CN109310990A - 用于制备钒基催化剂的方法 - Google Patents

用于制备钒基催化剂的方法 Download PDF

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CN109310990A
CN109310990A CN201780036392.9A CN201780036392A CN109310990A CN 109310990 A CN109310990 A CN 109310990A CN 201780036392 A CN201780036392 A CN 201780036392A CN 109310990 A CN109310990 A CN 109310990A
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J·W·赫耶
P·L·T·加布里埃尔森
C·S·约根森
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Umicore AG and Co KG
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Abstract

本发明公开了一种用于制备包含负载在金属氧化物催化剂载体上的五氧化二钒的催化剂的方法，所述方法包括以下步骤：a)提供晶体五氧化二钒的颗粒和金属氧化物催化剂载体的颗粒；b)固态混合所述颗粒并且将所述五氧化二钒颗粒分散在所述金属氧化物载体颗粒的表面；c)通过在高于500℃的温度下煅烧来将所述分散的五氧化二钒颗粒锚定到所述金属氧化物载体颗粒的表面上，其特征在于，在步骤c)中的所述锚固期间，通过添加抗烧结金属氧化物组分诸如三氧化钨来抑制所述五氧化二钒颗粒的烧结。

Description

用于制备钒基催化剂的方法
本发明涉及钒基催化剂的制备。具体地讲，本发明基于用于制备负载在金属氧化物催化剂载体上的五氧化二钒的固态过程。
用于制备钒基催化剂的常规方法包括用溶解在水中的偏钒酸铵或草酸氧钒液相浸渍催化剂载体(诸如，氧化钛)，随后烧结浸渍的载体以在载体表面上形成五氧化二钒层。
通过固态过程来执行将五氧化二钒引入到金属氧化物载体上或中的另外方法。该方法更加简单，因为在将精细的五氧化二钒粉末与催化剂载体金属氧化物混合时可以避免预处理载体和活性相。由于五氧化二钒移动性相当好，其将基本上均匀地分散在载体材料的表面上，并且在被加热至高于500℃的温度时执行载体材料的固态浸渍。固态过程的缺点是将五氧化二钒锚定到催化剂载体金属氧化物必须要求高温。五氧化二钒颗粒的烧结导致晶粒尺寸的变化，并且V2O5的晶粒尺寸随烧结温度的增加而增加。
本发明提供了用于制备催化剂的固态方法，该催化剂包含负载在金属氧化物催化剂载体上的五氧化二钒，其中通过在将五氧化二钒颗粒锚定到载体期间添加抗烧结剂来减少烧结。
如本文上下文中所用，术语“固态方法”或“固态过程”在本发明的上下文中应当被理解为，在不使用液体或溶剂的情况下在干燥状态下通过热扩散和锚定来执行用五氧化二钒涂覆或浸渍催化剂载体材料的过程或方法。
因此，本发明提供了用于制备包含负载在金属氧化物催化剂载体上的五氧化二钒的催化剂的方法，该方法包括以下步骤：
a)提供晶体五氧化二钒的颗粒和金属氧化物催化剂载体的颗粒；
b)固态混合该颗粒并且将五氧化二钒颗粒分散在金属氧化物载体颗粒的表面；以及
c)通过在高于500℃的温度下煅烧来将分散的五氧化二钒颗粒锚定到金属氧化物载体颗粒的表面上，其特征在于，在步骤c)中的锚定期间，通过添加抗烧结金属氧化物组分来抑制五氧化二钒颗粒的烧结。
五氧化二钒颗粒的粒度优选地介于0.5μm至10μm之间，优选地介于2μm和5μm之间，以便实现载体颗粒和五氧化二钒颗粒的有效分布和混合。
将如此制备的混合物加热至高于500℃的温度，优选地介于550℃至650℃之间，由此五氧化二钒颗粒有效分散并锚定在载体材料的表面上。
在具体的实施方案中，载体金属氧化物为二氧化钛。
负载在二氧化钛上的五氧化二钒催化剂在氮氧化物的选择性的催化还原中表现出非常高的效率。负载有V2O5/TiO2的催化剂具有高的氧化活性并且可用于去除烃类，特别是卤代烃类，如来自发电厂和废物焚烧厂排放物中的二氧杂环己烯。
为了防止催化剂载体颗粒的烧结，优选用氧化钨和/或二氧化硅稳定金属氧化物载体。
在固定的应用中，通过根据本发明的方法来制备的五氧化二钒催化剂可以颗粒形式用于固定床方法中。
在汽车应用中，催化剂通常将被施用在整体式基材上。对于这些应用，可通过使用包含催化剂的载体涂层来将金属氧化物负载的五氧化二钒催化剂涂覆在基材上。
在制备载体涂层时，将所制备的负载五氧化二钒催化剂研磨或凝聚成所需的粒度并且悬浮在有机溶剂中，其中任选地添加粘结剂、粘度改性剂、发泡剂或如本领域已知的其他加工助剂。
以已知方式将如此制备的载体涂层涂覆在整体式基材上。随后在惰性气氛中煅烧经涂覆的整体式基材，然后在空气中煅烧。
整体式基材可由波纹非织造纤维组成，优选地包含玻璃纤维。
在另一个实施方案中，整体式基材由陶瓷挤出物组成，优选地由堇青石或碳化硅的挤出物组成。
通过根据本发明的方法制备的负载五氧化二钒催化剂的另一个应用是用于通过制备糊状物并且将该糊状物挤出到通体整体式催化剂中来制备通体催化剂。
实施例
通过用ZrO2珠干燥研磨的方式来将2份的V2O5与98份的纯TiO2(混合物1)或用10％WO3改性的TiO2(混合物2)充分混合。在静止空气中将每种物理混合物在575℃下煅烧4小时。
煅烧之后，混合物1的表面积为48.2m2/g，并且混合物2的表面积为61.3m2/g。

Claims (14)

1.一种用于制备包含负载在金属氧化物催化剂载体上的五氧化二钒的催化剂的方法，所述方法包括以下步骤：
a)提供晶体五氧化二钒的颗粒和金属氧化物催化剂载体的颗粒；
b)固态混合所述颗粒并且将所述五氧化二钒颗粒分散在所述金属氧化物载体颗粒的表面；以及
c)通过在高于500℃的温度下煅烧来将分散的五氧化二钒颗粒锚定到金属氧化物载体颗粒的表面上，其特征在于，在步骤c)中的锚定期间，通过添加抗烧结金属氧化物组分来抑制五氧化二钒颗粒的烧结。
2.根据权利要求1所述的方法，其中所述晶体五氧化二钒的所述粒度介于0.5um至10um之间。
3.根据权利要求2所述的方法，其中所述粒度介于2μm至5μm之间。
4.根据权利要求1至3中任一项所述的方法，其中所述金属氧化物催化剂载体包括二氧化钛。
5.根据权利要求1至4中任一项所述的方法，其中所述抗烧结金属氧化物组分包括氧化钨或二氧化硅及其混合物。
6.根据权利要求1至5中任一项所述的方法，包括通过将在步骤c)中获得的所述煅烧颗粒悬浮在有机溶剂中来制备载体涂层的所述另外步骤。
7.根据权利要求6所述的方法，其中所述载体涂层包含一种或多种分散体试剂。
8.根据权利要求6或7所述的方法，其中所述载体涂层包含一种或多种粘结剂，所述粘结剂选自氧化铝、二氧化硅和二氧化钛。
9.根据权利要求6至8中任一项所述的方法，包括将所述载体涂层施用在整体式基材上的所述另外步骤。
10.根据权利要求9所述的方法，其中所述整体式基材包括非织造纤维的一个或多个波纹片材。
11.根据权利要求10所述的方法，其中非织造纤维的所述一个或多个波纹片材包括玻璃纤维。
12.根据权利要求9中任一项所述的方法，其中所述整体式基材为陶瓷挤出物。
13.根据权利要求10所述的方法，其中所述陶瓷挤出物由堇青石或碳化硅组成。
14.根据权利要求1至5中任一项所述的方法，包括制备包含所述煅烧的颗粒的糊状物并且将所述糊状物挤出到通体催化剂整体料的所述另外步骤。
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