CN108440305A - The preparation method of 1,2- cyclohexanediamine - Google Patents
The preparation method of 1,2- cyclohexanediamine Download PDFInfo
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- CN108440305A CN108440305A CN201810442418.6A CN201810442418A CN108440305A CN 108440305 A CN108440305 A CN 108440305A CN 201810442418 A CN201810442418 A CN 201810442418A CN 108440305 A CN108440305 A CN 108440305A
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
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Abstract
The present invention relates to one kind 1, the preparation method of 2 cyclohexanediamine, catalyst, liquefied ammonia and water are mixed, in oxygen-free environment, 60 DEG C~110 DEG C dropwise addition 7-oxa-bicyclo[4.1.0 raw materials, reaction to pressure it is constant after, be filled with hydrogen, at 110 DEG C~210 DEG C reaction to pressure it is constant again after, obtain reaction solution, by the reaction solution separating-purifying up to 1,2 cyclohexanediamine.Above-mentioned 1, the preparation method of 2 cyclohexanediamine, using the 7-oxa-bicyclo[4.1.0 of excess capacity as raw material, in conjunction with water as accelerating agent, by controlling ladder-elevating temperature, and liquefied ammonia is made to be added at one time and be mixed with catalyst and water, generate 1,2 cyclohexanediamine to make 7-oxa-bicyclo[4.1.0 be reacted with liquefied ammonia, the downstream application of 7-oxa-bicyclo[4.1.0 is widened, stable source is provided to 1,2 cyclohexanediamine, reduces cost.
Description
Technical field
The present invention relates to chemosynthesis technical fields, more particularly to the preparation method of one kind 1,2- cyclohexanediamine.
Background technology
1,2- cyclohexanediamine is a kind of important epoxy hardener, industrial chemicals and medicine intermediate.Currently on the market
1,2- cyclohexanediamine is mainly derived from the by-product generated during adipic dinitrile hydrogenation production hexamethylene diamine.The production work of the adiponitrile
Skill route is complicated, and needs to use the industrial chemicals of severe toxicity, therefore the production technology is only grasped by several transnational company, is caused
The supply of adiponitrile is limited, to limit the development that adipic dinitrile hydrogenation produces hexamethylene diamine technique, also results in 1,2- rings indirectly
Hexamethylene diamine is insufficient.In addition, the byproduct compounds generated during adipic dinitrile hydrogenation production hexamethylene diamine are complicated, lead to 1,2- rings
The separating difficulty of hexamethylene diamine is larger, and cost is higher, constrains the downstream application of 1,2- cyclohexanediamine.
7-oxa-bicyclo[4.1.0 is mainly derived from the by-product during cyclohexane oxidation synthesizing cyclohexanone.Due to cyclohexane oxidation
The process route comparative maturity of synthesizing cyclohexanone, and production capacity is larger, therefore 7-oxa-bicyclo[4.1.0 supply surplus situation is obvious.
Therefore, the process route that synthesis 1,2- cyclohexanediamine is developed using 7-oxa-bicyclo[4.1.0 is become the focus of people's research.
Invention content
Based on this, it is necessary to provide a kind of using 7-oxa-bicyclo[4.1.0 as the preparation method of 1, the 2- cyclohexanediamine of raw material.
The preparation method of one kind 1,2- cyclohexanediamine, includes the following steps：
7-oxa-bicyclo[4.1.0 raw material is provided, in the 7-oxa-bicyclo[4.1.0 raw material mass content of 7-oxa-bicyclo[4.1.0 40% with
On；
Catalyst, liquefied ammonia and water are mixed, in oxygen-free environment, 60 DEG C 6110 DEG C are added dropwise the 7-oxa-bicyclo[4.1.0 raw material,
Reaction to pressure it is constant after, be filled with hydrogen, after 150 DEG C of 6250 DEG C of reactions are constant again to pressure, obtain reaction solution, the water
Dosage be the 0.5%610% of the 7-oxa-bicyclo[4.1.0 material quality, the molar ratio of the liquefied ammonia and the 7-oxa-bicyclo[4.1.0 is
(2610):1；
By the reaction solution separating-purifying, 1,2- cyclohexanediamine is obtained.
The 7-oxa-bicyclo[4.1.0 raw material is waste liquor of oxidized cyclohexane light oil in one of the embodiments,.
It is 40% that the 7-oxa-bicyclo[4.1.0 raw material, which is the mass content of 7-oxa-bicyclo[4.1.0, in one of the embodiments,
650% not purified waste liquor of oxidized cyclohexane light oil；Or the mass content of 7-oxa-bicyclo[4.1.0 is 75%685% to carry
Waste liquor of oxidized cyclohexane light oil after pure.
In one of the embodiments, the catalyst be selected from skeleton nickel, skeleton cobalt, skeletal copper, supported palladium, Supported Pt Nanoparticles and
Load at least one of molybdenum.
The dosage of the catalyst is the 5% of the 7-oxa-bicyclo[4.1.0 material quality in one of the embodiments,
630%.
The dosage of hydrogen is the 1%65% of the mole dosage of the liquefied ammonia in one of the embodiments,.
The method of the separating-purifying is in one of the embodiments,：Normal pressure dehydration is carried out successively, decompression takes off light and subtracts
Press rectifying.
The reflux ratio of the normal pressure dehydration is (263) in one of the embodiments,:1.
The de- light pressure of the decompression is 40KPa660KPa in one of the embodiments, the de- light reflux of decompression
Than for (365):1.
The pressure ＜ 10mbar of the rectification under vacuum in one of the embodiments,.
The preparation method of above-mentioned 1,2- cyclohexanediamine, using the 7-oxa-bicyclo[4.1.0 of excess capacity as raw material, in conjunction with water as rush
Into agent, by controlling ladder-elevating temperature, and liquefied ammonia is made to be added at one time and mix with catalyst and water, to make 7-oxa-bicyclo[4.1.0 and
Liquefied ammonia reaction generates 1,2- cyclohexanediamine, has widened the downstream application of 7-oxa-bicyclo[4.1.0, stabilization is provided to 1,2- cyclohexanediamine
Source, reduce cost.
Specific implementation mode
In order to make the foregoing objectives, features and advantages of the present invention clearer and more comprehensible, below to the specific reality of the present invention
The mode of applying is described in detail.Many details are elaborated in the following description in order to fully understand the present invention.But
The invention can be embodied in many other ways as described herein, and those skilled in the art can be without prejudice to this hair
Similar improvement is done in the case of bright intension, therefore the present invention is not limited to the specific embodiments disclosed below.
The preparation method of 1, the 2- cyclohexanediamine of one embodiment, includes the following steps S1106S120：
S110,7-oxa-bicyclo[4.1.0 raw material is provided.
Wherein, in 7-oxa-bicyclo[4.1.0 raw material the mass content of 7-oxa-bicyclo[4.1.0 40% or more.
Further, in the present embodiment, 7-oxa-bicyclo[4.1.0 raw material is waste liquor of oxidized cyclohexane light oil.
Further, 7-oxa-bicyclo[4.1.0 raw material be the mass content of 7-oxa-bicyclo[4.1.0 be 40%650% it is not purified
Waste liquor of oxidized cyclohexane light oil；Or the mass content of 7-oxa-bicyclo[4.1.0 is useless for the cyclohexane oxidation after 75%685% purification
Liquid light oil.
It should be noted that waste liquor of oxidized cyclohexane light oil is the by-product of generation during cyclohexane oxidation preparing cyclohexanone
Object light oil, light component is up to more than 30 kind, and wherein 7-oxa-bicyclo[4.1.0 content is 40%650%, but due to the presence of azeotropic mixture, i.e.,
Make, by rectifying, more than 20 kinds of fat (ring) hydrocarbon and aldehyde, ketone, alcohol to be also contained in the waste liquor of oxidized cyclohexane light oil after purification
Substance, as propyl alcohol, butyl formate, 2- amylalcohols, methyl-n-butyl ketone, 1- methyl pentanals, n-amyl alcohol, 1,3- dimethyl butyraldehydes, just oneself
Aldehyde, methoxycyclohexyl alkane, cyclohexanol, ethoxy butylcyclohexane, propyl cyclohexane etc., 7-oxa-bicyclo[4.1.0 content are 75%685%.It will
Waste liquor of oxidized cyclohexane light oil after waste liquor of oxidized cyclohexane light oil or purification is directly as preparing 1,2- cyclohexanediamine
Raw material is saved without being for further processing to the waste liquor of oxidized cyclohexane light oil after waste liquor of oxidized cyclohexane light oil or purification
50% or more consumption, 80% or more emission reduction can be saved.
S120, catalyst, liquefied ammonia and water are mixed, in oxygen-free environment, 606110 DEG C are added dropwise above-mentioned 7-oxa-bicyclo[4.1.0 original
Material, reaction to pressure it is constant after, be filled with hydrogen, after 150 DEG C of 6250 DEG C of reactions are constant again to pressure, obtain reaction solution.
Wherein, the dosage of water is the 0.5%610% of 7-oxa-bicyclo[4.1.0 material quality.Mole of liquefied ammonia and 7-oxa-bicyclo[4.1.0
Than for (2610):1.
It should be noted that water is added as accelerating agent together with liquefied ammonia, by the ionization hydrogen supply of water, epoxy bond can be promoted
Ring-opening reaction, open-loop rate is improved, to effectively slow down 7-oxa-bicyclo[4.1.0 and intermediate aminocyclohexanol in competitive reaction
Open loop improves reaction selectivity.
Wherein, 7-oxa-bicyclo[4.1.0 and the equation of aminocyclohexanol open loop competitive reaction are as follows：
Further, the catalyst is in skeleton nickel, skeleton cobalt, skeletal copper, supported palladium, Supported Pt Nanoparticles and load molybdenum
It is at least one.
Further, the dosage of catalyst is the 5%630% of 7-oxa-bicyclo[4.1.0 material quality.
It should be noted that it is anti-below constant main generation to pressure that 7-oxa-bicyclo[4.1.0 raw material is added dropwise at 60 DEG C 6110 DEG C
It answers：
It is main after 150 DEG C of 6250 DEG C of reactions to pressure are constant again that following reaction occurs after being filled with hydrogen：
Using active carbon-supported palladium as catalyst, it can effectively inhibit the autohemagglutination of competitive reaction intermediate aminocyclohexanol,
Improve reaction selectivity.
Wherein, the equation of aminocyclohexanol autohemagglutination competitive reaction is as follows:
Further, catalyst, without being detached to catalyst after having reacted, is handled by the way of solid-carried catalyst
Efficient, catalyst service life is and renewable up to 12618 months.
Further, the dosage of hydrogen is the 1%65% of liquefied ammonia mole dosage.
It is appreciated that 7-oxa-bicyclo[4.1.0 is added dropwise using oxygen-free environment, catalyst poisoning and ammoxidation can be prevented.
In the present embodiment, oxygen-free environment uses hydrogen displaced air.
S130, above-mentioned reaction solution is isolated and purified, obtains 1,2- cyclohexanediamine.
Wherein, the method isolated and purified is：Frequent press-dehydrating, the de- light and rectification under vacuum of decompression successively.
It is appreciated that cyclohexane oxidation after 7-oxa-bicyclo[4.1.0 raw material is waste liquor of oxidized cyclohexane light oil or purification is useless
When liquid light oil, contain there are many light component, and 1,2- cyclohexanediamine azeotrope with water in reaction solution, shipwreck is to deviate from, using normal pressure
Dehydration is discharged after settlement using light component reflux band water, water in reaction solution, and then decompression is de- light again by the part in reaction solution
Light component removes, and last rectification under vacuum obtains 1,2- cyclohexanediamine.
Wherein, the reflux ratio of normal pressure dehydration is (263):1.The de- light pressure of decompression is 40kPa660kPa, depressurizes and takes off light
Reflux ratio is (365):1.The pressure ＜ 10mbar of rectification under vacuum.
Be appreciated that if 7-oxa-bicyclo[4.1.0 raw material is pure 7-oxa-bicyclo[4.1.0, the method only normal pressure isolated and purified is de-
Water.
The preparation method of above-mentioned 1,2- cyclohexanediamine, using the 7-oxa-bicyclo[4.1.0 of excess capacity as raw material, in conjunction with water as rush
Into agent, by controlling ladder-elevating temperature so that be added at one time liquefied ammonia, so that it may so that 7-oxa-bicyclo[4.1.0 is reacted with liquefied ammonia and generate 1,2- rings
Hexamethylene diamine, simple operation, reaction selectivity are high, can greatly improve the production capacity of 1,2- cyclohexanediamine, widen 7-oxa-bicyclo[4.1.0
Downstream application provides stable source to 1,2- cyclohexanediamine, reduces cost.
In addition, the solvent-free addition of whole process, energy conservation and environmental protection.
It is specific embodiment below.
Embodiment 1
340g liquefied ammonia (20mol) and 12.25g water is added in the activated carbon supported palladium catalysts of the immobilized 122.5g of reaction kettle, uses
After hydrogen replaces the air in kettle, waste liquor of oxidized cyclohexane light oil is added dropwise at 60 DEG C, under stirring and (contains 40% epoxide ring
Hexane) 2450g is filled with 1.5MPa hydrogen after pressure in kettle is constant, then at 150 DEG C reaction to pressure it is constant again after, obtain
Reaction solution.By the reaction solution separating-purifying, 1,2- cyclohexanediamine is obtained.
After testing, the yield of 1,2- cyclohexanediamine is 73%.
Embodiment 2
The activated carbon supported palladium catalysts of the immobilized 39.3g of reaction kettle are added 170g liquefied ammonia (10mol) and 13.1g water, use hydrogen
After gas replaces the air in kettle, the waste liquor of oxidized cyclohexane light oil after purification is added dropwise at 110 DEG C, under stirring and (contains 75%
7-oxa-bicyclo[4.1.0) 131g is filled with 2.5MPa hydrogen after pressure in kettle is constant, then reacts constant again to pressure at 250 DEG C
Afterwards, reaction solution is obtained.By the reaction solution separating-purifying, 1,2- cyclohexanediamine is obtained.
After testing, the yield of 1,2- cyclohexanediamine is 95%.
Embodiment 3
The activated carbon supported palladium catalysts of the immobilized 24.5g of reaction kettle are added 85g liquefied ammonia (5mol) and 9.8g water, are set with hydrogen
After changing the air in kettle, the waste liquor of oxidized cyclohexane light oil after purification is added dropwise at 85 DEG C, under stirring and (contains 80% epoxy
Hexamethylene) 122.5g is filled with 2MPa hydrogen after pressure in kettle is constant, then at 200 DEG C reaction to pressure it is constant again after, obtain
To reaction solution.By the reaction solution separating-purifying, 1,2- cyclohexanediamine is obtained.
After testing, the yield of 1,2- cyclohexanediamine is 91%.
Comparative example 1
Comparative example 1 is substantially the same manner as Example 3, the difference is that the dosage of water is 98g in comparative example 1.
After testing, the yield of 1,2- cyclohexanediamine is 56%.
Comparative example 2
The activated carbon supported palladium catalysts of the immobilized 24.5g of reaction kettle are added 34g liquefied ammonia (2mol) and 9.8g water, are set with hydrogen
After changing the air in kettle, the waste liquor of oxidized cyclohexane light oil after purification is added dropwise at 85 DEG C, under stirring and (contains 80% epoxy
Hexamethylene) 122.5g, after pressure in kettle is constant, addition 51g liquefied ammonia (3mol) is re-filled with 2MPa hydrogen, is reacted extremely at 200 DEG C
After pressure is constant again, reaction solution is obtained.By the reaction solution separating-purifying, 1,2- cyclohexanediamine is obtained.
After testing, the yield of 1,2- cyclohexanediamine is 77%.
Comparative example 3
Comparative example 3 is substantially the same manner as Example 3, the difference is that being also added into 90g methanol as solvent in comparative example 3.
After testing, the yield of 1,2- cyclohexanediamine is 87%.
On the one hand the addition of methanol dilutes the ammonia density in reaction solution, on the other hand can be reacted with ammonia and generate carbinolamine,
Increase later separation difficulty and energy consumption.
Embodiment 4
Embodiment 4 is substantially the same manner as Example 3, the difference is that the catalyst of embodiment 4 is Raney's nickel.
After testing, the yield of 1,2- cyclohexanediamine is 83%.
Several embodiments of the invention above described embodiment only expresses, the description thereof is more specific and detailed, but simultaneously
Cannot the limitation to the scope of the claims of the present invention therefore be interpreted as.It should be pointed out that for those of ordinary skill in the art
For, without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the guarantor of the present invention
Protect range.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (10)
1. one kind 1, the preparation method of 2- cyclohexanediamine, which is characterized in that include the following steps：
7-oxa-bicyclo[4.1.0 raw material is provided, the mass content of 7-oxa-bicyclo[4.1.0 is 40% or more in the 7-oxa-bicyclo[4.1.0 raw material；
Catalyst, liquefied ammonia and water are mixed, in oxygen-free environment, 60 DEG C 6110 DEG C are added dropwise the 7-oxa-bicyclo[4.1.0 raw material, reaction
To pressure it is constant after, be filled with hydrogen, after 110 DEG C of 6210 DEG C of reactions are constant again to pressure, obtain reaction solution, the use of the water
Amount is the 0.1%610% of the 7-oxa-bicyclo[4.1.0 material quality, and the molar ratio of the liquefied ammonia and the 7-oxa-bicyclo[4.1.0 is
(2610):1；
By the reaction solution separating-purifying, 1,2- cyclohexanediamine is obtained.
2. the preparation method of 1,2- cyclohexanediamine according to claim 1, which is characterized in that the 7-oxa-bicyclo[4.1.0 raw material
For waste liquor of oxidized cyclohexane light oil.
3. the preparation method of 1,2- cyclohexanediamine according to claim 2, which is characterized in that the 7-oxa-bicyclo[4.1.0 raw material
The not purified waste liquor of oxidized cyclohexane light oil that mass content for 7-oxa-bicyclo[4.1.0 is 40%610%；Or epoxy hexamethylene
Waste liquor of oxidized cyclohexane light oil after the purification that the mass content of alkane is 71%681%.
4. according to claim 163 any one of them 1, the preparation method of 2- cyclohexanediamine, which is characterized in that the catalyst
Selected from least one of skeleton nickel, skeleton cobalt, skeletal copper, supported palladium, Supported Pt Nanoparticles and load molybdenum.
5. according to claim 163 any one of them 1, the preparation method of 2- cyclohexanediamine, which is characterized in that the catalyst
Dosage be the 7-oxa-bicyclo[4.1.0 material quality 1%630%.
6. according to claim 163 any one of them 1, the preparation method of 2- cyclohexanediamine, which is characterized in that the hydrogen
Dosage is the 1%61% of the liquefied ammonia mole dosage.
7. according to claim 163 any one of them 1, the preparation method of 2- cyclohexanediamine, which is characterized in that the separation carries
Pure method is：Normal pressure dehydration, the de- light and rectification under vacuum of decompression are carried out successively.
8. the preparation method of 1,2- cyclohexanediamine according to claim 7, which is characterized in that the reflux of the normal pressure dehydration
Than for (263):1.
9. the preparation method of 1,2- cyclohexanediamine according to claim 7, which is characterized in that the de- light pressure of decompression
For 40KPa660KPa, the de- light reflux ratio of decompression is (361):1.
10. the preparation method of 1,2- cyclohexanediamine according to claim 7, which is characterized in that the pressure of the rectification under vacuum
Power ＜ 10mbar.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109553538A (en) * | 2018-11-28 | 2019-04-02 | 南京红宝丽聚氨酯有限公司 | A kind of continuous preparation method of 1,2- cyclohexanediamine |
| CN111039803A (en) * | 2018-10-12 | 2020-04-21 | 中国石油化工股份有限公司 | Method for preparing amino-substituted cyclohexanol from cyclohexane oxidation by-product |
| CN111039801A (en) * | 2018-10-12 | 2020-04-21 | 中国石油化工股份有限公司 | Utilization method of cyclohexane oxidation by-product light oil |
| CN113831250A (en) * | 2020-06-23 | 2021-12-24 | 中国科学院过程工程研究所 | Method, device and catalyst for preparing 1, 2-butanediamine |
| CN115160146A (en) * | 2022-09-08 | 2022-10-11 | 淄博正大新材料科技有限公司 | Preparation method of 1,2-cyclohexanediamine by epoxy cyclohexane one-pot method |
| CN115991652A (en) * | 2023-01-17 | 2023-04-21 | 金浦新材料股份有限公司 | Method for continuously preparing 1, 2-cyclohexanediamine from epoxycyclohexane |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111039803A (en) * | 2018-10-12 | 2020-04-21 | 中国石油化工股份有限公司 | Method for preparing amino-substituted cyclohexanol from cyclohexane oxidation by-product |
| CN111039801A (en) * | 2018-10-12 | 2020-04-21 | 中国石油化工股份有限公司 | Utilization method of cyclohexane oxidation by-product light oil |
| CN109553538A (en) * | 2018-11-28 | 2019-04-02 | 南京红宝丽聚氨酯有限公司 | A kind of continuous preparation method of 1,2- cyclohexanediamine |
| CN109553538B (en) * | 2018-11-28 | 2021-10-22 | 南京红宝丽聚氨酯有限公司 | Continuous preparation method of 1, 2-cyclohexanediamine |
| CN113831250A (en) * | 2020-06-23 | 2021-12-24 | 中国科学院过程工程研究所 | Method, device and catalyst for preparing 1, 2-butanediamine |
| CN113831250B (en) * | 2020-06-23 | 2024-05-03 | 中国科学院过程工程研究所 | Method, device and catalyst for preparing 1, 2-butanediamine |
| CN115160146A (en) * | 2022-09-08 | 2022-10-11 | 淄博正大新材料科技有限公司 | Preparation method of 1,2-cyclohexanediamine by epoxy cyclohexane one-pot method |
| CN115991652A (en) * | 2023-01-17 | 2023-04-21 | 金浦新材料股份有限公司 | Method for continuously preparing 1, 2-cyclohexanediamine from epoxycyclohexane |
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