CN102378854A - 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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- CN102378854A CN102378854A CN2010800151730A CN201080015173A CN102378854A CN 102378854 A CN102378854 A CN 102378854A CN 2010800151730 A CN2010800151730 A CN 2010800151730A CN 201080015173 A CN201080015173 A CN 201080015173A CN 102378854 A CN102378854 A CN 102378854A
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- purification method
- fuel ratio
- emission control
- hydrocarbon
- air fuel
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Abstract
在内燃机排气通路内,从上游侧依次配置有烃供给阀(16)、氧化催化剂(13)、排气净化催化剂(14)。根据内燃机的运转状态来选择性地使用第1NOX净化方法和第2NOX净化方法,其中,该第1NOX净化方法是一边将流入排气净化催化剂(14)的废气的空燃比维持为稀空燃比,一边以预先规定的周期使该空燃比下降,由此在不使NOX以硝酸盐的形式被吸留地对NOX进行净化的方法,该第2NOX净化方法是以长于上述周期的周期将流入排气净化催化剂(14)的废气的空燃比从稀空燃比切换到浓空燃比,由此对NOX进行净化的方法。
Description
技术领域
本发明涉及内燃机的排气净化装置。
背景技术
已知有一种内燃机,其中,在内燃机排气通路中配置有NOX吸留催化剂,该NOX吸留催化剂在流入的废气的空燃比为稀空燃比时吸留废气中包含的NOX,在流入的废气的空燃比为浓空燃比时释放出所吸留的NOX,在NOX吸留催化剂上游的内燃机排气通路内,配置有具有吸附功能的氧化催化剂,在要从NOX吸留催化剂中释放出NOX时,向氧化催化剂上游的内燃机排气通路内供给烃,从而使流入吸留催化剂的废气的空燃比变为浓空燃比(例如参照专利文献1)。
在该内燃机中,要从NOX吸留催化剂释放出NOX时被供给的烃在氧化催化剂中成为气体状的烃,气体状的烃被送入NOX吸留催化剂。其结果,从NOX吸留催化剂释放出的NOX被良好地还原。
专利文献1:日本专利第3969450号
但是,存在有如下问题,即、在NOX吸留催化剂处于高温时,NOX净化率会降低。
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,其在排气净化催化剂的温度处于高温时,也能够得到较高的NOX净化率。
根据本发明,提供了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有用于供给烃的烃供给阀,在烃供给阀下游的内燃机排气通路内配置有用于使从烃供给阀喷射出且被部分氧化的烃与废气中包含的NOX发生反应的排气净化催化剂,在排气净化催化剂上担载有贵金属催化剂并且形成有碱性层,排气净化催化剂具有当一边将流入排气净化催化剂的废气的空燃比维持为稀空燃比,一边以预先规定的供给间隔从烃供给阀喷射烃时,对废气中包含的NOX进行还原的性质,并且具有当烃的供给间隔长于预先规定的供给间隔时,废气中包含的NOX的吸留量增大的性质,该排气净化装置在内燃机运转时根据内燃机的运转状态来选择性地使用第1NOX净化方法和第2NOX净化方法,其中,该第1NOX净化方法在是一边将流入排气净化催化剂的废气的空燃比维持为稀空燃比,一边以预先规定的供给间隔来从烃供给阀喷射烃,由此对废气中包含的NOX进行净化的方法,该第2NOX净化方法是以长于预先规定的供给间隔的间隔来将流入排气净化催化剂的废气的空燃比从稀空燃比切换到浓空燃比,由此对NOX进行净化的方法。
附图说明
图1是压缩点火式内燃机的整体图。
图2是对催化剂载体的表面部分进行图解表示的图。
图3是用于说明氧化催化剂中的氧化反应的图。
图4是表示向排气净化催化剂流入的废气的空燃比的变化的图。
图5是表示NOX净化率的图。
图6是用于说明排气净化催化剂中的氧化还原反应的图。
图7是用于说明排气净化催化剂中的氧化还原反应的图。
图8是表示向排气净化催化剂流入的废气的空燃比的变化等的图。
图9是表示排出NOX量NOXA的映射的图。
图10是表示燃料喷射正时的图。
图11是表示NOX净化率的图。
图12是表示烃的喷射量等的映射的图。
图13是表示NOX喷出速度等的图。
图14是表示从第2NOX净化方法切换到第1NOX净化方法时的废气的空燃比(A/F)in等的变化的时序图。
图15是用于进行NOX净化控制的流程图。
图16是表示示出图15所示的NOX净化方法决定部A的另一个实施例的流程图等的图。
图17是表示图15所示的NOX净化方法决定部A的另一个实施例的流程图。
图18是表示图15所示的NOX净化方法决定部A的另一个实施例的流程图。
图19是表示从第2NOX净化方法切换到第1NOX净化方法时的废气的空燃比(A/F)in等的变化的时序图。
图20是表示从第2NOX净化方法切换到第1NOX净化方法时的废气的空燃比(A/F)in等的变化的时序图。
图21是表示增量系数的图。
图22是用于净化NOX的其他催化剂的一部分的截面放大图。
具体实施方式
图1表示了压缩点火式内燃机的整体图。
参照图1可知,1表示内燃机主体,2表示各汽缸的燃烧室,3表示在各燃烧室2内分别用于喷射燃料的电子控制式燃料喷射阀,4表示进气岐管,5表示排气岐管。进气岐管4经由进气管道6与排气涡轮增压器7的压缩机7a的出口连结,压缩机7a的入口经由进气量检测器8与空气过滤器9连结。在进气管道6内配置有被步进电动机驱动的节气门10,另外在进气管道6周围还配置有用于对在进气管道6内流过的进气进行冷却的冷却装置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,进气被内燃机冷却水冷却。
另一方面,排气岐管5与排气涡轮增压器7的排气涡轮7b的入口连结,排气涡轮7b的出口经由排气管12与能够对烃HC进行部分氧化的烃部分氧化用催化剂13的入口连结。在图1所示的实施例中,该烃部分氧化用催化剂13包括氧化催化剂。烃部分氧化用催化剂、即氧化催化剂13的出口与排气净化催化剂14的入口连结,排气净化催化剂14的出口与用于捕集废气中包含的微粒子的微粒过滤器15连结。氧化催化剂13上游的排气管12内配置有用于供给烃的烃供给阀16,该烃包括被用作压缩点火式内燃机的燃料的轻油等燃料。在图1所示的实施例中,作为从烃供给阀16供给的烃,使用了轻油。另外,本发明也能够应用于在稀空燃比的基础上进行燃烧的火花点火式内燃机。在这种情况下,从烃供给阀16供给由作为火花点火式内燃机的燃料而使用的汽油等燃料构成的烃。
另一方面,排气岐管5和进气岐管4经由废气再循环(以下称为EGR)通路17相互连结,在EGR通路17内配置有电子控制式EGR控制阀18。另外,在EGR通路17周围,配置有用于对流过EGR通路17内的EGR气体进行冷却的冷却装置19。在图1所示的实施例中,内燃机冷却水被导入冷却装置19内,EGR气体被内燃机冷却水冷却。另一方面,各燃料喷射阀3经由燃料供给管20与共轨21连结,该共轨21经由电子控制式的喷出量可变的燃料泵22与燃料贮藏罐23连结。燃料贮藏罐23内贮藏的燃料通过燃料泵22被供给至共轨21内,被供给到共轨21内的燃料经由各燃料供给管20供给至燃料喷射阀3。
电子控制单元30由数字计算机构成,具备通过双方向性总线31相互连接的ROM(只读存储器)32、RAM(随机存取存储器)33、CPU(微处理器)34、输入端口35和输出端口36。氧化催化剂13上安装有用于对氧化催化剂13的温度进行检测的温度传感器24,排气净化催化剂14上安装有用于对排气净化催化剂14的温度进行检测的温度传感器25。这些温度传感器24、25以及进气量检测器8的输出信号经由各自对应的AD转换器37输入至输入端口35。另外,加速器踏板40上连接有产生与加速器踏板40的踏入量L成比例的输出电压的负载传感器41,负载传感器41的输出电压经由对应的AD转换器37输入至输入端口35。并且,输入端口35上还连接有曲轴转角传感器42,该曲轴转角传感器42在曲轴每当旋转例如15°时就产生输出脉冲。另一方面,输出端口36经由对应的驱动电路38与燃料喷射阀3、节气门10的驱动用步进电动机,烃供给阀16、EGR控制阀18和燃料泵22连接。
图2的(A)对氧化催化剂13的基体上所担载的催化剂载体的表面部分进行了图解表示。如图2的(A)所示那样,例如在由氧化铝构成的催化剂载体50上,担载有由铂Pt那样的贵金属、或者银Ag或铜Cu那样的过渡金属构成的催化剂51。
另一方面,图2的(B)对排气净化催化剂14的基体上所担载的催化剂载体的表面部分进行了图解表示。在该排气净化催化剂14中,如图2的(B)所示那样,在例如由氧化铝构成的催化剂载体52上担载有贵金属催化剂53、54,另外,在该催化剂载体52上还形成有碱性层55,该碱性层55至少包含一种从钾K、钠Na、铯Cs那样的碱金属、钡Ba、钙Ca那样的碱土类金属、镧系元素那样的稀土类以及银Ag、铜Cu、铁Fe、铱In那样的能够向NOX提供电子的金属中选择出的金属。由于废气沿着催化剂载体52上流过,所以可以说贵金属催化剂53、54被担载在排气净化催化剂14的废气流通表面上。另外,由于碱性层55的表面呈碱性,所以碱性层55的表面被称为碱性的废气流通表面部分56。
在图2的(B)中,贵金属催化剂53由铂Pt构成,贵金属催化剂54由铑Rh构成。即,被催化剂载体52担载的贵金属催化剂53、54由铂Pt和铑Rh构成。另外,在排气净化催化剂14的催化剂载体52上,除了担载铂Pt和铑Rh以外还可以担载钯Pd,或者可以担载钯Pd来取代铑Rh。即,被催化剂载体52担载的贵金属催化剂53、54由铂Pt、和铑Rh以及钯Pd中的至少一方构成。
若从烃供给阀16向废气中喷射了烃,则该烃在氧化催化剂13中被氧化。在本发明中,此时使烃在氧化催化剂13中被部分氧化,并利用被部分氧化的烃来在排气净化催化剂14中净化NOX。在这种情况下,若氧化催化剂13的氧化能力过强,则会使烃在氧化催化剂13中不是被部分氧化而是被氧化,在使烃部分氧化时,需要减弱氧化催化剂13的氧化能力。因此,在本发明的实施例中,作为氧化催化剂13,采用贵金属催化剂的担载量少的催化剂、担载卑金属的催化剂、或容量小的催化剂。
图3对氧化催化剂13中进行的氧化反应进行了图解表示。如图3所示那样,从烃供给阀16喷射的烃HC由于催化剂51而成为碳数量较少的自由基状的烃HC。另外,此时一部分烃HC与NO结合,如图3所示那样,成为亚硝基化合物,另外,一部分烃HC与NO2结合成为硝基化合物。在氧化催化剂13中生成的这些自由基状的烃HC等被送入排气净化催化剂14。
接着,参照图4到图6对本发明者研究出的第1NOX净化方法进行说明。
另外,图4表示了向排气净化催化剂14流入的废气的空燃比(A/F)in的变化,图5针对排气净化催化剂14的各催化剂温度TC,表示了如图4所示那样使向排气净化催化剂14流入的废气的空燃比(A/F)in发生了变化时的排气净化催化剂14的NOX净化率。
于是,本发明者历经较长期间着重对NOX净化进行了研究,在该研究过程中,判明了如下事实,即若如图4所示那样,使向排气净化催化剂14流入的废气的空燃比(A/F)in相隔后面说明的某个时间间隔而在稀空燃比的范围内间隙性地下降,则会如图5所示那样,即使在400℃以上的高温区域,也能够得到非常高的NOX净化率。并且判明了如下事实,即、此时包含氮和烃的大量的还原性中间体被持续保持或吸附在碱性层55的表面上、即排气净化催化剂14的碱性废气流通表面部分56上,在该还原性中间体得到了较高NOX净化率的基础上实现了核心作用。
接着,参照图6的(A)和(B)对该情况进行说明。另外,上述的图6的(A)和(B)对排气净化催化剂14的催化剂载体52的表面部分进行了图解表示,在上述的图6的(A)和(B)中,表示了被推测为在如图4所示那样使向排气净化催化剂14流入的废气的空燃比(A/F)in在稀空燃比的范围内间隙性下降时所产生的反应。
即,根据图4可知,由于流入排气净化催化剂14的废气的空燃比被维持为稀空燃比的状态,所以流入排气净化催化剂14的废气处于氧过剩的状态。因此,如图6的(A)所示那样,废气中包含的NO在铂53上被氧化,从而变成NO2。接着,该NO2被进一步氧化,从而变成稳定的硝酸离子NO3 -。
另一方面,若硝酸盐NO3 -被生成,则该硝酸盐NO3 -通过已被送入碱性层55的表面上的烃HC,被拉回还原的方向,因氧被脱离而变成不稳定的NO2 *。该不稳定的NO2 *活性较强,下面将该不稳定的NO2 *称为活性NO2 *。该活性NO2 *如图6的(A)所示那样,与主要附着于碱性层55的表面上或者铑Rh54上的自由基状的烃HC、或者主要在废气中包含的自由基状的烃HC在铑Rh54上发生反应,由此生成还原性中间体。该还原性中间体被附着或吸附在碱性层55的表面上。
另外,此时认为最初生成的还原性中间体是硝基化合物R-NO2。虽然该硝基化合物R-NO2若被生成则会成为腈化合物R-CN,但是该腈化合物R-CN在该状态下只是瞬间存在,因此会立刻变成异氰酸盐化合物R-NCO。该异氰酸盐化合物R-NCO若加水分解则变成胺类化合物R-NH2。但是,在这种情况下,认为被加水分解的是异氰酸盐化合物R-NCO的一部分。因此,可以认为,如图6的(A)所示那样,在碱性层55的表面上保持或者吸附的还原性中间物的大部分是异氰酸盐化合物R-NCO和胺类化合物R-NH2。
另一方面,如图6的(B)所示那样,生成的活性NO2 *在铑Rh54上与还原性中间体R-NCO、R-NH2发生反应,从而变成N2、CO2和H2O,由此NOX被净化。即,若碱性层55上没有保持或吸附还原性中间体R-NCO、R-NH2,则不进行NOX的净化。因此,为了得到较高的NOX净化率,在使生成的活性NO2 *成为N2、CO2、H2O时,需要总是在碱性层55上、即碱性废气流通表面部分26上持续存在充足量的还原性中间体R-NCO、R-NH2。
即,如图6的(A)和(B)所示那样,为了在铂Pt53上使NO氧化,废气的空燃比(A/F)in必须为稀空燃比,为了使生成的活性NO2 *成为N2、CO2、H2O,碱性层55的表面上必须预先保持充足量的还原性中间体R-NCO、R-NH2,即,为了预先保持还原性中间体R-NCO、R-NH2,必须预先设置碱性的废气流通表面部分26。
因此,如图6的(A)和(B)所示那样,为了使废气中包含的NOX和被部分氧化的烃发生反应而生成包含氮和烃的还原性中间体R-NCO、R-NH2,排气净化催化剂14的废气流通表面上担载有贵金属催化剂53、54,为了将生成的还原性中间体R-NCO、R-NH2预先保持在排气净化催化剂14内,在贵金属催化剂53、54的周围形成有碱性的废气流通表面部分26,NOX由于碱性的废气流通表面部分26上保持的还原性中间体R-NCO、R-NH2的还原作用而被还原。因此,在该第1NOX净化方法中,在将从烃供给阀16流入排气净化催化剂14的废气的空燃比维持为稀空燃比的同时,以预先规定的供给间隔间隙性地供给烃HC,该烃HC的预先规定的供给间隔被设为使还原性中间体R-NCO、R-NH2在碱性的废气流通表面部分56上持续存在时所需要的供给间隔。
在这种情况下,若喷射量过多,或者喷射间隔过短,则烃量变得过剩,大量的烃HC被从排气净化催化剂14排出,若喷射量过少,或者喷射间隔过长,则在碱性的废气流通表面部分56上不再存在还原性中间体R-NCO、R-NH2。因此在该情况下,重要的是按照剩余的烃HC不从排气净化催化剂14排出、且碱性的废气流通表面部分26上持续存在还原性中间体R-NCO、R-NH2的方式来设定烃的喷射量和喷射间隔。这里,在图4所示的例子中,喷射间隔被设为3秒。
接着,参照图7到图11对第2NOX净化方法进行说明。在图4所示的情况下,若将烃HC的供给间隔设定得长于上述的预先规定的供给间隔,则烃HC、还原性中间体R-NCO、R-NH2从碱性层55的表面上消失,此时对于铂Pt53上生成的硝酸离子NO3 -来说,将硝酸离子NO3 -拉回还原方向的力不起作用。因此,此时,硝酸离子NO3 -如图7的(A)所示那样在碱性层55内扩散,从而成为硝酸盐。即,此时,废气中的NOX以硝酸盐的形式被吸收进碱性层55内。
另一方面,图7的(B)表示了如上述那样NOX以硝酸盐的形式被吸收进碱性层55内时,流入排气净化催化剂14内的废气的空燃比成为理论空燃比或者浓空燃比的情况。在该情况下,由于废气中的氧浓度降低,所以反应朝着反方向(NO3 -→NO2)进行,由此,碱性层55内被吸收的硝酸盐依次成为硝酸离子NO3 -并如图7的(B)所示那样以NO2的形式被从碱性层55释放出。接着,释放出的NO2由于废气中包含的烃HC和CO而被还原。
图8表示了利用了该NOX的吸收释放出作用的第2NOX净化方法。即,在该第2NOX净化方法中,如图8所示那样,在碱性层55所吸留的吸留NOX量∑NOX超过了预先规定的容许量MAX时,流入排气净化催化剂14的废气的空燃比(A/F)in暂时为浓空燃比。若废气的空燃比(A/F)in为浓空燃比,则在废气的空燃比(A/F)in为稀空燃比时碱性层55内所吸收的NOX被从碱性层55一次全部释放出并被还原。由此NOX被净化。
例如根据从内燃机排出的NOX量来计算吸留NOX量∑NOX。在本发明的实施例中,从内燃机每单位时间排出的排出NOX量NOXA作为内燃机负载L和内燃机转速N的函数,以图9所示的映射的形式被预先存储在ROM32内,根据该排出NOX量NOXA来计算吸留NOX量∑NOX。废气的空燃比(A/F)in为浓空燃比的周期远远长于如图4所示那样使废气的空燃比(A/F)in下降的周期,废气的空燃比(A/F)in为浓空燃比的周期通常在1分钟以上。
在第2NOX净化方法中,在废气的空燃比(A/F)in为稀空燃比时,废气中包含的NOX被吸收到碱性层55内,因此碱性层55实现了用于暂时吸收NOX的吸收剂的作用。另外,在有些情况下,此时碱性层55也暂时吸附NOX,因此若使用吸留这样的包含吸收和吸附双方的用语,则此时碱性层55实现了用于暂时吸留NOX的NOX吸留剂的作用。即,若将被供给到内燃机进气通路、燃烧室2和排气净化催化剂14上游的排气通路内的空气和燃料(烃)的比称为废气的空燃比,则在该第2NOX净化方法中,排气净化催化剂14作为NOX吸留催化剂而发挥作用,其中,该NOX吸留催化剂在废气的空燃比为稀空燃比时吸留NOX,在废气中的氧浓度下降时释放出所吸留的NOX。
另外,在该第2NOX净化方法中,如图10所示那样,除了从燃料喷射阀3向燃烧室2内喷射燃烧用燃料M以外,还喷射追加的燃料W,由此,流入排气净化催化剂14的废气的空燃比(A/F)in为浓空燃比。另外,图10的横轴表示曲轴转角。该追加的燃料W在燃烧虽然进行但是没有出现内燃机输出的正时,即快到压缩上死点后ATDC90°处被喷射。当然,在这种情况下,通过增大来自烃供给阀16的烃的供给量,也能够使废气的空燃比(A/F)in为浓空燃比。
图11表示了使排气净化催化剂14作为NOX吸留催化剂发挥作用时的NOX净化率。另外,图11的横轴表示了排气净化催化剂14的催化剂温度TC。在使排气净化催化剂14作为NOX吸留催化剂而发挥作用的情况下,如图11所示那样,在催化剂温度TC为300℃到400℃时,得到了非常高的NOX净化率,而当催化剂温度TC成为400℃以上的高温时,NOX净化率会下降。
如上述那样,当催化剂温度TC成为400℃以上时NOX净化率会下降,这是因为当催化剂温度TC成为400℃以上时硝酸盐发生热分解而以NO2的形式从排气净化催化剂14释放出。即,只要以硝酸盐的形式吸留了NOX,则在催化剂温度TC较高时难以得到较高的NOX净化率。但是,在从图4到图6的(A)、(B)所示的第1NOX净化方法中,根据图6的(A)、(B)可知,不会生成硝酸盐或者即使生成也是极其微量,由此如图5所示那样,即使在催化剂温度TC较高时,也会得到较高的NOX净化率。
即,在利用了形成有担载贵金属催化剂且能够吸收NOX的碱性层的排气净化催化剂的情况下,从图4到图6的(A)、(B)所示的第1NOX净化方法可以说是以基本不形成硝酸盐来净化NOX的方式进行净化的新的NOX净化方法。实际上,在利用了该第1NOX净化方法的情况下,与利用了第2NOX净化方法的情况相比,从碱性层55检测出的硝酸盐是极其微量的。
另一方面,在利用第1NOX净化方法来净化NOX时,即使在废气中的NOX浓度较低时,也需要以较短的周期来供给一定量以上的烃。因此,在废气的NOX浓度较低时,NOX净化效率下降。与此相对,在第2NOX净化方法中,在废气中的NOX浓度较低时,由于吸留NOX量∑NOX达到容许值MAX为止的时间变长,因此仅是使废气的空燃比(A/F)in为浓空燃比的周期变长,NOX净化效率没有特别的恶化。因此可以说,在废气中的NOX浓度较低时,与第1NOX净化方法相比,优选使用第2NOX净化方法。
即,应该使用第1NOX净化方法和第2NOX净化方法中的哪一个,是根据内燃机的运转状态而变化的。因此,在本发明中,在排气净化催化剂14上担载有贵金属催化剂53、54、并且形成有碱性层55,排气净化催化剂14具有若将流入排气净化催化剂14的废气的空燃比维持为稀空燃比,同时以预先规定的供给间隔从烃供给阀16喷射烃,则对废气中包含的NOX进行还原的性质,并且具有若使烃的供给间隔长于该预先规定的供给间隔,则废气中包含的NOX的吸留量增大的性质,根据内燃机的运转状态来选择性地使用第1NOX净化方法和第2NOX净化方法,其中,该第1NOX净化方法通过将内燃机运转时流入排气净化催化剂14的废气的空燃比维持为稀空燃比,同时以该预先规定的供给间隔从烃供给阀16喷射烃,对废气中包含的NOX进行净化,第2NOX净化方法通过以比该预先规定的供给间隔长的间隔来将流入排气净化催化剂14的废气的空燃比从稀空燃比切换到浓空燃比,从而对NOX进行净化。
接着参照图12到图15对本发明的代表实施例进行说明。图12的(A)表示了来自烃供给阀16的烃供给量QE,图12的(B)表示了被供给到燃烧室2内的追加的燃料量W。烃供给量QE作为内燃机负载QE和内燃机转速N的函数,以图12的(A)所示那样的映射的形式被预先存储在ROM32内,追加的燃料量W也作为内燃机负载QE和内燃机转速N的函数,以图12的(B)所示那样的映射的形式被预先存储在ROM32内。
图13的(A)表示了废气的空燃比(A/F)in为稀空燃比时,从排气净化催化剂14喷出的吸留NOX的喷出速度NOXD。如上述那样,以硝酸盐的形式吸留的NOX当排气净化催化剂14的温度TC上升时进行热分解从而被喷出,此时的NOX喷出速度NOXD、即每单位时间喷出的NOX量NOXD当排气净化催化剂14的温度TC超过了450℃左右的热分解开始温度时急速地上升。
另一方面,图13的(B)表示了通过第1NOX净化方法来进行NOX的净化作用时,排气净化催化剂14所吸留的NOX的吸留率SX。在通过第1NOX净化方法来进行NOX的净化作用时,通常,在排气净化催化剂14中NOX不会被吸留。但是,若废气的流速变快,即进气量GA增大,则由于反应时间变短,反应不再被充分地进行,所以不会变成活性NO2 *,从而被碱性层55吸收的NOX量增大。因此,如图13的(B)所示那样,当进气量GA变得大于一定值时,NOX吸留率SX开始增大。
这样,即使在通过第1NOX净化方法来进行NOX净化作用时,有时也会在排气净化催化剂14中吸留NOX,此时,每单位时间吸留的NOX量成为来自内燃机的每单位时间的排出NOX量NOXA与NOX吸留率SX相乘而得到的值SX·NOXA。在本发明的实施例中,通过对SX·NOXA进行乘法运算,计算通过第1NOX净化方法来进行NOX净化作用时被吸留的吸留NOX量,在从第1NOX净化方法切换到了第2NOX净化方法时,以进行第1NOX净化方法时计算出的吸留NOX量为基础,开始进行吸留NOX量的计算。
即,在本发明的代表实施例中,在从第1NOX净化方法切换到第2NOX净化方法时,对第1NOX净化方法被使用时计算出的NOX吸留量和切换到第2NOX净化方法后计算出的NOX吸留量进行合计,在该合计值ZNOX超过了预先规定的容许值MAX时,流入排气净化催化剂14的废气的空燃比暂时为浓空燃比。在这种情况下,若假设无视使用了第1NOX净化方法时的吸留NOX量,则在切换到第2NOX净化方法时,使废气的空燃比(A/F)in为浓空燃比的时间点变迟,由此一部分的NOX不会被吸留而是被排出到大气中。但是,在本发明的实施例中,考虑了第1NOX净化方法被使用时的NOX吸留量,因此不会产生上述那样的问题。
另一方面,在从第2NOX净化方法切换到第1NOX净化方法的情况下,若在排气净化催化剂14内残存有吸留NOX,则在因烃的供给而导致排气净化催化剂14的温度TC上升时,吸留NOX被从NOX净化催化剂14喷出。在基于第1NOX净化方法的NOX净化作用被进行时,这样被喷出的NOX的还原作用不被进行,由此NOX被向大气中排出。
但是,若使废气的空燃比(A/F)in为浓空燃比,则能够对排气净化催化剂14内残存的吸留NOX进行还原,由此能够阻止NOX被排出到大气中的情况。于是,在本发明的实施例中,如图14所示那样,在从第2NOX净化方法切换到第1NOX净化方法时,为了使排气净化催化剂14中吸留的NOX被释放出并被还原,流入排气净化催化剂14的废气的空燃比暂时为浓空燃比。
在这种情况下,在如图14所示的实施例中,在将要从第2NOX净化方法切换到第1NOX净化方法之前,通过向燃烧室2内供给追加的燃料W,流入排气净化催化剂14的废气的空燃比为浓空燃比。另外,图14表示了流入排气净化催化剂14的废气的空燃比(A/F)in的变化、和被排气净化催化剂14吸留的吸留NOX量∑NOX的变化。根据图14可知,在第1NOX净化方法开始时,吸留NOX量∑NOX成为零,由此NOX向大气中排出的情况被阻止。
另一方面,对于基于第1NOX净化方法的NOX净化作用来说,只要氧化催化剂13没有活性化就不被进行。因此,在本发明的实施例中,第1NOX净化方法仅在氧化催化剂13的温度TB成为了活性温度TB0以上时被使用,在氧化催化剂13的温度TB低于活性温度TB0时,第1NOX净化方法的使用被禁止。此时,即、在氧化催化剂13的温度TB低于活性温度TB0时,使用第2NOX净化方法。
另外,在本发明的代表实施例中,在氧化催化剂13的温度TB在活性温度TB0以上时,使用第1NOX净化方法和第2NOX净化方法的其中一种。在这种情况下,在与使用第2NOX净化方法相比使用第1NOX净化方法NOX净化效率较高时,使用第1NOX净化方法,在与使用第1NOX净化方法相比使用第2NOX净化方法NOX净化效率较高时,使用第2NOX净化方法。
图15表示了用于执行本发明的代表实施例的NOX净化控制过程。该过程每隔一定时间就被插入执行。
参照图15,首先,在最初的步骤60中,根据图9所示的映射计算每单位时间的排出NOX量NOXA。接着,进行至决定是使用第1NOX净化方法还是使用第2NOX净化方法的NOX净化方法决定部A。在该NOX净化方法决定部A中,首先在最初的步骤61中,判别氧化催化剂13的温度TB是否在活性温度TB0以上。在TB<TB0时,判断为应该使用第2NOX净化方法,此时进行至步骤64。
与此相对,在TB≥TB0时,进行至步骤62,计算利用了第1NOX净化方法时的NOX净化效率F1和利用了第2NOX净化方法时的NOX净化效率F2。该NOX净化效率F1、F2表示为了得到单位NOX净化率所需要的每单位时间的燃料或者烃的消耗量。在这种情况下,NOX净化效率F1根据图12的(A)所示的烃供给量QE、烃的喷射间隔和图5所示的NOX净化率来计算,NOX净化效率F2根据图12的(B)所示的追加的燃料量W、在图8中成为浓空燃比的时间点之间的间隔和图11所示的NOX净化率被计算。
接着,在步骤63中,判别NOX净化效率F1是否高于NOX净化效率F2。在F1≥F2时,判断为应该使用第1NOX净化方法,此时进行至步骤68。与此相对,在F1<F2时判断为应该使用第2NOX净化方法,进行至步骤64。
接着,先对从步骤64到步骤67中所执行的第2NOX净化方法进行说明。首先,在开始的步骤64中,通过对∑NOX加上图9所示的排出NOX量NOXA来计算吸留NOX量∑NOX。接着,在步骤65中判别吸留NOX量∑NOX是否超过了容许值MAX。若∑NOX>MAX,则进行至步骤66,根据图12的(B)所示的映射计算追加的燃料量W,进行追加的燃料的喷射作用。接着,在步骤67中,∑NOX被清零。
接着,对从步骤68到步骤74所进行的第1NOX净化方法进行说明。首先,在开始的步骤68中,判别用于对排气净化催化剂14内残存的吸留NOX进行处理的吸留NOX处理是否被进行。在吸留NOX处理没有被进行时,进行至步骤69,判别当前是否做出了从第2NOX净化方法切换到第1NOX净化方法的决定。在当前做出了从第2NOX净化方法切换到第1NOX净化方法的决定时,进行至步骤70,判别吸留NOX量∑NOX是否少于预先规定的较小的值MIN。
在∑NOX>MIN时,进行至步骤71,进行吸留NOX处理。在该实施例中,如图14所示那样,在将要从第2NOX净化方法切换到第1NOX净化方法之前,废气的空燃比(A/F)in暂时为浓空燃比。接着,在步骤72中,∑NOX被清零。另外,在吸留NOX处理开始时,从步骤68跳到步骤71,直到吸留NOX处理结束。
另一方面,当在步骤69中判断为当前没有做出从第2NOX净化方法切换到第1NOX净化方法的决定时,进行至步骤73。另外,在步骤70中,在判断为∑NOX<MIN时,即在判断为NOX基本没有被吸留时,也进行至步骤73。在步骤73中,根据图12的(A)所示的映射来计算烃供给量QE,进行烃的喷射处理。接着,在步骤74中,根据下式计算在基于第1NOX净化方法的NOX净化作用中被排气净化催化剂14吸留的NOX量∑NOX。∑NOX←∑NOX+SX·NOXA-NOXD
这里,SX·NOXA是如上述那样每单位时间吸留的NOX量,NOXD是图13的(A)所示的喷出速度。在从第1NOX净化方法切换到了第2NOX净化方法时,在步骤64中,对在步骤74中计算出的∑NOX加上NOXA。
图16表示了另一个实施例。在该实施例中,与NOX净化效率F1相比一般认为NOX净化效率F2较高的内燃机的运转范围,如在图16的(A)中被阴影表示那样,例如预先被设定为内燃机负载L和内燃机转速N的函数,在氧化催化剂13活性化时,按照图16的(A)来决定NOX净化方法。
图16的(B)表示了图15的NOX净化方法决定部A的另一个实施例。参照图16的(B),在步骤61中,在氧化催化剂13的温度TB低于活性温度TB0时,判断为应该使用第2NOX净化方法,进行至图15的步骤64。与此相对,在步骤61中,在判别为TB≥TB0时进行至步骤61a,判别内燃机的运转状态是否是在图16的(A)中被阴影所示的、应该使用第2NOX净化方法的范围。在内燃机的运转状态是应该使用第2NOX净化方法的范围时,进行至图15的步骤64。与此相对,在判断为内燃机的运转状态不是应该使用第2NOX净化方法的范围时,进行至图15的步骤68。
图17表示了图15的NOX净化方法决定部A的又一个实施例。即,利用了第1NOX净化方法时的NOX净化率如图5所示那样,当排气净化催化剂14的温度TC成为临界温度TC0以下时开始急速地下降。与此相对,如图11所示那样,利用了第2NOX净化方法时的NOX净化率在排气净化催化剂14的温度TC下降时比较缓慢地下降。因此,在该实施例中,在排气净化催化剂14的温度TC高于临界温度TC0时利用第1NOX净化方法,在排气净化催化剂14的温度TC低于临界温度TC0时利用第2NOX净化方法。
即,参照图17,在步骤61中,在氧化催化剂13的温度TB低于活性温度TB0时,判断为应该利用第2NOX净化方法,进行至图15的步骤64。与此相对,在步骤61中,在判别为TB≥TB0时进行至步骤61a,判别排气净化催化剂14的温度TC是否高于临界温度TC0。在TC<T0时进行至图15的步骤64。与此相对,在TC≥T0时判断为应该利用第1NOX净化方法,进行至图15的步骤68。
图18表示了图15的NOX净化方法决定部A的又一个实施例。即,在第1NOX净化方法与第2NOX净化方法相比,待还原的NOX量较多时,即在废气中的NOX浓度D较高时,能够得到较高的NOX净化率。因此,在该实施例中,根据废气中的NOX浓度D是否超过了设定值D0,来判断是利用第1NOX净化方法还是利用第2NOX净化方法。
即,参照图18,在步骤61中,在氧化催化剂13的温度TB低于活性温度TB0时,判断为应该利用第2NOX净化方法,进行至图15的步骤64。与此相对,在步骤61中,在判别为TB≥TB0时进行至步骤61a,判别排气净化催化剂14的温度TC是否高于临界温度TC0。在TC<T0时进行至图15的步骤64。与此相对,在TC≥T0时进行至步骤61b,判别例如由NOX浓度传感器检测出的废气中的NOX浓度D是否高于设定值D0。在D<D0时进行至图15的步骤64。与此相对,在D≥D0时,判断为应该利用第1NOX净化方法,进行至图15的步骤68。
图19表示了在图15的步骤71中进行的吸留NOX处理的另一个实施例。在该实施例中,在从第2NOX净化方法切换到了第1NOX净化方法后,紧接着流入排气净化催化剂14的废气的空燃比(A/F)in为浓空燃比。此时,通过使从烃供给阀16供给的烃量增大,废气的空燃比(A/F)in为浓空燃比。
即,在做出了从第2NOX净化方法切换到第1NOX净化方法的决定时,在吸留NOX量∑NOX较多的情况下,仅仅通过向燃烧室2内喷射追加的燃料来只进行一次使废气的空燃比(A/F)in为浓空燃比的处理,有时会无法释放出并还原全部的吸留NOX。在这样的情况下,如图19所示那样,在基于第1NOX净化方法的NOX净化作用开始时,通过增加烃的供给量,废气的空燃比(A/F)in为浓空燃比,由此全部的吸留NOX被释放出并被还原。
另一方面,若向燃烧室2内喷射追加的燃料,则燃烧室2内的温度升高。因此有时会发生如下情况,即、在燃烧温度变高的高负载运转时,无法通过向燃烧室2内喷射追加的燃料来使废气的空燃比(A/F)in为浓空燃比。在这种情况下,通过停止喷射追加的燃料,并增加烃的供给量,废气的空燃比(A/F)in为浓空燃比。
图20中表示了在图15的步骤71中进行的吸留NOX处理的又一个实施例。在该实施例中,在从第2NOX净化方法切换到了第1NOX净化方法后,在基于第1NOX净化方法的NOX净化作用开始后流入排气净化催化剂14的废气的空燃比(A/F)in为浓空燃比。在该实施例中,在吸留NOX被从排气净化催化剂14喷出时,为了还原该被喷出的NOX,通过向燃烧室2内供给追加的燃料,或者通过增加烃的供给量,废气的空燃比(A/F)in为浓空燃比。
另一方面,若废气中包含的硫黄附着在贵金属表面上,即贵金属发生了硫中毒,则活性NO2 *变得难以生成。因此,优选贵金属的硫中毒量越增大则越增大烃的供给量QE,以使得即使贵金属发生了硫中毒,活性NO2 *的生成量也不会下降。在图21所示的实施例中,随着硫中毒量的增大也使针对烃供给量QE的增量系数增大,以使得即使硫中毒量增大,活性NO2 *的生成量也不会下降。
图22表示了由一种催化剂形成图1所示的烃部分氧化用催化剂13和排气净化催化剂14的情况。该催化剂例如具备在废气的流动方向上延伸的多个废气流通路,图22表示了该催化剂的废气流通路的内周壁80的表面部分的截面放大图。如图22所示那样,在废气流通路的内周壁80的表面上形成有下部涂层81,下部涂层81上形成有上部涂层82。在图22所示的例子中,涂层81、82都是由粉体的集合体构成,图22中表示了构成各涂层81、82的粉体的放大图。根据这些粉体的放大图可知,上部涂层82包括图2的(A)所示的烃部分氧化用催化剂、例如氧化催化剂,下部涂层81包括图2的(B)所示的排气净化催化剂。
在图22所示的催化剂被使用的情况下,如图22所示那样,废气中包含的烃HC扩散到上部涂层82内并被部分氧化,被部分氧化的烃扩散到下部涂层81内。即,在图22所示的例子中,也和图1所示的例子同样,烃部分氧化用催化剂和排气净化催化剂按照在烃部分氧化用催化剂上被部分氧化的烃流入排气净化催化剂的方式被配置而成。另一方面,当在图22所示的催化剂上利用了第1NOX净化方法的情况下,废气中包含的NOX扩散到下部涂层81内并成为活性NO2 *。此时在下部涂层81内,由活性NO2 *和被部分氧化的烃生成还原性中间体R-NCO、R-NH2,并且活性NO2 *与还原性中间体R-HCO、R-NH2发生反应,成为N2、CO2、H2O。
另一方面,如图2的(B)所示那样,在排气净化催化剂14的催化剂载体52上担载有贵金属53、54,因此在排气净化催化剂14内,也能够将烃改良成碳数量较少的自由基状的烃HC。在这种情况下,如果在排气净化催化剂14内能够对烃进行充分地改良,即能够在排气净化催化剂14内对烃进行充分地部分氧化,则无需再在排气净化催化剂14的上游如图1所示那样配置氧化催化剂13。因此,在本发明的一实施例中,没有在内燃机排气通路内安装氧化催化剂13,因此在该实施例中,从烃供给阀16喷射的烃被直接供给到排气净化催化剂14。
在该实施例中,从烃供给阀16喷射的烃在排气净化催化剂14内被部分氧化,并且在排气净化催化剂14内由废气中包含的NOX生成活性NO2 *。在排气净化催化剂14内,由这些活性NO2 *和被部分氧化的烃生成还原性中间体R-NCO、R-NH2,并且活性NO2 *与还原性中间体R-NCO、R-NH2发生反应从而成为N2、CO2、H2O。即,在该实施例中,在烃供给阀16下游的内燃机排气通路内配置有排气净化催化剂14,该排气净化催化剂14用于使从烃供给阀16喷射的且被部分氧化的烃和废气包含的NOX发生反应。
附图标记说明:
4...进气岐管;5...排气岐管;7...排气涡轮增压器;12...排气管;13...氧化催化剂;14...排气净化催化剂;16...烃供给阀。
Claims (18)
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有用于供给烃的烃供给阀,在烃供给阀下游的内燃机排气通路内配置有用于使从烃供给阀喷射出且被部分氧化的烃与废气中包含的NOX发生反应的排气净化催化剂,在该排气净化催化剂上担载有贵金属催化剂并且形成有碱性层,该排气净化催化剂具有当一边将流入排气净化催化剂的废气的空燃比维持为稀空燃比,一边以预先规定的供给间隔从烃供给阀喷射烃时,对废气中包含的NOX进行还原的性质,并且具有当烃的供给间隔长于该预先规定的供给间隔时,废气中包含的NOX的吸留量增大的性质,该排气净化装置在内燃机运转时根据内燃机的运转状态来选择性地使用第1NOX净化方法和第2NOX净化方法,其中,该第1NOX净化方法是一边将流入排气净化催化剂的废气的空燃比维持为稀空燃比,一边以上述预先规定的供给间隔来从烃供给阀喷射烃,由此对废气中包含的NOX进行净化的方法,该第2NOX净化方法是以长于上述预先规定的供给间隔的间隔来将流入排气净化催化剂的废气的空燃比从稀空燃比切换到浓空燃比,由此对NOX进行净化的方法。
2.根据权利要求1所述的内燃机的排气净化装置,其中,
在烃供给阀下游的内燃机排气通路内,将上述排气净化催化剂和能够对从烃供给阀喷射出的烃进行部分氧化的烃部分氧化用催化剂配置成使得在烃部分氧化用催化剂中被部分氧化的烃流入排气净化催化剂。
3.根据权利要求2所述的内燃机的排气净化装置,其中,
上述烃部分氧化用催化剂包括在上述排气净化催化剂上游的内燃机排气通路内配置的氧化催化剂。
4.根据权利要求2所述的内燃机的排气净化装置,其中,
在包括上述排气净化催化剂的下部涂层上,形成有包括上述烃部分氧化用催化剂的上部涂层。
5.根据权利要求1或2所述的内燃机的排气净化装置,其中,
在上述第1NOX净化方法中,废气中包含的NOX和被部分氧化的烃由于上述贵金属催化剂而发生反应,而生成包含氮和烃的还原性中间体,并且所生成的还原性中间体被保持在上述碱性层上,NOX由于保持在该碱性层上的还原性中间体的还原作用而被还原,其中,上述烃的预先规定的供给间隔是使还原性中间体在该碱性的废气流通表面部分上持续存在所需要的供给间隔。
6.根据权利要求1所述的内燃机的排气净化装置,其中,
在上述第2NOX净化方法中,在流入排气净化催化剂的废气的空燃比为稀空燃比时,废气中的NOX被吸收到碱性层内,当流入排气净化催化剂的废气的空燃比为浓空燃比时,被吸收的NOX被从碱性层释放出并被还原。
7.根据权利要求1所述的内燃机的排气净化装置,其中,
上述贵金属催化剂由铑Rh和钯Pd中的至少一种和铂Pt构成。
8.根据权利要求1所述的内燃机的排气净化装置,其中,
上述碱性层包含碱金属、或者碱土类金属、或者稀土类、或者能够向NOX提供电子的金属。
9.根据权利要求1所述的内燃机的排气净化装置,其中,
上述第1NOX净化方法仅在上述氧化催化剂的温度处于活性温度以上时被使用,在该氧化催化剂的温度低于活性温度时,该第1NOX净化方法的使用被禁止。
10.根据权利要求9所述的内燃机的排气净化装置,其中,
在氧化催化剂的温度在活性温度以上时,使用第1NOX净化方法和第2NOX净化方法中的任意一种。
11.根据权利要求10所述的内燃机的排气净化装置,其中,
在与使用第2NOX净化方法相比使用第1NOX净化方法时NOX净化效率高的情况下,使用第1NOX净化方法,在与使用第1NOX净化方法相比使用第2NOX净化方法时NOX净化效率高的情况下,使用第2NOX净化方法。
12.根据权利要求10所述的内燃机的排气净化装置,其中,
使用了第1NOX净化方法时的NOX净化率当排气净化催化剂的温度成为临界温度以下时开始下降,在排气净化催化剂的温度高于该临界温度时,使用第1NOX净化方法,在排气净化催化剂的温度低于该临界温度时,使用第2NOX净化方法。
13.根据权利要求9所述的内燃机的排气净化装置,其中,
在氧化催化剂的温度低于活性温度时,使用第2NOX净化方法。
14.根据权利要求1所述的内燃机的排气净化装置,其中,
在从第2NOX净化方法向第1NOX净化方法切换时,为了使排气净化催化剂中吸留的NOX被释放出并被还原,使流入排气净化催化剂的废气的空燃比暂时为浓空燃比。
15.根据权利要求14所述的内燃机的排气净化装置,其中,
在将要从第2NOX净化方法向第1NOX净化方法切换之前,使流入排气净化催化剂的废气的空燃比为浓空燃比。
16.根据权利要求15所述的内燃机的排气净化装置,其中,
在刚从第2NOX净化方法切换到第1NOX净化方法之后,也使流入排气净化催化剂的废气的空燃比为浓空燃比。
17.根据权利要求14所述的内燃机的排气净化装置,其中,
在从第2NOX净化方法切换到第1NOX净化方法后,在基于第1NOX净化方法的NOX净化作用开始后,使流入排气净化催化剂的废气的空燃比为浓空燃比。
18.根据权利要求1所述的内燃机的排气净化装置,其中,
当第2NOX净化方法被使用时计算出的排气净化催化剂的NOX吸留量超过了预先规定的容许值时,使流入排气净化催化剂的废气的空燃比暂时为浓空燃比,在从第1NOX净化方法切换到第2NOX净化方法时,对第1NOX净化方法被使用时计算出的NOX吸留量和在切换到第2NOX净化方法后计算出的NOX吸留量进行合计,在该合计值超过了预先规定的容许值时,流入排气净化催化剂的废气的空燃比暂时为浓空燃比。
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RU2011139713A (ru) | 2013-04-10 |
EP2402572A4 (en) | 2012-07-18 |
WO2011114501A1 (ja) | 2011-09-22 |
US20140007557A1 (en) | 2014-01-09 |
BRPI1012611B1 (pt) | 2020-08-11 |
CN102378854B (zh) | 2014-06-18 |
EP2402572A1 (en) | 2012-01-04 |
ES2508365T3 (es) | 2014-10-16 |
CA2755977C (en) | 2014-01-21 |
US9458745B2 (en) | 2016-10-04 |
US20120124971A1 (en) | 2012-05-24 |
US8683784B2 (en) | 2014-04-01 |
RU2480592C1 (ru) | 2013-04-27 |
EP2402572B1 (en) | 2014-08-06 |
BRPI1012611A2 (pt) | 2018-06-19 |
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CA2755977A1 (en) | 2011-09-22 |
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