CN103437864A - 压燃式发动机废气净化方法及装置 - Google Patents

压燃式发动机废气净化方法及装置 Download PDF

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CN103437864A
CN103437864A CN2013101617216A CN201310161721A CN103437864A CN 103437864 A CN103437864 A CN 103437864A CN 2013101617216 A CN2013101617216 A CN 2013101617216A CN 201310161721 A CN201310161721 A CN 201310161721A CN 103437864 A CN103437864 A CN 103437864A
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catalyzer
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S.达尔
K.约翰森
S.佩尔森
G.莫根森
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Abstract

本申请涉及压燃式发动机废气净化方法及装置。本申请提供了一种用于从贫燃压燃式发动机除去NO2排放物的方法和装置，其中含有NO2的发动机废气与催化剂接触，所述催化剂具有将NO2还原为NO的活性，并且包含至少一种铂族金属且该铂族金属不为铂，和至少一种具有氧化还原作用活性的金属氧化物，由此废气中含有的NO2通过与废气中存在的CO、碳氢化合物和/或煤烟反应被还原为NO。

Description

压燃式发动机废气净化方法及装置
本申请为一项发明专利申请的分案申请，其母案的申清日为2007年10月23日、申请号为2007101929833、发明名称为“压燃式发动机废气净化方法及装置”。
技术领域
本发明涉及一种贫燃压燃式发动机，例如柴油机产生的废气的净化方法及装置，以及该方法所用的装置。特别地，本发明用来通过将二氧化氮(NO2)与废气中含有的一氧化碳(CO)、碳氢化合物HC)和/或煤烟(soot)煤烟在催化剂的存在下进行反应还原为一氧化氮(NO)来将其去除。适用于该方法的装置包括涂布有该催化剂的颗粒过滤器。
本发明特别适用于贫燃压燃式发动机。
背景技术
传统的贫燃压燃式发动机，例如柴油机，产生柴油微粒物质(PM)排放物，包括煤烟和可挥发且可溶的有机级分。未来法律方面对PM的限制需要在排气系统中设置颗粒过滤器。
煤烟过滤器一个已知的问题是它们在操作过程中会被煤烟阻塞，这需要连续的或周期性的再生以防止通过过滤器时的压力过度下降。传统的周期性再生方法是将排气系统增加到一定温度，在该温度下被捕获的煤烟被氧化为气相组分从而从过滤器除去。
典型地，所需的温度提升通过注入额外的燃料来获得，该燃料在位于过滤器上游的排气系统中的柴油氧化催化剂(DOC)上燃烧。许多柴油汽车都已经安装了DOC以符合碳氧化合物和CO的排放物限制。与没有颗粒过滤器的发动机排气系统相比，通过过滤器时增加的压降和周期性再生都增加了油耗。
不同的系统被开发出来以降低这种油耗。美国专利No.4902487公开了一种这样的系统，其已经作为“连续再生阱”被商业化。在该系统中，NO2被用来燃烧沉积在过滤器上的柴油微粒，该燃烧相比于用在气相中也可获得的氧气的燃烧，可在更低的温度下进行。NO2通过在位于过滤器上游的适宜催化剂上使存在于废气中的NO氧化而获得。这种NO氧化能化剂典型地含有Pt，它作为一种优异的NO氧化催化剂是已知的。为了进一步增加废气中NO2的含量，过滤器也被涂布上含有Pt的催化剂。这种系统的缺点是，当过滤器上没有足够的PM与产生于氧化催化剂的NO2反应，或者废气的温度低于优选的PM在NO2中的燃烧范围时，NO2可能滑过过滤器并被排放到大气中，这是不被期望的。
DE102005027063A1公开了一种用于含氧气的内燃机废气的后处理的装置，该装置具有二氧化氮还原催化转换器，该转换器位于废气后处理装置气流末端，废气后处理装置具有氧化催化剂和/或煤烟过滤器。用于二氧化氮还原的SCR催化剂浸渍有少量的铂金属。
WO06040533A1涉及通过酸性金属氧化物与废气接触以在贫燃内燃机中将二氧化氮分解为一氧化氮。该酸性金属氧化物选自由沸石、钨掺杂的氧化钛、氧化硅-氧化钛、氧化锆-氧化钛、γ-氧化铝、非晶相氧化硅-氧化铝以及它们的混合物所组成的组。
低剂量的NO2有毒。令人不安的是，欧洲城市和高速公路的NO2水平在增长[参见来自于“NO2研讨会，慕尼黑2006年2月”的介绍]。因此立法机构开始讨论将废气中NO2的量限制到一个可以接受的水平才被允许。例如，2004年斯图加特市区的年度平均值为68μg/m3，这个数字按正常情况将于2010年减少到40μg/m3NO2(年度平均值)的限度。因此可以推测，将有法律要求减少排放到大气的废气中的PM和NO2。
因此，本发明的总的发明目的为提供一种大量减少压燃式发动机废气中的NO2，优选NO2和PM的方法和装置。
发明内容
依照上述总发明目的，本发明提供一种除去来自于贫燃压燃式发动机的NO2排放物的方法，其中含NO2的发动机废气与催化剂接触，该催化剂具有将NO2还原为NO的活性，并且包含至少一种铂族金属且该铂金属不是铂，和至少一种具有氧化还原作用活性的金属氧化物，因而通过与废气中存在的CO、碳氧化合物和/或煤烟反应将废气中所含NO2还原为NO。
本发明方法的优选实施方案在从属权利要求2至6和本发明的详细说明中得到公开。
本发明进一步提供一种用于上述方法的装置。该装置以其最通常的形式包括具有对NO2与CO、HC和/或煤烟反应生成NO有效的催化剂的发动机排气系统，其中该催化剂包括至少一种铂族金属且该铂族金属不是铂，和至少一种具有氧化还原作用活性的金属氧化物。
根据本发明的装置的优选实施方案在从属权利要求8至12和本发明的详细说明中得到公开。
附图说明
图1是一种柴油机排气系统。
图2是另一种柴油机排气系统。
图3是测量到的NO和NO2的浓度汇总。
具体实施方式
根据本发明的一优选实施例，NO2还原催化剂被涂布到柴油颗粒过滤器上。这种过滤器可以是任何已知类型，例如陶瓷壁流整料过滤器、陶瓷纤维过滤器或烧结金属过滤器。壁流整料过滤器的主要组件为优选的碳化硅、堇青石或钛酸铝。
催化涂层优选包括钯的量为0.2到5g/L过滤器，更优选为0.5到2g/L过滤器。
催化涂层还含有至少一种具有氧化还原作用活性的氧化物。氧化还原作用活性是指金属可以存在不同的氧化态。氧化还原作用活性氧化物优选的量为1到100g/L过滤器，更优选为5到60g/L过滤器。
优选的氧化物是MnO2、Fe2O3、SnO2、PrO2和CeO2。最优选的氧化还原作用活性氧化物是CeO2。
任选地，催化涂层和氧化还原作用活性金属氧化物通过选自由TiO2、WO3、SiO2、HfO2、ZrO2、MgO、CaO、Al2O3、La2O3和BaO组成的组中的一种或多种氧化物获得稳定。
当氧化物是CeO2时，最优选的起稳定作用的氧化物为ZrO2。
催化涂层的组分可使用任何本领域的已知方法负载到过滤器上。这些方法包括如下工序：洗涂、浸渍、干燥、焙烧和还原。催化剂可设置在过滤器壁内部和/或过滤器壁外部。
本发明的一个实施方案中，该过滤器被设置在贫燃压燃式发动机，例如图1所示的柴油机的排气系统中，其中
(1)为贫燃压燃式发动机，任选包括用于注入额外燃料的系统，以通过燃烧煤烟来提高用于颗粒过滤器再生的排气温度，和任选包括用于注入负载有催化剂的燃料的系统，以降低颗粒过滤器中煤烟的燃烧温度：
(2)为负载在流体上的柴油氧化催化剂(DOC)，通过能够氧化碳氧化合物和CO以降低这些组分的排放，并且如果有额外的燃料注入以再生颗粒过滤器时用于提高排放温度的整料上。任选地，DOC还能够将NO氧化为NO2，用以连续地在较低温下经由NO2氧化煤烟：
(3)为根据本发明进行涂布的颗粒过滤器，其使得NO2和PM排放物的量减少。NO2通过与CO、碳氢化台物和/或煤烟反应被还原为NO。催化涂层还降低了再生颗粒过滤器需要的温度。
本发明的另一个实施例中，过滤器3被放置在贫燃压燃式发动机，例如图2所示的柴油机的排气系统中。(1)为贫燃压燃式发动机，任选包括用于注入额外燃料的系统，以通过燃烧煤烟来提高用于颗粒过滤器再生的排放温度，和任选包括用于注入负载有催化剂的燃料的系统，以降低颗粒过滤器中煤烟的燃烧温度：(3)为根据本发明进行涂布的颗粒过滤器，其使得NO2和PM排放物减少。NO2通过与存在于废气中的还原剂反应大部分被还原为NO。这些还原剂可以是CO、碳氢化合物和煤烟。催化涂层还降低了再生颗粒过滤器需要的温度。进一步地，催化过滤器能够降低CO和碳氢化合物的排放。
实施例
实施例1：
一3.3L可商购的SiC壁流柴油颗粒过滤器，通过传统的浸渍、干燥和焙烧步骤，在过滤器壁内部涂布有CeO2、ZrO2和PdO。Ce含量为45g/L过滤器，Zr含量为9.4g/L过滤器，Pd含量为1.5g/L过滤器。
过滤器在一装备有Citroen C2-2004型1.4L HDI发动机的发动机平台的排气系统中进行测试。安装如图1所示。测试中，通过过滤器之后的废气中CO、碳氧化合物、NO和NOx的水平受到监测。发动机以2500rpm运转，通过改变负荷以确定在不同的过滤器温度下的催化剂活性。
测量到的NO和NO2的浓度汇总于表1和图3中，其中通过与在未涂布的过滤器上的测量值进行比较而获得的NO2转化率作为过滤器温度的函数被绘制。气体中NO2浓度通过从NOx浓度中减去NO浓度来确定。据观察，当过滤器温度低于300℃时，所有NO2基本上转化为NO，而当过滤器温度高于300℃时，形成了额外的NO2。由于废气温度大体上低于300℃，这导致在一个标淮驾驶周期中NO2的净去除。这在实施例2中进行描述。
过滤器燃烧煤烟的能力通过平衡点温度，即过滤器温度定量，其中由于被过滤器捕获的煤烟的量与被氧化除去的煤烟相等，过滤器的压降为一常数。平衡点温度为400℃。对于未涂布的过滤器，在同一发动机平台测试规程下，该温度高于450℃。
CO和碳氧化合物的转化率用同一方法进行确定。这两种废气组分的50％转化率的温度低于200℃。
表1：用于未涂布的SiC壁流颗粒过滤器和实施例1中描述的过滤器的在实施例1中描述的发动机平台上测量到的NO和NOx浓度。
表1
Figure BDA00003146787100051
实施例2：
实施例1中描述的涂布有催化剂的3.3L SiC壁流过滤器用来替换CitroenXsara Picasso 1.6L HDI-2006年型号中的未涂布的过滤器。过滤器置于含有Pt的DDC催化剂的下游。负载有催化剂的燃料被加入到柴油中以降低煤烟氧化温度。安装如图2所示。
替换过滤器之前和之后，汽车在NEDC标准化驾驶周期中进行测试，同时排放物被监测。累计结果在表2中显示。
表2：在装备有1.6L HDI发动机和位于过滤器上游的含有Pt的DOC的Citroen Xsara Picasso上进行NEDC测试而测量到的排放物。未涂布的颗粒过滤器被用来与实施例1中的催化剂涂布过滤器进行比较。
表2

Claims (12)

1.一种用于从贫燃压燃式发动机除去NO2排放物的方法，其中含有NO2的发动机废气与催化剂接触，所述催化剂具有将NO2还原为NO的活性，并且包含至少一种铂族金属且该铂金属不为铂，和至少一种具有氧化还原作用活性的金属氧化物，由此废气中含有的NO2通过与废气中存在的CO、碳氢化合物和/或煤烟反应被还原为NO。
2.权利要求1的方法，其中所述的至少一种铂族金属包括钯。
3.权利要求1的方法，其中所述的至少一种具有氧化还原作用活性的金属氧化物选自由MnO2、Fe2O3、SnO2、Pr2和CeO2组成的组。
4.权利要求1的方法，其中所述的至少一种具有氧化还原作用活性的金属氧化物通过选自由TiO2、WO3、SiO2、HfO2、ZrO2、MgO、CaO、Al2O3、LaO3和BaO组成的组中的一种或多种氧化物稳定。
5.权利要求1的方法，其中所述催化剂由Pd和通过ZrO2稳定的CeO2组成。
6.根据前述权利要求任一项的方法，其中所述催化剂被负载于颗粒过滤器的壁上或其内部。
7.用于根据权利要求1的方法的装置，包括具有对NO2与CO、HC和/或煤烟反应生成NO有效的催化剂的发动机排气系统，其中所述催化剂包括至少一种铂族金属且该铂金属不为铂，和至少一种具有氧化还原作用活性的金属氧化物。
8.权利要求7的装置，其中所述的至少一种铂族金属包括钯。
9.权利要求7的装置，其中所述的至少一种具有氧化还原作用活性的金属氧化物选自由MnO2、Fe2O3、SnO2、PrO2和CeO2组成的组。
10.权利要求7的装置，其中所述的至少一种具有氧化还原作用活性的金属氧化物通过选自由TiO2、WO3、SiO2、HfO2、ZrO2、MgO、CaO、Al2O3、La2O3和BaO组成的组中的一种或多种氧化物稳定。
11.权利要求7的装置，其中所述催化剂由Pd和通过ZrO2稳定的CeO2组成。
12.根据权利要求7-11任一项的装置，其中所述催化剂被负载于颗粒过滤器的壁上或其内部。
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