CN103796756A - 涂覆催化颗粒过滤器以及颗粒过滤器的方法 - Google Patents

涂覆催化颗粒过滤器以及颗粒过滤器的方法 Download PDF

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CN103796756A
CN103796756A CN201280034845.1A CN201280034845A CN103796756A CN 103796756 A CN103796756 A CN 103796756A CN 201280034845 A CN201280034845 A CN 201280034845A CN 103796756 A CN103796756 A CN 103796756A
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P·L·加布里伊尔森
K·约翰逊
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Abstract

制备壁流式颗粒过滤器的方法，在其入口侧利用对去除残余烃和一氧化碳有活性并且在富燃发动机操作条件下催化氮氧化物与氢和／或一氧化碳生成氨的反应的催化剂进行催化，并且在其出口侧利用对NOx与入口侧形成的氨反应的选择性还原有活性的催化剂进行催化。该方法包括提供粒径大于过滤器壁平均孔径的第一催化剂，以及粒径小于过滤器壁平均孔径的第二催化剂，并将所述第一和第二催化剂混合成悬浮液，该悬浮液用于从入口端的洗涂。从而使所述第二催化剂扩散到间壁中。

Description

涂覆催化颗粒过滤器以及颗粒过滤器的方法
本发明涉及一种多效催化的发动机排放颗粒过滤器。特别地，本发明是一种制备多效颗粒催化过滤器的方法，该过滤器利用三元催化剂(TWC)以及对通过已知的NH3-选择性催化还原(SCR)过程去除氮氧化物具有活性的催化剂进行催化，以及任选用对过量氨氧化成氮有活性的催化剂进行催化。
所述多效催化过滤器特别可用于稀燃汽油机尾气的净化，例如汽油直接喷射式发动机(GDI)的尾气。
GDI发动机比汽油预混喷射发动机产生更多的含碳烟尘。在欧洲，欧5+柴油的法规预期未来将用于GDI，将颗粒物质限度为4.5mg/km，这就要求对发动机尾气过滤以满足上述限制。
一般地，用于汽车应用的过滤器是由蜂窝结构主体组成的壁流式过滤器，其中，颗粒物在蜂窝结构的间壁上或里面被捕获。这些过滤器具有被可透气间壁隔开的多个纵向流动通道。气体入口通道在其气体入口侧打开和在相对的出口端堵塞，气体出口通道在出口端打开和在入口端堵塞，从而迫使进入壁流式过滤器的气流在进入出口通道之前通过间壁。
来自汽油发动机的尾气除了含有烟尘，还含有氮氧化物(NOx)、一氧化碳和未燃烧的烃，其为呈现健康和环境风险的化合物，必须从尾气里还原或消除。
对NOx、一氧化碳和烃的去除或还原为无害的化合物的过程有活性的催化剂本身为本领域已知的。
专利文献公开了许多包括分离催化剂单元用于从发动机尾气中去除有害化合物的净化***。
涂覆有催化剂的尾气颗粒过滤器在本领域也是已知的，所述催化剂催化烃和颗粒物质的氧化以及NOx与氨(作为氨或其前体加入尾气中)反应的选择性催化还原(SCR)。
涂覆有催化上述反应的不同催化剂的多效柴油机颗粒过滤器在本领域也是已知的。
在已知的多效过滤器中，不同的催化剂部分地或者分区地涂覆在过滤器的不同区域。
在所述过滤器上部分地或者分区地涂覆不同的催化剂是一个昂贵且困难的制备过程。
与已知技术相比，本发明提出一种更加容易的制备颗粒过滤器的方法，所述过滤器利用用氨选择性还原氮氧化物，并去除烃、一氧化碳和过量氨的不同催化剂来催化。
因此，本发明提供一种制备壁流式催化过滤器的方法，其包括以下步骤：
a)提供壁流式过滤器主体，该主体具有由气体可渗透的多孔间壁所分隔的多个纵向入口流动通道和出口流动通道；
b)提供催化剂洗涂层(washcoat)，所述洗涂层包括对氮氧化物与一氧化碳和氢生成氨的反应具有活性的第一催化剂组合物，和对氮氧化物与氨反应生成氮的选择性还原具有活性的第二催化剂组合物，所述第一催化剂组合物的众数粒径大于所述多孔间壁的平均孔直径，并且所述第二催化剂组合物的众数粒径小于所述多孔间壁的平均孔直径；
c)通过将所述催化剂洗涂层引至所述入口通道的入口端，用所述催化剂洗涂层对所述过滤器主体进行涂部；和
d)对所述经涂覆的过滤器主体干燥并热处理以得到催化颗粒过滤器。
第二催化剂具有比间壁平均孔直径更小的众数粒径和第一催化剂具有比壁的平均孔直径更大的众数粒径的优点是，使得第二催化剂颗粒有效地扩散进入间壁并防止第一催化剂扩散进入不期望特定催化活性的通道。
那么，可用不同的催化剂涂覆过滤器主体，用单一的洗涂层涂覆入口和出口流动通道。
可用于通过下述反应将NOx反应生成氨的催化剂是钯、铂、钯和铑的混合物以及钯、铂和铑的混合物。
NOx+H2／CO＝NH3+CO2+H2O
在汽油发动机富燃操作条件下(即λ＜1)，这些催化剂催化氨生成。钯是优选的催化剂，有最高的氨生成。
在入口通道内通过上述反应如此形成的氨通过过滤器的间壁渗透至出口通道内，并且在富操作条件下被出口流动通道中的SCR催化剂吸收。
生成氨的催化剂和SCR催化剂两者优选分别沉积在面向入口通道和出口通道侧的间壁上。由于其粒径小于间壁中孔直径的粒径，所以SCR催化剂也分布在所述壁的孔内。
在随后的发动机贫燃操作周期中，废气中存在的NOx通过下述反应与存储在SCR催化剂中的氨反应。
NOx+NH3＝N2+H2O
如上已讨论，SCR催化剂本身在本领域是已知的。为了本发明的应用，在选择性还原氮氧化物中具有活性的优选催化剂包括以下中的至少一种：沸石、硅铝磷酸盐、离子交换沸石、利用铁和／或铜促进的硅铝磷酸盐和一种或多种碱金属氧化物。
进一步优选的用于本发明的SCR催化剂是具有菱沸石结构的硅铝磷酸盐，例如SAPO34，用铜和／或铁促进。
为了去除未与NOx反应的过量氨，本发明的一个实施方案中的壁流式过滤器另外包含氨氧化催化剂，所述催化剂布置在每个出口通道或至少在过滤器的出口端的区域。
优选的氨氧化催化剂包括钯、铂或它们的混合物。
通过与涂覆在SCR催化剂上的选择生氨氧化催化剂接触，氨氧化成氮和水。
氨氧化催化剂可直接沉积在过滤器出口通道内的间壁上，在出口区域处，或可提供为SCR催化剂层表面上的表面层。
本发明另外还提供了一种壁流式催化过滤器，其根据前面公开的本发明制备方法来制备。
当制备本发明中使用的洗涂层时，通常为颗粒形式的催化剂经研磨或聚结成期望的粒径，并悬浮于水或有机溶剂中，任选添加粘合剂、粘度改进剂、发泡剂或其它加工助剂。
然后该过滤器根据通常的实践来洗涂，包括在过滤器中应用真空，对洗涂层加压，或通过浸涂。
涂覆在过滤器上的第一催化剂的量通常为10-100克／升，而在过滤器上的第二催化剂的量通常是10-140克／升。在过滤器上的总催化剂负载量通常为40-200克／升的范围。
用于本发明的合适的过滤器材料的实例是碳化硅、钛酸铝、堇青石、氧化铝、莫来石或它们的组合。
实施例
在第一步中，由在众数粒径大于过滤器壁平均孔径的氧化铈和氧化铝颗粒上沉积钯和铑的粉末混合物，制备第一催化剂组合物的悬浮液。
对于每升过滤器，通过在40毫升去矿物质水中混合20克的这些粉末，制备第一催化剂混合物的悬浮液。加入分散剂Zephrym PD-7000和消泡剂。最终悬浮液的众数粒径必须大于壁流式过滤器的壁中孔的平均孔直径。
对于每升过滤器，通过在200毫升去矿物质水中混合和分散100克用2％铜促进的硅铝磷酸盐SAPO-34，制备第二催化剂的悬浮液。加入分散剂Zephrym PD-7000和消泡剂。在珠磨机中对悬浮液研磨。众数粒径必须小于壁流式过滤器的壁中孔的平均孔直径。
然后将第一催化剂和第二催化剂的悬浮液混合成一个悬浮液。
使用了高孔隙率(约60％，且壁的平均孔径约为18μm)常规堵塞的SiC壁流式过滤器。
使用标准的洗涂方法侧将第一催化剂和第二催化剂的混合悬浮液从过滤器分散侧的入口端洗涂到过滤器，在750℃下干燥和煅烧。

Claims (6)

1.一种制备壁流式催化过滤器的方法，其包括以下步骤：
a)提供壁流式过滤器主体，该主体具有由气体可渗透的多孔间壁所分隔的多个纵向入口流动通道和出口流动通道；
b)提供催化剂洗涂层，所述洗涂层包括对氮氧化物与一氧化碳和氢生成氨的反应具有活性的第一催化剂组合物，和对氮氧化物与氨反应生成氮的选择性还原具有活性的第二催化剂组合物，所述第一催化剂组合物的众数粒径大于所述多孔间壁的平均孔直径，并且所述第二催化剂组合物的众数粒径小于所述多孔间壁的平均孔直径；
c)通过将所述催化剂洗涂层引至所述入口通道的入口端，用所述催化剂洗涂层对所述过滤器主体进行涂部；和
d)对所述经涂覆的过滤器主体干燥并热处理以得到催化颗粒过滤器。
2.权利要求1的方法，其中，对氮氧化物转化成氨具有活性的催化剂包括钯、铂、钯和铑的混合物以及钯、铂和铑的混合物。
3.权利要求1的方法，其中，对氮氧化物转化成氨具有活性的催化剂由钯组成。
4.权利要求1～3中任一项的方法，其中，对氮氧化物的选择性还原具有活性的催化剂包括以下中的至少一个：沸石、硅铝磷酸盐、离子交换沸石、利用铁和／或铜促进的硅铝磷酸盐以及一种或多种碱金属氧化物。
5.前述权利要求中任一项的方法，其进一步包括以下步骤：提供包含对氨的选择性氧化具有活性的催化剂组合物的第二洗涂层；和
对出口端区域的出口通道的一部分利用第二洗涂层涂覆。
6.一种按照前述权利要求中任一项的方法制备的壁流式催化过滤器。
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