CN101402051A - 催化剂 - Google Patents

催化剂 Download PDF

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CN101402051A
CN101402051A CNA2008101714501A CN200810171450A CN101402051A CN 101402051 A CN101402051 A CN 101402051A CN A2008101714501 A CNA2008101714501 A CN A2008101714501A CN 200810171450 A CN200810171450 A CN 200810171450A CN 101402051 A CN101402051 A CN 101402051A
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catalyst
carrier
active component
palladium
gold
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R·迈尔
K·席默尔
R·伦内克
V·阿鲁娜雅特森
A·盖塞曼
H·G·J·兰辛克勒特格因克
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Evonik Operations GmbH
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Abstract

本发明提供一种催化剂，其包含在载体上作为催化活性组分的钯、金和碱金属乙酸盐，所述载体通过钛、铁、镧、铈、钇和/或钼或它们的氧化物改性。所述催化剂可用于制备乙酸乙烯酯单体。

Description

催化剂
技术领域
本发明涉及一种催化剂、其制备方法、以及其用于制备乙酸乙烯酯单体的用途。
背景技术
包含金、钯和碱金属化合物的负载催化剂用于制备乙酸乙烯酯。基于该目的，在气相中、加入或不加入惰性气体、温度100-250℃、常压或高于大气压的压力、在负载催化剂存在下，反应乙烯、乙酸和分子氧或空气。
乙酸乙烯酯单体的制备方法已知于DE 16 68 088、EP-A-0 464 633、EP-A-0 519 435、EP-A 0 634 208、EP-A 0 723 810、EP-A 0 634 209、EP-A 0632 214、EP-A 0 654 301、EP-A 0 723 810、US 4,048,096、US 5,185,308和US 5,371,277。这些文献也描述了负载催化剂的制备方法。根据具体实施方式，制备如下负载催化剂，其载体横截面上均匀分布贵金属，并且其具有或多或少的显著的外壳轮廓。
DE-B 21 00 778、US 4,902,823、US 5,250,487、US 5,292,931、US5,808,136、EP 0 807 615、EP 0 916 402、EP 0 997 192 A1、EP 1 323 469 A2和EP 0 987 058公开了在制备乙酸乙烯酯单体中，使用基于热解法二氧化硅的成型体作为催化剂载体。
EP-A 0 464 633公开了一种用于制备乙酸乙烯酯单体的负载催化剂，其基于具有至少一个可通过液体的通道的催化剂载体。特别地，可参考空心圆柱体，其中至少95％的钯、金和/或其化合物位于载体表面至载体表面以下0.5mm的区域内。
这些专利文献也公开了包含金、钯和碱金属化合物的负载催化剂的制备方法。根据具体实施方式，得到如下催化剂，其载体横截面上均匀分布贵金属，并且其具有或多或少的显著的外壳轮廓。
这些催化剂通常是通过用碱性溶液和包含金和钯盐的溶液浸渍载体得到，浸渍过程同时进行或顺次进行，包含或不包含中间干燥过程。随后，洗涤载体以除去存在的任何氯化物。在洗涤步骤之前或之后，沉淀在载体上的不溶性贵金属化合物减少。用该方法获得的催化剂前体被干燥，并用碱金属乙酸盐或碱金属化合物浸渍，所述碱金属化合物在制备乙酸乙烯酯单体的反应条件下，完全或部分地转化成碱金属乙酸盐以活化催化剂。优选的碱金属化合物是钾化合物，尤其是乙酸钾。
催化剂的还原可以在含水相或气相中进行。若在含水相中进行还原，合适的还原剂例如是甲醛或肼。可以利用氢气或氢气/氮气的混合物(95％体积的N2+5％重量的H2)或乙烯进行在气相中的还原。根据EP 0 634 209，利用氢气，在温度40-260℃，优选70-200℃下进行还原。然而，催化剂通常是仅当被碱金属乙酸盐活化后，在制备反应器中被乙烯直接还原。
在制备过程中，首先，缓慢地将催化剂供至反应物。在该起始阶段，催化剂的活性提高，通常仅几天或数周后就达到其最终水平。
文献EP 0 431 478公开了一种在气相中在催化剂上由乙烯、乙酸和氧气制备乙酸乙烯酯的方法，该催化剂包含在载体上的钯和金。该载体包含SiO2/Al2O3混合物，利用C2-C20羧酸的Li、Mg、Al、Zn或Mn盐作为粘合剂压制载体颗粒。
文献EP 0 723 810 A1公开了用于制备乙酸乙烯酯单体的负载催化剂，其包含在载体上作为催化活性组分的钯、金和碱金属乙酸盐，该载体由二氧化硅、硅铝酸盐或氧化铝组成，该载体另外地包含元素周期表IA、IIA、IIIA和IVB族的至少一种元素。
发明内容
本发明提供了一种催化剂，其包含在载体上作为催化活性组分的钯、金和碱金属乙酸盐，其特征在于该载体通过作为掺杂组分的钛、铁、镧、铈、钇和/或钼或它们的氧化物改性。
载体材料可以有利地包含0.1-10重量％的相应掺杂组分。
作为载体材料，可以使用硅铝酸盐，例如来自Südchemie的KA-160；二氧化硅，例如Aerolyst 3045(Degussa)；或二氧化钛，例如Aerolyst 7751(Degussa)。
本发明进一步提供了催化剂的制备方法，其特征在于将载体用至少一种掺杂组分的盐浸渍，煅烧，然后用催化活性组分浸渍；或者将载体材料与掺杂组分的氧化物混合，成型，然后用催化活性组分浸渍。
在本发明的一个实施方式中，至少一种掺杂组分可以与催化活性组分同时施加至载体。
本发明催化剂的优点在于可以降低需要实现已知的时空收率的催化剂中贵金属的比例。
实施例
实施例催化剂A的载体材料包含4％的氧化钇和96％的二氧化硅(Degussa Aerolyst 3045)。活性组分为钯、金和乙酸钾。
对比例催化剂B仅包含施加至作为载体材料的硅铝酸盐(SüdchemieKA-160)的钯、金和乙酸钾的活性组分。
实施例催化剂C中，活性组分钯、金和乙酸钾施加至含4.5％二氧化钛，4.5％氧化铁和91％二氧化硅(Degussa Aerolyst 3045)的载体材料。
实施例催化剂D包含施加至二氧化钛(Degussa Aerolyst 7751)上并用0.3％氧化铈，0.8％氧化铁和0.01％氧化钼改性的活性组分。
实施例催化剂E的载体材料包含1％的氧化钇，0.65％的氧化铁和98.35％的二氧化硅(Degussa Aerolyst 3045)。
实施例催化剂F中，将含3.5％的氧化镧和6％的氧化钼的二氧化硅用作载体材料，并用活性组分钯、金和乙酸钾浸渍，同时还用0.9％的氧化铁浸渍。
对于实施例催化剂G，使用包含1.5％的氧化镧和98.5％的二氧化钛(Degussa Aerolyst 7751)的载体材料，并用活性组分浸渍。
对比例催化剂H包含1％的氧化硼和99％的二氧化硅作为载体材料，加上活性组分钯、金和乙酸钾。
下表报道了在温度155℃，压力7bar，GHSV为3000h-1的条件下以每小时每克钯的乙酸乙烯酯单体的克数计的乙酸乙烯酯单体的收率作为催化剂活性的量度：
  催化剂   收率[g/h·g]
  A   197.4
  B   133.9
  C   198.3
  D   215.5
  E   237.2
  F   216.8
  G   217.1
  H   82.5
                 。

Claims (4)

1.一种催化剂，其包含在载体上作为催化活性组分的钯、金和碱金属乙酸盐，其特征在于所述载体通过钛、铁、镧、铈、钇和/或钼或它们的氧化物改性。
2.如权利要求1所述的催化剂的制备方法，其特征在于将所述载体用至少一种掺杂组分的盐浸渍，煅烧，然后用所述催化活性组分浸渍；或者将所述载体材料与所述掺杂组分的氧化物混合，成型，然后用所述催化活性组分浸渍。
3.根据权利要求2的方法，其特征在于所述掺杂组分与所述催化活性组分同时施加至所述载体。
4.如权利要求1所述的催化剂的用途，其用于制备乙酸乙烯酯单体。
CNA2008101714501A 2007-10-04 2008-09-26 催化剂 Pending CN101402051A (zh)

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DE102007047430A DE102007047430A1 (de) 2007-10-04 2007-10-04 Katalysator
DE102007047430.1 2007-10-04

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US (1) US20090093653A1 (zh)
EP (1) EP2045008A3 (zh)
JP (1) JP2009090283A (zh)
KR (1) KR20090034772A (zh)
CN (1) CN101402051A (zh)
DE (1) DE102007047430A1 (zh)
RU (1) RU2008139191A (zh)
TW (1) TW200934580A (zh)

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DE102004050585A1 (de) * 2004-10-15 2006-04-20 Degussa Ag Mikroreaktor und Verfahren zur Synthese von Vinylacetat-Monomer (VAM) in der Gasphase
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KR20090034772A (ko) 2009-04-08
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