CN1043758C - Improved production method of N-methyl pyrrolidone and alpha-pyrrolidone - Google Patents
Improved production method of N-methyl pyrrolidone and alpha-pyrrolidone Download PDFInfo
- Publication number
- CN1043758C CN1043758C CN 93121036 CN93121036A CN1043758C CN 1043758 C CN1043758 C CN 1043758C CN 93121036 CN93121036 CN 93121036 CN 93121036 A CN93121036 A CN 93121036A CN 1043758 C CN1043758 C CN 1043758C
- Authority
- CN
- China
- Prior art keywords
- pressure
- reaction
- reaction system
- gamma
- butyrolactone
- 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.)
- Expired - Lifetime
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- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 title claims abstract description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 238000004519 manufacturing process Methods 0.000 title description 6
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 10
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 38
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 24
- 229910021529 ammonia Inorganic materials 0.000 claims description 19
- 239000002994 raw material Substances 0.000 claims description 7
- 230000001143 conditioned effect Effects 0.000 claims description 3
- 230000008676 import Effects 0.000 claims description 3
- GUQGYHBUINQTSV-UHFFFAOYSA-N azane;methanamine Chemical compound N.NC GUQGYHBUINQTSV-UHFFFAOYSA-N 0.000 abstract 1
- 239000007789 gas Substances 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- GMZVRMREEHBGGF-UHFFFAOYSA-N Piracetam Chemical compound NC(=O)CN1CCCC1=O GMZVRMREEHBGGF-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 150000003956 methylamines Chemical class 0.000 description 1
- 229960004526 piracetam Drugs 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Pyrrole Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to an improved method for preparing N-methyl pyrrolidone (alpha-pyrrolidone) by using gamma-butyrolactone, methylamine (ammonia) and water, and is characterized by that in the pressure control tank of reaction system an inert gas is used as pressure-stabilizing gas source to regulate pressure of reaction system, and the liquid level in the pressure control tank is displayed by means of liquid level meter and controlled to retain a certain level so as to maintain the continuous and stable flow of material fed in and discharged from reaction system.
Description
The invention belongs to organic chemical industry's production field.Particularly relate to a kind of use gamma-butyrolactone and methylamine or ammonia) and the method for water prepared in reaction N-Methyl pyrrolidone (or alpha-pyrrolidone).
N-Methyl pyrrolidone (hereinafter to be referred as NMP) is a kind of excellent solvent, and can reclaim by water.It is refining and as aspects such as the solvent of polymer reaction, electrical appliance cleaners to be widely used in acetylene concentration, separate butadiene, aromatic hydrocarbons extracting, senior lubricant.
(hereinafter to be referred as α-P) is high bp polar solvent to alpha-pyrrolidone, also is the intermediate of organic synthesis.For example it is a raw material of producing polyvinylpyrrolidone, piracetam medicine.
The industrial product route of NMP and α-P is to use gamma-butyrolactone and methylamine condensation system NMP, with gamma-butyrolactone and ammonia condensation system α-P.Because NMP and α-P all belong to the series product of γ-Ding lactones, production technique of the two and major equipment are basic identical, so generally carry out the switching production of two kinds of products by the market requirement in same set of device.
English Patent GB1,312,463 (BASF AG) provide a kind of production method about α-P, are that raw material is produced continuously with gamma-butyrolactone and liquefied ammonia or ammoniacal liquor, and the ammonia concn of use is generally 15～100% (wt), preferred 50～100% (wt).180～340 ℃ of temperature of reaction, residence time of material 10 minutes to 28 hours keeps the pressure above reactant dividing potential drop summation 10% under temperature of reaction, preferably high 20% simultaneously.This patent claims that the requirement to pressure is the principal feature of this invention.The weight ratio of employed liquefied ammonia and water is higher than 1: 1 in this patent working example, in embodiment 3, and 270 ℃ of temperature of reaction, α during system pressure 70atm-P productive rate is 91.0% (mol), productive rate is 95.0% (mol) during 120atm.
Japanese Patent JP76-42107 has introduced a kind of preparation method of pyrrolidone, and this method points out to add water in reaction system can improve speed of response, shortens the reaction times, increases product yield.In embodiment, used 45～50kg/cm
2System pressure, the mol ratio of methylamine and water 1.4: 4,250 ℃ of temperature of reaction, gamma-butyrolactone transformation efficiency 99.5%, 2 hours residence time.But the yield of not mentioned NMP.
By above-mentioned prior art as can be seen, raw material and the processing condition of synthetic NMP or α-P are substantially the same, but the yield of product still can not be very satisfactory.And exist the problem that reaction system pressure is had relatively high expectations.And the immediate problem that the latter brings promptly is to the equipment requirements height, and is expensive many.Therefore, it is gentle relatively to need to seek a kind of reaction conditions, and facility investment is few, the preparation method that NMP and α-the P yield is high.
The inventor has carried out deep research for this reason, found that for high NMP and α-productive rate, keeps higher system pressure, and keeps the pressure-stabilisation of reaction system, and this reaction is had material impact.The present invention can obtain higher productive rate under pressure same as the prior art, raw material is had adaptability (referring to different methylamines, ammonia soln concentration) widely, and the residence time is shorter.That is to say that obtaining under the precondition of identical productive rate, preparation method of the present invention can use the system pressure more much lower than prior art.
Particularly, the present invention relates to a kind of use gamma-butyrolactone and methylamine (or ammonia) and the water prepared in reaction NMP (method of or α-P), it is characterized in that using rare gas element to introduce reaction system as pressure-stabilized air source, the pressure of conditioned reaction system is not less than 5.5MPa, preferably is not less than 6MPa reactant is reacted.Wherein temperature of reaction is 200～320 ℃, preferred 220～290 ℃; Preferred 1～the 3hr of the residence time 0.5～5hr; Gamma-butyrolactone: methylamine (ammonia): the mol ratio 1 of water: (1.1～4): (2～9).Be reflected under the liquid phase and carry out, show liquid level and control outlet valve, make tank level keep certain, import and export material (liquid) mobile in the reaction system continuously with stable thereby keep by the liquid level instrument that is positioned at reaction system rear portion pressure-controlling jar.
The invention will be further described by the narration of following diagram and embodiment.
Key of the present invention is to have used following method (flow process is seen Fig. 1).
At first gamma-butyrolactone and methylamine or aqueous methylamine solution (ammonia or ammonia soln) are squeezed into reactive system by volume pump respectively in when beginning preparation, enter reactor after being preheating to temperature of reaction.Stop 0.5～5 hour postcooling and enter the pressure-controlling jar in reactor, indifferent gas regulation system pressure is filled in the utilization of pressure-controlling jar; The pressure-controlling jar has pressure to show and reports to the police, and has liquid level to show, control and report to the police.When continuous production, control continuous discharging, guarantee that tank level is at certain altitude with liquid level.The material that goes out the pressure-controlling jar enters the crude product jar through reducing valve, obtains high-quality NMP and α-P through normal pressure, rectification under vacuum.
Embodiment 1:
With high-pressure metering pump the aqueous methylamine solution of gamma-butyrolactone and 30 (wt) % is squeezed into reactor, gamma-butyrolactone: methylamine: water=1: 1.4: 5.6 (mol),, react 2 hours residence time by about 280 ℃ in temperature of reaction under the reaction pressure 6 MPa conditions.It is 99.5% NMP that reaction product obtains purity by normal pressure, rectification under vacuum, and gamma-butyrolactone transformation efficiency 100%, NMP productive rate are 97% (mol).
Embodiment 2:
With high-pressure metering pump with the ammonia soln of gamma-butyrolactone and 30 (wt) the % reactor of hitting the person, gamma-butyrolactone: ammonia: water=1: 1.4: 3.1 (mol), 250 ℃ of temperature of reaction, reaction pressure 7MPa, 2 hours residence time.It is 99.5% α-P that reaction product obtains purity through normal pressure and rectification under vacuum, gamma-butyrolactone transformation efficiency 100%, α-P yield 95% (mol).
The present invention compared with the prior art
| The embodiment of the invention 1 | The embodiment of the invention 2 | BASF embodiment 3 | |
| Reaction temperature: ℃ | 280 | 250 | 270 |
| Reaction pressure: MPa | 6 | 7 | 12 |
| The time of staying: hr | 2 | 2 | 2 |
| Raw material proportioning: gamma-butyrolacton: ammonia: water | 1: 1.4: 5.6 (mol ratio) | 1: 1.4: 3.1 (mol ratio) | 1: 1.07: 1 (Parts ratio) |
| Ammonia (first amine) concentration wt% | 30 (first amine) | 30 (ammonia) | 52 (ammonia) |
| Product yield: (mol) % | 97.0 | 95.0 | 95.0 |
The present invention compared with prior art has following advantage:
Under the condition of temperature of reaction, material concentration and the proportioning close with prior art, because pressure-stabilized air source is introduced the use of reaction system and tank level control technology, make pressure-stabilisation in the reaction system, thereby can under the pressure condition more much lower, obtain good productive rate and feed stock conversion than prior art, reduce facility investment, reduced product cost.
Fig. 1 is a process flow diagram of the present invention, wherein: 1-reactive system 2-pressure-controlling jar 3-crude product jar 4,5-distillation tower
Claims (10)
1, a kind of with gamma-butyrolactone, methylamine and water are raw material, the method for preparing N-Methyl pyrrolidone, 200～320 ℃ of temperature of reaction, residence time of material 0.5～5hr, it is characterized in that, use rare gas element to be pressure-stabilized air source, the pressure of conditioned reaction system is 5.5～7MPa, gamma-butyrolactone: methylamine: the mol ratio of water is 1: 1.1～4: 2～9.
According to the method for claim 1, it is characterized in that 2, the pressure of reaction system is 6～7Mpa.
3, according to the method for claim 1, it is characterized in that gamma-butyrolactone: methylamine: the mol ratio of water is 1: 1.4: 5.6.
4, according to the method for claim 1, it is characterized in that pressure-controlling jar in the reaction system is with rare gas element regulation system pressure, and show by the liquid level instrument of pressure-controlling jar, make its liquid level keep certain, import and export the continuous and stable of Flow of Goods and Materials in the reaction system to keep.
According to the method for claim 1, it is characterized in that 5, temperature of reaction is 220～290 ℃, the residence time 1～3hr.
6, a kind of with gamma-butyrolactone, ammonia and water are raw material, the method for preparing alpha-pyrrolidone, 200～320 ℃ of temperature of reaction, residence time of material 0.5～5hr, it is characterized in that, use rare gas element to be pressure-stabilized air source, the pressure of conditioned reaction system is 5.5～7Mpa, gamma-butyrolactone: ammonia: the mol ratio of water is 1: 1.1～4: 2～9.
According to the method for claim 6, it is characterized in that 7, the pressure of reaction system is 6～7Mpa.
8, according to the method for claim 6, it is characterized in that gamma-butyrolactone: ammonia: the mol ratio of water is 1: 1.4: 3.1.
9, according to the method for claim 6, it is characterized in that pressure-controlling jar in the reaction system is with rare gas element regulation system pressure, and show by the liquid level instrument of pressure-controlling jar, make its liquid level keep certain, import and export the continuous and stable of Flow of Goods and Materials in the reaction system to keep.
10,, it is characterized in that temperature of reaction is 220～290 ℃, the residence time 1～3hr according to the method for claim 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93121036 CN1043758C (en) | 1993-12-27 | 1993-12-27 | Improved production method of N-methyl pyrrolidone and alpha-pyrrolidone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93121036 CN1043758C (en) | 1993-12-27 | 1993-12-27 | Improved production method of N-methyl pyrrolidone and alpha-pyrrolidone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1104635A CN1104635A (en) | 1995-07-05 |
| CN1043758C true CN1043758C (en) | 1999-06-23 |
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93121036 Expired - Lifetime CN1043758C (en) | 1993-12-27 | 1993-12-27 | Improved production method of N-methyl pyrrolidone and alpha-pyrrolidone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1043758C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1964943B (en) * | 2004-06-09 | 2010-12-15 | 戴维加工技术有限公司 | Process for the preparation of n-akyl-pyrrolidones |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1054843C (en) * | 1996-08-12 | 2000-07-26 | 中国石油化工总公司 | Method for prepn. of N-methyl pyrrolidone |
| BE1012013A6 (en) * | 1998-04-09 | 2000-04-06 | Pantochim Sa | METHOD FOR PRODUCING N-methyl. |
| JP4036580B2 (en) * | 1998-11-24 | 2008-01-23 | 三菱化学株式会社 | Method for producing N-alkyl-2-pyrrolidone |
| US6603021B2 (en) | 2001-06-18 | 2003-08-05 | Battelle Memorial Institute | Methods of making pyrrolidones |
| US7199250B2 (en) | 2002-12-20 | 2007-04-03 | Battelle Memorial Institute | Process for producing cyclic compounds |
| KR101125853B1 (en) * | 2009-07-29 | 2012-03-28 | 에스케이종합화학 주식회사 | Process for preparing of n-methyl pyrrolidone |
| KR101103512B1 (en) * | 2009-11-25 | 2012-01-09 | 에스케이종합화학 주식회사 | Process for preparing of n-methyl pyrrolidone from 1,4-butanediol |
| CN103351321B (en) * | 2013-06-20 | 2015-08-26 | 滨州裕能化工有限公司 | The continuous production method of a kind of NMP |
| CN104672122B (en) * | 2015-02-10 | 2017-06-09 | 沈阳化工大学 | A kind of preparation method of continuous aminating reaction Piracetam |
| CN104725293A (en) * | 2015-02-11 | 2015-06-24 | 沈阳化工大学 | Continuous production method of alpha-pyrrolidone |
| WO2017021976A1 (en) | 2015-07-31 | 2017-02-09 | Council Of Scientific & Industrial Research | An improved process for the selective production of n-methyl-2-pyrrolidone (nmp) |
| CN112341339A (en) * | 2020-11-30 | 2021-02-09 | 江苏凯美普瑞工程技术有限公司 | Method and device for synthesizing 1, 4-butanediamine |
| CN113548995A (en) * | 2021-08-27 | 2021-10-26 | 江西盛源新材料有限公司 | Preparation method of alpha-pyrrolidone |
-
1993
- 1993-12-27 CN CN 93121036 patent/CN1043758C/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1964943B (en) * | 2004-06-09 | 2010-12-15 | 戴维加工技术有限公司 | Process for the preparation of n-akyl-pyrrolidones |
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| Publication number | Publication date |
|---|---|
| CN1104635A (en) | 1995-07-05 |
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| SE01 | Entry into force of request for substantive examination | ||
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Expiration termination date: 20131227 Granted publication date: 19990623 |