CN1170803C - 环状α,β-不饱和酮的制备 - Google Patents
环状α,β-不饱和酮的制备 Download PDFInfo
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 22
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- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
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- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229960001296 zinc oxide Drugs 0.000 description 1
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
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Abstract
一种在催化剂存在下,在气相中,于升高的温度下,通过使与结构式I一致的环酮的脱氢化作用,而制备结构式II的环状α,β-不饱和酮的方法,式中,n表示1-10的整数,并且所述酮可以被取代;其中,反应是在没有氧或每摩尔化合物I低于0.5摩尔氧的存在下,在250-600℃的温度下,并且利用表面积(BET)大于0.5m2/g的催化剂进行的。
Description
本发明涉及一种:在表面积(BET)至少为0.5m2/g的催化剂存在下,在没有氧或每摩尔原料酮低于0.5摩尔氧的存在下,于升高的温度,通过环酮的脱氢化作用制备环状α,β-不饱和酮的方法。
通过在532-581℃的真空非催化气相热解,由相应的饱和酮气相制备环状α,β-不饱和酮,例如环戊烯酮,由F.Delles,在《美国化学会志》
J.Am.Chem.Soc.(91,27(1969)中进行了描述。然而,由于降解反应占主导地位,因此,环戊酮能够获得的产率和选择性很低。
另外,US 3364264还描述了在每摩尔酮至少一摩尔氧存在下,在气相中,在氧化催化剂上使酮转化至烯酮。由于没有对总的转化率和副产物进行说明,因此,实施例没有揭示所达到的产率和选择性。除可以达到的实际产率以外,该方法还有如下主要缺点:由于在爆炸极限附近或之内,需要计量大量的氧,因此,当形成大规模操作的尺寸时,需要特别的安全措施。
因此,本发明的目的是提供一种方法,借助该方法,利用工业简单的方式,能够在气相中连续地合成高产率的环状α,β-不饱和酮,而不会有任何不可控制的分解的危险。
在本发明中,在催化剂存在下,在气相中,于升高的温度下,通过使与结构式I一致的环酮的脱氢化作用,通过结构式II的环状α,β-不饱和酮的制备方法,特别是连续制备方法,实现了本发明的目的,
式中,n表示1-10的整数,并且所述酮可以被取代;其中,反应是在没有氧或每摩尔化合物I低于0.5摩尔氧的存在下,在250-600℃的温度下,并且利用表面积(BET)大于0.5m2/g的催化剂存在下进行的。
结构式II和I的环状烯酮和酮,如果需要可以在环碳原子上带有取代基。所述取代基例如为烷基或芳基。优选的原料酮为环巳酮,和特别是环戊酮。
优选的是,在没有氧的存在下进行所述反应,但是,如果需要,反应可以在特定量的氧的存在下进行,例如每摩尔酮至多0.2摩尔氧。
在本发明方法中使用的反应温度通常为250℃-600℃,优选为300℃-575℃,特别优选为350℃-550℃。反应压力通常为0.1-10巴,优选为0.5-6巴,更优选为0.9-3巴。
环酮的转化可以在有或没有载气的情况下进行。如果使用载气的话,惰性气体如甲烷,氮和氩气将是合适的。
如果计量加入氧的话,那么,可以通过计量加入空气或空气与惰性气体的混合物,或者计量加入纯氧或氧与惰性气体的混合物来完成。在该操作期间,氧与酮的摩尔比通常不应超过0.1∶1。优选的是,所述摩尔比在0.01∶1以下,更优选的是,在没有氧的存在下进行所述方法。
本发明的方法可以在水的存在下进行。所用的水量通常并不关键,但优选的是,每kg环酮0.01-1kg,更优选的是0.05-0.2kg。添加水通常将使催化剂连续开工时间延长。
合适的催化剂是:理论上,在反应条件下不会发生改变且表面积(BET)大于0.5m2/g的所有固体。优选催化剂的表面积大于1m2/g。理论上,对于能够利用的表面积没有上限,但出于实际的考虑,表面积(BET)通常不超过2000m2/g。
因此,在本发明中使用的催化剂的表面积(BET)通常为0.5-2000,优选为1-500,更优选为2-200m2/g。
特别合适的催化剂组合物是氧化物材料。这些氧化物材料主要包含如下的催化剂,所述催化剂含有第2族至第14族元素的氧化物或由其组成。
催化剂的例子是:氧化镁,氧化钛(IV),氧化锆(IV),氧化铬(III),氧化钴,氧化铜,氧化锌,氧化铝和二氧化硅。
所述氧化可以是均一的或混合的。当一起进行沉淀时,不同氧化物可以形成均匀的混合氧化物,或者它们可以以机械生产的掺混物形式存在。
具有大表面积的催化活性的基料的其它例子是活性炭和氮化硅。
具有大表面积的上述催化材料可以包含:例如0.01-5wt%第1族、第15族和第16族元素的化合物,这些元素例如是Na,K,P或S,通常为其氧化物形式。
最后,特别是在所述氧化物原料的情况下,另外还可以应用金属组份,优选同样是呈氧化物形式的第7族至第12族元素。作为其例子,可以提及的是:铼,钌,钴,铑,镍,钯,铂,铜和银。
具体地说,例如,下列催化剂将是合适的:
CuO、AgO、PdO、NiO、Mn2O3或Re2O7/ZnO、CaO、BaO、SiO2或Al2O3。
例如,通过浸渍和煅烧或通过使氢氧化物或碳酸盐沉淀然后进行煅烧,用已知的方法完成这些催化剂的制备,例如,如Charles N.Satterfield在
工业实践中的多相催化剂(第2版,New York,McGraw-Hill)所述。
本发明的方法可以在固定催化剂或搅拌催化剂上进行。合适的反应器类型的例子是固定床反应器、流化床反应器和提升管反应器。
当催化剂活性,例如由于有机物沉积而下降时,如果催化剂是无机性质的话,通常,可以借助在空气中,例如在400-500℃燃烧掉沉积物,而使催化剂充分再生。
转化可以用直接通过来完成,然后对产物的混合物进行提纯并回用任何未转化的离析物,或在提纯之前将反应产物回用至反应器中,以便增加转化率。
环烯酮如环戊烯酮或环己烯酮是用于制备药物或农药的重要中间体。
下面将参考如下实施例阐明本发明的方法,然而,这些实施例并不构成对本发明的限定。在实施例中的百分数由气相色谱分析来确定。
实施例1
向装有外部电加热装置的石英管中填充约100ml ZnO(表面积(BET)15m2/g;3×5mm挤出物)并在该催化剂挤出物上面放置大约100ml玻璃环以形成蒸发区。通过电加热将该反应器加热至希望的反应温度并将气体速率设置在每小时20升(STP)氮气。以滴流方式,引入约20ml/h的环戊酮。借助水冷对气体流出物进行冷凝,然后对收集的产物进行气相色谱分析。表1给出了反应温度和所得流出物的组分(wt%)。
实施例2-7
如表1所述,利用其它的催化剂重复实施例1,给出所述的结果。在实施例5中,除20L/h(STP)氮气以外,还计量加入4L/h(STP)空气。在反应之前,于500℃,用氧对实施例5中使用的铜环进行处理。在实施例7中,使用环戊酮,其包含5%的水。
表1
实施例 | 催化剂 | 温度 | 环戊酮 | 环戊烯酮 |
1 | ZnO,表面积(BET)15m2/g | 400450500 | 427767 | 7.11629 |
2 | CuO(20%)/ZnO(80%),表面积(BET)15m2/g | 350400450500 | 66616657 | 6.225.326.932.5 |
3 | CuO(17.5%)/SiO2,表面积(BET)29m2/g | 350400450500 | 70686663 | 4.810.42126 |
4 | CaO(44%)/ZnO(56%),表面积(BET)15m2/g | 400450500 | 766856 | 112839 |
5 | Cu环,表面积(BET)1m2/g | 450500 | 96.792.2 | 2.76.6 |
6 | CuO(10%)/活性炭,表面积(BET)1000m2/g | 400450500 | 90.483.472.8 | 3.57.618.9 |
7 | ZnO,表面积(BET)15m2/g | 450 | 89 | 10.5 |
8 | Pd(9.5%)/Pt(0.5%)/ZrO2,表面积(BET)70m2/g | 400 | 79 | 8.5 |
9 | Fe2O3(77%)/K2O(12.5)/WO3(3.8%)/Ce2O3(4.7%)/CaO(2%)/,表面积(BET)3.5m2/g | 400 | 93.7 | 3.1 |
实施例10
以实施例1中所述的方式,在500℃,在100ml ZnO上使环戊酮进行转化。在约1升/小时供料速率下连续运行约48小时之后,发现流出物包含85.1wt%环戊酮和14.5wt%环戊烯酮。在40厘米的填充柱中于101 3毫巴下对收集的流出物进行蒸馏。结果得到了纯度为约99.6%的环戊烯酮。
实施例11
如实施例1所述,在400℃,在ZnO上使环戊酮进行反应。在0.5小时的启动阶段之后,收集反应产物约20小时。产物的组分如下:环戊酮95.1wt%,环戊烯酮4.2wt%。然后,回用该产物的混合物。结果发现,流出物包含92.5wt%环戊酮和6.6wt%环戊烯酮。
实施例12
在实施例2的条件(CuO/ZnO;表面积(BET):15m2/g)下,于400℃使环庚酮进行反应。结果发现流出物包含95wt%未转化的离析物1wt%环庚烯酮和1.3wt%甲酚以及少量的其它产物。
Claims (10)
2.如权利要求1的方法,其中所述反应在没有氧或每摩尔结构式I的化合物低于0.2摩尔氧的存在下进行。
3.如权利要求1的方法,其中所述反应在没有氧或每摩尔结构式I的化合物低于0.1摩尔氧的存在下进行。
4.如权利要求1的方法,其中所述反应在0.1-10巴压力下进行。
5.如权利要求1的方法,其中所述反应在水存在下进行。
6.如权利要求1的方法,其中所述反应在氧化催化剂存在下进行。
7.如权利要求1的方法,其中所述反应在含第2族至第14族氧化物的催化剂或由其组成的催化剂的存在下进行。
8.如权利要求7的方法,其中所述反应在其中另外还应用了第7族至第12族元素或其氧化物的催化剂的存在下进行。
9.如权利要求1的方法,其中所用的结构式I的原料环酮是环戊酮。
10.如权利要求1的方法,其中所用的结构式I的原料环酮是环己酮。
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DE102004011543A1 (de) | 2004-03-08 | 2005-10-06 | Basf Ag | Verfahren zur Herstellung optisch aktiver Carbonylverbindungen |
CN102442895B (zh) * | 2011-12-22 | 2015-04-08 | 江苏扬农化工集团有限公司 | 一种用环己烯合成环己烯酮的方法 |
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CN107952459B (zh) * | 2017-12-07 | 2020-08-28 | 万华化学集团股份有限公司 | 大环烯酮的合成方法、及一种催化剂和它的应用 |
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