CN101343260A - Method for synthesis epoxy cyclohexane with titanium molecular sieve catalysis - Google Patents
Method for synthesis epoxy cyclohexane with titanium molecular sieve catalysis Download PDFInfo
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- CN101343260A CN101343260A CNA2007100353516A CN200710035351A CN101343260A CN 101343260 A CN101343260 A CN 101343260A CN A2007100353516 A CNA2007100353516 A CN A2007100353516A CN 200710035351 A CN200710035351 A CN 200710035351A CN 101343260 A CN101343260 A CN 101343260A
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- tetrahydrobenzene
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- epoxy cyclohexane
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention relates to a method for using a titanium silicate molecular sieve to catalytically synthesize cyclohexene oxide, which is characterized in that: cyclohexene and peroxide are taken as raw materials, the titanium silicate molecular sieve serves as a catalyst for catalysis and epoxidation, and the cyclohexene oxide is generated through the reaction with high selectivity; and the catalyst and a solvent used in the reaction can be recycled. The method has advantages of low production cost, environmental friendship and reasonable preparing route, and is suitable for the industrialized production of cyclohexene oxide.
Description
Technical field
The present invention relates to use the titanium molecular sieve catalysis epoxidation reaction, specifically a kind of method with synthesis epoxy cyclohexane with titanium molecular sieve catalysis.
Background technology
Epoxy cyclohexane is a kind of important fine-chemical intermediate.It can be directly as the reactive thinner of Resins, epoxy, but also compounds such as synthesizing cyclohexane 1 glycol, Trans-4-Amino Cyclohexanol, hexanedial; Or higher effective and lower toxic pesticide propargite and some medical important intermediate.The utilization of continually developing along with the epoxy cyclohexane purposes also increases rapidly its demand.
At present, the method that reclaims a small amount of epoxy cyclohexane from the by product of the technological process of cyclohexane oxidation preparing cyclohexanone, hexalin is arranged both at home and abroad.Take alkaline process to remove low-boiling-point substance as JP/1975/95248 and change into high boiling material and reclaim epoxy cyclohexane in the by-product, wash with water again, obtain product through underpressure distillation except that lixiviating; By product is taked to add hydrochloric acid to CN1106784A and alkali reaction obtains the epoxy cyclohexane product.The method of epoxy cyclohexane is underproduce to satisfy the demand that increases day by day in this recovery by-product.Problems such as and tradition is low with the yield of chlorohydrination synthesis epoxy cyclohexane, exists equipment corrosion serious simultaneously, and environmental pollution is serious.CN 1401640A has taked a kind of reaction-controlled phase transfer catalysis epoxidation to prepare the epoxy cyclohexane method, this method process environments close friend and selectivity height, but even and heterogeneous conversion of expensive catalysts is influenced by several factors in this method, seems restive; And the defective that also has catalyst loss and sex change.
Summary of the invention
The object of the invention provides a kind of method with synthesis epoxy cyclohexane with titanium molecular sieve catalysis.
The object of the present invention is achieved like this: with tetrahydrobenzene and superoxide is raw material, with HTS is the catalyst epoxidation reaction, highly selective generates epoxy cyclohexane, the temperature of epoxidation reaction is 10 ℃~100 ℃, catalyzer and solvent that reaction is used can be recycled, catalyst levels is equivalent to drop into 0.1%~20% of tetrahydrobenzene weight, and tetrahydrobenzene and superoxide mole proportioning are 1: 0.1~1.0.
The catalyzer that the present invention uses in epoxidation reaction is a HTS, can be the TS-1 HTS; And the particle diameter of TS-1 HTS is generally 0.01 μ m~10 μ m.Catalyst levels is equivalent to drop into 0.1%~20% of tetrahydrobenzene weight, preferable input weight 0.5%~5%.
The superoxide that uses in the reaction can be hydrogen peroxide, alkyl peroxide or peroxide organic acid.The most frequently used superoxide is a hydrogen peroxide, and its concentration is all can use in 10%~75%.
Epoxidation reaction temperature scope of the present invention is 10 ℃~100 ℃, and temperature of reaction is 35 ℃~75 ℃ preferably.
Solvent of the present invention comprises: pure ether solvent can be methyl alcohol, ethanol, Virahol, the trimethyl carbinol, n-Octanol, polypropylene glycol or amyl ether, epoxy chloropropane; Halogenated hydrocarbon solvent can be trichloromethane, tetrachloromethane, monochlorethane, ethylene dichloride chlorocyclohexane; Esters solvent can be fatty acid ester such as ethyl acetate, aromatic esters such as methyl benzoate, or mineral acid alkyl ester such as Tributyl phosphate ester; Nitrogenous kind solvent can be nitrile such as acetonitrile, hydrazine, amine, hydramine or acid amides.
Positively effect of the present invention is: reaction process is simple, and catalyst is active high, but high conversion, highly selective prepare epoxy cyclohexane, and the selectivity of epoxidation reaction reaches 93%, and tetrahydrobenzene is 98% to the transformation efficiency of hydrogen peroxide; And catalyzer can recycle easily, and the catalyzer of catalyst life length and inactivation is easily regenerated, and is environmentally friendly, can satisfy the requirement of Technological Economy, is a novel process that is suitable for the large-scale commercial production epoxy cyclohexane.
Embodiment
The present invention is described in detail below by example.
Embodiment 1
Get 1.0mol tetrahydrobenzene, 200ml methyl alcohol and 5.0gTS-1 molecular sieve (particle diameter is 0.02 μ m~0.1 μ m), at 35 ℃ of 10% aqueous hydrogen peroxide solutions (w/w) that drip 0.7mol down.Drip under the same temperature in back and reacted 3 hours again, the transformation efficiency of tetrahydrobenzene is 64.0%, and hydrogen peroxide utilization ratio 91%, the selectivity of epoxy cyclohexane are 92.6%.Obtain the intact tetrahydrobenzene of methyl alcohol and unreacted and the product epoxy cyclohexane of content 99.7% by rectifying.Methyl alcohol that steams and tetrahydrobenzene and the catalyzer that does not steam promptly are used for secondary response down.
Embodiment 2
Get 1.5mol tetrahydrobenzene, 500ml acetonitrile and 4.0gTS-1 molecular sieve (particle diameter is 0.1 μ m~0.8 μ m), at 70 ℃ of 35% aqueous hydrogen peroxide solutions (w/w) that drip 0.75mol down.Drip under the same temperature in back and reacted 1 hour again, the transformation efficiency of tetrahydrobenzene is 47.5%, and hydrogen peroxide utilization ratio 95%, the selectivity of epoxy cyclohexane are 89.7%.By filtration, and catalyzer 3.9g on the worry paper of oven dry; Filtrate obtains the intact tetrahydrobenzene of acetonitrile and unreacted and the product epoxy cyclohexane of content 99.5% by rectifying.The catalyzer of acetonitrile that steams and tetrahydrobenzene and recovery promptly is used for secondary response down.
Embodiment 3
Get 1.5mol tetrahydrobenzene, 500ml ethyl acetate and 4.0gTS-1 molecular sieve, at 70 ℃ of 35% aqueous hydrogen peroxide solutions (w/w) that drip 0.75mol down.Drip under the same temperature in back and reacted 1 hour again, the transformation efficiency of tetrahydrobenzene is 48.0%, and hydrogen peroxide utilization ratio 96%, the selectivity of epoxy cyclohexane are 87.0%.By filtration, and catalyzer 3.9g on the worry paper of oven dry; Filtrate obtains the intact tetrahydrobenzene of ethyl acetate and unreacted and the product epoxy cyclohexane of content 99.5% by rectifying.The catalyzer of ethyl acetate that steams and tetrahydrobenzene and recovery promptly is used for secondary response down.
Embodiment 4
Get 2.0mol tetrahydrobenzene, 500ml trichloromethane and 8.0gTS-1 molecular sieve, at 45 ℃ of 27.5% aqueous hydrogen peroxide solutions (w/w) that drip 1.2mol down.Drip under the same temperature in back and reacted 2 hours again, the transformation efficiency of tetrahydrobenzene is 57.4%, and hydrogen peroxide utilization ratio 95.7%, the selectivity of epoxy cyclohexane are 94.1%.Obtain the intact tetrahydrobenzene of trimethylbenzene and unreacted and the product epoxy cyclohexane of content 99.5% by rectifying.The catalyzer that is not steamed continues to repeat aforesaid operations process, no significant difference as a result, physical record such as following table that circulating reaction is eight times.
The above embodiments show, according to the condition that invention is provided, can realize that high conversion and highly selective generate epoxy cyclohexane with the tetrahydrobenzene catalysis epoxidation, are the novel methods that is fit to the large-scale commercial production epoxy cyclohexane.
Claims (9)
1. method with synthesis epoxy cyclohexane with titanium molecular sieve catalysis, it is characterized in that: with tetrahydrobenzene and superoxide is raw material, with HTS is the catalyst epoxidation reaction, highly selective generates epoxy cyclohexane, the temperature of epoxidation reaction is 10 ℃~100 ℃, catalyzer and solvent that reaction is used can be recycled, and catalyst levels is equivalent to drop into 0.1%~20% of tetrahydrobenzene weight, and tetrahydrobenzene and superoxide mole proportioning are 1: 0.1~1.0.
2. in accordance with the method for claim 1, it is characterized in that employed superoxide can be hydrogen peroxide, alkyl peroxide or peroxide organic acid.
3. in accordance with the method for claim 2, it is characterized in that employed superoxide is a hydrogen peroxide.
4. in accordance with the method for claim 3, the concentration that it is characterized in that employed hydrogen peroxide is 10%~75%.
5. in accordance with the method for claim 1, it is characterized in that epoxidation reaction temperature is 30 ℃~70 ℃.
6. in accordance with the method for claim 1, it is characterized in that catalyst levels is equivalent to drop into 0.5%~5% of tetrahydrobenzene weight.
7. in accordance with the method for claim 1, it is characterized in that described catalyst Ti-si molecular sieves is the TS-1 molecular sieve.
8. in accordance with the method for claim 7, the particle diameter that it is characterized in that described TS-1 HTS is 0.01 μ m-10 μ m.
9. in accordance with the method for claim 1, it is characterized in that described solvent comprises: pure ether solvent can be methyl alcohol, ethanol, Virahol, the trimethyl carbinol, n-Octanol, polypropylene glycol or amyl ether, epoxy chloropropane; Halogenated hydrocarbon solvent can be trichloromethane, tetrachloromethane, monochlorethane, ethylene dichloride, chlorocyclohexane; Esters solvent can be fatty acid ester such as ethyl acetate, aromatic esters such as methyl benzoate, or mineral acid alkyl ester such as Tributyl phosphate ester; Nitrogenous kind solvent can be nitrile such as acetonitrile, hydrazine, amine, hydramine or acid amides.
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Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
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CN102079695A (en) * | 2009-11-27 | 2011-06-01 | 中国石油化工股份有限公司 | Method for catalytically oxidizing cyclohexane |
CN102361861A (en) * | 2009-03-25 | 2012-02-22 | 昭和电工株式会社 | Method for producing epoxy compound |
CN102452870A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Method for catalytically oxidizing cyclic olefin |
CN103130613A (en) * | 2011-11-29 | 2013-06-05 | 岳阳昌德化工实业有限公司 | Cyclohexene oxidizing method |
CN103130749A (en) * | 2011-11-29 | 2013-06-05 | 岳阳昌德化工实业有限公司 | Method for preparing cyclohexene oxide through oxidation of cyclohexene |
CN103130750A (en) * | 2011-11-29 | 2013-06-05 | 岳阳昌德化工实业有限公司 | Cyclohexene oxidizing method |
CN103130747A (en) * | 2011-11-29 | 2013-06-05 | 岳阳昌德化工实业有限公司 | Cyclohexene oxidizing method |
CN103130748A (en) * | 2011-11-29 | 2013-06-05 | 岳阳昌德化工实业有限公司 | Cyclohexene oxidizing method |
CN105037117A (en) * | 2015-05-26 | 2015-11-11 | 岳阳昌德化工实业有限公司 | Method for simultaneously synthesizing vanillin and isovanillin |
CN105037299A (en) * | 2015-05-26 | 2015-11-11 | 岳阳昌德化工实业有限公司 | 3,4-epoxy cyclohexyl methylal diol, and synthesis method and application thereof |
CN105524023A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Cyclohexene oxidation method |
CN105628855A (en) * | 2015-12-31 | 2016-06-01 | 浙江理工大学 | Method for efficiently predicting service life of catalyst for alkene epoxidation |
CN109369356A (en) * | 2018-12-29 | 2019-02-22 | 郑州大学 | A kind of cyclohexene selective oxidation preparation 1,6- hexandial method |
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2007
- 2007-07-13 CN CNA2007100353516A patent/CN101343260A/en active Pending
Cited By (22)
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CN102361861A (en) * | 2009-03-25 | 2012-02-22 | 昭和电工株式会社 | Method for producing epoxy compound |
CN102361861B (en) * | 2009-03-25 | 2015-09-02 | 昭和电工株式会社 | The manufacture method of epoxy compounds |
CN102079695B (en) * | 2009-11-27 | 2014-01-15 | 中国石油化工股份有限公司 | Method for catalytically oxidizing cyclohexane |
CN102079695A (en) * | 2009-11-27 | 2011-06-01 | 中国石油化工股份有限公司 | Method for catalytically oxidizing cyclohexane |
CN102452870A (en) * | 2010-10-29 | 2012-05-16 | 中国石油化工股份有限公司 | Method for catalytically oxidizing cyclic olefin |
CN103130750B (en) * | 2011-11-29 | 2015-04-29 | 岳阳昌德化工实业有限公司 | Cyclohexene oxidizing method |
CN103130748A (en) * | 2011-11-29 | 2013-06-05 | 岳阳昌德化工实业有限公司 | Cyclohexene oxidizing method |
CN103130750A (en) * | 2011-11-29 | 2013-06-05 | 岳阳昌德化工实业有限公司 | Cyclohexene oxidizing method |
CN103130747B (en) * | 2011-11-29 | 2015-04-29 | 岳阳昌德化工实业有限公司 | Cyclohexene oxidizing method |
CN103130749A (en) * | 2011-11-29 | 2013-06-05 | 岳阳昌德化工实业有限公司 | Method for preparing cyclohexene oxide through oxidation of cyclohexene |
CN103130748B (en) * | 2011-11-29 | 2015-04-29 | 岳阳昌德化工实业有限公司 | Cyclohexene oxidizing method |
CN103130613A (en) * | 2011-11-29 | 2013-06-05 | 岳阳昌德化工实业有限公司 | Cyclohexene oxidizing method |
CN103130613B (en) * | 2011-11-29 | 2015-09-30 | 岳阳昌德化工实业有限公司 | A kind of method of cyclohexene oxide |
CN103130747A (en) * | 2011-11-29 | 2013-06-05 | 岳阳昌德化工实业有限公司 | Cyclohexene oxidizing method |
CN103130749B (en) * | 2011-11-29 | 2015-12-02 | 岳阳昌德化工实业有限公司 | A kind of cyclohexene oxide prepares the method for epoxy cyclohexane |
CN105524023A (en) * | 2014-09-29 | 2016-04-27 | 中国石油化工股份有限公司 | Cyclohexene oxidation method |
CN105524023B (en) * | 2014-09-29 | 2018-04-13 | 中国石油化工股份有限公司 | A kind of method of cyclohexene oxide |
CN105037117A (en) * | 2015-05-26 | 2015-11-11 | 岳阳昌德化工实业有限公司 | Method for simultaneously synthesizing vanillin and isovanillin |
CN105037299A (en) * | 2015-05-26 | 2015-11-11 | 岳阳昌德化工实业有限公司 | 3,4-epoxy cyclohexyl methylal diol, and synthesis method and application thereof |
CN105628855A (en) * | 2015-12-31 | 2016-06-01 | 浙江理工大学 | Method for efficiently predicting service life of catalyst for alkene epoxidation |
CN109369356A (en) * | 2018-12-29 | 2019-02-22 | 郑州大学 | A kind of cyclohexene selective oxidation preparation 1,6- hexandial method |
CN109369356B (en) * | 2018-12-29 | 2021-08-10 | 郑州大学 | Method for preparing 1, 6-hexanedial by selectively oxidizing cyclohexene |
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