CN1072665C - 不饱和环醚的制备 - Google Patents

不饱和环醚的制备 Download PDF

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CN1072665C
CN1072665C CN96111524A CN96111524A CN1072665C CN 1072665 C CN1072665 C CN 1072665C CN 96111524 A CN96111524 A CN 96111524A CN 96111524 A CN96111524 A CN 96111524A CN 1072665 C CN1072665 C CN 1072665C
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cobalt
cyclic ethers
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J·施罗德尔
T·费泽尔
C·W·雷克尔
K·爱贝尔
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Abstract

从通式Ⅱ的二醇制备通式Ⅰ的不饱和环醚的方法，
式中
Z 表示-(CHR4)q或-(CHR4)q-O-
q 是0，1，2或3
R1，R2，R3和R4表示氢或C1-C4烷基
式中，R1，R2和R3意义同前，在一种被载体支持的含钴催化剂的存在下，所用的钴催化剂含有承载在一种惰性载体上的钴和一种贵金属，以及可选择的还含碱金属和碱土金属盐，钪，钒，铬，锰，铁，镍，铜，锌，锗，锡，铅，锑，铋或它们的混合物，此反应在温度150℃-300℃的液相中进行。

Description

不饱和环醚的制备
本发明涉及一种在液相中在载体支持的含钴催化剂的催化下，从二醇中制备不饱和环醚的方法和涉及新的特别是靠溶胶浸渍而制成的载体支持的含钴催化剂。
DE-A2346943公开了一种在氢气流下从二醇制备不饱和环状化合物的方法。在该方法中所用的催化剂是一种被载体支持的含铜铬催化剂或被载体支持的含铜催化剂和正钨酸或杂多钨酸的混合物。转化率和产量不令人满意的。
JP01/287079公开了一种在600℃时由氢气还原的含钴催化剂下的分别从1,4-丁二醇和1,5-戊二醇制备二氢呋喃和二氢吡喃的方法。
US-A2993910公开了一种在300℃到450℃范围内由氢气还原的钴催化剂存在下，从1,4-丁二醇制备二氢呋喃的方法。
本发明的目的是克服以上缺陷。相应地，我们发现了一种新的改进的以通用分子式Ⅱ的二醇制备通用分子式Ⅰ的不饱和环醚的方法。
Figure C9611152400041
式中Z    表示-(CHR4)q或-(CHR4)q-O-q    为0,1,2或3R1,R2、R3和R4表示氢原子或C1-C4烷基
Figure C9611152400042
式中，Z、R1、R2和R3意义同前，在一种被载体支持的含钴催化剂的存在下，在此，所用的钴催化剂含有承载在一种惰性载体上的钴和一种贵金属、重量比0.5∶1-70000∶1，该贵金属从铂，钯，铑，铱，钌，锇，铼或它们的混合物中选择，以及可选择地还含有碱金属和碱土金属盐，钪，钒，铬，锰，铁，镍，铜，锌，锗，锡，铅，锑，铋，或它们的混合物，此反应在温度150℃-300℃内液相中进行和特别地依靠溶胶浸渍制备的新的被载体支持的含钴催化剂的存在。
本发明方法可如下操作：
二醇Ⅱ通常是在1-20wt％，优选为2-10wt％的被载体支持的含钴催化剂存在下，在150-300℃，优选160-240℃温度范围下进行反应而生成的。所得的混合物可从不饱和环醚和反应中的水中间歇地或优选连续地蒸馏出。可供选择地，在反应中形成的不饱和环醚可在反应条件下为惰性的气体和氮气或氩气汽提。在连续操作方式中，依靠加入新的二醇Ⅱ可保持反应器中的液面高度。为了降低饱和环醚的含量，该饱和环醚不容易与不饱和环醚分离，向反应器中计量加入0.05-1wt％，优选0.1-0.3wt％的碱金属化合物和/或碱土金属化合物，例如以氢氧化物或碳酸盐的形式。
适宜的被载体支持的含钴催化剂是在一个有孔载体上的钴氧化物或钴金属粒子。它含有一种或多种稀有金属，这些金属可从铂，钯，铑，铱，钌，锇，铼或它们的混合物中选择，优选铂，钯，铼或它们的混合物，更优选铂，钯或它们的混合物，可以选择地还含有碱金属盐或碱土金属盐，钪，钒，铬，锰，铁，镍，铜，锌，锗，锡，铅，锑，铋或它们的混合物(化合物A)，其用量可为总金属存在量的0.01-10wt％，优选0.1-5wt％，更优选0.5-3wt％，优选锂，钾，钠，钙，锶，钡，锰，铁，镍，铜，锌，锑或它们的混合物，更优选钾，钠，锰，铁，镍，铜，锌或它们的混合物。
被载体支持的催化剂中钴或氧化钴的百分含量通常为1-70wt％，优选5-50wt％，更优选10-40wt％。
为增加催化剂活性，可加入一种或多种从下组元素中选择的元素：铂，钯，铑，铱，钌，锇，铼或它们的混合物，优选铂，钯，铼或它们的混合物，更优选铂，钯或它们的混合物。
这些元素的重量为0.001-2wt％，优选0.005-1wt％，更优选0.01-0.5wt％。
被载体支持的催化剂中通常钴和贵金属的重量比为0.5∶1-70,000∶1，优选5∶1-10,000∶1，更优选20∶1-4,000∶1。
适宜的载体是惰性载体。如SiO2,Al2O3,TiO2,ZrO2，各种类型的沸石如孔隙细的如A-型沸石，孔隙一般的如ZSM-5,ZSM-11，镁碱沸石，孔隙组的如八面沸石，β-沸石，发光沸石，硅铝钾沸石，热液处理制成的磷酸盐如AlPO和SAPO，活性炭或碱土金属氧化物，优选SiO2,ZrO2和沸石，更优选SiO2。
被载体支持的催化剂的表面积(BET)通常为1-600m2/g，优选10-500m2/g，更优选50-400m2。
被载体支持的催化剂的孔隙率通常为0.01-1.5ml/g，优选0.1-1.2ml/g，更优选0.2-1ml/g。
已知被载体支持的催化剂的制备方法，一种有效的方法是用一种可溶性钴化合物(如亚硝酸盐，硝酸盐，亚硫酸盐，硫酸盐，碳酸盐，氢氧化物，如此以外，还有羧酸盐，卤化物，石盐，卤酸盐)或同时或依次用类似的可溶性化合物A(如亚硝酸盐，硝酸盐，亚硫酸盐，硫酸盐，碳酸盐，氢氧化物，羧酸盐，卤化物，石盐，卤酸盐)浸渍多孔载体材料，然后是阴离子的热分解形成氧化物。另一种可能性包括把一种钴化合物和载体材料(干燥的或以悬浮液或特别是依靠喷洒干燥)混合，可选择地同时与化合物A混合，材料的压制(如依靠捏合，可选择地添加适宜的成形剂)，挤出成形和干燥，然后在200-1300℃，优选300℃-1000℃，更优选400-800℃的温度范围内煅烧。
依靠浸渍，喷洒或使用一些其它技术，成份A可被交替的多次使用。
依靠利用一种可溶性化合物(亚硝酸盐，硝酸盐，亚硫酸盐，硫酸盐，亚磷酸盐，磷酸盐，碳酸盐，氢氧化物，除此以外，还有羧酸盐，卤化物，石盐，卤酸盐)或作为酸浸渍来施加一种或多种贵金属组份。特别优选的是以溶胶形式应用一种或几种这样的金属。
化合物Ⅰ和Ⅱ中，取代基R1,R2,R3,R4；连接组分Z；代码q有如下含义。
R1,R2,R3和R4独立地表示-氢原子，-C1-C4烷基，如甲基，乙基，n-丙基，异丙基、n-丁基、异丁基、仲丁基和叔丁基，优选C1-C3烷基如甲基，乙基，n-丙基和异丙基，更优选甲基和乙基，Z表示--(CHR4)q或-(CHR4)q-O,q为
-0,1,2或3，优选0或1，更优选1。
适宜的二醇Ⅱ如1,4-丁二醇，1,5-戊二醇，1,6-己二醇或二甘醇。
适宜的不饱和环醚如3,4-二氢-2H-吡喃。2,3-二氢呋喃和1,4-二氧杂环己烷，优选3,4-二氢-2H-吡喃。
不饱和环醚Ⅰ是对乙醇有价值的保护基团。
实例：
催化剂F-H制备。
向555ml由291.3g Co(NO3)26H2O和一种金属硝酸盐组成的水溶液中加入300g SiO2粉末(水吸收1.85ml/g)搅拌约2小时，在120℃下干燥16小时，在500℃下煅烧2小时。
置这种混合物(重量如表2所示)和一旋转台上，与一种贵金属溶胶275ml(每升0.6g)一起喷雾2小时，然后干燥，在500℃下煅烧1小时，这种溶胶是在700ml水中的一种贵金属盐与5g聚乙烯基吡咯烷酮和300ml乙醇混合，并回流4小时而制成的。
表1列出有关此催化剂制备和性质的更具体的细节。
表1
催化剂 硝酸金属盐(g) 贵金属盐(g) 含钴SiO2的重量(g) 贵金属溶胶体积(ml) 贵金属的含量[wt％] 表面积BET[m2/g]
    F     0.98NaNO3  1.46Pt(NO3)2     330.1     275     0.05     231
    G     1.11KNO3  1.46Pt(NO3)2     340.5     284     0.05     198
    H  11.4Cu(NO3)2·3H2O  1.46Pt(NO3)2     308     257     0.05     350
对比催化剂X(在US-A2992910中介绍)
向740ml含有388.4g Co(NO3)2·6H2O的水溶液中加入400g SiO2粉末(水吸收1.85ml/g)搅拌约2小时，在120℃下干燥16小时，在500℃下煅烧2小时(表面积(BET):230m2/g)。
置1.4升1,5-戊二醇和一定量的催化剂F-H中的一种(如表2所示)于一容器中，搅拌加热至允许加热范围的最低限度。所形成的3,4-二氢-2H-吡喃/水混合物通过蒸馏不断移出。在表3所示的时间段内不断的计量1,5-戊二醇总量(如表2所示)，随后相分离的馏出物3,4-二氢-2H-吡喃的用量和说明如表2所示。
表2
实施例 催化剂[g] 温度[℃] 时间[h]  1,5-戊二醇的总重量(g) 3,4-二氢-2H-吡喃的产率(g/％) 纯度[wt％] 四氢吡喃的含量[wt％]
    6     45F  185-225  200     11,109     8613/98     95     1.8
    7     45G  185-235  200     10,830     8361/98     96     1.3
    8     45H  160-215  200    10,008     7671/97     95     1.4
 V1**     45X  185-240  200     8,090     5897/92     91     6.7
**对比例(如US-A2993910所介绍)。

Claims (5)

1．由通式Ⅱ的二醇制备通式Ⅰ的不饱和环醚的方法，
Figure C9611152400021
式中Z表示-(CHR4)q或-(CHR4)q-O-,q为0,1,2或3，R1、R2、R3和R4表示氢原子或C1-C4烷基，式中，Z、R1、R2和R3定义同前，在一种被载体支持的含钴催化剂的存在下，在此所用的含钴催化剂在反应开始前未还原并含有承载在一种惰性载体上的钴和一种贵金属，重量比0.5∶1-70000∶1，该贵金属从铂，钯，铑，铱，钌，锇，铼或它们的混合物中选择，其中该贵金属是以溶胶形式应用到载体支持的含钴催化剂上的，以及可选择地还含有碱金属和碱土金属盐，钪，钒，铬，锰，铁，镍，铜，锌，锗，锡，铅，锑，铋，或它们的混合物，此反应在温度150℃-300℃内液相中进行。
2．如权利要求1的不饱和环醚Ⅰ的制备方法，其中所用的被载体支持的含钴催化剂含有1-70wt％的钴和0.001-2wt％的一种或多种贵金属。
3．如权利要求1或2的不饱和环醚Ⅰ的制备方法，其中所用的被载体支持的含钴催化剂含有基于金属总存在量的0.01-10wt％的碱金属盐或碱土金属盐或其混合物。
4．如权利要求1的不饱和环醚Ⅰ的制备方法，其中在反应中加入基于Ⅰ的0.05-1wt％的碱金属盐或碱土金属盐或其混合物。
5．如权利要求1的不饱和环醚Ⅰ的制备方法，其中所用的被载体支持的含钴催化剂含有基于金属总存在量的0.01-10wt％的钪，钒，铬，锰，铁，镍，铜，锌，锗，锡，铅，锑，铋或它们的混合物。
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WO1997011779A1 (fr) * 1995-09-26 1997-04-03 Kabushiki Kaisha Kobe Seiko Sho Agent d'elimination de gaz toxiques
DE19803368A1 (de) * 1998-01-29 1999-08-05 Basf Ag Verbessertes Verfahren zur Herstellung von ungesättigten cyclischen Ethern
JP4020410B2 (ja) * 2001-12-28 2007-12-12 大研化学工業株式会社 炭素物質製造用触媒
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