CN101284767A - Process for preparing cyclohexanol by cyclohexene hydration reaction - Google Patents
Process for preparing cyclohexanol by cyclohexene hydration reaction Download PDFInfo
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- CN101284767A CN101284767A CNA2008100619213A CN200810061921A CN101284767A CN 101284767 A CN101284767 A CN 101284767A CN A2008100619213 A CNA2008100619213 A CN A2008100619213A CN 200810061921 A CN200810061921 A CN 200810061921A CN 101284767 A CN101284767 A CN 101284767A
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- exchange resin
- sulfonic acid
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Abstract
The invention discloses a method for preparing cyclohexanol by cyclohexene hydration. A high-pressure reactor is replaced for two to three times with nitrogen; 1 to 20g of sulfonic acid strongly acid cation-exchange resin with 200 to 300 aperture, 5 to 20 ml of cyclohexene and 15 to 30ml of water are added in the high-pressure reactor; the high-pressure reactor is positioned in an oil bath; the temperature rises to 100 to 150 DEG C; agitation and reaction are performed for 1 to 8 hours; then cooling is performed; vacuum filtration is performed to the reaction liquid; and then the filtrate is rectified to obtain cyclohexanol; the sulfonic acid strongly acid cation-exchange resin is washed with acetone for two to three times, and then is recycled. Compared with the molecular sieve as the catalyst, the method has the advantages that the conversion rate of the cyclohexene is higher, and the yield and the selectivity of the cyclohexanol are obviously improved. The stability of the catalyst is higher, the repeated test can be performed for four to five times, and the catalytic activity can be basically maintained.
Description
Technical field
The present invention relates to be used to produce the method for hexalin, more particularly, relate to a kind of method of preparing cyclohexanol by cyclohexene hydration reaction.
Background technology
Hexalin a kind of good in high boiling organic chemical industry's product, have a wide range of applications in the every field of Chemical Manufacture.It is the important intermediate of preparation hexanodioic acid and hexanolactam (monomers of polymkeric substance such as preparation nylon 6 and nylon 66), be the indispensable intermediates of amides product, it also is the main raw material of the various ethenoid resin lacquers of preparation, and be widely used as the solvent of many high molecular polymers, and be used to prepare softening agent, sterilant and spices etc.Therefore, hexalin has important use and market widely at aspects such as organic chemical industry's industry, coating, textile industries.
As the method that cyclohexene hydration is produced hexalin, the method for knowing is to use solid acid catalyst such as strong-acid ion exchange resin and zeolite as catalyzer.One of these methods is characterised in that, compares with inorganic acid catalyst with homogeneous system, has advantages such as separating simple, easy recovery.
The patent that the zeolite catalysis cyclohexene hydration is produced hexalin is existing a lot, mainly is that chemical company of Japanese Asahi Chemical Industry (Asahi chemical industry Co., Ltd) deliver by research.As far back as nineteen eighty-three, Japan company of Asahi Chemical Industry has just applied for the patent (seeing JP83-209150 and JP 60104031A) of the cyclohexene hydrating process research of employing solid acid molecular sieve catalytic, when the Si/Al of catalyzer mol ratio is 24, at 120 ℃, to obtain yield be 12.7% hexalin to tetrahydrobenzene catalytic hydration in autoclave under the 2h.The said firm discloses preparation method's (seeing JP 61180735 A) of efficient hydrate molecule sieve catalyst in 1986, containing SiO
2, Al
2O
3, alkali-metal raw material adds alkyl sulfur urine, reacts 10-200h under 100-180 ℃ of stirring, the mixture that obtains is through mixing, heat with vitriolic compound etc., and the crystal that obtains after centrifugal is washed, at 120 ℃ times dry 4h, at 500 ℃ of following roasting 5h, process and NH
4Cl ion-exchange, 400 ℃ of heating 2h obtain Si/Al mol ratio 28: 1, and cyclohexene hydration can obtain 10.8% hexalin behind 120 ℃ of following 3h, and catalyst performance keeps 240h.For the catalyst deactivation problem, the said firm has also applied for an olefin hydration molecular sieve catalyst liquid phase regenerated patent (seeing JP 61234945 A), and spent catalyst is handled and used H
2O
2, O
3, organic peroxide acid, NO
x, HNO
3Or HNO
2Deng oxide compound.During Si/Al mol ratio 63, the oil phase hexalin through 0,3 and 2100h after contain 10.6%, 10.4%, 8.1%, this moment, 15 parts of catalyzer were with 50 parts of 30%H
2O
2Stir 24h, the catalyzer oil phase after the regeneration can make hexalin content reach 10.5% again.Makoto etc. (seeing JP 63267438) have studied cyclohexene hydration on the amorphous Nb-SiOx catalyzer, obtain 150 ℃, and transformation efficiency 4% under the 3h, selectivity 94%.The Kralik of Mitsubishi Chemical industrial etc. (sees .Petroleum and Coal such as M Kralik, 37 (10): 60-62,1995) on faujusite, mordenite, ZSM-5 catalyzer, discover that the dealuminium mordenite catalytic efficiency is best, reach transformation efficiency 25%, selectivity 99%.(CN 1257840C) invented a kind of small-grain ZSM-5 prepare zeolite method in the domestic king hall, is about to SiO
2/ Al
2O
3Mol ratio 20-600, granularity are the aqueous solution of 20-300 purpose alumino silica gel particle and organic formwork agent, make mixture carry out hydrothermal crystallizing having or do not have in the presence of the ZSM-5 zeolite grain, then through once filtering, dry, roasting, can make silica alumina ratio like this is 15-200, and elementary crystal grain is the ZSM-5 zeolite of 0.1-0.5 μ m.Because this method is used the raw material that contains sodium ion in synthetic system, sequence of operations such as ammonium exchange, filtration, roasting have been reduced, thereby improved the yield of zeolite product, simplified Production Flow Chart, the transformation efficiency when this zeolite is used for the tetrahydrobenzene conversion can reach 7.4%.
E.I.Du Pont Company has applied for the patent of cyclohexene hydration on the perfluorinated sulfonic resin (seeing USP4595786 A) in 1986, but the report of other ion-exchange resin catalyzed cyclohexene hydration production hexalin is also less.
As mentioned above, use zeolite molecular sieve to make catalyzer, the method for preparing hexalin by cyclohexene hydration reaction is comparative maturity, and part industrialization, but when continuous production, exist catalyst activity to prolong in time and the rapid problem that descends, and catalyst loss is serious in reaction process.Ion exchange resin then can remedy the deficiency of this respect, and not only reaction process transformation efficiency height, selectivity are good, and easily separated, good stability.
Summary of the invention
The objective of the invention is to overcome the deficiencies in the prior art, a kind of method of preparing cyclohexanol by cyclohexene hydration reaction is provided.
Autoclave nitrogen replacement 2～3 times with 1～20g aperture are
Sulfonic acid type strong-acid cation-exchange resin, 5～20ml tetrahydrobenzene, 15～30ml water joins in the autoclave, and autoclave is placed oil bath, be warming up to 100～150 ℃, stirring reaction 1～8 hour, cooling, the reaction solution vacuum filtration, filtrate rectifying obtains hexalin; With washing with acetone sulfonic acid type strong-acid cation-exchange resin 2～3 times, reclaim the sulfonic acid type strong-acid cation-exchange resin.
The present invention compares with sieve peg-raking catalyst, and the transformation efficiency of tetrahydrobenzene is higher, and the yield and the selectivity of hexalin obviously improve.Catalyst stability is better, revision test 4～5 times, and catalytic activity remains unchanged substantially.
Embodiment
Embodiment 1
Autoclave nitrogen replacement 3 times with the 3g aperture are
The sulfonic acid type strong-acid cation-exchange resin (Zhengguang Resin Co., Ltd. produces, model C D550), the 10ml tetrahydrobenzene, 25ml water joins in the autoclave, and autoclave is placed oil bath, is warming up to 107 ℃, stirring reaction 3 hours, cooling, the reaction solution vacuum filtration, filtrate rectifying obtains hexalin; With washing with acetone sulfonic acid type strong-acid cation-exchange resin 3 times, the sulfonic acid type strong-acid cation-exchange resin is preserved standby in 80 ℃ of dry 6h down.Tetrahydrobenzene transformation efficiency and selectivity are respectively 5.90%, 87.13%.
Embodiment 2
Autoclave nitrogen replacement 3 times with the 5g aperture are
The sulfonic acid type strong-acid cation-exchange resin (Zhengguang Resin Co., Ltd. produces, model C D650), the 5ml tetrahydrobenzene, 30ml water joins in the autoclave, and autoclave is placed oil bath, is warming up to 132 ℃, stirring reaction 4 hours, cooling, the reaction solution vacuum filtration, filtrate rectifying obtains hexalin; With washing with acetone sulfonic acid type strong-acid cation-exchange resin 2 times, the sulfonic acid type strong-acid cation-exchange resin is preserved standby in 80 ℃ of dry 6h down.Tetrahydrobenzene transformation efficiency and selectivity are respectively 9.97%, 99.64%, and the hexalin yield is 9.93%.
Embodiment 3
Autoclave nitrogen replacement 3 times with the 5g aperture are
The sulfonic acid type strong-acid cation-exchange resin (Zhengguang Resin Co., Ltd. produces, model ZGC107), the 5ml tetrahydrobenzene, 30ml water joins in the autoclave, and autoclave is placed oil bath, is warming up to 132 ℃, stirring reaction 4 hours, cooling, the reaction solution vacuum filtration, filtrate rectifying obtains hexalin; With washing with acetone sulfonic acid type strong-acid cation-exchange resin 2 times, the sulfonic acid type strong-acid cation-exchange resin is preserved standby in 80 ℃ of dry 6h down.Tetrahydrobenzene transformation efficiency and selectivity are respectively 11.08%, 99.46%, and the hexalin yield is 11.02%.
Embodiment 4
Autoclave nitrogen replacement 3 times with the 5g aperture are
The sulfonic acid type strong-acid cation-exchange resin (U.S. Rhom and Hass produces, model Amberlyst 35 wet), the 5ml tetrahydrobenzene, 30ml water joins in the autoclave, and autoclave is placed oil bath, is warming up to 137 ℃, stirring reaction 4 hours, cooling, the reaction solution vacuum filtration, filtrate rectifying obtains hexalin; With washing with acetone sulfonic acid type strong-acid cation-exchange resin 3 times, the sulfonic acid type strong-acid cation-exchange resin is preserved standby in 80 ℃ of dry 6h down.Hexamethylene transformation efficiency and hexalin yield and selectivity are respectively 11.81%, 99.74%, 11.78%.
Embodiment 5
Autoclave nitrogen replacement 3 times with the 4g aperture are
The sulfonic acid type strong-acid cation-exchange resin (U.S. Rhom and Hass produces, model Amberlyst 36 wet), the 10ml tetrahydrobenzene, 25ml water joins in the autoclave, and autoclave is placed oil bath, is warming up to 150 ℃, stirring reaction 4 hours, cooling, the reaction solution vacuum filtration, filtrate rectifying obtains hexalin; With washing with acetone sulfonic acid type strong-acid cation-exchange resin 3 times, the sulfonic acid type strong-acid cation-exchange resin is preserved standby in 80 ℃ of dry 6h down.Hexamethylene transformation efficiency and hexalin yield and selectivity are respectively 7.88%, 99.8%, 7.86%.
Embodiment 6
Autoclave nitrogen replacement 3 times with the 5g aperture are
The sulfonic acid type strong-acid cation-exchange resin (U.S. Rhom and Hass produces, model Amberlyst 36 wet), the 5ml tetrahydrobenzene, 30ml water joins in the autoclave, and autoclave is placed oil bath, is warming up to 140 ℃, stirring reaction 4 hours, cooling, the reaction solution vacuum filtration, filtrate rectifying obtains hexalin; With washing with acetone sulfonic acid type strong-acid cation-exchange resin 3 times, the sulfonic acid type strong-acid cation-exchange resin is preserved standby in 80 ℃ of dry 6h down.Hexamethylene transformation efficiency and hexalin yield and selectivity are respectively 12.05%, 99.74%, 12.02%.
Embodiment 7
Autoclave nitrogen replacement 3 times with the 5g aperture are
The sulfonic acid type strong-acid cation-exchange resin (U.S. Rhom and Hass produces, model Amberlyst 36 wet), the 10ml tetrahydrobenzene, 25ml water joins in the autoclave, and autoclave is placed oil bath, is warming up to 140 ℃, stirring reaction 4 hours, cooling, the reaction solution vacuum filtration, filtrate rectifying obtains hexalin; With washing with acetone sulfonic acid type strong-acid cation-exchange resin 3 times, the sulfonic acid type strong-acid cation-exchange resin is preserved standby in 80 ℃ of dry 6h down.Hexamethylene transformation efficiency and hexalin yield and selectivity are respectively 12.55%, 99.31%, 12.46%.
Embodiment 8
Autoclave nitrogen replacement 3 times use 1 time, 2 times, 3 times, 4 times, 5 times back aperture to be 5g
The sulfonic acid type strong-acid cation-exchange resin (U.S. Rhom and Hass produces, model Amberlyst 36 wet), the 10ml tetrahydrobenzene, 25ml water joins respectively in the autoclave, and autoclave is placed oil bath, is warming up to 140 ℃, stirring reaction 4 hours, cooling, the reaction solution vacuum filtration, filtrate rectifying obtains hexalin; With washing with acetone sulfonic acid type strong-acid cation-exchange resin 2 times, the sulfonic acid type strong-acid cation-exchange resin is preserved standby in 80 ℃ of dry 6h down.Hexamethylene transformation efficiency and hexalin yield and selectivity see Table 1.
Table 1
| The experiment sequence number | The tetrahydrobenzene transformation efficiency, % | The hexalin selectivity, % | The hexalin yield, % |
| 1 | 12.85 | 98.71 | 12.23 |
| 2 | 12.62 | 98.63 | 12.46 |
| 3 | 12.25 | 99.24 | 11.76 |
| 4 | 12.12 | 98.18 | 11.80 |
| 5 | 11.13 | 98.70 | 10.66 |
Claims (1)
1. the method for a preparing cyclohexanol by cyclohexene hydration reaction is characterized in that autoclave nitrogen replacement 2～3 times, with 1～20g aperture is
Sulfonic acid type strong-acid cation-exchange resin, 5～20ml tetrahydrobenzene, 15～30ml water joins in the autoclave, and autoclave is placed oil bath, be warming up to 100～150 ℃, stirring reaction 1～8 hour, cooling, the reaction solution vacuum filtration, filtrate rectifying obtains hexalin; With washing with acetone sulfonic acid type strong-acid cation-exchange resin 2～3 times, reclaim the sulfonic acid type strong-acid cation-exchange resin.
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| CNA2008100619213A CN101284767A (en) | 2008-05-27 | 2008-05-27 | Process for preparing cyclohexanol by cyclohexene hydration reaction |
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|---|---|---|---|
| CNA2008100619213A CN101284767A (en) | 2008-05-27 | 2008-05-27 | Process for preparing cyclohexanol by cyclohexene hydration reaction |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805244A (en) * | 2010-04-08 | 2010-08-18 | 华东理工大学 | Cyclohexene hydrating process |
| CN101851151A (en) * | 2010-05-17 | 2010-10-06 | 河北工业大学 | Method for preparing cyclohexanol by using cyclohexene |
| CN102180772A (en) * | 2011-03-15 | 2011-09-14 | 天津大学 | Method for preparing cyclohexanol by hydrating cyclohexene |
| CN102399134A (en) * | 2011-11-29 | 2012-04-04 | 开滦能源化工股份有限公司 | Method for preparing cyclohexanol by cyclohexene hydration |
| CN103664529A (en) * | 2012-09-18 | 2014-03-26 | 中国石油化工股份有限公司 | Method for coproducing cyclohexanol and ethanol |
| CN103664530A (en) * | 2012-09-18 | 2014-03-26 | 中国石油化工股份有限公司 | Method for coproducing cyclohexanol and ethanol |
| CN104001541A (en) * | 2014-02-25 | 2014-08-27 | 江苏海普功能材料有限公司 | Preparing method of nanopore fluororesin acid catalysts used for olefin hydration reaction |
| CN108440241A (en) * | 2018-04-10 | 2018-08-24 | 成都凯特力华科技有限公司 | A kind of purification system and method for high purity cyclohexanol |
| CN111153766A (en) * | 2020-03-04 | 2020-05-15 | 福州大学 | Method for preparing cyclohexanol by cyclohexene normal pressure direct hydration continuous |
-
2008
- 2008-05-27 CN CNA2008100619213A patent/CN101284767A/en active Pending
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805244A (en) * | 2010-04-08 | 2010-08-18 | 华东理工大学 | Cyclohexene hydrating process |
| CN101805244B (en) * | 2010-04-08 | 2013-06-26 | 华东理工大学 | Cyclohexene hydrating process |
| CN101851151A (en) * | 2010-05-17 | 2010-10-06 | 河北工业大学 | Method for preparing cyclohexanol by using cyclohexene |
| CN101851151B (en) * | 2010-05-17 | 2013-04-24 | 河北工业大学 | Method for preparing cyclohexanol by using cyclohexene |
| CN102180772A (en) * | 2011-03-15 | 2011-09-14 | 天津大学 | Method for preparing cyclohexanol by hydrating cyclohexene |
| CN102180772B (en) * | 2011-03-15 | 2013-05-08 | 天津大学 | Method for preparing cyclohexanol by hydrating cyclohexene |
| CN102399134A (en) * | 2011-11-29 | 2012-04-04 | 开滦能源化工股份有限公司 | Method for preparing cyclohexanol by cyclohexene hydration |
| CN102399134B (en) * | 2011-11-29 | 2014-01-15 | 开滦能源化工股份有限公司 | Method for preparing cyclohexanol by cyclohexene hydration |
| CN103664529A (en) * | 2012-09-18 | 2014-03-26 | 中国石油化工股份有限公司 | Method for coproducing cyclohexanol and ethanol |
| CN103664530A (en) * | 2012-09-18 | 2014-03-26 | 中国石油化工股份有限公司 | Method for coproducing cyclohexanol and ethanol |
| CN103664529B (en) * | 2012-09-18 | 2015-10-28 | 中国石油化工股份有限公司 | The method of coproduction hexalin and ethanol |
| CN104001541A (en) * | 2014-02-25 | 2014-08-27 | 江苏海普功能材料有限公司 | Preparing method of nanopore fluororesin acid catalysts used for olefin hydration reaction |
| CN104001541B (en) * | 2014-02-25 | 2016-03-30 | 江苏海普功能材料有限公司 | For the preparation method of olefin hydration reaction nano-pore fluoride resin acidic catalyst |
| CN108440241A (en) * | 2018-04-10 | 2018-08-24 | 成都凯特力华科技有限公司 | A kind of purification system and method for high purity cyclohexanol |
| CN108440241B (en) * | 2018-04-10 | 2021-12-07 | 中国化学赛鼎宁波工程有限公司 | Purification system and method of high-purity cyclohexanol |
| CN111153766A (en) * | 2020-03-04 | 2020-05-15 | 福州大学 | Method for preparing cyclohexanol by cyclohexene normal pressure direct hydration continuous |
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Open date: 20081015 |