CN101600860B - 内燃机的排气净化装置 - Google Patents
内燃机的排气净化装置 Download PDFInfo
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Abstract
对于内燃机，在内燃机排气通路内配置NOx选择还原催化剂(14)，在NOx选择还原催化剂(14)的上游配置可吸藏排气中含有的NOx的NOx吸藏催化剂(12)。向NOx吸藏催化剂(12)供给雾状的燃料，被NOx吸藏催化剂(12)吸藏的NOx与供给的燃料在NOx吸藏催化剂(12)上反应，生成由相对于一个NOx分子为当量比以上的烃分子与NH2的结合分子形成的中间生成物。这些中间生成物吸附于NOx选择还原催化剂(14)，利用所吸附的中间生成物还原排气中的NOx。
Description
技术领域
本发明涉及内燃机的排气净化装置。
背景技术
已知一种内燃机，其在内燃机排气通路内配置了NOx吸藏催化剂，在该NOx吸藏催化剂上游的内燃机排气通路内配置了小型的三元催化剂，所述NOx吸藏催化剂，在流入的排气的空燃比为稀薄时，吸藏排气中含有的NOx，在流入的排气的空燃比为理论空燃比或浓时，释放所吸藏的NOx(例如参照日本特开2004-108176号公报)。该内燃机，在NOx吸藏催化剂的NOx吸藏能力接近于饱和时，使排气的空燃比暂时为浓，由此，NOx从NOx吸藏催化剂释放并被还原。
然而，对于这样的内燃机，在为了使NOx从NOx吸藏催化剂释放而向NOx吸藏催化剂的上游供给雾状的燃料的情况下，存在不能很好地还原从NOx吸藏催化剂释放的NOx的问题。
发明内容
本发明的目的在于，提供一种内燃机的排气净化装置，其能够很好地还原从NOx吸藏催化剂释放的NOx。
根据本发明，提供一种内燃机的排气净化装置，其中，在内燃机排气通路内配置NOx选择还原催化剂，在NOx选择还原催化剂上游的内燃机排气通路内配置可吸藏排气中含有的NOx的NOx吸藏催化剂，在NOx吸藏催化剂上游的内燃机排气通路内配置燃料供给阀，由该燃料供给阀向NOx吸藏催化剂供给雾状的燃料，使NOx吸藏催化剂中吸藏的NOx与供给的燃料在NOx吸藏催化剂上反应，从而生成由相对于一个NOx分子为当量比以上的烃分子与NH2的结合分子形成的中间生成物，使在NOx吸藏催化剂中生成的中间生成物吸附于NOx选择还原催化剂，由所吸附的中间生成物还原排气中的NOx。
即，在本发明中，通过从燃料供给阀供给雾状的燃料，而使NOx从NOx吸藏催化剂中释放，通过将该释放出的NOx还原至NH2，而使NOx被净化。
附图说明
图1是压缩点火式内燃机的整体图；
图2是NOx吸藏催化剂的催化剂载体的表面部分的剖面图。
具体实施方式
图1表示压缩点火式内燃机的整体图。
参照图1，下述标号分别表示如下：1-内燃机主体、2-各气缸的燃烧室、3-用于向各燃烧室2内分别喷射燃料的电子控制式燃料喷射阀、4-吸气歧管、5-排气歧管。吸气歧管4介由吸气导管6与排气涡轮增压器7的压缩机7a的出口连接，压缩机7a的入口介由检测吸入空气量的吸入空气量检测器8与空气滤清器9连接。参照图1，下述标号分别表示如下：1-内燃机主体、2-各气缸的燃烧室、3-用于向各燃烧室2内分别喷射燃料的电子控制式燃料喷射阀、4-吸气歧管、5-排气歧管。吸气歧管4介由吸气导管6与排气涡轮增压器7的压缩机7a的出口连接，压缩机7a的入口介由检测吸入空气量的吸入空气量检测器8与空气滤清器9连接。在吸气导管6内配置由步进电动机驱动的节气门10，而且在吸气导管6周围配置用于冷却在吸气导管6内流动的吸入空气的冷却装置11。在图1所示的实施例中，内燃机冷却水被导入冷却装置11内，吸入空气由内燃机冷却水冷却。
在吸气导管6内配置由步进电动机驱动的节气门10，而且在吸气导管6周围配置用于冷却在吸气导管6内流动的吸入空气的冷却装置11。在图1所示的实施例中，内燃机冷却水被导入冷却装置11内，吸入空气由内燃机冷却水冷却。
另一方面，排气歧管5与排气涡轮增压器7的排气涡轮7b的入口连接，排气涡轮7b的出口与可吸藏排气中含有的NOx的NOx吸藏催化剂12的入口连接。NOx吸藏催化剂12的出口介由排气管13与NOx选择还原催化剂14连接。另外，在排气歧管5上安装用于向在排气歧管5内流动的排气中供给燃料的燃料供给阀15。
排气歧管5和吸气歧管4，介由排气再循环(以下称为EGR)通路16相互连接，在EGR通路16内配置有电子控制式EGR控制阀17。另外，在EGR通路16周围配置用于冷却在EGR通路16内流动的EGR气体的冷却装置18。在图1所示的实施例中，内燃机冷却水被导入冷却装置18内，EGR气体被内燃机冷却水冷却。另一方面，各燃料喷射阀3介由燃料供给管19与共轨20连接。由电子控制式的喷出量可变的燃料泵21向该共轨20内供给燃料，供给到共轨20内的燃料，介由各燃料供给管19供给至各燃料喷射阀3。
首先，起初对NOx吸藏催化剂12进行说明。NOx吸藏催化剂12具有担载例如由氧化铝构成的催化剂载体的基体，图2(A)、(B)图解示出该催化剂载体30的表面部分的剖面。如图2(A)、(B)所示，在催化剂载体30的表面上，分散地担载有贵金属催化剂31，而且在催化剂载体30的表面上形成有NOx吸收剂32的层。
在本发明的实施例中，作为贵金属催化剂31使用了铂(Pt)。作为构成NOx吸收剂32的成分，使用了选自例如钾(K)、钠(Na)、铯(Cs)之类的碱金属、钡(Ba)、钙(Ca)之类的碱土类、镧(La)、钇(Y)之类的稀土类中的至少一种。
向内燃机吸气通路、燃烧室2以及NOx吸藏催化剂12上游的排气通路内供给的空气与燃料(烃)之比称为排气的空燃比时，NOx吸收剂32进行NOx的吸放作用，即当排气的空燃比为稀薄时吸收NOx，当排气中的氧浓度降低时释放所吸收的NOx，。
即，以使用钡(Ba)作为构成NOx吸收剂32的成分的情况为例进行说明，在排气的空燃比为稀薄时，即在排气中的氧浓度高时，排气中含有的NO如图2(A)所示，在铂(Pt)31上被氧化变成NO2，接着，被吸收到NOx吸收剂32内，一边与氧化钡(BaO)结合一边以硝酸根离子(NO3 -)的形式向NOx吸收剂32内扩散。这样一来，NOx被吸收到NOx吸收剂32内。只要排气中的氧浓度高，就在铂(Pt)31的表面生成NO2，只要NOx吸收剂32的NOx吸收能力没有饱和，NO2就被吸收到NOx吸收剂32内，生成硝酸根离子(NO3 -)。
与此相对，当排气的空燃比为浓或为理论空燃比时，由于排气中的氧浓度降低，因此反应向反向(NO3 -→NO2)进行，这样一来，NOx吸收剂 32内的硝酸根离子(NO3 -)以NO2的形式从NOx吸收剂32释放出来。
另一方面，NOx选择还原催化剂14，由在排气的空燃比为稀薄的条件下，可利用氨选择性地还原排气中的NOx的氨吸附型的Fe沸石构成，或者，由没有吸附氨的功能的二氧化钛-钒系的催化剂构成。在图1所示的实施例中，NOx选择还原催化剂14由氨吸附型的Fe沸石构成。
如上述那样，在排气的空燃比为稀薄时，即在稀空燃比的条件下进行燃烧时，排气中的NOx被吸收到NOx吸收剂32内。然而，当继续进行在稀空燃比的条件下的燃烧时，其间NOx吸收剂32的NOx吸收能力饱和，这样一来，就不能利用NOx吸收剂32吸收NOx。因此，在本发明的实施例中，在NOx吸收剂32的吸收能力饱和之前，由燃料供给阀15供给燃料，使NOx从NOx吸藏催化剂12释放出来。接着，对该情况进行说明。
在本发明的实施例中，轻油或以轻油为主成分的重质燃料，以雾状即以微粒的形态由燃料供给阀15供给。该供给燃料的一部分被氧化，但其大部分如图2(B)所示那样，附着于铂(Pt)31的表面、NOx吸收剂32的表面。当供给燃料附着于铂(Pt)31的表面时，铂(Pt)31的表面上的氧浓度降低，因此如图2(B)所示那样，NOx吸收剂32的NO3 -以NO2的形式释放出来。
此时，当由燃料供给阀15供给排气的空燃比为相当浓的程度的大量的燃料时，即当大量供给用于还原NOx的还原剂时，如图2(B)所示，释放的NO2经由NO还原为NH2。接着，该NH2与附着于铂(Pt)31的烃(HC)立即反应，如图2(B)所示，生成由烃(HC)与NH2的结合分子形成的中间生成物33。另外，供给燃料中的烃(HC)的碳数相当多，因此由被NOx吸藏催化剂12吸藏的NOx和供给的燃料，生成由相对于一个NOx分子为当量比以上的烃分子与NH2的结合分子形成的中间生成物。
这样，被NOx吸藏催化剂12吸藏的NOx，利用供给的燃料而从NOx吸藏催化剂12释放，释放出的NOx被还原。
接着，在NOx吸藏催化剂12中生成的中间生成物被送入NOx选择还原催化剂14，被NOx选择还原催化剂14吸附。吸附于NOx选择还原催化剂14的中间生成物，在NOx选择还原催化剂14的温度上升时，在NOx选择还原催化剂14上分解为烃(HC)和氨(NH3)。在排气的空燃比为稀薄时，该烃(HC)被排气中含有的氧氧化，排气中含有的NOx被吸附于NOx选择还原催化剂14的氨(NH3)还原。
这样，被NOx吸藏催化剂12吸藏的NOx，以胺(NH2)的形式被输送到NOx选择还原催化剂14，在NOx选择还原催化剂14中被转换成氨(NH3)，用手NOx的净化。
Claims (3)
1.一种内燃机的排气净化装置，其中，在内燃机排气通路内配置NOx选择还原催化剂，在该NOx选择还原催化剂上游的内燃机排气通路内配置可吸藏排气中含有的NOx的NOx吸藏催化剂，在该NOx吸藏催化剂上游的内燃机排气通路内配置燃料供给阀，由该燃料供给阀向NOx吸藏催化剂供给雾状的燃料，使NOx吸藏催化剂中吸藏的NOx与供给的燃料在NOx吸藏催化剂上反应，从而生成由相对于一个NOx分子为当量比以上的烃分子与NH2的结合分子形成的中间生成物，使在NOx吸藏催化剂中生成的该中间生成物吸附于所述NOx选择还原催化剂，由所吸附的该中间生成物还原排气中的NOx。
2.根据权利要求1所述的内燃机的排气净化装置，其中，所述NOx吸藏催化剂，由在流入的排气的空燃比为稀薄时吸藏排气中含有的NOx、在流入的排气的空燃比为理论空燃比或为浓时释放所吸藏的NOx的NOx吸藏催化剂构成。
3.根据权利要求1所述的内燃机的排气净化装置，其中，所述NOx选择还原催化剂，由在排气的空燃比为稀薄的条件下利用氨选择性地还原排气中含有的NOx的NOx选择还原催化剂构成。
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| KR101393221B1 (ko) * | 2010-03-23 | 2014-05-08 | 도요타지도샤가부시키가이샤 | 내연 기관의 배기 정화 방법 |
| KR101321294B1 (ko) | 2010-04-01 | 2013-10-28 | 도요타지도샤가부시키가이샤 | 내연 기관의 배기 정화 장치 |
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| JP2008267217A (ja) | 2008-11-06 |
| US20090266057A1 (en) | 2009-10-29 |
| EP2148050A1 (en) | 2010-01-27 |
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