CN102791972A - 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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- CN102791972A CN102791972A CN2010800652236A CN201080065223A CN102791972A CN 102791972 A CN102791972 A CN 102791972A CN 2010800652236 A CN2010800652236 A CN 2010800652236A CN 201080065223 A CN201080065223 A CN 201080065223A CN 102791972 A CN102791972 A CN 102791972A
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Abstract
本发明的内燃机的控制装置,在内燃机排气系统中配置有银-氧化铝系催化装置和NOX还原催化装置,在银-氧化铝系催化装置达到高温侧的第一设定温度T1时(步骤110),在NOX还原催化装置中由还原剂还原净化从银-氧化铝系催化装置释放出的NOX(步骤115),在银-氧化铝系催化装置达到低温侧的第二设定温度时(步骤104),也在NOX还原催化装置中由还原剂还原净化从银-氧化铝系催化装置释放出的NOX(步骤107)。
Description
技术领域
本发明涉及内燃机的排气净化装置。
背景技术
以氧化铝为载体涂层材料并担载了氧化银的催化装置众所周知(参照专利文献1),这样的银-氧化铝系催化装置发挥功能以使得吸附排气(废气)中的NOX,当达到设定温度时释放所吸附的NOX。
现有技术文献
专利文献1:日本专利2801423
专利文献2:日本特开2009-275631
发明内容
在如上述那样的银-氧化铝系催化装置中,在达到设定温度、释放NOX时,一般地,在下游侧的催化装置中,由所供给的还原剂将释放的NOX还原净化。
但是,仅靠银-氧化铝系催化装置达到设定温度时的NOX还原净化,有时不能充分地降低向大气中释放的NOX。
因此,本发明的目的是在内燃机排气系统中配置有银-氧化铝系催化装置和NOX还原催化装置的内燃机的排气净化装置中,充分地降低NOX的大气释放量。
本发明的权利要求1所述的内燃机的排气净化装置,其特征在于,在内燃机排气系统中配置有银-氧化铝系催化装置和NOX还原催化装置,在上述银-氧化铝系催化装置达到高温侧的第一设定温度时,在上述NOX还原催化装置中由还原剂还原净化从上述银-氧化铝系催化装置释放出的NOX,在上述银-氧化铝系催化装置达到低温侧的第二设定温度时也在上述NOX还原催化装置中由还原剂还原净化从上述银-氧化铝系催化装置释放出的NOX。
本发明的权利要求2所述的内燃机的排气净化装置,其特征在于,在权利要求1所述的内燃机的排气净化装置中,在为上述第二设定温度以上且低于上述第一设定温度时,推定向上述银-氧化铝系催化装置吸附的高温侧NOX吸附量。
本发明的权利要求3所述的内燃机的排气净化装置,其特征在于,在权利要求2所述的内燃机的排气净化装置中,仅在推定出的上述高温侧NOX吸附量为第一设定量以上时,在上述银-氧化铝系催化装置达到上述第一设定温度时,在上述NOX还原催化装置中由还原剂还原净化从上述银-氧化铝系催化装置释放出的NOX。
本发明的权利要求4所述的内燃机的排气净化装置,其特征在于,在权利要求2或3所述的内燃机的排气净化装置中,在上述银-氧化铝系催化装置达到上述第一设定温度,在上述NOX还原催化装置中还原净化从上述银-氧化铝系催化装置释放出的NOX时,基于推定出的上述高温侧NOX吸附量,确定向上述NOX还原催化装置供给的还原剂的量。
本发明的权利要求5所述的内燃机的排气净化装置,其特征在于,在权利要求1所述的内燃机的排气净化装置中,在低于上述第二设定温度时,推定向上述银-氧化铝系催化装置吸附的低温侧NOX吸附量。
本发明的权利要求6所述的内燃机的排气净化装置,其特征在于,在权利要求5所述的内燃机的排气净化装置中,仅在推定出的上述低温侧NOX吸附量为第二设定量以上时,在上述银-氧化铝系催化装置达到上述第二设定温度时,在上述NOX还原催化装置中由还原剂还原净化从上述银-氧化铝系催化装置释放出的NOX。
本发明的权利要求7所述的内燃机的排气净化装置,其特征在于,在权利要求5或6所述的内燃机的排气净化装置中,在上述银-氧化铝系催化装置达到上述第二设定温度,在上述NOX还原催化装置中还原净化从上述银-氧化铝系催化装置释放出的NOX时,基于推定出的上述低温侧NOX吸附量,确定向上述NOX还原催化装置供给的还原剂的量。
根据本发明的权利要求1所述的内燃机的排气净化装置,不仅在银-氧化铝系催化装置达到高温侧的第一设定温度时,在NOX还原催化装置中由还原剂还原净化从银-氧化铝系催化装置释放出的NOX,而且在银-氧化铝系催化装置达到低温侧的第二设定温度时,由于低于第二设定温度时吸附的NOX被释放,因此此时也在NOX还原催化装置中由还原剂还原净化从银-氧化铝系催化装置释放出的NOX,由此,可以充分地降低NOX的大气释放量。
根据本发明的权利要求2所述的内燃机的排气净化装置,在权利要求1所述的内燃机的排气净化装置中,在为第二设定温度以上且低于第一设定温度时,推定向银-氧化铝系催化装置吸附的高温侧NOX吸附量。
根据本发明的权利要求3所述的内燃机的排气净化装置,在权利要求2所述的内燃机的排气净化装置中,仅在推定出的高温侧NOX吸附量为第一设定量以上时,在银-氧化铝系催化装置达到第一设定温度时,在NOX还原催化装置中由还原剂还原净化从银-氧化铝系催化装置释放出的NOX,在银-氧化铝系催化装置达到第一设定温度时所释放的NOX量少时,中止向NOX还原催化装置供给还原剂,抑制还原剂的消耗量。
根据本发明的权利要求4所述的内燃机的排气净化装置,在权利要求2或3所述的内燃机的排气净化装置中,在银-氧化铝系催化装置达到第一设定温度,在NOX还原催化装置中还原净化从银-氧化铝系催化装置释放出的NOX时,基于推定出的高温侧NOX吸附量,确定向NOX还原催化装置供给的还原剂的量,抑制还原剂的消耗量以使得不供给超过需要的还原剂。
根据本发明的权利要求5所述的内燃机的排气净化装置,在权利要求1所述的内燃机的排气净化装置中,在低于第二设定温度时,推定向银-氧化铝系催化装置吸附的低温侧NOX吸附量。
根据本发明的权利要求6所述的内燃机的排气净化装置,在权利要求5所述的内燃机的排气净化装置中,仅在推定出的低温侧NOX吸附量为第二设定量以上时,在银-氧化铝系催化装置达到第二设定温度时,在NOX还原催化装置中由还原剂还原净化从银-氧化铝系催化装置释放出的NOX,在银-氧化铝系催化装置达到第二设定温度时所释放的NOX量少时,中止向还原催化装置供给还原剂,抑制还原剂的消耗量。
根据本发明的权利要求7所述的内燃机的排气净化装置,在权利要求5或6所述的内燃机的排气净化装置中,在银-氧化铝系催化装置达到第二设定温度,在NOX还原催化装置中还原净化从银-氧化铝系催化装置释放出的NOX时,基于推定出的低温侧NOX吸附量,确定向NOX还原催化装置供给的还原剂的量,抑制还原剂的消耗量以使得不供给超过需要的还原剂。
附图说明
图1是表示本发明的内燃机的排气净化装置的概略图。
图2是表示银-氧化铝系催化装置中的温度和NOX释放量的关系的曲线图。
图3是用于在本发明的排气净化装置中实施的NOX还原的流程图。
具体实施方式
图1是表示本发明的内燃机的排气净化装置的概略图,在该图中,1是内燃机的排气通路。内燃机是柴油发动机或缸内喷射式火花点火内燃机之类的实施稀薄燃烧的内燃机。在这样的内燃机的排气中,含有比较多的NOX,因此在排气通路1中配置有吸附NOX的银-氧化铝系催化装置2,另外,在银-氧化铝系催化装置2的下游侧配置有用于还原NOX的NOX还原催化装置3,在银-氧化铝系催化装置2和NOX还原催化装置3之间,配置有用于供给还原剂的还原剂供给装置4。
银-氧化铝系催化装置2是以氧化铝为载体涂层材料并担载了氧化银的装置,可将排气中NOX以硝酸银的形式吸附,如果达到第一设定温度(约300℃)则释放所吸附的NOX。所释放的NOX可在NOX还原催化装置3中由从还原剂供给装置4供给的还原剂还原净化。
银-氧化铝系催化装置2,是例如在蜂窝状的基材上形成氧化铝(Al2O3)载体涂层,相对于氧化铝200g(为提高耐热性也可以混入镧(La))以0.2摩尔银的比例,在氧化铝载体涂层上担载了氧化银(Ag2O)的装置。
作为这样的催化剂的调制方法,例如将1600g氧化铝MI386(La/Al2O3)粉末、710.4g粘结剂A520和3600g水利用磨碎机(attritor)搅拌20分钟,将搅拌物在基材上按每单位体积200g/L进行涂覆。接着,将其在大气中在250℃烧成30分钟,接着,在500℃烧成1小时,在基材上形成氧化铝载体涂层。
另一方面,向236.2g硝酸银中加入离子交换水使其溶解形成为1700cc,调制Ag浓度为0.82摩尔/L的硝酸银水溶液。
在这样的硝酸银水溶液中,将上述的氧化铝载体涂层浸渍30分钟,通过吸水担载来担载每单位体积0.2摩尔/L的Ag。接着,使鼓风干燥机工作使其干燥20分钟,在大气中在550℃烧成3小时后,在每分钟通过7L的含有5%氢气的氮气中在500℃烧成3小时。
在这样调制出的催化剂中,氧化银(Ag2O)从氧化铝(Al2O3)载体涂层露出,使排气中的NO氧化成为NO2后可以作为硝酸银(AgNO3)良好地保持。
NOX还原催化装置3可以为三元催化装置,在该情况下,可从还原剂供给装置4供给作为还原剂的例如燃料,使三元催化装置内的排气的空燃比为浓来还原净化NOX。
另外,NOX还原催化装置3可以为使用氨(NH3)选择性地还原净化NOX的选择还原型NOX催化装置,在该情况下,可从还原剂供给装置4供给作为还原剂的例如尿素,在选择还原型NOX催化装置中,通过尿素的水解来产生氨,从而还原净化NOX。
另外,在NOX还原催化装置3由能够部分氧化排气中的烃的上游侧的氧化催化装置(担载铂(Pt)、银(Ag)或铜(Cu)等)、和净化由部分氧化了的烃和排气中的NOX在氧化催化装置中生成的含氮烃化合物(胺化合物、异氰酸酯化合物和亚硝基化合物)的下游侧的催化装置(担载铂(Pt)或铑(Rh))构成的情况下,为了净化NOX,可从还原剂供给装置4供给作为还原剂的烃(燃料)。特别是如果利用所供给的烃使排气的空燃比为15.5以下的稀空燃比,则在氧化催化装置中容易生成含氮烃化合物,可以将排气中的NOX的大体全部进行净化。
但是,仅在银-氧化铝系催化装置2达到第一设定温度时,利用还原剂供给装置4供给还原剂,在NOX还原催化装置3中还原从银-氧化铝系催化装置2释放出的NOX,也不能充分地降低向大气中释放的NOX。
图2表示银-氧化铝系催化装置2中的温度T和NOX释放量的关系。认为在银-氧化铝系催化装置2中,不仅作为硝酸银吸附NOX,也作为亚硝酸银(AgNO2)吸附NOX,认为作为硝酸银被吸附的NOX在第一设定温度T1下被释放,作为亚硝酸银被吸附的NOX在比第一设定温度T1低的第二设定温度T2(约150℃)下被释放。在此,认为在银-氧化铝系催化装置2低于第二设定温度T2时,排气中的NOX主要作为亚硝酸银被吸附,在银-氧化铝系催化装置2高于第二设定温度T2且低于第一设定温度T1时,排气中的NOX主要作为硝酸银被吸附。
本实施方式的内燃机的排气净化装置,利用电子控制装置(未图示)按照图3所示的流程图控制还原剂供给装置4,充分地降低向大气中的NOX释放量。
首先,在步骤101中,判断银-氧化铝系催化装置2的温度T(测定温度或推定温度)是否低于第二设定温度T2。在该判断为肯定时,排气中的NOX作为亚硝酸银被银-氧化铝系催化装置2吸附。由此,在步骤102中,基于每个运行状态的每单位时间的从汽缸排出的NOX量确定的每单位时间的作为亚硝酸银被银-氧化铝系催化装置2新吸附的吸附量a2,基于当前的运行状态(内燃机负荷和内燃机转速)和当前的银-氧化铝系催化装置2的温度T(温度T越低就越容易吸附)使用映射图(map)等确定。在此的单位时间成为本流程图的重复间隔。
接着,在步骤103中,将步骤102中确定的吸附量a2累计到作为亚硝酸银被银-氧化铝系催化装置2吸附的低温侧NOX吸附量A2中。这样,在银-氧化铝系催化装置2的温度低于第二设定温度T2时,排气中的NOX作为亚硝酸银向银-氧化铝系催化装置2吸附,低温侧NOX吸附量A2逐渐增加。
另一方面,如果步骤101的判断为否定,则在步骤104中,判断银-氧化铝系催化装置2的温度T是否达到第二设定温度T2。如果该判断为肯定,则作为亚硝酸银被吸附的NOX从银-氧化铝系催化装置2基本被释放出。接着,在步骤105中,判断被银-氧化铝系催化装置2作为亚硝酸银吸附的低温侧NOX吸附量A2是否为设定量A2’以上,在该判断为否定时,以亚硝酸银形式只吸附了很少量的NOX,所释放的NOX量也很少,因此在步骤108中,将被银-氧化铝系催化装置2作为亚硝酸银吸附的低温侧NOX吸附量A2定为0(或很少的规定量),在该状态下结束。
但是,在步骤105的判断为肯定时,从银-氧化铝系催化装置2释放作为亚硝酸银被吸附的比较多的NOX,因此在步骤106中,基于作为亚硝酸银被吸附的低温侧NOX吸附量A2,确定由还原剂供给装置4供给的还原剂量RA。即,低温侧NOX吸附量A2越多,则还原剂量RA就越多,优选:确定将从银-氧化铝系催化装置2释放的NOX在下游侧的NOX还原催化装置3中没有过分与不足地还原所需要的还原剂量RA。
在NOX还原催化装置3是选择还原型NOX催化装置的情况下,还原剂量RA设为相对于被银-氧化铝系催化装置2作为亚硝酸银吸附的低温侧NOX吸附量A2的当量比的尿素量。另外,在NOX还原催化装置3是三元催化装置的情况下,使当前的排气达到理论空燃比所需要的燃料量,加上将从银-氧化铝系催化装置2释放的作为亚硝酸银被吸附NOX没有过分与不足地还原所需要的燃料量,作为还原剂量RA。
接着,在步骤107中,由还原剂供给装置4供给在步骤106中确定的还原剂量RA,在步骤108中,将被银-氧化铝系催化装置2作为亚硝酸银吸附的低温侧NOX吸附量A2定为0(或很少的规定量)从而结束。
这样,在将从银-氧化铝系催化装置2在第二设定温度T2下释放的NOX在NOX还原催化装置3中还原净化时,不会供给超过需要量的还原剂,可以抑制还原剂的消耗量,并且,也可以抑制还原剂的大气释放。也可以省略步骤105的判断,在银-氧化铝系催化装置2达到第二设定温度T2时,始终在步骤106中确定还原剂的需要量RA,并在步骤107中供给还原剂。
另外,在步骤104的判断为否定时,在步骤109中,判断银-氧化铝系催化装置2的温度T是否低于第一设定温度T1。在该判断为肯定时,即,银-氧化铝系催化装置2的温度T高于第二设定温度T2且低于第一设定温度T1时,排气中的NOX作为硝酸银被银-氧化铝系催化装置2吸附。由此,在步骤111中,基于每个运行状态的每单位时间的从汽缸排出的NOX量确定的每单位时间的作为硝酸银被银-氧化铝系催化装置2新吸附的吸附量a1,基于当前的运行状态(内燃机负荷和内燃机转速)和当前的银-氧化铝系催化装置2的温度T(温度T越低就越容易吸附)使用映射图(map)等确定。在此的单位时间成为本流程图的重复间隔。
接着,在步骤112中,将在步骤111中确定的吸附量a1累计到作为硝酸银被银-氧化铝系催化装置2吸附的高温侧NOX吸附量A1中。这样,在银-氧化铝系催化装置2的温度高于第二设定温度T2且低于第一设定温度T1时,排气中的NOX作为硝酸银向银-氧化铝系催化装置2吸附,高温侧NOX吸附量A1逐渐增加。
另一方面,如果步骤109的判断为否定,则在步骤110中,判断银-氧化铝系催化装置2的温度T是否达到第一设定温度T1。如果该判断为肯定,则从银-氧化铝系催化装置2作为硝酸银吸附的NOX基本被释放出。接着,在步骤113中,判断被银-氧化铝系催化装置2作为硝酸银吸附的高温侧NOX吸附量A1是否为设定量A1’以上,在该判断为否定时,只吸附了很少量的NOX,所释放的NOX量也很少,因此在步骤116中,将作为硝酸银向银-氧化铝系催化装置2吸附的高温侧NOX吸附量A1定为0(或很少的规定量),在该状态下结束。
但是,在步骤113的判断为肯定时,从银-氧化铝系催化装置2释放作为硝酸银被吸附的比较多的NOX,因此在步骤114中,基于作为硝酸银被吸附的高温侧NOX吸附量A1,确定由还原剂供给装置4供给的还原剂量RA。即,高温侧NOX吸附量A1越多,还原剂量RA就越多,优选:确定将从银-氧化铝系催化装置2释放的NOX在下游侧的NOX还原催化装置3中没有过分与不足地还原所需要的还原剂量RA。
在NOX还原催化装置3是选择还原型NOX催化装置的情况下,还原剂量RA设为相对于被银-氧化铝系催化装置2作为硝酸银吸附的高温侧NOX吸附量A1的当量比的尿素量。另外,在NOX还原催化装置3是三元催化装置的情况下,使当前的排气达到理论空燃比所需要的燃料量,加上将从银-氧化铝系催化装置2释放的作为硝酸银被吸附的NOX没有过分与不足地还原所需要的燃料量,作为还原剂量RA。
接着,在步骤115中,由还原剂供给装置4供给在步骤114中确定的还原剂量RA,在步骤116中,将被银-氧化铝系催化装置2作为硝酸银吸附的高温侧NOX吸附量A1定为0(或很少的规定量)从而结束。
这样,在将从银-氧化铝系催化装置2在第一设定温度T1下释放的NOX在NOX还原催化装置3中还原净化时,不会供给超过需要量的还原剂,可以抑制还原剂的消耗量,并且,也可以抑制还原剂的大气释放。也可以省略步骤113的判断,在银-氧化铝系催化装置2达到第一设定温度T1时,始终在步骤114中确定还原剂的需要量RA,并在步骤115中供给还原剂。
另外,在步骤110的判断为否定时,即,银-氧化铝系催化装置2的温度T比第一设定温度T1高时,为了排气中的NOX作为硝酸银向银-氧化铝系催化装置2吸附,与上述同样地,在步骤111中确定每单位时间的吸附量a1,在步骤112中,将在步骤111中确定的吸附量a1累计到被银-氧化铝系催化装置2作为硝酸银吸附的高温侧NOX吸附量A1中。但是,在银-氧化铝系催化装置2的温度T比第一设定温度T1高时,排气中NOX作为硝酸银被吸附的比例降低,因此在步骤110的判断为否定时,也可以中止高温侧NOX吸附量A1的累计。
这样,根据本实施方式的内燃机的排气净化装置,不仅在银-氧化铝系催化装置2达到高温侧的第一设定温度T1时,在NOX还原催化装置3中由还原剂还原净化从银-氧化铝系催化装置释放出的NOX,而且在银-氧化铝系催化装置2达到低温侧的第二设定温度T2时,在低于第二设定温度T2时吸附的NOX被释放,因此此时也在NOX还原催化装置3中由还原剂还原净化从银-氧化铝系催化装置2释放出的NOX,由此,可以充分地降低NOX的大气释放量。
在上述流程图中,为了使说明简单,将从银-氧化铝系催化装置2释放NOX的温度T设为第一设定温度T1(例如约300℃)和第二设定温度T2(例如约150℃),但这些温度不会仅限定于一个温度点,也可以分别为第一设定温度范围(例如290℃~310℃)以及第二设定温度范围(例如140℃~160℃)。
还原剂供给装置4也可以配置在银-氧化铝系催化装置2的上游侧,另外,在将燃料作为还原剂使用的情况下,作为还原剂供给装置也可以使用向汽缸内喷射燃料的燃料喷射阀,可以利用燃料喷射阀在例如膨胀冲程中向汽缸内喷射燃料。
另外,在图1所示的实施方式中,银-氧化铝系催化装置2和NOX还原催化装置3设为分体的,但这并不限定本发明。例如,如果在堇青石等基材上形成担载NOX还原催化装置的催化剂的NOX还原层,在该NOX还原层的上侧形成由担载氧化银的氧化铝构成的银-氧化铝系催化剂层,则可以将银-氧化铝系催化装置2和NOX还原催化装置3形成为一体化装置。
在该情况下,在银-氧化铝系催化剂层达到第一设定温度和第二设定温度,从银-氧化铝系催化剂层释放NOX时,向一体化装置供给还原剂,所释放的NOX在银-氧化铝系催化剂层的下侧的NOX还原层中使用所供给的还原剂还原净化。
附图标记说明
1…排气通路; 2…银-氧化铝系催化装置;
3…NOX还原催化装置; 4…还原剂供给装置。
Claims (7)
1.一种内燃机的排气净化装置,其特征在于,在内燃机排气系统中配置有银-氧化铝系催化装置和NOX还原催化装置,在所述银-氧化铝系催化装置达到高温侧的第一设定温度时,在所述NOX还原催化装置中由还原剂还原净化从所述银-氧化铝系催化装置释放出的NOX,在所述银-氧化铝系催化装置达到低温侧的第二设定温度时,也在所述NOX还原催化装置中由还原剂还原净化从所述银-氧化铝系催化装置释放出的NOX。
2.根据权利要求1所述的内燃机的排气净化装置,其特征在于,在为所述第二设定温度以上且低于所述第一设定温度时,推定向所述银-氧化铝系催化装置吸附的高温侧NOX吸附量。
3.根据权利要求2所述的内燃机的排气净化装置,其特征在于,仅在推定出的所述高温侧NOX吸附量为第一设定量以上时,在所述银-氧化铝系催化装置达到所述第一设定温度时,在所述NOX还原催化装置中由还原剂还原净化从所述银-氧化铝系催化装置释放出的NOX。
4.根据权利要求2或3所述的内燃机的排气净化装置,其特征在于,在所述银-氧化铝系催化装置达到所述第一设定温度,在所述NOX还原催化装置中还原净化从所述银-氧化铝系催化装置释放出的NOX时,基于推断出的所述高温侧NOX吸附量,确定向所述NOX还原催化装置供给的还原剂的量。
5.根据权利要求1所述的内燃机的排气净化装置,其特征在于,在低于所述第二设定温度时,推定向所述银-氧化铝系催化装置吸附的低温侧NOX吸附量。
6.根据权利要求5所述的内燃机的排气净化装置,其特征在于,仅在推定出的所述低温侧NOX吸附量为第二设定量以上时,在所述银-氧化铝系催化装置达到所述第二设定温度时,在所述NOX还原催化装置中由还原剂还原净化从所述银-氧化铝系催化装置释放出的NOX。
7.根据权利要求5或6所述的内燃机的排气净化装置,其特征在于,在所述银-氧化铝系催化装置达到所述第二设定温度,在所述NOX还原催化装置中还原净化从所述银-氧化铝系催化装置释放出的NOX时,基于推定出的所述低温侧NOX吸附量,确定向所述NOX还原催化装置供给的还原剂的量。
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CN1246070C (zh) * | 2002-04-29 | 2006-03-22 | 清华大学 | 一种稀薄燃烧型汽车尾气催化净化方法和装置 |
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