CN108043456B - Polyacid ionic liquid catalyst, preparation method and method for preparing cyclohexanol by catalyzing hydrolysis of cyclohexyl acetate with polyacid ionic liquid catalyst - Google Patents
Polyacid ionic liquid catalyst, preparation method and method for preparing cyclohexanol by catalyzing hydrolysis of cyclohexyl acetate with polyacid ionic liquid catalyst Download PDFInfo
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Abstract
The invention discloses a polyacid ionic liquid catalyst, a preparation method and a method for preparing cyclohexanol by catalyzing hydrolysis of cyclohexyl acetate with the polyacid ionic liquid catalyst. The method for preparing cyclohexanol by hydrolysis takes cyclohexyl acetate as a raw material and takes disulfonic acid functionalized polyacid ionic liquid as a catalyst to prepare cyclohexanol by hydrolysis reaction. The invention has the advantages that the conversion rate of the cyclohexyl acetate is up to 91 percent, the cyclohexanol selectivity is up to 95 percent, and the cyclohexanol yield is up to 87 percent. The method has the advantages of fast hydrolysis reaction, high cyclohexanol selectivity, mild reaction conditions, easy reuse of the catalyst and the like.
Description
Technical Field
The invention relates to a polyacid ionic liquid catalyst, a preparation method thereof and a method for preparing cyclohexanol by catalyzing hydrolysis of cyclohexyl acetate with the polyacid ionic liquid catalyst, and relates to the field of catalytic synthesis of cyclohexanol and the field of ionic liquid.
Background
Cyclohexanol is an intermediate material for producing important chemical products such as adipic acid, hexamethylene diamine, caprolactam, cyclohexanone and the like, and is widely applied to the fields of organic chemical industry, textile, coating, dye and the like. At present, the production method of cyclohexanol mainly comprises a cyclohexane oxidation method, a phenol hydrogenation method and a cyclohexene direct hydration method. Industrially, cyclohexanol is produced mainly by a cyclohexane oxidation method. However, the development of the method is limited by the defects that the raw materials are easy to form explosive mixtures with air, the conversion rate of cyclohexane is low, the selectivity of cyclohexanol is poor, the energy consumption is high, the three wastes are serious and the like. The phenol hydrogenation process has been slow in development due to the high cost of phenol and the large amount of hydrogen consumed in the reaction. The direct cyclohexene hydration method has high atom utilization rate and no waste and environmental pollution. But the application of cyclohexene is limited due to the extremely poor intersolubility of cyclohexene and water, the reaction rate is slow, the single-pass conversion rate is low, the energy consumption is increased due to the product separation and recycling, and the production process is difficult to operate. In order to overcome various defects of a direct cyclohexene hydration method, numerous scholars at home and abroad research and develop a process for preparing cyclohexanol by a cyclohexene indirect method, namely, cyclohexene and carboxylic acid (such as acetic acid) are esterified firstly and then hydrolyzed to prepare cyclohexanol. Of these, hydrolysis is of self-evident importance as the second step of the overall reaction.
Some novel catalysts are applied to the reaction process of preparing cyclohexanol by hydrolyzing cyclohexyl acetate, and catalysts such as acidic cation exchange resin, molecular sieve and the like are used for hydrolysis reaction, so that a certain yield is obtained, a better ideal reaction effect cannot be achieved, and the conversion rate and the selectivity of cyclohexanol are poor. For example, acidic cation exchange resin catalysts exhibit good catalytic activity, but also suffer from drawbacks such as poor thermal stability, susceptibility to poisoning and deactivation, and mass transfer problems.
In summary, there are some difficulties and challenges in efficiently converting cyclohexyl acetate into cyclohexanol in hydrolysis reaction, such as low hydrolysis reaction rate, generation of cyclohexene as a byproduct in the reaction process, and low cyclohexanol yield. Therefore, there is an urgent need to develop an environmentally friendly catalytic system with high activity and reusability and a green synthesis process to solve the above-mentioned key problems.
The invention synthesizes a bis-dimethylamino ethyl ether butyl sultone heteropoly acid salt catalyst, and the catalyst is applied to the hydrolysis of cyclohexyl acetate to synthesize cyclohexanol.
Disclosure of Invention
The invention aims to solve the defects of the background technology and provides a novel method for preparing cyclohexanol by hydrolyzing cyclohexyl acetate, which is characterized in that disulfonic acid group functionalized polyacid ionic liquid is used as a catalyst, cyclohexyl acetate is used as a raw material, and cyclohexanol is generated by hydrolysis reaction.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the polyacid ionic liquid catalyst is characterized in that the catalyst is a disulfonic acid group functionalized polyacid ionic liquid which is bis-dimethylaminoethylether butyl sultone heteropoly acid salt, and the structural formula of the disulfonic acid group functionalized polyacid ionic liquid is as follows: [ Bis-Bs-BDMAEE ] X
In the formula, X is more than one of the following heteropoly acid radical ions: HPW12O40 2-，HPMo12O40 2-，H2SiW12O40 2-，H2PW11VO40 2-，H2PMo11VO40 2-Or H3SiW11VO40 2-。
The disulfonic acid functionalized polyacid ionic liquid comprises:
[Bis-Bs-BDMAEE]HPW12O40、
[Bis-Bs-BDMAEE]HPMo12O40、
[Bis-Bs-BDMAEE]H2SiW12O40、
[Bis-Bs-BDMAEE]H2PW11VO40、
[Bis-Bs-BDMAEE]H2PMo11VO40、
[Bis-Bs-BDMAEE]H3SiW11VO40and the like.
A method for catalyzing hydrolysis of cyclohexyl acetate by using polyacid ionic liquid comprises the following steps: putting a reaction mixture of cyclohexyl acetate and water and a polyacid ionic liquid catalyst in a certain volume ratio into a reaction kettle for hydrolysis reaction, discharging the obtained cyclohexanol mixture after the reaction is finished, cooling and standing, gradually precipitating the polyacid ionic liquid catalyst from the feed liquid, simply filtering to realize recycling of the polyacid ionic liquid catalyst, and further distilling the liquid phase mixture to obtain the product cyclohexanol.
The volume ratio of the raw material cyclohexyl acetate to water is 1: 0.5-6; the mass of the polyacid ionic liquid catalyst accounts for 1-15% of the total mass of the raw materials; the hydrolysis reaction temperature is 50-120 ℃; the reaction time is 1-12 h.
The preparation method of the disulfonic acid functionalized polyacid ionic liquid comprises the following steps:
putting a certain molar amount of ylide in a water bath at 70-100 ℃, dissolving heteropoly acid in distilled water to form a solution, dropwise adding the solution into the onium salt, stirring, condensing and refluxing for 10-20h, removing water by reduced pressure distillation after the reaction is finished, washing, and drying in vacuum to obtain a target product; the molar ratio of the ylide to the heteropoly acid is 1: 1-1.5.
The ylide is obtained by taking bis-dimethylamino ethyl ether and 1, 4-butyl sultone with certain molar weight, stirring at 50-80 ℃ and reacting quickly to obtain white solid; washing the white solid with ethyl acetate for 3 times, filtering, and drying in vacuum at 60-100 ℃ for 10-15h to obtain a ylide; the molar ratio of the bis-dimethylamino ethyl ether to the 1, 4-butyl sultone is 1: 2-3.
Said heteropolyacid is selected from phosphotungstic acid (H)3PW12O40) Phosphomolybdic acid (H)3PMo12O40) Silicotungstic acid (H)4SiW12O40) Phosphotungstic vanadic acid (H)4PW11VO40) Phosphomolybdic acid (H)4PMo11VO40) And silicotungstic vanadic acid (H)5SiW11VO40) More than one of (1).
Compared with the prior art, the method has the remarkable advantages that:
(1) the novel disulfonic acid group functionalized polyacid ionic liquid catalyst has high catalytic activity, mild reaction conditions, higher conversion rate of cyclohexyl acetate and high selectivity of cyclohexanol;
(2) the synthesis method of the disulfonic acid group functionalized polyacid ionic liquid catalyst provided by the invention is simple, good in stability, green and environment-friendly, and solves the problems that an inorganic liquid acid catalyst is easy to generate side reaction, equipment is seriously corroded, a large amount of waste acid water is generated, and the environment pollution is caused;
(3) the disulfonic acid group functionalized polyacid ionic liquid catalyst provided by the invention is solid, can be recycled after being subjected to simple filtration, washing and drying treatment after reaction, can still keep higher catalytic activity after being used for many times, and has wide industrial application prospect.
Detailed Description
The present invention is further illustrated by the following specific examples, but the scope of the present invention is not limited to these examples.
Example 1:
a preparation method of a polyacid ionic liquid catalyst comprises the following steps:
(1) a certain amount of dimethylamino ethyl ether (0.1mol) and 1, 4-butyl sultone (0.2mol) are taken to be placed in a round-bottomed flask, and the round-bottomed flask is placed at 60 ℃ to be stirred and react quickly to obtain white solid.
(2) The obtained solid was washed with ethyl acetate 3 times, filtered and dried under vacuum at 80 ℃ for 12 hours to obtain a white solid as the ylide. An amount of the ylide (0.1mol) was then placed in a round bottom flask and placed in a water bath at 80 ℃. Taking 0.1mol of phosphotungstic acid (H)3PW12O40) Dissolved in distilled water and added drop-wise to a round bottom flask, stirred and condensed under reflux for 16 h. Removing water by reduced pressure distillation after the reaction is finished to obtain light yellow solid, washing the obtained solid for 3 times by using diethyl ether and methylbenzene in sequence, and drying the solid in vacuum at the temperature of 80 ℃ for 12 hours to obtain the catalyst [ Bis-Bs-BDMAEE ]]HPW12O40。
Mixing phosphotungstic acid (H)3PW12O40) Replacement by phosphomolybdic acid (H)3PMo12O40) Silicotungstic acid (H)4SiW12O40) Phosphotungstic vanadic acid (H)4PW11VO40) Phosphomolybdic acid (H)4PMo11VO40) Silicotungstic vanadic acid (H)5SiW11VO40) Can be prepared by the same method
[Bis-Bs-BDMAEE]HPMo12O40、
[Bis-Bs-BDMAEE]H2SiW12O40、
[Bis-Bs-BDMAEE]H2PW11VO40、
[Bis-Bs-BDMAEE]H2PMo11VO40、
[Bis-Bs-BDMAEE]H3SiW11VO40And the like.
Example 2:
a method for catalyzing hydrolysis of cyclohexyl acetate by polyacid ionic liquid comprises the following steps of sequentially adding 20m L of cyclohexyl acetate, 60m L of water and [ Bis-Bs-BDMAEE ] prepared in example 1 into a reaction kettle]HPMo12O408.74g of catalyst (accounting for 11 percent of the total mass of the raw materials), stirring, heating to the reaction temperature of 90 ℃, reacting at constant temperature for 6 hours, wherein the conversion rate of the cyclohexyl acetate is 91 percent, the selectivity of the cyclohexanol is 95 percent, and the yield of the cyclohexanol is 87 percent.
Example 3:
a method for catalyzing hydrolysis of cyclohexyl acetate by polyacid ionic liquid comprises the following steps of sequentially adding 40m L cyclohexyl acetate, 20m L water and [ Bis-Bs-BDMAEE ] prepared in example 1 into a reaction kettle]HPW12O402.94g of catalyst (accounting for 5 percent of the total mass of the raw materials), stirring, heating to 120 ℃, reacting at constant temperature for 3 hours, wherein the conversion rate of the cyclohexyl acetate is 34 percent, the selectivity of the cyclohexanol is 65 percent, and the yield of the cyclohexanol is 22 percent.
Example 4:
a method for catalyzing hydrolysis of cyclohexyl acetate by polyacid ionic liquid comprises the following steps of sequentially adding 10m L of cyclohexyl acetate, 60m L of water and [ Bis-Bs-BDMAEE ] prepared in example 1 into a reaction kettle]H2SiW12O4010.46g of catalyst (accounting for 15 percent of the total mass of the raw materials), stirring, heating to the reaction temperature of 70 ℃, reacting at constant temperature for 12 hours, wherein the conversion rate of the cyclohexyl acetate is 36 percent, the selectivity of the cyclohexanol is 84 percent, and the yield of the cyclohexanol is 30 percent.
Example 5:
a method for catalyzing hydrolysis of cyclohexyl acetate by polyacid ionic liquid comprises the following steps of sequentially adding 20m L of cyclohexyl acetate, 40m L of water and [ Bis-Bs-BDMAEE ] prepared in example 1 into a reaction kettle]H2PW11VO405.35g of catalyst (accounting for 9 percent of the total mass of the raw materials), stirring, heating to the reaction temperature of 100 ℃, reacting at constant temperature for 8 hours, wherein the conversion rate of the cyclohexyl acetate is 81 percent, the selectivity of the cyclohexanol is 83 percent, and the yield of the cyclohexanol is 67 percent.
Example 6:
a method for catalyzing hydrolysis of cyclohexyl acetate by polyacid ionic liquid comprises the following steps of sequentially adding cyclohexyl acetate 15m L, water 60m L and [ Bis-Bs-BDMAEE ] prepared in example 1 into a reaction kettle]H3SiW11VO400.75g of catalyst (accounting for 1 percent of the total mass of the raw materials), stirring, heating to the reaction temperature of 100 ℃, reacting at constant temperature for 10 hours, wherein the conversion rate of the cyclohexyl acetate is 33 percent, the selectivity of the cyclohexanol is 72 percent, and the yield of the cyclohexanol is 24 percent.
Example 7:
a method for catalyzing hydrolysis of cyclohexyl acetate by polyacid ionic liquid comprises the following steps of sequentially adding 40m L cyclohexyl acetate, 40m L water and [ Bis-Bs-BDMAEE ] prepared in example 1 into a reaction kettle]H2PMo11VO4010.25g of catalyst (accounting for 13 percent of the total mass of the raw materials), stirring, heating to the reaction temperature of 50 ℃, reacting for 7 hours at constant temperature, wherein the conversion rate of the cyclohexyl acetate is 64 percent, the selectivity of the cyclohexanol is 70 percent, and the yield of the cyclohexanol is 45 percent.
Example 8:
a method for catalyzing hydrolysis of cyclohexyl acetate by polyacid ionic liquid comprises the following steps of sequentially adding 20m L of cyclohexyl acetate, 60m L of water and [ Bis-Bs-BDMAEE ] prepared in example 1 into a reaction kettle]HPW12O405.56g of catalyst (accounting for 7 percent of the total mass of the raw materials), stirring, heating to the reaction temperature of 80 ℃, reacting at constant temperature for 5 hours, wherein the conversion rate of the cyclohexyl acetate is 65 percent, the selectivity of the cyclohexanol is 89 percent, and the yield of the cyclohexanol is 58 percent.
Example 9:
a method for catalyzing hydrolysis of cyclohexyl acetate by polyacid ionic liquid comprises the following steps of sequentially adding 10m L of cyclohexyl acetate, 50m L of water and [ Bis-Bs-BDMAEE ] prepared in example 1 into a reaction kettle]H2SiW12O401.79g of catalyst (accounting for 3 percent of the total mass of the raw materials), stirring, heating to the reaction temperature of 110 ℃, reacting at constant temperature for 1 hour, wherein the conversion rate of the cyclohexyl acetate is 21 percent, the selectivity of the cyclohexanol is 75 percent, and the yield of the cyclohexanol is 16 percent.
Example 10:
a method for catalyzing hydrolysis of cyclohexyl acetate by polyacid ionic liquid comprises the following steps of sequentially adding 10m L of cyclohexyl acetate, 60m L of water and [ Bis-Bs-BDMAEE ] prepared in example 1 into a reaction kettle]HPMo12O406.27g of catalyst (accounting for 9 percent of the total mass of the raw materials), stirring, heating to the reaction temperature of 60 ℃, reacting at constant temperature for 10 hours, wherein the conversion rate of the cyclohexyl acetate is 89 percent, the selectivity of the cyclohexanol is 85 percent, and the yield of the cyclohexanol is 76 percent.
Example 11:
a method for catalyzing hydrolysis of cyclohexyl acetate by polyacid ionic liquid comprises the following steps of sequentially adding cyclohexyl acetate 15m L, water 60m L and [ Bis-Bs-BDMAEE ] prepared in example 1 into a reaction kettle]H2PW11VO4011.18g of catalyst (accounting for 15 percent of the total mass of the raw materials), stirring, heating to the reaction temperature of 90 ℃, reacting for 7 hours at constant temperature, wherein the conversion rate of the cyclohexyl acetate is 86 percent, the selectivity of the cyclohexanol is 88 percent, and the yield of the cyclohexanol is 76 percent.
Example 12:
a method for catalyzing hydrolysis of cyclohexyl acetate by polyacid ionic liquid comprises the following steps of sequentially adding 10m L of cyclohexyl acetate, 60m L of water and [ Bis-Bs-BDMAEE ] prepared in example 1 into a reaction kettle]H3SiW11VO406.27g of catalyst (accounting for 9 percent of the total mass of the raw materials), stirring, heating to the reaction temperature of 60 ℃, reacting at constant temperature for 12 hours, wherein the conversion rate of the cyclohexyl acetate is 26 percent, the selectivity of the cyclohexanol is 82 percent, and the yield of the cyclohexanol is 21 percent.
Example 13:
a method for catalyzing hydrolysis of cyclohexyl acetate by polyacid ionic liquid comprises the following steps of sequentially adding 10m L of cyclohexyl acetate, 50m L of water and [ Bis-Bs-BDMAEE ] prepared in example 1 into a reaction kettle]H2PMo11VO402.99g of catalyst (accounting for 5 percent of the total mass of the raw materials), stirring, heating to 120 ℃ of reaction temperature, reacting for 4 hours at constant temperature, wherein the conversion rate of the cyclohexyl acetate is 63 percent, the selectivity of the cyclohexanol is 80 percent, and the yield of the cyclohexanol is 50 percent.
The above description is only a preferred embodiment of the present invention, and therefore, the scope of the present invention should not be limited by the above description, and all equivalent changes and modifications made in the claims and the contents of the specification should be included in the scope of the present invention.
Claims (10)
1. The polyacid ionic liquid catalyst is characterized in that the catalyst is a disulfonic acid group functionalized polyacid ionic liquid which is bis-dimethylaminoethylether butyl sultone heteropoly acid salt, and the structural formula of the disulfonic acid group functionalized polyacid ionic liquid is as follows: [ Bis-Bs-BDMAEE ] X
In the formula, X is more than one of the following heteropoly acid radical ions: HPWl2O40 2-，HPMol2O40 2-，H2SiWl2O40 2-，H2PWl1VO40 2-，H2PMol1VO40 2-Or H3SiWl1VO40 2-。
2. The polyacid-based ionic liquid catalyst of claim 1, wherein the catalyst comprises:
[Bis-Bs-BDMAEE]HPWl2O40、
[Bis-Bs-BDMAEE]HPMol2O40、
[Bis-Bs-BDMAEE]H2SiWl2O40、
[Bis-Bs-BDMAEE]H2PWl1VO40、
[Bis-Bs-BDMAEE]H2PMol1VO40、
[Bis-Bs-BDMAEE]H3SiWl1VO40。
3. the method for preparing the polyacid-based ionic liquid catalyst of claim 1, comprising the steps of: putting a certain molar amount of ylide Bis-Bs-BDMAEE into a water bath at 70-100 ℃, dissolving heteropoly acid in distilled water to form a solution, dropwise adding the solution into the ylide Bis-Bs-BDMAEE, stirring and condensing and refluxing for 10-20h, removing water by reduced pressure distillation after the reaction is finished, washing, and drying in vacuum to obtain a target product; the molar ratio of the ylide Bis-Bs-BDMAEE to the heteropoly acid is 1: 1-1.5.
4. The method for preparing polyacid ionic liquid catalyst of claim 3, wherein the ylium salt Bis-Bs-BDMAEE is obtained by the following method: taking bis-dimethylamino ethyl ether and 1, 4-butyl sultone in certain molar weight, stirring at 50-80 ℃ for rapid reaction to obtain white solid; washing the white solid with ethyl acetate for 3 times, filtering, and drying in vacuum at 60-100 ℃ for 10-15h to obtain a ylide Bis-Bs-BDMAEE; the molar ratio of the bis-dimethylamino ethyl ether to the 1, 4-butyl sultone is 1: 2-3.
5. The method for preparing the polyacid-based ionic liquid catalyst according to claim 3, characterized in that: the heteropoly acid is selected from phosphotungstic acid H3PWl2O40Phosphomolybdic acid H3PMol2O40Silicotungstic acid H4SiWl2O40Phosphotungstic vanadic acid H4PWl1VO40Phosphomolybdic acid H4PMol1VO40And silicotungstic vanadic acid H5SiWl1VO40More than one of (1).
6. The method for preparing the polyacid-based ionic liquid catalyst according to claim 3, characterized in that: the washing condition is that diethyl ether and toluene are used for washing for 3 times in sequence; the vacuum drying condition is vacuum drying for 10-15h at 60-100 ℃.
7. A method for preparing cyclohexanol by catalyzing hydrolysis of cyclohexyl acetate with polyacid ionic liquid is characterized in that: using cyclohexyl acetate and water as raw materials, using the polyacid ionic liquid as the catalyst in claim 1 or 2, and preparing cyclohexanol through hydrolysis reaction.
8. Process for the preparation of cyclohexanol according to claim 7, wherein: the volume ratio of the cyclohexyl acetate to the water is 1: 0.5-6; the mass of the polyacid ionic liquid catalyst accounts for 1-15% of the total mass of the raw materials.
9. Process for the preparation of cyclohexanol according to claim 7 or 8, characterised in that: the hydrolysis reaction temperature is 50-120 ℃; the reaction time is 1-12 h.
10. Process for the preparation of cyclohexanol according to claim 7, wherein: the polyacid ionic liquid catalyst is filtered, washed and dried to realize the recycling of the catalyst.
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