CN103384564A - 制造催化微粒过滤器的方法及催化微粒过滤器 - Google Patents

制造催化微粒过滤器的方法及催化微粒过滤器 Download PDF

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CN103384564A
CN103384564A CN2011800530500A CN201180053050A CN103384564A CN 103384564 A CN103384564 A CN 103384564A CN 2011800530500 A CN2011800530500 A CN 2011800530500A CN 201180053050 A CN201180053050 A CN 201180053050A CN 103384564 A CN103384564 A CN 103384564A
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K·约翰森
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Abstract

本发明关于催化微粒过滤器及其制造方法，在催化微粒过滤器的整个分散侧并在其隔壁内提供了在氮氧化物的选择性催化还原中有活性的第一催化剂，并在其整个渗透侧具有在氨氧化中有活性的催化剂与在一氧化碳和烃氧化中有活性的催化剂相混合的第二催化剂组合。第一催化剂的平均粒度小于纵向多孔壁的平均孔径，第二催化剂组合的平均粒度大于纵向壁的平均孔径。在实施例中，第一催化剂为采用2％铜促进的磷酸硅铝SAPO-34，第二催化剂是负载于氧化铝颗粒和带有1.0％铜的β沸石粉末上的铂和钯混合物(摩尔比3∶1)的混合物。

Description

制造催化微粒过滤器的方法及催化微粒过滤器
本发明涉及多功能催化柴油微粒过滤器。特别是，本发明涉及制造催化柴油微粒过滤器的方法，该过滤器既具有通过已知的选择性催化还原(SCR)法除去氮氧化物的活性还具有将废气中含有的烃和一氧化碳氧化转化成水和二氧化碳及将SCR中用作还原剂的过量氨转化成氮气的氧化活性。
此外，本发明提供了催化颗粒过滤器，在其入口/分散通道，过滤器壁中采用SCR催化剂催化，在出口/渗透通道中采用氨泄漏催化剂(ammonia slipcatalyst)与氧化催化剂一起催化。
除了未燃烧的烃，柴油废气还含有氮氧化物(NOx)和微粒物质。NOx、烃和微粒物质是代表对健康和环境有危害的材料和化合物，必须减少或除去来自发动机的废气，其通过使废气通过颗粒过滤器和一些催化剂单元进行。
一般地，这些过滤器是蜂窝壁流式过滤器，其中在蜂窝过滤器的隔壁上或其中捕获微粒物质。
除了微粒过滤器，若干在现有技术中公开的柴油废气清洁***包括通过与氨反应生成氮气而具有选择性还原NOx的活性的催化剂单元和柴油氧化催化剂。
为了除去注入到废气中用于SCR的过量的氨，若干废气清洁***另外包括将氨催化转化成氮气的下游催化剂单元，所谓的氨泄漏催化剂。
涂覆有催化上述反应的催化剂的多功能柴油微粒过滤器在现有技术中也是已知的。
在已知的多功能过滤器中，不同的催化剂分段或分区涂覆在过滤器的不同区域中。
分段或分区涂覆不同的催化剂在过滤器上是昂贵和困难的制造方法。
US 2010/0175372在一个实施方式中公开了具有过滤器的柴油废气处理***，其在过滤器的分散侧采用SCR催化剂催化，并在渗透侧采用氨氧化催化剂和柴油氧化催化剂催化。SCR催化剂载体涂覆(washcoat)在整个过滤器基材上，随后将氨氧化催化剂施涂在出口过滤器通道处。柴油氧化催化剂以重叠层施涂在出口通道处的氨氧化催化剂上。
与已知的制造方法相比，本发明提出更简单的制造微粒过滤器的方法，该过滤器采用不同的催化剂催化以用氨选择性还原氮氧化物并除去烃、一氧化碳和过量的氨。
因此，本发明提供了制造催化微粒过滤器的方法，其包括以下步骤
a)提供微粒过滤器本体，其具有由纵向多孔壁界定的纵向流动通道，该纵向多孔壁限定了分散侧和渗透侧；
b)提供第一催化剂载体涂层，其含有对选择性催化还原氮氧化物具有活性的第一催化剂组合物，
c)提供第二催化剂载体涂层，其以对将氨选择性氧化成氮气有活性的催化剂和对氧化一氧化碳和烃有活性的催化剂的混合物形式含有第二组合型催化剂组合物；
d)将微粒过滤器本体涂覆成在过滤器本体的整个分散侧和隔壁内具有第一催化剂载体涂层，并将微粒过滤器涂覆成在过滤器本体的整个渗透侧具有第二催化剂载体涂层；以及
e)干燥和热处理涂覆的过滤器以得到催化微粒过滤器。
在本文中使用的术语“分散侧”和“渗透侧”分别指的是面向未过滤的废气的过滤器的流动通道，和面向过滤后的废气的流动通道。
根据本发明的方法的主要优点是过滤器可涂覆两种载体涂层得到四元催化微粒过滤器，其中一种载体涂层包含氧化催化剂与氨泄漏催化剂的组合。因此，多功能催化过滤器的制造在更简单和更廉价的生产装置方面改进很大。
在冷启动过程中，发现用催化不同反应的催化剂颗粒的混合物涂覆过滤器在改进的传热及加热(warm up)方面的进一步的优点。结果是，可能在发动机已经启动后不久启动还原剂的注入和SCR反应。
根据本发明的一个优选的实施方案，第一载体涂层中的第一催化剂组合物在选择性催化还原NOx中具有活性，该组合物包含沸石、磷酸硅铝、离子交换沸石、用铁和/或铜促进的磷酸硅铝的至少一种、一种或多种碱性金属氧化物(base metal oxides)和铈钨氧化物在氧化钛载体、氧化铝载体、氧化锆载体、氧化硅载体或它们的混合物上的至少一种的催化剂载体。
优选地，沸石催化剂选自β沸石或菱沸石。
优选地，沸石催化剂选自β沸石或菱沸石。
本发明中使用的进一步优选的SCR催化剂是具有菱沸石结构的用铜和/或铁促进的磷酸硅铝，如SAPO 34。
根据本发明的一个优选实施方案，在烃、一氧化碳和氨的氧化中有活性的第二催化剂组合物包含负载在氧化铝，氧化钛，氧化铈和氧化锆的至少一种上的铂和钯的催化剂颗粒与铜和/或铁促进的沸石，优选β沸石或菱沸石，如菱沸石结构的SAPO 34的催化剂颗粒相混合。
当制造在本发明中使用的载体涂层时，催化剂通常为颗粒形式，将其研磨或附聚成所要求的粒度，并悬浮在水或有机溶剂中，任选地加入粘合剂、粘度改良剂、发泡剂或其它加工助剂。
为了在载体涂覆过滤器期间使SCR催化剂颗粒有效地扩散到隔壁中，并防止氧化催化剂颗粒从渗透侧扩散至分散侧，优选SCR催化剂，即第一催化剂的粒度小于过滤器的纵向多孔壁的平均孔径，并且混合后的氧化催化剂微粒，即第二组合型催化剂组合物的粒度大于平均孔径。
然后根据普遍做法载体涂覆过滤器，包括在过滤器中施加真空，对载体涂层加压，或通过浸涂。当用含有SCR催化剂颗粒的第一载体涂层涂覆过滤器时，将载体涂层从分散侧的入口引入到过滤器中，并且当用含有混合的氧化催化剂颗粒的第二载体涂层涂覆时从渗透侧的出口引入到过滤器中。
根据本发明的一个优选实施方案，过滤器是壁流式整料形式，具有多个由纵向多孔壁分成的纵向通道，该通道的分散侧具有开放的入口端和用塞子塞住的出口端，该通道的渗透侧具有用塞子塞住的入口端和开放的出口端。
在上文及以下描述中使用的术语“入口端”是指过滤器和通道的端部，其与未过滤的气体接触，“出口端”是指过滤器和通道的端部，过滤后的气体在此离开过滤器本体。
此外，本发明提供了催化微粒过滤器，在其整个分散侧及其隔壁内提供在氮氧化物的选择性催化还原中有活性的第一催化剂，在其整个渗透侧提供在氨氧化中有活性的催化剂与在一氧化碳和烃氧化中有活性的催化剂相混合的第二催化剂组合。
在本发明中使用的优选的过滤器为壁流式整料，其具有多个由纵向多孔壁分成的纵向通道，其中所述通道的分散侧具有开放的入口端和用塞子塞住的出口端，并且其中所述通道的渗透侧具有用塞子塞住的入口端和开放的出口端。
在本发明中使用的合适的过滤器材料的实例为碳化硅、钛酸铝、堇青石，氧化铝，富铝红柱石或它们的组合。
涂覆在过滤器上的第一载体涂层的量一般是20至180g/l，在过滤器上的第二载体涂层的量一般是10至80g/l。负载在过滤器上的催化剂总量一般是在40至200g/l范围内。
实施例
在SCR中有活性的第一催化剂的悬浮液形式的第一载体涂层通过将100克用2％的铜促进的磷酸硅铝SAPO-34混合并分散在200毫升去矿质水/升过滤器中制得。添加分散剂Zephrym PD-7000和消泡剂。悬浮液在砂磨机中研磨。粒度必须小于壁流式过滤器隔壁中的孔隙的平均孔径。
第二载体涂层是在第一步中由负载在粒度大于过滤器壁平均孔径的氧化铝颗粒上的铂和钯(摩尔比3∶1)的混合物制成。因此，制得的催化剂混合物的悬浮液通过将20克混合物混合到40毫升去矿质水/升过滤器中制成。在第二步中，将另一悬浮液制成含有具有1.0％铜的β沸石粉末，其粒度大于过滤器壁的平均孔径。悬浮液是通过将20克铜β沸石粉末混合并分散在40毫升去矿质水/升过滤器中制成。添加分散剂Zephrym PD-7000和消泡剂。然后将在第一和第二步骤中制造的悬浮液混合并进一步分散得到第二载体涂层。最终的载体涂层的粒度必须大于壁流式过滤器壁中的孔隙的平均孔径。
采用高孔隙率(约60％和壁平均孔径约18μm)常规塞入的SiC壁流式过滤器。
第一催化剂的悬浮液从过滤器分散侧载体涂覆。然后干燥由此部分涂覆的过滤器并在750℃下煅烧。
具有第二组合型催化剂的第二载体涂层悬浮液从过滤器渗透侧载体涂覆。然后干燥过滤器并在750℃下煅烧。

Claims (13)

1.制造催化微粒过滤器的方法，包括以下步骤
a)提供微粒过滤器本体，其具有由纵向多孔壁界定的纵向流动通道，该纵向多孔壁限定了分散侧和渗透侧；
b)提供第一催化剂载体涂层，其含有在选择性催化还原氮氧化物中有活性的第一催化剂组合物，
c)提供第二催化剂载体涂层，其以对将氨选择性氧化成氮气有活性的催化剂和对氧化一氧化碳和烃有活性的催化剂的混合物形式含有第二组合型催化剂组合物；
d)将微粒过滤器本体涂覆成在整个分散侧和过滤器本体的隔壁内具有第一催化剂载体涂层，并将微粒过滤器涂覆成在过滤器本体的整个渗透侧具有第二催化剂载体涂层；以及
e)干燥和热处理涂覆的过滤器以得到催化微粒过滤器。
2.权利要求1的方法，其中第一催化剂包含沸石、磷酸硅铝、离子交换的沸石、用铁和/或铜促进的磷酸硅铝的至少一种、一种或多种碱性金属氧化物和铈钨氧化物在氧化钛载体、氧化铝载体、氧化锆载体、氧化硅载体或它们的混合物的至少一种上的催化剂载体。
3.权利要求2的方法，其中沸石是β沸石、菱沸石或具有菱沸石结构的磷酸硅铝及其混合物。
4.权利要求3的方法，其中具有菱沸石结构的磷酸硅铝为用铜和/或铁促进的SAPO 34。
5.权利要求1至4任一项的方法，其中第二催化剂组合物包含负载在氧化铝、氧化钛、氧化铈、氧化锆和氧化硅至少一种上的铂和钯与含有铜和/或铁的沸石或具有菱沸石结构的磷酸硅铝相混合的混合物。
6.权利要求5的方法，其中沸石为β沸石或菱沸石。
7.根据前述任一权利要求的方法，其中过滤器是壁流式整料形式，具有多个由纵向多孔壁分成的纵向通道，所述通道的分散侧具有开放的入口端和用塞子塞住的出口端，并且所述通道的渗透侧具有用塞子塞住的入口端和开放的出口端。
8.权利要求7的方法，其中壁流式整料从分散侧的入口载体端涂覆第一催化剂载体涂层，从渗透侧的出口端载体涂覆第二载体涂层。
9.根据前述任一权利要求的方法，其中第一载体涂层中的第一催化剂的众数粒度小于纵向壁的平均孔径，其中第二载体涂层的众数粒度大于纵向壁的平均孔径。
10.催化微粒过滤器，在其整个分散侧及其隔壁内提供在氮氧化物的选择性催化还原中有活性第一催化剂，并且在其整个渗透侧提供在氨氧化中有活性的催化剂与在一氧化碳和烃氧化中有活性的催化剂相混合的第二催化剂组合。
11.权利要求10的催化微粒过滤器，其中过滤器为壁流式整料形式，具有多个由纵向多孔壁分成的纵向通道，其中所述通道的分散侧具有开放的入口端和用塞子塞住的出口端，并且其中所述通道的渗透侧具有用塞子塞住的的入口端和开放的出口端。
12.权利要求10或11的催化微粒过滤器，其中第一催化剂的众数粒度小于纵向多孔壁的平均孔径，并且其中第二催化剂组合的众数粒度大于纵向壁的平均孔径。
13.根据权利要求1至9任一项制造的催化微粒过滤器。
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BR112013010559A2 (pt) 2016-08-02

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