CN103118780A - 组合的逸失催化剂和烃放热催化剂 - Google Patents
组合的逸失催化剂和烃放热催化剂 Download PDFInfo
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- CN103118780A CN103118780A CN2011800443803A CN201180044380A CN103118780A CN 103118780 A CN103118780 A CN 103118780A CN 2011800443803 A CN2011800443803 A CN 2011800443803A CN 201180044380 A CN201180044380 A CN 201180044380A CN 103118780 A CN103118780 A CN 103118780A
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Abstract
本发明公开了一种催化剂,包含:(a)第一层,所述第一层包含具有有效PGM载荷的氧化催化剂以使得烃的氧化产生足以再生烟粒的热,其中所述有效量的PGM为大于约10g/ft3;和(b)第二层,所述第二层与所述第一层相邻并包含用于选择性还原NOx的还原催化剂。
Description
相关申请的参考
该申请主张于2010年9月15日提交的美国临时申请61/383,112号的优先权,通过参考以其完整的形式并入本文中。
技术领域
本发明一般涉及贫燃发动机的排放控制,更具体地,涉及有助于烃的放热氧化并从尾气中除去含氮污染物气体两方面的催化剂。
发明背景
由于环境问题,所以一直需要减少内燃机的排放。本文中特别关注的是使用贫空气/燃料混合物运行的内燃机,称作“贫燃发动机”。普通的贫燃发动机是柴油机。在贫燃发动机的尾气中的排放物能够分为两类:一次排放物和二次排放物。一次排放物涉及通过燃料在发动机中的燃烧过程而直接形成的并在穿过尾气净化装置之前存在于原始排放物中的污染物气体。贫燃发动机的尾气包含一氧化碳(CO)、烃(HC)、氮氧化物(NOx)和烟粒(也称作微粒物质或PM)的普通一次排放物以及高达15体积%的相对高的氧气含量。二次排放物为在尾气净化单元中作为副产物形成的污染物气体。这种二次排放物可包括例如如下所述的“逸失(slip)”的氨(NH3)和NOx。
排放物控制系统具有各种构造。例如参考图1,显示了柴油机的典型的排放物控制系统100。就在尾气离开发动机(未示出)之后,柴油机氧化催化剂(DOC)101对诸如未耗尽的燃料(烃)和一氧化碳的主要污染物进行氧化以使其无害。其他主要污染物如NOx不能被氧化,但改为必须将其还原成氮气。然而,还原NOx,因为尾气流股中的高氧气含量而更加困难。
在氧气存在下从尾气中除去NOx的已知方法是选择性催化还原(SCR)工艺。在如图1中所示的合适催化剂即SCR催化剂103上,SCR使用氨作为还原剂。使用注射喷嘴102将还原剂引入尾气气门机构(train)中。作为氨的替代,能够将易于分解成氨的化合物如脲用于该用途。
为了确保NOx的完全还原,必须以对氮氧化物至少为化学计量比的方式向尾气中添加氨,并优选过量的氨以提高NOx的转化率。然而,过量的氨显著提高了氨滑流过SCR催化剂并变为二次排放物的风险。将突破或滑流过SCR催化剂的氨称作“逸失氨”。由于氨是即使在低浓度下仍具有穿透性气味的气体,所以期望减少逸失氨。然而,因为机动车辆的波动运行条件(例如加速/减速)而在机动车辆的内燃机中难以对氨进行精确计量。因此,不可避免地向系统中注入过量的氨,导致在SCR催化剂下游造成大量的氨的逸失。
系统100还包含位于SCR103之后的柴油放热催化剂(DEC)105,以有助于周期性的放热反应以产生足以从催化的烟粒过滤器(CSF)106中再生烟粒的热。为此,烃注射器104仅靠着DEC位于其上游。在尾气温度超过DEC的起燃温度时,注射器104向尾气流股中注射燃料或HC。然后,所述DEC将HC氧化以放热,接着所述热对过滤器进行加热以从其中清除烟粒。因为DEC位于SCR之后,所以SCR不会经历与除去烟粒相关的有害高温。
尽管DEC善于氧化,但是仍存在非选择性地将从SCR催化剂逸失的所有氨氧化并将其转化成NOx的可能,由此提高了NOx的排放。为了解决该问题,一种方法涉及使用如图2中所示的氨逸失催化剂(ASC)201。在SCR催化剂103之后,但在HC注射器104之前,所述ASC在将NH3氧化成NOx最少的条件下选择性地除去NH3。典型地,ASC具有低铂族金属(PGM)载荷(例如0.5~10g/ft3)以最大化对N2的选择性。该系统的劣势是在已经足够大的排放控制系统200中NH3逸失催化剂所需要的额外的催化剂体积。
因此,申请人意识到,需要一种简化的尾气系统,所述系统在消除氨逸失的同时对尾气流股进行加热以周期性地从烟粒过滤器再生烟粒。本发明满足了其中的这种需要。
发明概述
下面提供了本发明的简要概述以提供本发明某些方面的基本含义。该概述不是本发明的详尽阐述。不往往确定本发明的核心/关键元素或描绘本发明的范围。其唯一目的是以简化形式提供本发明的某些概念以作为下述更详细说明的前奏。
本发明提供一种组合催化剂,所述组合催化剂不仅在足以产生足以再生烟粒的热量的放热反应中将逸失的氨和烃氧化,还将得自这种氧化的NOx还原。更具体地,申请人惊奇地发现,通过紧邻氧化催化剂的SCR催化剂抵消掉了为产生足以再生烟粒的热所需要的氧化催化剂中的高载荷浓度。这有助于传统DOC和ASC的集成,由此简化尾气系统以消除氨的逸失,并同时对尾气流股进行周期性地加热以从烟粒过滤器再生烟粒。
因此,本发明的一个方面涉及组合的DOC/ASC催化剂,所述催化剂消除NH3的逸失并对尾气流股进行周期性地加热以从烟粒过滤器中再生烟粒,同时对二次NOx排放物进行还原。在一个实施方案中,该组合催化剂包含:(a)基材;(b)在所述基材上的第一层,所述第一层包含具有有效PGM载荷的氧化催化剂,以使得烃的氧化产生足以再生烟粒的热,其中在一个实施方案中,所述有效量的PGM为大于约10g/ft3;和(c)第二层,所述第二层与所述第一层相邻并包含用于选择性还原NOx的还原催化剂。
本发明的另一个方面涉及一种使用组合的催化剂对尾气流股进行周期性加热以在消除逸失的胺和NOx排放物的同时再生烟粒的方法。在一个实施方案中,所述方法包括:(a)将含氮的还原剂注入具有NOx的尾气流中;(b)在SCR催化剂存在下使用所述含氮的还原剂将NOx还原以形成NOx还原了的气体流股,该气体流股至少间歇地含有逸失的含氮还原剂;(c)将HC注入NOx还原了的气体流股中以形成HC富集的气体流股;和(d)将所述HC富集的气体流股与组合的催化剂接触以形成加热的气体流股,所述组合的催化剂包含第一层和第二层,所述第一层具有氧化催化剂以对逸失的含氮还原剂和HC进行氧化,从而对所述加热的气体流股进行加热,且所述第二层具有SCR催化剂以对在所述第一层中形成的NOx进行还原。
本发明的还另一个方面是一种尾气系统,所述尾气系统使用组合催化剂在消除氨的逸失的同时对所述尾气流股进行周期性地加热以从所述烟粒过滤器再生烟粒。在一个实施方案中,所述系统包含:(a)导管,所述导管用于将具有NOx的尾气从发动机传送到大气;(b)注射器,所述注射器用于将含氮的还原剂注入尾气中;(c)SCR催化剂,所述SCR催化剂以接触所述尾气的方式放置并使用含氮的还原剂将所述NOx还原以形成NOx还原了的气体流股,该气体流股至少间歇地含有逸失的含氮还原剂;(d)HC注射器,所述HC注射器用于将HC注入NOx还原了的气体流股中以形成HC富集的气体流股;(e)组合催化剂,所述组合催化剂以接触HC富集的气体流股的方式放置以形成加热的气体流股,所述组合催化剂包含第一层和第二层,所述第一层具有氧化催化剂以对逸失的含氮还原剂和HC进行氧化,从而对所述加热的气体流股进行加热,且所述第二层具有SCR催化剂以对在所述加热的气体流股中的NOx进行还原;和(f)过滤器,所述过滤器以接触所述加热的气体流股的方式布置以对在所述过滤器中含有的烟粒进行再生。
附图简述
图1显示了具有下游燃料注射器的典型的脲SCR系统构造。
图2显示了在SCR之后具有氨逸失催化剂(ASC)的图1的SCR系统,以通过柴油放热催化剂(DEC)最小化非选择性的NH3氧化。
图3显示了本发明的实施方案,其中具有下游燃料注射器的脲SCR系统构造包含组合的氨逸失催化剂和柴油放热催化剂。
图4显示了关于标准DEC、标准ASC和本发明的组合的DEC/SCR催化剂在高烃(放热)条件下在起燃试验中HC的转化率。
图5显示了使用与图4中的试验相同的催化剂在低烃条件下的NH3转化性能。
图6显示了使用与图4和5中的试验相同的催化剂在低烃条件下将NH3选择性转化成N2的性能。
图7显示了本发明组合催化剂的一个实施方案的示意图。
发明详述
参考图3,对本发明的尾气系统300进行了示意性描绘。如图所示,系统300包含用于将尾气从发动机307传送到大气的导管301。已知的是,这种尾气流股含有NOx。发动机307的下游是用于将含氮的还原剂注入尾气流中的注射器302。在注射器302之后是选择性催化还原(SCR)催化剂303。其以接触尾气的方式放置并使用含氮的还原剂将所述NOx还原以形成N2并产生NOx还原了的气体流股。因为尾气流股中NOx的量易于随例如发动机的加速/减速、运行温度、环境温度等而明显变化,所以在含氮的还原剂与NOx之间难以保持精确的化学计量平衡。因此,将充裕的含氮的还原剂注入尾气流股中,导致其一部分穿过SCR并进入NOx还原了的气体流股。将其称作逸失的含氮的还原剂或更特别地,称作逸失氨。
SCR的下游是用于将HC注入NOx还原了的气体流股中以形成HC富集的流股的烃(HC)注射器304。组合催化剂305以接触HC富集的流股的方式放置以形成温度足以将催化剂烟粒过滤器(CSF)306中含有的烟粒再生(例如400℃)的加热的气体流股。再生烟粒所需要的温度能够随应用而变化。例如,典型地,加热的气体流股应为550~650℃,然而,可向气体流股中添加添加剂以将所需要的温度降至约450℃且或许更低。
参考图7,显示了组合催化剂700的一个实施方案的示意图。组合的催化剂700包含基材701,在所述基材701上布置具有氧化催化剂的第一层702。所述氧化催化剂将逸失的含氮的还原剂和HC富集的流股中注入的HC氧化。所述氧化催化剂具有有效量的PGM(例如大于10g/ft3)以诱发氧化反应而充分放热,以将加热的气体流股加热至合适的再生温度(例如400~550℃)。催化剂700还包含第二层703,在该实施方案中,所述第二层703覆盖所述第一层702。所述第二层包含用于将富集的流股中的NOx或从第一层702中HC和含氮的还原剂的氧化而产生的NOx还原的SCR催化剂。
下面参考某些非限制性实施方案对所述系统、组合催化剂及其用途进行更详细描述。
返回参考图3,发动机307可以为任意贫燃型发动机,包括例如柴油机、贫燃汽油机或由液体石油气或天然气提供动力的发动机。
在图3中所示的实施方案中,系统300还具有柴油机氧化催化剂(DOC)308。所述DOC308是一种熟知的使用化学过程将尾气流股中的污染物分解成危害更轻的成分的装置。更具体地,DOC典型地利用贵金属催化剂以通过简单氧化减少柴油机尾气的微粒物质(PM)、烃类可溶性有机馏分(SOF)和一氧化碳的含量。典型的DOC是流动穿过装置,包含含有蜂巢状结构或基材的滤毒器。所述基材具有涂布有活性催化剂层的大表面积。这种活性层含有少量良好分散量的贵金属。随着尾气穿过催化剂,一氧化碳、气态烃和液态烃粒子(未燃烧的燃料和油)被氧化,由此减少了有害的排放物。
DOC308的下游是含氮的还原剂的注射器302,其也是熟知的。其向尾气系统中计量加入合适量的含氮的还原剂。用于SCR应用中的几种还原剂包括氨本身、肼、无水氨、含水氨或选自脲((NH2)2CO)、碳酸铵、氨基甲酸铵、碳酸氢铵和甲酸铵中的氨的前体。纯的无水氨具有毒性且难以安全储存,但不需要进一步转化以与SCR催化剂反应。含水氨必须水解以加以使用,但在储存和运输方面其比无水氨更安全。对于储存,脲是最安全的,但需要通过热分解转化成氨以用作有效的还原剂。
已知的是,通过控制器(未示出)对注射器302进行控制,所述控制器对发动机数和尾气参数进行监测并确定注入的含氮的还原剂的合适量。这种参数包括例如尾气的NOx浓度、尾气的温度、催化剂床的温度、加速器的位置、系统中尾气的质量流量、歧管真空、点燃时机、发动机的速度、尾气的λ值、在发动机中注入的燃料的量和尾气再循环(EGR)阀的位置以及由此的EGR的量和增压压力。
所述SCR催化剂也是熟知的且典型地包含含有一种或多种过渡金属的微孔材料。所述SCR催化剂由用作载体的各种陶瓷材料如氧化钛制造,且活性催化成分通常为碱金属(例如钒和钨)的氧化物、分子筛如沸石以及各种贵金属。所使用的SCR催化剂的几何形状的两种最普通设计是蜂巢和板。蜂巢形式通常是均匀施加在整个陶瓷载体或涂布在基材上的挤出的陶瓷材料。板型催化剂比蜂巢型具有更低的压降且不易堵塞和结垢,但板构造更大且更贵。蜂巢构造比板型小,但具有更高的压降且更易堵塞。例如在分子筛/沸石基催化剂中公开了适用于本发明中的SCR催化剂。在一个实施方案中,SCR催化剂为过渡金属交换的沸石。
在图3中所示的实施方案中,SCR催化剂在组合催化剂305的上游。对于间歇运行的发动机,通常优选(但不是必需的)这种安排,从而SCR303快速加热并由此快速达到峰值效率。此外,在这种构造中,其不暴露在对SCR催化剂有害的加热的气体流股下。
在SCR催化剂的下游但在组合催化剂305之前,HC注射器将HC(典型地为发动机用燃料)注入低NOx气体流股中以形成HC富集的气体流股。与含氮的还原剂注射器类似,利用控制器(未示出)对HC注射器进行控制,对所述控制器进行构造以周期性地使得特定量的HC注入流股中,从而周期性地再生捕集在CSF306中的烟粒。烟粒需要被再生的频率以及由此需要注入HC的频率和量是所述系统的最优化的结果,这对本领域技术人员是熟知的。
本发明的重要方面是组合催化剂305。其将ASC201和DEC105的功能合并。如上所述,已经发现,尽管相对高PGM载荷的氧化催化剂改进了HC和含氮的还原剂的氧化,但惊奇地是,SCR催化剂的涂层能够限制NOx的形成。由此本发明的催化剂能够在选择性氧化逸失的氨的同时通过放热反应产生足够的热以用于烟粒的再生。
可推断,该组合催化剂的多功能性是由于在组合催化剂内的大量反应和相互作用。不期望受限于任何特殊理论,可推断,首先,源自氧化的NOx和源自尾气的逸失氨被吸附在作为SCR活性涂层的第二层上并以选择性催化反应的方式发生反应而形成水和氮气,所述氮气在反应结束之后脱附。此处,氨以超化学计量的量存在。第二,未使用或未吸附入SCR层中的逸失氨以及HC穿过第二层而到达第一层。第二层具有强力的氧化作用,从逸失氨产生氮气和氮氧化物并从HC产生水、一氧化碳并放热。形成的氮气以不发生变化的方式扩散/穿过第二层并进入大气。第三,在第一层中形成氮氧化物之后,其穿过或绕过第二层的SCR催化剂,在那里其以SCR反应的方式与提前储存的/逸失氨反应以形成N2。因此,在HC富集的气体穿过组合催化剂时发生的SCR/氧化/SCR过程充当自调节系统,其中促进氧化,但控制过度氧化。
参考图7,显示了催化剂700的一个实施方案。催化剂包含基材701,其可包含用于该应用中的任意一种已知的基材材料,包括例如氧化铝。或者,所述催化剂可以为本领域中熟知的挤出催化剂。此外,所述基材可以以任意一种已知构造进行构造,包括例如蜂巢或单块。在一个具体实施方案中,所述基材为蜂巢状氧化铝。
如图7中所示,以第二层703覆盖第一层702的方式构造所述第一层702和第二层703。然而应理解,其他构造也在本发明的范围内。例如,可以以第一层在第二层的上游的方式沿基材布置所述第一层和第二层。或者,可使用一系列交替的第一层和第二层。根据本发明,对于本领域中的技术人员,另外的其他构造也是明显的。
如上所述,第一层包含氧化催化剂。应对所述催化剂进行选择以确保在实现明显放热反应的程度内氧化HC和含氮的还原剂。具体地,放热反应必须足以将加热的气体流股加热至其能够对CSF306中的烟粒进行再生的点。通常,这要求将该气体加热到至少约400℃。最佳再生发生在约550℃~约650℃下。为此,所述催化剂应包含微孔材料如沸石或非沸石(例如氧化铝、氧化铈、氧化锆、氧化钛或单独或组合的类似材料),所述微孔材料负载有足够的PGM以提供期望的放热。通常,PGM的载荷越大,催化剂的反应性越高。
除了具有足够的PGM载荷以确保足以产生上述再生温度之外,所述PGM载荷还应足以使得由HC的放热产生的热的起燃温度低于约350℃。通常,期望更低的起燃温度。如果起燃温度高于约350℃,则要求辅助系统对上游的尾气进行加热。这种系统提高了尾气系统的复杂性并降低了燃料效率,由此通常是不期望的。申请人已经发现,到达DEC的尾气的温度通常(但不是必需的)低于350℃。因此,在一个实施方案中,本发明的催化剂具有足以使得催化剂的起燃温度低于350℃且在更具体的实施方案中低于325℃的PGM类型和载荷。根据本发明,提供这种期望性能的氧化层的制备对于本领域技术人员而言是已知的。
如果需要高的再生温度和相对低的起燃温度,则所需要的PGM载荷典型地大于传统ASC催化剂中所使用的载荷,所述PGM载荷往往小于10g/ft3。(典型地将ASC催化剂中的载荷保持为相对低以避免逸失氨的过度氧化和NOx的再生)。因此,在一个实施方案中,PGM的载荷大于传统ASC催化剂的载荷。在一个实施方案中,载荷大于约10g/ft3。在另一个实施方案中,载荷大于约10g/ft3且小于约100g/ft3。在另一个实施方案中,载荷为约15g/ft3~约70g/ft3。在还另一个实施方案中,载荷为约20g/ft3。
在一个实施方案中,PGM包含钯(Pd)和/或铂(Pt)。在另一个实施方案中,PGM包含Pd和Pt的组合。通常,Pd促进放热反应,且Pt往往从NH3产生NOx。因此,在Pd和Pt的混合物中的相对浓度往往取决于所期望的氧化对NOx的产生的量。Pd对Pt的相对载荷可以为1:10~10:1的比例。在一个具体实施方案中,对于约15~70g/ft3的总载荷,PGM包含基本相等比例的Pt和Pd的组合。
所述第二层包含SCR催化剂。这种催化剂是熟知的并在上面对SCR催化剂303进行了描述。通常,SCR催化剂包含一种SCR催化剂,该种SCR催化剂包含:至少(i)微孔结晶分子筛;和(ii)在分子筛中浸渍的过渡金属。
分子筛可以是任意一种已知的或后来开发的适合用作催化剂的微孔结构,包括沸石和非沸石筛(如同美国专利4,913,799号所限定的(通过参考并入本文中))。在一个实施方案中,分子筛包含至少硅、铝和磷并具有8-元环孔开放结构。在一个实施方案中,分子筛是硅铝磷酸盐(SAPO)分子筛。在一个实施方案中,SAPO分子筛具有由国际沸石协会结构委员会(the Structure Commission of the International ZeoliteAssociation)限定的一种或多种如下骨架类型:AEI、AFX、CHA、LEV、LTA。在一个实施方案中,骨架类型为CHA或与一种或多种不同骨架类型组合的CHA如AEI-CHA连生体。合适的CHA SAPO的实例包括SAPO-34和KYT-6。在一个具体实施方案,分子筛是SAPO-34。在另一个实施方案中,催化剂包含选自AEI、AFX、CHA、LEV和LTA中的两种以上不同SAPO的分子筛。在一个实施方案中,沸石具有选自AEI、AFX、CHA、LEV、LTA、BEA、MFI、FER、MOR和KFI中的骨架类型。合适的BEA沸石的实例为β沸石。
除了分子筛之外,SCR催化剂包含嵌入分子筛中的过渡金属。合适的过渡金属包括例如Cr、Mn、Fe、Co、Ce、Ni、Cu、Zn、Ga、Mo、Ru、Rh、Pd、Ag、In、Sn、Re、Ir、Au、Pr、Nd、W、Bi、Os和Pt。在一个实施方案中,过渡金属为Cu或Fe或其组合。在一个实施方案中,过渡金属的载荷为催化剂的约0.3重量%~约10重量%。过渡金属的类型和浓度能够随分子筛和应用而变化。例如,利用负载有约2重量%的Cu的SAPO-34和负载有约3重量%的Fe的β-沸石已经实现了合适的结果。根据本发明,分子筛、过渡金属和载荷浓度的另外的其他组合对于本领域技术人员是显而易见的。
SCR催化剂可包含由陶瓷材料如堇青石、莫来石、氧化硅、氧化铝、氧化钛或其组合制造的基材。或者,所述基材能够为金属材料。两种最普通的基材设计是单块或板和蜂巢。板型催化剂比蜂巢型具有更低的压降且不易堵塞和结垢,但板构造更大且更贵。蜂巢构造比板型小,但具有更高的压降且更易堵塞。或者,催化剂能够在具有或不具有基材的条件下挤出。在后面的实施方案中,催化剂不具有离散的基材。在还另一个实施方案中,根本未对催化剂进行负载,而是以块的形式提供。
使用已知技术能够制备组合催化剂305。例如,加拿大申请2,652,837号(基于PCT公布2007/137675号的)公开了一种合适的制备程序,但本发明的氧化层的PGM载荷需要高于所述文献中所公开的PGM载荷,通过参考将所述文献并入本文中。
加热的气体离开组合催化剂305并在再生烟粒的点处接触CSF306。这种过程是熟知的且本文中不再详细讨论。
实施例
如下非限制性实施例将本发明组合催化剂的五个实施方案(样品2~6)与常规DEC催化剂(样品1)和常规ASC(样品7)进行了比较,如下表1中所示。
表1
在这些样品中,通过在所示浓度下制备负载有所示PGM的氧化铝的湿浆料,并利用所述浆料对标准陶瓷蜂巢基材进行洗涤涂布,制备了氧化层。通过制备经过离子交换而负载有所示量的Cu或Fe的所示微孔材料(SAPO-34或β沸石)的混合物,将粘合剂添加至所述混合物中,然后利用所述混合物对所述氧化层进行洗涤涂布,制备了SCR层。
起燃温度
图4显示了在高HC浓度(对于DEC典型地是产生放热以清洁过滤器)下起燃试验(HC的氧化)的结果。这是在12%的O2、200ppm的NH3、200ppm的CO、1000ppm的C10H22、4.5%的H2O、4.5%的CO2且剩余物为N2的气氛中的稳态起燃试验。
尽管样品1即常规DEC具有最低的起燃温度(<200℃),但样品2即Pt/Pd组合催化剂和样品3~5即具有20~35重量%的Pt的Pt组合催化剂,也展示了合适的起燃温度(即<350℃)。样品6即10g/ft3的Pt的组合催化剂,具有约350℃的起燃温度,其通常(但不是必需的)太高。同样,样品7即低PGM载荷的标准NH3逸失催化剂(1g/ft3的Pt),也具有约350℃的起燃温度。因此,这些结果显示,利用具有超过10g/ft3的PGM浓度的氧化层实现了具有合适起燃温度的组合催化剂。
NH3的转化率
图5显示了在12%的O2、200ppm的NH3、200ppm的CO、100ppm的C3H6、4.5%的H2O、4.5%的CO2且剩余物为N2的气氛中在低烃浓度(无放热产生)下在标准柴油机运行条件下NH3的转化率。此处,所有样品都显示了可接受的NH3转化率,即在约325℃下接近100%的NH3的转化率。
选择性
图6显示了在将NH3选择性转化成N2中各种样品的性能。该实验为在与图5的NH3的转化中相同的气氛条件下的稳态起燃试验。样品1即标准DEC在相对低的温度下具有峰值为40%的最低选择性并在更高温度下降至10%以下。样品2~6即组合催化剂在约325~425℃下具有峰值约55~70%的明显更好的选择性,所述温度范围为普通的运行温度范围。样品4和5即35g/ft3和20g/ft3的Pt的组合催化剂,在325~425℃下显示了约70%的特别高的选择性。将这种选择性与作为传统ASC的样品7进行了比较。
因此,这些实施例显示,对于含氮的还原剂的逸失控制,本发明的组合催化剂提供了良好选择性的益处,其即使在用于改进的HC氧化以产生放热的氧化催化剂中的PGM载荷更高的条件下仍能够保持。向含Pt的下层中添加Pd也在提高NH3对N2的选择性的同时,提高催化剂的HC氧化能力。
Claims (20)
1.一种催化剂,包含:
第一层,所述第一层包含具有有效PGM载荷的氧化催化剂以使得烃的氧化产生足以再生烟粒的热,其中所述有效量的PGM为大于约10g/ft3;和
第二层,所述第二层与所述第一层相邻并包含用于选择性还原NOx的还原催化剂。
2.权利要求1的催化剂,其中所述有效量的PGM为大于约15g/ft3。
3.权利要求2的催化剂,其中所述有效量的PGM为约15g/ft3~70g/ft3。
4.权利要求3的催化剂,其中所述有效量的PGM为不小于约20g/ft3。
5.权利要求1的催化剂,其中所述PGM选自Pt和Pd及其组合。
6.权利要求5的催化剂,其中所述PGM为Pt和Pd的组合。
7.权利要求1的催化剂,其中所述催化剂在12%的O2、200ppm的NH3、200ppm的CO、1000ppm的C10H22、4.5%的H2O、4.5%的CO2且剩余物为N2的气氛中具有小于350℃的HC起燃温度。
8.权利要求7的催化剂,其中所述HC起燃温度不大于约325℃。
9.权利要求1的催化剂,其中所述SCR催化剂为负载有过渡金属的分子筛。
10.权利要求9的催化剂,其中所述过渡金属选自Cu、Fe及其组合。
11.权利要求10的催化剂,其中所述分子筛为SAPO、CHA或β沸石。
12.权利要求1的催化剂,还包含在其上布置了所述第一层的基材。
13.权利要求12的催化剂,其中所述第二层覆盖所述第一层。
14.权利要求12的催化剂,其中所述第一层在所述第二层上游。
15.一种在尾气系统中产生热以除去烟粒并减少NH3的逸失的方法,所述方法包括:
将含氮的还原剂注入具有NOx的尾气流中;
在SCR催化剂存在下使用所述含氮的还原剂将所述NOx还原以形成NOx还原了的气体流股,所述气体流股至少间歇地含有逸失的含氮还原剂;
将HC注入所述NOx还原了的气体流股中以形成HC富集的气体流股;和
将所述HC富集的气体流股与组合的催化剂接触以形成加热的气体流股,所述组合的催化剂包含第一层和第二层,所述第一层具有氧化催化剂以将所述HC的至少一部分氧化而对所述加热的气体流股进行加热,且所述第二层具有SCR催化剂以对所述加热的气体流股中的NOx的至少一部分进行还原。
16.权利要求15的方法,其中将所述加热的气体流股加热到至少400℃。
17.权利要求15的方法,其中所述HC富集的气体流股低于350℃。
18.权利要求15的方法,其中所述第一层负载有大于约15g/ft3的PGM。
19.权利要求15的方法,还包括:
将所述加热的气体流股与烟粒过滤器接触以在所述过滤器中对烟粒进行再生。
20.一种尾气处理系统,包含:
导管,所述导管用于将具有NOx的尾气从发动机传送到大气;
注射器,所述注射器用于将含氮的还原剂注入所述尾气中;
SCR催化剂,所述SCR催化剂以接触所述尾气的方式放置并使用所述含氮的还原剂将所述NOx还原以形成NOx还原了的气体流股,所述气体流股至少间歇地含有逸失的含氮还原剂;
HC注射器,所述HC注射器用于将HC注入NOx还原了的气体流股中以形成HC富集的气体流股;
组合催化剂,所述组合催化剂以接触所述HC富集的气体流股的方式放置以形成加热的气体流股,所述组合催化剂包含第一层和第二层,所述第一层具有氧化催化剂以对所述逸失的含氮还原剂和所述HC进行氧化,从而对所述加热的气体流股进行加热,且所述第二层具有SCR催化剂以对在所述加热的气体流股中的NOx进行还原;和
过滤器,所述过滤器以接触所述加热的气体流股的方式布置以对在所述过滤器中含有的烟粒进行再生。
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PCT/US2011/051750 WO2012037342A1 (en) | 2010-09-15 | 2011-09-15 | Combined slip catalyst and hydrocarbon exotherm catalyst |
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EP (1) | EP2616175B1 (zh) |
JP (2) | JP5882333B2 (zh) |
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BR112013005816A2 (pt) | 2016-05-10 |
KR101860741B1 (ko) | 2018-05-24 |
RU2583374C2 (ru) | 2016-05-10 |
EP2616175B1 (en) | 2021-01-27 |
KR20130103502A (ko) | 2013-09-23 |
JP6228179B2 (ja) | 2017-11-08 |
KR101996196B1 (ko) | 2019-07-03 |
CN103118780B (zh) | 2016-06-01 |
JP5882333B2 (ja) | 2016-03-09 |
KR20180058842A (ko) | 2018-06-01 |
WO2012037342A1 (en) | 2012-03-22 |
US20130078173A1 (en) | 2013-03-28 |
US8329127B2 (en) | 2012-12-11 |
JP2016147258A (ja) | 2016-08-18 |
US20120107204A1 (en) | 2012-05-03 |
BR112013005816B1 (pt) | 2019-04-30 |
RU2013116902A (ru) | 2014-10-20 |
JP2013542847A (ja) | 2013-11-28 |
EP2616175A1 (en) | 2013-07-24 |
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