CN103328098A - 制造催化微粒过滤器的方法及催化微粒过滤器 - Google Patents

制造催化微粒过滤器的方法及催化微粒过滤器 Download PDF

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CN103328098A
CN103328098A CN2011800530515A CN201180053051A CN103328098A CN 103328098 A CN103328098 A CN 103328098A CN 2011800530515 A CN2011800530515 A CN 2011800530515A CN 201180053051 A CN201180053051 A CN 201180053051A CN 103328098 A CN103328098 A CN 103328098A
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K·约翰森
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Abstract

制造催化微粒过滤器的方法及通过该方法制造的微粒过滤器。

Description

制造催化微粒过滤器的方法及催化微粒过滤器
本发明涉及多功能催化柴油微粒过滤器。特别是,本发明涉及制造催化微粒过滤器的方法,其既具有通过已知的选择性催化还原(SCR)法除去氮氧化物的活性还具有将废气中含有的烃和一氧化碳氧化转化成水和二氧化碳及将SCR中用做还原剂的过量的氨转化成氮气的氧化活性。
此外,本发明提供了催化颗粒过滤器,在其入口/分散侧和过滤器壁中采用SCR催化剂催化,在过滤器的出口/渗透侧中采用氨泄漏催化剂(ammonia slipcatalyst)与氧化催化剂一起催化。
除了未燃烧的烃,柴油废气还含有氮氧化物(NOx)和微粒物质。NOx、烃和微粒物质是代表对健康和环境有危害的材料和化合物,必须减少或除去来自发动机的废气,其通过使废气通过颗粒过滤器和一些催化剂单元进行。
一般地,这些过滤器是蜂窝壁流式过滤器,其中在蜂窝过滤器的隔壁上或其中捕获微粒物质。
除了微粒过滤器,在现有技术中公开的废气清洁***除了包括通过与氨反应生成氮气而具有选择性还原NOx的活性的催化剂单元之外还包括柴油氧化催化剂。
为了除去注入到废气中用于SCR的过量的氨,若干已知的废气清洁***另外包括将氨催化转化成氮气的下游催化剂单元,所谓的氨泄漏催化剂。
涂覆有催化上述反应的催化剂的多功能柴油微粒过滤器在现有技术中也是已知的。
在已知的多功能过滤器中,不同的催化剂分段或分区涂覆在过滤器的不同区域中。
分段或分区涂覆不同的催化剂在过滤器上是昂贵和困难的制造方法。
US 2010/0175372在一个实施方式中公开了具有过滤器的柴油废气处理***,其在过滤器的分散侧采用SCR催化剂催化,并在渗透侧采用氨氧化催化剂和柴油氧化催化剂催化。SCR催化剂载体涂覆(washcoat)在整个过滤器基材上,随后将氨氧化催化剂施涂在出口过滤器通道处。柴油氧化催化剂以重叠层施涂在出口通道处的氨氧化催化剂上。
与已知技术相比,本发明提出更简单的制造微粒过滤器的方法,该过滤器采用不同的催化剂催化以用氨选择性还原氮氧化物并除去烃、一氧化碳和过量的氨。
因此,本发明提供了制造催化颗粒过滤器的方法,包括以下步骤
a)提供多孔过滤器本体,其具有分散侧和渗透侧;
b)提供催化剂载体涂层(washcoat),包含具有选择性催化还原氮氧化物的活性的第一催化剂组合物颗粒,和具有氧化一氧化碳、烃和氨的活性的第二催化剂组合物颗粒,以及与第二催化剂组合物组合的具有将氨选择性氧化成氮气的活性的第三催化剂组合物颗粒,其中第一催化剂组合物颗粒的众数粒度小于微粒过滤器的平均孔径,并且其中第二和第三催化剂组合物颗粒的众数粒度大于微粒过滤器的平均孔径;
c)通过将载体涂层引入至渗透侧的出口端以用催化剂载体涂层涂覆过滤器本体;以及
d)干燥并热处理涂覆过的过滤器本体以得到催化微粒过滤器。
在前文及以下描述中使用的术语“入口端”是指与未过滤的气体接触的过滤器和通道的端部,“出口端”是指过滤后的气体从此离开过滤器本体的过滤器和通道的端部。
在本文中所使用的术语“分散侧”和“渗透侧”分别指的是面向含有废气的微粒的过滤器流动通道,和面向过滤后的废气的流动通道。
根据本发明的方法的主要优点是过滤器可涂覆含有催化不同反应的三种类型催化剂制剂的单一载体涂层。当将载体涂层引入渗透侧的出口端时,SCR催化剂颗粒将扩散至多孔过滤器壁中及分散侧,而将烃/一氧化碳氧化催化剂和氨氧化催化剂颗粒保留在过滤器渗透侧隔壁的孔隙外侧。因此多功能催化过滤器的制造在更简单和更廉价的生产装置方面已经改进很大。
在冷启动过程中,发现采用催化剂颗粒的混合物形式的不同类型的催化剂涂覆过滤器的进一步的优点是改善了传热及加热。结果是,可能在启动之后比迄今已知更早地开始注入还原剂和去除SCR NOx反应。
根据本发明的一个实施方案,载体涂层中的在选择性催化还原NOx中有活性的第一催化剂颗粒包含沸石、磷酸硅铝、离子交换沸石、或用铁和/或铜促进的磷酸硅铝的至少一种、一种或多种碱性金属氧化物(base metal oxides)和氧化铈和氧化钨混合物在氧化钛载体、氧化铝载体、氧化锆载体或氧化硅载体上的至少一种的催化剂载体。
本发明中使用的优选沸石为β沸石或菱沸石。
本发明中使用的具有菱沸石结构的优选的磷酸硅铝为用铜促进的SAPO 34。
根据本发明的另一个实施方案,在烃、一氧化碳和氨的氧化中有活性的第二催化剂组合物包含负载在氧化铝、氧化钛、氧化铈、氧化硅和氧化锆的至少一种上的铂和钯的混合物。
在本发明另一实施方案中,在将氨选择性氧化成氮气中有活性的第三催化剂组合物包含铜和/或铁促进的沸石或具有菱沸石结构的铜和/或铁促进的磷酸硅铝,促进的沸石优选为β沸石或菱沸石。
为了形成本发明使用的载体涂层,将通常为颗粒形式的第一、第二和第三催化剂组合物研磨或附聚成所要求的粒度,并悬浮在水或有机溶剂中,任选地加入粘合剂、粘度改良剂、发泡剂或其他加工助剂。
载体涂层的制造可通过悬浮第一、第二和第三催化剂颗粒成单一悬浮液,或通过制造三种不同的悬浮液,即具有SCR催化剂颗粒的第一悬浮液、具有烃/一氧化碳/氨氧化催化剂颗粒的第二悬浮液、和具有选择性氨氧化催化剂颗粒的第三悬浮液,并将这三种悬浮液按体积比混合制得具有所要求的量的第一、第二和第三催化剂颗粒的载体涂层。
如前文已提及的,在载体涂覆过滤器期间,为了使SCR催化剂颗粒有效地扩散到隔壁中,并防止氧化催化剂组合物从渗透侧扩散至分散侧,SCR催化剂的平均粒度小于过滤器的平均孔径,并且氨和烃/一氧化碳氧化催化剂组合物的平均粒度大于平均孔径。
根据本发明的一个优选实施方案,过滤器为壁流式整料形式,其具有多个由纵向多孔壁分成的纵向通道,所述通道的分散侧具有开放的入口端和用塞子塞住的出口端,所述通道的渗透侧具有用塞子塞住的入口端和开放的出口端。
根据普遍做法载体涂覆过滤器本体,包括在过滤器中施加真空吸力,对载体涂层加压,或通过浸涂。
当采用真空载体涂覆法时,在分散侧的入口端形成真空。
当采用浸涂法时,将过滤器浸渍并基本浸没于载体涂层浴中,最先从渗透侧的出口端开始。在这种方法中,在涂覆过程中可以不将渗透侧的入口端塞住。
本发明还提供了根据以上描述的根据本发明的实施方案任一项制造的催化微粒过滤器。
在本发明中使用的合适的过滤器材料的实例为碳化硅、钛酸铝、堇青石、氧化铝、富铝红柱石或它们的组合。
过滤器上的第一催化剂的量一般是20至180g/l,在过滤器上的组合型第二和第三催化剂组合物的量一般是10至80g/l。负载在过滤器上的催化剂总量一般是在40至200g/l范围内。
与具有分开的过滤器和催化剂单元的已知的废气清洁***相比,由此制得的过滤器的优点是具有更低的压降和改善的耗热率。
实施例
采用常规的高孔隙率塞入的SiC壁流式过滤器本体,其孔隙率约60%和壁平均孔径约18μm。
通过将100克用2%铜促进的磷酸硅铝SAPO-34混合并分散在200毫升去矿质水/升过滤器中来制造第一催化剂的悬浮液。添加了分散剂ZephrymPD-7000和消泡剂。将悬浮液在砂磨机中研磨。悬浮液的平均粒度为5-10μm,并小于壁流式过滤器壁中的孔隙的平均孔径。
第二催化剂组合物的悬浮液在第一步中通过将铂钯(摩尔比3∶1)的混合物沉积在平均粒度大于过滤器壁的平均孔径的氧化铝颗粒上制造。混合物的悬浮液通过将20克这种粉末混合于40毫升去矿质水/升过滤器中制得。在第二步中,第三催化剂组合物的悬浮液由具有1.0%铜、众数粒度大于过滤器壁的平均孔径的β沸石粉末制造。悬浮液通过将20克铜β沸石粉末混合并分散在40毫升去矿质水/升过滤器中制得。添加分散剂Zephrym PD-7000和消泡剂。然后将得自这两步的悬浮液混合并进一步分散。最终悬浮液的众数粒度大于壁流式过滤器壁中孔隙的平均孔径。
然后将组合型第二催化剂和第三催化剂组合物的悬浮液混合于第一SCR催化剂组合物的悬浮液中,由此获得最终载体涂覆的催化剂悬浮液。
通过标准载体涂覆方法将最终催化剂悬浮液从过滤器渗透侧的出口端载体涂覆于过滤器上。然后干燥涂覆过的过滤器并在750℃下煅烧。

Claims (11)

1.制造催化微粒过滤器的方法,包括以下步骤
a)提供多孔过滤器本体,其具有分散侧和渗透侧;
b)提供催化剂载体涂层,其包含具有选择性催化还原氮氧化物的活性的第一催化剂组合物颗粒,和具有氧化一氧化碳、烃和氨的活性的第二催化剂组合物颗粒,以及与第二催化剂组合物组合的具有将氨选择性氧化成氮气的活性的第三催化剂组合物颗粒,其中第一催化剂组合物颗粒的众数粒度小于微粒过滤器的平均孔径,并且其中第二和第三催化剂组合物颗粒的众数粒度大于微粒过滤器的平均孔径;
c)通过将载体涂层引入至渗透侧的出口端以用催化剂载体涂层涂覆过滤器本体;以及
d)干燥并热处理涂覆过的过滤器本体以得到催化微粒过滤器。
2.权利要求1的方法,其中第一催化剂组合物包含铁和/或铜促进的沸石、磷酸硅铝、离子交换沸石或磷酸硅铝的至少一种、一种或多种碱性金属氧化物和氧化铈和氧化钨混合物在氧化钛载体、氧化铝载体、氧化锆载体或氧化硅载体和它们的混合物上的至少一种的催化剂载体。
3.权利要求2的方法,其中沸石是β沸石或菱沸石。
4.权利要求2的方法,其中具有菱沸石结构的磷酸硅铝为用铜促进的SAPO34催化剂。
5.权利要求1至4任一项的方法,其中第二催化剂组合物包含负载在氧化铝、氧化钛、氧化铈、氧化硅和氧化锆载体的至少一种上的铂和钯的混合物。
6.权利要求1或5的方法,其中第三催化剂组合物包含铜和/或铁促进的沸石或铜和/或铁促进的具有菱沸石结构的磷酸硅铝。
7.权利要求6的方法,其中沸石是β沸石或具有菱沸石结构的沸石。
8.根据前述权利要求任一项的方法,其中过滤器为壁流式整料形式,其具有多个由纵向多孔壁分成的纵向通道,所述通道的分散侧具有开放的入口端和塞住的出口端,所述通道的渗透侧具有塞住的入口端和开放的出口端。
9.根据前述权利要求任一项的方法,其中将载体涂层从渗透侧的出口端引入。
10.根据权利要求1至7任一项的方法,其中在塞住渗透侧的入口端之前施涂载体涂层。
11.根据前述权利要求任一项制造的催化微粒过滤器。
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