CN1291957C - Method for preparing chlorocyclohexane - Google Patents
Method for preparing chlorocyclohexane Download PDFInfo
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- CN1291957C CN1291957C CN 200410011688 CN200410011688A CN1291957C CN 1291957 C CN1291957 C CN 1291957C CN 200410011688 CN200410011688 CN 200410011688 CN 200410011688 A CN200410011688 A CN 200410011688A CN 1291957 C CN1291957 C CN 1291957C
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- chlorocyclohexane
- chlorine
- hexanaphthene
- composite catalyst
- reaction
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Abstract
The present invention discloses a preparation method of chlorocyclohexane. Cyclohexane and chlorine are taken as synthesizing raw material. The preparation method is characterized in that cyclohexane and chlorine are synthesized by an intermittent liquid-phase catalyzing chlorination reaction in the existence of a composite catalyst to obtain chlorocyclohexane, wherein the mole ratio of chlorine gas to cyclohexane is 0.05 to 0.8:1, the amount of the composite catalyst accounts for 0.01 to 1 wt% of cyclohexane, and the reaction temperature is at 30 to 80 DEG C; chlorinated solution is neutralized, water washed, and distillated at normal pressure, and cyclohexane is reclaimed to be recycled; then at 81 to 85 DEG C fractions are collected at the vacuum degree of 0.08MPa; the product of chlorocyclohexane is obtained. The present invention has the advantages of low production cost, high product purity and safe operation.
Description
(1) technical field
The present invention relates to a kind of chemical products preparation method, specifically relate to a kind of preparation method of chlorocyclohexane.
(2) background technology
Up to now, the industrial production technology of chlorocyclohexane mainly contains two kinds of hexalin method and hexanaphthene light chlorination process, and the former is a raw material with hexalin and hydrochloric acid, and zinc chloride is a catalyzer; This method raw materials cost height, product purity is low, the production cycle is long, produces a large amount of dilute hydrochloric acid serious environment pollutions simultaneously.The latter is a raw material with hexanaphthene and chlorine, reacts under illumination; This method not only equipment complexity, transformation efficiency is low, and has serious safety problem, the accident of very easily blasting.Recently there is the people that the hexanaphthene light chlorination process is improved, promptly uses the blue light illumination of wavelength 350-425nm, and add a spot of cyclohexanone peroxide, yet fail to solve root problem.
(3) summary of the invention
The purpose of this invention is to provide low, the good product quality of a kind of cost, the chlorocyclohexane preparation method of operational safety.
The object of the present invention is achieved like this: raw material hexanaphthene, chlorine in the dark carry out liquid-phase catalysis chlorination reaction at intermittence in the presence of the composite catalyst of organo-peroxide and azo-compound composition.As long as catalyzer is suitable, processing condition control is suitable, just can obtain the higher hexanaphthene per pass conversion and the selectivity and the yield of chlorocyclohexane.
The technical scheme that adopts is: hexanaphthene and composite catalyst are added in the chlorination reactor, agitator speed 100-120 rev/min, 30-80 ℃ of control liquidus temperature slowly feeds gasiform chlorine from reactor bottom and causes chlorination reaction, and induction period is accelerated logical chlorine speed later and carried out chlorination reaction; After chlorinated exhaust was handled through ordinary method, water absorbs made commodity hydrochloric acid; Chlorated liquid is through neutralization, washing, and air distillation is reclaimed hexanaphthene and recycled; Under vacuum tightness 0.08MPa, collect 81-85 ℃ of cut then, obtain the chlorocyclohexane product.
Organo-peroxide comprises: di-cyclohexylperoxy dicarbonate, peroxy dicarbonate hexichol oxygen ethyl ester, peroxy dicarbonate two (the 4-tertiary butyl) cyclohexyl, peroxy dicarbonate two (2-ethylhexyl) ester, peroxy dicarbonate hexacosane ester, di-isopropyl peroxydicarbonate, peroxy dicarbonate two (2, the 4-dichloro) benzoyl, one or more in lauroyl peroxide, the benzoyl peroxide; Azo-compound comprises Diisopropyl azodicarboxylate and 2,2'-Azobis(2,4-dimethylvaleronitrile).
With above-mentioned organo-peroxide and azo-compound by weight 0.5-2.0: 1 mixes, and constitutes composite catalyst of the present invention.Catalyst levels generally accounts for the 0.01-1% of hexanaphthene weight, and preferred version is 0.02-0.8%.
The mol ratio of above-mentioned reaction raw materials chlorine and hexanaphthene is generally 0.05-0.8: 1, and preferred version is 0.1-0.6: 1.
Above-mentioned temperature of reaction generally is controlled at 30-80 ℃, preferred version 35-60 ℃.
Above-mentioned reaction pressure is normal pressure or adds and depress reaction.
According to method of the present invention, prepare chlorocyclohexane, the selectivity 88% of purpose product chlorocyclohexane, yield 85%, product purity 99% by hexanaphthene liquid-phase catalysis chlorination at intermittence.Have advantages such as production cost is low, product purity is high, production safety.
(4) embodiment
Embodiment one
Getting the adding of 158g hexanaphthene is equipped with in the four-hole boiling flask of agitator, thermometer, reflux exchanger and Chlorination tube, add the 0.1g composite catalyst, four-hole boiling flask is placed dark place, start stirring, 100 rev/mins of rotating speeds, heat temperature raising to 60 ℃ feeds chlorine with the speed of 0.05l/min, keeps 10-20min; Be cooled to 40 ℃ then, improve chlorine and feed speed, make in 4 hours, to feed 50g chlorine.Reaction mass is with after the yellow soda ash neutralization, washing, and at first air distillation gets unreacted hexanaphthene 101.5g, for synthetic use next time, collects 81-85 ℃ of cut then under vacuum tightness 0.08MPa, obtains chlorocyclohexane 68.2g.Product is through the HP6890 gas chromatographic analysis, content 99.65%, hexanaphthene per pass conversion 35.8%, selectivity 88.9%, yield 85.5%.
Embodiment two
Getting the adding of 158g hexanaphthene is equipped with in the four-hole boiling flask of agitator, thermometer, reflux exchanger and Chlorination tube, add the 0.2g composite catalyst, four-hole boiling flask is placed dark place, start stirring, 100 rev/mins of rotating speeds, heat temperature raising to 70 ℃ feeds chlorine with the speed of 0.05l/min, keeps 10min; Be cooled to 55 ℃ then, improve chlorine and feed speed, make in 4 hours, to feed 60g chlorine.Reaction mass is with after the yellow soda ash neutralization, washing, and at first air distillation gets unreacted hexanaphthene 90.7g, for synthetic use next time, collects 81-85 ℃ of cut then under vacuum tightness 0.08MPa, obtains chlorocyclohexane 80.9g.Product is through the HP6890 gas chromatographic analysis, content 99.35%, hexanaphthene per pass conversion 42.6%, selectivity 88.0%, yield 85.2%.
Embodiment three
The 1.5m of tetrafluoro sparger and cooling coil will be established in the adding of 800kg hexanaphthene
3In the glassed steel reaction vessels, add the 5.5kg composite catalyst, 110 rev/mins of mixing speed feed hot water in the glassed steel reaction vessels chuck, are warming up to 40 ℃, from the reactor bottom with 3m
3Speed about/h feeds chlorine, continues 40-60min, then with 20-30m
3The speed of/h feeds chlorine, after the condensation of chlorinated exhaust process reflux exchanger, handle through ordinary methods such as spray washing, gas-liquid separations and enter the absorption tower, water absorbs into hydrochloric acid, during the chlorination reaction, keep temperature of reaction at 40-50 ℃ by the conciliation of water coolant in chuck and the cooling coil.Feed 168kg chlorine, finish reaction.Reaction mass is with after the yellow soda ash neutralization, washing, and at first air distillation gets unreacted hexanaphthene 632kg, for synthetic use next time, collects 81-85 ℃ of cut then under vacuum tightness 0.08MPa, obtains chlorocyclohexane 203kg.Product is through the HP6890 gas chromatographic analysis, content 99.28%, yield 85.7%.
Claims (5)
1, a kind of preparation method of chlorocyclohexane, synthesis material comprises hexanaphthene and chlorine, it is characterized in that: hexanaphthene and chlorine in the dark carry out the synthetic chlorocyclohexane of liquid-phase catalysis chlorination at intermittence in the presence of composite catalyst, the mol ratio of chlorine and hexanaphthene is 0.05-0.8: 1, the composite catalyst consumption is the 0.01-1% of hexanaphthene weight, temperature of reaction 30-80 ℃; Composite catalyst is made up of organo-peroxide and azo-compound, and organo-peroxide and azo-compound are by weight 0.5-2.0: 1 mixes; Chlorated liquid is through neutralization, washing, and air distillation is reclaimed hexanaphthene and recycled; Under vacuum tightness 0.08MPa, collect 81-85 ℃ of cut then, obtain the chlorocyclohexane product.
2, the preparation method of a kind of chlorocyclohexane according to claim 1 is characterized in that: organo-peroxide is one or more in peroxy dicarbonate two (the 4-tertiary butyl) cyclohexyl or peroxy dicarbonate two (2-ethylhexyl) ester, peroxy dicarbonate hexacosane ester, lauroyl peroxide, the benzoyl peroxide; Described azo-compound is Diisopropyl azodicarboxylate or 2,2'-Azobis(2,4-dimethylvaleronitrile).
3, the preparation method of a kind of chlorocyclohexane according to claim 1, it is characterized in that: get the 158g hexanaphthene and add in the reactor, add the 0.1g composite catalyst again, reactor is placed dark place, start stirring, 100 rev/mins of agitator speeds, heat temperature raising to 60 ℃, speed with 0.05l/min feeds chlorine, keeps 10-20min; Be cooled to 40 ℃ then, improve chlorine and feed speed, make in 4 hours, to feed 50g chlorine; Reaction mass is with after the yellow soda ash neutralization, washing, and at first air distillation gets unreacted hexanaphthene 101.5g, for synthetic use next time, collects 81-85 ℃ of cut then under vacuum tightness 0.08MPa, obtains chlorocyclohexane.
4, the preparation method of a kind of chlorocyclohexane according to claim 1, it is characterized in that: get the 158g hexanaphthene and add in the reactor, add the 0.2g composite catalyst again, reactor is placed dark place, start stirring, 100 rev/mins of agitator speeds, heat temperature raising to 70 ℃, speed with 0.05l/min feeds chlorine, keeps 10min; Be cooled to 55 ℃ then, improve chlorine and feed speed, make and in 4 hours, feed 60g chlorine, reaction mass is with after the yellow soda ash neutralization, washing, at first air distillation gets unreacted hexanaphthene 90.7g, for synthetic use next time, under vacuum tightness 0.08MPa, collect 81-85 ℃ of cut then, obtain chlorocyclohexane.
5, the preparation method of a kind of chlorocyclohexane according to claim 1 is characterized in that: the 1.5m that establishes tetrafluoro sparger and cooling coil in the 800kg hexanaphthene is added
3In the glassed steel reaction vessels, add the 5.5kg composite catalyst, 110 rev/mins of mixing speed feed hot water in the glassed steel reaction vessels chuck, are warming up to 40 ℃, from the reactor bottom with 3m
3Speed about/h feeds chlorine, continues 40-60min, then with 20-30m
3The speed of/h feeds chlorine, after the condensation of chlorinated exhaust process reflux exchanger, handle through spray washing, gas-liquid separation ordinary method again and enter the absorption tower, water absorbs into hydrochloric acid, during the chlorination reaction, keep temperature of reaction at 40-50 ℃ by the conciliation of water coolant in chuck and the cooling coil, feed 168kg chlorine, finish reaction, after reaction mass neutralizes, washes with yellow soda ash, at first air distillation, get unreacted hexanaphthene 632kg, for synthetic use next time, under vacuum tightness 0.08MPa, collect 81-85 ℃ of cut then, obtain chlorocyclohexane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410011688 CN1291957C (en) | 2004-12-30 | 2004-12-30 | Method for preparing chlorocyclohexane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410011688 CN1291957C (en) | 2004-12-30 | 2004-12-30 | Method for preparing chlorocyclohexane |
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| CN1660730A CN1660730A (en) | 2005-08-31 |
| CN1291957C true CN1291957C (en) | 2006-12-27 |
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| CN 200410011688 Expired - Fee Related CN1291957C (en) | 2004-12-30 | 2004-12-30 | Method for preparing chlorocyclohexane |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101367708B (en) * | 2008-08-27 | 2011-02-02 | 山东阳谷华泰化工股份有限公司 | Preparation of chloro-cyclohexane under nitrogen protection |
| CN102146016B (en) * | 2011-01-26 | 2012-06-27 | 北京大学 | New method for simply and conveniently synthesizing chlorocyclohexane |
| CN106831314A (en) * | 2016-12-23 | 2017-06-13 | 河北科技大学 | A kind of halogenation method of cycloalkane |
| CN110156561A (en) * | 2019-06-25 | 2019-08-23 | 芮城县斯普伦迪生物工程有限公司 | A kind of the derivative chloro limonene and preparation method of limonene |
| CN110698452A (en) * | 2019-10-27 | 2020-01-17 | 淮安瀚康新材料有限公司 | Preparation method of chlorinated ethylene carbonate by using novel initiator |
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