CN101743220B - 氨肟化方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 26
- 230000008569 process Effects 0.000 title claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 20
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 11
- 150000002576 ketones Chemical class 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 40
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 claims description 16
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 11
- 229910017119 AlPO Inorganic materials 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000908 ammonium hydroxide Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 125000003544 oxime group Chemical group 0.000 claims 1
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- 150000003624 transition metals Chemical group 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 24
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 22
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- SFZULDYEOVSIKM-UHFFFAOYSA-N chembl321317 Chemical compound C1=CC(C(=N)NO)=CC=C1C1=CC=C(C=2C=CC(=CC=2)C(=N)NO)O1 SFZULDYEOVSIKM-UHFFFAOYSA-N 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- ZICQBHNGXDOVJF-UHFFFAOYSA-N diamantane Chemical compound C1C2C3CC(C4)CC2C2C4C3CC1C2 ZICQBHNGXDOVJF-UHFFFAOYSA-N 0.000 description 13
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 12
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- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
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- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
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Classifications
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- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
- B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/187—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
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Abstract
一种氧化还原氨肟化方法,其中,酮或醛在催化剂存在下与氨和氧反应;其中,所述催化剂为铝磷酸盐类的氧化还原催化剂,该催化剂具有包含不同过渡金属原子的至少两种不同的氧化还原催化位点。
Description
技术领域
本发明涉及一种使用包含铝磷酸盐的氧化还原催化剂的氨肟化方法,该氧化还原催化剂通常被称为“AlPO”体系。
背景技术
AlPO类化合物是众所周知的,并且已知被用作分子筛和催化剂用于多种过程,例如在US4567029、EP0132708、US5000931、US4801364、US5107052、US4853197、EP0293920、US6293999、和US6296688中所描述的。它们是通道遍穿整个材料的纳米多孔固体,因而赋予该材料以大量的表面积,可以被用于催化。其基本结构包含铝原子和氧原子,其中一些铝原子被一种或多种其他原子所替代,以提供所需的催化活性。
J.M.Thomas和R.Raja,[Design of a“green”one-step catalyticproduction of ε-caprolactam(precursor of nylon-6),Proceedings Natl.Acad.Sci.USA,102,13732-13736(2005)];R.Raja,G.Sankar和J.M.Thomas,[Bifunctional molecular sieve catalysts for the benign ammoximation ofcyclohexanone:One-step,solvent-free production of oxime and ε-caprolactamwith a mixture of air and ammonia,J.Am.Chem.Soc.123,8153-8154(2001)];和Nature(2005,10月,437卷;1243页)描述了尼龙的某些前体,特别是ε-己内酰胺的制备方法,该方法使用此类AlPO催化剂,特别是具有至少两种活性位点的AlPO催化剂,所述两种活性位点中一种为通常基于Co(III)、Mn(III)或Fe(III)原子的氧化还原位点,另一种为通常基于Zn(II)、Mg(II)或Co(II)原子的布朗斯台德(acid)位点。该两种类型的位点在AlPO三维结构中很好地分开,并且分别作用于原料。由此,其可以使得环己酮原料以超过70%、高达约80%的效率,一步转化为ε-己内酰胺,而无需使用目前所使用的多步法-参见Nature(出处同上)。
发明内容
然而,对于商业目的,70%的转化率是不够的。因而,虽然上述文献中提出的反应非常不错,并具有相当的科学价值,但是其目前几乎没有商业价值。
此外,还需要制备能用作其他有用产品中间体的化合物。这些中间体包括肟,特别是环己酮-肟。
我们现在已惊奇地发现用于上述反应的催化剂的改性能够以高达100%效率的更好产率进行氨肟化。利用众所周知的反应,可以将获得的肟进而有效地转化为所需的ε-己内酰胺。令人惊奇地是,该两步反应实际上比上述文献所述的一步反应更加有效。
本发明提供一种氧化还原氨肟化的方法,其中,酮或醛在催化剂存在下与氨和氧反应;其中,所述催化剂为铝磷酸盐类氧化还原催化剂,该催化剂具有包含不同过渡金属原子的至少两种不同的氧化还原催化位点。例如,该催化剂可以用下述定性用通式(I)或(II)表示:
M1M2AlPO(I)
或
(II):
M1M2SAlPO(II)
其中:M1和M2互不相同,且各自代表具有氧化还原催化能力的金属原子,并且部分磷(P(V))原子可以被其他等价的原子所替代。应当指出的是,这些通式仅表示存在的原子的性质,而并不代表它们的相对比例。
可由M1和M2表示的金属的例子包括Co(III)、Mn(III)、Fe(III)、Ti(IV)、Cr(VI)、Cu(III)、V(V)和Ru(III)。
部分优选的催化剂组合包括(但是不局限于):
(a)M1M2AlPO-5,其中M1≡Mn(III),且M2≡Co(III)或Fe(III)或Ru(III);
(b)M1M2SAPO-5,其中M1≡Co(III),M2≡Mn(III),且另外PV可被Ti(IV)、Cr(VI)或V(V)替代;
(c)M1M2AlPO-36,其中M1≡Co(III),且M2≡Mn(III)或Fe(III)或Ru(III);
(d)M1M2SAPO-36,其中M1≡Mn(III),M2≡Fe(III),且另外PV可被Ti(IV)、Cr(VI)或V(V)替代;
(e)M1M2AlPO-31,其中M1≡Fe(III),且M2≡Co(II)或Mn(III)或Ru(III);
(f)M1M2SAPO-31,其中M1≡Co(III),M2≡Fe(III),且另外PV可被Ti(IV)、Cr(VI)或V(V)替代;
(g)M1M2SAPO-18,其中M1≡Co(III),M2≡Mn(III),且另外PV可被Ti(IV)、Cr(VI)或V(V)替代;
(h)M1M2AlPO-18,其中M1≡Mn(III),且M2≡Co(III)或Fe(III)或Ru(III);
(i)M1M2SAPO-37,其中M1≡Mn(III),M2≡Co(III),且另外PV可被Ti(IV)、Cr(VI)或V(V)替代;
(j)M1M2AlPO-37,其中M1≡Fe(III),且M2≡Co(III)或Fe(III)或Ru(III)。
该类型催化剂是已知的,并且其制备方法同样也是已知的。例如,在US-A-4567029、“Catalytically active centres in porous oxides:design andperformance of highly selective new catalysts”、J.M.Thomas和R.Raja,Chem.Comm.,2001,675-687和“Design of a green one-step catalyticproduction of ε-caprolactam(precursor of nylon-6)”、J.M.Thomas和R.Raja.,PNAS,Vol 102/39,13732-13736中描述了含有单一氧化还原催化剂位点的催化剂。具有两种氧化还原位点的催化剂可以用类似的方式制备。在US-A-4956165、US-A-4917876、US-A-4801364和US-A-4567029中描述了具有两种或更多氧化还原位点的催化剂。
大体的制备过程方法如下:首先将磷源(典型地为85%的H3PO4)和必要量的蒸馏去离子H2O,例如在温和搅拌(400rpm)条件下,例如在特氟隆衬里的高压釜中使用机械搅拌器进行混合。向其中加入铝源(典型地为Al(OH)3),优选缓慢加入。将两种氧化还原金属源(M1和M2)溶于水,然后(优选缓慢地)加入到前述制备好的Al-H3PO4混合物中(优选在搅拌条件下)。然后在强烈搅拌(例如在1700rpm)下逐滴加入适当的(取决于所需的结构类型)模板(结构导向剂),使凝胶进行老化,例如,在298K条件下老化约1小时~2小时。而后加热该凝胶,以合成所需的结构类型,例如可以将其密封于特氟隆衬里的不锈钢高压釜中,在自生压力下加热到所需温度并持续所需量的时间。将固体产物优选以过滤或离心(在结晶后)分离,用大量的蒸馏去离子水洗涤,并真空干燥(90℃~120℃)。如此制备的产物在作为催化剂使用前,要在例如550℃下焙烧,首先在氮中焙烧4小时,而后在干燥氧中焙烧16小时。
最终催化剂的相纯度、结构完整性和结晶度可以通过组合使用粉末X-射线衍射术(XRD)、X-射线吸收光谱法(XAS)和高分辨电子断层成像术来确认。可以通过ICP(金属)分析来确定精确的化学计量(误差为ca±3×10-3)。
例如,该催化剂可以为AlPO-5、18、31、36或37型,优选为M1M2AlPO-5、M1M2AlPO-18或M1M2AlPO-36型,但是优选M1M2AlPO-5型。用于环己酮的氨肟化的这些催化剂的特别优选的实例为CoIIIMnIIIAlPO-5、CoIIIFeIIIAlPO-5和MnIIIFeIIIAlPO-5。
在本发明的方法中,将酮或醛与氨和氧反应。所述酮或醛可以为任何酮或醛,例如C3-C20酮或C2-C20醛,并且可以为直链的、支链的或环状的。优选的酮为环酮,例如C5-C12环酮,C6和C12的酮是最优选的。优选的醛包含环或芳香环,特别是C6环。优选的醛为苯甲醛。所述酮或醛可以没有取代基或有取代基,例如被C1-C4烷基或烯基、-OH或卤素取代。氨可以为气体形式或溶于例如水等溶剂的形式。优选其为氢氧化铵水溶液形式。除了来自氢氧化铵水溶液的水,通常不需要额外的溶剂,但是如果需要也可以使用。氧以气体的形式例如O2或空气提供。
反应产物通常为与原料酮或醛相对应的肟。因此,例如,本发明可以用于将环己酮氨肟化成环己酮-肟,该肟为ε-己内酰胺的前体,ε-己内酰胺本身是尼龙-6的重要前体,其具有广阔且不断增长的市场,因此本反应特别优越。本发明也可以用于将苯甲醛氨肟化成苯甲醛-肟。在所述反应中,环己酮或苯甲醛在催化剂存在下与氨(通常并且优选为氢氧化铵水溶液的形式)和氧(可以以纯氧或空气的形式提供)反应。
所述反应可以在很宽范围的温度和压力下进行,并且所选的确切温度和压力不是本发明的关键所在。然而,我们通常优选通过加热,例如50℃~95℃,更优选70℃~90℃温度范围内进行反应。所用压力例如优选为1个大气压~500个大气压的压力,更优选为1个大气压~100个大气压,并且最优选为1个大气压~10个大气压。
可将生成的肟转化为其他化合物,例如内酰胺。PNAS 102(39)13732-13736描述了一种利用贝克曼重排的适当方法,其使用发烟硫酸,随后使用酸例如硫酸。
本发明的方法以出乎意料的高的转化率和良好的选择性提供肟产物。J.Am.Chem.Soc.2001,123,8153-4中表1数据显示6小时的转化率高达20%。而如下述实施例所述,本发明的方法实现了至少50%、优选至少70%的转化率。
具体实施方式
实施例
通用实验装置和分析规程
催化反应在衬有聚醚醚酮(PEEK)的不锈钢催化反应器(100ml,Parr)中进行。之后将底物(环己酮)、氨(28%的氢氧化铵-双蒸去离子水溶液)、合适的内标(金刚烷)和催化剂(例如CoIIIMnIIIAlPO-5,其使用特殊设计的催化剂给送系统进入到反应范围中)引入到反应器中,接下来将反应器密封。在反应前,用干燥氮气将反应器和进、出口吹扫三遍。然后用氧化剂(动压下的干燥空气或纯氧)给反应器加压,在连续的搅拌下将内容物加热到所需温度。
当反应结束时,停止加热并使反应器中的内容物冷却(骤冷)。对反应器减压,在此阶段进行质量平衡计算以检查处理和质量损失。在研究动力学和速率的影响情况下,采用微型机器人液体取样阀在反应进程中移取少量等分(0.1μl)样品(水相和有机相)。通过采用HP-1毛细管柱(25m×0.32mm)的气相色谱(GC,Varian,Model 3400CX),和利用斜坡变温程序(50℃-300℃)的火焰电离检测器可以在线(利用与GC和/或LCMS相连的具有在线计算机控制系统的自动控制单元)或离线(使用适合的内标)分析产物。在离线分析方法中,将产物分离,并且在GC分析前用硫酸镁将有机层干燥。首先使用经鉴定的标准物对产物身份进行确认,然后对它们各自的响应因子使用校准法以合适的内标(金刚烷)来确定。根据上述获得的(GC)响应因子对总产率进行标准化。
按照下述方程式的限定来确定转化率和选择性,并根据上述获得的响应因子对产率进行标准化:
转化率%=[(起始底物摩尔数-剩余底物摩尔数)/起始底物摩尔数]×100
选择性%=[单种产物摩尔数/总产物摩尔数]×100
对于内标GC方法,单种产物的响应因子(RF)和摩尔%通过下述方程式计算:
RF=(产物摩尔数/标准物摩尔数)×(标准物面积/产物面积)
产物摩尔%=RF×标准物摩尔数×(产物面积/标准物面积)×100/样品摩尔数
通过使用LCMS(Shimadzu LCMS-QP8000)对产物身份进行进一步的确认,其同样可以使用在线或离线的方法。分别独立地进行水性与有机混合物的热过滤实验和ICP测量,以检查是否发生浸取。
实施例1
利用CoIIIMnIIIAlPO-5对环己酮进行氨肟化
本实验以上述方案进行,其使用25g环己酮,14.6g氨,0.5g金刚烷(内标),0.75CoIIIMnIIIAlPO-5(0.10),30巴干燥空气,在353K进行6小时。
环己酮向肟产物的转化率经计算为77%,对环己酮肟的选择性为88%。
实施例2
利用CoIIIMnIIIAlPO-5对环己酮进行氨肟化
本实验以上述方案进行,其使用25g环己酮,14.6g氨,0.5g金刚烷(内标),0.75CoIIIMnIIIAlPO-5(0.10),15巴纯氧,在353K进行6小时。
环己酮向肟产物的转化率经计算为71%,对环己酮肟的选择性为84%。
实施例3
利用CoIIIFeIIIAlPO-5对环己酮进行氨肟化
本实验以上述方案进行,其使用25g环己酮,14.6g氨,0.5g金刚烷(内标),0.5CoIIIFeIIIAlPO-5(0.10),30巴干燥空气,在353K进行6小时。
环己酮向肟产物的转化率经计算为56%,对环己酮肟的选择性为89%。
实施例4
利用MnIIIFeIIIAlPO-5对环己酮进行氨肟化
本实验以上述方案进行,其使用25g环己酮,14.6g氨,0.5g金刚烷(内标),0.5MnIIIFeIIIAlPO-5(0.10),30巴干燥空气,在353K进行6小时。
环己酮向肟产物的转化率经计算为78%,对环己酮肟的选择性为92%。
实施例5
利用CoIIIMnIIIAlPO-5对环己酮进行氨肟化
本实验以上述方案进行,其使用15g环己酮,14.6g氨,0.5g金刚烷(内标),0.75CoIIIMnIIIAlPO-5(0.10),30巴干燥空气,在373K进行6小时。
环己酮向肟产物的转化率经计算为91%,对环己酮肟的选择性为86%。
实施例6
利用CoIIIMnIIIAlPO-5对环己酮进行氨肟化
本实验以上述方案进行,其使用15g环己酮,29.2g氨,0.5g金刚烷(内标),1.0CoIIIMnIIIAlPO-5(0.10),30巴干燥空气,在353K进行6小时。
环己酮向肟产物的转化率经计算为95%,对环己酮肟的选择性为84%。
实施例7
利用CoIIIMnIIIAlPO-5对环己酮进行氨肟化
本实验以上述方案进行,其使用14.6g氨,0.5g金刚烷(内标),0.75
CoIIIMnIIIAlPO-5(0.10),30巴干燥空气,在353K进行6小时。
当反应结束时,停止加热并使反应器中的内容物冷却(骤冷)。使反应器减压,并在此阶段进行质量平衡计算以检查处理和质量损失。然后将溶解于20g甲苯的15g环己酮加入到上述反应混合物中,在相同反应器中,将内容物在298K、氮气(5巴)下进一步搅拌60分钟。然后在减压前将反应器冷却到室温。在此阶段进行质量平衡分析以检查处理和其它损失。随后分离有机成分并且用硫酸镁对其进行干燥。而后按照如前所述方案进行分析。
环己酮向肟产物的转化率经计算为86%,对环己酮肟的选择性为100%。
实施例8
利用CoIIIMnIIIAlPO-5对环己酮进行氨肟化
本实验以上述方案进行,其使用29.2g氨,0.5g金刚烷(内标),0.75CoIIIMnIIIAlPO-5(0.10),30巴干燥空气,在353K进行6小时。
当反应结束时,停止加热并使反应器中的内容物冷却(骤冷)。使反应器减压,在此阶段进行质量平衡计算以检查处理和质量损失。然后将溶解于20g甲苯的15g环己酮加入到上述反应混合物中,在相同反应器中,将内容物在298K、氮气(5巴)条件下进一步搅拌60分钟。然后在减压前将反应器冷却到室温。在此阶段进行质量平衡分析以检查处理和其它损失。随后分离有机成分并且用硫酸镁对其进行干燥。而后按照如前所述方案进行分析。
环己酮向肟产物的转化率经计算为88%,对环己酮肟的选择性为100%。
实施例9
利用CoIIIFeIIIAlPO-5对环己酮进行氨肟化
本实验以上述方案进行,其使用14.6g氨,0.5g金刚烷(内标),0.75CoIIIFeIIIAlPO-5(0.10),30巴干燥空气,在353K进行6小时。
当反应结束时,停止加热并使反应器中的内容物冷却(骤冷)。使反应器减压,在此阶段进行质量平衡计算以检查处理和质量损失。然后将溶解于20g甲苯的15g环己酮加入到上述反应混合物中,在相同反应器中,将内容物在298K、氮气(5巴)条件下进一步搅拌60分钟。然后在减压前将反应器冷却到室温。在此阶段进行质量平衡分析以检查处理和其它损失。随后分离有机成分并且用硫酸镁对其进行干燥。而后按照如前所述方案进行分析。
环己酮向肟产物的转化率经计算为81%,对环己酮肟的选择性为100%。
实施例10
利用MnIIIFeIIIAlPO-5对环己酮进行氨肟化
本实验以上述方案进行,其使用14.6g氨,0.5g金刚烷(内标),0.75MnIIIFeIIIAlPO-5(0.10),30巴干燥空气,在353K进行6小时。
当反应结束时,停止加热并使反应器中的内容物冷却(骤冷)。使反应器减压,在此阶段进行质量平衡计算以检查处理和质量损失。然后将溶解于20g甲苯的15g环己酮加入到上述反应混合物中,在相同反应器中,将内容物在298K、氮气(5巴)条件下进一步搅拌60分钟。然后在减压前将反应器冷却到室温。在此阶段进行质量平衡分析以检查处理和其它损失。随后分离有机成分并且用硫酸镁对其进行干燥。而后按照如前所述方案进行分析。
环己酮向肟产物的转化率经计算为94%,对环己酮肟的选择性为100%。
实施例11
利用CoIIIMnIIIAlPO-5对环己酮进行氨肟化
本实验以上述方案进行,其使用29.2g氨,0.5g金刚烷(内标),0.75CoIIIMnIIIAlPO-5(0.10),30巴干燥空气,在373K进行8小时。
当反应结束时,停止加热并使反应器中的内容物冷却(骤冷)。使反应器减压,在此阶段进行质量平衡计算以检查处理和质量损失。然后将溶解于20g甲苯的15g环己酮加入到上述反应混合物中,在相同反应器中,将内容物在298K、氮气(5巴)条件下进一步搅拌60分钟。然后在减压前将反应器冷却到室温。在此阶段进行质量平衡分析以检查处理和其它损失。随后分离有机成分并且用硫酸镁对其进行干燥。而后按照如前所述方案进行分析。
环己酮向肟产物的转化率经计算为97%,对环己酮肟的选择性为94%。
Claims (10)
1.一种氧化还原氨肟化方法,其中,酮或醛在催化剂存在下与氨和氧反应,其中,所述催化剂具有下述定性用通式(I):
M1M2AlPO(I)
其中,M1和M2各自代表选自Co(III)、Mn(III)和Fe(III)的不同原子。
2.如权利要求1所述的方法,其中,所述催化剂为M1M2AlPO-5、M1M2AlPO-18或M1M2AlPO-36型。
3.如权利要求2所述的方法,其中,所述催化剂为CoIIIMnIIIAlPO-5、CoIIIFeIIIAlPO-5或MnIIIFeIIIAlPO-5。
4.如权利要求1~3中任一项所述的方法,其中,所述氨为氢氧化铵水溶液的形式。
5.如权利要求1~3中任一项所述的方法,所述方法在50℃~95℃的温度进行。
6.如权利要求5所述的方法,所述方法在70℃~90℃的温度进行。
7.如权利要求1~3中任一项所述的方法,其中,原料为酮。
8.如权利要求1~3中任一项所述的方法,其中,反应产物为肟。
9.如权利要求8所述的方法,其中,环己酮被转化为环己酮-肟。
10.如权利要求9所述的方法,其中,所述环己酮-肟被转化为ε-己内酰胺。
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2013
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Non-Patent Citations (2)
Title |
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Bifunctional Molecular Sieve Catalysts for the Benign Ammoximation of Cyclohexanone: One-Step, Solvent-Free Production of Oxime and ε-Caprolactam with a Mixture of Air and Ammonia;Robert Raja等;《J. Am. Chem. Soc. 》;20010822;第123卷(第33期);8153–8154 * |
Robert Raja等.Bifunctional Molecular Sieve Catalysts for the Benign Ammoximation of Cyclohexanone: One-Step, Solvent-Free Production of Oxime and ε-Caprolactam with a Mixture of Air and Ammonia.《J. Am. Chem. Soc. 》.2001,第123卷(第33期), |
Also Published As
Publication number | Publication date |
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RU2010103509A (ru) | 2011-08-10 |
US8450526B2 (en) | 2013-05-28 |
KR101180335B1 (ko) | 2012-09-06 |
JP5399383B2 (ja) | 2014-01-29 |
RU2453535C2 (ru) | 2012-06-20 |
JP2010531867A (ja) | 2010-09-30 |
WO2009004342A1 (en) | 2009-01-08 |
CN101743220A (zh) | 2010-06-16 |
US20100179317A1 (en) | 2010-07-15 |
EP2170812B1 (en) | 2013-12-18 |
PL2170812T3 (pl) | 2014-05-30 |
KR20100032401A (ko) | 2010-03-25 |
US20130245323A1 (en) | 2013-09-19 |
GB2450711A (en) | 2009-01-07 |
US8779125B2 (en) | 2014-07-15 |
ES2441804T3 (es) | 2014-02-06 |
EP2170812A1 (en) | 2010-04-07 |
GB0712903D0 (en) | 2007-08-15 |
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