CN1535947A - Method of preparing adipic acid by air-oxidating hexacarbocyclic compound - Google Patents
Method of preparing adipic acid by air-oxidating hexacarbocyclic compound Download PDFInfo
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- CN1535947A CN1535947A CNA031182496A CN03118249A CN1535947A CN 1535947 A CN1535947 A CN 1535947A CN A031182496 A CNA031182496 A CN A031182496A CN 03118249 A CN03118249 A CN 03118249A CN 1535947 A CN1535947 A CN 1535947A
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- metalloporphyrin
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Abstract
The present invention relates to a new process for preparing adipic acid by air oxidating cyclohexane, cyclohexanol, cyclohexanone and cyclohexene or mixture of cyclohexanol and cyclohexanone under the catalysis of metal porphyrin. Under the condition of 1-20 atm air and reaction temp. is 50-200 deg.C it can select and use mu-oxidized metal porphyrin and monometal porphyrin or their fixed carrier material as catalyst independently, also can select and use metal porphyrin or their fixed carrier material as main catalyst, and use transition metal salt or oxide as co-catalyst. The metal porphyrin like biological-enzyme can high-effectively and high-selectivity catalyze air under the biologicae concentration to directly oxidate the cyclohexane into adipic acid. Said invented dose of metal porphyrin is less, and its catalytic effect is good, it can make homogeneous catalysis, also can make heterogeneous catalysis after the carrier is fixed.
Description
Technical field
The present invention relates under catalysis of metalloporphyrin, hexanaphthene, hexalin, pimelinketone and tetrahydrobenzene oxidation by air become the method for hexanodioic acid.
Background technology
Hexanodioic acid is the important source material of preparation nylon 66.At present, industrial hexanodioic acid mainly prepares by the nitric acid liquid phase oxidation of pimelinketone.Because strongly-acid, strong oxidizing property and the corrodibility of nitric acid, there is the serious environmental pollution problem in the technology of nitric acid oxidation Cyclohexanone Production hexanodioic acid, and reaction conversion ratio and selectivity of product are also undesirable.The science and technology circle is being devoted to the research of hexanodioic acid new preparation process always.ZL 99121017.4 discloses and has used peroxide tungstate-organic carboxyl acid class coordination compound catalyzing hydrogen peroxide cyclohexene oxide to prepare the method for hexanodioic acid, ZL 92106038.6 discloses from using the organic high conductivity polymer cluster of transition metal compound for catalysis cyclohexane oxidation to prepare the method for hexanodioic acid, and WO 96.3365 and WO 99.40058 disclose the method for using cobalt salt catalytic air oxidation hexanaphthene to prepare hexanodioic acid.Use the serious problem of environmental pollution that nitric acid oxidation brought though these methods have solved, but still have reaction conversion ratio and adipic acid yield is low or production cost is high problem.
Summary of the invention
The consumption that the purpose of this invention is to provide a kind of catalyst system therefor is little.The catalytic efficiency height.Temperature of reaction and reaction pressure are lower.The oxidizing reaction degree of depth is easy to control.The product purity height, separate easily.Department is efficient, the mixture of highly selective catalytic air oxidation hexanaphthene, hexalin, pimelinketone, tetrahydrobenzene or hexalin and pimelinketone becomes the novel process of hexanodioic acid.And can be by selecting different processing condition, for example temperature of reaction, pressure, catalyst type and concentration realize the oxidation production hexanodioic acid of air to different hydrogenation of six carbocyclic raw materials of compound.
The object of the present invention is achieved like this:
Feeding under the 1-20atm air conditions, control reaction temperature 50-200 ℃, select for use by general formula (I) or (II) supported metalloporphyrin that constitutes by physics or chemical process of μ-oxygen bimetallic porphyrin and monometallic porphyrin or above-mentioned metalloporphyrin and inorganic and organic polymer separately as catalyzer, catalyst concn is 1-100PPM, realizes the oxidation production hexanodioic acid of air to different hydrogenation of six carbocyclic raw materials of compound.
Also can select for use by general formula (I) or (II) metalloporphyrin or their immobilized thing as Primary Catalysts, with transition metal salt or oxide compound as co-catalyst, Primary Catalysts concentration is 1-100PPM, the mol ratio of Primary Catalysts and co-catalyst is 1: 3-5, metalloporphyrin can be efficient as biological enzyme under biological concentration, the highly selective catalytic air is to the oxidation of different hydrogenation of six carbocyclic compounds.
Employed hydrogenation of six carbocyclic compound can be hexanaphthene, hexalin, pimelinketone, tetrahydrobenzene among the present invention, also can be the hexalin of different ratios and the mixture of pimelinketone.
Described μ-oxygen bimetallic porphyrin and monometallic porphyrin are following structural formula:
Atoms metal M in the above-mentioned metal porphyrins structure, M
1, M
2Can be transition metal atoms or lanthanide series metal atom; Substituent R on the phenyl ring
1, R
2, R
3Can be hydrogen, alkyl, alkoxyl group, hydroxyl, halogen, amido, amino, glycosyl replaces glycosyl and cyclodextrin.Dentate X can be an acetate, methyl ethyl diketone, halogen.
The carrier that constitutes the supported metalloporphyrin catalyzer with above-mentioned metalloporphyrin has: silica gel, molecular sieve, aluminum oxide, zeolite, sepiolite, porous ceramics, polyvinyl chloride, polyvinyl chloride, polystyrene etc.
Described transition metal salt or oxide compound as co-catalyst has: Cu, Zn, Fe, Co, Mn, Cr, Ni etc.These metal-salts or oxide compound can obviously improve the catalytic performance of metalloporphyrin to atmospheric oxidation alkyl hexamethylene hydrocarbon.
The composite catalyst that is made of metalloporphyrin or they and transition metal and oxide compound shows through on probation, and the reaction that the mixture of air oxidation of cyclohexane, hexalin, pimelinketone, tetrahydrobenzene or hexalin and pimelinketone is generated hexanodioic acid has good catalytic performance.With the variation of catalysis of metalloporphyrin agent composition and temperature of reaction, hydrogenation of six carbocyclic conversion of compounds rate is between 5-70%, and the selectivity of product hexanodioic acid is between 50-90%.
Embodiment
Below in conjunction with embodiment the present invention is made an explanation:
Embodiment 1:
3mg had the metalloporphyrin of general formula (I), R
1=R
2=R
3=CH
3, M=Mn adds in the 400ml hexanaphthene, feeds the 8atm air, and 180 ℃ of following reaction stirred 4 hours, cyclohexane conversion was 38%, and adipic acid yield 60% in the reaction product.
Embodiment 2:
5mg had the metalloporphyrin of general formula (II), R
1=R
2=R
3=Cl, M
1=M
2=Fe adds in the 400ml tetrahydrobenzene, feeds the 3atm air, and 140 ℃ of following reaction stirred 6 hours, the tetrahydrobenzene transformation efficiency was 65%, and adipic acid yield 53% in the reaction product.
Embodiment 3:
8mg had the metalloporphyrin of general formula (I), R
1=R
2=R
3=Cl, M=Fe and 15mg CoCl
2Add in the 500ml hexalin, feed the 10atm air, 100 ℃ of following reaction stirred 3 hours, the hexalin transformation efficiency was 72%, and adipic acid yield 83% in the reaction product.
Embodiment 4:
4mg had the metalloporphyrin of general formula (II), wherein R
1=R
2=R
3=Cl, M=Fe adds in the 500ml pimelinketone, feeds the 15atm air, and 100 ℃ of following reaction stirred 8 hours, the pimelinketone transformation efficiency was 48%, and adipic acid yield 90% in the reaction product.
Embodiment 5:
10mg had the metalloporphyrin of general formula (II), wherein R
1=R
2=R
3=Cl, M=Fe adds 500ml hexalin and pimelinketone and respectively accounts in 50% the mixture, feeds the 17atm air, and 80 ℃ of following reaction stirred 2 hours, adipic acid yield 85% in the reaction product.
Embodiment 6:
2mg had the metalloporphyrin of general formula (I), wherein R
1=R
2=R
3=Cl, M=Co adds in the 500ml hexanaphthene, feeds the 6atm air, and 120 ℃ of following reaction stirred 8 hours, cyclohexane conversion was 21%, and adipic acid yield 59% in the reaction product.
Embodiment 7:
5mg had the metalloporphyrin of general formula (I), wherein R
1=R
2=R
3=Cl, M=Co adds 500ml and contains in the mixture of hexalin 40% and 60% pimelinketone, feeds the 13atm air, and 170 ℃ of following reaction stirred 5 hours, adipic acid yield 93% in the reaction product.
Embodiment 8:
4mg had the metalloporphyrin of general formula (I), wherein R
1=R
2=R
3=Cl, M=Mn adds in the 500ml pimelinketone, feeds the 8atm air.150 ℃ of following reaction stirred 4 hours, the pimelinketone transformation efficiency was 53%, and adipic acid yield 80% in the reaction product.
Claims (6)
1. the method for a catalytic air oxidation hydrogenation of six carbocyclic compound hexanodioic acid, it is characterized in that feeding under the 1-20atm air conditions, control reaction temperature 50-200 ℃, select that the supported metalloporphyrin that constitutes by physics or chemical process of μ-oxygen bimetallic porphyrin and monometallic porphyrin or above-mentioned metalloporphyrin and inorganic and organic polymer is separately as catalyzer by general formula (I) or (II) for use, catalyst concn is 1-100PPM;
General formula (I)
General formula (II)
Atoms metal M in the said structure, M
1, M
2Can be transition metal atoms or lanthanide series metal atom;
Substituent R on the phenyl ring
1, R
2, R
3Can be hydrogen, alkyl, alkoxyl group, hydroxyl, halogen, amido, amino, glycosyl replaces glycosyl and cyclodextrin.
Dentate X can be an acetate, methyl ethyl diketone, halogen.
2, a kind of method of catalytic air oxidation hydrogenation of six carbocyclic compound hexanodioic acid, it is characterized in that, feeding under the 1-20atm air conditions, control reaction temperature 50-200 ℃, select that metalloporphyrin or above-mentioned metalloporphyrin and inorganic and organic polymer are made Primary Catalysts by the supported metalloporphyrin that physics or chemical process constitute by general formula (I) or (II) for use, the consumption of Primary Catalysts is 1-100PPM, make co-catalyst with transition metal salt or oxide compound, the mol ratio of Primary Catalysts and co-catalyst is 1: 3-5.
According to claim 1 or 2 described methods, it is characterized in that 3, described hydrogenation of six carbocyclic compound can be hexanaphthene, hexalin, pimelinketone, tetrahydrobenzene,
According to claim 1 or 2 described methods, it is characterized in that 4, described hydrogenation of six carbocyclic compound can be the hexalin of different ratios and the mixture of pimelinketone.
5. it is characterized in that according to claim 1 or 2 described methods: described supported metalloporphyrin is that metalloporphyrin and following carrier constitute: silica gel, molecular sieve, aluminum oxide, zeolite, sepiolite, porous ceramics, polyvinyl chloride, polyvinyl chloride, polystyrene, chitin, Mierocrystalline cellulose.
6. according to the described method of claim 2, it is characterized in that described transition metal salt or oxide compound as co-catalyst can be the salt or the oxide compound of following metal: Cu, Zn, Fe, Co, Mn, Cr, Ni.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03118249 CN1218922C (en) | 2003-04-08 | 2003-04-08 | Method of preparing adipic acid by air-oxidating hexacarbocyclic compound |
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|---|---|---|---|
| CN 03118249 CN1218922C (en) | 2003-04-08 | 2003-04-08 | Method of preparing adipic acid by air-oxidating hexacarbocyclic compound |
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| CN1218922C CN1218922C (en) | 2005-09-14 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010020080A1 (en) * | 2008-08-18 | 2010-02-25 | Guo Cancheng | Process and apparatus for preparing adipic acid by catalytic air oxidation of cyclohexane |
| CN101239899B (en) * | 2008-03-10 | 2010-06-02 | 华南理工大学 | Method for preparing adipic acid by using cyclohexane catalytic oxidation one-step method |
| CN102614920A (en) * | 2012-03-19 | 2012-08-01 | 北京旭阳化工技术研究院有限公司 | Silicon dioxide or polystyrene resin immobilized decatungstate catalyst and method for synchronizing adipic acid by catalytic oxidation of cyclohexene by using catalyst |
| CN102924263A (en) * | 2012-11-08 | 2013-02-13 | 中国天辰工程有限公司 | Method for preparing 6-hydroxy caproic acid |
| CN105017002A (en) * | 2015-07-09 | 2015-11-04 | 沅江华龙催化科技有限公司 | Simultaneous reaction and separation technology for preparing adipic acid through hydrogen peroxide oxidation of cyclohexene |
| CN108084012A (en) * | 2016-11-22 | 2018-05-29 | 中国科学院大连化学物理研究所 | A kind of method that peroxyester prepares adipic acid |
| CN109456167A (en) * | 2018-12-20 | 2019-03-12 | 福州大学 | A method of using micro passage reaction by cyclohexanone synthesizing adipic acid |
| CN110128260A (en) * | 2019-02-26 | 2019-08-16 | 沅江华龙催化科技有限公司 | A kind of method of energy-saving and environment-friendly air oxidation of cyclohexane synthesizing adipic acid |
| CN110872224A (en) * | 2018-09-04 | 2020-03-10 | 湖南师范大学 | Process for preparing adipic acid by catalytic oxidation of cyclohexane and preparation method of acid modified sepiolite catalyst |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100445255C (en) * | 2007-04-21 | 2008-12-24 | 中国科学院新疆理化技术研究所 | Method for catalytic hydrogenation of six carbocyclic compound by schiff bases-porphyrin metallic compound |
-
2003
- 2003-04-08 CN CN 03118249 patent/CN1218922C/en not_active Expired - Fee Related
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101239899B (en) * | 2008-03-10 | 2010-06-02 | 华南理工大学 | Method for preparing adipic acid by using cyclohexane catalytic oxidation one-step method |
| WO2010020080A1 (en) * | 2008-08-18 | 2010-02-25 | Guo Cancheng | Process and apparatus for preparing adipic acid by catalytic air oxidation of cyclohexane |
| CN102614920A (en) * | 2012-03-19 | 2012-08-01 | 北京旭阳化工技术研究院有限公司 | Silicon dioxide or polystyrene resin immobilized decatungstate catalyst and method for synchronizing adipic acid by catalytic oxidation of cyclohexene by using catalyst |
| CN102614920B (en) * | 2012-03-19 | 2014-10-22 | 北京旭阳化工技术研究院有限公司 | Silicon dioxide or polystyrene resin immobilized decatungstate catalyst and method for synchronizing adipic acid by catalytic oxidation of cyclohexene by using catalyst |
| CN102924263A (en) * | 2012-11-08 | 2013-02-13 | 中国天辰工程有限公司 | Method for preparing 6-hydroxy caproic acid |
| CN105017002A (en) * | 2015-07-09 | 2015-11-04 | 沅江华龙催化科技有限公司 | Simultaneous reaction and separation technology for preparing adipic acid through hydrogen peroxide oxidation of cyclohexene |
| CN105017002B (en) * | 2015-07-09 | 2020-11-20 | 沅江华龙催化科技有限公司 | Reaction separation synchronous process for preparing adipic acid by oxidizing cyclohexene with hydrogen peroxide |
| CN108084012A (en) * | 2016-11-22 | 2018-05-29 | 中国科学院大连化学物理研究所 | A kind of method that peroxyester prepares adipic acid |
| CN108084012B (en) * | 2016-11-22 | 2019-12-31 | 中国科学院大连化学物理研究所 | Method for preparing adipic acid by oxidizing cyclohexanone |
| CN110872224A (en) * | 2018-09-04 | 2020-03-10 | 湖南师范大学 | Process for preparing adipic acid by catalytic oxidation of cyclohexane and preparation method of acid modified sepiolite catalyst |
| CN109456167A (en) * | 2018-12-20 | 2019-03-12 | 福州大学 | A method of using micro passage reaction by cyclohexanone synthesizing adipic acid |
| CN110128260A (en) * | 2019-02-26 | 2019-08-16 | 沅江华龙催化科技有限公司 | A kind of method of energy-saving and environment-friendly air oxidation of cyclohexane synthesizing adipic acid |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1218922C (en) | 2005-09-14 |
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