CN108698026A - 具有低压降的催化的织物过滤器的方法 - Google Patents

具有低压降的催化的织物过滤器的方法 Download PDF

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Publication number
CN108698026A
CN108698026A CN201780014994.4A CN201780014994A CN108698026A CN 108698026 A CN108698026 A CN 108698026A CN 201780014994 A CN201780014994 A CN 201780014994A CN 108698026 A CN108698026 A CN 108698026A
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China
Prior art keywords
fabric filter
base material
filter base
catalyst
maceration extract
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CN201780014994.4A
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F·卡斯特利诺
托马士·胡尔特·科林
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Topsoe AS
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Haldor Topsoe AS
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    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/08—Filter cloth, i.e. woven, knitted or interlaced material
    • B01D39/086—Filter cloth, i.e. woven, knitted or interlaced material of inorganic material
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Abstract

用于制备催化的织物过滤器的方法，包括以下步骤：a)提供具有气体入口表面和气体出口表面的织物过滤器基材，其优选由玻璃纤维组成，所述气体入口表面涂布有聚合物膜，其优选由聚四氟乙烯组成；b)提供包含一种或多种催化剂金属前体化合物的水性浸渍液；c)用浸渍液浸渍织物过滤器基材；和d)在低于300℃的温度下干燥和热活化经浸渍的织物过滤器基材，以将一种或多种催化剂前体的金属化合物转化为其催化活性形式，其中在步骤d)中，经浸渍的织物过滤器基材的干燥是从气体出口表面进行的。

Description

具有低压降的催化的织物过滤器的方法
本发明涉及催化的织物过滤器的制备和使用该方法制备的催化的织物过滤器。
织物过滤器通常用于从工业过程和燃烧过程中产生的烟道气中去除颗粒材料。
这些过滤器是用织造或非织造的织物纤维材料生产的，提供用于捕获细颗粒物质的多孔过滤介质，而不会导致通过介质的气体中出现不期望的高压降。
通常，废气和烟道气含有额外的气态化合物，这引起环境或健康危害。
因此，已经期望同时减少或去除废气和烟道气中的颗粒物质和有害化合物两者的含量。
为此目的，采用在将有害化合物转化为较少或无害的化合物中具有活性的催化剂催化的过滤介质已经被用于工业和汽车应用中的清洁***。
例如过滤袋形式的织物过滤器在许多行业中被广泛用于从工艺气体中去除颗粒物质。它们是可用的最有效类型的集尘器之一，并且可以实现超过99％的颗粒收集效率。过滤器可以由各种织造、非织造或毡合的材料或其混合物制成，所述材料包括天然纤维、合成纤维或其他纤维，例如玻璃纤维、陶瓷或金属纤维。
织物过滤器的高颗粒去除效率部分是由于在过滤袋表面上形成的尘饼，并且部分是由于过滤袋组成和生产质量以及织物过滤器构造本身的质量。织物提供表面，在该表面上收集灰尘颗粒。由于构成过滤器的纤维的组成，这些通常在低于280℃的温度下操作，这对将催化剂施加到织物过滤器材料上的方法产生若干要求和限制。
基于玻璃纤维的灰尘过滤袋通常具有两个具有不同表面的侧面。外侧是脏气体的入口侧，涂布有聚合物膜，其作为物理屏障并将细灰尘与脏气体分离。膜对于跨袋压降也是决定性的。内侧未涂布有聚合物膜。
如上文所述，在许多应用中，还期望从脏气体中除去或减少有害的气态化合物。为此目的，用一种或多种在去除有害化合物中具有活性的催化剂浸渍过滤袋。
在制备催化材料如织物材料时，由于环境和健康原因，水性浸渍液是优选的。
为此，在织物过滤器的制造中使用的许多纤维由防水材料组成，当采用使用水性浸渍液的浸渍方法时，这额外增加了对将催化材料施加到纤维上的要求。
当制备催化的织物过滤器时，重要的是将催化材料精细地分散在织物过滤器基材的整个厚度上，其量提供最佳的催化效率并防止由涂布在过滤器基材上的催化材料的量形成过大压降。
浸渍具有聚合物膜的过滤袋的另一个问题在于催化剂颗粒主要积聚在面向聚合物膜的外表面中，这使压降增加到不可接受的值。
本发明提供了一种施加高达15wt％的高催化剂载量而没有显著的压降不利后果的方法，以同时获得细灰尘分离和排放减少。催化剂主要被置于织物过滤器的内侧，即在膜的相对侧。因此，催化剂的添加不显著增加压降。然而，相反，我们的数据显示，放置在外部膜侧的少量催化剂(>2.8wt％)显著增加了压降。
在催化领域中普遍接受的是，有效的负载型催化剂需要将催化活性材料作为单层覆盖在催化剂载体颗粒的表面上。因此，可能限制织物基材上所需的负载型催化剂的量。
另外，要求催化剂颗粒在经浸渍的织物过滤器的干燥和活化过程中不形成大的附聚物。
如上文所述，用于制备织物过滤器的许多纤维材料是防水的，并且通常用于例如催化陶瓷表面的水性浸渍液具有有限的润湿能力或没有润湿能力，以在纤维表面上容易且均匀地铺展，以形成薄且连续的催化剂层。
因此，本发明的一般目的是提供一种通过用符合上述要求的含有催化活性材料的水性浸渍液浸渍织物材料来制备催化的织物过滤器的方法。
根据上述发现，本发明提供了一种用于制备催化的织物过滤器的方法，包括以下步骤：
a)提供具有气体入口表面和气体出口表面的织物过滤器基材，该气体入口表面涂布有聚合物膜；
b)提供包含一种或多种催化剂金属前体化合物的水性浸渍液；
c)用浸渍液浸渍织物过滤器基材；和
d)在低于300℃的温度下干燥和热活化经浸渍的织物过滤器基材，以将一种或多种催化剂前体的金属化合物转化为其催化活性形式，其中
在步骤d)中，经浸渍的织物过滤器基材的干燥是从气体出口表面进行的。
以下公开和讨论了本发明的优选实施方案。这些实施方案可以各自单独使用或以其组合使用。
在一个实施方案中，步骤d)中的热活化是从气体出口表面进行的。优选地，热活化温度为250至280℃。
在另一个实施方案中，织物过滤器基材的浸渍是从气体出口表面进行的。
在进一步的实施方案中，织物过滤器基材为袋的形式。
在气体入口侧涂布有聚合物膜的过滤袋通常具有约0.8mm的厚度。根据本发明的一个优选实施方案，用浸渍液从气体出口侧浸渍过滤袋，其选择性地将催化材料置于膜的相对侧以进一步降低压降。
为此目的，优选地，将袋相对于在过滤袋的操作中使用的方式而翻转，即，在干燥之前和在用催化剂液体浸渍之前将气体出口侧翻出。
然后从气体出口侧进行干燥，且催化剂迁移到水蒸发表面，即，气体出口侧，防止催化剂颗粒在涂布有聚合物膜的气体入口部位上积聚。
已经发现，许多织物过滤器基材的热稳定性低，而其他材料使催化材料失活。
因此，优选的织物过滤器基材由织造或非织造的玻璃纤维组成。该基材可承受高达280℃的温度。
出于同样的原因，聚合物膜优选由具有高温稳定性的聚四氟乙烯组成。
含颗粒的废气或烟道气大多含有氮氧化物(NOx)、挥发性有机化合物(VOC)、SO2、CO、Hg、NH3、二英和呋喃，根据当地法规必须减少其浓度。通过与催化剂接触可以有效地减少气态污染物，如NOx、VOC、二英和呋喃。
在本发明的优选实施方案中，一种或多种催化剂金属前体化合物包括偏钒酸铵、偏钨酸铵、七钼酸铵四水合物、硝酸钯、四氨合碳酸氢铂(II)或其混合物，且催化剂金属前体化合物的催化活性形式包括氧化钒、氧化钨、氧化钼、氧化锰、氧化铜、氧化铁以及氧化和/或金属形式的铂和钯中的一种或多种。
特别地，负载在二氧化钛、氧化铝、二氧化铈、氧化锆或其混合物上的氧化钒基催化剂是在固定和汽车应用中通过用NH3选择性还原NOx来减少NOx的常用催化剂。有效的氧化催化剂是氧化和/或金属形式的钯或铂。
因此，进一步优选的是一种或多种催化剂前体金属化合物由偏钒酸铵和硝酸钯组成，且催化剂金属前体化合物的催化活性形式由五氧化二钒和钯组成。
这些催化剂在去除烃(VOC)和一氧化碳中以及在通过采用NH3的SCR反应去除NOx中均具有活性。
氧化金属载体优选地包含钛、铝、铈、锆的氧化物或其混合物和化合物。
进一步优选的是，氧化金属载体由粒度为10至150nm的氧化钛纳米颗粒组成。
在如以下更详细地公开的浸渍液的制备中，浸渍溶液中的一部分氧化金属载体水溶胶在储存过程中胶凝，并附聚成比优选粒度更大的粒度。伯胺分散剂防止附聚或分解已形成的附聚物。
当已经被以产生上文公开的目的的量添加时，优选伯胺可溶于水性浸渍液中。具有少于7个碳原子的伯胺是水溶性的，用于本发明的优选的伯胺是单甲胺、单乙胺、单丙胺、单丁胺或其混合物。其中，最优选的分散剂是单乙胺。
当将伯胺分散剂以使浸渍液的pH值高于7的量添加到浸渍液中时，获得良好的结果。
在本发明的所有以上实施方案中，进一步优选的是，制备的催化的织物过滤器包含约5至约15重量％的催化活性材料。
在以上实施方案中，干燥步骤和活化步骤暗示将热空气施加到经浸渍的织物过滤器的气体出口侧上，或者通过例如微波或辐射热(如红外波)将热施加到气体出口侧上。
实施例1
将过滤袋用催化液润湿，从气体入口表面干燥并在>240℃下热处理。由此，催化剂主要被置于外部膜侧。将催化液用水稀释，以改变催化剂的量，参见表1。
表1
样品 干燥 Wt％催化剂 200Pa下的渗透性，l/m2/s
X–空白 无 0 65.2
A 从气体入口 3.25 22.6
B 从气体入口 4.7 19.1
C 从气体入口 6.8 20.9
D 从气体入口 10.2 20.8
E 从气体入口 13.5 15.3
实施例2
将过滤袋用催化液润湿，从气体出口表面干燥并在>240℃下热处理。由此，催化剂主要被置于内侧而不是膜上。将催化液用水稀释，以改变催化剂的量，参见表2。
表2
样品 干燥 Wt％催化剂 200Pa下的渗透性，l/m2/s
X-空白 无 0 65.2
F 从气体出口 6.6 65.7
G 从气体出口 6.6 62.4
H 从气体出口 10.0 58.6
I 从气体出口 10.0 49.1

Claims (18)

1.一种用于制备催化的织物过滤器的方法，包括以下步骤：
a)提供具有气体入口表面和气体出口表面的织物过滤器基材，所述气体入口表面涂布有聚合物膜；
b)提供包含一种或多种催化剂金属前体化合物的水性浸渍液；
c)用所述浸渍液浸渍所述织物过滤器基材；和
d)在低于300℃的温度下干燥和热活化经浸渍的织物过滤器基材，以将一种或多种催化剂前体的金属化合物转化为其催化活性形式，其中
在步骤d)中，经浸渍的织物过滤器基材的干燥是从气体出口表面进行的。
2.如权利要求1所述的方法，其中步骤d)中的热活化是从气体出口表面进行的。
3.如权利要求1或2所述的方法，其中织物过滤器基材的浸渍是从气体出口表面进行的。
4.如权利要求1至3中任一项所述的方法，其中织物过滤器基材是袋的形式。
5.如权利要求4所述的方法，其中在步骤c)和/或步骤d)之前将袋的气体出口表面翻出。
6.如权利要求1至5中任一项所述的方法，其中织物过滤器基材由织造或非织造的玻璃纤维组成。
7.如权利要求1至6中任一项所述的方法，其中聚合物膜由聚四氟乙烯组成。
8.如权利要求1至7中任一项所述的方法，其中一种或多种催化剂金属前体化合物包括偏钒酸铵、偏钨酸铵、七钼酸铵、硝酸钯、四氨合碳酸氢铂(II)或其混合物。
9.如权利要求1至7中任一项所述的方法，其中一种或多种催化剂金属前体化合物的催化活性形式包括氧化钒、氧化钨、氧化钼、氧化锰、氧化铜、氧化铁以及氧化和/或金属形式的铂和钯中的一种或多种。
10.如权利要求9所述的方法，其中一种或多种催化剂金属前体化合物的催化活性形式由五氧化二钒和金属和/或氧化形式的钯组成。
11.如权利要求1至10中任一项所述的方法，其中氧化金属载体包括钛、铝、铈、锆的氧化物或其混合物和化合物。
12.如权利要求11所述的方法，其中氧化金属载体由粒度为10至150nm的氧化钛纳米颗粒组成。
13.如权利要求1至12中任一项所述的方法，其中水性浸渍液包含分散剂，所述分散剂包括选自单甲胺、单乙胺、单丙胺和单丁胺中的一种或多种的伯胺。
14.如权利要求13所述的方法，其中所述分散剂由单乙胺组成。
15.如权利要求13或14所述的方法，其中所述分散剂以使浸渍液的pH值高于7的量添加到水性浸渍液中。
16.如权利要求1至15中任一项所述的方法，其中催化的织物基材包含约5至约15重量％的催化活性物质。
17.如权利要求1至16中任一项所述的方法，其中一种或多种催化剂前体金属化合物是偏钒酸铵和硝酸钯。
18.一种催化的织物过滤器基材，其通过前述权利要求中任一项所述的方法制备。
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