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CN107427770B - 催化的陶瓷烛式过滤器和清洁工艺尾气或废气的方法 - Google Patents

催化的陶瓷烛式过滤器和清洁工艺尾气或废气的方法 Download PDF

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Publication number
CN107427770B
CN107427770B CN201580077975.7A CN201580077975A CN107427770B CN 107427770 B CN107427770 B CN 107427770B CN 201580077975 A CN201580077975 A CN 201580077975A CN 107427770 B CN107427770 B CN 107427770B
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palladium
gas
exhaust gas
ceramic
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CN107427770A (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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    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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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；以及布置在过滤器的渗透侧并且位于过滤器朝向渗透侧的壁内的含钯催化剂。

Description

催化的陶瓷烛式过滤器和清洁工艺尾气或废气的方法
本发明涉及陶瓷烛式过滤器和清洁工艺尾气或废气的方法。更具体地，本发明提供了一种催化的陶瓷烛式过滤器，其用于除去工艺尾气或发动机废气中的灰尘和颗粒物质以及这些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。
含颗粒的工艺气体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 BDA0001411816220000011
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 BDA0001411816220000012
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。
该催化剂通过组合的氧化和与NH3的SCR反应在烃(VOC)和NOx的去除中均是有活性的。
也已知钒氧化物是活性的氧化催化剂。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，而是需要存在贵金属催化剂，例如钯。
我们已经发现，当在内表面即钒氧化物催化的烛式过滤器的渗透侧或朝向该渗透侧的壁部分提供非常少量的钯时，会导致来自过滤器的氨和一氧化碳的更低逸出。
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；和
布置在过滤器的渗透侧和/或过滤器朝向渗透侧的壁内的含钯催化剂。
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，并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；
通过氧化减少在过滤器的分散侧上捕获的颗粒物质中的烟灰量，并减少尾气或废气中的烃的量；以及通过氮氧化物与含氮还原剂的选择性催化还原(SCR)来减少氮氧化物的量，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；和
使气体通过过滤器的壁，并且通过与含钯催化剂接触而减少通过过滤器壁的气体中的一氧化碳和氨的量，该含钯催化剂布置在过滤器的渗透侧和/或过滤器朝向渗透侧的壁内。
优选地，组合的SCR和氧化催化剂包含钒氧化物和二氧化钛。
进一步优选的是，含钯催化剂还包含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V/Ti和Pd/V/Ti分别表示由钒氧化物和二氧化钛组成的催化剂和由钯、钒氧化物和二氧化钛组成的催化剂。
还优选的是，钒氧化物/二氧化钛催化剂与含钯催化剂一起另外分散在过滤器的渗透侧上。
优选地，含钯催化剂含有量为20至1000ppm/过滤器重量的钯。
由于以下原因，优选这些催化剂。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。
例如，当含有氨和VOC的工艺气体通过负载有基于钒氧化物的催化剂的分散侧时，通过NOx的NH3-SCR在氨与渗透侧接触之前将氨从气体中去除。在通过分散侧期间，由于VOC的不完全氧化，在与V/Ti催化剂直接接触之后，形成了一定量的CO。通过只在过滤器的渗透侧和/或壁负载Pd催化剂或Pd/V/Ti催化剂，CO和剩余量的VOC被有效地氧化成CO2。以这种方式，可以实现过滤器的壁内和/或渗透侧上的昂贵钯的最小负载。
另外的优点是，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，其也将经由V/Ti和Pd/V/Ti催化剂二者被氧化成SO2。
在高温陶瓷过滤器的情况下，可以使用多种类型的纤维来生产。这些可以例如由硅酸铝盐、硅酸钙镁、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。
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盐形式)的浆料浸渍分散体侧和过滤器壁和用钯盐的溶液或二氧化钛微粒以及钒和钯的盐的浆料浸渍渗透侧来将催化活性材料应用至陶瓷过滤器上。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所需的温度。
实施例1
以下实施例说明了由长度为3m，壁厚为20mm的硅酸钙镁纤维制备的陶瓷烛式过滤器可获得的性能。过滤器的壁内涂覆有含有1.26重量％的V和2.36重量％的Ti的V/Ti催化剂，基于过滤器的总重量计算。经涂覆的过滤器的孔隙率为83％。在含有40ppm干甲苯、19体积％O2、8体积％H2O的入口气体中的甲苯氧化中测试该过滤器。
V/Ti涂覆的过滤器上的甲苯氧化
Figure BDA0001411816220000041
从上表可以看出，在240℃下85％的甲苯被转化。在相同温度下，CO排放量等于35ppm，湿的。
实施例2
以下实施例说明了实施例1的陶瓷烛式过滤器的CO氧化性能，不同之处在于其另外涂覆有36ppm的Pd。用含有约150ppm湿的CO、19％的O2和8％的H2O的气体来进行测试。
Figure BDA0001411816220000042
在240℃下，97％的CO被氧化为CO2。
通过结合实施例1和实施例2中报告的陶瓷烛式过滤器的性能，可以得出以下结论，通过在分散侧用V/Ti催化剂催化并在渗透侧用Pd/V/Ti催化剂催化的烛式过滤器，仅排放出1ppm的CO。

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，所述组合的SCR和氧化催化剂包含钒氧化物和二氧化钛；和
布置在过滤器的渗透侧和过滤器朝向渗透侧的壁内的含钯催化剂。
2.如权利要求1所述的陶瓷烛式过滤器，其中含钯催化剂还包含钒氧化物和二氧化钛。
3.如权利要求1或2所述的陶瓷烛式过滤器，其中含钯催化剂含有量为20至1000ppm/过滤器重量的钯。
4.如权利要求1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4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工艺尾气或废气；
将尾气或废气通过陶瓷烛式过滤器，并在过滤器的分散侧上捕获颗粒物质；
通过氧化减少在过滤器的分散侧上捕获的颗粒物质中的烟灰量，并减少尾气或废气中的烃的量，以及通过氮氧化物与含氮还原剂的选择性催化还原(SCR)来减少氮氧化物的量，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，所述组合的SCR和氧化催化剂包含钒氧化物和二氧化钛；和
使气体通过过滤器的壁，并且通过与含钯催化剂接触而减少通过过滤器壁的气体中的一氧化碳和氨的量，所述含钯催化剂布置在过滤器的渗透侧和/或过滤器朝向渗透侧的壁内。
7.如权利要求6所述的方法，其中含钯催化剂还包含钒氧化物和二氧化钛。
8.如权利要求6或7所述的方法，其中含钯催化剂含有量为20至1000ppm/过滤器重量的钯。
9.如权利要求6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所述的方法，其中过滤器的陶瓷材料包括选自硅酸钙镁的生物可溶性纤维。
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CN107427770A (zh) 2017-12-01
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US20180008963A1 (en) 2018-01-11
EP3271049A1 (en) 2018-01-24
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AR103897A1 (es) 2017-06-14
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