CN103796757A - 催化颗粒过滤器及涂覆颗粒过滤器的方法 - Google Patents

催化颗粒过滤器及涂覆颗粒过滤器的方法 Download PDF

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CN103796757A
CN103796757A CN201280034846.6A CN201280034846A CN103796757A CN 103796757 A CN103796757 A CN 103796757A CN 201280034846 A CN201280034846 A CN 201280034846A CN 103796757 A CN103796757 A CN 103796757A
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P·L·加布里伊尔森
K·约翰逊
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Abstract

壁流式颗粒过滤器，在其入口侧使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，并在其出口侧使用对NOx与在入口侧生成的氨反应的选择性还原有活性的催化剂进行催化。

Description

催化颗粒过滤器及涂覆颗粒过滤器的方法
本发明涉及一种催化发动机尾气的多效颗粒过滤器。特别地，本发明是一种壁流式颗粒过滤器，使用三元催化剂(TWC)在其入口侧进行催化，该催化剂对去除残余烃和一氧化碳具有活性，并且在富燃发动机操作条件下催化氮氧化物与氢气和/或一氧化碳生成氨的反应。在其出口侧，过滤器涂覆通过已知的NH3-选择性催化还原(SCR)过程去除氮氧化物的催化剂，并任选涂覆对过量氨氧化成氮有活性的催化剂。
此外，本发明提供了一种制备根据本发明的催化颗粒过滤器(多效催化颗粒过滤器)的方法。
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，壁流类型的过滤器为蜂窝状壁流式过滤器，其中，颗粒物在蜂窝过滤器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。
来自稀燃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、一氧化碳和未燃烧的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系统。
涂覆有催化剂的尾气颗粒过滤器在本领域也是已知的，所述催化剂催化未燃烧的烃和颗粒物质的氧化以及NOx与氨(作为氨或其前体加入)反应的选择性催化还原(SCR)。
本发明利用特定催化剂的能力，通过与烃和未燃烧的烃反应生成氨，将氨的SCR与从汽油发动机尾气中脱除颗粒相结合。
因此，本发明提供了一种壁流式催化过滤器，其由被气体可渗透的多孔间壁分隔的多个纵向入口流动通道和出口流动通道组成，每个入口流动通道具有开放的入口端和封闭的出口端，并且每个出口流动通道具有封闭的入口端和开放的出口端，其中
每个入口流动通道包括对氮氧化物与一氧化碳和氢生成氨的反应有活性的第一催化剂；
每个出口通道包括对氮氧化物与氨反应生成氮的选择还原有活性的第二催化剂；
并且其中，第一或第二催化剂的众数粒径小于气体可渗透多孔间壁的平均孔径，而不具有较小众数粒径的催化剂的众数粒径大于气体可渗透间壁的平均孔径。
第一或第二催化剂具有比间壁平均孔直径更小的粒径，而另一种催化剂颗粒具有比壁的平均孔直径更大的粒径的优点是，使得其中一种催化剂有效地扩散进入间壁而防止另一催化剂扩散进入不期望特定催化活性的通道。
可用于通过以下反应由NOx生成氨的反应的催化剂是钯、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(即入<1)，这些催化剂催化氨生成。钯是优选的催化剂，具有最高的氨生成。
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。
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催化剂涂层的一部分上的氨氧化催化剂接触，氨选择性地氧化成氮和水。
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催化剂层上表面上的背离间壁的表面层。
本发明另外还提供了一种壁流式催化过滤器的制备方法。
在其广泛的实施方案中，根据本发明的方法包括以下步骤：
a)提供壁流式过滤器主体，该主体具有被气体可渗透的间壁分隔的多个纵向入口流动通道和出口流动通道，每个入口流动通道具有开放的入口端和封闭的出口端，并且每个出口流动通道具有封闭的入口端和开放的出口端；
b)提供第一催化剂洗涂层(washcoat)，其包含对氮氧化物与一氧化碳和氢生成氨的反应有活性的第一催化剂组合物；
c)提供第二催化剂洗涂层，其包含对氮氧化物与氨反应生成氮的选择性还原有活性的第二催化剂组合物；
d)用所述第一催化剂洗涂层涂覆所述过滤器主体的入口流动通道；
e)用所述第二催化剂洗涂层涂覆所述过滤器主体的出口流动通道；
f)干燥和热处理所述经涂覆的过滤器主体以得到所述壁流式催化过滤器，其中，所述第一或第二催化剂洗涂层的众数粒径小于所述气体可渗透间壁的平均孔径，而不具有较小众数粒径的催化剂洗涂层的众数粒径大于所述气体可渗透间壁的平均孔径。
在另一个广泛的实施方案中，在涂覆通道后，可进行入口通道和出口通道的出口端和入口端的分别堵塞。
因此，此外，本发明是一种壁流式催化过滤器的制备方法，其包括以下步骤：
a)提供壁流式过滤器主体，该主体具有被气体可渗透的间壁分隔的多个纵向入口流动通道和出口流动通道；
b)提供第一催化剂洗涂层，其包含对氮氧化物与一氧化碳和氢生成氨的反应有活性的第一催化剂组合物；
c)提供第二催化剂洗涂层，其包含对氮氧化物与氨反应生成氮的选择性还原有活性的第二催化剂组合物；
d)用所述第一催化剂洗涂层涂覆所述过滤器主体的入口流动通道；
e)用所述第二催化剂洗涂层涂覆所述过滤器主体的出口流动通道；
f)堵塞如此涂覆的入口流动通道的出口端，堵塞如此涂覆的出口流动通道的入口端；和
g)干燥和热处理所述经涂覆的过滤器主体以得到所述壁流式催化过滤器，其中，所述洗涂层中的第一或第二催化剂的众数粒径小于所述气体可渗透间壁的平均孔径，而所述涂层中不具有较小众数粒径的催化剂的众数粒径大于所述气体可渗透间壁的平均孔径。
本发明所使用的特定的催化剂组合物在上文中已经提及，并进一步在权利要求9-11中披露。
在本发明的另一实施方案中，过滤器另外涂覆有所谓的氨漏失催化剂，其为对过量的氨氧化为氮和水有活性的催化剂。
因此，在该实施方案中，本发明方法包括以下步骤：提供第三洗涂层，其包含对氨的氧化有活性的第三催化剂；和在用第二洗涂层涂覆后，用第三洗涂层涂覆出口通道的至少一部分。
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冼涂，包括在过滤器中应用真空，对洗涂层加压，或通过浸涂。
众数粒径小于过滤器间壁平均孔径的催化剂的量通常是20-140克/升，具有较大众数粒径的催化剂的量通常为10-100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。
应用了常规的高孔隙率(约60％，且壁的平均孔径约为18μm)堵塞的SiC壁流式过滤器主体。
通过标准的洗涂方法，将第一催化剂悬浮液从过滤器分散侧的入口端洗涂(100克/立方英尺)到过滤器上，在750℃下干燥和煅烧。
通过标准的洗涂方法，将第二催化剂悬浮液从过滤器渗透侧的出口端洗涂到过滤器上，在750℃下干燥和煅烧。

Claims (12)

1.一种壁流式催化过滤器，其由被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组成，每个入口流动通道具有开放的入口端和封闭的出口端，并且每个出口流动通道具有封闭的入口端和开放的出口端，其中
每个入口流动通道包括对氮氧化物与一氧化碳和氢气生成氨的反应有活性的第一催化剂；
每个出口通道包括对氮氧化物与氨反应生成氮的选择性还原有活性的第二催化剂；
并且其中，所述第一或第二催化剂的众数粒径小于所述气体可渗透多孔间壁的平均孔径，而不具有较小众数粒径的催化剂的众数粒径大于所述气体可渗透间壁的平均孔径。
2.权利要求1的壁流式催化过滤器，其中，对氮氧化物转化成氨的有活性的所述催化剂包括钯、铂、钯和铑的混合物以及钯、铂和铑的混合物。
3.权利要求1的壁流式催化过滤器，其中，对氮氧化物转化成氨有活性的所述催化剂由钯组成。
4.权利要求1-3中任一项的壁流式催化过滤器，其中，对氮氧化物的选择性还原有活性的所述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、用铁和/或铜促进的硅铝磷酸盐、一种或多种碱金属氧化物。
5.权利要求1-4中任一项的壁流式催化过滤器，其进一步包括布置在每个出口流动通道中的氨氧化催化剂。
6.权利要求5的壁流式催化过滤器，其中，所述氨氧化催化剂包括钯、铂或它们的混合物。
7.壁流式催化过滤器的制备方法，其包括以下步骤：
a)提供壁流式过滤器主体，该主体具有被气体可渗透的间壁分隔的多个纵向入口流动通道和出口流动通道；
b)提供第一催化剂洗涂层，其包含对氮氧化物与一氧化碳和氢生成氨的反应有活性的第一催化剂组合物；
c)提供第二催化剂洗涂层，其包含对氮氧化物与氨反应生成氮的选择性还原有活性的第二催化剂组合物；
d)用所述第一催化剂洗涂层涂覆所述过滤器主体的入口流动通道；
e)用所述第二催化剂洗涂层涂覆所述过滤器主体的出口流动通道；
f)堵塞如此涂覆的入口流动通道的出口端，堵塞如此涂覆的出口流动通道的入口端；和
g)干燥和热处理所述经涂覆的过滤器主体以得到所述壁流式催化过滤器，其中，所述洗涂层中的第一或第二催化剂的众数粒径小于所述气体可渗透间壁的平均孔径，而所述涂层中不具有较小众数粒径的催化剂的众数粒径大于所述气体可渗透间壁的平均孔径。
8.壁流式催化过滤器的制备方法，其包括以下步骤：
a)提供壁流式过滤器主体，该主体具有被气体可渗透的间壁分隔的多个纵向入口流动通道和出口流动通道，每个入口流动通道具有开放的入口端和封闭的出口端，并且每个出口流动通道具有封闭的入口端和开放的出口端；
b)提供第一催化剂洗涂层，其包含对氮氧化物与一氧化碳和氢生成氨的反应有活性的第一催化剂组合物；
c)提供第二催化剂洗涂层，其包含对氮氧化物与氨反应生成氮的选择性还原有活性的第二催化剂组合物；
d)用所述第一催化剂洗涂层涂覆所述过滤器主体的入口流动通道；
e)用所述第二催化剂洗涂层涂覆所述过滤器主体的出口流动通道；
f)干燥和热处理所述经涂覆的过滤器主体以得到所述壁流式催化过滤器，其中，所述洗涂层中的第一或第二催化剂的众数粒径小于所述气体可渗透间壁的平均孔径，而所述涂层中不具有较小众数粒径的催化剂的众数粒径大于所述气体可渗透间壁的平均孔径。
9.权利要求7或8的方法，其中，对氮氧化物转化成氨有活性的所述催化剂包括钯、铂、钯和铑的混合物以及钯、铂和铑的混合物。
10.权利要求7或8的方法，其中，对氮氧化物转化成氨有活性的所述催化剂由钯组成。
11.权利要求7-10中任一项的方法，其中，对氮氧化物的选择性还原有活性的所述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、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。
12.权利要求7-11中任一项的方法，其包括进一步的步骤：
提供第三洗涂层，其包含对氨的选择性氧化有活性的第三催化剂；和
在用所述第二洗涂层涂覆后，用所述第三洗涂层涂覆所述出口通道的至少一部分。
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