
表1：NOx储存能力结果
*对比实施例
表2：发动机测试结果，显示了总烃(THC)排放
催化剂 累积尾管THC(mg/英里)
1A 10
2A* 14
2B* 14
*对比实施例。

Claims (9)

1.三元催化剂，其包含：(1)含银挤出沸石基材，其中所述含银挤出沸石基材包含1-700g/ft3的银；和(2)布置在含银挤出沸石基材上的催化剂层，其中所述催化剂层包含负载的铂族金属催化剂，所述负载的铂族金属催化剂包含一种或多种铂族金属和一种或多种无机氧化物载体。
2.根据权利要求1所述的三元催化剂，其中所述沸石选自β沸石、八面沸石、L-沸石、ZSM沸石、SSZ-沸石、AEI骨架沸石、丝光沸石、菱沸石、菱钾沸石、毛沸石、斜发沸石、硅质岩、铝磷酸盐沸石、中孔沸石及其混合物。
3.根据权利要求1或2所述的三元催化剂，其中所述沸石选自β沸石、ZSM-5、SSZ-33、Y-沸石及其混合物。
4.根据权利要求1或2所述的三元催化剂，其中所述一种或多种铂族金属选自铂、钯、铑及其混合物。
5.根据权利要求1或2所述的三元催化剂，其中所述一种或多种铂族金属为钯和铑。
6.根据权利要求1或2所述的三元催化剂，其中所述一种或多种无机氧化物载体选自氧化铝、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、钨氧化物及其混合氧化物或复合氧化物。
7.根据权利要求1或2所述的三元催化剂，其中所述挤出沸石基材为流通式基材。
8.用于内燃机的排气系统，其包括根据权利要求1-7中任一项所述的三元催化剂。
9.权利要求8的排气系统，其进一步包括：选择性催化还原催化剂系统；颗粒过滤器；选择性催化剂还原过滤器系统；NOx吸附剂催化剂；或其组合。
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