CN103826745A - 涂布催化的颗粒过滤器的方法和颗粒过滤器 - Google Patents

涂布催化的颗粒过滤器的方法和颗粒过滤器 Download PDF

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CN103826745A
CN103826745A CN201280034636.7A CN201280034636A CN103826745A CN 103826745 A CN103826745 A CN 103826745A CN 201280034636 A CN201280034636 A CN 201280034636A CN 103826745 A CN103826745 A CN 103826745A
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carbon monoxide
filter
ammonia
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P.L.加布里伊尔森
K.约翰森
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Topsoe AS
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Abstract

本发明涉及制备壁流颗粒过滤器的方法，所述壁流颗粒过滤器的入口侧用在去除残余烃和一氧化碳并在富燃发动机操作条件下催化氮氧化物与氢气和/或一氧化碳的反应形成氨方面具有活性的第一催化剂催化，且所述壁流颗粒过滤器的出口侧用在通过与在所述入口侧形成的氨反应而选择性还原NOx方面具有活性的第二催化剂催化。所述方法包括提供具有小于所述过滤器壁平均孔径的粒度的第一催化剂和具有大于所述过滤器壁平均孔径的粒度的第二催化剂，并将所述第一催化剂和所述第二催化剂混合成一种悬浮液，将所述悬浮液用于从所述出口端洗涂。所述第一催化剂由此散布到间壁中。

Description

涂布催化的颗粒过滤器的方法和颗粒过滤器
本发明涉及多功能催化的发动机排气颗粒过滤器。具体地讲，本发明为制备多功能催化的颗粒过滤器的方法，所述颗粒过滤器用三效催化剂(TWC)和在通过已知NH3-选择性催化还原(SCR)工艺除去氮氧化物方面具有活性的催化剂及任选地用在将过量的氨氧化成氮气方面具有活性的催化剂催化。
所述多功能催化的过滤器尤其可用于净化来自诸如汽油直接喷射(GDI)发动机的稀燃汽油发动机的排出气体。
与汽油预混喷射发动机相比，GDI发动机产生更多的碳质烟灰。在欧洲，未来期望将欧5＋柴油法规用于GDI，其中颗粒质量极限为4.5mg/km，这需要过滤发动机排气以达到上述极限。
通常，在汽车应用中使用的过滤器为由蜂窝状构造体组成的壁流型过滤器，其中颗粒物质捕获在蜂窝结构的间壁上或这些间壁中。这些过滤器具有由可透气的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开放且在相对出口端封闭且气体出口通道在出口端开放且在入口端封闭，从而进入壁流过滤器的气流受迫通过间壁，之后进入出口通道。
除了烟灰粒子之外，来自汽油发动机的排出气体还含有氮氧化物(NOx)、一氧化碳和未燃烧的烃，它们是代表着健康和环境危险的化合物且必须从排出气体中减少或除去。
在将NOx、一氧化碳和烃去除或减少以得到无害化合物方面有活性的催化剂在本领域中本身已知。
专利文献公开了用于从发动机排气中除去有害化合物的包括单独的催化单元的众多净化***。
本领域中还已知用催化烃和颗粒物质的氧化以及通过与原样或作为其前体加入排出气体中的氨反应而选择性催化还原(SCR) NOx的催化剂涂布的排出气体颗粒过滤器。
在本领域中还已知用催化上述反应的不同催化剂涂布的多功能柴油机颗粒过滤器。
在已知的多功能过滤器中，不同的催化剂在过滤器的不同区中分段或分区地涂布。
将不同催化剂分段或分区涂布在过滤器上是一项昂贵且困难的制备工艺。
与已知的技术相比，本发明提出了制备用用于用氨选择性还原氮氧化物和去除烃、一氧化碳和过量的氨的不同催化剂催化的颗粒过滤器的较简单的方法。
因此，本发明提供制备催化的壁流过滤器的方法，其包括以下步骤：
a) 提供具有由可透气的多孔间壁隔开的多个纵向入口流动通道和出口流动通道的壁流过滤器体；
b) 提供催化剂载体涂料，其包含在使氮氧化物与一氧化碳和氢气反应形成氨方面有活性的第一催化剂组合物，以及在通过使氮氧化物与氨反应形成氮气而催化还原氮氧化物方面有活性的第二催化剂组合物，所述第一催化剂组合物具有小于所述多孔间壁的平均孔径的粒度且所述第二催化剂组合物具有大于所述多孔间壁的平均孔径的粒度；
c) 通过将所述载体涂料引入所述出口通道的出口端而用所述催化剂载体涂料涂布所述过滤器体；和
d) 干燥并热处理所述涂布的过滤器体以获得所述催化的颗粒过滤器。
所述第一催化剂具有比所述间壁的平均孔径小的粒度且所述第二催化剂粒子具有比所述壁的平均孔径大的粒度，这两个优势将允许第一催化剂粒子有效地散布到间壁中并防止第二催化剂散布到其中不希望有该特定催化活性的通道中。
因此可以用单一载体涂料涂布具有不同催化剂的入口和出口流动通道的过滤器体。
通过以下反应：NOx + H2/CO = NH3 + CO2 + H2O使NOx反应形成氨的有用的催化剂有：钯；铂；钯和铑的混合物；以及钯、铂和铑的混合物。
这些催化剂在汽油发动机的富燃操作条件即λ<1下催化氨的形成。钯是优选的催化剂，其中氨形成程度最高。
通过上述反应在入口通道内如此形成的氨渗透穿过过滤器的间壁而进入出口通道且在富燃操作条件(rich operating condition)期间吸附在出口流动通道中的SCR催化剂中。
氨形成催化剂和SCR催化剂两者优选分别沉积在面对入口通道的侧上的间壁上和面对出口通道的侧上的间壁上。
在发动机的随后贫燃操作循环中，在排出气体中存在的NOx与在SCR催化剂中储存的氨通过发生以下反应：
NOx + NH3 = N2 + H2O。
如上文已经提到，SCR催化剂在本领域中本身已知。对于在本发明中使用，在选择性还原氮氧化物方面有活性的优选催化剂包括沸石、氧化硅磷酸铝(silica aluminium phosohate)、离子交换的沸石、用铁和/或铜促进的氧化硅磷酸铝、一种或多种贱金属氧化物中的至少一种。
在本发明中使用的另一优选的SCR催化剂为用铜和/或铁促进的具有菱沸石结构的氧化硅磷酸铝如SAPO 34。
为了除去未与NOx反应的过量的氨，在本发明的一个实施方案中，所述壁流过滤器额外地包括布置在至少在所述过滤器的出口端区域的各个出口流动通道中的氨氧化催化剂。
优选的氨氧化催化剂包括钯、铂或其混合物。
通过与所述氨氧化催化剂接触，将氨氧化成氮气和水。
所述氨氧化催化剂可直接沉积在出口区域中在过滤器的出口通道中的间壁上或作为在SCR催化剂层的表面上的表面层而提供。
本发明另外提供制备催化的壁流过滤器的方法。
在广泛的实施方案中，本发明提供制备催化的壁流过滤器的方法，其包括以下步骤：
a) 提供具有由可透气的多孔间壁隔开的多个纵向入口流动通道和出口流动通道的壁流过滤器体；
b) 提供催化剂载体涂料，其包含在使氮氧化物与一氧化碳和氢气反应形成氨方面有活性的第一催化剂组合物，以及在通过使氮氧化物与氨反应形成氮气而催化还原氮氧化物方面有活性的第二催化剂组合物，所述第一催化剂组合物具有小于所述多孔间壁的平均孔径的众数粒度(mode particle size)且所述第二催化剂组合物具有大于所述多孔间壁的平均孔径的众数粒度；
c) 通过将所述载体涂料引入所述出口通道的出口端而用所述催化剂载体涂料涂布所述过滤器体；和
d) 干燥并热处理所述涂布的过滤器体以获得所述催化的颗粒过滤器。
在本发明中使用的具体催化剂组合物在上文中提到且在权利要求2-4中进一步公开。
在本发明的另一实施方案中，所述过滤器另外用所谓逃逸氨催化剂(ammonia slip catalyst)涂布，所述逃逸氨催化剂为在将过量的氨氧化成氮气和水方面有活性的催化剂。
因此，在该实施方案中，本发明的方法包括以下步骤：
提供含有在选择性氧化氨方面有活性的催化剂组合物的第二载体涂料；和
随后用所述催化剂载体涂料涂布所述出口通道的至少一部分，得到具有所述催化剂载体涂料的涂层。
在制备在本发明中使用的载体涂料时，任选在加入粘合剂、粘度改进剂、起泡剂或其他加工助剂的情况下将通常以粒子形式的催化剂研磨或团聚到所需要的粒度并使其悬浮在水或有机溶剂中。
随后根据通常实践对所述过滤器进行洗涂，包括在所述过滤器中应用真空，加压洗涂或浸涂。
涂布在所述过滤器上的第一催化剂的量通常为10-140g/l，且涂布在所述过滤器上的第二催化剂的量通常为10-100g/l。加载在所述过滤器上的总催化剂通常在40-200g/l范围内。
在本发明中使用的合适过滤材料的实例有碳化硅、钛酸铝、堇青石、氧化铝、莫来石或其组合。
实施例
第一催化剂组合物的悬浮液在第一步骤中由沉积在氧化铈上的钯铑的粉末混合物和粒度小于过滤器壁平均孔径的氧化铝粒子来制备。
第一催化剂混合物的悬浮液通过将20g的这些粉末在40ml脱矿质水/L过滤器中混合来制备。加入分散剂Zephrym PD-7000和消泡剂。将该悬浮液在珠粒研磨机中研磨。最终悬浮液的粒度必须小于在壁流过滤器的壁中的孔的平均孔径。
第二催化剂的悬浮液通过混合并分散100g用2%铜促进的氧化硅磷酸铝SAPO-34在200ml脱矿质水/L过滤器中来制备。加入分散剂Zephrym PD-7000和消泡剂。所述粒度必须大于在壁流过滤器的壁中的孔的平均孔径。
随后将第一催化剂和第二催化剂的悬浮液混合成一种悬浮液。
使用高孔隙度(约60%且壁平均孔径为约18μm)的常规插塞SiC壁流过滤器。
将第一催化剂和第二催化剂的混合悬浮液通过标准载体涂料方法从过滤器渗透侧的过滤器出口端洗涂渗透侧，将其干燥并在750℃下煅烧。

Claims (6)

1. 制备催化的壁流过滤器的方法，其包括以下步骤：
a) 提供具有由可透气的多孔间壁隔开的多个纵向入口流动通道和出口流动通道的壁流过滤器体；
b) 提供催化剂载体涂料，其包含在使氮氧化物与一氧化碳和氢气反应形成氨方面有活性的第一催化剂组合物，以及在通过使氮氧化物与氨反应形成氮气而选择性还原氮氧化物方面有活性的第二催化剂组合物，所述第一催化剂组合物具有小于所述多孔间壁的平均孔径的众数粒度且所述第二催化剂组合物具有大于所述多孔间壁的平均孔径的众数粒度；
c) 通过将所述载体涂料引入所述出口通道的出口端而用所述催化剂载体涂料涂布所述过滤器体；和
d) 干燥并热处理所述涂布的过滤器体以获得所述催化的颗粒过滤器。
2. 权利要求1的方法，其中在将氮氧化物转化成氨方面有活性的催化剂包括钯；铂；钯和铑的混合物；和钯、铂和铑的混合物。
3. 权利要求1的方法，其中在将氮氧化物转化成氨方面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，其中在选择性还原氮氧化物方面有活性的催化剂包括沸石、氧化硅磷酸铝、离子交换的沸石、用铁和/或铜促进的氧化硅磷酸铝、一种或多种贱金属氧化物中的至少一种。
5. 前述权利要求中任一项的方法，其还包括以下步骤：
提供含有在氧化氨方面有活性的催化剂组合物的第二载体涂料；和
用所述第二载体涂料涂布在所述出口端的区域中的一部分出口通道。
6. 根据前述权利要求中的任一项来制备的催化的壁流过滤器。
CN201280034636.7A 2011-07-13 2012-06-14 涂布催化的颗粒过滤器的方法和颗粒过滤器 Pending CN103826745A (zh)

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