CN107427771B - 催化的陶瓷烛式过滤器和清洁尾气或废气的方法 - Google Patents

催化的陶瓷烛式过滤器和清洁尾气或废气的方法 Download PDF

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CN107427771B
CN107427771B CN201580077976.1A CN201580077976A CN107427771B CN 107427771 B CN107427771 B CN 107427771B CN 201580077976 A CN201580077976 A CN 201580077976A CN 107427771 B CN107427771 B CN 107427771B
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filter
exhaust gas
ceramic
amount
oxidation catalyst
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CN107427771A (zh
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F·卡斯特利诺
L·S·佩德森
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Topsoe AS
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Haldor Topsoe AS
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Abstract

本发明涉及陶瓷烛式过滤器以及所述过滤器在除去工艺尾气或发动机废气中存在的烟灰、灰分、金属和金属化合物形式的颗粒物质以及烃和氮氧化物中的用途，该过滤器包括至少布置在过滤器的分散侧和/或壁内的组合的SCR和氧化催化剂；该组合的SCR和氧化催化剂包含钯、钒氧化物和二氧化钛。

Description

催化的陶瓷烛式过滤器和清洁尾气或废气的方法
本发明涉及陶瓷烛式过滤器和清洁尾气或废气的方法。更具体地，本发明提供了一种催化的陶瓷烛式过滤器，其用于除去工艺气体中的灰尘和颗粒物质以及工艺气体中包含的有害组分。催化的陶瓷烛式过滤器特别用于清洁来自涉及燃烧的工业过程(如矿物、玻璃、水泥的生产、废物焚烧)或来自燃煤锅炉和发动机的工艺或原料气体。
过滤器烛形式的陶瓷过滤器用于许多工业以从工艺气体中除去颗粒物质。它们是可用的最有效类型的集尘器之一，并且可以对颗粒物的收集效率达到大于99％。过滤器可以由多种陶瓷材料(包括由碱金属和碱土金属硅酸盐或铝硅酸盐制成的陶瓷纤维)制成。
陶瓷烛式过滤器的高颗粒去除效率部分是由于在烛式过滤器表面形成的灰尘饼，并且部分是由于烛式过滤器的组成和多孔性。为了提供足够的过滤活性和经过滤器的可接受的低压降，常规的陶瓷烛式过滤器的孔隙率为70-90％。这些过滤器的壁厚应在10-20mm范围内，以获得足够的稳定性和机械强度。
含颗粒的工艺尾气和发动机废气通常含有多种污染物，例如NOx、挥发性有机化合物(VOC)、SO2、CO、NH3、二
Figure BDA0001411807210000011
英和呋喃，其浓度必须根据当地法规来降低。为此，可以使用几种常规方法。可以通过与催化剂接触来有效地减少气体污染物如NOx、VOC、二
Figure BDA0001411807210000012
英和呋喃。特别地，基于钒氧化物的催化剂是通常使用的催化剂，其用于通过NOx与NH3的选择性还原来减少在静态应用和汽车应用中的NOx。
该催化剂在烃(VOC)的氧化去除以及NOx通过与NH3反应的选择性催化还原(SCR)中都是有活性的。
与贵金属催化剂(如Pd催化剂)相比，钒氧化物催化剂在CO2形成中的选择性较低，并且在氧化反应期间产生一定量的CO。CO不能通过与钒氧化物催化剂接触而以可行的反应速率氧化成二氧化碳。
我们已经发现，当提供具有包含钒氧化物和钯二者的催化剂的烛式过滤器时，造成了烃和烟灰的有效氧化，以及NOx的氨-SCR和氨和一氧化碳从过滤器的更低逸出。
根据这一发现，本发明提供了一种适用于除去工艺尾气或发动机废气中存在的烟灰、灰分、金属和金属化合物形式的颗粒物质以及烃和氮氧化物的陶瓷烛式过滤器，该过滤器包括至少布置在过滤器的分散侧和/或壁内的组合的SCR和氧化催化剂；该组合的SCR和氧化催化剂包含钯、钒氧化物和二氧化钛。
本文所用的术语“分散侧”和“渗透侧”分别是指过滤器朝向未过滤的废气的流动侧，和朝向过滤的尾气或废气的流动侧。
本发明另外提供了一种用于除去工艺尾气或发动机废气中存在的烟灰、灰分、金属和金属化合物形式的颗粒物质以及烃和氮氧化物的方法，该方法包括以下步骤：
提供含有含氮还原剂的工艺尾气或发动机废气或添加含氮还原剂至尾气或废气；
将尾气或废气通过陶瓷烛式过滤器，并捕获颗粒物质；
通过烃的氧化和通过氮氧化物与含氮还原剂的选择性催化还原(SCR)来减少在至少一个颗粒过滤器上捕获的颗粒物质中的烟灰量并减少尾气或废气中的氮氧化物和烃的量，所述含氮还原剂与布置在过滤器的分散侧和/或壁内的组合的SCR和氧化催化剂接触，其中组合的SCR和氧化催化剂包含钯、钒氧化物和二氧化钛。
术语“钒氧化物”是指钒(II)氧化物(一氧化钒)，VO；或者钒(III)氧化物(三氧化二钒)，V2O3；或者钒(IV)氧化物(二氧化钒)，VO2；或者钒(V)氧化物(五氧化二钒)，V2O5。
优选地，用于本发明的钒氧化物包括钒(V)氧化物(五氧化二钒)V2O5或由其组成。
术语“二氧化钛”是指二氧化钛(TiO2)。
钯的催化活性形式是金属和/或氧化形式的钯。
缩写Pd/V/Ti表示由钯、钒氧化物和二氧化钛组成的催化剂。
Pd/V/Ti催化剂具有i)双重功能(去除NOx和去除VOC，挥发性有机化合物)；ii)耐硫性；和iii)与其它催化剂组合物例如基于Pt的催化剂相比，更低的SO2氧化活性。
当使用Pd/V/Ti催化剂时，催化的过滤器烛是耐硫的，即不会发生硫去活化。Pd/V/Ti催化剂还减少SO2氧化形成的SO3的量。如果进入过滤器的工艺气体中也存在H2S，其也将在Pd/V/Ti催化剂上被氧化成SO2。
通过用含有催化活性材料(二氧化钛微粒形式和活性材料的前体即钒和钯的盐形式)的浆料浸渍，可以将催化活性材料应用至陶瓷过滤器。一旦浸渍，就随后将过滤器干燥并加热至分解所有催化剂前体并活化催化剂的所需温度。
与整体式成型过滤器(monolithic formed filter)或壁流式过滤器相比，钯金属颗粒和气体中的反应物之间的有效气体接触要高得多，这导致获得合理氧化活性所需的钯量大大降低。
通常，本发明中使用的催化剂含有量为20至1000ppm/过滤器重量，优选小于200ppm/过滤器重量的钯。
在高温陶瓷过滤器的情况下，可以使用多种类型的纤维来用于其生产。这些可以例如由硅铝酸盐和硅酸钙纤维或它们的混合物组成。
其它优选的陶瓷纤维包括选自硅酸钙镁的生物可溶性纤维。

Claims (10)

1.一种适用于除去工艺尾气或发动机废气中存在的烟灰、灰分、金属和金属化合物形式的颗粒物质以及烃和氮氧化物的陶瓷烛式过滤器，所述过滤器包括至少布置在过滤器的分散侧和/或壁内的组合的SCR和氧化催化剂，组合的SCR和氧化催化剂包含钯、钒氧化物和二氧化钛。
2.如权利要求1所述的陶瓷烛式过滤器，其中所述催化剂含有量为20至1000ppm/过滤器重量的钯。
3.如权利要求1所述的陶瓷烛式过滤器，其中所述催化剂含有量为20至200ppm/过滤器重量的钯。
4.如权利要求1至3中任一项所述的陶瓷烛式过滤器，其中过滤器的陶瓷材料选自硅铝酸盐、硅酸钙镁、硅酸钙纤维或其混合物。
5.如权利要求1至3中任一项所述的陶瓷烛式过滤器，其中过滤器的陶瓷材料由选自硅酸钙镁的生物可溶性纤维组成。
6.一种用于除去工艺尾气或发动机废气中存在的烟灰、灰分、金属和金属化合物形式的颗粒物质以及烃和氮氧化物的方法，所述方法包括以下步骤：
提供含有含氮还原剂的工艺尾气或发动机废气或添加含氮还原剂至尾气或废气；
将尾气或废气通过陶瓷烛式过滤器，并捕获颗粒物质；
通过烃的氧化并通过氮氧化物与含氮还原剂的选择性催化还原(SCR)来减少在至少一个颗粒过滤器上捕获的颗粒物质中的烟灰量并减少尾气或废气中的氮氧化物和烃的量，所述含氮还原剂与布置在过滤器的分散侧和/或壁内的组合的SCR和氧化催化剂接触，其中组合的SCR和氧化催化剂包含钯、钒氧化物和二氧化钛。
7.如权利要求6所述的方法，其中组合的SCR和氧化催化剂含有量为20至1000ppm/过滤器重量的钯。
8.如权利要求6所述的方法，其中组合的SCR和氧化催化剂含有量为20至200ppm/过滤器重量的钯。
9.如权利要求6至8中任一项所述的方法，其中过滤器的陶瓷材料选自硅铝酸盐、硅酸钙镁、硅酸钙纤维或其混合物。
10.如权利要求6至8中任一项所述的方法，其中过滤器的陶瓷材料包含选自硅酸钙镁的生物可溶性纤维。
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