CN108530318A - A kind of method of Adiponitrile - Google Patents
A kind of method of Adiponitrile Download PDFInfo
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- CN108530318A CN108530318A CN201810267865.2A CN201810267865A CN108530318A CN 108530318 A CN108530318 A CN 108530318A CN 201810267865 A CN201810267865 A CN 201810267865A CN 108530318 A CN108530318 A CN 108530318A
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- cyclohexene
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- adiponitrile
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/18—Preparation of carboxylic acid nitriles by reaction of ammonia or amines with compounds containing carbon-to-carbon multiple bonds other than in six-membered aromatic rings
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of methods of Adiponitrile.Its step are as follows：By cyclohexene and concentrated ammonia liquor according to volume ratio 1：3~6 ratio mixing, is added 3,5 two trifluoromethyl, 4 n-butylbenzene selenous acid catalyst, the ratio of the catalyst mole dosage and cyclohexene volume is 0.01~0.05mol/L, in pure oxygen atmosphere, reaction is heated at 120~140 DEG C, you can obtain target product adiponitrile.Compared with adipic acid ammoniation process, the raw material of synthetic method of the present invention is more easy to get, and reaction temperature is lower；With butadiene process ratio, the present invention does not use hypertoxic raw material；Compared with acrylonitrile electrolysis method, consersion unit of the present invention is of less demanding, and energy consumption is relatively low.
Description
Technical field
The present invention relates to a kind of methods of Adiponitrile, belong to technical field of organic synthesis.
Background technology
Adiponitrile is important chemical intermediate, mainly for the preparation of nylon -66.The compound by adipic acid ammoniation process,
Butadiene process or the synthesis of Electrolytic Dimeric Acrylonitrile method.In these three methods, adipic acid ammoniation process needs higher reaction temperatures
(270~290 DEG C), and reaction process will produce solid waste；Butadiene process needs, using the hydrogen cyanide of severe toxicity, there is higher danger
Property；Electrolytic synthesis needs to consume a large amount of electric energy to equipment requirement height.Therefore, new adiponitrile synthetic method, gesture are developed
It must go.
Invention content
The object of the present invention is to provide a kind of methods of Adiponitrile.The present invention is using cyclohexene, ammonium hydroxide as raw material, oxygen
For oxidant, 3,5- bis- trifluoromethyl -4- n-butylbenzene selenous acid are catalyst, Adiponitrile.
To solve above-mentioned technical problem, technical solution provided by the invention is：
A kind of method of Adiponitrile, by cyclohexene and concentrated ammonia liquor according to volume ratio 1：3~6 ratio mixing, is added
The ratio of 3,5- bis- trifluoromethyl -4- n-butylbenzene selenous acid catalyst, the catalyst mole dosage and cyclohexene volume is
0.01~0.05mol/L is heated 24 hours or more in 1MPa pure oxygen atmospheres at 120~140 DEG C, you can obtain target product oneself
Dintrile.
In the present invention, cyclohexene is 1 with concentrated ammonia liquor volume ratio：3~6, preferably 1:4.5；Adiponitrile yield is most under this ratio
It is high.Concentrated ammonia liquor dosage is reduced, and reactant concentration improves, and can accelerate to react, but ammonification effect is bad, observe more adipic acid pair
Product；And concentrated ammonia liquor dosage increases, then because dilution effect so that reaction speed declines, raw material has portion of non-converted complete.
In the present invention, 3,5- bis- trifluoromethyl -4- n-butylbenzenes selenous acid catalyst mole dosages and cyclohexene volume
Ratio is 0.01~0.05mol/L.Wherein preferred 0.03mol/L.Under this dosage, reaction speed is moderate, you can so that reaction
It is steady to carry out, and can prevent product from decomposing.
In the present invention, reaction temperature is 120~140 DEG C；Wherein preferably 130 DEG C.At a temperature of this, reaction yield highest.
In the present invention, the mass concentration of concentrated ammonia liquor is 25~28%.
Compared with prior art, the present invention has the advantages that：
Compared with adipic acid ammoniation process, the raw material of synthetic method of the present invention is more easy to get, and reaction temperature is lower；With fourth two
Alkene method ratio, the present invention do not use hypertoxic raw material；Compared with acrylonitrile electrolysis method, consersion unit of the present invention is of less demanding, and energy
It consumes relatively low.
Specific implementation mode
The following examples illustrate the present invention in more detail, rather than limitation of the invention further.
In this application, inventor has found, 3,5- bis- trifluoromethyl -4- n-butylbenzene selenous acid have unique catalysis to imitate
Fruit, under the catalyst, cyclohexene that can be by being easy to get under the oxygen of certain pressure, heats in ammonium hydroxide and directly synthesizes oneself
Dintrile, yield can reach 87%.Reaction temperature needed for this method significantly reduces, and reaction process relatively cleans, and has and applies valence well
Value.
Embodiment 1
Addition 100mL cyclohexene in a kettle, 450mL concentrated ammonia liquors (industrial ammonia, mass concentration about 25-28%),
Bis- trifluoromethyl -4- n-butylbenzene selenous acid of 3mmol 3,5- heats 24 hours for 130 DEG C in 1MPa pure oxygens, gas spectrum analysis oneself two
Nitrile yield 87%.
Embodiment 2
Other conditions examine the experiment of different cyclohexene/concentrated ammonia liquor volume ratio, experimental result to be shown in Table 1 with embodiment 1.
The experiment of the different cyclohexene/concentrated ammonia liquor volume ratios of table 1
From the above results, cyclohexene/concentrated ammonia liquor volume ratio preferably 1:4.5 (embodiments 1).
Embodiment 3
Other conditions with embodiment 1, examine bis- trifluoromethyl -4- n-butylbenzene selenous acid catalyst mole of different 3,5- with
The experiment of amount and the ratio of cyclohexene volume, experimental result are shown in Table 2.
The experiment of the ratio of 2 different catalysts mole dosage of table and cyclohexene volume
From the above results, 3,5-, bis- trifluoromethyl -4- n-butylbenzenes selenous acid catalyst mole dosages and cyclohexene
The preferred 0.03mol/L of ratio (embodiment 1) of volume.
Embodiment 4
Other conditions examine differential responses temperature, experimental result as shown in table 3 with embodiment 1.
The experiment of 3 differential responses temperature of table
From the above results, reaction temperature preferably 130 DEG C (embodiments 1).
Embodiment 5
Other conditions examine different catalyst performances containing selenium, experimental result as shown in table 4 with embodiment 1.
The inspection of the different catalyst performances containing selenium of table 4
From the above results, 3,5-, bis- trifluoromethyl -4- butyl-benzene selenous acid has unique catalytic effect, other to be
Catalyst similar in structure therewith, activity is set all to can not show a candle to its (embodiment 1).
The above is only presently preferred embodiments of the present invention, is not intended to limit the present invention in any form, any ripe
Professional and technical personnel is known, without departing from the scope of the present invention, according to the technical essence of the invention, to above real
Apply any simple modification, equivalent replacement and improvement etc. made by example, still fall within technical solution of the present invention protection domain it
It is interior.
Claims (7)
1. the method for Adiponitrile, which is characterized in that by cyclohexene and concentrated ammonia liquor according to volume ratio 1：3~6 ratio mixing,
3,5-, bis- trifluoromethyl -4- n-butylbenzene selenous acid catalyst, the ratio of the catalyst mole dosage and cyclohexene volume is added
Example is 0.01~0.05mol/L, in pure oxygen atmosphere, reaction is heated at 120~140 DEG C, you can obtain target product adiponitrile.
2. the method as described in claim 1, which is characterized in that cyclohexene is 1 with concentrated ammonia liquor volume ratio：3~6.
3. the method as described in claim 1, which is characterized in that cyclohexene is 1 with concentrated ammonia liquor volume ratio:4.5.
4. the method as described in claim 1, which is characterized in that 3,5- bis- trifluoromethyl -4- n-butylbenzene selenous acid catalyst
The ratio of mole dosage and cyclohexene volume is 0.03mol/L.
5. the method as described in claim 1, which is characterized in that reaction temperature is 130 DEG C.
6. the method as described in claim 1, which is characterized in that the reaction time is 24 hours or more.
7. the method as described in claim 1, which is characterized in that the pressure of pure oxygen atmosphere is 1MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810267865.2A CN108530318B (en) | 2018-03-29 | 2018-03-29 | Method for synthesizing adiponitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810267865.2A CN108530318B (en) | 2018-03-29 | 2018-03-29 | Method for synthesizing adiponitrile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108530318A true CN108530318A (en) | 2018-09-14 |
| CN108530318B CN108530318B (en) | 2021-01-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810267865.2A Active CN108530318B (en) | 2018-03-29 | 2018-03-29 | Method for synthesizing adiponitrile |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113956180A (en) * | 2021-11-08 | 2022-01-21 | 中国天辰工程有限公司 | Synthesis method of adiponitrile |
| WO2022029583A1 (en) | 2020-08-07 | 2022-02-10 | Inv Nylon Chemicals Americas, Llc | Production of dinitriles |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1732148A (en) * | 2002-12-02 | 2006-02-08 | 罗狄亚聚酰胺中间体公司 | Process for preparing nitrile compound from olefinic unsaturated compound |
| CN102503774A (en) * | 2011-10-20 | 2012-06-20 | 江苏扬农化工集团有限公司 | Method for synthesizing 1,2-cyclohexanediol by cyclohexene under selenium catalysis |
-
2018
- 2018-03-29 CN CN201810267865.2A patent/CN108530318B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1732148A (en) * | 2002-12-02 | 2006-02-08 | 罗狄亚聚酰胺中间体公司 | Process for preparing nitrile compound from olefinic unsaturated compound |
| CN102503774A (en) * | 2011-10-20 | 2012-06-20 | 江苏扬农化工集团有限公司 | Method for synthesizing 1,2-cyclohexanediol by cyclohexene under selenium catalysis |
Non-Patent Citations (1)
| Title |
|---|
| JIN-HUI XU ET AL.: "Phenyliodonium Diacetate Mediated Direct Synthesis of Benzonitriles from Styrenes through Oxidative Cleavage of C=C Bonds", 《THE JOURNAL OF ORGANIC CHEMISTRY》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2022029583A1 (en) | 2020-08-07 | 2022-02-10 | Inv Nylon Chemicals Americas, Llc | Production of dinitriles |
| CN113956180A (en) * | 2021-11-08 | 2022-01-21 | 中国天辰工程有限公司 | Synthesis method of adiponitrile |
| CN113956180B (en) * | 2021-11-08 | 2024-04-09 | 中国天辰工程有限公司 | Synthesis method of adiponitrile |
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| Publication number | Publication date |
|---|---|
| CN108530318B (en) | 2021-01-26 |
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