CN102180772A - Method for preparing cyclohexanol by hydrating cyclohexene - Google Patents
Method for preparing cyclohexanol by hydrating cyclohexene Download PDFInfo
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Abstract
The invention discloses a method for preparing cyclohexanol by hydrating cyclohexene. The method comprises the following steps of: a) performing phase separation on mixed liquid obtained through hydration reaction of the cyclohexene and water in an oil water phase splitter; b) allowing the oil phase obtained in the step a to enter a filter for separation; c) allowing the aqueous phase obtained in the step a to enter an extraction phase splitter, extracting by using a light component which enters the extraction phase splitter from the top of a first rectifying tower in the step d as an extractant, allowing the extracted aqueous phase to return to a reactor for recycling, and allowing the extracted oil phase to enter the filter in the step b for filtration; d) allowing the oil phase filtered by the filter in the step b to enter the first rectifying tower, allowing one part of the cyclohexene-containing light component obtained on the top of the tower to enter the extraction phase splitter in the step c, and allowing the other part of the light component to enter the reactor for recycling; and e) allowing a tower bottom material obtained at the bottom of the first rectifying tower in the step d to enter a second rectifying and separating tower, and withdrawing the cyclohexanol product from the middle part of the tower. By the method, the cyclohexanol with the purity of over 99.6 percent can be prepared.
Description
Technical field
The present invention relates to a kind of method for preparing hexalin, particularly relate to a kind of method of preparing cyclohexanol by cyclohexene hydration reaction.
Background technology
Hexalin is the main raw material of the various ethenoid resin lacquers of preparation, and is widely used as the solvent of many high molecular polymers,
The method of traditional mode of production hexalin is that benzene hydrogenation is made hexanaphthene, and again through catalyzed oxidation system hexalin and pimelinketone, this method exists one-pass yield low, energy consumption height, and problem such as equipment corrosion.Along with benzene selective hydrogenation prepares deepening continuously of tetrahydrobenzene research, be that the synthetic method of feedstock production hexalin has existed certain application prospect significantly with the tetrahydrobenzene.Compare with traditional technology, the production technique for preparing hexalin by tetrahydrobenzene has that the hydrogen source of saving, transformation efficiency height, side reaction are few, reaction temperature and etc. characteristics.Production equipment and operation that Japan company of Asahi Chemical Industry builds up 60kt/a in nineteen ninety, the refreshing horse of China group introduction in recent years, digestion foreign technology also put into production.
As far back as the seventies in 20th century, the US3988379 report is that catalyzer can make cyclohexene hydration make hexalin with sulfuric acid.Because sulfuric acid is corrosive to equipment, chemical company of Japanese Asahi Chemical Industry has proposed to adopt the cyclohexene hydrating process of solid acid molecular sieve catalytic in nineteen eighty-three, has opened the gate of solid acid catalysis cyclohexene hydration research.JP1998-218812 prepares corresponding cyclic alcohol technology continuously to the cycloolefin hydration and reports, mainly comprise following step: (1) carries out the continuous hydration reaction of cyclenes in the presence of molecular sieve solid acid and high boiling point organic additive; (2) separate oil phase and water; (3) oil phase is delivered to the first rectifying tower rectifying after, cat head obtains unreacted cyclenes, obtains cyclic alcohol and organic additive at the bottom of the tower; (4) two tower rectifying are delivered in the bottom of a tower after, a cat head part is circulated to hydration reactor, most of cyclic alcohol is as product, organic additive is recycled to hydration reactor.The method that the disclosed cyclenes hydration of JP1999-080056 prepares cyclic alcohol is the earlier preliminary rectifying of the mixture that contains cyclic alcohol A, unreacted cyclenes B and by product C, reclaim cyclic alcohol A, simultaneously cyclenes B and by product C are delivered in the knockout tower, remove by product C after, B utilizes again cyclenes.The disclosed preparation technology of JP1999-228456 is with after the phase-splitting of hydration reaction liquid, after oil phase is delivered to the separation of first rectifying tower, cat head obtains unreacted cyclenes etc., obtain the hexalin product at the bottom of the tower, after the top of one tower delivered to two tower rectifying, a part is circulated to hydration reactor at the bottom of the tower, and the cat head light constituent is discharged as impurity.
There is weak point in existing technology, shows as:
(1) the hydration reaction compound is after oily water separation, and water still is dissolved with a certain amount of hexalin, because hydration reaction is a reversible reaction, contains the direct Returning reacting system of water of hexalin, can reduce the per pass conversion of hydration reaction;
(2) the hydration reaction compound is after oily water separation, oil phase is still carried a certain amount of hydration catalyst secretly, because cyclohexene hydration process catalyzer also has dehydrating function, in follow-up tetrahydrobenzene-hexalin rectifying separation process, with steaming of tetrahydrobenzene, hexalin easily dehydration shifts to tetrahydrobenzene balance direction, and the hexalin product yield is reduced.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of method of preparing cyclohexanol by cyclohexene hydration reaction, can access high purity cyclohexanol, hexalin selectivity height, and can make catalyzer obtain effective recycling, reduce catalyst attrition.
For solving the problems of the technologies described above, the invention provides a kind of method of preparing cyclohexanol by cyclohexene hydration reaction, comprise the steps:
A) tetrahydrobenzene and water are carried out the heterogeneous catalysis hydration reaction in hydration reactor under catalyst action, the reaction product mixed solution that obtains carries out phase-splitting in the profit phase splitter, make oil phase and aqueous phase separation, contain materials such as hexalin, tetrahydrobenzene, hexanaphthene in the oil phase, water is the outstanding slurry that contains catalyzer;
B) separate the oil phase that obtains through the profit phase splitter among the step a and enter strainer, isolate solidss such as catalyzer;
C) separate the water that obtains through the profit phase splitter among the step a and enter the extraction phase splitter, enter into the light constituent that contains tetrahydrobenzene of extraction phase splitter as extraction agent by the first rectifying tower cat head in the steps d, described aqueous phase dissolved hexalin is extracted, the reactor cycles that the water that obtains through the separation of extraction phase splitter turns back among the step a is used, and the strainer that the oil phase that extraction obtains enters into step b filters;
D) enter the first rectifying separation tower through filter filtering oil phase among the step b and carry out rectifying separation, the light constituent part that contains tetrahydrobenzene that cat head obtains enters into the extraction phase splitter of step c, and a part is returned in the reactor of described step a and recycled;
E) the tower still material that contains hexalin that obtains at the bottom of the first rectifying Tata in the steps d enters the second rectifying separation tower, the light constituent that contains tetrahydrobenzene that the second rectifying separation column overhead obtains returns the first rectifying separation tower, and the product hexalin is from the middle part extraction of the second rectifying separation tower.
The method of above-mentioned preparing cyclohexanol by cyclohexene hydration reaction, wherein, the light constituent that contains tetrahydrobenzene from the first rectifying separation column overhead that enters the extraction phase splitter among the described step c be 0.1-2 from the mass flux ratio of separating the water that obtains through the profit phase splitter among the step a.
The method of above-mentioned preparing cyclohexanol by cyclohexene hydration reaction wherein, is separated the reactor cycles use that the described solids that obtains returns described step a through filter among the described step b.
The method of above-mentioned preparing cyclohexanol by cyclohexene hydration reaction, wherein, the first rectifying separation tower is operated under normal pressure or reduced pressure in the described steps d, and working pressure is 0.03-0.1MPa, and tower top temperature is 45-85 ℃.
The method of above-mentioned preparing cyclohexanol by cyclohexene hydration reaction, wherein, the second rectifying separation tower is operated under normal pressure or reduced pressure among the described step e, and working pressure is 0.04-0.1MPa, and tower top temperature is 55-85 ℃.
The method of above-mentioned preparing cyclohexanol by cyclohexene hydration reaction, wherein, catalyzer is selected from mineral acid, Phenylsulfonic acid, strong-acid ion exchange resin or molecular sieve catalyst among the described step a, is preferably aluminium silicon salt catalyst, for example ZSM-5 (SiO
2/ Al
2O
3＞20), form is Powdered crystal grain.
The method of above-mentioned preparing cyclohexanol by cyclohexene hydration reaction, wherein, the temperature of reactor is 70-150 ℃ among the described step a, is preferably 100-130 ℃.
The method of above-mentioned preparing cyclohexanol by cyclohexene hydration reaction, wherein, the pressure of reactor is 0.1-1.0MPa (gauge pressure) among the described step a, is preferably 0.4-0.6MPa (gauge pressure).
The method of above-mentioned preparing cyclohexanol by cyclohexene hydration reaction, wherein, hydration reaction is carried out under inert atmosphere among the described step a, and gas is selected from nitrogen, helium, argon gas or carbonic acid gas.
The method of above-mentioned preparing cyclohexanol by cyclohexene hydration reaction, wherein, the content of oxygen is less than 100ppm, preferably less than 20ppm in the described step a reactor.
The method of preparing cyclohexanol by cyclohexene hydration reaction of the present invention, to in the extraction phase splitter, adopt the light constituent that contains tetrahydrobenzene of the first rectifying separation column overhead to extract through the water after the profit phase splitter separates as extraction agent, aqueous phase dissolved hexalin is extracted, afterwards again with the water Returning reacting system, because cyclohexene hydration reaction is reversible reaction, can avoid like this being dissolved with the direct Returning reacting system of water of hexalin and the per pass conversion that reduces hydration reaction.Still can carry a certain amount of hydration catalyst secretly in the oil phase after the profit phase splitter separates, because this hydration catalyst also has dehydrating function, in follow-up tetrahydrobenzene-hexalin rectifying separation process, along with steaming of tetrahydrobenzene, hexalin easily shifts and the yield of reduction hexalin to tetrahydrobenzene balance direction under the effect of catalyzer, in the present invention, to filter through the oil phase after the profit phase splitter separates, can isolate granules of catalyst, can avoid dehydration of cyclohexanol to generate tetrahydrobenzene, improved the yield of hexalin, and can fully recycle catalyzer, reduce the loss of catalyzer, prevent the generation of equipment scaling problem in the follow-up rectifying separation operation.Preparing cyclohexanol by cyclohexene hydration reaction can produce by products such as two hexamethylene ethers, and hexalin of the present invention is from the extraction of second rectifying separation tower middle part, can prevent that by product such as heavy constituent two hexamethylene ethers is contained in the hexalin product, has improved the purity of hexalin product.
The method of preparing cyclohexanol by cyclohexene hydration reaction of the present invention, can make the high purity cyclohexanol product, purity reaches more than 99.6% (weight), and the selectivity of hexalin is more than 99%, the loss of catalyzer can be reduced by method of the present invention, and equipment scaling can be prevented.
Description of drawings
Fig. 1 is the process flow sheet of preparing cyclohexanol by cyclohexene hydration reaction of the present invention.
Embodiment
Describe the present invention in detail below in conjunction with drawings and Examples.
Embodiment 1
As shown in Figure 1, reaction mass tetrahydrobenzene stream thigh 1 is joined among the hydration reactor R continuously with water stream 2, tetrahydrobenzene carries out the heterogeneous catalysis hydration reaction under catalyst action, catalyzer adopts strong-acid ion exchange resin to make catalyzer, temperature of reaction is 100 ℃ in the reactor, and reaction pressure is 0.4MPa (gauge pressure), adopts nitrogen to keep inert atmosphere in the reactor, the content of oxygen is 80ppm, obtains reaction product mixed solution stream thigh 3 through hydration reaction.
Stream thigh 3 carries out phase-splitting in profit phase splitter S1, make oil phase and aqueous phase separation, obtains oil phase stream thigh 4 and aqueous phase stream thigh 5, contains materials such as hexalin, tetrahydrobenzene, hexanaphthene in the oil phase, and water is the outstanding slurry that contains catalyzer.Oil phase stream thigh 4 enters filter F, separate solidss 12 such as obtaining catalyzer and oil phase stream thigh 11, recycle among solidss such as the catalyzer 12 Returning reactor R, oil phase stream thigh 11 enters the first rectifying separation tower T1 and carries out rectifying separation, cat head obtains containing the light component stream thigh of tetrahydrobenzene, part in the light component stream thigh 6 enters into extraction phase splitter S2 with stream thigh 7, in extraction phase splitter S2, carry out extracting and separating with aqueous phase stream thigh 5 from profit phase splitter S1, the tetrahydrobenzene that contains in the stream thigh 7 is as extraction agent, dissolved hexalin in the aqueous phase stream thigh 5 is extracted, stream thigh 7 is 0.5 with stream burst 5 mass flux ratios that enter extraction phase splitter S2, separate the aqueous phase stream thigh 10 that obtains through extraction phase splitter S2 and turn back among the reactor R and recycle, the oil phase stream that extraction obtains strands 9 enters into filter F and filters.
The stream thigh 8 that the light component stream thigh 6 of the first rectifying separation column overhead is told loops back recycle among the reactor R, and the light constituent of rectifying tower T1 cat head discharging on a small quantity obtains stream thigh 16, to discharge small amount of impurities.The working pressure of the first rectifying separation tower is 0.05MPa, and tower top temperature is 56 ℃.The tower still stream strands 13 that the tower still of the first rectifying separation tower T1 obtains containing hexalin enters into the second rectifying tower T2 and carries out rectifying separation, the working pressure of the second rectifying separation tower T2 is 0.06MPa, tower top temperature is 60 ℃, the stream thigh 14 that contains tetrahydrobenzene that the second rectifying separation tower T2 cat head obtains returns among the first rectifying tower T1, the tower still that obtains hexalin product flow thigh 15, the second rectifying separation tower T2 from second rectifying separation tower T2 middle part extraction is discharged reorganization shunting thigh 17.
The hexalin product purity that present embodiment makes can reach more than 99.6% (weight), and the selectivity of hexalin reaches 99.6%.
Embodiment 2
As shown in Figure 1, reaction mass tetrahydrobenzene stream thigh 1 is joined among the hydration reactor R continuously with water stream 2, tetrahydrobenzene carries out the heterogeneous catalysis hydration reaction under catalyst action, catalyzer adopts the ZSM-5 molecular sieve catalyst, temperature of reaction is 130 ℃ in the reactor, and reaction pressure is 0.6MPa (gauge pressure), adopts helium to keep inert atmosphere in the reactor, the content of oxygen is 20ppm, obtains reaction product mixed solution stream thigh 3 through hydration reaction.
Stream thigh 3 carries out phase-splitting in profit phase splitter S1, make oil phase and aqueous phase separation, obtains oil phase stream thigh 4 and aqueous phase stream thigh 5, contains materials such as hexalin, tetrahydrobenzene, hexanaphthene in the oil phase, and water is the outstanding slurry that contains catalyzer.Oil phase stream thigh 4 enters filter F, separate solidss 12 such as obtaining catalyzer and oil phase stream thigh 11, recycle among solidss such as the catalyzer 12 Returning reactor R, oil phase stream thigh 11 enters the first rectifying separation tower T1 and carries out rectifying separation, cat head obtains containing the light component stream thigh of tetrahydrobenzene, part in the light component stream thigh 6 enters into extraction phase splitter S2 with stream thigh 7, in extraction phase splitter S2, carry out extracting and separating with aqueous phase stream thigh 5 from profit phase splitter S1, the tetrahydrobenzene that contains in the stream thigh 7 is as extraction agent, dissolved hexalin in the aqueous phase stream thigh 5 is extracted, stream thigh 7 is 1 with stream burst 5 mass flux ratios that enter extraction phase splitter S2, separate the aqueous phase stream thigh 10 that obtains through extraction phase splitter S2 and turn back among the reactor R and recycle, the oil phase stream that extraction obtains strands 9 enters into filter F and filters.
The stream thigh 8 that the light component stream thigh 6 of the first rectifying separation column overhead is told loops back recycle among the reactor R, and the light constituent of rectifying tower T1 cat head discharging on a small quantity obtains stream thigh 16, to discharge small amount of impurities.The working pressure of the first rectifying separation tower is 0.03MPa, and tower top temperature is 45 ℃.The tower still stream strands 13 that the tower still of the first rectifying separation tower T1 obtains containing hexalin enters into the second rectifying tower T2 and carries out rectifying separation, the working pressure of the second rectifying separation tower T2 is 0.04MPa, tower top temperature is 55 ℃, the stream thigh 14 that contains tetrahydrobenzene that the second rectifying separation tower T2 cat head obtains returns among the first rectifying tower T1, the tower still that obtains hexalin product flow thigh 15, the second rectifying separation tower T2 from second rectifying separation tower T2 middle part extraction is discharged reorganization shunting thigh 17.
The hexalin product purity that present embodiment makes can reach more than 99.7% (weight), and the selectivity of hexalin reaches 99.2%.
Embodiment 3
As shown in Figure 1, reaction mass tetrahydrobenzene stream thigh 1 is joined among the hydration reactor R continuously with water stream 2, tetrahydrobenzene carries out the heterogeneous catalysis hydration reaction under catalyst action, catalyzer adopts the ZSM-5 molecular sieve catalyst, temperature of reaction is 70 ℃ in the reactor, and reaction pressure is 0.1MPa (gauge pressure), adopts argon gas to keep inert atmosphere in the reactor, the content of oxygen is 50ppm, obtains reaction product mixed solution stream thigh 3 through hydration reaction.
Stream thigh 3 carries out phase-splitting in profit phase splitter S1, make oil phase and aqueous phase separation, obtains oil phase stream thigh 4 and aqueous phase stream thigh 5, contains materials such as hexalin, tetrahydrobenzene, hexanaphthene in the oil phase, and water is the outstanding slurry that contains catalyzer.Oil phase stream thigh 4 enters filter F, separate solidss 12 such as obtaining catalyzer and oil phase stream thigh 11, recycle among solidss such as the catalyzer 12 Returning reactor R, oil phase stream thigh 11 enters the first rectifying separation tower T1 and carries out rectifying separation, cat head obtains containing the light component stream thigh of tetrahydrobenzene, part in the light component stream thigh 6 enters into extraction phase splitter S2 with stream thigh 7, in extraction phase splitter S2, carry out extracting and separating with aqueous phase stream thigh 5 from profit phase splitter S 1, the tetrahydrobenzene that contains in the stream thigh 7 is as extraction agent, dissolved hexalin in the aqueous phase stream thigh 5 is extracted, stream thigh 7 is 0.1 with stream burst 5 mass flux ratios that enter extraction phase splitter S2, separate the aqueous phase stream thigh 10 that obtains through extraction phase splitter S2 and turn back among the reactor R and recycle, the oil phase stream that extraction obtains strands 9 enters into filter F and filters.
The stream thigh 8 that the light component stream thigh 6 of the first rectifying separation column overhead is told loops back recycle among the reactor R, and the light constituent of rectifying tower T1 cat head discharging on a small quantity obtains stream thigh 16, to discharge small amount of impurities.The working pressure of the first rectifying separation tower is 0.04MPa, and tower top temperature is 51 ℃.The tower still stream strands 13 that the tower still of the first rectifying separation tower T1 obtains containing hexalin enters into the second rectifying tower T2 and carries out rectifying separation, the working pressure of the second rectifying separation tower T2 is 0.05MPa, tower top temperature is 59 ℃, the stream thigh 14 that contains tetrahydrobenzene that the second rectifying separation tower T2 cat head obtains returns among the first rectifying tower T1, the tower still that obtains hexalin product flow thigh 15, the second rectifying separation tower T2 from second rectifying separation tower T2 middle part extraction is discharged reorganization shunting thigh 17.
The hexalin product purity that present embodiment makes can reach more than 99.7% (weight), and the selectivity of hexalin reaches 99.7%.
Embodiment 4
As shown in Figure 1, reaction mass tetrahydrobenzene stream thigh 1 is joined among the hydration reactor R continuously with water stream 2, tetrahydrobenzene carries out the heterogeneous catalysis hydration reaction under catalyst action, catalyzer adopts the ZSM-5 molecular sieve catalyst, temperature of reaction is 150 ℃ in the reactor, and reaction pressure is 1.0MPa (gauge pressure), adopts carbonic acid gas to keep inert atmosphere in the reactor, the content of oxygen is 20ppm, obtains reaction product mixed solution stream thigh 3 through hydration reaction.
Stream thigh 3 carries out phase-splitting in profit phase splitter S1, make oil phase and aqueous phase separation, obtains oil phase stream thigh 4 and aqueous phase stream thigh 5, contains materials such as hexalin, tetrahydrobenzene, hexanaphthene in the oil phase, and water is the outstanding slurry that contains catalyzer.Oil phase stream thigh 4 enters filter F, separate solidss 12 such as obtaining catalyzer and oil phase stream thigh 11, recycle among solidss such as the catalyzer 12 Returning reactor R, oil phase stream thigh 11 enters the first rectifying separation tower T1 and carries out rectifying separation, cat head obtains containing the light component stream thigh of tetrahydrobenzene, part in the light component stream thigh 6 enters into extraction phase splitter S2 with stream thigh 7, in extraction phase splitter S2, carry out extracting and separating with aqueous phase stream thigh 5 from profit phase splitter S 1, the tetrahydrobenzene that contains in the stream thigh 7 is as extraction agent, dissolved hexalin in the aqueous phase stream thigh 5 is extracted, stream thigh 7 is 2 with stream burst 5 mass flux ratios that enter extraction phase splitter S2, separate the aqueous phase stream thigh 10 that obtains through extraction phase splitter S2 and turn back among the reactor R and recycle, the oil phase stream that extraction obtains strands 9 enters into filter F and filters.
The stream thigh 8 that the light component stream thigh 6 of the first rectifying separation column overhead is told loops back recycle among the reactor R, and the light constituent of rectifying tower T1 cat head discharging on a small quantity obtains stream thigh 16, to discharge small amount of impurities.The working pressure of the first rectifying separation tower is 0.1MPa, and tower top temperature is 85 ℃.The tower still stream strands 13 that the tower still of the first rectifying separation tower T1 obtains containing hexalin enters into the second rectifying tower T2 and carries out rectifying separation, the working pressure of the second rectifying separation tower T2 is 0.1MPa, tower top temperature is 85 ℃, the stream thigh 14 that contains tetrahydrobenzene that the second rectifying separation tower T2 cat head obtains returns among the first rectifying tower T1, the tower still that obtains hexalin product flow thigh 15, the second rectifying separation tower T2 from second rectifying separation tower T2 middle part extraction is discharged reorganization shunting thigh 17.
The hexalin product purity that present embodiment makes can reach more than 99.6% (weight), and the selectivity of hexalin reaches 99.7%.
Embodiment 5
As shown in Figure 1, reaction mass tetrahydrobenzene stream thigh 1 is joined among the hydration reactor R continuously with water stream 2, tetrahydrobenzene carries out the heterogeneous catalysis hydration reaction under catalyst action, catalyzer adopts the ZSM-5 molecular sieve catalyst, temperature of reaction is 120 ℃ in the reactor, and reaction pressure is 0.5MPa (gauge pressure), adopts carbonic acid gas to keep inert atmosphere in the reactor, the content of oxygen is 15ppm, obtains reaction product mixed solution stream thigh 3 through hydration reaction.
Stream thigh 3 carries out phase-splitting in profit phase splitter S1, make oil phase and aqueous phase separation, obtains oil phase stream thigh 4 and aqueous phase stream thigh 5, contains materials such as hexalin, tetrahydrobenzene, hexanaphthene in the oil phase, and water is the outstanding slurry that contains catalyzer.Oil phase stream thigh 4 enters filter F, separate solidss 12 such as obtaining catalyzer and oil phase stream thigh 11, recycle among solidss such as the catalyzer 12 Returning reactor R, oil phase stream thigh 11 enters the first rectifying separation tower T1 and carries out rectifying separation, cat head obtains containing the light component stream thigh of tetrahydrobenzene, part in the light component stream thigh 6 enters into extraction phase splitter S2 with stream thigh 7, in extraction phase splitter S2, carry out extracting and separating with aqueous phase stream thigh 5 from profit phase splitter S1, the tetrahydrobenzene that contains in the stream thigh 7 is as extraction agent, dissolved hexalin in the aqueous phase stream thigh 5 is extracted, stream thigh 7 is 1 with stream burst 5 mass flux ratios that enter extraction phase splitter S2, separate the aqueous phase stream thigh 10 that obtains through extraction phase splitter S2 and turn back among the reactor R and recycle, the oil phase stream that extraction obtains strands 9 enters into filter F and filters.
The stream thigh 8 that the light component stream thigh 6 of the first rectifying separation column overhead is told loops back recycle among the reactor R, and the light constituent of rectifying tower T1 cat head discharging on a small quantity obtains stream thigh 16, to discharge small amount of impurities.The working pressure of the first rectifying separation tower is 0.08MPa, and tower top temperature is 70 ℃.The tower still stream strands 13 that the tower still of the first rectifying separation tower T1 obtains containing hexalin enters into the second rectifying tower T2 and carries out rectifying separation, the working pressure of the second rectifying separation tower T2 is 0.09MPa, tower top temperature is 78 ℃, the stream thigh 14 that contains tetrahydrobenzene that the second rectifying separation tower T2 cat head obtains returns among the first rectifying tower T1, the tower still that obtains hexalin product flow thigh 15, the second rectifying separation tower T2 from second rectifying separation tower T2 middle part extraction is discharged reorganization shunting thigh 17.
The hexalin product purity that present embodiment makes can reach more than 99.7% (weight), and the selectivity of hexalin reaches 99.6%.
Comparative Examples 1
Adopt experimental installation and the method identical, in processing method, remove the filter F device, the reduction by 2.0% of comparing with embodiment 1 of hexalin yield with embodiment 1.
Comparative Examples 2
Adopt experimental installation and the method identical, in processing method, remove extraction phase splitter S2, the reduction by 1.5% of comparing with embodiment 1 of tetrahydrobenzene transformation efficiency with embodiment 1.
Claims (10)
1. the method for a preparing cyclohexanol by cyclohexene hydration reaction comprises the steps:
A) tetrahydrobenzene and water are carried out the heterogeneous catalysis hydration reaction in hydration reactor under catalyst action, the reaction product mixed solution that obtains carries out phase-splitting in the profit phase splitter, make oil phase and aqueous phase separation;
B) separate the oil phase that obtains through the profit phase splitter among the step a and enter strainer, isolate solidss such as catalyzer;
C) separate the water that obtains through the profit phase splitter among the step a and enter the extraction phase splitter, enter into the light constituent that contains tetrahydrobenzene of extraction phase splitter as extraction agent by the first rectifying tower cat head in the steps d, described aqueous phase dissolved hexalin is extracted, the reactor cycles that the water that obtains through the separation of extraction phase splitter turns back among the step a is used, and the strainer that the oil phase that extraction obtains enters into step b filters;
D) enter the first rectifying separation tower through filter filtering oil phase among the step b and carry out rectifying separation, the light constituent part that contains tetrahydrobenzene that cat head obtains enters into the extraction phase splitter of step c, and a part is returned in the reactor of described step a and recycled;
E) the tower still material that contains hexalin that obtains at the bottom of the first rectifying Tata in the steps d enters the second rectifying separation tower, the light constituent that contains tetrahydrobenzene that the second rectifying separation column overhead obtains returns the first rectifying separation tower, and the product hexalin is from the middle part extraction of the second rectifying separation tower.
2. the light constituent that contains tetrahydrobenzene from the first rectifying separation column overhead that enters the extraction phase splitter among the method for claim 1, wherein described step c be 0.1-2 from the mass flux ratio of separating the water that obtains through the profit phase splitter among the step a.
3. method as claimed in claim 1 or 2 wherein, is separated the reactor cycles use that the described solids that obtains returns described step a through filter among the described step b.
4. method as claimed in claim 1 or 2, wherein, the working pressure of the first rectifying separation tower is 0.03-0.1MPa in the described steps d, tower top temperature is 45-85 ℃.
5. method as claimed in claim 1 or 2, wherein, the working pressure of the second rectifying separation tower is 0.04-0.1MPa among the described step e, tower top temperature is 55-85 ℃.
6. method as claimed in claim 1 or 2, wherein, catalyzer is selected from mineral acid, Phenylsulfonic acid, strong-acid ion exchange resin or molecular sieve catalyst among the described step a.
7. method as claimed in claim 1 or 2, wherein, the temperature of reactor is 70～150 ℃ among the described step a, is preferably 100～130 ℃.
8. method as claimed in claim 1 or 2, wherein, the pressure of reactor is 0.1～1.0MPa (gauge pressure) among the described step a, is preferably 0.4～0.6MPa (gauge pressure).
9. method as claimed in claim 1 or 2, wherein, hydration reaction is carried out under inert atmosphere among the described step a, and gas is selected from nitrogen, helium, argon gas or carbonic acid gas.
10. method as claimed in claim 9, wherein, the content of oxygen is less than 100ppm, preferably less than 20ppm in the described step a reactor.
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Cited By (5)
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| CN107118079A (en) * | 2017-07-03 | 2017-09-01 | 郑州大学 | The method that cyclohexanol is reclaimed from cyclohexanol rectifying column kettle liquid |
| CN108164396A (en) * | 2018-01-04 | 2018-06-15 | 中石化上海工程有限公司 | The method for efficiently separating refined cyclopentanol |
| CN108997081A (en) * | 2018-05-18 | 2018-12-14 | 河北科技大学 | A kind of reaction and rectification device and method of cyclohexene hydration cyclohexanol |
| CN112010736A (en) * | 2020-09-27 | 2020-12-01 | 重庆华峰化工有限公司 | Separation and recovery process of cyclohexanol process raw material |
| CN113694556A (en) * | 2021-09-30 | 2021-11-26 | 杭州浥能科技有限公司 | Energy-saving device and method for separating cyclohexanol in hydration method |
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| CN101284767A (en) * | 2008-05-27 | 2008-10-15 | 浙江大学 | Process for preparing cyclohexanol by cyclohexene hydration reaction |
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