CN103998113B - 汽车催化后处理*** - Google Patents
汽车催化后处理*** Download PDFInfo
- Publication number
- CN103998113B CN103998113B CN201280061513.2A CN201280061513A CN103998113B CN 103998113 B CN103998113 B CN 103998113B CN 201280061513 A CN201280061513 A CN 201280061513A CN 103998113 B CN103998113 B CN 103998113B
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- upstream
- oxidation catalyst
- catalyst
- diesel
- diesel oxidation
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Abstract
描述了一种用于柴油机废气的催化后处理***。该***包括柴油机氧化催化剂(DOC)和位于该柴油机氧化催化剂(DOC)下游的后处理装置,该后处理装置需要定期热处理,和用于在该后处理装置中产生温度增加的装置,所述柴油机氧化催化剂(DOC)包括长度为0.5‑2英寸(12.7‑50.81mm)的上游区,该上游区对于烃(HC)的氧化活性高于该柴油机氧化催化剂(DOC)的其余部分。
Description
发明领域
本发明涉及一种催化后处理***,特别是用于汽车应用,例如用于柴油机。更具体地,本发明涉及催化后处理***,其引入了柴油机氧化催化剂(DOC)和位于该柴油机氧化催化剂(DOC)下游的可再生后处理装置。本发明进一步涉及一种在后处理装置的主动热处理过程中保持柴油机氧化催化剂(DOC)活性的方法,和一种在主动热处理事件过程中避免柴油机氧化催化剂(DOC)衰减(extinction)的方法。
发明背景
对车辆排放物的不断提高的规格通过工程设计(包括高级发动机管理)和多种催化后处理装置的组合来满足。
在来自压缩点火(下文称作“柴油机”)发动机的废气的情况中,所控制的排放物是一氧化碳(CO)、烃(HC)、氮氧化物(NOx)和颗粒物。颗粒物虽然经常简称为“烟灰”,但是它们是复杂的固体,碳颗粒形成其大部分。以前,颗粒物的排放是柴油机发出的特征“烟雾”,特别是当在重负荷下运行例如在爬山过程中更是如此。碳颗粒还携带了不同量的吸收或吸附的烃和氧化副产物。
柴油机氧化催化剂(DOC)是引入用于轻型柴油车辆中的第一催化后处理装置。DOC包含催化剂,几乎专门基于铂族金属(PGM),特别是铂,任选地组合有另一种PGM和/或催化贱金属,其沉积在高表面积的流通式催化剂基底上。基底单元俗称“砖块”。DOC对氧化CO和HC和降低颗粒物的重量有效,并且一些年来,DOC足以满足轻型柴油机排放物的规格。
随着引入了对来自于柴油机车辆的排放物控制的更高标准,处理颗粒物已经变成必需的。柴油机通常产生比火花点火或者汽油发动机更低水平的NOx,并且柴油机可以经工程设计来降低颗粒物,不过要以NOx增加为代价,或者反之亦然。在欧洲现行和将要引入美国的规格下,现有技术的柴油机车辆目前具有DOC和烟灰过滤器的组合,并且还可以具有NOx还原***。烟灰过滤器经常但非排他地是催化烟灰过滤器(CSF),并且虽然它们的细节可能不同,但是它们通常引入陶瓷壁流式过滤器,或者不太经常地引入烧结金属过滤器。催化过滤器带有烟灰氧化催化剂的沉积物,例如PGM和碱金属或碱土金属组合。
这种过滤器能够满足颗粒物排放的规格。虽然在涉及高速区的正常驾驶周期期间,这种过滤器不会遭受烟灰聚集,但是现实的情形例如在城市中,会包括长时间的低速驾驶和/或延长的空转期,在此期间烟灰会在过滤器中聚集,但是废气温度不足以催化氧化该烟灰。过滤器面的堵塞或者过滤器通道内烟灰的聚集会例如导致背压增加到严重影响发动机效率的程度,或者在极端的情况中损坏发动机本身。因此必需提供某种形式的过滤器再生来清洁该过滤器。
被动再生包括使车辆以足够高的速度运行,以使得废气达到聚集的烟灰开始氧化的温度。
替代的主动再生描述在例如GB2406803A中。将废气中补充的HC形式的燃料供给到DOC,在这里它燃烧并将废气温度提高到催化烟灰过滤器上聚集的烟灰开始催化燃烧的点。涉及主动再生的GB2406803A(Johnson Matthey)公开了一种DOC,其具有在砖块上游端中的Pt-组分和在砖块下游端中的Pd-组分。关于尺寸唯一的其他公开内容记载“基本上无Pd的含Pt区域可以达到基底整料长度的一半或者“条纹”类型尺寸。要注意的是,不同组成的目的来源于由含硫柴油燃料所产生的硫酸盐化作用。虽然在欧洲国家中目前柴油燃料具有低的或者超低的硫含量,但是在许多其他国家中仍然存在着硫含量较高的问题。
WO00/29726(Engelhard)在一种实施方案中描述了在催化烟灰过滤器上游的一种流通式催化剂或者DOC(在一些地方易混淆地称为第二催化剂)。该DOC组成均匀,但是CSF可以具有4英寸的富含Pt的端。在一些测试中,该DOC与CSF一起测试,在一些实验中,CSF单独使用。在一些CSF实验中,富含Pt的端是上游,在一些实验中富含Pt的端是下游。该早期CSF公开文献没有想到CSF的主动再生。
WO2009/005910(Cummins)描述了一种废气后处理装置,其中砖块的前端面具有物理形式或者化学涂层,来有效防止暴露于含有柴油机颗粒物的废气流的砖块的“遮蔽”或者堵塞或者面栓塞(face-plugging)。当使用化学涂层时,需要明确指出的是,这意在砖块的前端面上进行,并且不延伸到砖块的流体通道中。
WO2007/077462(Johnson Matthey)公开了一种三个区域的DOC,目的是改进具有均匀组成的DOC或者在砖块的上游端具有较高Pt负载的单个区域的DOC的性能。没有公开主动再生***,因此不存在废气的定期富集。虽然该发明打算处理“衰减(light-out)”问题,但是该问题产生于New European Drive Cycle的较冷部分。WO2007/077462的发明人发现。PGM在DOC上的均匀负载,或者在前部区域上具有相对高负载的DOC,表现出衰减或者熄灭(extinguish)的倾向。WO2007/077462中提出的解决方案是在DOC的下游端引入第三更高负载的区域。其所处理的问题与本发明不同。
发明内容
已经发现,在DOC/过滤器组合***中过滤器的主动再生仍然显著地取决于废气进入DOC时的温度。当DOC已经老化时更能观察到这种现象。即,甚至当DOC已经“起燃(lightoff)”时,如果废气温度是约250℃,则起燃的DOC仍然会在主动再生事件过程中熄灭。考虑到过量的HC燃料被供给到DOC来将废气温度升高,以使烟灰过滤器催化剂起燃,并且预期在起燃方面DOC本身应当保持运行,这个结果是令人惊讶的。应当观察到这一情况在250℃的废气温度发生,其在柴油机废气中并不罕见,这对管理所控制的排放物提出了问题。
在车辆催化后处理中,术语“起燃”的含义是本领域公知的。除非另外指示,否则催化剂被认为在50%(例如50wt%)的组分被催化转化时的温度起燃。
位于废气***中的其他装置也会需要定期再生或者其他热处理。例如,选择性催化还原(SCR)催化剂例如基于铜组分的那些可能需要脱硫酸盐,这可以通过热处理来方便地进行。因此,通过将另外的燃料供入废气***或者废气中,所产生的放热能够再生许多不同的废气后处理装置。
所以本发明的一个目标是提供***和方法,来改进主动再生***中DOC的效果。本发明的一个重要部分是提供这样的DOC:其具有比例如该DOC的其余部分更具活性的第一区。
所以本发明提供一种用于柴油机废气的催化后处理***,所述***包括柴油机氧化催化剂(DOC)和位于该柴油机氧化催化剂(DOC)下游的后处理装置,该后处理装置需要定期热处理,和用于在该后处理装置中产生温度增加的装置,所述柴油机氧化催化剂(DOC)包括长度为0.5-2英寸(12.7-50.81mm)的上游区,该上游区对于烃(HC)的氧化活性高于该柴油机氧化催化剂(DOC)的其余部分。
令人惊讶地,与WO2007/077462相比,具有这种特定上游区尺寸的柴油机氧化催化剂在所关注的区域中不表现出“衰减”性能,而是保持起燃,这与均匀组成或者具有较小的高活性“条纹”的分区DOC形成对比,甚至当保持相同的总PGM负载时也是如此。显示本发明令人惊讶的效果的实验结果在下面进行更详细的描述。
用于废气催化剂和用于废气过滤器的常规后处理装置例如可再生装置(基于流通式金属或陶瓷基底)是本领域已知的,并且本发明将参考这种装置来描述。但是本发明不应当被认为局限于这种装置,并且使用更少见的流通式催化剂基底或者过滤器构造包括在本发明的范围内。
本发明还提供一种保持柴油机氧化催化剂(DOC)的活性的方法,该方法在柴油机废气后处理***中位于柴油机氧化催化剂(DOC)下游的后处理装置的主动热处理过程中在200-375℃的废气温度通过将该废气送过柴油机氧化催化剂(DOC)来进行,该催化剂具有或者包括长度为0.5-2英寸(12.7-50.81mm)的上游区,该上游区对于烃(HC)的氧化活性高于该柴油机氧化催化剂(DOC)的其余部分。
本发明进一步提供一种避免柴油机氧化催化剂(DOC)衰减的方法,该方法在用于位于柴油机氧化催化剂(DOC)下游的后处理装置的主动热处理事件过程中在200-375℃的废气温度通过将富含烃(HC)的废气送过柴油机氧化催化剂(DOC)来进行,该催化剂具有或者包括长度为0.5-2英寸(12.7-50.81mm)的上游区,该上游区对于烃(HC)的氧化活性高于该DOC的其余部分。
本发明的另一方面涉及一种车辆,其包括柴油机和本发明的催化后处理***。
本发明进一步涉及柴油机氧化催化剂(DOC)中的区域的用途,在位于该柴油机氧化催化剂(DOC)下游的后处理装置的主动热处理过程中典型地在200-375℃的废气温度,通过将富含烃(HC)的废气送过柴油机氧化催化剂(DOC)来(a)保持该柴油机氧化催化剂(DOC)的活性,和/或(b)避免该柴油机氧化催化剂(DOC)衰减,其中该区域的长度是0.5-2英寸(12.7-50.81mm),并且具有比该柴油机氧化催化剂(DOC)的其余部分更高的对于烃(HC)的氧化活性。通常,该区域处于该柴油机氧化催化剂的上游(即在上游端)。
本发明的另一方面涉及柴油机氧化催化剂(DOC)的用途,用来再生典型地在用于柴油机废气的催化后处理***中位于该柴油机氧化催化剂(DOC)下游的后处理装置,其中该柴油机氧化催化剂(DOC)包括长度0.5-2英寸(12.7-50.81mm)的上游区,该上游区对于烃(HC)的氧化活性高于该柴油机氧化催化剂(DOC)的其余部分。通常,该后处理装置需要定期热处理。典型地,本发明进一步涉及该柴油机氧化催化剂(DOC)的用途,用来再生位于该柴油机氧化催化剂(DOC)下游,结合有用于在该后处理装置中产生温度增加的装置的后处理装置。
附图说明
为了能够更充分地理解本发明,参考仅以示例性方式并参照附图的以下实施例。
图1的图显示了当废气经过常规的柴油机氧化催化剂(DOC1)时,在它内部的三个区域的温度。DOC1具有均匀的PGM负载。
图2的图显示了当废气经过具有10mm“条纹”的较高PGM浓度的柴油机氧化催化剂(DOC2)时,在它内部的三个区域的温度。
图3的图显示了当废气经过根据本发明的柴油机氧化催化剂(DOC3)时,在它内部的三个区域的温度。
具体实施方式
通常,作为此处使用的,任何提及的废气典型地指的是来自柴油机的废气。
典型地,经过该柴油机氧化催化剂(DOC)的废气的温度是200-375℃。因此,本发明涉及用途或方法的方面可以包括将200-375℃温度的废气与该柴油机氧化催化剂(DOC)接触,或者使200-375℃温度的废气经过或穿过该柴油机氧化催化剂(DOC)的步骤。
本发明涉及具有上游区的柴油机氧化催化剂(DOC),该上游区对于烃(HC)的氧化活性高于该DOC的其余部分(例如下游区)。当废气的温度低于DOC其余部分的“起燃”温度时,具有对于烃的更高反应性的区域会产生放热(即热)。所产生的热可以例如经由废气转移并通过基底单元或砖块,来将DOC的其余部分升高到它的“起燃”温度。当废气温度降低时(例如当发动机空转时),也可以将DOC的其余部分保持在它的起燃温度。该上游区和DOC其余部分对于烃(HC)的氧化活性可以使用本领域已知的任何常规技术来测量。
上游区和DOC其余区或下游区对于烃(HC)的氧化活性优选作为对于烃的T50来测量。因此,上游区对于烃的T50低于DOC其余区或下游区对于烃的T50。T50是本领域公知的,代表具体的反应物(在本发明中是烃)50%转化时的最低温度。T50典型地涉及柴油机(例如依靠根据EN590:1993标准的柴油燃料(例如B7)运行的柴油机)的废气中烃的50%转化率,优选根据EN590:1999的柴油燃料,更优选根据EN590:2004或者EN590:2009的柴油燃料。
上游区的长度是0.5-2英寸(12.7-50.81mm)。优选上游区的长度是0.5-1.75英寸,例如0.5-1.5英寸或者0.6-1.75英寸,更优选0.75-1.25英寸。典型地,上游区的长度是约1英寸(2.54cm)。在这里所用的上游区的上下文中提及的长度指的是它的平均长度。作为本领域公知的,该区域的精确长度会根据它的制造方法而存在着一些偏差。通常,长度相对于平均值的偏离不超过10%,优选相对于长度的平均值偏离不超过5%,更优选不超过1%。为了避免疑义,上游区的长度通常平行于DOC的纵轴从它的入口端来测量。
典型地,DOC的直径可以是2.5-15英寸,例如4-15英寸,优选5-12.5英寸,例如6-10英寸。
DOC的长度(即总长度)典型地是2.5-15英寸,例如3-12.5英寸,优选4-11英寸(例如5-10英寸)。
通常,DOC的尺寸是常规的。例如DOC的直径可以是4-15英寸和长度是2.5-10英寸。作为此处使用的,在DOC上下文中任何提及的长度或直径指的是平均长度或平均直径。通常,长度或直径相对于平均值偏离不超过10%,优选分别相对于长度或者直径的平均值不超过5%,更优选不超过1%。
虽然上游区的性质(即长度和/或氧化活性)是重要的,但是DOC的其余区或者下游区会具有多种组成。因此,例如DOC的其余部分可以具有非均匀的组成(例如DOC的其余部分可以包括多个区和/或层,例如两个或三个区或层)。但是,因为PGM的稀缺性和它们因此的高价格,优选的趋势是使DOC中的PGM总量最小化。本发明可以提供改进的DOC性能,而没有更大的PGM总负载,并且在某些情形中,可以在DOC上使用更低的总PGM负载。
DOC通常包含负载在基底单元(例如“砖”)上的催化剂组合物。该催化剂组合物典型地包含至少一种PGM,优选至少两种PGM。
优选该催化剂组合物包含选自下面的至少一种PGM,更优选至少两种不同的PGM:铂、钯、铑及其两种或更多种的混合物或合金。更优选该催化剂组合物包含铂和钯。
典型地,DOC包含的PGM总量(例如铂(Pt)和钯(Pd)的总量)是15-400g ft-3。优选PGM总量是20-300g ft-3,更优选25-250g ft-3,仍然更优选35-200g ft-3和甚至更优选50-175g ft-3。
当DOC包含铂和钯时,则Pt与Pd的重量比(在柴油机氧化催化剂(DOC)的上游区和其余部分中)典型地是1:3-5:1,优选1:2-3:1,更优选1:1.5-2:1(例如1:1.5-1.5:1)。
典型地,上游区的PGM浓度是10-150g ft-3。优选上游区的PGM浓度是15-135g ft-3,更优选20-125g ft-3,例如25-100g ft-3。
在本发明的一种普通实施方案中,上游区包含铂(Pt)和钯(Pd)。因此,该上游区可以包含上游催化剂组合物,该上游催化剂组合物包含由铂(Pt)和钯(Pd)组成的PGM。在该实施方案中,铂和钯可以是DOC的上游区中仅有的PGM。
典型地,上游区中铂(Pt)的浓度大于DOC的其余区或下游区中铂(Pt)的浓度。更优选上游区中钯(Pd)的浓度小于DOC的其余区或下游区中钯(Pd)的浓度。
当上游区包含铂(Pt)和钯(Pd)时,则典型地铂(Pt)与钯(Pd)的重量比≥1:1。优选铂(Pt)与钯(Pd)的重量比≥1.1:1,更优选≥1.25:1,特别地≥1.5:1,例如≥1.75:1(例如≥2:1),仍然更优选≥2.5:1(例如≥5:1)。因此,DOC的上游区包含重量比为10:1-1:1(例如2:1-1.1:1或者7.5:1-5:1)的铂(Pt)和钯(Pd),更优选8:1-1.25:1(例如7:1-1.5:1),仍然更优选6:1-2.5:1。
催化剂组合物可以任选地进一步包含烃吸附剂(例如沸石)和/或一种或多种载体材料。烃吸附剂是本领域公知的。合适的载体材料的例子包括氧化铝、二氧化硅-氧化铝、二氧化铈、二氧化铈-氧化锆和二氧化钛。
DOC适宜但非排他地基于常规的陶瓷流通式砖块。每平方英寸中可以存在100或者更多个孔,例如400个。
因此,该基底单元或“砖块”典型地是流通式基底单元,例如流通式整料。流通式整料典型地包括蜂窝状整料(例如金属或陶瓷蜂窝状整料),其具有多个贯穿其中的通道,该通道在两端开口。
通常,该基底单元是陶瓷材料或者金属材料。优选该基底由以下制成或者包含以下:堇青石(SiO2-Al2O3-MgO)、碳化硅(SiC)、Fe-Cr-Al合金、Ni-Cr-Al合金或不锈钢合金。
典型地,后处理装置(位于DOC下游)是烟灰过滤器或者选择性催化还原(SCR)催化剂(例如用于选择性催化还原的催化剂装置)。
当后处理装置是烟灰过滤器时,据信该烟灰过滤器的具体类型、形式或者构造对于本发明并不重要,并且它可以是催化的或非催化的。
通常,烟灰过滤器包括基底单元,其是过滤整料或者流通式整料,例如上述流通式整料。优选基底单元是过滤整料。基底单元可以涂覆有催化剂组合物。
过滤整料通常包括多个入口通道和多个出口通道,其中该入口通道在上游端(即废气入口侧)开口和在下游端(即废气出口侧)堵塞或密封,该出口通道在上游端堵塞或密封和在下游端开口,和其中各入口通道通过多孔结构与出口通道隔开。
当烟灰过滤器的基底单元是过滤整料时,优选该过滤整料是壁流式过滤器。在壁流式过滤器中,各入口通道通过多孔结构的壁与出口通道交替隔开,反之亦然。优选入口通道和出口通道具有蜂窝状布置。当存在蜂窝状布置时,优选与入口通道垂直和横向相邻的通道在上游端堵塞,并且反之亦然(即与出口通道垂直和横向相邻的通道在下游端堵塞)。当从任一端观察时,通道交替地堵塞和开口的端部呈现棋盘状外观。
当烟灰过滤器包含催化剂组合物时,则该催化剂组合物可以适于氧化(i)颗粒物质(PM)和/或(ii)一氧化碳(CO)和烃(HC)。当该催化剂组合物适于氧化PM时,则所得到的后处理装置被称作催化烟灰过滤器(CSF)。典型地,该催化剂组合物包含铂和/或钯。
后处理装置可以是SCR催化剂。SCR催化剂也是本领域公知的。
当本发明的催化后处理***包括SCR催化剂作为后处理装置时,则该催化后处理***可以进一步包括喷射器,其用于将含氮还原剂例如氨或尿素注入到DOC下游和SCR催化剂上游的废气中。代替喷射器或者除喷射器外,该催化后处理***可以进一步包括发动机管理装置,其用于使废气富集烃。SCR催化剂然后可以使用烃作为还原剂来还原NOx。当SCR催化剂的基底是过滤整料时,则该催化剂是SCRF催化剂。
用于在后处理装置内产生温度增加的装置(例如依靠主动热处理来再生该装置)对本发明来说并不重要,并且可以选自本领域已知的那些。该装置因此可以选自发动机管理***(其促进延迟的燃料注入或者废气冲程过程中的燃料注入)、涡轮机后面的燃料燃烧器、电阻加热线圈和烃或燃料喷射器。该喷射器可以位于DOC上游或者DOC下游和后处理装置上游。
主动热处理事件可以在***中存在某种(即不可接受的)背压时触发,或者可以通过计算机装置(其跟踪与颗粒物产生、硫酸盐化或者其他有关的发动机运行条件)来启动。除了已经掺入废气中之外的HC可以通过管理直接或间接注入到一个或多个气缸中的燃料来提供,例如另外的或者延长的燃料注入;注入后燃烧,或者注入到废气集管或废气管道***中。
催化后处理***可以进一步包括重型柴油机。本发明适用于重型柴油机应用,但是在必需或者有利的情况下也可以用于其他发动机。
在重型应用的情况中,DOC入口处的废气温度典型地是约225-275℃。
本发明进一步涉及一种车辆,其包括柴油机和催化后处理***。该车辆优选是重型柴油机车辆(HDV),例如如美国立法所规定的毛重>8,500磅(US lbs)的柴油机车辆。
本发明的一方面还涉及避免DOC衰减,特别是在主动热处理事件(即再生该后处理装置)过程中。作为此处使用的,所提及的避免衰减指的是减少或防止衰减。当DOC的T50,通常是对于烃和/或一氧化碳的T50,超过DOC的温度并且典型地还超过废气温度时,发生衰减。
优选本发明所用的DOC如下来制备:用第一涂层来涂覆整个砖块,该第一涂层包含表面积增强剂例如热稳定的高表面积氧化铝和所需催化金属的溶液或悬浮液,其任选地已经沉积在载体例如氧化铝上。一种优选的涂覆方法是使用真空增强的精确涂覆(JohnsonMatthey商标)方法来施涂第一催化溶液,例如由WO99/47260所述的设备和方法来形成。随后,使用相同的精确涂覆方法,以一定量和在一定条件下施涂第二催化溶液,来沉积所需的上游区。该区的下游边缘不必是直的,条件是它提供0.5英寸的平均或者最小长度。可以使用替代的涂覆方法,条件是它们提供足够均匀的催化剂涂层。这种替代选项是本领域技术人员可利用的,并且可以包括浸渍、活化涂覆和化学气相沉积,不过目前据认为的优选方法是提供了最简单的控制和最成本有效的方法。
上游区典型地如下来制备或可获得:(a)另外的精确涂覆步骤,其将第二催化涂层施涂到已经均匀涂覆有催化剂的砖块的一个区域,(b)浸渍已经均匀涂覆有催化剂的砖块的一个区域,(c)催化活化涂覆已经均匀涂覆有催化剂的砖块的一个区域,或者(d)化学气相沉积一种或多种催化金属到已经均匀涂覆有催化剂的砖块的一个区域。
用于第一和第二溶液的催化金属的浓度可以由本领域技术人员根据需要计算,以提供催化金属所需的浓度或者负载量。例如,第一溶液可以具有PGM浓度来产生10至100g/cu ft的PGM,Pt和Pd重量比是1:2-2:1的合适的混合物或合金。第二溶液可以具有PGM浓度来产生10-150g/cu ft的PGM,并且Pt:Pd比是1:3-5:1,例如1:2-2:1。
因为制造容易和成本的原因,DOC的下游区优选均匀负载催化金属。但是,可以包括不同的浓度,例如一个或多个另外的催化剂“条纹”,而不脱离本发明的范围。
实施例
现在将通过下面的非限定性实施例来说明本发明。
制备柴油机氧化催化剂
使用相同的砖块来制备三种DOC,并且它们全部具有40g ft-3的相同的总PGM负载量。各DOC的直径是10.5英寸(266.7mm)和长度是4英寸(101.6mm)。全部DOC通过在炉中于750℃加热12.5小时来进行常规老化,以使这些DOC代表已经使用过的DOC。
DOC1:-制备常规的和商购的柴油机氧化催化剂(DOC1),其具有比值为7:6的均匀负载的Pt:Pd。
DOC2:-制备柴油机氧化催化剂(DOC2),其具有约40g ft-3的均匀负载量,但是具有PGM浓度更高的10mm“条纹”。DOC2通过将DOC和它的第一涂层浸入Pt:Pd比为1:1的另外的催化剂浆料/溶液中来制备,以产生在100g ft-3的高浓度条纹。
DOC3:-使用用于DOC2所述的方法制备柴油机氧化催化剂(DOC3),其具有约40gft-3的均匀涂层,和具有100g ft-3的更高PGM负载量、Pt:Pd比为1:1的1英寸(25.4mm)深的区域。
测试方法
各柴油机氧化催化剂的热分析如下来进行:送过来自柴油机的废气,该柴油机用EUV B7燃料(7%生物燃料)来提供燃料,用于发动机运行和富集,以2200rpm运行。该发动机是7升容量EUVI6气缸发动机,以2500rpm产生235kW,安装有位于DOC上游废气管中的第7喷射器。
将热电偶沿着DOC砖块的中心线***,从上游面所测量的深度是7.6mm(T1)、25.6mm(T5)和94.6mm(T9)。T5因此处于下游区的开始处,不过它在后面被描述为“中部”位置。运转1700秒或1800秒后,将废气富集来代表在过滤器再生事件过程中250℃的富HC气体,并且将废气送过DOC。
结果
结果显示于图1-3中,其是各经测试的DOC的温度与时间(秒)的绘图。
图1证实了在常规DOC(DOC1)的前面仅存在小的放热。在“中部”位置存在着稍大的放热,虽然达到了450℃的峰值温度,但是仅持续短时间。初始的起燃在2100秒时完全熄灭。
DOC2的结果显示于图2中。当在1800秒开始富集时,全部位置上的峰值温度均高于DOC1。但是,很显然起燃没有持续,并且放热在2100秒时同样完全熄灭。
DOC3的结果显示于图3中。当在1700秒开始富集时,全部热电偶位置的温度图非常不同于DOC1和DOC2的结果。据发现,温度初始时急剧升高,然后在2000秒时在全部热电偶位置达到了稳定的温度。该温度得以保持,直到富集于3000秒终止。
这些测试清楚地显示了在测试条件下本发明的益处。在重型应用的情况中,DOC入口处的废气温度典型的是约225-275℃。
此外,进行了测试来检测来自各DOC的出口气体中的HC。鉴于上述测试,对于DOC1和DOC2,在起燃熄灭后检测到高水平的HC滑逸(slip),而对于DOC3,HC被有效除去,与此同时产生了所需的放热,足以用于过滤器再生,这也许并不令人惊讶。
为了避免任何疑义,这里引用的任何和所有文献的全部内容引入本申请作为参考。
Claims (15)
1.一种用于柴油机废气的催化后处理***,所述***包括:
柴油机氧化催化剂,其直径是2.5-15英寸和长度是2.5-15英寸;和
位于该柴油机氧化催化剂下游的后处理装置,该后处理装置需要定期热处理,和用于在该后处理装置中产生温度增加的装置;
其中该柴油机氧化催化剂包括上游区,并且该柴油机氧化催化剂包含负载在基底单元上的铂和钯的催化剂组合物;
其中该上游区包含上游催化剂组合物,该上游催化剂组合物包含由铂和钯组成的铂族金属,并且该上游区中铂的浓度大于该柴油机氧化催化剂的其余部分中铂的浓度;
其中该上游区的长度为0.5-1.75英寸,并且该上游区对于烃的氧化活性高于该柴油机氧化催化剂的其余部分;
其中该柴油机氧化催化剂包含Pt和Pd的混合物,或者Pt和Pd的合金,在该柴油机氧化催化剂的上游区和其余部分中,Pt与Pd的重量比均是1:3-5:1;和
其中该基底单元是流通式整料。
2.根据权利要求1所述的催化后处理***,其中该上游区的长度是0.5-1.5英寸。
3.根据权利要求2所述的催化后处理***,其中该上游区的长度是1英寸。
4.根据前述权利要求中任一项所述的催化后处理***,其中该柴油机氧化催化剂的直径是4-15英寸和长度是2.5-10英寸。
5.根据权利要求1-3任一项所述的催化后处理***,其中该柴油机氧化催化剂的其余部分包括多个区和/或层。
6.根据权利要求1-3中任一项所述的催化后处理***,其中该上游区中铂与钯的重量比≥1:1。
7.根据权利要求1-3中任一项所述的催化后处理***,其中该上游区的PGM浓度是10-150g ft-3。
8.根据权利要求1-3中任一项所述的催化后处理***,其中该后处理装置是烟灰过滤器。
9.根据权利要求1-3中任一项所述的催化后处理***,其中该后处理装置是用于选择性催化还原的催化剂单元。
10.一种车辆,其包括柴油机和根据权利要求1-9中任一项所述的催化后处理***。
11.一种保持柴油机氧化催化剂的活性的方法,该方法在柴油机废气后处理***中位于该柴油机氧化催化剂下游的后处理装置的主动热处理过程中在200-375℃的废气温度通过将该废气送过柴油机氧化催化剂来进行,其中该柴油机氧化催化剂的直径是2.5-15英寸和长度是2.5-15英寸;和
其中该后处理装置需要定期热处理,和用于在该后处理装置中产生温度增加的装置;
其中该柴油机氧化催化剂包括上游区,并且该柴油机氧化催化剂包含负载在基底单元上的铂和钯的催化剂组合物;
其中该上游区包含上游催化剂组合物,该上游催化剂组合物包含由铂和钯组成的铂族金属,并且该上游区中铂的浓度大于该柴油机氧化催化剂的其余部分中铂的浓度;
其中该上游区的长度为0.5-1.75英寸,并且该上游区对于烃的氧化活性高于该柴油机氧化催化剂的其余部分;
其中该柴油机氧化催化剂包含Pt和Pd的混合物,或者Pt和Pd的合金,在该柴油机氧化催化剂的上游区和其余部分中,Pt与Pd的重量比均是1:3-5:1;和
其中该基底单元是流通式整料。
12.一种避免柴油机氧化催化剂衰减的方法,该方法在用于位于该柴油机氧化催化剂下游的后处理装置的主动热处理事件过程中在200-375℃的废气温度通过将富含烃的废气送过柴油机氧化催化剂来进行,其中该柴油机氧化催化剂的直径是2.5-15英寸和长度是2.5-15英寸;和
其中该后处理装置需要定期热处理,和用于在该后处理装置中产生温度增加的装置;
其中该柴油机氧化催化剂包括上游区,并且该柴油机氧化催化剂包含负载在基底单元上的铂和钯的催化剂组合物;
其中该上游区包含上游催化剂组合物,该上游催化剂组合物包含由铂和钯组成的铂族金属,并且该上游区中铂的浓度大于该柴油机氧化催化剂的其余部分中铂的浓度;
其中该上游区的长度为0.5-1.75英寸,并且该上游区对于烃的氧化活性高于该柴油机氧化催化剂的其余部分;
其中该柴油机氧化催化剂包含Pt和Pd的混合物,或者Pt和Pd的合金,在该柴油机氧化催化剂的上游区和其余部分中,Pt与Pd的重量比均是1:3-5:1;和
其中该基底单元是流通式整料。
13.根据权利要求11或12所述的方法,其中该上游区通过将第二催化涂层施涂到已经均匀涂覆有催化剂的砖块的一个区域来制备。
14.根据权利要求11或12所述的方法,其中该上游区通过浸渍已经均匀涂覆有催化剂的砖块的一个区域来制备。
15.根据权利要求11或12所述的方法,其中该上游区通过在已经均匀涂覆有催化剂的砖块的一个区域上化学气相沉积一种或多种催化金属来制备。
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CN201280061513.2A Active CN103998113B (zh) | 2011-12-14 | 2012-12-13 | 汽车催化后处理*** |
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US (1) | US9341098B2 (zh) |
EP (1) | EP2790814B1 (zh) |
JP (4) | JP2015508468A (zh) |
KR (2) | KR20190112178A (zh) |
CN (1) | CN103998113B (zh) |
BR (1) | BR112014013254B1 (zh) |
DE (1) | DE102012223021B4 (zh) |
GB (2) | GB201121468D0 (zh) |
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US9789442B2 (en) * | 2012-12-13 | 2017-10-17 | Johnson Matthey Public Limited Company | Automotive catalytic aftertreatment system |
EP3689456B1 (en) * | 2013-07-30 | 2024-05-22 | Johnson Matthey Public Limited Company | Ammonia slip catalyst |
GB201315892D0 (en) | 2013-07-31 | 2013-10-23 | Johnson Matthey Plc | Zoned diesel oxidation catalyst |
US9662636B2 (en) * | 2014-04-17 | 2017-05-30 | Basf Corporation | Zoned catalyst composites |
EP3487617B1 (de) * | 2016-07-19 | 2021-09-08 | Umicore AG & Co. KG | Dieseloxidationskatalysator |
JP6865664B2 (ja) | 2017-09-25 | 2021-04-28 | 株式会社キャタラー | 排ガス浄化用酸化触媒装置 |
BR112021008125A2 (pt) * | 2018-11-13 | 2021-08-03 | Johnson Matthey Public Limited Company | sistema, gerador de potência terrestre, industrial, comercial, marinho ou aéreo, veículo terrestre, marinho ou aéreo móvel, e, métodos para a operação do sistema de motor de turbina a gás e para a operação de um motor de turbina a gás de recuperação |
CN113784789B (zh) * | 2019-06-26 | 2023-12-12 | 庄信万丰股份有限公司 | 用于压缩点火内燃机的复合分区氧化催化剂 |
GB201914958D0 (en) | 2019-06-26 | 2019-11-27 | Johnson Matthey Plc | Composite, zoned oxidation catalyst for a compression ignition internal combustion engine |
GB202004769D0 (en) | 2019-10-16 | 2020-05-13 | Johnson Matthey Plc | Composite, zoned oxidation catalyst for a compression ignition internal combustion engine |
EP3888774A1 (en) | 2020-03-31 | 2021-10-06 | Johnson Matthey Public Limited Company | Composite, zone-coated oxidation and exotherm generation catalyst |
CN114514364B (zh) | 2019-10-16 | 2023-10-31 | 庄信万丰股份有限公司 | 用于压缩点火内燃机的复合分区氧化催化剂 |
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Also Published As
Publication number | Publication date |
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GB2497669A (en) | 2013-06-19 |
CN103998113A (zh) | 2014-08-20 |
EP2790814A1 (en) | 2014-10-22 |
GB201222460D0 (en) | 2013-01-30 |
EP2790814B1 (en) | 2020-10-14 |
DE102012223021B4 (de) | 2019-05-02 |
KR20140105568A (ko) | 2014-09-01 |
GB2497669B (en) | 2015-11-18 |
JP2015508468A (ja) | 2015-03-19 |
JP2020097939A (ja) | 2020-06-25 |
GB201121468D0 (en) | 2012-01-25 |
JP6974145B2 (ja) | 2021-12-01 |
BR112014013254B1 (pt) | 2021-02-23 |
WO2013088152A1 (en) | 2013-06-20 |
BR112014013254A2 (pt) | 2017-06-13 |
JP2022176975A (ja) | 2022-11-30 |
US9341098B2 (en) | 2016-05-17 |
KR20190112178A (ko) | 2019-10-02 |
RU2617770C2 (ru) | 2017-04-26 |
DE102012223021A1 (de) | 2013-06-20 |
JP2018087572A (ja) | 2018-06-07 |
KR102025922B1 (ko) | 2019-11-11 |
US20130152548A1 (en) | 2013-06-20 |
BR112014013254A8 (pt) | 2017-06-13 |
RU2014128529A (ru) | 2016-02-10 |
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