CN101948375A - Method for preparing cyclohexanone or cyclohexanol by recovering phenol - Google Patents
Method for preparing cyclohexanone or cyclohexanol by recovering phenol Download PDFInfo
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- CN101948375A CN101948375A CN2010102719660A CN201010271966A CN101948375A CN 101948375 A CN101948375 A CN 101948375A CN 2010102719660 A CN2010102719660 A CN 2010102719660A CN 201010271966 A CN201010271966 A CN 201010271966A CN 101948375 A CN101948375 A CN 101948375A
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- hydrogen
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- storage alloy
- hydrogen storage
- pimelinketone
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Abstract
The invention relates to a method for preparing cyclohexanone or cyclohexanol by recovering phenol. According to the method, phenol serves as a substrate, an activated hydrogen storage alloy serves as a catalyst and a hydrogen source and the reaction temperature is controlled within the range of 20 DEG C to 300 DEG C. The invention has the characteristics that as the activated hydrogen storage alloy which goes through hydrogen pickup serves both as the catalyst and the hydrogen source, the product is easily separated, cyclohexanone/cyclohexanol enjoys high selectivity, the catalyst can be repeatedly used and no pollution is caused to the environment.
Description
Technical field
The present invention relates to the method that a kind of phenol reduction prepares pimelinketone or hexalin.
Background technology
Pimelinketone, hexalin are important Organic Chemicals, be widely used in industry such as fiber, synthetic rubber, industrial coating, medicine, agricultural chemicals, organic solvent, also be the monomer hexanolactam of synthon nylon 66 and the main raw material of hexanodioic acid, but also be the raw material of producing spices, rubber antiager etc., also can be used as the auxiliary agent of fine chemicals.
The phenol hydrogenation one step method of producing hexalin and pimelinketone has two kinds of gas phase and liquid phases.1967, Dutch States Mines at first realized the industrialization that one step of phenol hydrogenation is produced hexalin and pimelinketone.Exploitation of U.S. Unichem and the phenol liquid-phase hydrogenatin technology primary product that comes into operation are pimelinketone, phenol conversion 95%, pimelinketone yield 97% can save the cyclohexanol dehydrogenation operation, but the loss of the complicated and expensive platinum metals of its troublesome poeration, device is difficult to avoid.The gas phase hydrogenation method adopts 3-5 reactors in series usually, and the yield of pimelinketone and hexalin can reach about 90%.(the main catalyzer of phenol hydrogenation reaction has Pd, Ru etc., and carrier mainly contains MgO, SiO but existent method is all used noble metal catalyst
2, gac etc.), make that the production cost of pimelinketone and hexalin is higher, catalyst surface also easily carbon deposit cause catalyst activity reduction, the lost of life, application is restricted.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art and a kind of highly selective that has is provided, process is simple, and phenol conversion is higher, and pimelinketone/hexalin selectivity is higher, catalyzer can reuse, environmentally safe prepare the method for pimelinketone or hexalin from phenol reduction.
Technical scheme of the present invention is: adopting the hydrogen storage alloy after activating is catalyzer and hydrogen source, is reactant with phenol, reacts in the organic solvent airtight vacuum, and control reaction temperature is carried out under 20-300 ℃.
The present invention is to be catalyzer and hydrogen source with hydrogen storage alloy, preparation pimelinketone/the hexalin of oxidation phenol highly selective, process is simple, phenol conversion is higher, pimelinketone/hexalin selectivity is higher, and hydrogen storage alloy not only had been catalyzer but also had been hydrogen source, and hydrogen storage alloy can with solution separating, can reuse environmentally safe.
Hydrogen storage alloy both can be the group of the lanthanides hydrogen storage alloy, also can be the ferrotianium base hydrogen storage alloy, can also be the zirconium base hydrogen storage alloy, or Mg base hydrogen bearing alloy.
Among the present invention, the activation of hydrogen storage alloy is that alloy pig is broken for fritter, puts into autoclave, inhales hydrogen in room temperature to 180-220 ℃ hydrogen atmosphere, vacuumizes-fill hydrogen activation 2-5 time then repeatedly.
The amount that adds the catalyzer hydrogen storage alloy among the present invention in every 10g phenol is 0.1-10.0g.
The time of preparation feedback of the present invention is 1-48h.
Product is selected from chloroform, monochloro methane, methylene dichloride or tetrachloromethane for the ring organic solvent of alcohol; Product is that the organic solvent of cyclohexanone is selected from ethanol, propyl alcohol, hexanaphthene, normal hexane, acetonitrile or ethyl acetate.
The concrete embodiment of the present invention is: adopting the activation hydrogen storage alloy is catalyzer and hydrogen source, and hydrogen storage alloy, solvent, phenol after the activation are joined in the autoclave, obtains reaction product at 20-300 ℃ of following stirring reaction 1-48h.
Characteristics of the present invention are to be catalyzer and hydrogen source with hydrogen storage alloy, the product separate easily, and catalyzer can reuse; Need not to introduce in addition hydrogen, safety in the reaction process; Environmentally safe.Because, existing industrial preparative method the phenol preparing cyclohexanone or the hexalin of existing hexalin and pimelinketone, the platinum catalyst of usefulness etc., troublesome poeration, device complexity, and platinum catalyst is relatively more expensive.And the present researchist of hydrogen storage alloy mainly is storage and the transportation that is used for studying hydrogen, and also not having the technician to expect or having relevant report will adopt the activation hydrogen storage alloy is the reduction that catalyzer and hydrogen source are used as phenol.The present invention compares with traditional phenol liquid phase method, has following several advantage: (1) catalysts does not use precious metal, low price; (2) pimelinketone/hexalin selectivity height (greater than 88%); (3) need not to add hydrogen, safety in the reaction process; Environmentally safe; (4) catalyzer can with solution separating, the recycling.Thereby be a kind of economy, eco-friendly synthetic method.
Embodiment
Following examples are intended to illustrate the present invention rather than limitation of the invention further.The present invention can implement by the described arbitrary mode of summary of the invention.
Embodiment 1
Catalyzer: hydrogen storage alloy LaNi
5Activation (alloy pig is broken for fritter, puts into autoclave, reductase 12 h in the hydrogen atmosphere of room temperature vacuumizes-fill hydrogen 2-5 time then repeatedly.With the hydrogen storage alloy LaNi after the 5g activation
5, 10ml chloroform, 1g phenol join in the autoclave, and be airtight, vacuumizes (removing oxygen and water vapour in the system), in 130 ℃ of reaction 48h down, uses the gas chromatographic analysis reaction solution, phenol conversion is 53%, the selectivity of pimelinketone is 88%.
Embodiment 2
Catalyzer: LaNi
5(adopt hydrogen reduction method, alloy pig is broken for fritter, put into autoclave, reductase 12 h in the hydrogen atmosphere of room temperature vacuumizes-fill hydrogen 2-5 time then repeatedly in the activation of hydrogen storage alloy.With the hydrogen storage alloy LaNi after the 5g activation
5, 10ml hexanaphthene, 1g phenol join in the autoclave, and be airtight, vacuumizes (removing oxygen and water vapour in the system), in 130 ℃ of reaction 48h down, uses the gas chromatographic analysis reaction solution, phenol conversion is 66%, the selectivity of hexalin is 93%.
Embodiment 3-5
According to method and the step of embodiment 1, but LaNi
5Type hydrogen storage alloy makes ferrotianium base hydrogen storage alloy TiFe, zirconium base hydrogen storage alloy ZrMn into
2Or Mg base hydrogen bearing alloy Mg
2Ni.It is 45% that the result is respectively phenol conversion, and the selectivity of pimelinketone is 89%; Phenol conversion is 49%, and the selectivity of pimelinketone is 90%; Phenol conversion is 52%, and the selectivity of pimelinketone is 92%.
Embodiment 6-8
According to method and the step of embodiment 2, but alloy LaNi
5Type hydrogen storage alloy makes ferrotianium base hydrogen storage alloy TiFe, zirconium base hydrogen storage alloy ZrMn into
2Or Mg base hydrogen bearing alloy Mg
2Ni.It is 55% that the result is respectively phenol conversion, and the selectivity of hexalin is 89%; Phenol conversion is 59%, and the selectivity of hexalin is 90%; Phenol conversion is 62%, and the selectivity of hexalin is 92%.
Claims (7)
1. a phenol reduction prepare method of pimelinketone or hexalin, it is characterized in that, the hydrogen storage alloy that adopts activation to inhale behind the hydrogen is catalyzer and hydrogen source, is reactant with phenol, and airtight vacuum reacts in organic solvent, and control reaction temperature is 20-300 ℃.
2. described a kind of phenol reduction prepares the method for pimelinketone or hexalin according to claim 1, and it is characterized in that: control reaction temperature is carried out under 100-150 ℃.
3. described a kind of phenol reduction prepares the method for pimelinketone or hexalin according to claim 1, and it is characterized in that: hydrogen storage alloy is group of the lanthanides hydrogen storage alloy, ferrotianium base hydrogen storage alloy, zirconium base hydrogen storage alloy or Mg base hydrogen bearing alloy.
4. each described a kind of phenol reduction prepares the method for pimelinketone or hexalin according to claim 1-3, it is characterized in that: the activation of hydrogen storage alloy is that alloy pig is broken for fritter, put into autoclave, to 180-220 ℃ hydrogen atmosphere, inhale hydrogen in room temperature, vacuumize-fill hydrogen activation 2-5 time then repeatedly.
5. described a kind of phenol reduction prepare the method for pimelinketone or hexalin according to claim 1, and it is characterized in that: the amount of adding hydrogen storage alloy is 0.1-10.0g in every 10g phenol.
6. described a kind of phenol reduction prepares the method for pimelinketone or hexalin according to claim 1, and it is characterized in that: the time of reaction is 1-48h.
7. described a kind of phenol reduction prepare the method for hexalin or hexalin according to claim 1, and it is characterized in that: product is selected from chloroform, monochloro methane, methylene dichloride or tetrachloromethane for the pure organic solvent of ring; Product is that the organic solvent of cyclohexanone is selected from ethanol, propyl alcohol, hexanaphthene, normal hexane, acetonitrile or ethyl acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010271966 CN101948375B (en) | 2010-09-05 | 2010-09-05 | Method for preparing cyclohexanone or cyclohexanol by recovering phenol |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 201010271966 CN101948375B (en) | 2010-09-05 | 2010-09-05 | Method for preparing cyclohexanone or cyclohexanol by recovering phenol |
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| CN101948375A true CN101948375A (en) | 2011-01-19 |
| CN101948375B CN101948375B (en) | 2013-07-03 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104428276A (en) * | 2012-06-28 | 2015-03-18 | 帝斯曼知识产权资产管理有限公司 | Process for the production of a mixture comprising cyclohexanone and cyclohexanol from phenol |
| CN104672069A (en) * | 2015-01-21 | 2015-06-03 | 中国科学院兰州化学物理研究所 | Method for preparing cyclohexanone or substituted cyclohexanone |
| CN105198709A (en) * | 2014-06-18 | 2015-12-30 | 中国科学院兰州化学物理研究所 | Substituted cyclohexanol synthesis method |
| CN109896937A (en) * | 2019-03-18 | 2019-06-18 | 厦门中坤化学有限公司 | A kind of synthetic method preparing 3- methyl cyclohexanone by metacresol |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0616580A (en) * | 1991-10-28 | 1994-01-25 | Snow Brand Milk Prod Co Ltd | Process for hydrogenative reduction of compound having carbon-carbon multiple bond |
| CN1847206A (en) * | 2006-05-10 | 2006-10-18 | 浙江工业大学 | Synthesis process of cyclohexanone and cyclohexanol |
-
2010
- 2010-09-05 CN CN 201010271966 patent/CN101948375B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0616580A (en) * | 1991-10-28 | 1994-01-25 | Snow Brand Milk Prod Co Ltd | Process for hydrogenative reduction of compound having carbon-carbon multiple bond |
| CN1847206A (en) * | 2006-05-10 | 2006-10-18 | 浙江工业大学 | Synthesis process of cyclohexanone and cyclohexanol |
Non-Patent Citations (1)
| Title |
|---|
| 余学斌 等: "储氢合金的活化及活化性能的改善", 《材料导报》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104428276A (en) * | 2012-06-28 | 2015-03-18 | 帝斯曼知识产权资产管理有限公司 | Process for the production of a mixture comprising cyclohexanone and cyclohexanol from phenol |
| CN105198709A (en) * | 2014-06-18 | 2015-12-30 | 中国科学院兰州化学物理研究所 | Substituted cyclohexanol synthesis method |
| CN104672069A (en) * | 2015-01-21 | 2015-06-03 | 中国科学院兰州化学物理研究所 | Method for preparing cyclohexanone or substituted cyclohexanone |
| CN104672069B (en) * | 2015-01-21 | 2016-08-24 | 中国科学院兰州化学物理研究所 | A kind of Ketohexamethylene or the preparation method of substituted cyclohexanone |
| CN109896937A (en) * | 2019-03-18 | 2019-06-18 | 厦门中坤化学有限公司 | A kind of synthetic method preparing 3- methyl cyclohexanone by metacresol |
| CN109896937B (en) * | 2019-03-18 | 2022-06-24 | 厦门中坤化学有限公司 | Synthetic method for preparing 3-methylcyclohexanone from m-cresol |
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| CN101948375B (en) | 2013-07-03 |
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