CN115160146B - Preparation method of 1,2-cyclohexanediamine by epoxy cyclohexane one-pot method - Google Patents
Preparation method of 1,2-cyclohexanediamine by epoxy cyclohexane one-pot method Download PDFInfo
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- CN115160146B CN115160146B CN202211094807.7A CN202211094807A CN115160146B CN 115160146 B CN115160146 B CN 115160146B CN 202211094807 A CN202211094807 A CN 202211094807A CN 115160146 B CN115160146 B CN 115160146B
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- cyclohexanediamine
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- epoxy cyclohexane
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/14—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups
- C07C209/16—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of hydroxy groups or of etherified or esterified hydroxy groups with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/82—Purification; Separation; Stabilisation; Use of additives
- C07C209/84—Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/04—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reaction of ammonia or amines with olefin oxides or halohydrins
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Abstract
The invention belongs to the technical field of 1,2-cyclohexanediamine preparation, and particularly relates to a preparation method for 1,2-cyclohexanediamine by an epoxy cyclohexane one-pot method, which comprises the following steps: mixing a catalyst, liquid ammonia and a cocatalyst, dropwise adding epoxy cyclohexane raw material at 60-100 ℃ in an oxygen-free environment, reacting until the pressure is constant, filling hydrogen, reacting at 180-210 ℃ until the pressure is constant again to obtain a reaction liquid, and separating and purifying the reaction liquid to obtain 1,2-cyclohexanediamine. The method takes the epoxy cyclohexane and the liquid ammonia as raw materials, combines with a cocatalyst such as sodium methoxide and the like, and enables the liquid ammonia to be added at one time and mixed with the catalyst, so that the epoxy cyclohexane and the liquid ammonia are reacted in one step to generate the 2-aminocyclohexanol, the 2-aminocyclohexanol is synthesized into the 1,2-cyclohexanediamine under the hydroamination condition, the downstream application of the epoxy cyclohexane is widened, a stable source is provided for the 1,2-cyclohexanediamine, and the cost is reduced.
Description
Technical Field
The invention belongs to the technical field of 1,2-cyclohexanediamine preparation, and particularly relates to a preparation method for 1,2-cyclohexanediamine by an epoxy cyclohexane one-pot method.
Background
1,2-cyclohexanediamine is an important chemical raw material, has wide application, can be used as an epoxy resin curing agent in coating, can be used as an intermediate in medicine synthesis, can be used as a chelating agent in water treatment, and can also be used for producing polyurethane, polyamide and the like.
The 1,2-cyclohexanediamine on the market at present is mainly derived from a byproduct generated in the process of producing the hexamethylenediamine by hydrogenating adiponitrile. The process route is very complex, the technology is only controlled by a few international companies, the supply of adiponitrile is limited, and the 1,2-cyclohexanediamine is insufficient and has very high price.
CN201110072086.5 discloses that 1,2-cyclohexanediamine can be prepared by hydrogenation of o-phenylenediamine, the adopted catalyst uses noble metal Ru as active component, re, co, ni and Fe as auxiliary metal and Al 2 O 3 Or SiO 2 As a carrier, naNO 2 As an auxiliary agent, ammonia and catalyst at a certain temperatureThe hydrogenation of o-phenylenediamine is realized under the action of a catalyst, but the o-phenylenediamine raw material still has the problem of high price.
The patent CN201610893045.5 discloses a preparation method of trans-cyclohexanediamine, epoxy cyclohexane is used as a raw material, the epoxy cyclohexane and ammonia water are subjected to ring opening, then sulfuric acid is added for dehydration and salt formation, alkali is added for dissociation, then ammonia water is added for ring opening, and finally, the trans-cyclohexanediamine is obtained through distillation. The method has complex process route and generates waste residue and waste water in the process.
The patent CN201510745480.9 discloses a preparation method of 1,2-cyclohexanediamine, the method adopts 2-aminocyclohexanol as a raw material, and the raw material reacts with ammonia under the action of a catalyst to prepare 1,2-cyclohexanediamine, one or more solvents are needed, and the steps of post-treatment and energy consumption are increased.
The cyclohexene oxide is mainly derived from byproducts in the process of synthesizing cyclohexanone by oxidizing cyclohexane. The process route for synthesizing cyclohexanone by oxidizing cyclohexane is mature, the productivity is high, and the situation of epoxy cyclohexane excess supply is obvious. Therefore, the development of a process route for synthesizing 1,2-cyclohexanediamine by using cyclohexene oxide has been a hot point of research.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the existing 1,2-cyclohexanediamine preparation process has a complex route and high cost, and causes insufficient supply; the invention overcomes the defects of the prior art, provides a preparation method for preparing 1,2-cyclohexanediamine by an epoxy cyclohexane one-pot method, reduces the preparation cost, and has high yield and stable product.
In order to solve the technical problems, the technical scheme of the invention is as follows:
the invention relates to a preparation method of 1,2-cyclohexanediamine by an epoxycyclohexane one-pot method, which comprises the following steps:
mixing a catalyst, liquid ammonia and a cocatalyst, dropwise adding an epoxy cyclohexane raw material at 60-100 ℃ in an oxygen-free environment, reacting until the pressure is constant, filling hydrogen, reacting at 180-210 ℃ until the pressure is constant again to obtain a reaction liquid, and separating and purifying the reaction liquid to obtain 1,2-cyclohexanediamine.
Wherein:
the molar ratio of the liquid ammonia to the epoxy cyclohexane is (1-10) to 1.
The catalyst is at least one of Raney nickel, raney cobalt, raney copper, supported nickel, supported palladium or supported ruthenium.
The dosage of the catalyst is 5-50% of the mass of the raw material of the cyclohexene oxide.
The cocatalyst is at least one of sodium methoxide, potassium methoxide, sodium hydroxide, potassium hydroxide or lithium hydroxide, and preferably sodium methoxide; the dosage of the cocatalyst is 0.1-1.2% of the mass of the raw material of the epoxy cyclohexane.
The filling pressure of the hydrogen is 2-12 MPa.
The separation and purification method comprises the following steps: and carrying out normal pressure dehydration and reduced pressure rectification in sequence.
The reflux ratio of the atmospheric dehydration is 15-25, preferably 20.
The pressure of the vacuum rectification is less than 1KPa.
In the invention, the following reactions mainly occur when the epoxy cyclohexane raw material is dripped until the pressure is constant:
after filling with hydrogen, the following reactions mainly take place after the reaction has been carried out until the pressure is once again constant:
the catalyst can effectively inhibit the auto-polymerization of the intermediate aminocyclohexanol in the competitive reaction, and improve the reaction selectivity.
Wherein the formula of the aminocyclohexanol self-polymerization competition reaction is as follows:
compared with the prior art, the invention has the following beneficial effects:
the method takes the cyclohexene oxide and the liquid ammonia as raw materials, combines with a cocatalyst such as sodium methoxide and the like, and adds the liquid ammonia at one time and mixes the liquid ammonia with a catalyst, so that the cyclohexene oxide and the liquid ammonia react in one step to generate the 2-aminocyclohexanol, and the 2-aminocyclohexanol synthesizes 1,2-cyclohexanediamine under the hydroamination condition, thereby widening the downstream application of the cyclohexene oxide, providing a stable source for 1,2-cyclohexanediamine, and reducing the cost.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1
50g of Raney nickel catalyst is immobilized in a reaction kettle, nitrogen is used for replacement, 340g of liquid ammonia and 1.2g of potassium methoxide are added, 1000g of epoxy cyclohexane is dropwise added under the stirring state at 60 ℃, 12.0MPa of hydrogen is filled after the pressure in the kettle is constant, the reaction is carried out at 180 ℃ until the pressure is constant again to obtain a reaction liquid, and the reaction liquid is subjected to normal-pressure dehydration (reflux ratio is 15: 1) and reduced-pressure rectification (pressure: 8 KPa) in sequence for separation and purification to obtain 1,2-cyclohexanediamine.
The detection proves that the yield of 1,2-cyclohexanediamine is 92%.
Example 2
35g of Raney cobalt catalyst is immobilized in a reaction kettle, nitrogen is used for replacement, 170g of liquid ammonia and 1g of sodium methoxide are added, 300g of epoxy cyclohexane is dropwise added under the stirring state at 100 ℃, 6MPa of hydrogen is charged after the pressure in the reaction kettle is constant, the reaction is carried out at 210 ℃ until the pressure is constant again to obtain reaction liquid, and the reaction liquid is subjected to normal-pressure dehydration (reflux ratio is 20.
The detection result shows that the yield of 1,2-cyclohexanediamine is 95%.
Example 3
Carrying 20g of Raney copper on a reaction kettle, replacing with nitrogen, adding 85g of liquid ammonia and 0.8g of sodium hydroxide, dropwise adding 120g of epoxy cyclohexane under the stirring state at 85 ℃, filling 2MPa of hydrogen after the pressure in the kettle is constant, reacting at 200 ℃ until the pressure is constant again to obtain a reaction liquid, and separating and purifying the reaction liquid sequentially by normal-pressure dehydration (reflux ratio is 18.
The detection proves that the yield of 1,2-cyclohexanediamine is 93%.
Example 4
60g of activated carbon-supported nickel catalyst is immobilized in a reaction kettle, nitrogen is used for replacement, 170g of liquid ammonia and 1.4g of potassium hydroxide are added, 120g of epoxy cyclohexane is dropwise added at 70 ℃ under a stirring state, 8MPa of hydrogen is filled after the pressure in the kettle is constant, the reaction is carried out at 190 ℃ until the pressure is constant again to obtain a reaction liquid, and the reaction liquid is subjected to normal-pressure dehydration (reflux ratio is 22: 1) and reduced-pressure rectification (pressure: 8 KPa) in sequence for separation and purification to obtain 1,2-cyclohexanediamine.
The detection proves that the yield of 1,2-cyclohexanediamine is 92%.
Example 5
40g of activated carbon supported palladium catalyst is immobilized in a reaction kettle, nitrogen is used for replacement, 170g of liquid ammonia and 1.1g of lithium hydroxide are added, 100g of cyclohexene oxide is dropwise added at 75 ℃ under the stirring state, 4MPa of hydrogen is charged after the pressure in the kettle is constant, the reaction is carried out at 195 ℃ until the pressure is constant again to obtain a reaction solution, and the reaction solution is subjected to normal-pressure dehydration (reflux ratio is 20: 1) and reduced-pressure rectification (pressure: 8 KPa) in sequence for separation and purification to obtain 1,2-cyclohexanediamine.
The detection proves that the yield of 1,2-cyclohexanediamine is 91%.
Example 6
50g of activated carbon supported ruthenium catalyst is immobilized in a reaction kettle, nitrogen is used for replacement, 170g of liquid ammonia and 1.2g of sodium methoxide are added, 150g of epoxy cyclohexane is dropwise added under the stirring state at 65 ℃, 10MPa of hydrogen is filled after the pressure in the kettle is constant, the reaction is carried out at 185 ℃ until the pressure is constant again to obtain a reaction liquid, and the reaction liquid is subjected to normal-pressure dehydration (reflux ratio is 25: 1) and reduced-pressure rectification (pressure: 8 KPa) in sequence for separation and purification to obtain 1,2-cyclohexanediamine.
The detection proves that the yield of 1,2-cyclohexanediamine is 91.5%.
Comparative example 1
The method comprises the steps of loading 20g of activated carbon-loaded ruthenium catalyst in a reaction kettle, adding 34g of liquid ammonia and 0.8g of sodium hydroxide, replacing air in the kettle with hydrogen, dropwise adding 120g of cyclohexene oxide at 80 ℃ under a stirring state, adding 40g of liquid ammonia after the pressure in the kettle is constant, recharging 2MPa of hydrogen, and reacting at 200 ℃ until the pressure is constant again to obtain a reaction solution. Separating and purifying the reaction liquid to obtain the 1, 2-cyclohexanediamine.
The detection proves that the yield of 1,2-cyclohexanediamine is 77%.
Comparative example 2
Comparative example 2 is substantially the same as example 3 except that 20g of isopropyl alcohol was further added as a solvent in comparative example 2.
The addition of isopropanol dilutes the ammonia concentration in the reaction solution on one hand, and reacts with ammonia to generate isopropanolamine on the other hand, thereby increasing the difficulty and energy consumption of subsequent separation.
The detection proves that the yield of 1,2-cyclohexanediamine is 83%.
Of course, the foregoing is only a preferred embodiment of the invention and should not be taken as limiting the scope of the embodiments of the invention. The present invention is not limited to the above examples, and equivalent changes and modifications made by those skilled in the art within the spirit of the present invention should be included in the scope of the present invention.
Claims (1)
1. A method for preparing 1,2-cyclohexanediamine by an epoxy cyclohexane one-pot method is characterized by comprising the following steps: 35g of Raney cobalt catalyst is immobilized in a reaction kettle, nitrogen is replaced, 170g of liquid ammonia and 1g of sodium methoxide are added, 300g of epoxy cyclohexane is dropwise added at 100 ℃ under the stirring state, after the pressure in the kettle is constant, 6MPa of hydrogen is charged, the reaction is carried out at 210 ℃ until the pressure is constant again to obtain a reaction liquid, the reaction liquid is sequentially subjected to normal pressure dehydration and reduced pressure rectification, the reflux ratio is 20, 1 is 6KPa, and after separation and purification, 1,2-cyclohexanediamine is obtained.
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