CN102844535B - 用于排出柴油机废气、具有氨解模块的设备 - Google Patents

用于排出柴油机废气、具有氨解模块的设备 Download PDF

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CN102844535B
CN102844535B CN201180020327.XA CN201180020327A CN102844535B CN 102844535 B CN102844535 B CN 102844535B CN 201180020327 A CN201180020327 A CN 201180020327A CN 102844535 B CN102844535 B CN 102844535B
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韩贤植
金垠锡
金载邮
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Xi Xing Catalyst Co Ltd
Heesung Catalysts Corp
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    • F01N3/18Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by methods of operation; Control
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Abstract

本发明涉及一种通过使用氢气来排出柴油机废气的设备,其包括有氨解模块。更具体地,本发明涉及一种用于净化柴油机废气的设备,其中所述的用于排出柴油机废气的设备包括以串联的模式形成在柴油机下游的DOC-DPF-LNT模块,进一步包括氨解模块;所述的用于排出柴油机废气的设备包括以串联的模式形成在柴油机下游的DOC-DPF-HC-SCR模块,进一步包括氨解模块;并且所述设备包括LNT-DPF模块和氨解模块。

Description

用于排出柴油机废气、具有氨解模块的设备
技术领域
本发明涉及一种用于后处理柴油机废气的设备,尤其是涉及一种用于排出柴油机废气的设备,其通过使用在氨解模块中产生的氢气改善了净化柴油机废气的能力,特别是净化氮氧化物的能力。
背景技术
通常,具有固有的高热效率(即,高燃料燃烧效率)和在低速下具有高扭矩的柴油机对于给车辆提供驱动力的设备是有用的,并且可以在高A/F(空气对燃料)比,缺乏燃料混合物的条件下进行驱动。为此,柴油机表现出高的HC和CO转化率,但是柴油机废气排放出高含量的NOx和颗粒。所述NOx(氮氧化物)和颗粒均为难转化成无害材料的柴油机废气的组分。然而,涉及其的排放标准因为相关的环境问题而逐渐地严格化。
为了减少颗粒,对它们进行后处理的方法聚焦于催化型柴油颗粒过滤器(CDPF或者DPF),其也被称为催化型烟尘过滤器(CSF)。广义上讲,这些过滤器被构造为从废气中捕获并回收颗粒。首先为了捕获颗粒,已经公开了适用于吸收柴油机废气颗粒的各种过滤系统并且其包括蜂窝壁流过滤器等等(参见图1)。在过滤器内捕获并累积所述颗粒之后,应当在过滤器内连续地或者周期性地燃烧(回收)获得的颗粒。由此,向所述过滤器提供催化剂,从而降低燃烧的温度,并且还用于制造催化型柴油颗粒过滤器。通常,CDPF或CSF可降低90%或者更多的颗粒,并且在颗粒累积和过滤器回收之后进行被动燃烧。在DPF中,碳颗粒可以在550℃下燃烧,但在NOx的存在下甚至在250℃就可以被氧化。因此,为了产生NOx并降低回收温度,将包括Pt和/或Pd的贵金属装载在DPF上,因为它们会将柴油机排放的废气中的氮氧化物氧化成NO2。因此,一种通常被称为柴油氧化催化剂(DOC)的附加模块可以被安装在前端。当经过所述DOC的时候,所获得的由柴油机排放的气体可以产生NO2作为副产物,其可以氧化HC(碳氢化合物)和CO,并且同时降低安装在后端的DPF内的燃烧温度。
对于这样的过滤器回收,当在CDPF或CSF的前端附加地喷射氢气的时候,碳颗粒就可以在相对低的温度下氧化,例如在200℃或者更低。与此同时,当在DOC的前端注射氢气的时候,DOC的性能由于LOT的降低也会有所改善,进一步地脱硫效率也会变得更好。
如现有技术中所公开的,已经尝试了用于从柴油机废气中除去氮氧化物的不同的方法,例如使用包括选择性催化还原(SCR)或者稀燃氮氧化物捕集器(LNT)的催化体系。特别是在SCR体系中,尿素-SCR(NH3-SCR)模块通过包括如下步骤的方法产生无害的含氮组分:将安装在运输工具上的存储容器(桶)内的尿素向废气的上游喷射;之后,通过使用水解催化剂将尿素转化为氨;并且通过使用氨作为还原剂来还原氮氧化物(NO、NO2)。图2示出了用于后处理废气的系统的概括图,其包括尿素-SCR模块。图3示出了尿素-SCR模块的详述图。
此外,公开了所谓的HC-SCR模块。具体地,其为通过使用HC(碳氢化合物)作为还原剂来选择性减少NOx的催化转化器,并且所述的HC选择性地与NOx反应生成N2、CO2和水(H2O)。此外,在最近的研究中阐明了当在HC-SCR模块的前端喷射氢气的时候,极大地改善了选择性还原。
此外,LNT(稀燃氮氧化物捕集器)被认为是一种用于还原氮氧化物的系统,其以如下的机制来实施,即,在贫乏区域捕获氮氧化物并且在富集区域将其释放,以由此通过使用催化剂将它们转化为氮和二氧化碳。这一NOx捕集器是有利的,其在高温下具有良好的耐久性。然而,它也是存在问题的,燃料内的含硫组分会对其产生抑制并且当在富集区域回收的时候具有HC和CO的低的回收效率。
发明内容
本发明的发明者已经认识到,当根据需要引入氢气时,DOC、DPF和HC-SCR(或LNT)模块可以分别降低传统DOC的LOT,提高脱硫效率,降低DPF的回收温度,并且提高作为除去氮氧化物的选择性模块的HC-SCR(或LNT)效率。然后,我们改进了当前使用的尿素-SCR模块,以水解尿素产生氨并将所获得的氢气分别地或者可选地引入至上述的模块中。因此,我们确定解决了之前的问题并且成功地完成了本发明。
发明详述
本发明涉及一种用于排出柴油机废气、包括氨解模块的设备,尤其是涉及一种用于排出柴油机废气、并由在柴油机下游串联的DOC-DPF-LNT模块组成且进一步包括氨解模块的设备。此外,本发明涉及一种用于排出柴油机废气、并由在柴油机下游串联的DOC-DPF-HC-SCR模块组成且进一步包括氨解模块的设备。此外,本发明涉及一种用于净化柴油机废气、包括LNT-DPF模块和氨解模块的设备。
根据本发明,所述的氨解模块可以是催化体系,其涂覆有用于尿素水解和氨解的催化剂并且形成为蜂窝状,但是其不限于此。提供氨作为氨前体,例如以像尿素、异氰酸等形式保存在可运输存储容器中。所述前体被水解以产生氨。因此,所述的氨解模块可以由单一的或者两个及以上的系统构成,其包括以混合物形式共同存在的用于前体水解的催化剂以及用于氨解的催化剂,或者独立地包括它们。
效果
本发明的系统有效地降低DOC模块内的LOT、降低DPF的回收温度以及降低在所述模块中使用的贵金属含量。此外,它们能够获得由于使用氢气作为还原剂的脱硫效果并且提高在LNT或HC-SCR模块中氮氧化物的还原效率。尤其是,如果其被改进的话,本发明的系统可以安装在之前的用于排出气体的并装备有尿素-SCR模块的设备中。因此,本发明的特征可以简单地在不改变现有系统的情况下被实施。
附图说明
图1示出了本发明中应用的DPF的概括图。
图2示出了常规DOC、DPF和尿素-SCR排列的一个实施方式。
图3示出了尿素-SCR模块的详细视图。
图4示出了根据本发明的用于排出柴油机废气的系统。
图5示意性地示出了LNT模块的机理。
具体实施方式
图4中阐明了根据本发明的用于排出废气的设备。也就是说,它们为包括DOC-DPF-LNT(或HC-SCR)或者LNT-DPF模块排列的系统。
在本发明中,废气的“下游”指的是针对一个基准元件的废气流向。“模块”指的是实现一个功能的最小单元。举例来说,“DPF”模块指的是用于捕获由柴油机排出的颗粒的过滤器设备,并且根据需要其能够实现回收功能。“HC-SCR模块”指的是涂覆有所谓的SCR催化剂从而通过使用碳氢化合物(HC)作为还原剂来除去NOx的载体。此外,“LNT模块”指的是涂覆有在贫乏区域捕获NOx、吸收NOx并将其储存,当喷射燃料或到达富集区域的时候净化所获得的NOx,并且相应地恢复NOx捕获功能的催化剂的载体。
本发明提供用于排出柴油机废气的设备,其串联地包括柴油氧化催化模块、催化型柴油颗粒过滤器模块以及串联地布置在所述催化型柴油颗粒过滤器模块的废气下游的HC-SCR模块(或LNT模块),其中分别地或者可选地在柴油氧化催化模块、催化型柴油颗粒过滤器模块和HC-SCR模块(或LNT模块)的前端注射氢气。所述氢气由氨解单元产生,并且所述氨衍生自氨前体,特别是通过尿素溶液的水解。
此外,本发明提供用于排出柴油机废气的设备,其串联地包括LNT模块和催化型柴油颗粒过滤器模块,其中分别地或者可选地在LNT模块和催化型柴油颗粒过滤器模块的前端注射氢气。所述氢气由氨解单元产生,并且所述氨衍生自氨前体的水解。
在下文中,将更加清楚地描述上述元件。这些元件已经被公开并且在本发明中,组合了在现有技术中公开的部件。为了完成上述目的,分别地或者可选地在模块的前端注射由氨解模块产生的氢气,或者将其注射至所有模块。已经公开了很多用于调整注射至每个模块的氢气的电子方法,用于监测并控制温度的相关方法,以及其它的方法,并且在下文中将不对其进行描述。
1)柴油氧化催化模块(DOC)
如现有技术中所揭示的,DOC为涂覆有降低由柴油机释放的HC和CO的氧化催化剂的模块。通常地,其所包括的构造体中,铂和/或钯装载于基体上,并且之后将其涂覆于多孔陶瓷载体上,例如堇青石。
柴油机氧化催化模块通过废气管安装在柴油机和DPF模块之间。根据本发明,所引入的氢气能够降低DOC内的LOT,并且由此改善HC和CO的氧化条件。这导致了放热反应并平稳地促进下游的DPF回收。
2)催化型柴油颗粒过滤器模块(CDPF或DPF)
一种典型的柴油颗粒过滤器模块为用于捕获由柴油机释放的颗粒物(PM)的过滤器。先前已经公开了各种过滤器系统,包括陶瓷单体过滤器、陶瓷纤维过滤器、烧结金属过滤器等等。最优选的模块为由例如堇青石的多孔陶瓷构成的陶瓷单体过滤器,其也被称为陶瓷壁流过滤器。其在这一模块内的通道入口端和出口端可选地闭合,由此依赖于闭合的出口端使流入的废气穿过多孔壁,并且之后通过相邻通道的出口端释放出该气体。而且,其能够在流入通道内吸收颗粒物。图1示出了陶瓷单体入口的正视图以及废气流的剖视图。壁的孔径尺寸被认为是选择模块类型的重要因素,因为其直接影响了所捕获颗粒的直径以及引擎的背压。优选地,壁的孔径尺寸被设定为约10μm。在这样的多孔结构中,颗粒物优选具有0.01μm或更大的颗粒直径,并且被移除85%或更多。在过滤器中吸收的颗粒物在尽可能短的时间内被引燃,并且所述的过滤器被再生为能够再次捕获颗粒物的状态。特别地,取决于在过滤器通道内施加催化剂的方式,相比于550至600℃,这一模块可以相对于降低引燃温度至约250℃。
DPF被布置在DOC模块的下游以吸收颗粒物。在用于再生的过程中,由于布置在下游的DOC的放热反应,可以容易地达到所捕获的颗粒物的燃烧温度。此外,氢气被引入至DPF的前端,进一步改善了所捕获的颗粒的氧化条件,并且最大化了DPF效率。
3)HC-SCR(HC-选择性催化还原)
还原剂HC选择性地与NOx反应以产生N2、CO2、水(H2O)。事实上,通过使用废气的HC来减少NOx的系统可以被应用。而且,包括用于改进柴油机的方法或者用于喷射HC至排出设备的方法的直接设计的方法可以被使用,但是不限于此。通常使用包括Cu/ZSM5和Pt/Al2O3的两组典型的催化剂。
在本发明中,HC-SCR为通过引擎废气中的HC而选择性地降低并减少NOx的模块,并且形成在DPF的下游。在模块前端引入的氢气变为额外的还原剂以降低NOx。特别地,甚至是在低温下也能够实现还原反应,从而提高HC-SCR模块的效率。
4)LNT(稀燃氮氧化物捕集器)
NOx在贫乏区域被捕捉并且在富集区域被释放(再生),并且之后通过使用催化剂会将NOx转化为氮和二氧化碳。也就是说,如图5中所示,LNT模块被定义为通过两个阶段来降低氮氧化物的模块。
对于氮氧化物的存储材料来说,利用Ba、Sr、K等。在贫乏区域,通过使用Pt来使NO变为NO2,并且在NOx捕集器中进行存储。当在HC和CO组分的帮助下达到富集区域的时候,存储在NOx捕集器中的NOx被还原为N2
根据本发明,所述的LNT模块为用于除去氮氧化物的模块并且能够取代HC-SCR模块。应当理解,在模块的前端引入氢气影响了通过HC和CO的NOx还原,其是在富集的情况下,也就是在NOx回收的条件下。
此外,本发明的LNT模块利用DOC模块来取代,并且最终可以提供包括串联模式的LNT-DPF的系统。
5)氨解模块
根据本发明,从安装在传输工具中的存储容器引入的成分通过尿素的水解来加工,并且氨解以产生氢气。尿素以固体形式和/或尿素溶液的液体形式存储在存储容器中,并且通过热解和/或水解喷射以产生氨。在热解的情况中,尿素((NH2)2CO)被热转化为氨和异氰酸(HCNO),并且之后它们被水解。在本文中,异氰酸与水反应以形成氨和二氧化碳。
((NH2)2CO)->NH3+HCNO,HCNO+H2O->NH3+CO
所获得的氨通过使用氨解的催化剂而被降解,从而产生氢气。
在氨解模块中,传统的水解催化剂和氨解催化剂可以在典型的载体上相结合或者相分离。由此,所获得的涂覆有上述物质的结构可以被组装,并根据需要通过电子控制器提供给DOC、DPF、SCR和/或LNT模块。
在下文中,将清楚地描述用于操作所述系统的过程。
由柴油机排出的废气包含CO、HC、NOx、颗粒物(PM)等等。如图4中所,当CO、HC和NO物质经过DOC的时候,其被氧化为CO2和NO2。在这一阶段中,由氨解模块产生的氢气可以降低DOC内的LOT,以由此改善HC和CO的氧化条件。其导致了放热反应并平稳地促进了下游中的DPF回收。一旦经过DOC,废气中的颗粒物就在下游被捕获。特别是对于DPF回收,在DOC中产生的NO2相当大地降低DPF中的回收温度,从而除去颗粒物。此外,在DPF前端引入的氢气可以改善所捕获颗粒的氧化条件,并最大化DPF效率。
根据本发明的一个实施方式,在从DPF的废气中释放之后,大部分的NOx会到达HC-SCR模块,并且之后通过选择性还原的方式而被除去。特别地,当经过SCR的时候,在前端引入的氢气可以将氮氧化物还原为氮气,因为其作为辅助还原剂能够通过催化剂最适宜地进行选择性还原。
根据本发明的另一个实施方式,可以用LNT模块取代HC-SCR。如上所述,在从DPF的废气中释放之后,大部分的NOx在LNT中被吸收。之后,在前端的富集条件下引入的氢气可以通过DPF的回收过程利用HC和CO将NOx还原为氮。结果,整体系统效率会变得更高。
根据本发明的另一个实施方式,整个系统可以包括以串联模式布置的LNT-DPF,因为LNT取代了DOC模块。在这样的系统中,从引擎中释放的废气的氮氧化物组分被吸附在LNT上。之后,在前端富集条件下引入的氢气可以通过LNT的回收过程利用HC和CO将NOx还原为氮,并且同时,其在高温下产生废气。结果是,接下来的下游DPF模块的回收过程可以更有效率地完成。
如上所述,本发明提供用于后处理废气的方法,其中氢气被使用。特别地,在本发明中,氢气衍生自尿素,并且尿素为安装在使用尿素-SCR的传输工具内的现有元素。因此,之前的系统可以被改进以产生如下的氢气。涂覆有相结合的模式或者相分离的模式的水解催化剂和氨解催化剂的氨解模块被安装在尿素存储容器的底部。
在本说明书中描述了各种实施例,其中氢气衍生自尿素,所述的氢气被施用于后处理废气的方法,但是本发明不限于此。
尽管出于清楚地理解的目的,前述的发明已经通过阐明和实施例的方式在某些细节上进行了说明,但是对于本领域技术人员来说,在本发明的教导下可以做出特定的变化和修改,其均没有脱离附加权利要求的精神或范围,这是显而易见的。为了特别地指出并清楚地提出本发明所主张的主旨,下述的权利要求概括了本说明。

Claims (3)

1.一种用于排出柴油机废气的设备,所述设备包括根据废气的流向串联地设置的DOC模块、DPF模块和HC-SCR模块,其中分别地或者可选地在所述DOC模块、DPF模块和HC-SCR模块的前端注射氢气,其特征在于,所述设备具有氨解模块,所述氢气衍生自氨解模块,并且所述氨解模块包括用于尿素水解和氨解的催化剂,所述尿素为安装在使用尿素-SCR 的传输工具内的现有元素。
2.一种用于排出柴油机废气的设备,具有氨解模块,所述设备包括根据废气的流向串联地设置的DOC模块、DPF模块和LNT模块,其中分别地或者可选地在所述DOC模块、DPF模块和LNT模块的前端注射氢气,所述氢气衍生自氨解模块,并且所述的氨解模块包括用于尿素水解和氨解的催化剂。
3.一种用于排出柴油机废气的设备,具有氨解模块,所述设备包括根据废气的流向串联地设置的LNT模块和DPF模块,其中分别地或者可选地在所述LNT模块和DPF模块的前端注射氢气,所述氢气衍生自氨解模块,并且所述氨解模块包括用于尿素水解和氨解的催化剂。
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