CN101631935A - 催化转化器系统及其应用 - Google Patents

催化转化器系统及其应用 Download PDF

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CN101631935A
CN101631935A CN200880007950A CN200880007950A CN101631935A CN 101631935 A CN101631935 A CN 101631935A CN 200880007950 A CN200880007950 A CN 200880007950A CN 200880007950 A CN200880007950 A CN 200880007950A CN 101631935 A CN101631935 A CN 101631935A
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catalytic converter
catalyst system
waste gas
catalytic
catalyst
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P·施普克
S·弗朗茨
T·勒塔莱克
O·泰塞特
W·米勒
G·耶斯克
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Umicore AG and Co KG
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
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    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/023—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles
    • F01N3/025—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters using means for regenerating the filters, e.g. by burning trapped particles using fuel burner or by adding fuel to exhaust
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    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
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    • F01N13/009—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series
    • F01N13/0093—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series the purifying devices are of the same type
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    • F01N13/0097—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00 having two or more separate purifying devices arranged in series the purifying devices are arranged in a single housing
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    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust 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
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    • F01N3/18—Exhaust 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
    • F01N3/20—Exhaust 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 specially adapted for catalytic conversion ; Methods of operation or control of catalytic converters
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    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
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    • F01N3/24—Exhaust 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 constructional aspects of converting apparatus
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    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
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    • F01N3/10—Exhaust 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
    • F01N3/24—Exhaust 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 constructional aspects of converting apparatus
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    • F01N2340/00—Dimensional characteristics of the exhaust system, e.g. length, diameter or volume of the apparatus; Spatial arrangements of exhaust apparatuses
    • F01N2340/02—Dimensional characteristics of the exhaust system, e.g. length, diameter or volume of the apparatus; Spatial arrangements of exhaust apparatuses characterised by the distance of the apparatus to the engine, or the distance between two exhaust treating apparatuses
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    • F01N2430/00—Influencing exhaust purification, e.g. starting of catalytic reaction, filter regeneration, or the like, by controlling engine operating characteristics
    • F01N2430/08—Influencing exhaust purification, e.g. starting of catalytic reaction, filter regeneration, or the like, by controlling engine operating characteristics by modifying ignition or injection timing
    • F01N2430/085—Influencing exhaust purification, e.g. starting of catalytic reaction, filter regeneration, or the like, by controlling engine operating characteristics by modifying ignition or injection timing at least a part of the injection taking place during expansion or exhaust stroke
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    • F01N2510/00—Surface coverings
    • F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
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Abstract

用于从稀薄的燃烧发动机的废气中去除烟尘的烟尘过滤器(6)由于烟尘的沉积而随着操作工作时间的增长会变得堵塞，因此必须定期进行更新恢复。已经发现，只有时不时地通过将废气温度增大到烟尘点燃温度执行主动的更新恢复时才可以使烟尘过滤器可靠地工作。为此，氧化催化转化器(2)通常设置在烟尘过滤器(6)的上游，且废气温度通过附加喷射的燃料的催化燃烧得到增大。氧化催化转化器(2)因此经受高的热负荷，因此加快老化。已经惊讶地发现，如果所述氧化催化转化器分成至少两个分离的催化转化器且所述分离的催化转化器之间的距离在2－30mm之间，氧化催化转化器(2)的老化可变慢。

Description

催化转化器系统及其应用
技术领域
本发明涉及一种催化转化器系统以及其用于净化内燃机的废气的应用，所述催化转化器系统包括位于共同的转化器壳体中的至少两个催化转化器，所述催化转化器在废气的流动方向上串联设置且彼此间隔开，而且可以以催化反应的方式燃烧稀薄的废气中的碳氢化合物和一氧化碳。催化转化器系统用于柴油发动机的排气系统中，以将废气加热到烟尘点燃温度，从而可主动地更新恢复位于下游的烟尘过滤器。
背景技术
由柴油发动机产生的烟尘必须通过烟尘过滤器从废气中去除，以防止污染空气。随着过滤器中烟尘沉积的增加，由过滤器产生的排气背压增大，从而降低了发动机的功率。因此，过滤器必须定期通过燃烧掉烟尘被更新恢复。
该更新恢复特别是在现代柴油发动机中存在一个问题，这是因为在正常操作中所述发动机的废气太凉而不能点燃过滤器上的烟尘。为此，需要500-700℃的废气温度。
现有用于更新恢复烟尘过滤器的被动和主动方法。在例如根据EP0341832A2的被动方法中，烟尘过滤器通过作为氧化剂的氧化氮连续地在400℃以下的废气温度下被氧化。为此，氧化催化转化器设置在烟尘过滤器的上游，所述氧化催化转化器将存在于废气中的一氧化氮转化为二氧化氮。所述方法需要废气包含足量的一氧化氮。不足在于，废气中存在的碳氢化合物阻止一氧化氮氧化变为二氧化氮。根据US6877313B1，这种缺点可通过设置在烟尘过滤器的上游的两个氧化催化转化器得到补救，其中第一催化转化器主要燃烧废气中的碳氢化合物，第二催化转化器将废气中的残余的一氧化氮氧化为二氧化氮。
被动方法不能确保烟尘过滤器的可靠工作。该过滤器必须至少时不时地被主动更新恢复。为此，燃料喷射到位于氧化催化转化器的上游的废气流中，并在氧化催化转化器上燃烧，或废气中的未燃烧的碳氢化合物的浓度通过发动机内部的措施增加。根据发动机的当前工作状态，氧化催化转化器中的催化燃烧必须将废气加热200至400℃，以达到烟尘点燃温度。在此，高温峰值出现在氧化催化转化器的内部，该温度峰值可导致催化转化器的过早老化。这样，随着工作时间的增加，碳氢化合物和一氧化碳在氧化催化转化器上的转化会恶化。
DE102005017378A1描述了一种具有催化转化器本体的废气净化装置，所述催化转化器本体由多个催化转化器盘构成，所述催化转化器盘在废气的流动方向上串联设置。催化转化器盘由用于将包含在废气中的碳氢化合物、一氧化碳和一氧化氮转化为二氧化碳、水和氮的烧结的金属粉末构成。催化转化器盘之间的距离为近似3mm。
US2003/0099583A1描述了一种废气净化装置，其包括用于转化定比的废气中的碳氢化合物、一氧化碳和一氧化氮的三元催化转化器A和催化转化器B，所述催化转化器B设置在下游，且具有用于吸收碳氢化合物的沸石。
发明内容
本发明的目的是提供一种催化转化器系统，所述催化转化器系统在碳氢化合物的催化燃烧过程中的老化降低，因此可有利地用于烟尘过滤器的主动更新恢复。
所述目的通过这样一种催化转化器系统实现，所述催化转化器系统包括：位于共同的转化器壳体中的至少两个催化转化器，所述催化转化器在废气的流动方向上串联布置并彼此间隔开，而且所述催化转化器可以以催化反应的方式燃烧稀薄的废气中的碳氢化合物和一氧化碳。该催化转化器系统的特征在于，两个相邻的催化转化器之间的距离在2-30mm之间。
已经发现，如果催化转化器分成至少两个单独的催化转化器且所述单独的催化转化器彼此之间仅以数毫米的小的距离间隔开，则所述催化转化器在催化燃烧过程中的老化可变慢。该结果是令人惊讶的，这是因为相继的催化转化器之间的仅数毫米的小的距离并不能冷却废气。显然的情况是，催化转化器的分开对催化转化器中的温度分布具有积极的影响。这样，避免了可导致催化转化器的快速老化的温度峰值。
催化燃烧所需的碳氢化合物可以通过设置在第一催化转化器的上游的配量装置喷射到废气流中，或发动机的废气中的未燃烧的碳氢化合物的部分可以通过发动机内部的措施、例如通过向发动机的汽缸中后补喷射燃料得到增加。
对于催化转化器系统，可氧化稀薄的废气中的碳氢化合物的任何催化转化器均是合适的；这些催化转化器特别是包括氧化催化转化器和三元催化转化器，它们也可组合起来使用。
催化转化器优选包括施加到陶瓷或金属蜂窝体上的氧化活性催化剂涂层，所述催化剂涂层包括从以下组中选择的至少一种贵金属：铂、钯和铑，所述贵金属位于从以下组中选择的基底材料上：活性氧化铝、氧化硅、氧化钛、氧化锆、氧化铈以及它们的混合物或混合氧化物。为了储存碳氢化合物，催化转化器涂层可另外具有沸石。这两个催化转化器可具有相同或不同的成分。
催化转化器系统优选用于柴油发动机的排气区段中，以通过在催化转化器上燃烧燃料将稀薄废气在最后的催化转化器的下游加热到500-700℃之间的温度。为此所需的燃料可借助于配量装置在第一催化转化器的上游喷射到废气流中，其中，应当确保，净废气组分仍具有氧化性能。可选地，废气中的未燃烧的碳氢化合物的比例可通过发动机内部措施、例如通过向柴油发动机的汽缸中后补喷射燃料增加，其中，还应确保，净废气组分仍具有氧化性能。设置在催化转化器系统的下游的烟尘过滤器可通过以这种方式加热的废气被主动地更新恢复。
所提出的催化转化器系统的目的是通过废气中包含的或单独供给的废气可燃成分的燃烧将废气优选加热到500℃以上、最高为700℃的温度。包含在废气中的可燃成分例如是来自柴油发动机燃料的未燃烧或未完全燃烧的碳氢化合物、和一氧化碳。
两个催化转化器之间的距离令人惊讶地使得催化转化器系统的老化更慢，这显现于在已发生老化之后的一氧化碳和碳氢化合物的改进转化。因此，与相应的整体式催化转化器或串联设置但未间隔开的两个催化转化器相比，根据本发明的催化转化器系统在已发生老化之后具有更低的一氧化碳和碳氢化合物的排放。
一方面，催化转化器之间的距离不能太小，以确保具有已观察到的效果；另一方面，由于空间和热量方面的原因，应避免过大的距离，这是因为随着距离的增大，废气会在催化转化器之间冷却。对于直径为10-20厘米的机动车辆废气催化转化器的常规横截面尺寸，两个催化转化器之间的距离为2-30mm被证明是有利的。5-20mm的距离是优选选择的。
然而，两个催化转化器之间的距离仅对在废气流上位于下游的催化转化器的老化有影响。因此，为了改善上游催化转化器的老化稳定性，应尽可能选择在温度方面稳定的催化转化器系统。由经验可知，包括铂和钯的催化转化器可比纯铂的催化转化器更好地承受高温。第一或上游催化转化器的铂/钯比应优选位于4∶1至1∶1之间。第二催化转化器具有尽可能完全地燃烧第一催化转化器未完全转化的一氧化碳和碳氢化合物。比第一催化转化器具有更低的钯含量的铂/钯催化转化器、或纯铂的催化转化器适合于该目的。
因此，两个催化转化器的催化转化器涂层彼此可具有不同的组分，以最优地在催化转化器系统中执行它们各自的功能。然而，优选地，两个催化转化器涂层是相同的。
在冷启动阶段柴油发动机的未经处理的排放物主要由未燃烧的碳氢化合物组成。在冷启动阶段，所述组分不能由仍冷的催化转化器转化。为了阻止所述排放，根据本发明的催化转化器系统的上游和/或下游催化转化器可包含临时储存碳氢化合物的沸石。随着废气的温度的增大，储存的碳氢化合物再次被释放，然后可由在较高的温度下激活的催化转化器转化。
附图说明
下面，基于示例和两幅图更详细地解释本发明，附图包括：
图1示出了具有烟尘过滤器并具有用于过滤器的主动更新恢复的根据本发明的催化转化器系统的排气系统的设计；以及
图2示出了三个不同的催化转化器系统的排放量的对比。
具体实施方式
附图示出了柴油发动机的排气系统1。该排气系统包括第一转化器壳体2，两个氧化活性催化转化器3和4位于所述第一转化器壳体2中，且彼此间隔开。两个催化转化器之间的距离d在2-30mm之间的范围内。两个催化转化器可以具有相同或不同的长度。具有烟尘过滤器6的第二转化器壳体5位于催化转化器系统的下游。下游的烟尘过滤器可通过在催化转化器系统中的附加燃料的燃烧主动地被更新恢复。
示例
在具有2.2升排量的柴油车上，以新欧洲行驶循环(NEDC)对三个催化转化器系统的残余排放量进行相互比较。作为催化转化器载体，均使用的是由堇青石构成的蜂窝体，所述蜂窝体具有62cm-2的单元密度和0.17mm的管壁厚度，所述蜂窝体以每升的蜂窝体体积3.18g铂涂覆传统的柴油机氧化催化剂。
系统1：整体式蜂窝体
       直径14.4cm；长度8.9cm
系统2：两个蜂窝体
       直径14.4cm；每个蜂窝体的长度为4.45cm；蜂窝体之间的距离
       d：0.00cm
系统3：两个根据本发明的蜂窝体
       直径14.4cm；每个蜂窝体的长度为4.45cm；蜂窝体之间的距离
       d：1cm
催化转化器系统在接近真实的条件下通过后补喷射老化21个小时。所述催化转化器系统的残余排放随后以NEDC在柴油车上测量。图2示出了结果。
与传统的整体式系统1和具有两个蜂窝体但蜂窝体之间无间隔的系统2相比，根据本发明的催化转化器系统3在试验过程中具有明显减少的CO和HC排放量。

Claims (13)

1.一种用于净化内燃机的废气的催化转化器系统，包括：位于共同的转化器壳体(2)中的至少两个催化转化器(3)和(4)，所述催化转化器在废气的流动方向上串联布置且彼此间隔开距离d，而且所述催化转化器可以以催化反应的方式燃烧稀薄的废气中的碳氢化合物和一氧化碳，
其特征在于，
两个相邻的催化转化器之间的距离d在2-30mm之间。
2.如权利要求1所述的催化转化器系统，
其特征在于，
用于将燃料喷射到废气中的配量装置设置在第一催化转化器(3)的上游。
3.如权利要求1或2所述的催化转化器系统，
其特征在于，
所述催化转化器(3，4)是氧化催化转化器、或是氧化催化转化器和三元催化转化器的组合。
4.如权利要求3所述的催化转化器系统，
其特征在于，
所述氧化催化转化器包括施加到陶瓷或金属蜂窝体上的氧化活性催化剂涂层。
5.如权利要求4所述的催化转化器系统，
其特征在于，
所述催化剂涂层包括从以下组中选择的至少一种贵金属：铂、钯和铑，所述贵金属位于从以下组中选择的基底材料上：活性氧化铝、氧化硅、氧化钛、氧化锆、氧化铈以及它们的混合物或混合氧化物。
6.如权利要求5所述的催化转化器系统，
其特征在于，
在废气的流动方向上位于上游的催化转化器(3)的催化剂涂层包括铂和钯。
7.如权利要求6所述的催化转化器系统，
其特征在于，
在废气的流动方向上位于下游的催化转化器(4)的催化剂涂层包括铂和钯，其中，钯的含量低于上游催化转化器中的钯的含量。
8.如权利要求6所述的催化转化器系统，
其特征在于，
在废气的流动方向上位于下游的催化转化器(4)的催化剂涂层仅包括铂作为催化活性成分。
9.如权利要求5-8中任一所述的催化转化器系统，
其特征在于，
第一和/或第二催化转化器的催化剂涂层还包括沸石。
10.根据前面权利要求中任一所述的催化转化器系统在柴油发动机的排气区段(1)中的应用，以用于通过在催化转化器上燃烧燃料或来自发动机的未燃烧的碳氢化合物成分将稀薄的废气在最后的催化转化器(4)的下游加热到500-700℃之间的温度。
11.如权利要求10所述的应用，
其特征在于，
燃料借助于配量装置在第一催化转化器(3)的上游喷射到废气流中。
12.如权利要求10所述的应用，
其特征在于，
废气中的未燃烧的燃料成分通过向柴油发动机的汽缸中后补喷射燃料产生。
13.如权利要求10至12中任一所述的应用，其用于通过由催化转化器系统产生的热的废气流来更新恢复设置在催化转化器系统的下游的烟尘过滤器(6)。
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