CN101542083B - 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
对于内燃机而言,在内燃机排气通路内配置有包含NOx吸藏催化剂的前段催化剂(12)和后段催化剂(14),在应解救这些催化剂(12、14)的SOx中毒时,进行SOx中毒解救处理,即使相对应的催化剂(12、14)的温度上升至SOx释放温度,同时使流入到相对应的催化剂(12、14)中的排气的空燃比为浓。在这种情况下,使进行后段催化剂(14)的SOx中毒解救处理的频率高于进行前段催化剂(12)的SOx中毒解救处理的频率。
Description
技术领域
本发明涉及内燃机的排气净化装置。
背景技术
将NOx吸藏催化剂配置在内燃机排气通路内的内燃机是众所周知的,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所含的NOx,在流入的排气的空燃比变为理论空燃比或者变为浓时将吸藏的NOx释放。该内燃机,在稀空燃比的条件下进行燃烧时,产生的NOx被NOx吸藏催化剂吸藏。另一方面,当NOx吸藏催化剂的对NOx吸藏能力接近饱和时,使排气的空燃比暂时变为浓,由此NOx从NOx吸藏催化剂中被释放出来并被还原。
然而,由于燃料中含有硫,所以排气中含有SOx。该SOx与NOx一起被NOx吸藏催化剂吸藏。但是,仅仅通过使排气的空燃比为浓,该SOx不会从NOx吸藏催化剂释放出来,因此被吸藏在NOx吸藏催化剂中的SOx的量逐渐增大。其结果,可吸藏的NOx量逐渐减少。
于是,为了阻止SOx被送入到NOx吸藏催化剂中,在NOx吸藏催化剂上游的内燃机排气通路内配置了SOx捕集催化剂的内燃机已被公知(参照日本特开2005-133610号公报)。对于该内燃机而言,排气中所含的SOx被SOx捕集催化剂捕获,这样一来就阻止了SOx流入NOx吸藏催化剂中。其结果,可以阻止由于吸藏SOx而导致对NOx的吸藏能力的降低。
因此,该SOx捕集催化剂只要是按照预定的使用方法,在预定的保证行驶距离以内,就可持续捕获排气中含有的SOx。但是,在例如使用者错误地使用了含有高浓度的硫的燃料、或车辆超过了预定的保证行使距离而行使时,容许容量以上的SOx被送入SOx捕集催化剂,这样一来就存在SOx捕集催化剂不能捕获SOx的问题。
考虑到这样的问题,在SOx捕集催化剂捕获了大量的SOx时,需要从SOx捕集催化剂中释放出SOx,恢复SOx捕集催化剂的捕获SOx能力。
发明内容
本发明的目的在于,提供一种可以高效地恢复这样的捕获SOx的能力或吸藏SOx的能力的内燃机排气净化装置。
根据本发明,提供一种内燃机的排气净化装置,其在内燃机排气通路内沿着排气气流依次配置有前段催化剂和后段催化剂,这些前段催化剂和后段催化剂由NOx吸藏催化剂构成,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所含的NOx,在流入的排气的空燃比变为理论空燃比或者浓时释放出所吸藏的NOx,在应解救前段催化剂的SOx中毒时,进行使前段催化剂的温度上升至SOx释放温度,同时使流入前段催化剂中的排气的空燃比为浓的SOx中毒解救处理,在应解救后段催化剂的SOx中毒时,进行使后段催化剂的温度上升至SOx释放温度,同时使流入后段催化剂中的排气的空燃比为浓的SOx中毒解救处理,并使进行后段催化剂的SOx中毒解救处理的频率高于进行前段催化剂的SOx中毒解救处理的频率。
即,由于后段催化剂比前段催化剂的热劣化程度低,所以后段催化剂的一方容易从SOx中毒中解救出来。因此,通过提高后段催化剂的SOx中毒解救处理的频率可以提高NOx净化率。
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;图3是表示排出SOx量SOXA的图谱的图;图4是表示NOx净化率的变化和SOx中毒解救处理的时机的时间图;图5是用于实施SOx中毒解救处理的流程图;图6是SOx捕集催化剂的基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1,1表示发动机主体,2表示各气缸的燃烧室,3表示用于向各燃烧室2内分别喷射燃料的电子控制式燃料喷射阀,4表示进气岐管,5表示排气岐管。进气岐管4借助于吸气管6与排气涡轮增压器7的压缩机7a的出口连接,压缩机7a的入口借助于吸入空气量检测器8与空气滤清器9连接。在吸气管6内配置有由步进电动机驱动的节气门10,进而在吸气管6周围设置有用于冷却在吸气管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,将内燃机冷却水导入到冷却装置11内,由内燃机冷却水将吸入空气冷却。
另一方面,排气岐管5与排气涡轮增压器7的排气涡轮7b的入口连接,排气涡轮7b的出口与前段催化剂12的入口连接。另外,前段催化剂12的出口借助于排气管13与后段催化剂14连接。在排气岐管5内配置有前段催化剂用还原剂供给阀15,该前段催化剂用还原剂供给阀15用于向流入到前段催化剂12中的排气中供给例如含有烃的还原剂,在排气管13内配置有后段催化剂用还原剂供给阀16,该后段催化剂用还原剂供给阀16用于向流入到后段催化剂14中的排气中供给例如含有烃的还原剂。进而,在与后段催化剂14的出口连接的排气管17内配置有NOx传感器18。
排气岐管5与进气岐管4借助于排气再循环(下面称作“EGR”)通路19相互连接,在EGR通路19内配置有电子控制式EGR控制阀20。另外,在EGR通路19周围设置有用于冷却在EGR通路19内流动的EGR气体的冷却装置21。在图1所示的实施例中,将内燃机冷却水导入冷却装置21内,由内燃机冷却水将EGR气体冷却。另一方面,各燃料喷射阀3借助于燃料供给管22与共轨23连接。从电子控制式的喷出量可变的燃料泵24向该共轨23内供给燃料,被供给到该共轨23内的燃料经由各燃料供给管22而被供给到燃料喷射阀3。
电子控制单元30包含数字计算机,具有由双向性总线31互相连接的ROM(只读存储器)32、RAM(随机存储器)33、CPU(微处理器)34、输入端口35以及输出端口36。吸入空气量检测器8、及NOx传感器18的输出信号分别借助于各自相对应的AD转换器37输入到输入端口35。在加速踏板40上连接有产生与加速踏板40的踏进量L成比例的输出电压的负荷传感器41,负荷传感器41的输出电压借助于相对应的AD转换器37输入到输入端口35。进而,在输入端口35上连接有曲轴每旋转例如15°就产生输出脉冲的曲轴转角传感器42。另一方面,输出端口36借助于相对应的驱动电路38与燃料喷射阀3、节气门10的驱动用步进电动机、前段催化剂用还原剂供给阀15、后段催化剂用还原剂供给阀16、EGR控制阀20和燃料泵24连接。
图1所示的前段催化剂12和后段催化剂14均含有NOx吸藏催化剂,因此首先对NOx吸藏催化剂进行说明,该NOx吸藏催化剂,在其基体上担载有例如由氧化铝形成的催化剂载体,图2图解性地表示该催化剂载体45的表面部分的剖面。如图2所示,在催化剂载体45的表面上分散担载有贵金属催化剂46,进而在催化剂载体45的表面上形成有NOx吸收剂47的层。
在本发明的实施例中,作为贵金属催化剂46可使用铂Pt,作为构成NOx吸收剂47的成分,可使用例如选自钾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。
如果将向内燃机进气通路、燃烧室2以及各催化剂12、14上游的排气通路内供给的空气与燃料(烃)的比称作排气的空燃比,则NOx吸收剂47起到了吸放NOx的作用,即在排气的空燃比为稀薄时吸收NOx,在排气中的氧气浓度降低时将吸收的NOx释放。
即,以使用钡Ba作为构成NOx吸收剂47的成分的情况为例进行说明,在排气的空燃比为稀薄时、即排气中的氧浓度较高时,如图2所示那样排气中所含的NO在铂Pt46上被氧化变成NO2,接着被吸收到NOx吸收剂47内,与氧化钡BaO结合,同时以硝酸根离子NO3 -的形态在NOx吸收剂47内扩散。这样,NOx被吸收到NOx吸收剂47内。只要排气中的氧浓度高,就会在铂Pt46的表面生成NO2,只要NOx吸收剂47的NOx吸收能力没有饱和,就会将NO2吸收到NOx吸收剂47内而生成硝酸根离子NO3 -。
与此相对,在通过由还原剂供给阀12、14供给还原剂而使排气的空燃比变为浓或者变为理论空燃比时,排气中的氧浓度下降,所以反应反向(NO3 -→NO2)进行,这样NOx吸收剂47内的硝酸根离子NO3 -以NO2的形式从NOx吸收剂47释放出来。接着,释放出的NOx被排气中所含的未燃烧HC、CO还原。
这样,在排气的空燃比为稀薄时,即在稀空燃比下进行燃烧时,排气中的NOx被吸收到NOx吸收剂47内。但是,如果在稀空燃比下继续进行燃烧,则在该期间NOx吸收剂47的NOx吸收能力会饱和,这样会变得不能由NOx吸收剂47吸收NOx。因此,在本发明的实施例中,在NOx吸收剂47的吸收能力饱和前由还原剂供给阀12、14供给还原剂,由此使排气的空燃比暂时为浓,从而从前段催化剂12和后段催化剂14的NOx吸收剂47释放NOx。
但是,在排气中含有SOx即含有SO2,在该SO2流入到NOx吸藏催化剂时,该SO2在铂Pt46上被氧化变成SO3。接着,该SO3被吸收到NOx吸收剂47内而与氧化钡BaO结合,同时以硫酸根离子SO4 2-的形式在NOx吸收剂47内扩散,生成稳定的硫酸盐BaSO4。但是,由于NOx吸收剂47具有强碱性,所以该硫酸盐BaSO4稳定,难以分解,如果只使排气的空燃比为浓,则硫酸盐BaSO4不分解而原样残留。因此,随着时间经过,在NOx吸收剂47内,硫酸盐BaSO4增多,这样随着时间经过,NOx吸收剂47能够吸收的NOx量降低。即NOx吸藏催化剂因SOx而中毒。
但是此时,在使NOx吸藏催化剂的温度上升到600℃以上的SOx释放温度的状态下,使流入NOx吸藏催化剂中的排气的空燃比为浓时,会从NOx吸收剂47释放SOx,这样可以解救NOx吸藏催化剂的SOx中毒。于是,在本发明的实施例中,在应解救前段催化剂12的SOx中毒时,使前段催化剂12的温度上升到SOx释放温度,同时使流入前段催化剂12中的排气的空燃比为浓,在应解救后段催化剂14的SOx中毒时,使后段催化剂14的温度上升到SOx释放温度,同时使流入后段催化剂中的排气的空燃比为浓。
这种情况下,在本发明的实施例中,通过由相对应的还原剂供给阀15、16供给燃料来使各催化剂12、14升温至SOx释放温度,并使流入各催化剂12、14中的排气的空燃比为浓。即,在进行前段催化剂12的SOx中毒解救处理时,由前段催化剂用还原剂供给阀15供给还原剂,在进行后段催化剂14的SOx中毒解救处理时,由后段催化剂用还原剂供给阀16供给还原剂。
另外,在本发明的实施例中,针对催化剂12、14均进行这样的用于解救SOx中毒的SOx中毒解救处理。具体地讲,在本发明的实施例中,在使用前段催化剂12和后段催化剂14这两方催化剂而得到的NOx净化率为预定的容许水平以下时,进行前段催化剂12的SOx中毒解救处理或后段催化剂14的SOx中毒解救处理中的任一个处理。此时,NOx净化率是由采用NOx传感器18检测出的NOx浓度计算出的。
即,由于在燃料中含有一定比例的硫,因此排气中含有的SOx量与燃料喷射量成比例。燃料喷射量为要求扭矩以及内燃机转速的函数,因此排气中含有的SOx量也成为要求扭矩以及内燃机转速的函数。在本发明的实施例中,将单位时间从燃烧室2排出的排出SOx量SOXA作为要求扭矩TQ以及内燃机转速N的函数,以图3所示的图谱的形式预先存储在ROM32内。另外,排气中含有的NOx量也是要求扭矩以及内燃机转速的函数,将单位时间从燃烧室2排出的排出NOx量作为要求扭矩TQ以及内燃机转速N的函数以图谱的形态预先存储在ROM32内。另一方面,单位时间从燃烧室2排出的排气量可以根据吸入空气量来求出,因此,可以根据所存储的单位时间的排出NOx量和吸入空气量计算出流入前段催化剂12的排气中的NOx浓度。根据该NOx浓度和由NOx传感器18检测出的NOx浓度计算出NOx净化率。
将前段催化剂12和后段催化剂14进行比较的话,由于前段催化剂12比后段催化剂14温度高,所以前段催化剂12与后段催化剂14相比更易热劣化。但如果热劣化的话,则即使供给还原剂,也不能充分解救SOx中毒。与此相对,当没有热劣化时,使用相同量的还原剂就可充分解救SOx中毒。因此,解救难以热劣化的后段催化剂14的SOx中毒可以提高NOx净化率,减少还原剂即燃料的消耗量。因此,在本发明中,优先解救后段催化剂14的SOx中毒。下面参照图4进行说明。
图4表示NOx净化率随着时间经过的变化、及对前段催化剂12和后段催化剂14进行SOx中毒解救处理的时机。另外,图4中的空白部分Fr表示前段催化剂12对NOx净化率作出贡献的部分,阴影部分Rr表示后段催化剂14对NOx净化率作出贡献的部分。另外,图4中NX表示NOx净化率的容许水平。
从图4可知,在最初时NOx净化率保持在100%。由于此时SOx中毒从位于上游侧的前段催化剂12开始,所以由前段催化剂12得到的NOx净化率逐渐降低。另一方面,即使由前段催化剂12得到的NOx净化率降低,也可以由后段催化剂14的对NOx的净化作用弥补,所以NOx净化率暂时维持在100%。然后,随着后段催化剂14的SOx中毒进行,NOx净化率逐渐降低。
接着,在时刻t1,若NOx净化率变为容许水平NX以下,则进行后段催化剂14的SOx中毒解救处理。其结果,由后段催化剂14得到的NOx净化率上升,这样由两方催化剂12、14得到的NOx净化率上升。然后,在时刻t2,若NOx净化率变为容许水平NX以下,则再次进行后段催化剂14的SOx中毒解救处理,使由后段催化剂14得到的NOx净化率上升。然后,在时刻t3,若NOx净化率变为容许水平NX以下,则再次进行后段催化剂14的SOx中毒解救处理,使由后段催化剂14得到的NOx净化率上升。
然后,在时刻t4,若NOx净化率再次变为容许水平NX以下,则此时,即使进行后段催化剂14的SOx中毒解救处理,NOx净化率也基本没有上升。因此,此时,如图4所示那样进行前段催化剂12的SOx中毒解救处理,由此使由两方催化剂12、14得到的NOx净化率上升。另外,此时,也可以同时进行后段催化剂14的SOx中毒解救处理。
这样,在本发明中,只要可以将NOx净化率恢复到目标NOx净化率,就可反复进行后段催化剂14的SOx中毒解救处理,即使进行后段催化剂14的SOx中毒解救处理也不能将NOx净化率恢复到目标SOx净化率时,进行前段催化剂12的SOx中毒解救处理。因此,在本发明中,由图4可知,使进行后段催化剂14的SOx中毒解救处理的频率比进行前段催化剂12的SOx中毒解救处理的频率高。
另外,由图4可知,进行后段催化剂14的SOx中毒解救处理的间隔逐渐变短。因此,从另外一个角度来看,在本发明中,当后段催化剂14的SOx中毒解救处理的间隔变得比预先确定的期间短时,就可进行前段催化剂12的SOx中毒解救处理。
图5示出了实行SOx中毒解救处理的程序。
参照图5,首先在步骤100中根据图3计算出排出的SOx量SOXA。接着,在步骤101中将该排出SOx量SOXA累积相加成∑SOX,由此计算出排出SOx量的累积值∑SOX。接着,在步骤102中根据排出NOx量和吸入空气量计算出排出的NOx浓度。接着,在步骤103中读取NOx传感器18的输出值,在步骤104中根据NOx传感器18的输出值和排出的NOx浓度计算出NOx净化率。
接着,在步骤105中判断NOx净化率是否比容许水平NX高,如果NOx净化率比容许水平NX低,则进入步骤106,判断刚刚进行了SOx中毒解救处理后的排出SOx量的累积值∑SOX是否为设定值SX以上。当∑SOX>SX时即在SOx中毒解救处理后吸藏了大量的SOx时,可判断为后段催化剂14的NOx净化率可充分恢复,此时进入步骤107进行后段催化剂14的SOx中毒解救处理。接着,进入步骤109使∑SOX清零。与此相对,当∑SOX≤SX时,可判断为后段催化剂14的NOx净化率不能充分恢复,此时进入步骤108进行前段催化剂12的SOx中毒解救处理。接着进入步骤109。
作为前段催化剂12,可以使用能够捕获排气中含有的SOx的SOx捕集催化剂。图6图解性地示出了该SOx捕集催化剂的基体50的表面部分的剖面。如图6所示,在基体50的表面上形成有涂层51,在该涂层51的表面上分散担载有贵金属催化剂52。
在该SOx捕集催化剂中,作为贵金属催化剂52可使用铂,作为构成涂层51的成分,可使用选自例如钾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。即,SOx捕集催化剂的涂层51呈强碱性。
排气中所含的SOx即SO2如图6所示那样在铂Pt52上被氧化,接着,被捕获到涂层51内。即,SO2以硫酸根离子SO4 2-的形式在涂层51内扩散,生成硫酸盐。另外,如上所述,涂层51呈强碱性,因此如图6所示那样,排气中所含的SO2的一部分被直接捕获到涂层51内。
图6中,涂层51内的浓淡表示所捕获的SOx的浓度。由图6可知,涂层51内的SOx浓度,在涂层51的表面附近最高,随着向内部深入而逐渐降低。当涂层51的表面附近的SOx浓度变高时,涂层51的表面的碱性减弱,对SOx的捕获能力减弱。对于该SOx捕集催化剂而言,此时如果在排气的空燃比为稀薄的情况下使SOx捕集催化剂温度上升,则可恢复SOx捕集率。
即,如果在排气的空燃比为稀薄的情况下使SOx捕集催化剂的温度上升,则涂层51内的集中存在于表面附近的SOx向涂层51的内部扩散,使得涂层51内的SOx浓度变得均匀。即,在涂层51内生成的硝酸盐从集中在涂层51的表面附近的不稳定状态向在整个涂层51内均匀分散的稳定状态变化。如果涂层51内的存在于表面附近的SOx向涂层51的内部扩散,则涂层51的表面附近的SOx浓度下降,这样如果使SOx捕集催化剂升温,则SOx捕集率恢复。
因此,在使用该SOx捕集催化剂的情况下,要定期使SOx捕集催化剂的温度升高。但是,在大量的SOx被送入SOx捕集催化剂中时,即使将SOx捕集催化剂升温,也不能恢复SOx捕集率。因此,即使是使用SOx捕集催化剂的情况下也需要进行SOx中毒解救处理,即,使SOx捕集催化剂的温度上升至SOx释放温度,同时使流入SOx捕集催化剂中的排气的空燃比为浓。
Claims (7)
1.一种内燃机的排气净化装置,其在内燃机排气通路内沿着排气气流依次配置有前段催化剂和后段催化剂,这些前段催化剂和后段催化剂由NOx吸藏催化剂构成,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所含的NOx,在流入的排气的空燃比变为理论空燃比或变为浓时释放出所吸藏的NOx,在应解救前段催化剂的SOx中毒时,进行使前段催化剂的温度上升至SOx释放温度,同时使流入到前段催化剂中的排气的空燃比为浓的SOx中毒解救处理,在应解救后段催化剂的SOx中毒时,进行使后段催化剂的温度上升至SOx释放温度,同时使流入到后段催化剂中的排气的空燃比为浓的SOx中毒解救处理,且使进行后段催化剂的SOx中毒解救处理的频率高于进行前段催化剂的SOx中毒解救处理的频率。
2.如权利要求1所述的内燃机的排气净化装置,其中,在前段催化剂上游的内燃机排气通路内配置有前段催化剂用还原剂供给阀,同时在前段催化剂与后段催化剂之间配置有后段催化剂用还原剂供给阀,在进行前段催化剂的SOx中毒解救处理时,由前段催化剂用还原剂供给阀供给还原剂,在进行后段催化剂的SOx中毒解救处理时,由后段催化剂用还原剂供给阀供给还原剂。
3.如权利要求1所述的内燃机的排气净化装置,其中,在前段催化剂和后段催化剂这两方催化剂的NOx净化率变为预先确定的容许水平以下时,进行前段催化剂的SOx中毒解救处理或后段催化剂的SOx中毒解救处理中的任一个处理。
4.如权利要求3所述的内燃机的排气净化装置,其中,在后段催化剂下游的内燃机排气通路内配置有NOx传感器,由采用该NOx传感器检测出的NOx浓度计算出NOx净化率。
5.如权利要求1所述的内燃机的排气净化装置,其中,只要能够将NOx净化率恢复到目标的NOx净化率,就反复进行后段催化剂的SOx中毒解救处理,在即使进行后段催化剂的SOx中毒解救处理也不能将NOx净化率恢复到目标的NOx净化率时,进行前段催化剂的SOx中毒解救处理。
6.如权利要求1所述的内燃机的排气净化装置,其中,只要能够将NOx净化率恢复到目标的NOx净化率,就反复进行后段催化剂的SOx中毒解救处理,在后段催化剂的SOx中毒解救处理的间隔变得比预先确定的期间短时,进行前段催化剂的SOx中毒解救处理。
7.如权利要求1所述的内燃机的排气净化装置,其中,所述前段催化剂包含SOx捕集催化剂,该SOx捕集催化剂具有在流入到SOx捕集催化剂中的排气的空燃比为稀薄时捕获排气中所含有的SOx,当在排气的空燃比为稀薄的情况下SOx捕集催化剂的温度上升时,所捕获的SOx逐渐向SOx捕集催化剂内部扩散的性质,同时具有当流入到SOx捕集催化剂中的排气的空燃比变为浓时,如果SOx捕集催化剂的温度为SOx释放温度以上,则释放出所捕获的SOx的性质。
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CN103459792B (zh) | 2011-03-21 | 2016-10-05 | 沃尔沃技术公司 | 供应到催化转化器的还原剂中添加有活化剂材料的排气后处理*** |
SE1250265A1 (sv) * | 2012-03-20 | 2013-09-21 | Scania Cv Ab | Förfarande vid ett SCR-system och ett SCR-system |
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