CN103804228B - A kind of method of alkene nitrile mixed solution By Direct Isomerization synthesis 3 pentene nitrile - Google Patents
A kind of method of alkene nitrile mixed solution By Direct Isomerization synthesis 3 pentene nitrile Download PDFInfo
- Publication number
- CN103804228B CN103804228B CN201410052580.9A CN201410052580A CN103804228B CN 103804228 B CN103804228 B CN 103804228B CN 201410052580 A CN201410052580 A CN 201410052580A CN 103804228 B CN103804228 B CN 103804228B
- Authority
- CN
- China
- Prior art keywords
- mixed solution
- nitrile
- pentene
- alkene
- zero
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses the method for a kind of alkene nitrile mixed solution By Direct Isomerization synthesis 3 pentene nitrile, zero-valent nickel catalyst, phosphorus-containing ligand and Lewis acid is added in the alkene nitrile mixed solution comprising 2-methyl-3-crotononitrile and 3 pentene nitrile, there is isomerization reaction, generate the product comprising 3 pentene nitrile.Present invention eliminates the process of rectification under vacuum purification 2M3BN, be 3PN by the alkene nitrile mixed solution By Direct Isomerization under the effect of zero-valent nickel catalyst, Lewis acid, phosphorus-containing ligand comprising 2M3BN and 3PN, the transformation efficiency of 2M3BN is greater than 95%, the selectivity of 3PN is greater than 95%, and this method is compared with traditional method, and yield is substantially suitable, and owing to eliminating alkene nitrile mixed solution rectifying separation process, whole operational path is shortened, simplifies technical process, reduce equipment cost and production cost.
Description
Technical field
The present invention relates to the production technical field of adiponitrile, relate to the method for a kind of alkene nitrile mixed solution By Direct Isomerization synthesis 3 pentene nitrile.
Background technology
3 pentene nitrile (3PN) is important organic intermediate, is mainly used in Adiponitrile, is also a kind of excellent organic solvent simultaneously.Adiponitrile is the important source material of synthetic nylon 66, and nylon66 fiber is the principal item of polyamide plastics.
The existing synthesis technique of 3PN is under the effect of zero-valent nickel catalyst, phosphorus-containing ligand, and divinyl and a prussic acid addition are synthesized 3PN, and this reaction produces by-product 2-methyl-3-crotononitrile (2M3BN); Wherein the selectivity of 3PN is the selectivity of 75%, 2M3BN is 25%, and the equation of above-mentioned addition reaction is as follows:
Therefore, for improving the reaction yield of 3PN, need by 2M3BN isomerization synthesis 3PN, the technique of existing 2M3BN isomerization synthesis 3PN is: first by above-mentioned reaction solution rectification under vacuum, isolate high purity 2M3BN, under zero-valent nickel catalyst, Lewis acid, phosphorus-containing ligand effect, 2M3BN isomery is turned to 3PN again, this reaction equation is:
But this method needs to obtain high purity 2M3BN from rectification under vacuum the alkene nitrile mixed solution comprising 2M3BN and 3PN, and 2M3BN and 3PN is isomers, boiling point difference only 18 DEG C under normal pressure, and distillation operation difficulty is comparatively large, and energy consumption is higher.Such as: publication number be CN103097342A patent document discloses a kind of method for the preparation of nitrile, it is disclosed that and the stream 825 comprising 3PN and 2M3BN is transferred to water distilling apparatus 830, in the apparatus, the distillation of the distillment of stream 825 is shown in the 0103rd section, its specification sheets, Fig. 4 to obtain 2M3BN rich stream 200 with the 2M3BN lean stream 838(comprising 3PN).
Summary of the invention
In view of this, the object of the present invention is to provide a kind of alkene nitrile mixed solution By Direct Isomerization to synthesize the method for 3 pentene nitrile, simplification of flowsheet, reduce equipment cost and production cost.
For achieving the above object, the invention provides following technical scheme:
The method of alkene nitrile mixed solution By Direct Isomerization synthesis 3 pentene nitrile of the present invention, zero-valent nickel catalyst, phosphorus-containing ligand and Lewis acid is added in the alkene nitrile mixed solution comprising 2-methyl-3-crotononitrile and 3 pentene nitrile, there is isomerization reaction, generate the product comprising 3 pentene nitrile.
Further, the mol ratio of described 2-methyl-3-crotononitrile and zero-valent nickel catalyst is 30 ~ 100:1, and the mol ratio of described phosphorus-containing ligand and zero-valent nickel catalyst is 5 ~ 15:1, and the mol ratio of described Lewis acid and zero-valent nickel catalyst is 1 ~ 50:1.
Further, the reaction pressure of described isomerization reaction is 0.1 ~ 0.2Mpa, and temperature of reaction is 80 ~ 120 DEG C, insulation reaction 6 ~ 12 hours.
Further, described Lewis acid is zinc chloride, aluminum chloride, zinc sulfate, iron protochloride, iron(ic) chloride or tin tetrachloride.
Further, described phosphorus-containing ligand is triphenyl phosphite, tricresyl phosphite o-toluene ester, tricresyl phosphite m-tolyl ester or tri-p-cresyl phosphite.
Beneficial effect of the present invention is:
Present invention eliminates the process of rectification under vacuum purification 2M3BN, be 3PN by the alkene nitrile mixed solution By Direct Isomerization under the effect of zero-valent nickel catalyst, Lewis acid, phosphorus-containing ligand comprising 2M3BN and 3PN, the transformation efficiency of 2M3BN is greater than 95%, the selectivity of 3PN is greater than 95%, and this method is compared with traditional method, and yield is substantially suitable, and owing to eliminating alkene nitrile mixed solution rectifying separation process, whole operational path is shortened, simplifies technical process, reduce equipment cost and production cost.
Embodiment
In order to make object of the present invention, technical scheme and beneficial effect clearly, will be described in detail the preferred embodiments of the present invention below.
embodiment 1
Zero-valent nickel catalyst, tricresyl phosphite o-toluene ester and aluminum chloride is added in the alkene nitrile mixed solution comprising 2-methyl-3-crotononitrile and 3 pentene nitrile, the mol ratio of 2-methyl-3-crotononitrile, tricresyl phosphite o-toluene ester, zero-valent nickel catalyst and aluminum chloride is 30:5:1:1, control reaction pressure is 0.1Mpa, temperature of reaction is 100 DEG C, insulation reaction 10 hours, the transformation efficiency of 2-methyl-3-crotononitrile is 96%, and the selectivity of 3 pentene nitrile is 97%.
embodiment 2
Zero-valent nickel catalyst, tricresyl phosphite m-tolyl ester and iron protochloride is added in the alkene nitrile mixed solution comprising 2-methyl-3-crotononitrile and 3 pentene nitrile, the mol ratio of 2-methyl-3-crotononitrile, tricresyl phosphite m-tolyl ester, zero-valent nickel catalyst and iron protochloride is 70:10:1:30, control reaction pressure is 0.1Mpa, temperature of reaction is 100 DEG C, insulation reaction 10 hours, the transformation efficiency of 2-methyl-3-crotononitrile is 96%, and the selectivity of 3 pentene nitrile is 96%.
embodiment 3
Zero-valent nickel catalyst, triphenyl phosphite and iron protochloride is added in the alkene nitrile mixed solution comprising 2-methyl-3-crotononitrile and 3 pentene nitrile, the mol ratio of 2-methyl-3-crotononitrile, triphenyl phosphite, zero-valent nickel catalyst and iron protochloride is 100:15:1:50, control reaction pressure is 0.1Mpa, temperature of reaction is 100 DEG C, insulation reaction 10 hours, the transformation efficiency of 2-methyl-3-crotononitrile is 98%, and the selectivity of 3 pentene nitrile is 96%.
What finally illustrate is, above preferred embodiment is only in order to illustrate technical scheme of the present invention and unrestricted, although by above preferred embodiment to invention has been detailed description, but those skilled in the art are to be understood that, various change can be made to it in the form and details, and not depart from claims of the present invention limited range.
Claims (5)
1. the method for an alkene nitrile mixed solution By Direct Isomerization synthesis 3 pentene nitrile, it is characterized in that: in the alkene nitrile mixed solution comprising 2-methyl-3-crotononitrile and 3 pentene nitrile, add zero-valent nickel catalyst, phosphorus-containing ligand and Lewis acid, there is isomerization reaction, generate the product comprising 3 pentene nitrile.
2. the method for alkene nitrile mixed solution By Direct Isomerization synthesis 3 pentene nitrile according to claim 1, it is characterized in that: the mol ratio of described 2-methyl-3-crotononitrile and zero-valent nickel catalyst is 30 ~ 100:1, the mol ratio of described phosphorus-containing ligand and zero-valent nickel catalyst is 5 ~ 15:1, and the mol ratio of described Lewis acid and zero-valent nickel catalyst is 1 ~ 50:1.
3. the method for alkene nitrile mixed solution By Direct Isomerization synthesis 3 pentene nitrile according to claim 1 and 2, is characterized in that: the reaction pressure of described isomerization reaction is 0.1 ~ 0.2Mpa, and temperature of reaction is 80 ~ 120 DEG C, insulation reaction 6 ~ 12 hours.
4. the method for alkene nitrile mixed solution By Direct Isomerization synthesis 3 pentene nitrile according to claim 3, is characterized in that: described Lewis acid is zinc chloride, aluminum chloride, zinc sulfate, iron protochloride, iron(ic) chloride or tin tetrachloride.
5. the method for alkene nitrile mixed solution By Direct Isomerization synthesis 3 pentene nitrile according to claim 3, is characterized in that: described phosphorus-containing ligand is triphenyl phosphite, tricresyl phosphite o-toluene ester, tricresyl phosphite m-tolyl ester or tri-p-cresyl phosphite.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410052580.9A CN103804228B (en) | 2014-02-17 | 2014-02-17 | A kind of method of alkene nitrile mixed solution By Direct Isomerization synthesis 3 pentene nitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410052580.9A CN103804228B (en) | 2014-02-17 | 2014-02-17 | A kind of method of alkene nitrile mixed solution By Direct Isomerization synthesis 3 pentene nitrile |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103804228A CN103804228A (en) | 2014-05-21 |
| CN103804228B true CN103804228B (en) | 2016-04-27 |
Family
ID=50701668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410052580.9A Active CN103804228B (en) | 2014-02-17 | 2014-02-17 | A kind of method of alkene nitrile mixed solution By Direct Isomerization synthesis 3 pentene nitrile |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103804228B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1914154A (en) * | 2004-01-29 | 2007-02-14 | 巴斯福股份公司 | Method for producing 3-pentenenitrile |
| CN103396340A (en) * | 2013-08-16 | 2013-11-20 | 山东海力化工股份有限公司 | 2-methyl-3-butenenitrile isomerization method |
-
2014
- 2014-02-17 CN CN201410052580.9A patent/CN103804228B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1914154A (en) * | 2004-01-29 | 2007-02-14 | 巴斯福股份公司 | Method for producing 3-pentenenitrile |
| CN103396340A (en) * | 2013-08-16 | 2013-11-20 | 山东海力化工股份有限公司 | 2-methyl-3-butenenitrile isomerization method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103804228A (en) | 2014-05-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| MY156181A (en) | Method and system for producing high-purity hydrogen chloride | |
| WO2014043706A8 (en) | Method of synthesizing thyroid hormone analogs and polymorphs thereof | |
| IN2014DN07599A (en) | ||
| CN102249929A (en) | Method for synthesizing trans-(1R,2S)-2-(3,4-difluorophenyl)cyclopropylamine | |
| Shakhmaev et al. | Stereoselective synthesis of allylamines by iron-catalyzed cross-coupling of 3-chloroprop-2-en-1-amines with grignard reagents. Synthesis of naftifine | |
| CN103694136B (en) | The method of divinyl one-step synthesis method adiponitrile | |
| CN103739516B (en) | A kind of method utilizing the isomerization liquid Adiponitrile of 2-methyl-3-crotononitrile | |
| EA201201666A1 (en) | INTERMEDIATE COMPOUNDS AGOMELATIN AND METHOD OF THEIR OBTAINING | |
| CN103804228B (en) | A kind of method of alkene nitrile mixed solution By Direct Isomerization synthesis 3 pentene nitrile | |
| MX2018010128A (en) | New toxin and method for preparing intermediate thereof. | |
| CN107266282B (en) | Preparation method of 1, 4-dimethylnaphthalene | |
| CN102675036B (en) | Method for preparing 7-bromine-1-heptylene | |
| WO2011099604A3 (en) | Process for producing fluorine-containing alkene | |
| CN103804227B (en) | A kind of method of alkene nitrile mixed solution By Direct Isomerization synthesis 2-methyl-2-butene nitrile | |
| CN102531983B (en) | Chemical synthesis method of S-phenyl-4-tosylate | |
| CN101735099B (en) | Synthesizing method of S-(+)-2, 2-dimethylcyclopropane carboxamide | |
| CN103804229A (en) | Method for inhibiting degradation of phosphorus containing ligand in process of synthesizing adiponitrile via butadiene method | |
| CN105017073A (en) | Recycle method of hydrocyanation catalyst for butadiene-based synthesis of adiponitrile | |
| CN102952020B (en) | Method for preparing single or dual-alkyl substitution product of propane diamine | |
| CN109134204B (en) | Synthesis method of intermediate 2-bromo-4-fluoro-5-chlorophenol | |
| CN103739463B (en) | A kind of short-cut method for producing high purity raw formic acid esters | |
| CN102976888A (en) | Synthesizing method of p-dichlorobenzene | |
| CN105130845A (en) | Method of inhibiting degradation of zero-valent nickel in synthesis of adiponitrile through butadiene method | |
| CN107001243A (en) | method for continuously preparing adiponitrile | |
| CN205501166U (en) | Piece -rate system of 2 - methyl - 3 - crotononitrile isomerization production 3 - allyl acetonitrile in -process accessory substance 2 - methyl - 2 - crotononitrile |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP02 | Change in the address of a patent holder |
Address after: 401220 Chongqing City, Changshou economic and Technological Development Zone, No. 1 North Road Patentee after: CHONGQING ZHONGPING ZIGUANG SCIENCE & TECHNOLOGY CO., LTD. Address before: 408200 Zhenjiang fine chemical industry park, Fengdu County, Chongqing Patentee before: CHONGQING ZHONGPING ZIGUANG SCIENCE & TECHNOLOGY CO., LTD. |
|
| CP02 | Change in the address of a patent holder | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A method for synthesis of 3-pentenylnitrile by direct isomerization of acrylonitrile mixture Effective date of registration: 20200904 Granted publication date: 20160427 Pledgee: Chongqing chemical medicine holding (Group) Co., Ltd Pledgor: CHONGQING ZHONGPING ZIGUANG SCIENCE & TECHNOLOGY Co.,Ltd. Registration number: Y2020500000013 |
|
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| CP03 | Change of name, title or address |
Address after: 467099 room 216, second floor, East distribution building, No. 63, middle section of Jianshe Road, Pingdingshan City, Henan Province (Shenma Industrial Co., Ltd.) Patentee after: Henan Zhongping Ziguang Technology Co.,Ltd. Address before: 401220 No. 1, Huabei 1st Road, Changshou economic and Technological Development Zone, Chongqing Patentee before: CHONGQING ZHONGPING ZIGUANG SCIENCE & TECHNOLOGY Co.,Ltd. |
|
| CP03 | Change of name, title or address | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20210809 Granted publication date: 20160427 Pledgee: Chongqing chemical medicine holding (Group) Co., Ltd Pledgor: CHONGQING ZHONGPING ZIGUANG SCIENCE & TECHNOLOGY Co.,Ltd. Registration number: Y2020500000013 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220323 Address after: 467000 room 416, management committee of nylon new material industry cluster, Gongdian Town, Ye County, Pingdingshan City, Henan Province Patentee after: Henan Shenma Aidian Chemical Co.,Ltd. Address before: 467099 room 216, second floor, East distribution building, No. 63, middle section of Jianshe Road, Pingdingshan City, Henan Province (Shenma Industrial Co., Ltd.) Patentee before: Henan Zhongping Ziguang Technology Co.,Ltd. |
|
| TR01 | Transfer of patent right |