CN1048652C - 多金属氧化物组合物 - Google Patents

多金属氧化物组合物 Download PDF

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CN1048652C
CN1048652C CN93107619A CN93107619A CN1048652C CN 1048652 C CN1048652 C CN 1048652C CN 93107619 A CN93107619 A CN 93107619A CN 93107619 A CN93107619 A CN 93107619A CN 1048652 C CN1048652 C CN 1048652C
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H·P·努曼
H·马坦
H·彼得森
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Abstract

本申请公开了式Ⅰ所示的多金属氧化物的组合物：[Xa 1Xb 2Ox]p[Xc 3Xd 4Xe 5Xf 6Xg 7Hh 2Oy]p，式中X1是铋、碲、锑、锡和/或铜，X2是钼和或/钨，X3是碱金属、铊和/或钐，X4是碱土金属、镍、钴、铜、锰、锌、锡、镉和/或汞，X5是铁、铬、铈和/或钒，X6是磷、砷、硼和/或锑，X7是稀土金属、钛、锆、铌、钽、铼、钌、铑、银、金、铝、镓、铟、硅、锗、铅、钍和/或铀，该组合物包含化学组成为Xa 1Xb 2Ox的三维区域，这些区域由于其化学组成不同于其局部环境，而与其局部环境划界，而且其最大直径是1-25微米。

Description

多金属氧化物组合物
本发明涉及式I的组合物：
[Xa 1Xb 2Ox]p[Xc 3Xd 4Xe 5Xf 6Xg 7Xh 2Oy]q           (I)式中
X1是铋、碲、锑、锡和/或铜，
X2是钼和/或钨，
X3是碱金属、铊和/或钐，
X4是碱土金属、镍、钴、铜、锰、锌、锡、镉和/或汞，
X5是铁、铬、铈和/或钒，
X6是磷、砷、硼和/或锑，
X7是希土金属、钛、锆、铌、钽、铼、钌、铑、银、金、铝、镓、铟、硅、锗、铅、钍和/或铀，
a是0.01-8，
b是0.1-30，
c是0-4，
d是0-20，
e是0-20，
f是0-6，
g是0-15，
h是8-16，x和y是由式I中除氧以外的元素的价数和出现的次数所决定的数目，p和q是数目，其比例p/q为0.1-10，该组合物包含化学组成为Xa 1Xb 2Ox的三维区域，这些区域由于其化学组成不同于其局部环境，而与其局部环境划界，并且其最大直径(通过该区域重心并连接该区域表面(界面)上两点的最长的直线)是1-25微米，较好是1-20微米，更好是5-15微米。
本发明也涉及这种组合物的制备方法及其用途(例如用散能X射线分析法(EDXA)，如用JEOL JCXA/733型电子束微探针进行最大直径的实验测定)。
式I的组合物已公开于EP-A 835。
关于这种组合物的制备方法，EP-A 835推荐首先在没有组合物I的其它成分的条件下制备混合氧化物Xa 1Xb 2Ox，然后将这种氧化物与组合物I的其它成分源混合，再干燥和焙烧该混合物。
详细地说，可从含有元素X1和X2的可溶性化合物的溶液用适当方式进行沉淀来制备Xa 1Xb 2Ox，沉淀产物经干燥及焙烧后在球磨机中进行碾磨，然后将粉末与含有组合物I的其它成分源的含水混合物混合，再将该混合物干燥并焙烧，或将其它成分源加入到含有由适当沉淀方法所制得的产物中，然后再将所得的混合物进行干燥和焙烧。
EP-A 835还公开了使用式I的组合物作为有机化合物气相催化氧化的催化剂。然而，EP-A 835中所公开的式I组合物用于有机化合物的气相催化氧化时其缺点是活性和选择性不能令人满意。
DE-C 33 38 380公开了式II的催化活性组合物：
Bia′Wb′Fec′Mod′Y1 e′Y2 f′Y3 g′Y4 h′Ox′  (II)式中：
Y1是镍和/或钴，
Y2是铊、碱金属和/或碱土金属，
Y3是磷、砷、硼、锑、锡、铈、铅和/或铌，
Y4是硅、铝、锆和/或钛，
d′是12，
a′是0.5-5，b′是0.5-4，而a′/b′＝0.1-4，
c′是0.2-5，
e′是3-10，
f′是0.02-2，
g′是0-5，
h′是0-10，
x′是由式II中除氧以外的元素的价数和出现的次数所决定的数
   目，这种组合物由如下方法制得：先在水介质中将铋化合物和钨化合物混合，干燥该含水混合物，在600-900℃焙烧所得的组合物，随后将焙烧好的组合物粉碎，使其粒度小于152微米，将得到的粉末与组合物II的其它成分源的水溶液混合，将所得到的混合物蒸发，然后将残留物成形并焙烧。
DE-C33 38 380也公开了组合物II适合于用作气相催化氧化制备不饱和醛的催化剂。
但是，DE-C 33 380中公开的组合物II在用于通过气相催化氧化法制备不饱和醛时其缺点是活性和选择性不能令人满意。
本发明的一个目的是提供式I的组合物，该组合物作为有机化合物气相催化氧化的催化剂，尤其是作为通过气相催化氧化法制备不饱和醛和不饱和羧酸的催化剂，具有提高的活性和选择性。
我们已经发现通过本文开头所定义的组合物已经达到了这一目的。
较好的组合物I是含有铁、铬、铈、钒中至少一种元素和另一种希土金属的那些组合物，其化学计量系数不等于0，较好是≥0.01。
按照本发明特别好的组合物I是其中X1是铋的那些组合物。而这些组合物中，较好的是式III所示的那些组合物：
[Bia″Z2 b″Ox″]p″[Z2 12Z3 c″Z4 d″Fee″Z5 f″Z6 g″Z7 h″Oy″]q″    (III)式中：
Z2是钼和/或钨，
Z3是镍和/或钴，
Z4是铊、碱金属和/或碱土金属，
Z5是磷、砷、硼、锑、锡、铈和/或铅，
Z6是硅、铝、钛和/锆，
Z7是铜、银和/或金，
a″是0.1-1，
b″是0.2-2，
c″是3-10，
d″是0.02-2，
e″是0.01-5，较好是0.1-3，
f″是0-5，
g″是0-10，
h″是0-1，x″和y″是由式III中除氧以外的元素的价数和出现的次数所决定的数目，p″和q″是数目，其比例p″/q″是0.1-5，较好是0.5-2，特别好的组合物III是其中Zb″ 2是(钨)b″，且Z12 2是(钼)12的那些组合物。
更好的是本发明的组合物I(组合物III)的所有[Xa 1Xb 2Ox]p([Bia″Zb″ 2Ox″]p″)中至少有50％摩尔(较好100％摩尔)是呈化学组成为Xa 1Xb 2Ox(Bia″Zb″ 2Ox″)的三维区域，这些区域由于其化学组成不同于其局部环境而与其局部环境划界，并且其最大直径部分地在1-25微米(较好1-20微米，更好5-15微米)范围。
其值在1-25微米(较好1-20微米，更好5-15微米)范围的各种最大直径数目的百分率(以所存在的区域总数为基准)越高，本发明的组合物就越好。
较好是最大直径至少有一半是在1-25微米范围(更好是在1-20微米范围，特别好是5-15微米范围)，而特别好的是最大直径全部都在这个范围。
按照本发明的组合物I可用特别适合的方法获得，例如，用本身已知的方法(参见：EP-A 835和DE-C 33 38 380)，首先制备焙烧的混合氧化物Xa 1Xb 2Ox(例如将X1的水溶性盐，如硝酸盐、碳酸盐、氢氧化物或乙酸盐与X2的酸或其铵盐在水中混合，干燥(较好是喷雾干燥)该混合物并焙烧该干燥后的组合物)，粉碎该氧化(例如在球磨机中或通过喷射碾磨)，从所得到的粉末中分离出最大粒径在上述对组合物I所规定的最大直径范围的颗粒级分，一般包含基本上球形颗粒，可用已知的分级方法(例如湿筛或干筛)，以及较好是将一这颗粒级分与较好为0.1-3％重量(以分离出的颗粒级分为基准计)的SiO2细粉(通常基本上为球形的SiO2颗粒的数均最大粒径有利地是10-50纳米)混合，得到起始组合物1。
首先制备的焙烧混合氧化物的化学计量关系式为BiZ2O6、Bi2Z2 2O9和/或Bi2Z3 2O12是有利的，其中以Bi2Z2 2O6为较好，尤其是当Z2是钨时。
焙烧温度为400-900℃较合适，较好是600-900℃。焙烧通常在空气流中进行。焙烧时间通常为几小时。
按照本发明所要求的组合物的其它成分的紧密的，较好是细分的干混合物可用本身已知的方法(参见EP-A 835和DE-C 33 38380)从适当的原料来原制备，(例如将诸如卤化物、硝酸盐、乙酸盐、碳酸盐或氢氧化物合并于水溶液中，然后将该水溶液喷雾干燥，或将水不溶的盐，例如氧化物，悬浮于水介质中，随后将该悬浮液喷雾干燥)。该干混合物本文中称为起始组合物2。唯一的主要特点是起始组合物2的成分或为现成的氧化物，或为通过加热可转变成氧化物的化合物，如有必要可在氧气存在下加热。
随后将起始组合物1和起始组合物2按所要求的混合比例互相混合，最好加压压实，然后焙烧(通常在空气流中)数小时，适宜的温度是400-600℃。在一个较差的优选实施方案中，最初所形成的焙烧混合氧化物Xa 1Xb 2Ox可以和按照本发明所要求的组合物的其余成分源也在液体介质中，较好在水介质中充分混合。随后将该混合物干燥以得到密实的干混合物，然后按上述方法进行焙烧，呈成形或重新成形的形式。其余成分源在这种液体介质中可呈溶解和/或悬浮形式，而起始形成的焙烧过的混合氧化物必须基本上不溶于这种液体介质中，即必须呈悬浮形式。
在无载体催化剂的情况下，压实最好能直接得到所需催化剂的几何形状，较好是外径和长为2-10毫米、壁厚为1-3毫米的空心园柱。但是，本发明的活性组合物I也可以在焙烧之后再粉碎，并涂布在惰性载体上以制备有载体的催化剂。涂布也可以在最终焙烧之前进行。在这种情况下，较好是按EP-B 293 859所述方法进行涂布。当然，本发明的组合物也可以以粉末形式使用。
本发明的组合物特别适于用作有机化合物气相催化氧化的高活性和选择性的催化剂，例如低级(C3-C6)链烷烃、链烷醇、链烷醛、链烯烃和链烯醛(alkenals)，经催化氧化得到烯键不饱和醛和/或羧酸，和相应的腈(氨氧化，主要是丙烯经氨氧化得到丙烯腈和2-甲基丙烯或叔丁醇经氨氧化得到甲基丙烯腈)。但是，本发明的组合物也适用于有机化合物的氧化脱氢。
本发明的组合物，尤其是组合物III，特别适用于通过气相催化氧化制备丙烯醛、丙烯酸、甲基丙烯醛和甲基丙烯酸，所用的起始化合物最好是丙烯、2-甲基丙烯或叔丁醇。本发明的组合物作为制备丙烯醛和甲基丙烯醛的催化剂特别有利。
按本身已知的方法，所用的氧化剂是氧，用惰性气体稀释较好。适用的惰性气体的例子有N2和蒸汽。反应温度和压力是本技术中的技术人员所知道的。
实例
a)起始组合物1的制备
在50千克Bi(NO3)3的稀硝酸溶液(11％重量的Bi，6.4％重量的HNO3，两种情况均以溶液为基准计)中加入6.7千克H2WO4，然后将该混合物在50℃搅拌1小时。
所生成的悬浮液喷雾干燥并在750℃焙烧2小时。这样制得的焙烧后的混合氧化物(Bi2W2O9，带有少量WO3杂质)经碾磨后按下述最大粒径(d)级分分类：
VF1：0.1微米＜d≤1微米，
F2：1微米＜d≤5微米，
F3：5微米＜d≤10微米，
F4：10微米＜d≤15微米，
F5：15微米＜d≤20微米，
F6：20微米＜d≤25微米，
VF7：30微米＜d≤50微米，
VF8：90微米＜d≤120微米，
然后将各级分分别与其重量1％的SiO2细粉(数均最大直径为28纳米)混合。
b)起始组合物2的制备
85.5千克钼酸铵在240升水中的溶液与含有溶于80升水中的11.9千克硝酸钴(II)和5.7千克硝酸铁(III)的溶液、7.8千克含20％重量胶体SiO2的含水混合物及377克48％(重量)KOH的水溶液混合。随后将该混合物搅拌3小时，并将生成的水悬浮液喷雾干燥。
c)组合物I的制备
含SiO2细粉的VF1至VF8的各级分分别与满足如下组成的组合物I所需量的起始组合物2混合，
[Bi2W2O9]0.5Mo12Co5Fe2.5Si1.6K0.05Ox，将该混合物压制成长5毫米，外径5毫米、壁厚1.5毫米的空心园柱，然后将这些园柱在470℃于空气流中焙烧6小时。用JEOL JCXA/733型电子束微探针对所制得的组合物I进行散能X射线分析表明所得到的组合物I含有化学组成为Bi2W2O9的三维区域，这些区域由于其化学组成不同于其局部环境，而与其局部环境划界，而且其最大直径基本上相当于制备它们时所用的颗粒级分VF1至VF8的最大粒径。
d)丙烯气相催化氧化
使组成为5％体积丙烯、9％体积氧气和86％体积氮气的气体混合物以每小时2400升(S.T.P.)的速率通过在每种情况下装有1200毫升由C)制得的各个组合物I的反应管(V2A，壁厚为2毫米、内径为25毫米，盐浴温控)。
在所有情况下均对盐浴温度加以调节，以便使一次通过的丙烯转化率约为98％摩尔。
在这方面所需的盐浴温度(所用组合物I活性的度量)是用于制备所用的组合物I的呈特定起始组合物1的级分VF1至VF8的函数，所得到的选择性(以所形成的丙烯醛和丙烯酸总量为基准计)示于下表中。表
  丙烯转化率(摩尔％)     盐浴温度[℃]    选择性[摩尔％]
 VF1     98     350     95.8
 F2     97.9     338     96.8
 F3     98.1     330     96.3
 F4     97.9     322     95.7
 F5     98.0     322     95.0
 F6     97.9     337     94.3
 VF7     98.0     355     93.8
 VF8     98.0     382     90.8
可以看出，无论是活性还是选择性都通过了宣布的最大值。如果把这两个参数合并起来考虑，可以发现特别有利的组合物I是其中存在于该组合物中组成为Bi2W2O9的化学界定区域的最大直径在1至25(包括1和25)微米范围的那些组合物。
在操作500小时之后，在各种情况所用的组合物I再次进行散能X射线分析。结果表明组成为Bi2W2O9的化学界定区域的最大直径基本不变。

Claims (9)

1.一种如式I所示的组合物：
[Xa 1Xb 2Or]p[Xc 3Xd 4Xe 5Xf 6Xg 7Xh 2Oy]q           (I)式中
X1是铋、碲、锑、锡和/或铜，
X2是钼和/或钨，
X3是碱金属、铊和/或钐，
X4是碱土金属、镍、钴、铜、锰、锌、锡、镉和/或汞，
X5是铁、铬、铈和/或钒，
X6是磷、砷、硼和/或锑，
X7是稀土金属、钛、锆、铌、钽、铼、钌、铑、银、金、铝、镓、铟、硅、锗、铅、钍和/或铀，
a是0.01-8，
b是0.1-30，
c是0-4，
d是0-20，
e是0-20，
f是0-6，
g是0-15，
h是8-16，x和y是由式I中除氧以外的元素的价数和出现的次数所决定的数目，p和q是数目，其比例p/q为0.1-10，该组合物包含化学组成为Xa 1Xb 2Ox的三维区域，这些区域由于其化学组成不同于其局部环境，而与其局部环境划界，而且其最大直径是1-25微米。
2.如权利要求1所提出的组合物，含有化学组成为Xa 1Xb 2Ox的呈三维区域形式的所有[Xa 1Xb 2Ox]p，这些区域由于其化学组成不同于其局部环境而与其局部环境划界。
3.如权利要求1所提出的组合物，其中最大直径在1-25微米范围、组成为Xa 1Xb 2Ox的局部限定区域的数目至少占组成为Xa 1Xb 2Ox的局部限定区域总数的50％。
4.如权利要求1所提出的组合物，其中组成为Xa 1Xb 2Ox的所有局部限定区域的最大直径在1-25微米范围。
5.如权利要求1所提出的组合物，其中X1是铋。
6.如权利要求1所提出的组合物，其中Xa 1Xb 2Ox是Bi2W2O9。
7.制备权利要求1所提出的组合物的方法，该方法包括首先从焙烧的混合氧化物Xa 1Xb 2Ox制备最大粒径为1-25微米范围的微细粉末，作为起始组合物1，再从所需的组合物I的其它成分源制备微细干燥的起始组合物2，起始组合物2所含的这些成分源处于紧密的混合物中并且呈已氧化和/或可通过焙烧而转化成氧化的形式，按所要求的混合比将起始组合物1和起始组合物2混合，然后将该混合物焙烧。
8.使用权利要求1所提出的组合物作为有机化合物气相催化氧化催化剂的方法。
9.由含有3至6个碳原子的链烷烃、链烷醇、链烯烃和/或链烯醛气相催化氧化制备含有相同数目碳原子的α，β-单烯键不饱和醛和/或羧酸的方法，该方法包含用权利要求1所提出的组合物作为催化剂。
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CZ284491B6 (cs) 1998-12-16
JPH0671177A (ja) 1994-03-15
EP0575897B1 (de) 1996-03-06
CA2096081A1 (en) 1993-12-26
DE59301767D1 (de) 1996-04-11
US5364825A (en) 1994-11-15
CZ105393A3 (en) 1994-02-16
DE4220859A1 (de) 1994-01-05
CN1087290A (zh) 1994-06-01
EP0575897A1 (de) 1993-12-29
US5449821A (en) 1995-09-12
ES2083799T3 (es) 1996-04-16

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