CN100482325C - 净化在稀薄燃烧工况下操作的内燃机产生的废气的催化剂布置和方法 - Google Patents

净化在稀薄燃烧工况下操作的内燃机产生的废气的催化剂布置和方法 Download PDF

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CN100482325C
CN100482325C CNB2004800291209A CN200480029120A CN100482325C CN 100482325 C CN100482325 C CN 100482325C CN B2004800291209 A CNB2004800291209 A CN B2004800291209A CN 200480029120 A CN200480029120 A CN 200480029120A CN 100482325 C CN100482325 C CN 100482325C
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nitrogen oxide
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马库斯·普法伊费尔
尼古拉·苏格尔
伊冯娜·德梅尔
托比亚斯·库尔
保罗·克里斯蒂安·斯普尔克
于尔根·吉斯霍夫
埃格伯特·劳克斯
托马斯·克罗伊策
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Umicore AG and Co KG
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Abstract

本发明涉及用于净化在稀薄燃烧工况下操作的内燃机产生的废气的催化剂布置。本发明提出在薄壁多孔载体的一侧上涂布氮的氧化物储存催化剂，在其另一侧上涂布SCR催化剂。当所述废气通过所述催化的涂层和该载体材料时，与在各自载体上串联布置的催化剂相比，本发明获得显著提高的氮的氧化物转化率。已发现壁流过滤器可用作所述薄壁载体。

Description

净化在稀薄燃烧工况下操作的内燃机产生的废气的催化剂布置和方法
技术领域
本发明涉及在稀薄燃烧工况(lean condition)下操作的内燃机产生的废气的净化，尤其是从柴油机产生的废气的净化。本发明描述了净化这些发动机的废气的催化剂布置和方法。
背景技术
在稀薄燃烧工况下操作的内燃机在此及后也将被称为稀燃发动机(lean burn engines)。它们使用稀燃料的空气/燃料混合物而操作。因此其废气不仅包括通常的污染物一氧化碳(CO)、氮的氧化物(NOx)、未燃烧的烃类(HC)和颗粒(PM)，还含有比例高达15体积％的氧气，以致使该废气具有净氧化作用。基于此原因，不能采用使用三效催化剂的废气净化方法，三效催化剂常规用于化学计量操作的内燃机。尤其是，在氧化性废气气氛中将氮的氧化物转化为氮气具有相当的难度。
稀燃发动机产生的废气中的氮的氧化物的主要组分是一氧化氮(NO)和二氧化氮(NO2)，其中一氧化氮是主要的组分。依赖于内燃机的操作条件，一氧化氮的比例占总的氮的氧化物为60至95体积％。
为了还原氧化性废气中的氮的氧化物，很久以前已知有选择性催化还原(SCR)的方法。在此，作为还原剂的氨被加入至废气中，然后将该气体混合物通过用于选择性还原的催化剂(SCR催化剂)。在SCR催化剂上氮的氧化物选择性地与氨反应，以形成氮气和水。该方法现在已商业地用于发电站的废气净化中。典型的SCR催化剂包括，例如作为催化活性组分的固态酸，其选自TiO2/WO3/MoO3/V2O5/SiO2/SO3体系。其它的SCR催化剂基于与过渡金属交换的耐酸性沸石，例如脱铝Y沸石、丝光沸石、硅沸石(silicalite)或ZSM-5。这些催化剂的工作温度从约300℃至500℃。
由于需要向废气中加入还原剂，SCR方法在应用于汽车中时非常复杂。基于该原因，已发展了NOx-储存技术作为SCR方法的代替。在此，存在于稀燃料废气中的氮的氧化物以硝酸盐的形式暂时地被储存在氮的氧化物储存催化剂上。当储存催化剂的储存容量耗尽后，它需要被再生。为此目的，使用浓燃料的空气/燃料混合物短暂地操作内燃机，即向空气/燃料混合物中引入比通过燃烧空气而完全消耗的燃料更多的燃料，从而使得废气为浓燃料废气。由此而含有未燃烧的烃类。储存的硝酸盐被分解为浓燃料废气中氮的氧化物，并与存在于浓燃料废气中的作为还原剂的未燃烧的烃反应以形成氮气和水。
为了以硝酸盐的形式储存氮的氧化物，氮的氧化物储存催化剂包括碱性组分，如碱金属和碱土金属的氧化物，以及稀土金属的氧化物，如二氧化铈和氧化镧。优选使用氧化钡和氧化锶。另外，氮的氧化物储存催化剂还包括催化活性的贵金属，通常是铂。这些贵金属的作用是将主要存在于废气中的一氧化氮氧化为二氧化氮。仅二氧化氮能够在废气中的水蒸汽存在下与储存的组分反应形成硝酸盐。在储存催化剂的再生中，解吸的氮的氧化物在催化活性的贵金属作用下被还原为氮气和水。
为了将氮的氧化物储存技术用于对稀燃发动机产生的废气的净化，循环操作具有交替变化的稀燃料和浓燃料的空气/燃料混合物的发动机是必需的。在此，稀薄燃烧工况是稀燃发动机的普通操作模式。在该稀燃烧操作期间，废气中的氮的氧化物被储存催化剂储存(储存阶段)。在浓燃料操作期间，氮的氧化物再次被解吸并反应(解吸阶段)。该储存阶段通常持续1至2分钟，而解吸阶段仅需要短暂的5至20秒。
当应用于稀燃发动机产生的废气的净化时，为了改进所述的两种方法，已知有各种途径。欧洲专利公开EP 0 733 354 A1描述了选择性催化还原方法，其中用于还原需要的氨从存在于废气中的氮的氧化物再生获得。为此目的，废气净化单元包含三效催化剂和下游的SCR催化剂。在氮的氧化物储存技术中，稀燃发动机在浓燃料和稀燃料的空气/燃料混合物交替下操作。在用浓燃料的空气/燃料混合物的操作中，通过三效催化剂由存在于废气中的氮的氧化物形成氨。在该阶段，氨被储存在下游的SCR催化剂上。在用稀燃料的空气/燃料混合物的操作中，氮的氧化物流过三效催化剂并通过SCR催化剂利用预先储存的氨选择性地转化为氮气和水。在由EP 0 733 354 A1所述的方法中，因此在车上产生氨而不必单独地向废气中引入氨。
德国专利公开DE 198 20 828 A1描述了对EP 0 733 354 A1方法的改进。为此目的，氮的氧化物储存催化剂被安置于三效催化剂的上游。在稀燃料操作阶段，氮的氧化物储存催化剂储存了存在于废气中的大部分氮的氧化物。在浓燃料操作阶段，氮的氧化物被解吸并通过三效催化剂被部分地转化为氨。由DE 198 20 828 A1描述的废气净化装置相比于EP 0 733 354 A1的装置具有改进的氮的氧化物转化程度。
然而，就装置而言，上述两种方法都是非常复杂的。它们需要至少两个独立的催化剂单元且它们所能获得的氮的氧化物的转化率需要进一步提高。因此，本发明的目的是提供具有比现有技术已知的装置的结构要显著简单的结构的装置，从而实现氮的氧化物的转化率的进一步提高。
发明内容
该目的是通过催化剂布置实现的，所述催化剂布置包括开孔的多孔载体，所述载体具有对于废气的进口表面和出口表面。在该催化剂布置中，所述载体的进口表面和出口表面涂布有不同的催化活性层，其中，在所述出口表面上的催化剂层由用于选择性催化还原的催化剂形成，和在所述进口表面上的催化剂层能够在稀燃料废气条件下储存氮的氧化物并在浓燃料废气条件下将氮的氧化物转化为氨。
附图说明
以下将借助图1和图2更详细地解释本发明。在附图中：
图1显示根据本发明的壁流过滤器的涂布结构。
图2显示在实施例中描述的催化剂布置1至4的NOx转化率曲线。
具体实施方式
根据本发明，催化剂布置仅包括一个具有两种不同催化剂的催化剂单元，所述两种不同的催化剂并不直接接触，而只是在催化剂单元上彼此相接近。在它们之间是开孔载体。该载体例如可以构造成盘状，废气以垂直的方向通过该载体。然而，优选使用壁流过滤器作为用于从柴油机产生的废气中除去煤烟颗粒的载体。
图1显示使用壁流过滤器作为载体的催化剂布置的横截面。壁流过滤器与由陶瓷材料制成的蜂窝状催化剂载体具有相似的结构。所述蜂窝状载体1具有大量间隔相近的流道，用于使废气从进口面2流至出口面3。在壁流过滤器中，这些流道被陶瓷塞6交替地封闭，从而形成进口流道4和出口流道5。归因于该结构，废气在从载体的进口面到出口面的流道上必须通过这些流道之间的多孔分隔的壁7。在此情形中，废气的进口表面由进口流道4的壁表面形成并载有第一催化剂层8。出口流道的壁表面形成出口表面并涂布有第二催化剂层9。
通过该多孔载体物理地隔开第一催化剂层8和第二催化剂层9。已发现尽可能小地保持载体的厚度是有利的。优选使得进口表面和出口表面彼此之间的距离小于1mm，尤其是小于0.5mm。载体必须具有开孔结构以使废气能流过。优选使用由陶瓷材料例如堇青石、碳化硅或钛酸铝制成的载体。
以分散涂层的形式将催化剂施加于催化剂布置的进口表面和出口表面。这些涂层包括细颗粒的氧化载体材料，催化活性组分已以细分散的形式施加于氧化载体材料上。所述氧化载体材料的粒径通常是5至9μm，基于过滤材料的所选平均孔径，催化剂基本不渗透进入该过滤体。
相反，用催化活性组分的前驱化合物溶液进行浸渍会导致这些组分渗透入过滤体。已发现当将这两种催化剂中的一种通过浸渍于过滤体中而引入，然后以分散涂层的形式将第二种催化剂施加于过滤体的进口表面或出口表面时，也可以实现这两种催化剂层的有利分离。
原则上，进口表面和出口表面可以涂布有各种不同的催化剂的组合。有用的组合是在进口表面上涂布三效催化剂或氮的氧化物储存催化剂和在出口表面上涂布SCR催化剂，以及在进口表面上涂布SCR催化剂、氮的氧化物储存催化剂、HC-DeNOx催化剂或烃类储存催化剂的组合和在出口表面上涂布柴油氧化催化剂。同样，在进口表面上的三效催化剂可以与在出口表面上的氮的氧化物储存催化剂结合。在进口表面上的氮的氧化物催化剂和在出口表面上的柴油氧化催化剂的组合也是有利的。
为了处理稀燃发动机的废气，根据本发明，优选在进口表面上施加第一催化剂层8，其在稀薄燃烧操作条件下可以吸收至少部分的存在于废气中的氮的氧化物，而在浓燃料废气条件下，将吸收的氮的氧化物部分地转化为氨。为了进行选择性催化还原，出口表面涂布有SCR催化剂。
在此情形中，第一催化剂层8可以是氮的氧化物储存催化剂或三效催化剂。在为氮的氧化物储存催化剂的情形中，在稀燃料废气条件下的氮的氧化物储存功能是尤其显著的，且由储存的氮的氧化物形成氨的能力是副效应，在为三效催化剂的情形中，这些条件正好相反。然而，也可以使用介于这两种极端之间的催化剂，例如通过加入氮的氧化物储存组分而增强了氮的氧化物储存能力的三效催化剂。在进口表面上的催化剂也可以是双层催化剂，其中一层由氮的氧化物储存催化剂形成，另一层由三效催化剂形成。
在载体进口表面上的催化剂的最优组成最终依赖于内燃机的性能和内燃机排出物中的污染物范围，并且可以由本领域技术人员通过简单的测试确定。通过建议的催化剂布置达到的氮的氧化物的转化率对于进口表面的给定催化剂也可以通过合适地对发动机控制系统进行编程而优化。
来自内燃机的待处理的废气，在本发明的催化剂布置中，首先通过在载体进口表面上的催化剂层，然后通过多孔载体，随后立即通过在出口表面上的SCR催化剂。通过实施例将显示，该布置与已知的包括氮的氧化物储存催化剂和SCR催化剂的两个单独的催化剂单元的串联布置相比，氮的氧化物转化率具有显著的提高。
该实验结果明显表明在此存在协同效应。原因被推测为是在从进口表面上的催化剂的出口至出口表面上的催化剂的进口之间的距离非常短。另外，在本发明的催化剂布置中，废气被迫流过催化剂层，而在为传统的蜂窝状催化剂的情形中，废气被切向地传送通过催化剂层，仅通过扩散效应与催化剂层发生作用。与此相反，在为本发明的催化剂布置中，发生与催化剂层的强制作用。
该布置的另一优点在于该催化剂层包括在进口表面上的贵金属，所述贵金属通过基本上惰性的多孔载体与施加至出口表面上的SCR催化剂隔开。这是由于物理分隔减少了这两种不同催化剂之间可能存在的破坏作用。已知的是，含钒的SCR催化剂与其它高表面积载体的催化剂接触时由于钒的热迁移其可能会失活。
用于进口处的催化剂层的催化剂优选是氮的氧化物储存催化剂，其包括用于储存氮的氧化物的碱土金属和催化活性铂族金属的碱性化合物。作为碱土金属，优选使用钡和/或锶，其可以以氧化物、氢氧化物或碳酸盐的形式加入至催化剂中。优选的铂族金属是铂和/或铑，其已以细分的形式施加至单独的载体材料上，如活性氧化铝、二氧化铈、氧化锆、二氧化硅或二氧化钛、或铈/锆的混合氧化物。尤其优选的氮的氧化物储存催化剂包括作为储存组分的碳酸钡、在铈/锆的混合氧化物上的铂和铑以及活性氧化铝。
在出口处的SCR催化剂优选包括至少一种与过渡金属，尤其是铁、铜、铈或锰交换的沸石。作为代替物，也可以使用基于固态酸体系TiO2/WO3/MoO3/V2O5/SiO2/SO3的催化剂。优选的固态酸体系是与V2O5或V2O5/WO3或V2O5/MoO3结合的TiO2或TiO2/Al2O3或TiO2/SiO2。
在以下的研究中，测量使用以各种组合的氮的氧化物储存催化剂和SCR催化剂获得的氮的氧化物转化率，其为催化剂布置的上游废气温度的函数。氮的氧化物储存催化剂和SCR催化剂具有如下的组成。
氮的氧化物储存催化剂：
为了制备氮的氧化物储存涂层，首先在铈/锆的混合氧化物(重量比70/30)上通过孔体积浸渍(pore volume impregnation)负载重量比为10/1的铂和铑。然后将该材料与氧化铝和碳酸钡一起处理以形成涂布悬浮液。
SCR催化剂：
通过固态离子交换使用氯化铁(FeCl3)将H-ZSM-5沸石(摩尔比SiO2/Al2O3＝40)与铁交换，然后悬浮于水中。交换的沸石含有3.5重量％的铁，以氧化物计。
对比例1：
由堇青石制成的壁流过滤器的进口表面上涂布有用于氮的氧化物储存催化剂的涂布悬浮液，该过滤器直径25.4mm，长度152.4mm和胞密度(cell density)46.5cm-2(300cpsi)。除去过量的涂布悬浮液后，将涂层干燥并在500℃下煅烧。涂布的过滤器具有的涂布浓度为每升过滤体150g，其中1.94g/l是铂和12.1g/l是钡，以氧化钡计。
以此方式制备的氮的氧化物储存催化剂在此及后将被称为催化剂布置C1。
对比例2：
按对比例1中所述制备另一氮的氧化物储存催化剂，并与通过在再一过滤体的进口表面上涂布沸石悬浮液而获得的SCR催化剂结合，将其干燥并煅烧。在此情形中的涂布浓度为100g/l过滤体。
氮的氧化物储存催化剂和下游的SCR催化剂形成催化剂布置C2。
对比例3：
具有上述尺寸的另一过滤体的进口表面涂布有SCR催化剂和氮的氧化物储存催化剂的双层催化剂。为此目的，过滤体的进口表面首先涂布有SCR催化剂(100g/l)然后涂布有氮的氧化物储存催化剂(150g/l)。
所完成的催化剂具有总的涂布浓度为250g/l过滤体，其中1.94g是铂和12.1g是钡，以氧化物计。在此及后将其称为催化剂布置3。
实施例1：
根据本发明的过滤体在其进口表面上涂布有氮的氧化物储存催化剂(150g/l)和在其出口表面上涂布有SCR催化剂(100g/l)。
该催化剂被称为催化剂布置4。
应用例：
将所述的催化剂布置在模型气体单元中进行检测，它们的氮的氧化物转化率是催化剂布置的上游废气温度的函数。
在模型气体单元中，催化剂布置交替地暴露于稀燃料和浓燃料的模型废气，并测定氮的氧化物转化率。该测试的条件示于下表中。
表1 测试条件
Figure C200480029120D0012133447QIETU
*)λ：空气比例(空气/燃料标准化至化学计量的条件)
所测的结果示于图2中。
催化剂布置1仅包括氮的氧化物储存催化剂。示于图2中的NOx转化率曲线是该催化剂的典型曲线。与催化剂布置1相比，催化剂布置2具有布置在氮的氧化物储存催化剂下游处的在分别的载体上的SCR催化剂。这使得NOx转化率增加，尤其是在高于230℃的温度范围内，但是转化率曲线的宽度几乎未改变。在230℃以下，仅通过NOx储存催化剂获得的NOx转化率和其与SCR催化剂结合的NOx转化率基本相同。在这些低温处，SCR催化剂没有在存在的不含NO2的模型废气中取得任何转化效果。
当将SCR催化剂和氮的氧化物储存催化剂作为双层应用于载体的进口侧时(催化剂布置3)，转化率曲线与仅使用氮的氧化物储存催化剂的情况相比明显变差。在高于300℃的温度时，该催化剂布置比纯的氮的氧化物储存催化剂得到更低的转化率。这是归因于来自于氮的氧化物储存催化剂的痕量贵金属对SCR催化剂的部分毒害。在相对高的温度下，这些导致在稀薄燃烧条件下储存在SCR催化剂中的氨的部分氧化，例如形成NO。这也证实了贵金属催化剂和SCR催化剂之间直接接触时的负面效应。
相反，本发明的催化剂布置4显示了同时就曲线的最大值和宽度而言显著改进的NOx转化率曲线。这证实了上述的在废气流向上彼此接近的两种催化剂层的协同效应。尽管相对于在废气流向上的催化剂顺序而言，该布置与催化剂布置2相同，但根据本发明的布置给出了显著改进的转化率曲线。基于已知的在分别的载体上的催化剂布置，这一点是无法实现的。本发明的催化剂布置显示了在整个温度范围内尤其是在低温和高温范围内显著提高的活性。

Claims (9)

1.用于净化内燃机产生的废气的催化剂布置，其包括开孔的多孔载体，所述载体具有对于所述废气的进口表面和出口表面，其中，所述载体的进口表面和出口表面涂布有不同的催化活性层，在所述出口表面上的催化剂层由用于选择性催化还原的催化剂形成，和在所述进口表面上的催化剂层由氮的氧化物储存催化剂或者三效催化剂形成，并且能够在稀燃料废气条件下储存氮的氧化物并在浓燃料废气条件下将氮的氧化物转化为氨。
2.如权利要求1所述的催化剂布置，其中，所述氮的氧化物储存催化剂包括碱土金属和催化活性的铂族金属的碱性化合物。
3.如权利要求2所述的催化剂布置，其中，所述氮的氧化物储存催化剂包括在铈/锆混合氧化物上的铂和铑、活性氧化铝和碳酸钡。
4.如权利要求1至3任一项所述的催化剂布置，其中，所述SCR催化剂包括至少一种与过渡金属交换的沸石。
5.如权利要求1至3任一项所述的催化剂布置，其中，所述SCR催化剂包括固态酸体系，该固态酸体系选自与钒、钒/钨氧化物或钒/钼氧化物结合的二氧化钛或二氧化钛/氧化铝或二氧化钛/二氧化硅。
6.如权利要求1所述的催化剂布置，其中，所述三效催化剂包括至少一种在高表面积载体材料上的选自铂族的贵金属，和至少一种基于二氧化铈的氧储存组分。
7.如权利要求1所述的催化剂布置，其中，所述开孔的多孔载体是壁流过滤器。
8.在稀薄燃烧工况下操作的内燃机产生的废气的净化方法，其中供应至发动机的空气/燃料混合物从稀燃料至浓燃料循环改变，其中，催化剂布置包括开孔的多孔载体，所述载体具有对于所述废气的进口表面和出口表面，所述载体的进口表面和出口表面涂布有不同的催化活性层，在所述出口表面上的催化剂层由用于选择性催化还原的催化剂形成，而在所述进口表面上的催化剂层由氮的氧化物储存催化剂或者三效催化剂形成，并且能够在稀燃料废气条件下储存氮的氧化物并在浓燃料废气条件下将氮的氧化物转化为氨，并且其中，待处理的废气首先通过在所述载体进口表面上的催化剂层，然后通过所述多孔载体，随后立即通过在所述出口表面上的SCR催化剂。
9.如权利要求8所述的方法，其中，所述开孔的多孔载体是壁流过滤器。
CNB2004800291209A 2003-08-05 2004-07-29 净化在稀薄燃烧工况下操作的内燃机产生的废气的催化剂布置和方法 Expired - Fee Related CN100482325C (zh)

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WO2005014146A1 (en) 2005-02-17
EP1660217B1 (en) 2009-11-25
BRPI0413367A (pt) 2006-10-17
CN1863586A (zh) 2006-11-15
KR101100066B1 (ko) 2011-12-29
JP2007501107A (ja) 2007-01-25
DE10335785A1 (de) 2005-03-10
US7799298B2 (en) 2010-09-21

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