CN1104635A - Improved process for producing N-methyl pyrrolidone and 2-pyrrolidone - Google Patents
Improved process for producing N-methyl pyrrolidone and 2-pyrrolidone Download PDFInfo
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- CN1104635A CN1104635A CN 93121036 CN93121036A CN1104635A CN 1104635 A CN1104635 A CN 1104635A CN 93121036 CN93121036 CN 93121036 CN 93121036 A CN93121036 A CN 93121036A CN 1104635 A CN1104635 A CN 1104635A
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- pyrrolidone
- butyrolactone
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Abstract
The process for preparing N-methyl pyrrolidone (alpha-pyrrolidone) with gamma-butyrolactone, methylamine and water features use of inertial gas as pressure-stabilizing gas source in pressure control container of reaction system to regulate system pressure, and use of level meter to indicate liquid level in the container to keep constant, which can ensure continuous and stable flow of material.
Description
The invention belongs to organic chemical industry's production field.
N-Methyl pyrrolidone (hereinafter to be referred as NMP) is a kind of excellent solvent, and can reclaim by water.It is refining to be widely used in acetylene concentration, separate butadiene, aromatic hydrocarbons extracting, senior lubricant; And as aspects such as the solvent of polymer reaction, electrical appliance cleaners.
(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 Polyvinylpyrolidone (PVP), 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 gamma-butyrolactone, 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 company) providing a kind of production method about α-P, is 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-P 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 the method for a kind of use gamma-butyrolactone and methylamine (or ammonia) and water prepared in reaction NMP(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 ℃; The residence time 0.5～5hr; Preferred 1～3hr; 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 narrow-necked earthen jar in reactor, indifferent gas regulation system pressure is filled in the utilization of pressure-controlling narrow-necked earthen jar; The pressure-controlling narrow-necked earthen 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 liquid level is at certain altitude in the narrow-necked earthen jar with liquid level.The material that goes out the pressure-controlling narrow-necked earthen jar enters the crude product narrow-necked earthen jar through reducing valve, obtains high-quality NMP and α-P through normal pressure, rectification under vacuum.
Embodiment 1:
With high-pressure metering pump with gamma-butyrolactone and 30(wt) aqueous methylamine solution of % squeezes into reactor, gamma-butyrolactone: methylamine: water=1: 1.4: 5.6(mol), about 280 ℃ in temperature of reaction, react under the reaction pressure 6MPa condition; 2 hours residence time.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 gamma-butyrolactone and 30(wt) ammonia soln of % squeezes into reactor, 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
| BASF |
The embodiment of the |
The embodiment of the |
|
| Temperature of reaction: ℃ | 270 | 230 | 280 |
| Reaction pressure: MPa | 12 | 7 | 6 |
| The residence time: |
2 | 1～2 | 1～2 |
| Proportioning raw materials gamma-butyrolactone: ammonia: water | (1:1.07:1 Parts ratio) | (1:1.4:3.1 mol ratio) | (1:1.4:5.6 mol ratio) |
| Ammonia (methylamine) concentration wt% | 52 | 30 | 30 |
| Product yield (mol) % | 91.0 | 95.6 | 99.1 |
The present invention compared with prior art has following advantage:
In the temperature of reaction close with prior art, under the condition of material concentration and proportioning, 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 narrow-necked earthen jar 3-crude product narrow-necked earthen jar 4,5-distillation tower
Claims (7)
1, a kind of by gamma-butyrolactone, methylamine (ammonia) and water prepare the method for N-Methyl pyrrolidone (alpha-pyrrolidone), it is characterized in that using rare gas element as pressure-stabilized air source, and the pressure of conditioned reaction system is not less than 5.5MPa reacts reactant.
2,, it is characterized in that the pressure of reaction system is not less than 6MPa according to the method for claim 1.
3,, it is characterized in that the pressure-controlling narrow-necked earthen jar rare gas element regulation system pressure in the reaction system according to the method for claim 1; Keep certain by liquid level in liquid level instrument demonstration and the control narrow-necked earthen jar in this pressure-controlling narrow-necked earthen jar, import and export the continuous and stable of Flow of Goods and Materials in the reaction system thereby keep.
4,, it is characterized in that temperature of reaction is 200～320 ℃, the residence time 0.5～5hr according to the method for claim 1.
5,, it is characterized in that temperature of reaction is 220～290 ℃, the residence time 1～3hr according to the method for claim 4.
6, according to the method for claim 1, it is characterized in that gamma-butyrolactone: methylamine (ammonia): the mol ratio of water is 1: (1.1～4): (2～9).
7, the compress control method of the present invention's narration is applicable to the pressure-controlling and the control of material turnover constant of liquid phase successive reaction system in other chemical techniquees.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93121036 CN1043758C (en) | 1993-12-27 | 1993-12-27 | Improved process for producing N-methyl pyrrolidone and 2-pyrrolidone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93121036 CN1043758C (en) | 1993-12-27 | 1993-12-27 | Improved process for producing N-methyl pyrrolidone and 2-pyrrolidone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1104635A true CN1104635A (en) | 1995-07-05 |
| CN1043758C CN1043758C (en) | 1999-06-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93121036 Expired - Lifetime CN1043758C (en) | 1993-12-27 | 1993-12-27 | Improved process for producing N-methyl pyrrolidone and 2-pyrrolidone |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999052867A1 (en) * | 1998-04-09 | 1999-10-21 | Pantochim S.A. | A process for the production of n-methyl pyrrolidone |
| EP1004577A1 (en) * | 1998-11-24 | 2000-05-31 | Mitsubishi Chemical Corporation | Process for preparing N-alkyl-2-pyrrolidones |
| CN1054843C (en) * | 1996-08-12 | 2000-07-26 | 中国石油化工总公司 | Method for prepn. of N-methyl 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 |
| CN101987831A (en) * | 2009-07-29 | 2011-03-23 | Sk能源株式会社 | Process for preparing of n-methyl pyrrolidone |
| CN102070501A (en) * | 2009-11-25 | 2011-05-25 | Sk能源株式会社 | Method for preparing n-methylpyrrolidone from 1,4-butanediol |
| CN103351321A (en) * | 2013-06-20 | 2013-10-16 | 滨州裕能化工有限公司 | Continuous energy-saving NMP (N-methyl pyrrolidone) production method |
| CN104672122A (en) * | 2015-02-10 | 2015-06-03 | 沈阳化工大学 | Preparation method for preparing acetamide pyrrolidone by virtue of continuous ammoniation |
| 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 |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB0412875D0 (en) * | 2004-06-09 | 2004-07-14 | Davy Process Techn Ltd | Process |
-
1993
- 1993-12-27 CN CN 93121036 patent/CN1043758C/en not_active Expired - Lifetime
Cited By (22)
| 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 |
| WO1999052867A1 (en) * | 1998-04-09 | 1999-10-21 | Pantochim S.A. | A process for the production of n-methyl pyrrolidone |
| EP1004577A1 (en) * | 1998-11-24 | 2000-05-31 | Mitsubishi Chemical Corporation | Process for preparing N-alkyl-2-pyrrolidones |
| JP2000219675A (en) * | 1998-11-24 | 2000-08-08 | Mitsubishi Chemicals Corp | Production of n-alkyl-2-pyrrolidone |
| US6706893B2 (en) | 2001-06-18 | 2004-03-16 | Battelle Memorial Institute | Methods of making pyrrolidones |
| US6670483B2 (en) | 2001-06-18 | 2003-12-30 | Battelle Memorial Institute | Methods of making pyrrolidones |
| 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 |
| US7674916B2 (en) | 2002-12-20 | 2010-03-09 | Battelle Memorial Institute | Process for producing cyclic compounds |
| US7973177B2 (en) | 2002-12-20 | 2011-07-05 | Battelle Memorial Institute | Process for producing cyclic compounds |
| US8501963B2 (en) | 2002-12-20 | 2013-08-06 | Battelle Memorial Institute | Process for producing cyclic compounds |
| CN105906542A (en) * | 2009-07-29 | 2016-08-31 | Sk新技术株式会社 | Process for preparing of n-methyl pyrrolidone |
| CN101987831A (en) * | 2009-07-29 | 2011-03-23 | Sk能源株式会社 | Process for preparing of n-methyl pyrrolidone |
| CN102070501A (en) * | 2009-11-25 | 2011-05-25 | Sk能源株式会社 | Method for preparing n-methylpyrrolidone 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 |
| CN103351321A (en) * | 2013-06-20 | 2013-10-16 | 滨州裕能化工有限公司 | Continuous energy-saving NMP (N-methyl pyrrolidone) production method |
| CN104672122A (en) * | 2015-02-10 | 2015-06-03 | 沈阳化工大学 | Preparation method for preparing acetamide pyrrolidone by virtue of continuous ammoniation |
| 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) |
| US10308603B2 (en) | 2015-07-31 | 2019-06-04 | Council Of Scientific & Industrial Research | 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 |
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| Publication number | Publication date |
|---|---|
| CN1043758C (en) | 1999-06-23 |
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Expiration termination date: 20131227 Granted publication date: 19990623 |