CN106457144A - 用于还原氮氧化物的scr方法和生产用于该方法的催化剂的方法 - Google Patents

用于还原氮氧化物的scr方法和生产用于该方法的催化剂的方法 Download PDF

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Publication number
CN106457144A
CN106457144A CN201580022605.3A CN201580022605A CN106457144A CN 106457144 A CN106457144 A CN 106457144A CN 201580022605 A CN201580022605 A CN 201580022605A CN 106457144 A CN106457144 A CN 106457144A
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Prior art keywords
catalyst
molecular sieve
active component
component
zeolite
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CN201580022605.3A
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Inventor
J·鲍尔
S·洛佩斯-奥罗斯科
J·W·明奇
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Johnson Matthey PLC
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Johnson Matthey PLC
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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • 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
    • B01D53/9404—Removing only nitrogen compounds
    • B01D53/9409—Nitrogen oxides
    • B01D53/9413—Processes characterised by a specific catalyst
    • B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
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    • F01N3/2066—Selective catalytic reduction [SCR]
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Abstract

一种通过选择性催化还原(SCR)来还原内燃机废气中的氮氧化物的方法，其包括使还含有氨和氧的该废气与催化转化器接触，该催化转化器包含催化剂(2)，该催化剂(2)包含至少一种结晶小孔分子筛催化活性组分(ZM,I)，该结晶小孔分子筛催化活性组分(ZM,I)具有8个四面体基本构成部件的最大环开口，该结晶小孔分子筛催化活性组分(ZM,I)包含中孔。

Description

用于还原氮氧化物的SCR方法和生产用于该方法的催化剂的 方法
本发明涉及一种通过选择性催化还原(SCR)来还原内燃机废气中的氮氧化物的方法，该方法包括将还含有氨和氧的废气与包含催化剂的催化转化器接触，以及涉及一种生产用于这样用途的催化剂的方法。
还原来自于固定的和移动的燃烧系统，更具体地机动车辆情况中的废气中的氮氧化物，使用已知的选择性催化还原(SCR)方法来完成。这包括在氨和氧存在下将氮氧化物还原成氮。用于加速这种反应的各种催化剂类型和体系原则上是已知的。最近受到关注，尤其是用于机动车辆中的移动应用的一类催化剂是基于结晶分子筛的催化剂，更具体地基于沸石的催化转化器。在此特别值得提及的催化活性组分包括铁交换的或铜交换的沸石。
分子筛，更具体地沸石，具有特定的形态和相对于体积的高微孔性，并且结果具有比较大的表面积，这使得它们适于压实安装。催化活性依靠引入铜或铁离子来获得。
目前用于机动车辆中的催化转化器通常是催化剂载体涂层(washcoat)，其涂覆在惰性陶瓷基底，尤其是蜂窝陶瓷基底上。
可选地，现代催化转化器可以是挤出的陶瓷催化剂，典型地为蜂窝体的形式。在运行中，待清洁的废气流过涂覆的基底或挤出催化剂体中的通道。
这里在所谓的全活性挤出物和涂覆的载体(称作“载体涂层”)之间存在着基本的区别。在全活性挤出物的情况中，挤出体包含催化活性催化剂材料，这意味着催化剂的单个通道壁完全由催化活性材料形成。在载体涂层的情况中，催化惰性的、挤出的载体体涂覆有实际的催化活性催化剂材料。这通常通过将挤出的载体体浸入含有催化剂材料的悬浮液中来进行。
为了生产挤出的催化剂体，通常提供陶瓷挤出组合物，它的流变性能已经设定来适于挤出方法。这种挤出配混物是塑性的(即容易成形或可模制)物质。为了设定所需的流变性能，通常将粘结剂或添加剂添加到挤出配混物中。
在全活性挤出物的情况中，催化活性组分存在于挤出组合物中。在基于例如二氧化钛/五氧化二钒体系的常规催化剂的情况中，粘结剂分数通常是几个重量百分比，例如2-8重量％。
但是，当沸石用作催化活性组分时，挤出更难以进行，因为沸石相对难以挤出。另一问题还在于基于沸石的催化剂体系降低的机械稳定性。由于此，与二氧化钛/五氧化二钒体系相比，必须使用明显更高的粘结剂分数，来设定适于挤出的流变性能以及来实现足够的机械稳定性。
但是，作为其的结果，催化活性组分的量相对于整个催化剂整体上减少，并且作为增加的粘结剂分数的结果，整体结果是比催化活性/单位体积减少。
术语“粘结剂”在此总体上指的是在烧结操作后赋予最终生产的陶瓷催化剂以强度和稳定性的组分。这种粘结剂具体地形成到催化活性组分的烧结桥，或者带来这些组分之间机械互连。
关于催化剂，目标原则上是使催化活性最大化，换言之，使NOx转化率的水平尽可能高。这个目标关键是催化活性材料和待清洁的废气之间极有效的接触。催化转化最主要是在废气流过的具体的流动通道的壁上的近表面区中进行。结果，尤其是在全活性挤出物蜂窝催化剂的情况中，其中整个挤出体由催化活性材料组成，并且催化剂材料的相当大体积区域保持未用于NOx转化。
在结晶分子筛，更具体地沸石，用作催化活性组分的情况中，这些组分的多孔性意味着在表面附近存在着催化剂可利用的非常大的表面积。但是，尤其是在所谓的小孔沸石的情况中，尤其是与在μm范围的高晶体尺寸相组合时，例如要清洁的废气更难以达到沸石深处的体积区域。
通常在所谓的小孔、中孔、宽孔和超宽孔分子筛之间存在不同。这种分类是基于孔的孔宽度，该孔宽度是气体分子从外面可到达的。这种孔宽度通过分子筛的环结构的环开口的直径来定义。合适的结晶分子筛具有开放孔或孔通道，其通过分子筛例如沸石的通常四面体基本构成部件的环结构来形成和分隔。“小孔”指的是最大环开口通过包含8个这样的基本构成部件的环来形成的孔结构。“中孔”和“宽孔”指的是最大环开口通过分别10-12个基本构成部件的环来形成的孔结构。超宽孔具有通过多于12个基本构成部件来形成的环开口。在目前已知的沸石中，最大环尺寸在于具有24个基本构成部件的环结构。在8块环的情况中，换言之在小孔沸石的情况中，孔宽度通常仅是约0.3nm，和在中孔沸石的情况中是约0.5nm。
基于此，本发明所解决的问题是确定一种通过使用基于具有良好催化活性的分子筛的催化剂，尤其是挤出的SCR催化剂的选择性催化还原(SCR)，来还原内燃机废气中的氮氧化物的方法。
该问题根据本发明，通过具有权利要求1的特征的方法来解决。催化剂具体采用SCR催化剂的形式，用于降低氮氧化物的水平。催化剂具有至少一个小孔、微孔催化活性组分。这种催化活性小孔组分包含通过具体的碱后处理所引入的中孔。
制造具有8个四面体基本构成部件的最大环开口和通过碱处理引入的中孔的结晶小孔分子筛催化活性组分(ZM,I)的方法是现有技术中已知的，例如US2012/0258852A1、US2011/0118107A1和US2013/0299389A1(其全部内容在此通过参考引入)。
中孔在此理解为根据IUPAC(国际理论和应用化学联合会)命名，孔宽度是2-50nm的孔。催化活性组分是初始态时，换言之在引入中孔之前，是微孔的组分。所以这种组分具有宽度通过具有最大8个基本构成部件的环开口来限定的孔的孔结构。在这种情况中孔结构根据IUPAC命名是微孔的，所以孔直径低于2nm。
原则上，以及小孔孔结构，微孔组分还可以具有更大的孔结构，即中孔或宽孔结构。但是优选地，小孔组分表示整个孔结构仅由不多于8块环孔形成的组分。仅作为处理是引入中孔的结果，其形成了孔宽度大于微孔的所谓的“流动通道”，并且其确保待清洁的废气改进的扩散，包括它扩散进入催化剂组分深处的层中。所以作为这种措施的结果，利用催化活性组分的更大的体积区域，因此改进了整体催化活性。
除了待清洁的废气达到催化剂内的活性腔室之外，在此还可能的是，作为这种达到性改进的一个结果是改进的NH3吸收和存储。这里存储在瞬时条件下，换言之在载荷变化的内燃机的情况中，特别重要。
在初始条件中，小孔组分通常由尺寸是几μm至几十μm的颗粒的粉末组成。单个颗粒在此表现出微孔性，并且最大孔宽度至多是约1nm。
中孔通过小孔组分的微孔晶体的碱后处理引入。用于引入中孔的程序的一个例子如下：
将起始沸石(为Na形式、H形成或已经离子交换的Cu形式)悬浮于0.2M的NaOH溶液中1小时，并且固体/液体比是0.05g/ml和温度是60℃，然后过滤，用去离子水清洗和在室温干燥12小时。为了获得催化活性形式，在这种碱处理之后是另外的处理步骤(例如铵交换、铜交换等)。
小孔催化活性组分更具体地包含结晶分子筛，优选沸石。术语“结晶分子筛”在此具体指的是较窄含义的沸石，即指的是结晶铝硅酸盐。另外采用结晶分子筛来还包括其他分子筛，其不是铝硅酸盐，但是其具有沸石骨架结构，如从国际沸石协会的结构委员会(IZA-SC)的沸石图谱所显见的。这具体地涉及到硅铝磷酸盐(SAPO)或铝磷酸盐(ALPO)，其同样包括在前述沸石图谱中。
优选分子筛通常包含金属活化剂(促进剂)。这尤其是铜或铁或铈或其混合物。更具体地，分子筛尤其是已经用这类金属离子交换的分子筛，更具体地是沸石。作为金属离子因此引入到骨架结构中的离子交换的分子筛的一个替代，还存在这些金属活化剂不引入到骨架结构中的可能性，和因此也就是说作为“游离”金属或金属化合物(例如金属氧化物)而存在于分子筛的单个通道中，其例如是用含有该化合物的溶液浸渍分子筛的结果。另一可能性是分子筛中的离子交换的金属和游离金属化合物的组合。
已经用催化活性金属离子进行交换的这类金属筛的催化活性特别好。将中孔引入小孔分子筛中的具体优点之一被认为是改进了离子交换，换言之金属离子插入到分子筛的骨架结构中，因为这些离子也能够经由中孔更容易地渗入体积中。对于铁离子来说尤其如此，其与铜离子相比具有更大的直径，因此几乎不能引入到小孔分子筛的骨架结构中。
替代地或组合地，可以用作小孔分子筛的是具有骨架类型CHA、AEI、AFX或ERI的分子筛。这些骨架类型具有最大8个基本构成部件的环开口。另外地或替代地，使用具有骨架类型AFR或AFS的沸石是优选的。这些类型以及8块环结构也具有更大的孔开口。
现在提及分子筛，更具体地沸石，通常被理解为指的是根据国际沸石协会的结构委员会(IZA-SC)的沸石图谱的分子筛。此处所用的命名追溯到沸石图谱中所用的命名。
小孔催化活性组分的分数优选为50-95重量％的范围，基于最终制作的、烧结的陶瓷催化剂体的总重量计。
另外，催化剂有用地具有无机粘结剂组分。这种组分一方面充当沸石颗粒之间的结合连接，来确保在烧结方法本身之后机械上坚固的催化剂。此外，粘结剂组分允许在挤出的催化剂的情况中有效的挤出能力。
这种无机粘结剂组分的分数优选是5-50重量％，更具体地是10-35重量％。除了活性组分，更具体地沸石，和粘结剂部分之外，还可以存在另外的残留组分例如纤维或其他挤出助剂等，但是这样的组分的分数优选不大于10重量％。
一种示例性催化剂组合物例如如下：
组分 分数(重量％)
Cu离子交换的CHA沸石 60
Al2O3和粘土 31
玻璃纤维 9
相对高的无机粘结剂分数的效果具体地是允许有效的挤出能力和同时产生高强度。考虑到这种相对高的无机粘结剂分数，为了进一步保持催化活性，在一个有用的方案中，对初始态时无催化活性的无机粘结剂组分进行催化活化。在初始态中，粘结剂组分由无催化活性的粉末颗粒组成。通过具体的处理，这些颗粒被给予催化活性，因此对催化剂的整体活性起作用。
为此目的，根据第一优选的实施方案，单个颗粒具有催化活性涂层。替代地或另外地，催化活化还通过将粉末颗粒的骨架结构至少部分的转化成沸石骨架结构，并且保持它们的颗粒形式来完成。“保持它们的颗粒形式”在此表示仅进行纳米结构范围，即高至1nm的范围内的变化，而保持了较大的结构，例如颗粒中的基本颗粒形式或中多孔性或大多孔性。
粘结剂组分的颗粒有用地是多孔的，并且具体地具有中多孔性或大多孔性，并且孔宽度是2-50nm(中多孔)或孔宽度大于50nm(大多孔)。类似于引入沸石中的中孔，粘结剂组分的多孔颗粒带来待清洁的废气的有效质量传输，包括进入催化剂深层的层中。
将催化活化的粘结剂颗粒用于催化转化器描述在与本申请人同时提交的DE102014205760.4，标题为“Process for producing a catalyst and catalyst”的德国专利申请中。该申请目前完全参考，并且它的公开内容在此引入。
粘结剂组分的颗粒尤其是粘土矿物或硅藻土或二氧化硅。硅藻土已经由于它的高多孔性表现出是特别合适的。硅藻土还具体地用于至少部分的转化成沸石。在转化成沸石后，优选另外地还进行金属离子交换，来产生离子交换的沸石，更具体地铁交换的或铜交换的沸石，其具有良好的催化活性。
已经表现为合适的另一材料是柱撑粘土矿物，其特征在于通过无机柱间隔开的粘土层。为了催化活化，优选将催化活性中心引入单个粘土层之间的间隙中。
催化剂优选为挤出的催化剂，更具体地蜂窝催化剂的形式。因此对于它的生产来说，提供一种可挤出的、糊状的催化剂材料，其包含催化剂的不同组分，然后通过挤出来由其形成催化剂体，更具体地蜂窝体，和随后干燥和烧结。
根据一种形式，这种催化剂体用催化活性涂层来涂覆，其与挤出体相同或不同。这类涂层例如作为活性涂层来施用，如DE102012213639A1(其全部内容在此通过参考引入)所述。更具体地，所讨论的催化剂是挤出的SCR蜂窝催化剂。根据一个替代的实施方案，不施用涂层。
在一个优选的实施方案中，挤出的催化剂，更具体地挤出的蜂窝催化剂，采用了所谓的壁流式过滤器的形式，其中废气在运行中流过多孔壁。相反，流通式整料(其同样经常采用陶瓷蜂窝催化剂的形式)具有在纵向上被用于废气的流动通道渗透的催化剂体。壁流式过滤器的开发通过对多孔性的合适调节来完成。这类壁流式过滤器例如描述在DE102011010106A1(其全部内容在此通过参考引入)中。
催化剂优选采用SCR催化剂的形式，因此具有用于所需的deNOx反应的催化活性。
但是，此处所述的概念不限于用于SCR催化剂。这种概念原则上适于全部类型的催化转化器，用于改进催化活性的目的。
更具体地，该催化剂构成了例如所谓的烃阱，更具体地没有另外的催化涂层。这类催化转化器也称作冷启动催化剂，因为由于它们存储烃的能力，它们控制了内燃机启动阶段过程中废气中的HC分数。一种这样的冷启动催化剂描述在例如WO2012/166868A1(其全部内容在此通过参考引入)中。这类催化剂具体采用了具有结晶分子筛的挤出的蜂窝催化剂的形式，还尤其是采用了这类分子筛与贵金属，更具体地例如是钯(Pd)的混合物的形式。贵金属在此也可以与贱金属一起添加到沸石。研究显示，钯浸渍的结晶分子筛，尤其是没有铁时，同样表现出冷启动催化剂所需的性能。这样的冷启动催化剂例如表现出良好的NOx存储和转化能力以及在低温对于N2的高选择性，在低温良好的烃存储能力和转化率，和改进的一氧化碳氧化活性。
作为这些烃阱形式的优选未涂覆的挤出的催化剂的替代，催化剂采用具有烃阱品质的涂覆的、挤出的蜂窝催化剂的形式。催化剂在这种情况中具有结晶分子筛，优选例如H+形式和更具体地“未金属化的”，即没有金属活化剂。可选地，结晶分子筛包含钯和/或银。在这种形式中，这类挤出的蜂窝体具有催化活性涂层，更具体地用于形成柴油氧化催化剂或三元催化剂，或者已经经历了到壁流式过滤器的转化，其随后涂覆有氧化催化剂来将它转化成所谓的催化型烟灰过滤器(CSF)，类似于柴油氧化催化剂。三元催化剂的一个例子公开在WO2011/092517A1(其全部内容在此通过参考引入)中，挤出的柴油氧化催化剂以及挤出的催化型烟灰过滤器的一个例子公开在例如WO2011/092519(其全部内容在此通过参考引入)中。
此外，催化剂还可以采用板型催化剂的形式，或者例如挤出的粒料形式的散装材料，或者一些其他形式。
除了通过引入中孔来处理小孔催化活性组分之外，原则上可以存在另外的催化活性组分作为催化体系的一部分。所讨论的体系在该情况中优选是基于贱金属的非沸石体系。
根据第一形式，催化剂在这种情况中是基于钛-钒的催化剂，并且钒作为催化活性组分。总之，在不同的形式中，使用不同的钛-钒体系。具体使用的是二氧化钛(TiO2)和五氧化二钒(V2O5)的混合物的氧化体系。可选地，钛-钒体系包含钒-铁化合物作为催化活性组分，具体地包含钒酸铁(FeVO4)和/或钒酸铁铝(Fe0.8Al0.2VO4)。这样的安排公开在WO2014/027207A1(其全部内容在此通过参考引入)中。
在氧化体系的情况中，它们更具体地是钛-钒-钨体系、钛-钒-钨-硅体系、钛-钒-硅体系。在具有钒-铁化合物的第二组的情况中，它们是钛-钒-钨-铁体系、钛-钒-钨-硅-铁体系或钛-钒-硅-铁体系。
钛/钒重量比(Ti/V)在此有用地是35-90。在氧化的钛-钒体系的情况中，二氧化钛与五氧化二钒的重量比(TiO2/V2O5)典型地是20-60。
根据基于贱金属的催化体系的第二形式中，将氧化钨-氧化铈体系或稳定化的氧化钨-氧化铈体系(WO3/CeO2)用于催化体系。稳定化的钨/铈体系更具体地包含含有Ce-锆混合氧化物的锆稳定化的体系。分散在这类载体材料中的过渡金属，更具体地铁是优选的。所用的过渡金属更具体地选自Cr、Ce、Mn、Fe、Co、Ni、W和Cu，更具体地选自Fe、W、Ce和Cu。
催化体系更具体地包含Fe-W/CeO2或Fe-W/CeZrO2体系，尤其是如涉及WO2009/001131(其全部内容在此通过参考引入)的图3所述。过渡金属在催化剂中的分数在这种情况中例如是0.5-20重量％，基于催化剂的总重量计。
问题进一步根据本发明，通过具有权利要求14的特征的生产催化剂的方法来解决。与催化剂相关所述的优点和优选的实施方案还可以进行必要的修正来用于所述方法。
根据在这种情况中的一个优选的实施方案，在第一步中，提供了将中孔引入小孔组分中，换言之，更具体地引入小孔沸石中，并且然后仅对于催化活性金属离子，更具体地铜离子或铁离子，通过离子交换引入骨架结构中来形成催化活性腔室。在离子交换程序之前形成中孔促进和简化了随后的离子交换程序，生产改进的、更均匀的插入金属离子和因此改进了催化活性。
在金属离子交换的沸石的生产中，通常进行多个生产步骤。在沸石合成中，首先获得碱起始形式(Na+形式)，其中将Na+离子引入晶格结构中。沸石通常接着转化成中间体阶段，尤其是转化成所谓的铵形式(NH4 +)，或者通过进一步的随后温度处理(煅烧)转化成H+形式，然后用例如铜离子或铁离子进行离子交换。
在用于引入中多孔性的碱处理中，铵或H+形式至少部分地转化回Na+起始形式。为了引入铜离子或铁离子，根据第一优选的选项，沸石首先在引入中多孔性之后转化成铵形式或H+形式，然后进行铜或铁离子交换。
但是，研究已经显示，Na+起始形式的钠离子和铜金属或铁金属离子之间的直接离子交换更好。因此，在第二形式中，优选省略产生铵形式或H+形式的中间步骤，并且在引入中孔之后直接进行与催化活性金属离子的金属离子交换，而不插入到铵形式或H+形式的转化。
有用的是早在提供沸石起始粉末的过程中放弃Na+初始形式的转化。通过这种手段，可以降低生产成本。
在一个有用的实施方案中，在方法中，首先提供可成形的催化剂材料，更具体地作为挤出配混物。随后由这种配混物形成成形体，更具体地具有用于待清洁的废气的流动通道的挤出的蜂窝体。仅在这种成形体形成后将中孔引入小孔沸石中。在这种情况中具体的优点可以视作，作为结果，中孔已经具有优先的方向，通过流动通道和催化剂材料之间的界面定向进入催化剂材料的体积。结果，以特别有效的方式，产生用于待清洁的废气的粗孔流动通道，进入催化剂材料的体积中。这个的整体结果是改进了催化剂体积内的活性腔室的可达性。使用这种形式，优选在引入中孔之后进行金属离子交换，来获得更有效的阳离子分布。
中孔的引入和随后的离子交换因此可选地在沸石的初始粉末态或在加工态进行，例如作为具有沸石的挤出的蜂窝体。
本发明的工作实施例在下面使用两幅图来更详细地说明，其以图示形式说明了以两种不同形式来生产催化剂的方法。
在两种形式中，挤出的SCR蜂窝催化剂2作为完全制造的烧结体来生产。在两种情况中，从不同的起始组分，首先提供了可挤出的催化剂材料E，并且挤出成具有流动通道6的蜂窝体4。在干燥后，将蜂窝体烧结来形成完全制作的催化剂2。在两种方法形式中，催化剂2由催化活性的、离子交换的和具有中孔的小孔沸石ZM,I，和催化活化的粘结剂组分BA，以及当需要时另外的固体组分R组成。
下标M和I在此表示具有引入的中孔(下标M)以及离子交换的沸石(下标I)的小孔沸石，在这种情况中，具体地，铜离子或铁离子已经引入微结构中。粘结剂组分B的下标A表示粘结剂组分B的单个颗粒是催化活化的。
沸石ZM,I优选包含具有骨架类型CHA的沸石。
替代地或组合地，作为小孔沸石，使用骨架类型AEI/ERI的沸石。替代地或另外地，使用骨架类型AFX、AFR和/或AFS的沸石。
优选用作粘结剂组分BA的是催化活化的硅藻土。催化活化在这种情况中具体地通过将微结构部分地或完全地转化成沸石微结构来完成，优选是与用作活性组分的沸石ZM,I相同的类型。
粘结剂组分BA不需要必需是催化活化的。研究已经表明,通过简单地引入多孔粘结剂组分B例如硅藻土，尽管伴随着催化活性材料量的减少，催化剂的催化活性(给定相同的整体重量)至少是恒定的，因为粘结剂组分B的中多孔性或大多孔性能够改进到催化剂材料内的活性中心的可达性。
在根据图1的形式中，还没有离子交换或具有中孔的小孔沸石Z，被初始用作起始材料。这种沸石通常为粉末形式。在第一处理阶段，将中孔以所述方式引入这个小孔沸石中，产生具有中孔的小孔沸石ZM。最后，以本身已知的方式进行离子交换，其中铜离子具体地引入骨架结构中，产生粉末形式的具有中孔的离子交换的沸石ZM,I。
粘结剂组分B在初步步骤中催化活化，产生催化活化的粘结剂组分BA。这种组分与具有中孔的离子交换的小孔沸石Z和任选地与包含例如无机多孔填料或纤维部分的残留部分R的混合物合并来形成可挤出的配混物E。唯一的随后步骤是挤出来形成蜂窝体4，和最后干燥和烧结来形成催化剂2。
在根据图2的形式中，中孔的形成和金属离子交换仅在挤出之后进行，或者通常在由催化剂材料成形为催化剂体之后进行。因此在载体涂层的情况中，这些步骤将直到将催化剂材料施用到惰性载体上之后才进行。
因此，没有离子交换和还不具有中孔的小孔沸石Z与在这个工作实施例中没有活化的粘结剂组分B以及当需要时与部分R一起合并来形成可挤出的配混物E，和随后挤出来产生蜂窝体4。在随后的方法步骤中，所生产的蜂窝体4进行了碱处理，将沸石Z转化成具有中孔的沸石ZM。这之后是金属离子交换，产生具有中孔的离子交换的沸石ZM,I的所需状态。此后，进行烧结来产生完全制作的催化剂2。
在这种情况中特别的优点可以在中孔始于流动通道6的事实中看见，因此具有规定的优先取向。结果，在随后的配置中，使得废气更有效地进入催化剂材料的体积成为可能。
本发明还可以根据以下中的一种或多种来定义：
1.催化剂(2)，尤其是SCR催化剂，其包含至少一种小孔的、微孔催化活性组分(ZM,I)，这种小孔催化活性组分(ZM,I)包含通过碱处理引入的中孔。
2.根据1的催化剂(2)，该小孔的、微孔催化活性组分是分子筛，更具体地是沸石(ZM,I)。
3.根据2的催化剂(2)，该分子筛包含金属活化剂，并且更具体地是离子交换的沸石(ZM,I)。
4.根据2或3的催化剂(2)，作为小孔催化活性分子筛(ZM,I)的替代或与之组合，使用具有骨架结构CHA、AEI、ERI或AFX的分子筛。
5.根据1-4中任一项的催化剂(2)，其中该小孔的、微孔催化活性组分(ZM,I)的分数是50-95重量％。
6.根据1-5中任一项的催化剂(2)，其包含无机粘结剂组分(B，BA)。
7.根据6的催化剂(2)，其中该无机粘结剂组分(Β，ΒΑ)包含多孔颗粒。
8.根据6或7的催化剂转化器(2)，其中该无机粘结剂组分(BA)是催化活化的。
9.根据8的催化剂(2)，其中该无机粘结剂组分(BA)包含涂覆有催化活性层或者至少部分地转化成沸石骨架结构的颗粒，并且保持它们的颗粒形式。
10.根据1-9中任一项的催化剂(2)，其是挤出的催化剂的形式，更具体地是蜂窝催化剂或壁流式过滤器。
11.生产催化剂(2)，更具体地根据1-10中任一项的催化剂的方法，该催化剂包含小孔催化活性组分(ZM,I)，通过碱处理将中孔引入该小孔组分(ZM,I)中。
12.根据11的方法，其中将分子筛，更具体地是沸石(ZM,I)用作小孔活性组分。
13.根据12的方法，其中在通过离子交换引入该中孔之后，将催化活性金属离子引入该小孔组分中来形成催化活性腔室。
14.根据13的方法，其中分子筛在该中孔引入之后可选地直接金属离子交换，或者首先转化成中间体形式，然后进行金属离子交换。
15.根据11-14中任一项的方法，其中提供可成形的催化剂组合物(E)，并且具体地通过挤出来形成成形体(4)，并且仅在形成该成形体(4)之后引入该中孔。
附图标记列表
2 催化剂
4 蜂窝体
6 流动通道
Z 小孔沸石
ZM 具有中孔的小孔沸石
ΖΜ,Ι 具有中孔和离子交换的小孔沸石
B 粘结剂组分
BA 催化活化的粘结剂组分
R 残留组分

Claims (17)

1.通过选择性催化还原(SCR)来还原内燃机废气中的氮氧化物的方法，该方法包括使还含有氨和氧的该废气与催化转化器接触，该催化转化器包含催化剂(2)，该催化剂(2)包含至少一种结晶小孔分子筛催化活性组分(ZM,I)，该结晶小孔分子筛催化活性组分(ZM,I)具有8个四面体基本构成部件的最大环开口，该结晶小孔分子筛催化活性组分(ZM,I)包含中孔。
2.根据权利要求1所述的方法，其中该至少一种结晶小孔催化活性组分是铝硅酸盐沸石、硅铝磷酸盐分子筛或铝磷酸盐分子筛(ZM,I)。
3.根据权利要求1或2所述的方法，其中该分子筛包含促进剂金属。
4.根据权利要求3所述的方法，其中该结晶分子筛用促进剂金属离子交换。
5.根据权利要求3或4所述的方法，其中该促进剂金属是铁或铜。
6.根据前述权利要求中任一项所述的方法，其中该结晶分子筛是骨架结构CHA、AEI、ERI或AFX中的一种或多种。
7.根据前述权利要求中任一项所述的方法，其包含无机粘结剂组分(Β，ΒΑ)。
8.根据权利要求7所述的方法，其中该无机粘结剂组分(Β，ΒΑ)包含多孔颗粒，该多孔颗粒具有孔宽度为2-50nm的中多孔性或孔宽度大于50nm的大多孔性。
9.根据权利要求7或8所述的方法，其中该无机粘结剂组分(BA)是催化活化的。
10.根据权利要求9所述的方法，其中该无机粘结剂组分(BA)包含涂覆有催化活性层或者转化成沸石骨架结构的颗粒，并且保持它们的颗粒形式。
11.根据前述权利要求中任一项所述的方法，其为挤出的催化剂形式，或者其中该催化剂作为载体涂层存在于催化惰性的、挤出的支撑体上。
12.根据权利要求11所述的方法，其中该挤出的催化剂为蜂窝催化剂或壁流式过滤器的形式。
13.根据权利要求11或12所述的方法，其中该结晶小孔分子筛催化活性组分(ZM,I)的分数为50-95重量％，基于最终制作的、烧结的陶瓷催化剂体的总重量计。
14.生产用于根据前述权利要求中任一项的方法中的挤出的成形体的方法，该挤出的成形体包含催化剂(2)，该催化剂(2)包含至少一种结晶小孔分子筛催化活性组分(ZM,I)，该结晶小孔分子筛催化活性组分(ZM,I)具有8个四面体基本构成部件的最大环开口，该结晶小孔分子筛催化活性组分(ZM,I)包含中孔，该方法包括制备可挤出的组合物，该组合物包含至少一种结晶小孔分子筛催化活性组分(ZM,I)和具有8个四面体基本构成部件的最大环开口，将可挤出的组合物挤出成成形体，并且通过碱处理将中孔引入该成形体中的该至少一种结晶小孔分子筛中。
15.根据权利要求14所述的方法，其中在引入该中孔后，将催化活性促进剂金属离子引入该结晶小孔分子筛组分中来形成催化活性腔室。
16.根据权利要求15所述的方法，其中在引入该中孔后，将该分子筛直接进行金属离子交换，或者首先转化成中间体形式，然后进行金属离子交换。
17.根据权利要求15或16所述的方法，其中该促进剂金属是铁或铜。
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