CN105980050A - 催化转化剂 - Google Patents

催化转化剂 Download PDF

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Publication number
CN105980050A
CN105980050A CN201580008084.6A CN201580008084A CN105980050A CN 105980050 A CN105980050 A CN 105980050A CN 201580008084 A CN201580008084 A CN 201580008084A CN 105980050 A CN105980050 A CN 105980050A
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CN
China
Prior art keywords
catalytic conversion
conversion agent
component
catalytic
agent
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Pending
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CN201580008084.6A
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English (en)
Inventor
J·鲍尔
R·多特泽尔
J·W·约德劳克
R·勒佩尔特
J·W·明奇
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Johnson Matthey PLC
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Johnson Matthey PLC
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Priority to CN201910414024.4A priority Critical patent/CN109999794A/zh
Publication of CN105980050A publication Critical patent/CN105980050A/zh
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Abstract

为了赋予催化转化剂(2)，特别是SCR催化转化剂以最大催化活性，这种催化转化剂具有至少一种催化活性组分(V)和另外的至少一种具有中孔性或大孔性的多孔无机填料组分(F)。该有机多孔填料组分(F)的比例是约5‑50重量％。更具体地，将硅藻土或柱撑粘土材料用作该多孔无机填料组分(F)。

Description

催化转化剂
本发明涉及一种催化转化剂，特别是SCR催化转化剂。
降低来自于固定式和来自于移动式燃烧系统二者，特别是机动车辆的废气中氮氧化物水平，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不同的催化转化剂类型和系统原则上是已知的。一种公知种类的催化转化剂基于钛-钒催化转化剂体系。这类钛-钒催化转化剂被用于固定式系统和移动式燃烧系统二者。最近成为关注焦点的另一类催化转化剂，特别是用于机动车辆中的移动式应用，是沸石基催化转化剂。这些催化活性组分更具体地包括所谓的铁或铜交换的沸石，优选是ZSM-5(MFI)、β(BEA)或菱沸石(CHA)类型。
目前机动车辆中所用的催化转化剂主要是陶瓷蜂窝体催化转化剂。例如，在运行中，待清洁的废气流过挤出的催化转化剂的通道。
一个基本的不同存在于所谓的全活性挤出物和涂覆的载体(称作“载体涂层(washcoat)”)之间。在全活性挤出物中，催化活性催化剂材料形成挤出体，这意味着该催化转化剂的通道壁完全由催化活性材料形成。在载体涂层中，催化惰性的挤出的载体涂覆有实际的催化活性催化剂材料。这例如通过将挤出的载体浸入包含催化剂材料的悬浮液中来进行。
原则上，目标是催化转化剂中最大的催化活性，即最大NOx转化率。
用于最大NOx转化率的一个关键因素是待清洁的废气和催化活性材料之间非常好的接触。催化转化率在废气流过其中的各流动通道壁处的接近表面区域中进行到临界程度。特别是在其中整个挤出体包含催化活性材料的全活性挤出物蜂窝体催化剂的情况中，这种效果是催化剂材料的相当大体积区域保持未用于NOx转化。
为此，本发明的一个目标是明确一种具有改进的催化活性的催化转化剂，特别是SCR催化转化剂。
该目标根据本发明，通过催化转化剂，特别是SCR催化转化剂来实现，该催化转化剂具有至少一种催化活性组分和另外地具有至少一种多孔无机填料组分(其具有至少中孔性或大孔性)。中孔性被理解为表示孔尺寸为至少2到不大于50nm的孔，和大孔性表示孔尺寸大于50nm的孔(IUPAC定义)。
因此“至少中孔性”通常被理解为表示填料组分的孔隙率具有大于2nm的孔。这种填料组分更具体地至少还包括或只具有微孔，和因此是多微孔的。另外，填料组分还可以具有大孔。最后，填料组分还可以只具有尺寸大于50nm的孔，即不表现出任何微孔性。
填料组分是这样的材料，其在初始态时是粉状的，并且包含粒度为几微米到几十微米的颗粒，例如1μm-100μm。该颗粒本身是多孔的。
这类多孔填料组分的添加实现了特别的效果，即与例如具有不大于1nm的孔的仅微孔性的沸石相比相对大的孔，也实现了待清洁的废气在催化转化剂体积内改进的扩散。总之，这实现了催化剂材料更好的开发，并且该催化剂材料下面的层也有效地对催化作用起作用，特别是对NOx还原。
总之，令人惊讶地实现了催化转化剂的高催化活性，即使另外的填料组分降低了催化活性组分的重量比例。因此，通过多孔填料组分改进了基于催化活性组分比例的特定的催化活性。
另一特别重要的因素是填料组分是无机填料组分，其甚至在烧结操作之后保留在最终的陶瓷催化转化剂中，和因此还对催化转化剂的机械稳定性产生了至关重要的贡献。相反，有机挤出助剂在烧结操作过程中挥发，和结果也会产生一定的多孔性水平。总之，这类多孔无机填料组分的添加实现了改进的催化活性和相同或甚至改进的催化转化剂的机械稳定性。这是特别重要的，特别是在全活性挤出物的情况中。
催化转化剂典型地由通常多种基础组分和多孔填料组分组成。这里催化活性组分是基础组分之一。并且这种催化活性组分，特别是用于机械稳定性的粘结剂组分和任选的纤维也用作基础组分。基础组分以相对于彼此的规定比率存在。与仅含有基础组分，该基础组分的比率与具有多孔填料组分的催化转化剂相同的对比催化转化剂相比，在适当的构造中，该具有多孔填料组分的催化转化剂具有至少相当和特别是相同或甚至更好的每单位催化转化剂体积的催化活性。
给定相同总重量的具有多孔填料组分的催化转化剂和对比催化转化剂，两种催化转化剂因此具有至少相当的催化活性。每单位所用单位催化剂材料的催化活性因此通过多孔填料组分而改进。这至少适用于例如约400℃的温度范围，其中用于NOx转化的催化转化剂典型地在机动车辆中运行。因此，用较低比例的催化活性组分实现了相同的催化活性。所以，相同的催化活性需要较低的催化活性材料。这实现了显著的成本节约。添加多孔填料材料还降低了催化转化剂的比重。
这种多孔填料组分的比例优选是5-50重量％，和特别是10-25重量％，在每种情况中基于最终的催化转化剂的总质量计。所以，相当大的质量比例被多孔填料组分替代。这里可以使用多种不同的多孔填料组分。其总比例在5-50重量％，和特别是10-25重量％的所述重量范围内。
在一种优选的构造中，至少一种多孔填料组分是粘土材料。这里合适地使用柱撑粘土材料(PILC)。这种粘土材料通常具有被无机柱隔开的二维粘土层。该柱例如由氧化钛或氧化铝组成。
在一种替代的构造中，至少一种多孔无机填料组分是硅藻土。后者确保了高孔隙率。研究已经显示，使用硅藻土作为填料材料实现了其余催化剂材料和催化活性组分的特别有效的开发。
对于所用的催化转化剂，不同的催化转化剂体系原则上是已知的。催化转化剂体系在此理解为表示部分地产生催化活性的组分体系。
在第一优选的组中，催化转化剂包括基于贱金属的催化的、非沸石的体系。
在第一实施方案变体中，这里的催化转化剂是基于以钒作为催化活性组分的钛-钒的催化转化剂。
总之，在不同的实施方案变体中，使用不同的钛-钒体系。更具体地，使用包含二氧化钛(TiO2)和五氧化二钒(V2O5)的混合氧化物的氧化物体系。可选地，钛-钒体系包含钒-铁化合物作为催化活性组分，其具体包含钒酸铁(FeVO4)和/或钒酸铁铝(Fe0.8Al0.2VO4)。
在氧化物体系的情况中，它们特别是钛-钒-钨体系、钛-钒-钨-硅体系、钛-钒-硅体系。在包含钒-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)适当地在35-90的范围内。在氧化物钛-钒体系的情况中，二氧化钛和五氧化二钒之间的重量比(TiO2/V2O5)典型地是20-60。
钛-钒体系典型的重量比例是70-90重量％，基于最终的催化转化剂计。其余的10-30重量％在多孔无机填料组分和粘结剂组分，以及可能的纤维组分之间分配。
在基于贱金属的催化体系的第二变体中，氧化钨-氧化铈体系或稳定化的氧化钨-氧化铈体系(WO3/CeO2)被用于催化体系。
稳定化的钨/铈体系特别是锆稳定化的体系，其包含铈-锆混合氧化物。优选地，过渡金属，特别是铁，分布在这样的载体材料内。所用的过渡金属特别地选自Cr、Ce、Mn、Fe、Co、Ni、W和Cu，和特别地选自Fe、W、Ce和Cu。
催化体系特别是Fe-W/CeO2或Fe-W/CeZrO2体系，具体如涉及WO2009/001131的图3所述，其在此全部作为参考。过渡金属在催化转化剂中的比例优选是0.5-20重量％，基于催化转化剂的总重量计。
作为这类非沸石催化体系的替代，至少一种催化活性组分优选是结晶分子筛。“结晶分子筛”在此理解为具体表示狭义的沸石，即结晶铝硅酸盐。此外，结晶分子筛还理解为表示另外的分子筛，其不是铝硅酸盐，而具有沸石骨架结构，这从国际沸石协会的结构委员会IZA-Sc的沸石图谱可以清楚看出。更具体地，这涉及硅铝磷酸盐(SAPO)或铝磷酸盐(ALPO)，其同样包括在所述沸石图谱中。
本文上下文所用的催化活性组分具体是这样的分子筛，其具有CHA骨架结构，特别是菱沸石、AEI，特别是ALPO 18、ERI、MFI、BEA、FAU、AFX或FER(此处所用命名指的是沸石图谱中所用命名)。
在具有根据沸石图谱的骨架结构的结晶分子筛的情况中，通常在小孔、中孔和大孔结晶分子筛之间加以区分。小孔分子筛是最大孔开口具有包含8个四面体原子结构的环结构的沸石。中孔和大孔分子筛最后被理解为表示最大孔开口通过在四面体排列中具有不大于10(中孔)或不大于12(大孔)原子结构的环的环开口来形成。所述BEA骨架结构是大孔骨架结构，MFI是中孔结构，和CHA是小孔结构。所述FAU骨架结构同样是大孔结构，优选Y沸石。AEI是小孔骨架结构，优选在此给出的是使用具有SSZ-39命名的沸石。FER是中孔骨架结构，所用材料优选是镁碱沸石或ZSM-35。ERI是小孔结构，所用材料优选是毛沸石。AFX是小孔骨架结构，所用材料优选是SSZ-16。BEA、MFI和FAU骨架结构(这里特别是沸石Y)优选用作烃阱。所述的全部骨架结构和材料可以用作SCR催化转化剂；它们合适地通过金属来活化，特别是用铜和/或铁和/或铈离子交换，优选用铜或铁活化。
适当地，分子筛通常包含金属活化剂(促进剂)。这特别是铜、铁或铈或者其混合物。更具体地，分子筛是用这类金属离子交换的分子筛，特别是沸石。作为离子交换的分子筛(其中金属离子因此掺入骨架结构中)的替代，还可能的是这些金属活化剂没有掺入骨架结构中，和因此作为“游离”金属或金属化合物(例如金属氧化物)，在分子筛的单个通道中有效存在，例如作为用含有该化合物的溶液浸渍该分子筛的结果。另一种可能是离子交换的金属和游离金属化合物在分子筛中的组合。
此处所述的不同的催化体系选择性或组合来使用。更具体地，使用基于钛-钒的体系和结晶分子筛的混合物。这类混合的催化转化剂特别包含作为第一组分的铝硅酸盐或硅酸铁分子筛，其处于所谓的H+形式，或者已经用一种或多种过渡金属，特别是用铁进行了离子交换。第二组分是选自以下金属氧化物载体上的氧化钒：铝、钛、锆、铈、硅或其组合。更具体地，用于第二组分的载体材料是氧化钛。第一组分特别是铁交换的MFI、BEA或FER铝硅酸盐分子筛(沸石)。这个混合物中第一组分与第二组分的比率是5:95-约40:60。
与催化活性组分相反，多孔填料优选是无催化活性的，因此纯粹充当多孔填料材料。
如已经提及的，除了多孔填料组分之外，催化转化剂进一步包含粘结剂组分，在适当的构造中还在挤出材料情况中具有纤维组分。粘结剂组分和纤维的比例优选在每种情况中处于几个重量百分比的区间中，例如4-10重量％。
催化转化剂特别是挤出的催化转化剂，优选蜂窝体催化转化剂。在一个实施方案变体中，催化转化剂体已经涂覆有催化活性涂层，其与挤出体相同或不同。这类涂层已经例如作为载体涂层来施涂，如DE102012213639A1公开的。更具体地，催化转化剂是挤出的SCR蜂窝体催化转化剂。在一个替代的实施方案中，没有施涂涂层。
在一种优选的构造中，挤出的催化转化剂，特别是挤出的蜂窝体催化转化剂，采用了所谓的壁流式过滤器的形式，其中废气在操作中流过多孔壁。相反，流通式过滤器(其同样经常采用陶瓷蜂窝体催化转化剂的形式)在纵向上被用于废气的流动通道透过。壁流式过滤器的形成通过适当调节孔隙率来完成。这类壁流式过滤器描述在例如DE102011010106A1中。
催化转化剂优选采用SCR催化转化剂的形式，即具有对于所需脱NOx反应的催化活性。
但是，此处所述的包括引入至少中孔性的无机过滤器组分的理念不限于用于SCR催化转化剂。
这个理念原则上适于全部种类的催化转化剂，用于改进催化活性。
更具体地，催化转化剂例如是所谓的烃阱，特别是没有另外的催化涂层。这类催化剂也称作冷启动催化转化剂，因为它们控制了废气中的HC含量，这归因于它们在内燃机启动阶段过程中存储烃的能力。这类冷启动催化转化剂描述在例如WO2012/166868A1中。这类催化转化剂更具体地采用具有结晶分子筛的挤出的蜂窝体催化转化剂的形式，特别还是这样的分子筛与贵金属，特别是例如钯(Pd)的混合物。这种贵金属也可以与贱金属一起添加到沸石中。研究表明，钯浸渍的结晶分子筛，特别是没有铁，同样表现出冷启动催化转化剂的所需性能。这类冷启动催化转化剂表现出例如良好的NOx存储和转化能力，具有在相对低的温度对于N2的高选择性，良好的存储能力和烃在低温的转化，和改进的一氧化碳氧化活性。
作为这些优选的烃阱形式的未涂覆的挤出的催化转化剂的替代，催化转化剂采用了涂覆的、挤出的蜂窝体催化转化剂的形式，其具有充当烃阱的倾向。这种催化转化剂优选同样包含结晶分子筛，优选例如为H+形式和特别是“未金属化”的形式，即没有金属活化剂。作为替代选项，结晶分子筛包含钯和/或银。在这种实施方案变体中，这类挤出的蜂窝体具有催化活性涂层，特别是用于形成柴油氧化催化转化剂或三元催化转化剂，或者已经转化成壁流式过滤器，其随后用氧化催化转化剂涂覆，从而将它以类似于柴油氧化催化转化剂的方式转化成所谓的催化型烟灰过滤器(CSF)。三元催化转化剂的一个例子公开在WO2011/092517A1中，并且挤出的柴油氧化催化转化剂和挤出的催化型烟灰过滤器的一个例子公开在例如WO2011/092519中。
附图作为示例，显示了一种生产这类挤出的蜂窝体催化转化剂的方法。
为了生产挤出的蜂窝体催化转化剂2，通常首先提供一种可挤出的催化剂材料F，其中单个组分，即基础组分M和填料组分F，典型地作为粉状起始材料来提供，其彼此混合和加工以产生糊状催化剂材料E。通过挤出操作，随后产生了具有流动通道6的挤出的成形体4，并且在干燥操作之后，烧结来形成最终的陶瓷蜂窝体催化转化剂。
但是原则上，催化转化剂2不限于这类挤出的全活性挤出物蜂窝体催化转化剂。替代地，催化活性催化剂材料E已经例如作为在载体材料上的涂层来施涂。催化转化剂2因此替代地采用例如载体涂层或平板催化转化剂或挤出粒料的形式。特别有利的是在挤出的全活性催化转化剂中使用多孔填料组分F，因为在这些情况中具体地实现了催化剂材料在更深的催化剂层中特别有效的开发。
在第一实施方案变体中，优选采用全活性挤出物形式的催化转化剂包含作为基础组分M的约60-80重量％的二氧化钛，约1-2.5重量％的五氧化二钒，约4-14重量％的三氧化钨，适于作为粘结剂组分的约4-10重量％的粘土矿物，以及如果需要时例如4-10重量％的纤维，特别是玻璃纤维，以改进机械稳定性。这些基础组分在图中表示为缩写T、V、W、B、G。另外，多孔无机填料组分F也以约4-20重量％添加。
作为多孔填料组分F，具体使用硅藻土。作为纤维，使用例如纤维直径是6μm的无机玻璃纤维G。催化转化剂2特别地具有根据下表1的组成：
该表将不具有多孔填料组分F的对比催化转化剂与具有7.6重量％和13.6重量％比例的填料组分F的两种催化转化剂催化剂1和催化剂2进行了比较。
基础组分M通过组分A、B、G来形成，其中A表示催化活性体系，在这个情况中是氧化物的钛-钒-钨体系。基础组分相对于彼此的比率在全部情况中相同。活性体系本身在对比催化转化剂的情况中组成为约65-70重量％的TiO2，约8-11重量％的WO3和约1-3重量％的V2O5，基于整个组合物计。
将以此方式生产的，并且具有规定组成的挤出的催化转化剂催化剂1和催化剂2在催化活性方面与对比催化转化剂进行比较，除了无机填料组分F之外，对比催化转化剂在比例方面具有与基础组分M相同的组成，如根据该表的催化转化剂。
此处所测量的是在相同实验条件下，作为温度函数的NOx转化率。因此，将恒定的废气质量流速引导过催化转化剂2和引导过对比催化转化剂，用于给定的流速和规定的废气组成。氮氧化物含量在催化转化剂2上游和下游测量，并且这被用于获得转化率。结果显示在下表2中。
这个表报告了在不同的温度(在实验条件：400cpsi(孔/平方英寸)的蜂窝体催化转化剂；NOx＝NH3＝100ppm(NO2＝0ppm)；H2O＝7％；O2＝9.3％；SV(空速)＝60000h-1)，所测量的每单位蜂窝体体积(催化转化剂体积)的NOx转化率(XNOx/V)和每单位蜂窝体质量(催化转化剂质量)的NOx转化率(XNOx/M)
可见，催化转化剂催化剂1和催化剂2在与正常的催化转化剂操作相关的温度范围内，每个具有基于催化转化剂质量计比对比催化转化剂明显更高的NOx转化率，而基于催化转化剂体积计仅稍微的改进是明显的。在最佳的情况中，实现了基于催化转化剂质量计转化率20％的提高(催化剂2，500℃)。

Claims (18)

1.催化转化剂(2)，特别是SCR催化转化剂，其具有至少一种催化活性组分(V)和具有至少一种多孔无机填料组分(F)，其中该无机填料组分(F)具有至少中孔性。
2.根据权利要求1所述的催化转化剂(2)，其包含多个基础组分(M)和该多孔填料组分(F)，该催化活性组分(V)是该基础组分(M)之一，和该基础组分(M)以相对于彼此的规定比率存在，并且该催化转化剂(2)与该多孔填料组分(F)一起，具有与对比催化转化剂相比至少相同的催化活性，该对比催化转化剂没有填料组分(F)，和有其他方面相同的、具有相对于彼此的规定比率的基础组分(M)。
3.根据权利要求1或2所述的催化转化剂(2)，其中该无机多孔填料组分(F)在5-50重量％的范围内，特别是10-25重量％的范围内。
4.根据前述权利要求中任一项所述的催化转化剂(2)，其中该至少一种多孔填料组分(F)是粘土材料。
5.根据前述权利要求中任一项所述的催化转化剂(2)，其中该至少一种多孔填料组分(F)是柱撑粘土材料。
6.根据前述权利要求中任一项所述的催化转化剂(2)，其中该至少一种多孔填料组分(F)是硅藻土。
7.根据前述权利要求中任一项所述的催化转化剂(2)，其包括基于贱金属的催化体系。
8.根据权利要求7所述的催化转化剂(2)，其中使用以钒作为催化活性组分(V)的钛-钒体系。
9.根据权利要求8所述的催化转化剂(2)，其中该钛-钒体系的重量比例是70-90重量％。
10.根据权利要求7所述的催化转化剂(2)，其中使用基于过渡金属的催化体系，特别是WO3/CeO2体系或稳定化的WO3/CeO2体系。
11.根据前述权利要求中任一项所述的催化转化剂(2)，其中该至少一种催化活性组分是结晶分子筛。
12.根据权利要求11所述的催化转化剂(2)，其中该分子筛是铝硅酸盐沸石。
13.根据权利要求11或12所述的催化转化剂(2)，其中所用的该至少一种催化活性组分是具有MFI、BEA、CHA、AEI、FAU、AFX或ERI骨架结构的分子筛。
14.根据权利要求11、12或13所述的催化转化剂(2)，其中该分子筛包含金属活化剂，和特别是离子交换的沸石。
15.根据前述权利要求中任一项所述的催化转化剂(2)，其中该多孔填料(F)是无催化活性的。
16.根据前述权利要求中任一项所述的催化转化剂(2)，其除了该多孔填料组分(F)之外，还包含粘结剂组分(B)。
17.根据前述权利要求中任一项所述的催化转化剂(2)，其为挤出的催化转化剂，特别是蜂窝体催化转化剂的形式。
18.根据前述权利要求中任一项所述的催化转化剂(2)，其为壁流式过滤器的形式。
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