CN109206343A - A kind of preparation method of adiponitrile - Google Patents
A kind of preparation method of adiponitrile Download PDFInfo
- Publication number
- CN109206343A CN109206343A CN201710540292.1A CN201710540292A CN109206343A CN 109206343 A CN109206343 A CN 109206343A CN 201710540292 A CN201710540292 A CN 201710540292A CN 109206343 A CN109206343 A CN 109206343A
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- CN
- China
- Prior art keywords
- preparation
- reaction
- ethylmethylimidazolium
- adiponitrile
- ionic liquid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/22—Preparation of carboxylic acid nitriles by reaction of ammonia with carboxylic acids with replacement of carboxyl groups by cyano groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of preparation methods of adiponitrile, belong to organic synthesis field, and step is specific as follows: (1) preparation of ethylmethylimidazolium biphosphate ionic liquid；(2) ethylmethylimidazolium biphosphate ionic liquid is as solvent and catalyst, during preparing adiponitrile for adipic acid nitrilation, reduces time and the temperature of reaction to a certain extent, reduces the side reaction of reaction, yield improves.
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to a kind of preparation method of adiponitrile.
Background technique
Adiponitrile is very important chemical intermediate, its derivative has very extensive purposes, for example, it derives
The hexamethylene diamine of one of object is exactly the base stock for producing nylon66 fiber etc..
The traditional adipic acid adiponitrile method industrially used is usually carboxylic acid ammoniation process, and widely used process is handle
Carboxylic acid or derivatives thereof dissolves by heating in open system, then lasting that ammonia is passed through in solution, so that system is in phosphoric acid
Or reacted in the presence of the catalyst such as phosphate, that there are reaction temperatures is higher for the technique, the reaction time is longer, and side reaction is tighter
The problems such as weight.
Ionic liquid has many excellent properties, and many ionic liquids have the dual function of solvent and catalyst, tool
There is a high thermal stability, acidic ion liquid, especially bronsted acid ionic liquid are due to green non-pollution, to nothing
The dissolubility that machine and organic compound have all had, acidic site difference is uniform, is easy to the features such as being separated with product, has
Good prospect.
Summary of the invention
Present invention aims to be prepared with ethylmethylimidazolium biphosphate ionic liquid for adipic acid nitrilation
During adiponitrile, to reach reduction reaction temperature, shortens the reaction time, reduce the purpose of side reaction.
A kind of preparation method of adiponitrile, step are specific as follows:
Adipic acid, ethylmethylimidazolium biphosphate ionic liquid are heated to 140~190 DEG C, make para hydroxybenzene first
Acid by staged leads to ammonia after being completely melt, then heats to 200~280 DEG C, insulation reaction 30~60 minutes up to para hydroxybenzene
Formonitrile HCN.
Described leads to ammonia by staged for the every heating one third of reaction temperature, leads to ammonia amount and reduces one third.
Preferable reaction temperature is 240 DEG C, and the reaction time is 40 minutes.
The step further includes that rectification and purification is carried out to adiponitrile crude product, and rectifying column kettle temperature is 220~260 DEG C, tower top
Temperature is 200~250 DEG C, and vacuum degree is 0.001~0.005MPa.
It is preferred that the rectifying column kettle temperature is 240 DEG C, tower top temperature is 220 DEG C, vacuum degree 0.002MPa.
A kind of preparation method of adiponitrile, preferred steps are as follows:
(1) adipic acid is added in cyanation device, and ethylmethylimidazolium biphosphate ionic liquid is added,
Dosage is the 5~50% of adipic acid volume；
(2) 140~190 DEG C are heated to, leads to ammonia by staged after being completely melt adipic acid, then heats to 220~300
DEG C, insulation reaction 30~60 minutes；
(3) after completion of the reaction, adiponitrile crude product carries out rectification and purification, and rectifying column kettle temperature is 220~250 DEG C, tower top temperature
It is 200~250 DEG C, vacuum degree is 0.001~0.005MPa.
The synthesis of the ethylmethylimidazolium biphosphate ionic liquid, step are specific as follows:
(1) it carries out diethyl sulfide acid esters and 1- methylimidazole to be mixed to get ethylmethylimidazolium base sulfate ion liquid
The molar ratio of body, diethyl sulfide acid esters and 1- methylimidazole is 1: 2~1: 4；
(2) ionic liquid obtained in step (1) is added in the ethanol solution containing NaOH, after reacting completely, mistake
Filter obtains colorless cleared solution；
(3) phosphoric acid is added in the colorless cleared solution that step (2) obtains, colourless transparent solution is obtained after filtering, evaporate, very
Sky is dried to obtain ethylmethylimidazolium dihydric phosphate.
The utility model has the advantages that
One beneficial effect of the invention patent is can to reduce time and the temperature of reaction to a certain extent, is made anti-
The side reaction answered is reduced, and yield improves.
Specific embodiment
With embodiment below, the invention will be further described, but it is necessary to note that following embodiment is served only for invention
The further explanation of content, does not constitute a limitation on the scope of protection of the present invention.
Embodiment 1
(1) 0.1mol 1- methylimidazole is added in there-necked flask, 0.1mol diethyl phosphate is added dropwise, after adding
Continue stirring 2 hours, reaction obtains colorless and transparent ionic liquid 1- methyl -3- ethyl imidazol(e) ethyl phosphate；
(2) it takes the NaOH of twice 1- methyl -3- ethyl imidazol(e) ethyl phosphate molal quantity to be dissolved in ethyl alcohol, is added dropwise
Into 1- methyl -3- ethyl imidazol(e) ethyl phosphate ethanol solution, white precipitate is generated, colourless transparent liquid is obtained by filtration,
Equimolar phosphoric acid solution is added in the liquid, has a small amount of solid to generate, liquid is obtained by filtration again；
(3) aforesaid liquid is evaporated and removes water and alcohol, then obtain product 1- methyl -3- ethyl imidazol(e) ethyl after being dried in vacuo
Phosphate, yield 97%；
(4) 50g adipic acid is added in cyanation device, and ethylmethylimidazolium biphosphate ionic liquid is added
10mL is heated to 150 DEG C, after adipic acid is completely melt, leads to ammonia by staged, then heats to 240 DEG C, insulation reaction 40 is divided
Clock, after completion of the reaction, adiponitrile crude product carry out rectification and purification, and rectifying column kettle temperature is 240 DEG C, and tower top temperature is 220 DEG C of (vacuum degrees
For 0.002MPa), yield 75%.
Embodiment 2
(1) 0.5mol 1- methylimidazole is added in there-necked flask, 0.5mol diethyl phosphate is added dropwise, after adding
Continue stirring 1.5 hours, reaction obtains colorless and transparent ionic liquid 1- methyl -3- ethyl imidazol(e) ethyl phosphate；
(2) it takes the NaOH of twice 1- methyl -3- ethyl imidazol(e) ethyl phosphate molal quantity to be dissolved in ethyl alcohol, is added dropwise
Into 1- methyl -3- ethyl imidazol(e) ethyl phosphate ethanol solution, white precipitate is generated, colourless transparent liquid is obtained by filtration,
Equimolar phosphoric acid solution is added in the liquid, has a small amount of solid to generate, liquid is obtained by filtration again；
(3) aforesaid liquid is evaporated and removes water and alcohol, then obtain product 1- methyl -3- ethyl imidazol(e) ethyl after being dried in vacuo
Phosphate, yield 98%；
(4) 100g adipic acid is added in cyanation device, and ethylmethylimidazolium dihydric phosphate ionic liquid is added
Body 20mL is heated to 160 DEG C, after adipic acid is completely melt, leads to ammonia by staged, then heats to 300 DEG C, insulation reaction 80
Minute, after completion of the reaction, adiponitrile crude product carries out rectification and purification, and rectifying column kettle temperature is 240 DEG C, and tower top temperature is 220 DEG C of (vacuum
Degree is 0.002MPa), yield 71%.
Claims (7)
1. a kind of preparation method of adiponitrile, it is characterised in that: step is specific as follows:
Adipic acid, ethylmethylimidazolium biphosphate ionic liquid are heated to 140~190 DEG C, keep P-hydroxybenzoic acid complete
Lead to ammonia by staged after running down, then heats to 200~280 DEG C, insulation reaction 30~60 minutes up to p-HBN.
2. preparation method according to claim 1, it is characterised in that: described leads to ammonia by staged for every liter of reaction temperature
Warm one third leads to ammonia amount and reduces one third.
3. preparation method according to claim 1, it is characterised in that: reaction temperature is 240 DEG C, and the reaction time is 40 points
Clock.
4. preparation method according to claim 1, it is characterised in that: the step further includes carrying out to adiponitrile crude product
Rectification and purification, rectifying column kettle temperature are 220~260 DEG C, and tower top temperature is 200~250 DEG C, and vacuum degree is 0.001~0.005MPa.
5. the preparation method according to claim 4, it is characterised in that: the rectifying column kettle temperature is 240 DEG C, tower top temperature
It is 220 DEG C, vacuum degree 0.002MPa.
6. preparation method according to claim 1, it is characterised in that: its step are as follows:
(1) adipic acid is added in cyanation device, and ethylmethylimidazolium biphosphate ionic liquid, dosage is added
It is the 5~50% of adipic acid volume；
(2) 140~190 DEG C are heated to, leads to ammonia by staged after being completely melt adipic acid, then heats to 220~300 DEG C,
Insulation reaction 30~60 minutes；
(3) after completion of the reaction, adiponitrile crude product carries out rectification and purification, and rectifying column kettle temperature is 220~250 DEG C, tower top temperature 200
~250 DEG C, vacuum degree is 0.001~0.005MPa.
7. preparation method described in -6 any one according to claim 1, it is characterised in that: the ethylmethylimidazolium phosphoric acid
The synthesis of dihydro ionic liquid, step are specific as follows:
(1) diethyl sulfide acid esters and 1- methylimidazole be mixed to get ethylmethylimidazolium base sulfate ion liquid, two
The molar ratio of ethyl sulfuric acid ester and 1- methylimidazole is 1: 2~1: 4；
(2) ionic liquid obtained in step (1) is added in the ethanol solution containing NaOH, after reacting completely, is filtered
To colorless cleared solution；
(3) phosphoric acid is added in the colorless cleared solution that step (2) obtains, colourless transparent solution, evaporation is obtained after filtering, vacuum is done
It is dry to obtain ethylmethylimidazolium dihydric phosphate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710540292.1A CN109206343A (en) | 2017-07-04 | 2017-07-04 | A kind of preparation method of adiponitrile |
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| CN201710540292.1A CN109206343A (en) | 2017-07-04 | 2017-07-04 | A kind of preparation method of adiponitrile |
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| CN109206343A true CN109206343A (en) | 2019-01-15 |
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| CN201710540292.1A Pending CN109206343A (en) | 2017-07-04 | 2017-07-04 | A kind of preparation method of adiponitrile |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110790678A (en) * | 2019-11-07 | 2020-02-14 | 常州瑞华化工工程技术股份有限公司 | Method for synthesizing adiponitrile by liquid-phase ammoniation and high-temperature dehydration of adipic acid |
| CN111056972A (en) * | 2019-12-16 | 2020-04-24 | 中国科学院大连化学物理研究所 | Application of alkyl quaternary phosphonium salt ionic liquid in synthesis of adiponitrile from adipic acid |
| CN111848447A (en) * | 2019-04-24 | 2020-10-30 | 山东华鲁恒升化工股份有限公司 | Method for preparing adiponitrile by gas-phase ammoniation and dehydration of adipic acid |
-
2017
- 2017-07-04 CN CN201710540292.1A patent/CN109206343A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111848447A (en) * | 2019-04-24 | 2020-10-30 | 山东华鲁恒升化工股份有限公司 | Method for preparing adiponitrile by gas-phase ammoniation and dehydration of adipic acid |
| CN110790678A (en) * | 2019-11-07 | 2020-02-14 | 常州瑞华化工工程技术股份有限公司 | Method for synthesizing adiponitrile by liquid-phase ammoniation and high-temperature dehydration of adipic acid |
| CN111056972A (en) * | 2019-12-16 | 2020-04-24 | 中国科学院大连化学物理研究所 | Application of alkyl quaternary phosphonium salt ionic liquid in synthesis of adiponitrile from adipic acid |
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Application publication date: 20190115 |