CN101018597A - 用于减少废气排放的混合催化剂体系 - Google Patents
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Abstract
废气处理系统具有在LNT之后的SCR反应器。使用合成气再生LNT。在一种实施方案中,提供与LNT分开的氨源。在另一实施方案中,该系统具有第一LNT和第二LNT以及在所述LNT下游的一个或多个SCR。另外描述了控制策略。该策略涉及启动再生循环的时间、终止再生循环的时间、LNT再生期间的还原剂注射速率中的一个或多个。
Description
发明领域
本发明涉及用于内燃机、尤其是柴油机和稀燃汽油机的污染控制装置领域。
背景技术
来自内燃机车辆的NOx排放是举世公认的环境问题。包括美国在内的数个国家具有长期以来悬而未决的将限制车辆NOx排放的法规。制造商和研发人员为了符合那些法规的要求已经付出了相当大的努力。在采用化学计量的燃料-空气混合物的常规汽油动力车辆中,已经展示了三元催化剂来控制NOx排放。然而,在柴油动力车辆和稀燃汽油机车辆中,所述废气对于三元催化剂而言过于富氧以至于不能有效地发挥作用。
为了控制柴油动力车辆和稀燃汽油机的NOx排放已经提出了若干解决方案。一套方法集中在发动机上。诸如废气循环和均化燃料-空气混合物的技术可以减少NOx排放。然而,仅凭这些技术无法消除NOx排放。另一套方法是从车辆废气中除去NOx。这些包括使用稀燃NOx催化剂、稀NOx捕集器(LNT)和选择催化还原(SCR)。
稀燃NOx催化剂可促进富氧条件下NOx的还原。在氧化氛围中NOx的还原是困难的。寻找具有所需活性、耐久性和操作温度范围的稀燃NOx催化剂已经证明富有挑战性。稀燃NOx催化剂还倾向于热液不稳定。在相对短暂的使用之后会出现活性的显著损失。稀燃NOx催化剂通常采用沸石封闭涂层(zeolite wash coat),据认为其可提供还原微环境。通常要求将还原剂如柴油燃料引入所述废气中,并且这种引入会造成3%以上的燃料经济性损失。目前,对于稀燃催化剂而言的峰值NOx转化效率无法接受地低。
LNT是与NOx还原用催化剂相结合的NOx吸附器。该吸附器从稀废气(lean exhaust)中除去NOx。周期性地,通过引入还原环境使该吸附器再生。在还原环境中,NOx解吸并在所述催化剂上被还原。所述吸附剂通常是碱土金属氧化物吸附剂如BaCO3以及所述催化剂可以是贵金属如Ru。
SCR涉及通过氨还原NOx。该反应甚至在氧化环境中进行。可以将NOx暂时存储在吸附剂中或者可以将氨连续地供入所述废气中。SCR可以实现超过90%的NOx还原,然而,存在缺乏分配氨或适宜前体的基础结构的顾虑。SCR还会带来有关氨可能释放到环境中的顾虑。
U.S.6,560,958描述了LNT系统,其中将包括H2和CO的富含氢气的合成气(syn gas)用作还原剂以再生所述吸附器。该合成气在等离子体转换器中由柴油燃料制得。周期性地,将所述吸附器从废气系统中取走离线并向其提供合成气。还描述了双吸附器系统。
U.S.6,732,507描述了串联使用LNT和SCR反应器的混合废气处理系统。该SCR反应器捕获再生期间由LNT产生的氨并用所述被捕获的氨提高NOx转化的程度。
长期存在对从柴油机和稀燃汽油机的废气中除去NOx的可靠的、可负担的有效系统的需要。
发明概述
以下介绍简要的概述以便提供对本发明一些方面的基本了解。该概述并非本发明的全面综述。此概述的主要目的在于以简要形式介绍本发明的一些概念作为后面介绍的更详细描述的序言。
本发明的一方面涉及具有在NOx吸附器下游的SCR反应器的废气处理系统,其中将来自燃料重整器的合成气用于再生该NOx吸附器。优选地,该NOx吸附器具有催化剂以及用于在再生期间还原NOx。与向废气系统中直接注入燃料相比,来自燃料重整器的合成气可提高再生循环的效率。该SCR反应器通过捕获再生期间产生的氨和在稀燃运行(lean operation)期间用所述氨还原NOx而进一步提高转化率。
本发明的另一方面涉及具有在LNT下游的SCR反应器以及与LNT分开的氨源的废气处理系统。LNT会产生一些氨,但是独立的氨源可以使得实现高NOx转化率简化。氨需求显著低于纯SCR系统以及通过将使得少于所有从LNT中选出的NOx转化作为目标可以简化控制系统。在一种实施方案中,所述氨源包括由提取自部分废气流的NOx与得自燃料重整器的合成气之间的反应产生氨的氨装置。
本发明的另一方面涉及废气系统,其包括第一LNT和第二LNT以及用于选择性地将所述废气引入一个LNT或另一LNT的一个或多个阀。该系统另外包括在所述LNT下游的一个或多个SCR。该系统可以用于减少与再生有关的燃料损失以及使得LNT以更高的还原剂浓度和更长的停留时间再生。在一个优选实施方案中,将所述LNT的废气流合并并且通向氧化催化剂。该设计可以使过量的还原剂被氧化而不必将空气或其他氧气源注入所述废气中。
本发明的另一方面涉及可以用于实现上述方面的装置。该装置包括容纳在单一外套中的第一NOx吸附器和第二NOx吸附器以及用于选择性地将所述废气引入一个吸附器或另一吸附器的一个或多个阀。该一个或多个阀可以是简单的气流调节器。本发明的这一方面提供了实现基于双吸附器的废气处理系统的简单、紧凑和经济的方法。本发明的另一方面涉及用氧化催化剂涂布废气系统中的活动部件从而减轻污垢。
本发明的其他方面涉及LNT/SCR废气处理系统的控制。根据这些方面之一,测量LNT与SCR反应器之间的氨浓度并将其用于确定何时终止再生循环。这些方面中的另一个涉及保持对SCR反应器中氨吸附量的评估并且基于该评估选择性地启动LNT再生操作,由此可以在所述LNT中的氨耗尽之前开始再生。这可以减少或防止再生循环期间NOx的渗漏。本发明的有关方面包括基于在LNT和SCR反应器之间测定的NOx浓度选择性地启动再生操作。本发明的另一方面涉及基于对LNT中的NOx吸附量的评估开始再生。在一种实施方案中,在LNT实质上低于其NOx存储容量时启动再生循环,由此再生期间转化成氨的NOx部分实质上大于如果推迟再生直至LNT更接近饱和的情况中的相应部分。本发明的另一方面涉及提供再生期间还原剂供应速率的反馈控制。可以使还原剂供应速率最大化从而减少再生时间,减少燃料损失,以及提高受到能够从所述LNT逸出的还原剂量限制的氨产量。
为了前述和相关目标的实现,下列说明书和附图详细阐述了本发明的某些说明性方面和实施过程。这些只说明了可能采用本发明原理的多种方式中的一些。本发明的其他方面、优点和新颖特征可在结合附图思考时从对本发明的以下详细描述中变得显而易见。
附图说明
图1是用于辅助描述本发明若干方面的车辆的示意图。
图2是根据本发明一个方面的车辆的示意图。
图3是根据本发明另一方面的具有氨装置的车辆的示意图。
图4是根据本发明另一方面的具有两个LNT的车辆的示意图。
图5是根据本发明另一方面的在单一外套中包含两个NOx吸附器的装置的图解。
发明详述
图1是辅助描述本发明若干方面的车辆10的示意图。车辆10包括内燃机11、稀NOx捕集器(LNT)12、选择催化还原(SCR)反应器14、还原剂源13、非必要的氨源15和传感器16-20。车辆10通常产生稀废气。LNT 12从所述稀废气中吸附NOx。不时地,通过注入来自还原剂源13的还原剂使得所述废气变浓。浓废气导致NOx从LNT 12解吸。一部分NOx从LNT中逸出,一部分被还原成N2,一部分被还原成NH3。
再生期间从LNT选出的NOx和稀燃运行期间未被LNT吸附的NOx传输到达SCR反应器14。在SCR反应器14中,所述NOx中的一部分通过与NH3反应而被还原。所述NH3可以是在LNT 12中产生的NH3和/或由非必要的氨源15提供的NH3。SCR反应器14催化与氨的反应以及一般具有吸附和存储过量氨的能力。传感器16-20通常测量浓度以及任选地提供并用于控制启动再生循环的时间、终止再生循环的时间、再生循环期间还原剂供应速率、以及如果合适的话来自氨源15的氨供应速率中的一个或多个。另外的控制信息通常包括LNT 12的温度、SCR反应器14的温度、以及有时从发动机控制单元(未示出)得到的车辆运行信息(如速度和扭矩)。可以由发动机控制单元或者由与所述发动机控制单元联系的单独控制器来实现控制功能。
车辆10通常由化石燃料如柴油、汽油、天然气或丙烷提供动力。所述燃料在内燃机11中燃烧从而产生包含NOx的废气。NOx包括NO、NO2、N2O和N2O2。一般该废气是稀的,这意味着其包含实质上多于燃烧所述燃料含有的任何烃类所需的氧气。通常,稀废气合有3~5%的氧。
稀NOx捕集器(LNT)包括NOx吸附床和在还原环境中可有效还原NOx的催化剂。尽管可以任选地在该吸附床下游的独立床中装配所述催化剂,但是一般而言在NOx吸附床中装配所述催化剂。该吸附床包含在氧化(稀)环境中有效量的NOx吸附剂。稀NOx捕集器在还原环境中还原和/或解吸NOx,条件是该稀NOx捕集器处于适当的温度范围内。
所述吸附床可以包含任何适宜的吸附剂材料。吸附剂材料的实例包括分子筛,如沸石、氧化铝、二氧化硅、和活性炭。其他实例是碱土金属(如Mg、Ca、Sr和Be)或碱金属(如K或Ce)的氧化物、碳酸盐和氢氧化物。另外的实例包括金属磷酸盐如磷酸钛和磷酸锆。
分子筛是具有限定内部空腔和规则尺寸的互连孔隙的晶体结构的材料。沸石是最常见的实例。沸石具有一般基于通过氧桥彼此呈四面体相连的原子的晶体结构。所述原子最常见地是铝和硅(产生铝硅酸盐),但是P、Ga、Ge、B、Be和其他原子也可以构成四面体骨架。可以通过离子交换改变沸石的性质,例如用稀土金属或铬。优选的沸石一般包括稀土沸石和杆沸石。稀土沸石是已经大量(即至少约50%)或完全与稀土金属如镧发生离子交换的沸石。一般对于LNT,优选的吸附剂是负载有贵金属的碱金属或碱土金属氧化物。
所述吸附剂通常与粘结剂结合以及成型为自支撑结构或作为涂层施加在惰性基体上。粘结剂例如可以是粘土、硅酸盐、或水泥。可以将波特兰水泥用于粘结分子筛晶体。一般而言,使用最少量粘结剂时所述吸附剂最有效。优选地,所述吸附剂床含有约3~约20%、更优选约3~约12%、最优选约3~约8%的粘结剂。
一般使得根据本发明的吸附剂床和催化剂床适合于用在车辆废气系统中。车辆废气系统对重量、尺寸和耐久性具有限制。例如,用于车辆废气系统的吸附床必须在车辆运行期间遇到的振动下适度地耐降解。
具有吸附功能的床倾向于比仅具有催化功能的床更大。为了限制总质量,所述吸附剂床优选包含以每单位床质量计的高吸附剂负载量。优选地,吸附剂床包含以重量计至少约40%的吸附剂。吸附剂床的重量包括任何惰性基体和任何粘结剂,但是不包括任何外套。优选地吸附剂床包含以体积计至少约20%的吸附剂。
吸附剂床和催化剂床任选地装配加热和/或冷却用的机构。例如,可以贯穿所述床装配与用于吸附气体和解吸气体的通路流体隔离的热交换通路。将热或冷的流体循环经过该热交换通路从而加热或冷却所述吸附器。冷却流体例如可以是发动机冷却剂或环境空气。加热流体例如可以是热废气或者从热废气或生热装置如氨合成反应器、燃料重整器或吸附器中汲取热量的流体。另一选择是电阻式加热。在床包含金属基体的情况下,可以将该金属基体用作电阻式加热器。还可以使电阻式加热用的导线遍及该床。
吸附剂床或催化剂床可以具有任何适宜的结构。适宜结构的实例可以包括整体床、填充床和层状筛。优选通过烧结颗粒或用粘结剂粘合使填充床成型为粘聚体(cohesive mass)。当床具有吸附剂功能时,优选任何厚壁、大颗粒、或厚涂层具有有助于接近发生吸附的微孔的大孔结构。通过由烧结在一起或用粘结剂保持在一起的吸附剂小颗粒形成所述壁、颗粒或涂层可以形成大孔结构。
优选NOx吸附床具有在典型的吸附温度和废气分压下吸附NOx物种的大容量。优选地,所述吸附剂可以在典型的吸附温度和1托NOx物种分压下吸附以吸附剂重量计至少约3%、更优选以吸附剂重量计至少约5%、甚至更优选以吸附剂重量计至少约7%的NOx物种。吸附剂重量不包括任何粘结剂或惰性基体的重量。
LNT 12包含用于在还原环境下用NOx还原的催化剂。所述催化剂例如可以是一种或多种贵金属如Au、Ag和Cu;第VIII族金属如Pt、Pd、Ru、Ni和Co;Cr、Mo或K。典型的催化剂包括Pt和Rh,尽管可能希望减少或除去Rh以促进NH3超过N2而产生。有效的操作温度一般是约200~约450℃。从促进NH3超过N2而产生的方面考虑,更低的温度也可能是所希望的。
还原剂源13可以供应任何适宜的还原剂。适宜还原剂的实例包括合成气(syn gas)、烃类、和氧化烃类。合成气包含H2和CO。所述还原剂可以是内燃机11用的燃料。可以将该燃料注入所述废气中。任选地,内燃机11可以浓燃运行从而提供所述还原剂。
在还原剂源13不是内燃机11的情况下,它通常是产生简单烃类如合成气的燃料重整器。在LNT 12中简单烃类一般比更复杂的烃类更具活性。所述燃料重整器可以是催化重整器、蒸汽重整器、自热重整器、或等离子体重整器。就本发明目的而言,重整器催化剂是这样的催化剂:与氧化催化剂如Pt、Pd或过渡金属氧化物如MnO2相比,在柴油燃料和稀废气的进料下,其可促进CO和H2(合成气)和小分子烃类的产生超过完全氧化所述柴油燃料以形成CO2和H2O。特别地,相对大量H2的产生是重整器催化剂的标志。所述重整器催化剂的实例包括Al、Mg和Ni的氧化物,它们通常与CaO、K2O和稀土金属如Ce中的一种或多种组合以提高活性。一般为重整器供应内燃机11用的燃料。还可以为所述重整器提供氧气源,如空气或稀废气。可以从所述废气系统的高压部分提取稀废气,如从位于用在涡轮增压系统中的涡轮机上游的支管提取。
任选地将燃料重整器直接设置在所述废气流中。图2是将燃料重整器34设置在LNT 12上游的车辆30的示意图。再生期间,将来自燃料源35的燃料注入所述废气中。图中示出两个可能的注入点。第一注入点32位于颗粒过滤器31的上游。该颗粒过滤器31一般含有氧化催化剂并且会氧化一部分燃料。第二注入点33位于颗粒过滤器31的下游。任选地,使用这两个注入点,注入点32处的注入旨在消耗过量的氧而注入点33处的注入旨在供应足量燃料以再生LNT 12。
SCR反应器是具备有效量的用于在稀废气中将NOx与NH3反应以使NOx还原成N2的催化剂的反应器。SCR催化剂的实例包括金属如Cu、Zn、V、Cr、Al、Ti、Mn、Co、Fe、Ni、Pd、Pt、Rh、Rd、Mo、W和Ce的氧化物;沸石如ZSM-5或ZSM-11,其被金属离子如Cu、Co、Ag、Zn或Pt的阳离子替代;以及活性炭。可以在相对低的温度如约230~约450℃的温度下进行反应。
在提供氨源15的情况下,它可以是任何适宜的氨源。氨源15例如可以是氨、氨基甲酸铵或尿素的贮存器。可以通过从H2和N2或从H2和NOx形成氨的氨装置在车辆10上产生氨。N2可以从空气中得到而H2可以由燃料重整器产生。无论其来源,任选地将氨存储在一个或多个吸附床如分子筛吸附床中并根据需要解吸。
图3是根据本发明一个方面的具有氨装置100的车辆的示意图。氨装置100包括NOx吸附器101和氨合成反应器102。吸附器101接收来自内燃机11的部分废气流。一旦NOx浓度增加到足够的水平,为吸附器101供应还原剂以启动氨生产。还原剂优选是来自燃料重整器103的合成气。所述还原剂会引起从吸附器101的解吸。所述还原剂和解吸的NOx在反应器102中反应以产生氨。任选地,在氨生产期间中断该部分废气流,由此氨生产可以在实质上无氧环境中进行。任选地,吸附器101是具有合适催化剂的LNT。任选地,通过在吸附器101中分布合适的催化剂将反应器102与吸附器101结合。
氨合成用的适宜催化剂包括贵金属,如Au、Ag和Cu;第VIII族金属,如Pt、Pd、Ru、Ir、Ni和Co;Cr、Mo或K。所述催化剂可以组合,例如Au与Pt、Pd或Ru组合。可以将所述催化剂负载在沸石上,如Y沸石、β沸石、丝光沸石和ZSM-5;或在金属氧化物上,如Fe2O3、Al2O3、ZnO、ZrO2、TiO2、MnO2和CeO2。在无氧环境中于低温产生高转化率的一种优选催化剂是在金属氧化物载体、尤其是Fe2O3或Al2O3载体上的Au。高转化率可以在约150~约300℃的温度范围内得到。代替催化剂或者除了催化剂以外,反应器102可以提供等离子体放电以诱导氨形成反应。
氨源15使得实现非常高的NOx转化率的方法成为可能。可以监控来自LNT 12的NOx和NH3的比率。当来自LNT 12的氨比率小于NOx比率时,氨源15可以根据需要提供另外的氨从而在SCR 14中将NOx转化成N2。由于大多数NOx已经在LNT 12中转化,在一种实施方案中控制还原剂源15从而将从LNT 12传输的NOx转化率60~95%作为目标。通过将小于100%转化率作为目标,可以极大地减少氨泄漏。在暂时供应过量氨的情况下,它一般通过吸附而被存储在SCR 14中。在另一实施方案中,LNT12以产生少量氨的方式运行并且不需要测量来自LNT 12的氨比率。
在一种实施方案中,周期性地再生LNT 12。例如,可以每30秒注入所述还原剂5秒。该还原剂注入包含充足的还原剂以消耗所有的游离氧并留下足以提供还原剂目标浓度的还原剂。游离氧的反应可以在LNT之前或在LNT之中进行。在一种实施方案中,与氧的反应在其中提供所述废气流的燃料重整器中进行。在另一实施方案中,以两部分注入所述还原剂。第一部分是直接注入到所述废气中以消耗过量氧的燃料。第二部分是合成气,其对于消耗过量氧的有效性较低,但是对于还原NOx更为有效。
当周期性地再生LNT 12时,设定还原剂注射速率包括测量或评估废气流速及其氧浓度。所述流速可以通过发动机运行条件确定,该条件通常由发动机控制单元监控。作为选择,可以从流入发动机10的燃料流速或空气流速的测量确定该流速。可以使用传感器直接测量废气流速。废气中的氧浓度可以从发动机运行条件评估或用氧传感器测量。
与简单的周期再生方案相反,本发明在其若干方面中考虑控制下列参数中的一个或多个:启动再生循环的时间、再生循环的持续时间、和再生循环期间的还原剂浓度。
在结合LNT与SCR反应器的现有技术系统中可能考虑的确定何时启动再生循环的方法涉及测量SCR反应器下游的NOx浓度。当该浓度超过目标水平时,开始再生。
本发明的一个方面通过较早地启动再生而改进该方法。根据本发明的该方面,保持对在SCR反应器14中通过吸附而存储的氨量的评估。当存储的氨降低至目标水平时开始再生。
再生期间,NOx从LNT 12解吸。特别是在再生循环的第一部分期间,一部分所述NOx未发生反应就从LNT 12逸出。如果SCR反应器14中的氨在再生之前完全耗尽,如现有技术那样,那么选出的NOx被释放到大气中。然而,根据本发明,当SCR 14中留有氨时开始再生。该氨可以还原所有逸出的NOx或一部分选出的NOx。
实现该控制系统一般涉及测量LNT 12与SCR反应器14之间的氨浓度和NOx浓度。SCR反应器14吸附氨。除非SCR反应器14变得饱和,SCR反应器14中的氨量通过进入该反应器的氨流而增加。氨含量通过与NOx反应而减少。这种减少与NOx流速成比例,任选地由转化效率调节。
可以通过来自位于SCR反应器14下游的传感器的反馈控制而更新所述评估。如果检测到NOx渗漏,可以将吸附氨的量重设为零。如果检测到氨泄漏,可以将吸附氨重设为反映SCR反应器14饱和的量。任选地,无论何时出乎意料地出现NOx渗漏或氨泄漏,可以调节SCR反应器14中NOx与氨反应的转化效率因子,由此可以使得随后对氨浓度的评估更为精确。
在一种实施方案中,将再生时被吸附的氨量的目标设置为在前一再生循环期间观察到的NOx超出氨的量。预期LNT 12启动再生循环而放出比氨多的NOx。随着再生继续进行,预期NOx流速降低而预期氨流速提高。所述过量的NOx是整个循环过程中观察到的NOx超出氨的最大累积量。将再生开始时SCR反应器14中的氨量的目标设置为还原该过量所需的用量。
根据本发明的另一方面,为了增加还原成氨而不是N2的NOx的比例,及早启动再生循环。当LNT被NOx饱和时,观察到产生相对少量的氨。在饱和的LNT的再生循环过程中,随着LNT中NOx量的降低,氨的产生增加。通过在饱和之前启动再生循环,可以提高氨优于N2而产生。
在该实施方案中,优选当LNT 12为约5~约50%被NOx饱和、更优选约10~约30%被NOx饱和时开始再生。饱和程度可以从废气中NOx量的测量以及LNT 12吸附容量的模型来评估。该方法可导致相对频繁的再生循环,例如对于以55英里/小时的稳定速度行驶的已加热的车辆,平均约每10秒或更少时间进行1次。在一种实施方案中,转化成氨的吸附NOx的比例是至少约20%。在另一实施方案中,该比例是至少约40%。
使用前述控制方法,从LNT 12释放的氨量可能超过通过LNT 12的NOx量。该过量氨可以用于还原旁路绕过LNT 12的废气流。在一种实施方案中,将以前述方法控制的LNT 12用作非必要的氨源15。
在另一实施方案中,设定再生时间从而控制LNT 12释放的总共的氨与NOx之间的比例。可以将该比例设定为1∶1(化学计量比),由此通过LNT 12产生的氨刚好足以还原传输到达SCR反应器14的NOx。然而,优选地,该比例稍小一些,由此可以避免氨泄漏。较少量的氨优选是化学计量量的约60~约95%。还可以以导致以下事实的效率因子减少该用量:根据SCR反应器14的结构、催化剂加载量和温度,即使可获得足够的氨,供应至SCR反应器14的相当大部分的NOx也可能不与氨反应。反馈控制可以用于得到该目标比例。特别地,可以缩短再生循环之间的时间从而提高氨产生以及可以延长该时间从而减少氨产生,其最终目的在于实现来自LNT 12的氨产生和NOx排放之间的平衡。
本发明的另一方面涉及决定何时终止再生循环的方法。在现有技术中,将再生循环设定成固定的时间。通常,LNT的吸附容量是已知的并且认为再生LNT所需的还原剂用量是已知的,然而,根据本发明的这一方面,反馈控制被用于确定何时结束再生循环。在一个优选实施方案中,根据在LNT 12下游对氨浓度的测量终止再生循环。
随着再生循环进行,LNT下游的氨浓度首先增加,然后降低。可以在氨浓度曲线上的任何可辨认点终止再生循环。最优选地,在氨浓度下降低于峰值之后的目标值时终止再生循环。当氨浓度下降时,逐渐地更多未使用的还原剂经过LNT 12泄漏。因此,该目标值是反映在使得氨产生最大化与使得还原剂泄漏最小化之间权衡的一种设计选择。
本发明的另一方面涉及控制还原剂注射速率的方法。在现有技术中,还原剂注射速率通常设定为特定的当量比。当量比基于供至发动机11的燃料-空气混合物,其具有当量比为1的化学计量比。将注入发动机11下游的废气中的附加还原剂包括在就如同将其供至发动机11中时的当量比内。
根据本发明的这一方面,在受到还原剂渗漏限制的条件下使还原剂注射速率最大化。一般而言,提高所述当量比可增加氨产生速率和使得再生时间最小化。在将还原剂注入所述废气的情况下,减少再生时间可降低燃料损失。再生期间,必须供应还原剂以消耗废气中的游离氧。该还原剂超过用于还原NOx的还原剂量。被消耗的氧的总量取决于再生循环的时间长短。如果再生循环较短,则必须还原的氧的摩尔流量较小。
在一个优选实施方案中,通过SCR反应器14下游的可氧化物种传感器确定还原剂渗漏速率。所有可氧化物种都可以看作还原剂。为了达到控制目的,优选将渗漏速率表示为超过消耗游离氧所需的注射速率的注射速率比例。例如,如果将超过消耗游离氧所需量的过量注射速率加倍仅仅使得渗漏速率加倍的话,则还原剂的转化比例改变没有降低。在一种实施方案中,控制还原剂注射速率从而得到超过消耗游离氧所需量的约50~约95%还原剂转化率,在另一实施方案中是约70~约90%转化率。
减少燃料损失的另一种方法在于采用如图4中示意性说明的具有双吸附器系统的车辆120。车辆120具有稀NOx捕集器A 121、稀NOx捕集器B 122、还原剂源123、至少一个SCR反应器124、和非必要的柴油氧化催化剂125。在该实例中,将NOx捕集器A 121和B 122的流出物合并而且供应至单一的SCR反应器124和单一的氧化催化剂125。任选该流出物并不合并并对其单独处理。阀126和127选择性地将来自内燃机11的废气引导至稀NOx捕集器A 121和B 122中的一个或另一个。举例说明的是两个阀126和127,然而可以使用单一的三通阀。
所述双吸附器系统的一个优点在于不需要浪费还原剂消耗废气中的游离氧。另一优点在于不需要用废气稀释还原剂。这可提高还原剂的浓度以及由此提高其反应效率。另一优点在于可以增加还原剂在LNT A 121和B122中的停留时间。停留时间得以增加既是由于停留时间不受废气流速限制又是由于可以花费更多时间来再生所述LNT。更长的停留时间使得对于给定量的催化剂而言更高的转化效率成为可能。
当合并所述LNT的流出物时可以实现另外的优点。一个优点在于可以通过氧化催化剂125在不必注入氧的情况下减少来自所述LNT的过量还原剂以及从所述SCR泄漏的氨。在不具有合并流的系统中,再生期间在所述LNT下游的废气中不存在游离氧。必须注入空气或提供其他氧源以氧化未转化的烃类和NH3。在合并流的情况下,一般由所述废气提供充足的氧。
为了提供合并流,必须将还原剂注射压力调节至高于所述料流汇合处的废气压力的水平。这可以无额外泵的情况下实现,即使当所述还原剂是合成气时也是如此。例如,合成气可以由从废气体系中的高压点提取的废气和从普通线路提取的燃料生成。可以在保持于高压的情况下时使所述进料反应。
图5是具有成对稀NOx捕集器A 201和B 202的装置200的图解。通过回转气流调节器203提供废气流量的调节。提供注射口204和205以将还原剂注入LNT A 201和B 202中的一个或另一个。LNT A 201和B 202的流出物在通过活门调节装置206之后合并,设计该装置以促进这两股料流的混合。废气然后通过SCR反应器207和柴油氧化催化剂(DOC)208。所述部件全部容纳在单一外套209中。为了控制,提供取样口210和211以分别对LNT A 201和B 202的流出物取样。与其使用取样口,倒不如可以将传感器设置在外套209内。
本发明的另一方面涉及减轻活动部件如气流调节器203、特别是其枢轴机构附近的污垢的方法。根据本发明的这一方面,为活动部件的表面提供氧化催化剂。适宜的氧化催化剂包括贵金属,尤其是Pt。该涂层可促进烟灰的氧化,否则烟灰可能形成最终污染所述活动部件的污垢积累。
已经就某些方面、实例和实施方案表现和描述了本发明。虽然本发明的具体特征可能仅由若干方面、实例和实施方案中之一来揭示,但是当对于任意给定的或具体的应用可能有利时,可以将该特征与其他方面、实例或实施方案中的一个或多个其他的特征结合。
工业应用性
本发明可用于控制来自柴油和稀燃汽油发动机的NOx排放。
Claims (7)
1.一种车辆废气处理系统,其包括:
NOx吸附器-催化剂(12),其设计用于接收所述废气以及在废气是稀废气时从该废气中吸附NOx;
SCR反应器(14),其设置在NOx吸附器-催化剂(12)的下游以接收再生期间由所述NOx吸附器-催化剂(12)产生的氨;
氨源(15),其与所述NOx吸附器-催化剂(12)分开并设计用于为所述SCR反应器(14)提供附加氨;
其中使得所述NOx吸附器-催化剂(12)适合于在该NOx吸附器-催化剂(12)中的气氛变浓时将至少一部分所述被吸附的NOx还原成N2;和
使得所述SCR反应器(14)适合于使用氨将通过该NOx吸附器-催化剂(12)或者从其中解吸的至少一部分NOx还原。
2.权利要求1的车辆废气处理系统,其中所述氨源包括氨基甲酸铵或尿素的贮存器。
3.权利要求1的车辆废气处理系统,其进一步包括设计符合所述废气流的燃料重整器,其用于消耗过量的氧以及在所述NOx吸附器-催化剂(12)的再生期间为该NOx吸附器-催化剂(12)提供合成气。
4.一种废气处理系统,其包括:
NOx吸附器-催化剂(12),其适合于从稀废气中吸附和存储NOx;
设计用于将废气输送至所述NOx吸附器-催化剂(12)的管道,其中在所述废气处理系统的正常运行期间废气必须通过该管道而到达所述NOx吸附器-催化剂(12);
设置在所述管道中的燃料重整器(34),由此通过该管道的至少大部分废气也通过该燃料重整器(34);和
氨SCR催化剂(14),其设计用于接收从所述NOx吸附器-催化剂(12)解吸的气体;
其中所述NOx吸附器-催化剂(12)用于在再生期间产生氨以及所述SCR催化剂(14)用于吸附如此产生的氨;和
在刚好在所述NOx吸附器-催化剂(12)再生之后的时期内,所述SCR催化剂用于通过催化NOx与所述被吸附的氨反应而还原通过该NOx吸附器-催化剂(12)的NOx。
5.一种车辆,其包括:
权利要求4的废气处理系统;
柴油机(11);和
控制器;
其中所述控制器在所述NOx吸附器-催化剂(12)仍然能够有效地除去NOx时启动该NOx吸附器-催化剂(12)的再生,从而与推迟再生时被转化成氨的吸附NOx的比例相比,提高将在再生期间被转化成氨的吸附NOx的比例。
6.权利要求5的车辆,其中实施废气处理系统从而将吸附于所述NOx吸附器-催化剂(12)上的至少约40%的NOx转化成氨。
7.一种车辆,其包括:
权利要求4的废气处理系统;
柴油机(11);和
控制器;
其中所述控制器控制所述NOx吸附器-催化剂(12)的再生以将从该NOx吸附器-催化剂(12)释放的NOx量与氨量之间的比例作为目标。
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Also Published As
Publication number | Publication date |
---|---|
US7334400B2 (en) | 2008-02-26 |
US20060010857A1 (en) | 2006-01-19 |
JP2008506881A (ja) | 2008-03-06 |
US20060010859A1 (en) | 2006-01-19 |
EP1784247A1 (en) | 2007-05-16 |
JP4674695B2 (ja) | 2011-04-20 |
BRPI0513102A (pt) | 2008-04-29 |
US20070033928A1 (en) | 2007-02-15 |
US7213395B2 (en) | 2007-05-08 |
CA2573815A1 (en) | 2006-01-26 |
US7650746B2 (en) | 2010-01-26 |
WO2006008625A1 (en) | 2006-01-26 |
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