CN103842076A - 挤出蜂窝状催化剂 - Google Patents

挤出蜂窝状催化剂 Download PDF

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Publication number
CN103842076A
CN103842076A CN201280038515.XA CN201280038515A CN103842076A CN 103842076 A CN103842076 A CN 103842076A CN 201280038515 A CN201280038515 A CN 201280038515A CN 103842076 A CN103842076 A CN 103842076A
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China
Prior art keywords
catalyst
honeycombed
carrier
washcoat
zeolite
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Pending
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CN201280038515.XA
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English (en)
Inventor
G·R·钱德勒
N·R·科林斯
R·多特泽尔
J·W·曼奇
P·R·菲利普斯
G·斯迈德勒
A·P·沃尔克
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Johnson Matthey PLC
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Johnson Matthey PLC
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Priority claimed from GB201202182A external-priority patent/GB201202182D0/en
Application filed by Johnson Matthey PLC filed Critical Johnson Matthey PLC
Priority to CN201510809671.7A priority Critical patent/CN105363497A/zh
Priority to CN201910444285.0A priority patent/CN110193363A/zh
Publication of CN103842076A publication Critical patent/CN103842076A/zh
Pending legal-status Critical Current

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    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
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    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust 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
    • F01N3/18—Exhaust 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
    • F01N3/20—Exhaust 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
    • F01N3/2066—Selective catalytic reduction [SCR]
    • F01N3/208—Control of selective catalytic reduction [SCR], e.g. dosing of reducing agent
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    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
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Abstract

一种挤出蜂窝状催化剂，用于在来自机动车的废气中根据选择性催化还原(SCR)方法的氮氧化物还原，该催化剂包含蜂窝体形式的挤出活性载体和活化涂层，该挤出活性载体包含第一SCR催化活性组分并具有操作过程中废气所流经的多个通道，该活化涂层包含被施用到挤出体的第二SCR催化活性组分的，其中第一SCR催化活性组分和第二SCR催化活性组分各自独立地选自由以下组成的组：(i)钒作为催化活性组分的钒催化剂；(ii)具有一种或多种氧化物的混合氧化物催化剂，特别是过渡金属或镧系元素作为催化活性组分的氧化物；以及(iii)铁-或铜-沸石催化剂。

Description

挤出蜂窝状催化剂
本发明涉及一种挤出蜂窝状催化剂，特别用于废气净化，特别是在机动车领域，其中特别用于根据选择性催化还原(SCR)方法的氮氧化物还原，即，使用含氮还原剂的氮氧化物还原。本发明还涉及一组这种不同形式的蜂窝状催化剂和制备蜂窝状催化剂的方法。
挤出蜂窝状催化剂为整体的、整块的物体，其具有多个操作过程中废气流经的通道。这些通道具有的只有几毫米的开口宽度。限定各通道的网还典型地具有仅300μm的宽度。在固体材料具有催化活性的挤出蜂窝状催化剂中，高体积比例的固体由催化活性组分组成。其结果是，催化剂组分的任何改变，例如以适应不同的要求和通常追求精细化，都对可挤出性有关键影响。总之，对于固体材料具有催化活性并且非常昂贵的挤出蜂窝状催化剂来说，这将产生新的研发阶段。
WO2010／099395A1公开了挤出蜂窝状催化剂体及其制造方法。催化剂体包括选自由氧化钨、氧化钒及其组合组成的组中的第一氧化物，选自由氧化铈、氧化镧、氧化锆及其组合组成的组中的第二氧化物，和沸石。在一个实施方案中，挤出的沸石芯上涂有一层氧化铈、氧化锆和氧化钨的混合物。
在此基础上，本发明基于所详述的蜂窝状催化剂的问题，该该蜂窝状催化剂可以以低开发成本而适应新要求。
根据本发明，该问题由权利要求1解决。根据该权利要求，该蜂窝状催化剂作为整体由蜂窝状形式的挤出活性载体形成，其具有至少一种催化活性组分，并在其上另外施涂有催化活性涂层，特别是活化涂层(washcoatcoating)，其同样具有至少一种催化组分。
根据本发明，该问题进一步由一组蜂窝状催化剂解决，这些催化剂在功能性方面不同，但它们都有相同的载体，并且通过用于制备这种类型的蜂窝状催化剂的方法制备。
该实施方案基于这样的想法：研发和提供一种载体，其可以广泛用于几种应用领域，并通过特殊的活化涂层具体适应相应的需求。将从以下事实看出具体的优点：无需研发和提供不同的挤出物料用于不同的蜂窝状催化剂。同时，由于活性载体和同样具有催化活性的涂层之间的不同组合的选择，可以酌情调整和设计整体催化活性。原则上，这首先提供了研发催化剂的选择，为了在技术上优化的功能性，或者替代地为了在成本方面优化的催化剂。尤其是为了实现后者，相比于常规的催化活性的固体挤出物，降低了载体中催化活性组分的比例。
也能够提高催化剂的SCR活性，其另对气体组成敏感，例如NO2：NO的比例(参见EP1147801中的Fe／ZSM-5(MFI)SCR)。
优选实施方案由从属权利要求可知。
载体和活化涂层都形成为SCR催化剂。特别地，有三种不同类型的已知催化剂在本发明中使用：
-以下称为钒催化剂的催化剂，其中钒作为催化剂活性组分。这通常包含作为主要成分的氧化钒、氧化钛和氧化钨。在常规催化活性的固体挤出物中，这些具有催化活性的主要组分的体积比例是约75至85体积％。
-第二种类型的催化剂是混合氧化物催化剂，其中一种或多种氧化物或镧系元素作为催化活性组分。通常使用的金属氧化物是，例如氧化铈、氧化锆或氧化钨，其在常规催化剂具有约75至85％的体积比例。这种类型的混合氧化物催化剂通常不含沸石并且也不含钒。
-作为第三种SCR催化剂类型，金属-沸石催化剂是已知的，具有金属沸石作为催化活性组分。尤其是是铁-沸石或铜-沸石。在这种类型的沸石催化剂中，常规固体挤出物中的这些活性组分的体积比例在约60至70％的范围内。
固体挤出物的其余部分由非催化活性组分组成，如粘合剂，必要时的填充剂以增加强度，以及可选的增塑剂以在挤压过程中支承。
有利地，载体中活性组分的体积比例低于传统的固体挤出物催化剂，其中该比例在上述上限的范围内。总而言之，载体中的体积比例可从10体积％至上述的上限值调节。然而，特别地，设定低于50体积％或者10至60或10至40％的范围。因此，在一些不同的实施方案中，催化剂的更大体积比例由非活性组分形成。
在催化活性比例降低的不同的实施方案中，催化活性比例优选由相对于挤压过程为中性的组分代替。这意味着，这些是容易挤出的物料和／或材料。特别地，这些包括粘土(这意味着晶粒直径小于2μm的片状硅酸盐)、氧化铝或高岭土。
根据本发明的蜂窝状催化剂，特别是第二SCR催化剂活化涂层，至少在前部区域不含贵金属。在优选的实施方案中，将贵金属涂层，特别是作为活化涂层施涂后部(在操作中从废气的流动方向观察)区域。这用于防止氨滑逸(slip)。因此后部区域形成了所谓的ASC催化剂(氨滑逸催化剂)。
有益地，该贵金属涂层由此以夹层形式嵌入在载体和在整个长度延伸的活化涂层之间，这尤其是作为SCR催化剂实施。也就是说，将含贵金属的活化涂层作为层直接施涂在载体上，并且第二SCR催化剂活化涂层施涂在挤出活性载体的整个长度，包括含有贵金属的活化涂层。这种布置的优点在于，滑逸过第一和第二SCR催化剂的上游区域的氨可在下部的贵金属层被氧化成NOx，随后该NOx经过第二SCR催化层离开催化剂结构并接触进入的氨，从而使NOx在第二SCR催化剂上还原成N2。
对于所有变化的实施方案，活化涂层具有相对高的孔隙率，从而使待净化的废气也与催化活性载体相接触。
为了达到良好的催化活性，载体也具有高孔隙率。载体和活化涂层通常都具有约40至80m2／g范围内的大的BET表面积。
活化涂层的层厚优选在30至100μm的范围内，特别是在约40至60μm的范围内。有利地，只有单一的活化涂层施加到载体上。因为载体也是活性的，多层活化涂层不是必需的，并且优选不提供。但它是可能的。
特别地，当固体挤出物中催化活性固体挤出物的活性组分比例降低时，蜂窝状结构体的网的网宽度可以减小。由催化活性固体挤出物制成的常规挤出蜂窝状催化剂中，网宽度在约300μm的范围内。其优选降低到约150至220μm的范围内，特别是约180μm的范围内。
利用载体上的活性活化涂层的原理，可根据要求设计不同的活性蜂窝状催化剂，以满足不同的需要。
这些不同的组合考虑了各个催化剂的各种利弊，优选以增加优点和降低缺点的方式结合。因此，从经济观点看，各个催化剂首先其价格不同。例如，铜-沸石催化剂是最昂贵的，而钒催化剂是最便宜的。相对于它们的技术特性，在整个温度范围内的NOx活性特别重要，即在低温和高温下的NOx还原能力。此外，耐硫性和尤其是耐NO2性特别重要。最后，不同材料的温度稳定性也有关。
根据计划的用途，以下优选的组合可能性是合适的：
a)载体为具有活化涂层的混合氧化物催化剂的实施方案，其可为Fe-或Cu-沸石催化剂。此处的混合氧化物催化剂的优点在于它的低存储容量，特别是氨储存容量。氨通常作为典型的还原剂用于SCR方法。这使得简单给料成为当前需求的功能。混合氧化物催化剂在较高温度范围内显示出缺点，这由活化涂层补偿。相反，在较低温度范围内，它相比于Fe-沸石更好，所以总体而言，实现了在整个温度范围内提高活性。
b)将由钒催化剂制成的活化涂层施用于由混合氧化物催化剂制成的载体。钒催化剂的优点在于它良好的耐硫性，而这恰恰相反是混合氧化物催化剂的缺点。相反，混合氧化物催化剂在较低温度下具有更高的活性。可以看出混合氧化物催化剂的另一优点在于它良好的耐NO2性。
c)将由铜-沸石制成的活化涂层施用于由Fe-沸石制成的载体。铁沸石良好的耐硫性补充了铜沸石在较低温度范围内非常好的活性。并且，这种类型的组合特别耐NO2，因为当废气中NO2水平中等和高时，铁具有特别好的活性，而当废气中NO2水平低时，铜具有非常好的活性。
d)将Fe-沸石作为活化涂层施用于Cu-沸石。这里，适用如前述组合的相同优点。
e)将钒催化剂作为活化涂层施用于作为载体的Fe-沸石。这种组合提高了耐硫性和高的耐NO2性，因为当废气中NO2水平高时，铁-沸石催化剂有高活性，与钒催化剂相反。
f)相同催化剂的组合，例如Fe-沸石催化剂和Fe-沸石催化剂。这增加了整体的催化活性。
g)将Fe-沸石催化剂施用于由钒催化剂制成的载体。这实现了基于宽范围的NO2／NOx比例的非常好的活性。
这里描述的原理，即与活性活化涂层组合提供活性载体，因此在本发明的方法中得以体现。因而，为了生产具有不同特性的蜂窝状催化剂，根据应用的领域，供给和保存随后提供的具有不同活化涂层的载体类型。
根据另一方面，提供一种用于车辆贫燃内燃机的排气系统，其包括位于其流动管道中的本发明的挤出蜂窝状催化剂。
在一个实施方案中，排气系统包括用于将含氮还原剂或其前体注入到挤出蜂窝状催化剂上游的废气中的机构。
根据本发明的另一方面，提供了一种贫燃内燃机，其包括根据本发明的排气系统，该排气系统包括用于在挤出蜂窝状催化剂上游的废气中原位产生NH3的催化剂，和用于将废气组成改变为在用来原位产生NH3的催化剂上促进原位NH3的组成的控制机构。
在一个实施方案中，用于在挤出蜂窝状催化剂上游的排气中原位产生NH3的催化剂为柴油氧化催化剂或NOx吸收催化剂，并特别地包含铂族金属，优选还包含镧系元素，优选为任选与一种或多种稳定剂(例如氧化锆和／或稀土元素)组合的铈。
根据另一方面，提供了一种包括本发明的排气系统或本发明的贫燃内燃机的车辆。
为了可以更全面地理解本发明，仅以例示方式并参考附图提供下面的实施例，其中：
图1示出本发明的挤出蜂窝状催化剂在各种温度下的NOx转化活性，该挤出蜂窝状催化剂包括挤出活性载体，该挤出活性载体包含由WO3／CeO2-ZrO2第二SCR催化剂活化涂覆的V2O5／WO3／TiO2或Fe-ZSM-5(MFI)沸石第一SCR催化剂，相比于第二SCR催化剂涂覆在惰性堇青石蜂窝体上并且挤出活性载体没有第二SCR催化剂涂层；
图2示出本发明的挤出蜂窝状催化剂在各种温度下的NOx转化活性，该挤出蜂窝状催化剂包括挤出活性载体，该挤出活性载体包含由Cu-SAPO-34(CHA)第二SCR催化剂活化涂覆的Fe-ZSM-5(MFI)沸石第一SCR催化剂，相比于第二SCR催化剂涂覆在惰性堇青石蜂窝上并且挤出活性载体没有第二SCR催化剂涂层；
图3示出本发明的挤出蜂窝状催化剂在各种温度下的NOx转化活性，该挤出蜂窝状催化剂包括挤出活性载体，该挤出活性载体包含由Cu-SSZ-13(CHA)第二SCR催化剂以两种不同的活化涂层负载量活化涂覆的Fe-β沸石第一SCR催化剂，相比于相同负载量的第二SCR催化剂涂覆在惰性堇青石蜂窝上并且挤出活性载体没有第二SCR催化剂涂层；以及
图4示出本发明的挤出蜂窝状催化剂在各种温度下的NOx转化活性，该挤出蜂窝状催化剂包括挤出活性载体，该挤出活性载体包含由Cu-SSZ-13(CHA)第二SCR催化剂以两种不同的活化涂层负载量活化涂覆的V2O5／WO3／TiO2第一SCR催化剂，相比于相同负载量的第二SCR催化剂涂覆在惰性堇青石蜂窝上并且挤出活性载体没有第二SCR催化剂涂层。
实施例
实施例1-包含第一SCR催化剂的蜂窝体形式的挤出活性载体的制备
实施例1A-含有Fe-β沸石的挤出活性载体
将粉末状市售氢型β沸石与氧化铁(Fe2O3)、玻璃纤维、高岭土、粉末状合成勃姆石和增塑剂聚环氧乙烷(2.25重量％)以及油酸(1.62重量％)(均基于100％的总无机固体含量)混合，并在pH值为5-6的水溶液中加工为可成形和可流动的浆(slip)。当混合物充分塑化时，加入基于100％的总无机固体含量的2.25重量％的纤维素。选择起始材料的数量比例，以使制成的固体催化剂体的活性物质含有70.34重量％的沸石、铁和铁化合物；2.76重量％的高岭土；15.94重量％的γ-Al2O3；和4.84重量％的玻璃纤维。将可成形的混合物挤出成流通式蜂窝状催化剂体，即具有连续通道和圆形横截面，其显示出400cpsi(每平方英寸的单元数)的单元密度。随后，根据WO2009／080155(其全部内容在此引入作为参考)中描述的方法将催化剂体在2毫巴下冷冻干燥1小时，并在580℃的温度下焙烧以形成固体催化剂体。据发现，通过使用所描述的方法，至少一些引入到所述混合物中的铁开始与沸石离子交换。
实施例1B-含有V 2 O 5 ／WO 3 ／TiO 2 的挤出活性载体
将粉末状市售的10重量％钨的含钨TiO2与玻璃纤维、高岭土、低碱性粘土填料和粉末状合成勃姆石偏钒酸铵：1.88重量％；2-氨基乙醇：1.5升；乳酸90％：0.48重量％；氨25％：8.97重量％和增塑剂聚环氧乙烷(0.86重量％)以及油酸(0.14重量％)(均基于100％的总无机固体含量)混合，并在pH值为5-6的水溶液中加工为可成形和可流动的浆。当混合物充分塑化时，加入基于100％的总无机固体含量的0.86重量％的纤维素。选择起始材料的数量比例，以使制成的固体催化剂体的活性物质含有约72重量％的V2O5／WO3／TiO2；二氧化硅1.20重量％；高岭土2.85重量％；粘土2.85重量％；和玻璃纤维6.93重量％。将可成形的混合物挤出成流通式蜂窝状催化剂体，即具有连续通道和圆形横截面，其显示出400cpsi(每平方英寸的单元数)的单元密度。随后，根据WO2009／080155(其全部内容在此引入作为参考)中描述的方法将催化剂体在2毫巴下冷冻干燥1小时，并在580℃的温度下焙烧以形成固体催化剂体。
实施例1C-含有Fe-ZSM-5(MFI)沸石的挤出活性载体
选择离子交换的合成ZSM-5沸石作为沸石，其中的活性物质含有5重量％的铁。将粉末状ZSM-5沸石与玻璃纤维和粉末状合成勃姆石混合，并在pH值为3.5的醋酸水溶液中通过纤维素和油酸和聚乙二醇增塑剂的混合物加工为可成形和可流动的浆。选择起始材料的数量比例，以使制成的固体催化剂体的活性物质含有75重量％的含有铁和铁化合物的沸石；11.8重量％的γ-Al2O3和8重量％的玻璃纤维。将可成形的混合物挤出成流通式蜂窝状催化剂体，即具有连续通道和圆横截面，其显示出400cpsi(每平方英寸的单元数)的单元密度。
随后，将催化剂体在90℃的温度下干燥，并在600℃的温度下煅烧形成固体催化剂体。
实施例2-包含第二SCR催化剂的活化涂层组合物的制备
制造新鲜的3重量％铜/沸石的方法(实施例2A和2B)
将市售的SAPO-34(CHA)(实施例2A)和SSZ-13(CHA)(实施例2B)在NH4NO3溶液中与NH4 +离子交换，然后过滤。将所得到的材料搅拌加入到Cu(NO3)2的水溶液。将浆料过滤，然后洗涤和干燥。可以重复该过程，以获得所需的金属负载量。对最终产物进行焙烧。
实施例2C-制造WO x ／CeO 2 -ZrO 2 的方法
通过初始润湿浸渍方法制备包含承载在含有50∶50重量％的氧化铈和氧化锆的氧化铈-氧化锆混合氧化物上的15重量％的钨的催化剂，该方法包括溶解足够的偏钨酸铵以在去离子H2O中提供所需的15重量％的W负载量。溶液的总体积等于载体样品的孔体积(初始润湿技术)。将溶液加入混合氧化物载体材料，并将得到的混合物在105℃干燥整夜，然后在700℃进行3小时煅烧。
实施例3-挤出蜂窝状催化剂的制备
在实施例1的挤出活性载体上用活化涂层进行涂覆，该活化涂层包含实施例2的第二SCR催化剂，使用了WO99／47260中的方法，即包括步骤：(a)在挤出活性载体基底上面设置容纳机构，(b)投加预定量的液体组分到所述容纳机构，按照(a)然后(b)或者(b)然后(a)的顺序，以及(c)通过施加压力或真空，将所述液体组分引入挤出活性载体基底的至少一部分，并保持基本上所有所述量在挤出活性载体基底内。然后将涂覆的挤出活性载体在100℃下在空气中干燥1小时，并在500℃下煅烧2小时。
制备挤出活性载体和活化涂层的下列组合。
表1
Figure BPA0000186410210000081
实施例5-合成催化性能测试
从实施例3的各个挤出蜂窝状催化剂切割2.54cm×14cm的芯，并且催化剂在稳态并在如下温度点在稳态下进行测试：180℃、215℃、250℃、300℃、400℃和500℃，测试在合成催化活性测试实验装置中使用以下合成气体混合物：O29.3％；H2O7.0％；NOx100ppm(仅NO)；NH3100ppm；余量N2(活塞排量：60.000升／小时)。
包括比较数据的结果示于图1至4。
图1示出实施例3A和3B与以下相比较的结果：以400cpsi以3.4g／in3负载量涂覆在惰性堇青石蜂窝状载体上的相同活化涂层组分(即实施例2C)；和实施例1B和1C的挤出催化剂载体本身。从结果中可以看出，实施例3A和3B在整个温度范围内表现出提高的NOx转化性能。
图2示出实施例3C与以下相比较的结果：以400cpsi以1.8g／in3负载量涂覆在惰性堇青石蜂窝状载体上的相同活化涂层组分(即实施例2A)；和实施例1C的挤出催化剂载体本身。从结果中可以看出，在测试的200-500℃的温度范围内具有积极效果。
图3示出实施例3D1和3D2与以下相比较的结果：以400cpsi以1.5g／in3和0.5g／in3负载量涂覆在惰性堇青石蜂窝状载体上的相同涂层组分(即实施例2B)；和实施例1A的挤出催化剂载体本身。从结果中可以看出，实施例3D1和3D2在<300℃和>400℃表现出提高的NOx转化性能。
图4示出实施例3E1和3E2与以下相比较的结果：以400cpsi以1.5g／in3和0.5g／in3负载量涂覆在惰性堇青石蜂窝状载体上的相同涂层组分(即实施例2B)；和实施例1B的挤出催化剂载体本身。从结果中可以看出，实施例3E1和3E2在>400℃表现出提高的NOx转化性能。
为避免任何疑问，本文中引用的所有文件的全部内容在此整体引入作为参考。

Claims (28)

1.一种挤出蜂窝状催化剂，用于在来自机动车的废气中根据选择性催化还原(SCR)方法的氮氧化物还原，该催化剂包含蜂窝状形式的挤出活性载体和活化涂层，该挤出活性载体包含第一SCR催化活性组分并具有操作过程中废气所流经的多个通道，该活化涂层包含被施用到挤出体的第二SCR催化活性组分，其中第一SCR催化活性组分和第二SCR催化活性组分各自独立地选自由以下组成的组：
(i)钒作为催化活性组分的钒催化剂；
(ii)具有一种或多种氧化物的混合氧化物催化剂，特别是过渡金属或镧系元素作为催化活性组分的氧化物；以及
(iii)铁-或铜-沸石催化剂。
2.根据权利要求1的蜂窝状催化剂，其中在挤出催化剂载体中，
-钒催化剂具有体积比为10至85％的氧化钒、氧化钛、氧化钨作为活性主要成分，
-混合氧化物催化剂包含体积比为10至85％的特别是镧系元素或过渡金属的混合氧化物作为主要组分，特别是氧化铈，氧化锆和氧化钨，并且不含沸石和钒，
-金属沸石催化剂包含体积比为10至70％的Fe-沸石或Cu-沸石，
其中，各种情况中剩余部分均由无催化活性的组分形成，例如粘合剂、所需的填料和，当活性组分减少时对于挤出过程为中性的组分。
3.根据权利要求1或2的蜂窝状催化剂，其中挤出载体中活性组分的比例与常规的未涂覆的挤出蜂窝状催化剂相比减少，并且特别是在10至60体积％的范围内，优选在10至40体积％的范围内。
4.根据权利要求1、2或3的蜂窝状催化剂，其中催化活性组分与常规的未涂覆的蜂窝状催化剂相比所减少的比例被对于挤出过程为中性的组分，特别是粘土代替。
5.根据任何前述权利要求的蜂窝状催化剂，其中中性组分的比例在10至70体积％的范围内，特别是在20-50体积％的范围内。
6.根据任何前述权利要求的蜂窝状催化剂，其中活化涂层至少在相对于操作过程中废气流动方向的前部区域不含贵金属。
7.根据任何前述权利要求的蜂窝状催化剂，其中载体具有相对于操作过程中废气流动方向的后部区域，其上优选有贵金属涂层以防止氨滑逸。
8.根据权利要求7的蜂窝状催化剂，其中活化涂层延伸在载体的整个长度上，并覆盖贵金属涂层，特别是在后部区域。
9.根据任何前述权利要求的蜂窝状催化剂，其中活化涂层和特别是载体也具有高的孔隙率，特别是BET表面积在约40-80m2／g的范围内。
10.根据任何前述权利要求的蜂窝状催化剂，其中活化涂层的层厚在30至100μm，特别是在约40-60μm的范围内。
11.根据任何前述权利要求的蜂窝状催化剂，其中蜂窝状结构体具有网，并且网宽度与常规的未涂覆的挤出蜂窝状催化剂相比减小，特别是在约150-220μm的范围内。
12.根据任何前述权利要求的蜂窝状催化剂，其中挤出催化剂载体为混合氧化物催化剂，并且活化涂层为金属-沸石催化剂，特别是Fe-或Cu-催化剂。
13.根据权利要求1至11任一项所述的蜂窝状催化剂，其中挤出催化剂载体是混合氧化物催化剂，并且活化涂层是钒催化剂。
14.根据权利要求1至11任一项所述的蜂窝状催化剂，其中挤出催化剂载体是Fe-沸石催化剂，并且活化涂层是Cu-沸石催化剂。
15.根据权利要求1至11任一项所述的蜂窝状催化剂，其中挤出催化剂载体是Cu-沸石催化剂，并且活化涂层是Fe-沸石催化剂。
16.根据权利要求1至11任一项所述的蜂窝状催化剂，其中挤出催化剂载体是Fe-沸石催化剂，并且活化涂层是钒催化剂。
17.根据权利要求1至11任一项所述的蜂窝状催化剂，其中挤出催化剂载体和活化涂层由相同的催化剂形成，特别是均为Fe-沸石催化剂的形式。
18.根据权利要求1至11任一项所述的蜂窝状催化剂，其中挤出催化剂载体和活化涂层由相同的催化剂形成，特别是均为Cu-沸石催化剂的形式。
19.根据权利要求1至11任一项所述的蜂窝状催化剂，其中挤出催化剂载体和活化涂层由相同的催化剂形成，特别是均为钒催化剂的形式。
20.根据权利要求1至11任一项所述的蜂窝状催化剂，其中挤出催化剂载体和活化涂层由相同的催化剂形成，特别是均为具有一种或多种氧化物的混合氧化物催化剂的形式，特别是过渡金属或镧系元素作为催化活性组分的氧化物。
21.根据权利要求1至11任一项所述的蜂窝状催化剂，其中载体是钒催化剂，并且活化涂层是Fe-沸石催化剂。
22.多种具体化的根据任何前述权利要求的挤出蜂窝状催化剂的组，其中组中的所有蜂窝状催化剂具有相同的载体。
23.根据任何前述权利要求的蜂窝状催化剂的制造方法，其中提供相同具体化的载体并用不同的活化涂层涂覆。
24.一种用于车辆贫燃内燃机的排气系统，其包括设置在其流动管道中的根据权利要求1至21任一项所述的挤出蜂窝状催化剂。
25.根据权利要求24的排气系统，其包括用于将含氮还原剂或其前体注入到挤出蜂窝状催化剂上游的废气中的机构。
26.一种贫燃内燃机，其包括根据权利要求24的排气系统，该排气系统包括在挤出蜂窝状催化剂上游的排气中原位产生NH3的催化剂，和用于将废气组成改变为在用来原位产生NH3的催化剂上促进原位NH3的组成的控制机构。
27.根据权利要求26的贫燃内燃机，其中在挤出蜂窝状催化剂上游的废气中原位产生NH3的催化剂为柴油氧化催化剂或NOx吸收催化剂。
28.一种车辆，其包括根据权利要求24或25所述的排气系统，或者根据权利要求26或27所述的贫燃内燃机。
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