CN106062333A - 用于清洁来自压燃式发动机的废气的方法 - Google Patents

用于清洁来自压燃式发动机的废气的方法 Download PDF

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CN106062333A
CN106062333A CN201580011064.4A CN201580011064A CN106062333A CN 106062333 A CN106062333 A CN 106062333A CN 201580011064 A CN201580011064 A CN 201580011064A CN 106062333 A CN106062333 A CN 106062333A
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catalyst
waste gas
reducing agent
ammonia
zeolite
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CN106062333B (zh
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P·L·T·加里伊斯森
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Yuu Mikkel & Co GmbH
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Abstract

本发明涉及一种用于清洁来自压燃式发动机的废气的方法，其包括以下步骤：将第一量的尿素水溶液注入至气体中；在第一操作模式中并且在150至220℃的废气温度下，在包含负载在二氧化钛上的钒氧化物的第一催化剂的存在下使第一量的尿素水解为氨还原剂，和随后通过使与所述氨还原剂混合的气体与第二催化剂接触而除去废气中含有的部分氮氧化物，该第二催化剂包含负载在二氧化钛和/或氧化铝上的铂；在第二操作模式中并且在高于220℃的废气温度下，在第一催化剂和氨还原剂的存在下除去部分氮氧化物，随后通过使气体通过第二催化剂将还包含在废气中的烃、一氧化碳和剩余量的氨还原剂氧化。

Description

用于清洁来自压燃式发动机的废气的方法
本发明涉及用于减少存在于来自稀燃的内部压燃式发动机的废气的氮氧化物(NOx)和颗粒物质的排放的方法和***。特别地，本发明的方法和***提供在发动机的冷启动过程中改善的NOx的还原。
即将到来的法规要求来自卡车和客车具有非常低的排放。同时，所使用的测试循环在相对低的温度下开始。在这些冷循环中还原NOx是困难的，尤其是当所谓的后处理***因为具有许多不同的功能如烃氧化、烟灰过滤、NOx还原和逸出氨还原而变得更加复杂时。最可行的***以以下顺序由以下组件构成：氧化催化剂、烟灰过滤器、NOx还原催化剂和逸出氨催化剂。
常规的具有稀燃发动机的现代汽车和卡车的废气***配备有一系列的氧化催化剂、颗粒过滤器和用于在还原剂存在下的NOx的选择性还原的催化剂(SCR)。
在挥发性有机化合物和一氧化碳的氧化中为活性的氧化催化剂和SCR催化剂是本领域中已知的并且公开在许多出版物中。
通常使用的颗粒过滤器是具有多个入口和出口通道的所谓壁流式过滤器。入口通道在其出口关闭，并且出口通道在其入口关闭，从而使流入过滤器的气体被迫通过限定通道的多孔壁，由此过滤掉气体中的颗粒物质。
最难以处理的排放物为氮氧化物(NOx)。为了实现可接受的循环结果，NOx的还原需要在认证循环(certification cycle)的早期启动。在上述的常规废气清洁***中，SCR催化剂被置于***中作为第三废气清洁单元，并且在发动机启动之后，在该催化剂达到其反应温度之前需要一些时间。
在SCR处理中，一般使用氨作为还原剂。氨是有毒的化合物，并且优选通过使以氨前体形式注入至SCR催化剂上游的热废气中的尿素溶液热分解来原位产生氨。
即使尿素是无害的并相对容易储存在车辆上，液体溶液的尿素作为氨还原剂的前体的使用是有问题的，特别是在发动机的冷启动阶段，即当废气温度为200℃以下时。
当作为液体溶液注入至废气中时，尿素仅在高于约150℃的温度下分解为对SCR为足够的量的氨。然而，常规的SCR催化剂不是很活跃，直至温度达到200℃。
本发明通过将SCR催化剂布置为靠近发动机并且与含有铂的氧化催化剂紧密耦合(close coupled)来解决了这个问题。该SCR催化剂具有在较低温度水解尿素的额外活性和氧化催化剂SCR活性。
铂催化剂在具有氨的SCR中是活性的。然而，在其中铂氧化催化剂是活性的SCR催化剂的温度下使尿素在气相中分解为氨是困难的。
我们发现，在如上所述的废气***中钒氧化物催化剂在到达氧化催化剂之前可有效水解尿素。
根据上述发现和观察，本发明提供了一种用于清洁来自压燃式发动机的废气的方法，其包括以下步骤：
将尿素水溶液注入至废气中；在第一操作模式中并且在150至220℃的废气温度下，通过与包含负载在二氧化钛上的钒氧化物的第一催化剂接触而使尿素水溶液催化水解为氨还原剂，和随后通过使与所述氨还原剂混合的废气与第二催化剂接触而除去废气中含有的部分氮氧化物，第二催化剂布置在第一催化剂的下游并且包含负载在二氧化钛和/或氧化铝上的铂；在第二操作模式中并且在高于220℃的废气温度下，使尿素水溶液分解为氨还原剂并且通过在第一催化剂的存在下与氨还原剂反应而除去废气中含有的部分氮氧化物，随后通过使废气与第二催化剂接触将还包含在离开第一催化剂的废气中的烃、一氧化碳和氨氧化。
根据本发明的方法的优点在于，在靠近发动机的第一催化剂中的NOx还原将快速加热，使得NOx还原在测试循环的早期开始。为了节省空间，建议将NOx还原催化剂和烃还原催化剂集成在一个单元上。
在根据本发明的方法中，尿素注入器被布置在第一催化剂的上游。尿素注入点可以仅在冷启动时部分使用或在发动机的操作过程中连续使用以提高整个***的整体性能。
如前所述，Pt催化剂具有优异的低温SCR性能但是当温度达到Pt催化剂上的氨氧化的点火温度时，NOx还原减少，其导致在可以发生NOx还原之前的氨分解。
含有钒氧化物的第一催化剂实际上是在SCR中在与氨在含有Pt的催化剂上发生氧化时相同的温度范围内开始变为活性的。
在本发明的一个实施方案中，第一催化剂还包含钨氧化物。
在本发明的又一个实施方案中，第二催化剂还包含钯。
这些实施方案的优点是：通过在第一催化剂中包括钨氧化物而获得的增高的SCR活性和当在第二催化剂中包括钯时改善的温度稳定性。
在本发明的进一步的实施方案中，氨氧化催化剂层叠在至少部分第二催化剂上以去除剩余量的氨，其离开上游SCR。由此，来自SCR的逸出氨被大大降低。优选的氨氧化催化剂包含用铁和/或铜促进的铂和沸石，其在氨氧化为无害的氮和水的过程中具有高活性。
在又一个实施方案中，第一催化剂单元可以进一步包含在第一催化剂中的沸石SCR催化剂。优选的沸石是选自Y-沸石、β-沸石、SAPO-沸石和菱沸石组成的组。
在所有的实施方案中优选的是：第一和第二催化剂被布置为在单个催化剂单元中的紧耦合体(close couple)。
参照附图更详细地描述本发明，其中
图1A示意性地示出了常规的柴油废气清洁***，和图1B示意性地示出了根据本发明的柴油废气清洁***；
图2图示了在不同温度下钒氧化物/TiO2在尿素水合为氨的过程中的效率；和
图3a和b示出根据本发明的紧耦合体钒氧化物/TiO2(SCR)和Pt/TiO2(DOC)催化剂在两个不同温度范围的活性。
如图1所示，用于根据本发明的方法中的***B的组合的催化剂SCR/DOC替换了在常规废气清洁***A中的氧化催化剂DOC。SCR/DOC催化剂具有双重功能，一是与TiO2上的钒氧化物一起作为紧耦合体的SCR催化剂，和在低温下使用第二催化剂的Pt/TiO2，然后还使用钒氧化物/TiO2的催化剂的低温SCR，以在低温下使尿素水解为氨，其使得能够在低至150℃的较低温度下使用尿素作为氨还原剂的前体。
图2示出通过接触钒氧化物/TiO2催化剂使尿素水合为氨和HNCO的图。催化剂用32.5体积％的尿素/水溶液浸渍。
将催化剂以10K/min的速率加热，并以70ml/min用氩气和加湿器进行吹扫。
如从图2明显看出的，钒氧化物催化剂在150至220℃的温度下在使尿素水合为氨的过程中具有高活性。
图3a和3b示出根据本发明的紧耦合体SCR/DOC催化剂在两个不同温度范围的活性。
如从图3a明显看出的，在150至220℃的温度范围内，一定量的尿素经第一钒氧化物/TiO2(SCR)催化剂水解并且形成了氨。然后，氨与在第二Pt/TiO2(DOC)催化剂上的NOx反应，该催化剂在这样的温度范围内是SCR活性的。由于SCR反应，NOx和氨的浓度二者在氧化催化剂中均降低。
如图3b所示，当温度升高至220℃或更高时，第一SCR催化剂变得更活跃。反应区朝向催化剂的前面移动并且在DOC催化剂上未发生SCR反应。形成的氨浓缩物与NOx反应并且两个反应物都由于SCR反应而被减少。

Claims (8)

1.一种用于清洁来自压燃式发动机的废气的方法，其包括以下步骤：
将尿素水溶液注入至废气中；在第一操作模式中并且在150至220℃的废气温度下，通过与包含负载在二氧化钛上的钒氧化物的第一催化剂接触而使尿素水溶液催化水解为氨还原剂，和随后通过使与所述氨还原剂混合的废气与第二催化剂接触而除去废气中含有的部分氮氧化物，所述第二催化剂布置在所述第一催化剂的下游并且包含负载在二氧化钛和/或氧化铝上的铂；在第二操作模式中并且在高于220℃的废气温度下，使所述尿素水溶液分解为氨还原剂并且通过在所述第一催化剂的存在下与氨还原剂反应而除去废气中含有的部分氮氧化物，随后通过使所述废气与所述第二催化剂接触将还包含在离开所述第一催化剂的废气中的烃、一氧化碳和氨氧化。
2.如权利要求1所述的方法，其中所述第一催化剂还包含钨氧化物。
3.如权利要求1或2所述的方法，其中所述第二催化剂还包含钯。
4.如权利要求1至3中任一项所述的方法，其中氨氧化催化剂层叠在至少部分第二催化剂上。
5.如权利要求4所述的方法，其中所述氨氧化催化剂包含用铁和/或铜促进的铂和沸石。
6.如权利要求1至5中任一项所述的方法，其中所述第一催化剂还包含沸石SCR催化剂。
7.如权利要求6所述的方法，其中所述沸石SCR催化剂包括Y-沸石、β-沸石、SAPO-沸石和菱沸石中的至少一种。
8.如权利要求1至7中任一项所述的方法，其中所述第一和第二催化剂在单个催化剂单元中布置为紧耦合体。
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