CN109789373A - 具有scr活性涂层的颗粒过滤器 - Google Patents

具有scr活性涂层的颗粒过滤器 Download PDF

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CN109789373A
CN109789373A CN201780058832.0A CN201780058832A CN109789373A CN 109789373 A CN109789373 A CN 109789373A CN 201780058832 A CN201780058832 A CN 201780058832A CN 109789373 A CN109789373 A CN 109789373A
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palladium
particulate filter
wall
scr
copper
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CN109789373B (zh
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A·舒勒
F·多恩豪斯
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Umicore AG and Co KG
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Abstract

本发明公开了一种颗粒过滤器，所述颗粒过滤器包括壁流式过滤器和SCR催化活性材料，其中所述壁流式过滤器包括在所述壁流式过滤器的第一端与第二端之间平行延伸的管道，并且所述管道在所述第一端或所述第二端处以气密方式交替地封闭，并且由多孔壁隔开，并且其中所述SCR活性材料包括与铜和/或铁交换的沸石，并且所述沸石在所述壁流式过滤器的所述多孔壁中以涂层的形式存在，其特征在于，所述SCR催化活性涂层含有钯。

Description

具有SCR活性涂层的颗粒过滤器
本发明涉及用于同时减少内燃机的废气中的颗粒和氮氧化物的具有SCR活性涂层的颗粒过滤器。
配备主要以稀燃操作的内燃机的机动车辆的废气具体地含有除了颗粒排放物之外的主要排放物一氧化碳CO、碳氢化合物HC以及氮氧化物NOx。由于相对高的氧气含量为至多15体积％，因此一氧化碳和碳氢化合物可相对容易地借助于氧化而变得无害；然而，使氮氧化物还原为氮气要困难得多。
用于在存在氧气的情况下从废气中去除氮氧化物的一种已知方法是在合适的催化剂上借助于氨的选择性催化还原方法(SCR方法)。在该方法中，利用氨将废气中待去除的氮氧化物转化为氮和水。
用作还原剂的氨可通过将氨前体化合物例如尿素、氨基甲酸铵或甲酸铵进料到废气流中并且随后水解而可用。
颗粒主要由碳组成，并且借助颗粒过滤器可非常有效地从废气中除去颗粒。由陶瓷材料制成的壁流式过滤器已经特别地得到了证实。这些壁流式过滤器由多个平行管道构成，这些管道由多孔壁形成。管道在过滤器的两端中的一个处以气密方式交替地密封，使得形成管道A，其在过滤器的第一侧处敞开并且在过滤器的第二侧处密封；并且形成管道B，其在过滤器的第一侧处密封并且在过滤器的第二侧处敞开。流入管道A的废气例如可仅经由管道B再次离开过滤器，并且为此必须流通管道A与管道B之间的多孔壁。当废气通过该壁时，颗粒被滞留下来。
必须不时地或连续地除去由过滤器滞留下来的颗粒，以避免过滤器的背压过高或甚至堵塞。这具体地通过在约600℃的高温下用氧气燃烧碳来进行。
还已知使用SCR活性材料涂覆壁流式过滤器，从而从废气同时去除颗粒和氮氧化物。
至于将所需量的SCR活性材料施加到管道之间的多孔壁上(公知为壁上涂层)，然而这可能导致过滤器背压的不可接受的增加。
以此为背景，例如，JPH01-151706和WO2005/016497A1提出用SCR催化剂涂覆壁流式过滤器，使得SCR催化剂穿透多孔壁(公知为壁内涂层)。
颗粒过滤器与SCR催化剂的组合的重要要求尤其是正常驱动操作的低温活性、关于NOx转化的活性以及过滤器再生期间CO和HC二次排放的最小化。此外，SCR催化剂应具有尽可能高的选择性，即它应尽可能少地形成一氧化二氮。
本发明的目的是提供涂覆有SCR催化剂以及满足上述要求的壁流式过滤器。
本发明涉及包括壁流式过滤器和SCR活性材料的颗粒过滤器，其中
壁流式过滤器包括在壁流式过滤器的第一端与第二端之间平行延伸的管道，并且这些管道在第一端或第二端处以气密方式交替地封闭，并且由多孔壁隔开，并且其中
SCR活性材料含有与铜和/或铁交换的沸石并且在壁流式过滤器的多孔壁中以涂层的形式定位，
其特征在于，SCR活性材料含有钯。
在本发明的一个实施方案中，钯均匀地分布在SCR活性材料中。
在本发明的另一个实施方案中，钯承载在载体材料上。
本领域的技术人员为此目的已知的所有材料被认为是用于钯的载体材料。此类材料具有30m2/g至250m2/g(优选地100m2/g至200m2/g)的BET表面积(根据DIN 66132确定)，并且具体包括氧化铝、氧化硅、氧化镁、氧化钛以及它们的混合物或混合氧化物。
氧化铝和铝/硅混合氧化物是优选的。如果使用氧化铝，则特别优选地用例如氧化镧稳定化。
用钯涂覆载体材料是通过已知方法进行的，例如根据初始含浸法或注入法，在每种情况下使用水溶性钯化合物。
然而，在本发明的实施方案中，SCR活性材料可也用作钯的承载。在这种情况下，钯因此直接存在于SCR活性材料上。
还可以设想，一部分钯直接承载在SCR活性材料上，另一部分承载在单独的载体材料上。
在本发明的实施方案中，SCR活性涂层含有钯的量相对于SCR活性材料分别为10ppm至1000ppm，优选地50ppm至500ppm。
可根据本发明使用的壁流式过滤器是已知的并且可商购获得。它们由例如碳化硅、钛酸铝或堇青石组成。
在未涂覆状态下，它们具有例如30％至80％，特别是50％至75％的孔隙率。在未涂覆状态下，它们的平均孔径例如为5微米至30微米。
一般来讲，壁流式过滤器的孔为所谓的开口孔，即它们与管道连接。此外，一般来讲，孔彼此互连。这使得一方面能够容易地涂覆内孔表面，并且在另一方面使得废气容易通过壁流式过滤器的多孔壁。
在本发明的上下文中，术语“SCR活性材料”应理解为是指含有SCR催化剂和钯或者由SCR催化剂和钯组成的材料。
在本发明的实施方案中，使用与铜和/或铁交换的小孔沸石作为SCR催化剂沸石。
小孔沸石具有八个四面体原子的最大环尺寸，并且具体地属于结构类型AEI、AFX、CHA(菱沸石)、ERI(毛沸石)、LEV(插晶菱沸石)和KFI。结构类型AEI、菱沸石和插晶菱沸石是特别优选的。
在本发明的范围内，术语“沸石”不仅是硅铝酸盐，还是硅铝磷酸盐，它们有时也称为沸石类化合物。根据本发明待使用的硅铝磷酸盐也具体地属于结构类型AEI、CHA(菱沸石)、ERI(毛沸石)、LEV(插晶菱沸石)和KFI。示例为SAPO-34和SAPO-35。
特定的沸石与铁和/或铜交换，尤其是与铜交换。铁或铜的量特别是为0.2重量％至6重量％，该含量基于交换的沸石的总重量以及以Fe2O3或CuO计算。
在本发明的实施方案中，SCR活性材料包括SCR催化剂，其含有铜交换的沸石和钯，或者由铜交换的沸石和钯组成。
在本发明的实施方案中，SCR催化活性材料包括菱沸石类型的铜交换沸石以及钯，或者由菱沸石类型的铜交换沸石和钯和/或承载在载体材料上的钯组成。
在本发明的其他实施方案中，SCR催化活性材料包括插晶菱沸石类型的铜交换沸石以及钯，或者由插晶菱沸石类型的铜交换沸石和钯和/或承载在载体材料上的钯组成。
在本发明的其他实施方案中，SCR催化活性材料包括AEI类型的铜交换沸石以及钯，或者由AEI类型的铜交换沸石和钯和/或承载在载体材料上的钯组成。
在本发明的另一个实施方案中，具有SCR活性材料的涂层的量相对于壁流式过滤器的体积为70g/L至150g/L，特别是为90g/L至130g/L。
根据本发明的颗粒过滤器的制造可根据本领域技术人员熟悉的方法进行，例如，根据典型的浸涂方法或泵涂和吸涂方法，随后进行热后处理或煅烧。本领域技术人员已知，壁流式过滤器的平均孔径和SCR催化活性材料的平均粒度必须彼此适应，以便实现壁上涂层或壁内涂层。壁内涂层，即，涂覆多孔壁的内孔表面，是优选的。在这种情况下，SCR催化活性材料的平均粒度必须足够小以渗透到壁流式过滤器的孔中。
本发明在接下来的实施例和附图中有更详细的解释。
实施例1
使用乙酸铜将可商购获得的结构类型菱沸石的沸石与铜交换，使得铜含量相对于CuO为3.5重量％。将承载在可商购获得的掺杂有二氧化硅的氧化铝载体材料上的钯加入到所得的悬浮液中。以此方式计算量，使得钯的含量相对于悬浮液的总固体为200ppm。
将可商购获得的碳化硅壁流式过滤器用所得的悬浮液“壁内”涂覆。
将以此方式获得的SCR活性涂覆的壁流式过滤器随后称为C1。
比较例1
重复实施例1，不同之处在于没有将钯加入悬浮液中。
将以此方式获得的SCR活性涂覆的壁流式过滤器随后称为VC1。
比较例2
重复实施例1，不同之处在于向悬浮液中加入200ppm承载的铂而不是承载的钯。
将以此方式获得的SCR活性涂覆的壁流式过滤器随后称为VC2。
对比实验
测定C1、VC1和VC2的NOx转化率
a)首先，将C1、VC1和VC2在800℃下在水热气氛中老化16小时(10％H2O,10％O2，其余为N2)(为了比较，还比较了新鲜催化剂C1、VC1和VC2，参见图2)。
b)在所谓的NOx转化率测试中，在模型气体反应器中确定根据本发明的颗粒过滤器C1和作为催化剂的上游温度的函数的比较颗粒过滤器VC1和VC1[原文如此]的NOx转化率。
该NOx转化率测试由包括预处理和针对各种目标温度运行的测试循环的测试程序组成。所施加的气体混合物记录在表1中。
测试程序：
1.在600℃下在N2中预处理10分钟
2.针对目标温度重复测试循环
a.在气体混合物1中达到目标温度
b.加入NOx(气体混合物2)
c.加入NH3(气体混合物3)，等到NH3突破>20ppm，或持续最多30分钟
d.已编程的温度脱附温度最高500℃(气体混合物3)
表1：
NOx转化率测试的气体混合物。
气体混合物 1 2 3
N<sub>2</sub> 平衡 平衡 平衡
O<sub>2</sub> 10体积％ 10体积％ 10体积％
NOx 0ppm 500ppm 500ppm
NO<sub>2</sub> 0ppm 0ppm 0ppm
NH<sub>3</sub> 0ppm 0ppm 750ppm
CO 350ppm 350ppm 350ppm
C<sub>3</sub>H<sub>6</sub> 100ppm 100ppm 100ppm
H<sub>2</sub>O 5体积％ 5体积％ 5体积％
GHSV/h-1 60,000 60,000 60,000
针对每个温度点，确定测试程序范围2c的平均转换率。以各个温度点的平均NOx转化率作图得到如图1和图2所示的图绘。图1示出了在800℃下老化的催化剂的平均NOx转化率和N2O形成，图2示出了新鲜催化剂样本的结果。
从图1和图2中可以看出，与VC1相比，C1和VC2具有显著改善的平均NOx转化率。这是由于钯或铂的存在。
然而，与VC2相比，C1形成明显更少的N2O，即具有始终更好的选择性。

Claims (10)

1.一种颗粒过滤器，所述颗粒过滤器包括壁流式过滤器和SCR活性材料，其中
所述壁流式过滤器包括在所述壁流式过滤器的第一端与第二端之间平行延伸的管道，并且所述管道在所述第一端或所述第二端处以气密方式交替地封闭，并且由多孔壁隔开，并且其中
所述SCR活性材料包含与铜和/或铁交换的沸石[并且]在所述壁流式过滤器的所述多孔壁中以涂层的形式定位，
其特征在于，所述SCR催化活性材料含有钯。
2.根据权利要求1所述的颗粒过滤器，其特征在于，所述钯均匀地分布在所述SCR活性材料中。
3.根据权利要求1和/或2所述的颗粒过滤器，其特征在于，所述钯承载在载体材料上。
4.根据权利要求3所述的颗粒过滤器，其特征在于，所述载体材料的BET表面积为30m2/g至250m2/g(根据DIN66132测定)。
5.根据权利要求4所述的颗粒过滤器，其特征在于，所述载体材料是氧化铝、氧化硅、氧化镁、氧化钛、或这些氧化物中的至少两种的混合物或混合氧化物。
6.根据权利要求1至5中任一项所述的颗粒过滤器，其特征在于，所述SCR催化活性涂层含有钯的量为10ppm至1000ppm。
7.根据权利要求1至6中任一项所述的颗粒过滤器，其特征在于，所述SCR活性材料含有与铜和/或铁交换的小孔沸石。
8.根据权利要求7所述的颗粒过滤器，其特征在于，所述小孔沸石属于AEI、CHA(菱沸石)、ERI(毛沸石)、LEV(插晶菱沸石)和KFI结构类型中的一种。
9.根据权利要求1至8中任一项所述的颗粒过滤器，其特征在于，所述SCR活性材料含有所述菱沸石类型的铜交换沸石和钯，或者由所述菱沸石类型的铜交换沸石和钯和/或承载在载体材料上的钯组成。
10.根据权利要求1至8中任一项所述的颗粒过滤器，其特征在于，所述SCR活性材料含有所述插晶菱沸石类型的铜交换沸石和钯，或者由所述插晶菱沸石类型的铜交换沸石和钯和/或承载在载体材料上的钯组成。
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