CN105175306A - Synthetic method of N-methylpyrrolidone - Google Patents
Synthetic method of N-methylpyrrolidone Download PDFInfo
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- CN105175306A CN105175306A CN201510493500.8A CN201510493500A CN105175306A CN 105175306 A CN105175306 A CN 105175306A CN 201510493500 A CN201510493500 A CN 201510493500A CN 105175306 A CN105175306 A CN 105175306A
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- catalyst
- butyrolactone
- gamma
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D207/24—Oxygen or sulfur atoms
- C07D207/26—2-Pyrrolidones
- C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
- C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
Abstract
The present invention discloses a synthetic method of N-methylpyrrolidone. The method comprises the steps of: (1) preparation of gamma-butyrolactone by dehydrogenating 1,4-butanediol under hydrogen atmosphere and in the presence of a catalyst A, to prepare unpurified gamma-butyrolactone; (2) synthesis of mixed amine by converting ammonia and methanol to obtain mixed methyl amine; (3) conducting dehydration reaction on unpurified gamma-butyrolactone obtained in (1) in the presence of a catalyst B and the mixed methyl amine obtained in (2), conducting condensation, degassing and distillation on the reaction products, collecting fractions at 81-82 DEG C / mmHg column, wherein the distillate is N- methylpyrrolidone. The synthetic method has the advantages of low investment, low raw material prices and the high purity, and is applicable to large-scale continuous industrial production.
Description
Technical field
The present invention relates to a kind of synthetic method of N-Methyl pyrrolidone, more particularly, is generate with BDO dehydrogenation to obtain highly purified product without the need to the intermediate product gamma-butyrolactone of purifying and mixed methyl amine by continuous processing.
Background technology
N-Methyl pyrrolidone is important industrial chemicals, be the polar solvent of the strong and good stability of a kind of selectivity, have that toxicity is low, boiling point is high, solvency power is strong, nonflammable, biodegradable, recoverable, use safety and be applicable to the advantages such as multiple formulations purposes.Be widely used in the solvent of poly(vinylidene fluoride), the electrode subsidiary material of lithium ion battery, solvent when synthetic gas desulfurization, lube oil finishing, lubricating oil antifreezing agent, olefinic extracting agent, the polymerization of indissoluble engineering plastics, agricultural herbicide, insulating material, production of integrated circuits, cleaning of semicon industry precision instrument, wiring board, PVC tail gas recycle, clean-out system, colour additive, dispersion agent etc.Also for the solvent of polymkeric substance and the medium of polyreaction, as engineering plastics and aramid fiber.Also can be used on the aspects such as agricultural chemicals, medicine and sanitising agent in addition.Its main application is as follows: the extractions such as (1) acetylene concentration and divinyl, isoprene, aromatic hydrocarbons; (2) lubricating oil refining; (3) indissoluble engineering plastics (polyphenylene sulfide, polyimide) and aramid fiber polymer solvent; (4) electrical insulating material and lithium ion battery; (5) high-grade paint, ink and pigment; (6) inert ingredient; (7) de-oiling, degreasing, dewaxing, polishing, antirust and depainting; (8) artificial kidney function film liquid and sea water desalination membrane liquid.
Current N-Methyl pyrrolidone industrialized producing technology is standby by the Dehydration of monomethyl amine and gamma-butyrolactone, and its preparation method is roughly divided into the method using catalyzer and the method not using catalyzer, as the method not using catalyzer, disclose by gamma-butyrolactone and monomethyl amine are reacted the method preparing the N-Methyl pyrrolidone of 90 ~ 93% productive rates for 4 hours at 280 DEG C in batch reactor, as the method using catalyzer, disclosed by by gamma-butyrolactone and monomethyl amine at 280 DEG C, and the lower successive reaction of y-type zeolite catalyzer existence of Copper Ion Exchange prepares the method for the N-Methyl pyrrolidone of 98% productive rate, but these methods have defect, as productive rate is low, and still remain unreacted reactant with the gamma-butyrolactone of product N-Methyl pyrrolidone boiling-point difference little (about 2 DEG C), therefore make abstraction and purification difficulty and increase impurity.
Summary of the invention
Technical problem to be solved by this invention is to provide the low and synthetic method of the N-Methyl pyrrolidone that purity is high of a kind of cost, and its innovative point is, comprises the following steps:
(1) gamma-butyrolactone is prepared, by gamma-butyrolactone standby not purified for BDO Oxidative Dehydrogenation under existing with catalyst A in a hydrogen atmosphere;
(2) mixed amine synthesis, becomes mixed methyl amine with ammonia with methanol conversion;
(3) the mixed methyl amine generation dehydration reaction that not purified gamma-butyrolactone step (1) obtained under catalyst B and step (2) obtain, the product be obtained by reacting is through condensation, degassed and rectifying, collect cut at 81 ~ 82 DEG C/mmHg post overhead product, this overhead product is N-Methyl pyrrolidone.
Preferably, in described step (1) 1, the mol ratio of 4-butyleneglycol and hydrogen is 1:0.1 ~ 1:10, the methyl alcohol dropped in described step (2) and the mol ratio of ammonia are 1:1 ~ 1:5, described mixed methyl amine and 1, the mol ratio of 4-butyleneglycol is 1:1 ~ 1:5, and described step (1) and step (2) are carried out at the temperature of 150 ~ 350 DEG C and under the pressure of 0.1 ~ 2Mpa, and described step (3) is carried out at the temperature of 150 ~ 400 DEG C and under the pressure of 7 ~ 15Mpa.
The invention has the advantages that: cheap raw material and lower process consumption, from cost aspect, the cost that the raw material adopted more then more can be cut down the number of intermediate links toward upstream, comprise manpower, transport, engineering consumption etc., in addition with 1, 4-butyleneglycol is as raw material, its dehydrogenation intermediate product does not need just can participate in reaction through purifying, methylamine device reaction generates monomethylamine, dimethyl amine and the mixture of Trimethylamine do not need directly to participate in reaction through being separated of complexity, then corresponding operation steps just can reduce, energy consumption reduces, also can reduce costs.
Accompanying drawing explanation
The synthetic route chart of this synthetic method of Fig. 1.
Embodiment
Further describe the present invention below in conjunction with specific embodiment, these embodiments are only exemplary, do not form scope of the present invention and how to limit.Can modify to the details of technical solution of the present invention and form lower without departing from the spirit and scope of the present invention or replace, but these amendments and replacement all fall in scope.
embodiment 1
Step one: 90Kg catalyst A is loaded reactor 1, and in this step, catalyst A is the mixture of three kinds of materials, and its composition is: CuO65wt%, SiO
215wt% and CaO20wt%, reactor heating 1, keep temperature of reaction at 260 DEG C, pressure keeps 0.5Mpa, BDO and hydrogen is pressed the mixed in molar ratio of 1:3, with transferpump with 0.5h
-1wHSV join the bottom of reactor 1, wait for that tundish 8 have output object, enter degassing tower 4 through pipeline 9 backflow, sampling, by gas chromatographic analysis gamma-butyrolactone content (weight) more than 90%, enters reactor 23 through pipeline 10;
Step 2: methyl alcohol and ammonia are dropped into reactor 15 with the speed of 16Kg/h, reactor heating 15 simultaneously, keep temperature of reaction at 220 DEG C, pressure keeps 0.5Mpa, waits for that tundish 20 have output object, enters reactor 23 through pipeline 21;
Step 3: 90Kg catalyst B is loaded reactor 23, and in this step, catalyst B is the mixture of three kinds of materials, and its composition is: ZnO40wt%, Al
2o
355wt% and CuO5wt%, reactor heating 23, keep temperature of reaction at 300 DEG C, pressure keeps 8Mpa, enters reactor 23, through condensation, degassed, rectifying respectively with transferpump line of pipes 10 and the logistics of pipeline 21, collect cut at 81 ~ 82 DEG C/mmHg post overhead product, this overhead product is N-Methyl pyrrolidone, and be 99.96% by analyzing the content (weight ratio) of N-Methyl pyrrolidone, moisture content (weight ratio) is 0.02%.
embodiment 2
Step one: 90Kg catalyst A is loaded reactor 1, and in this step, catalyst A is the mixture of three kinds of materials, and its composition is: CuO65wt%, SiO
215wt% and CaO20wt%, reactor heating 1, keep temperature of reaction at 200 DEG C, pressure keeps 1.0Mpa, BDO and hydrogen is pressed the mixed in molar ratio of 1:3, with transferpump with 0.5h
-1wHSV join the bottom of reactor 1, wait for that tundish 8 have output object, enter degassing tower 4 through pipeline 9 backflow, sampling, by gas chromatographic analysis gamma-butyrolactone content (weight) more than 90%, enters reactor 23 through pipeline 10;
Step 2: methyl alcohol and ammonia are dropped into reactor 15 with the speed of 16Kg/h, reactor heating 15 simultaneously, keep temperature of reaction at 170 DEG C, pressure keeps 1Mpa, waits for that tundish 20 have output object, enters reactor 23 through pipeline 21;
Step 3: 90Kg catalyst B is loaded reactor 23, and in this step, catalyst B is the mixture of three kinds of materials, and its composition is: ZnO40wt%, Al
2o
355wt% and CuO5wt%, reactor heating 23, keep temperature of reaction at 300 DEG C, pressure keeps 8Mpa, enters reactor 23, through condensation, degassed, rectifying respectively with transferpump line of pipes 10 and the logistics of pipeline 21, collect cut at 81 ~ 82 DEG C/mmHg post overhead product, this overhead product is N-Methyl pyrrolidone, and be 99.95% by analyzing the content (weight ratio) of N-Methyl pyrrolidone, moisture content (weight ratio) is 0.04%.
embodiment 3
Step one: 90Kg catalyst A is loaded reactor 1, and in this step, catalyst A is the mixture of three kinds of materials, and its composition is: CuO65wt%, SiO
215wt% and CaO20wt%, reactor heating 1, keep temperature of reaction at 300 DEG C, pressure keeps 1.5Mpa, BDO and hydrogen is pressed the mixed in molar ratio of 1:3, with transferpump with 0.5h
-1wHSV join the bottom of reactor 1, wait for that tundish 8 have output object, enter degassing tower 4 through pipeline 9 backflow, sampling, by gas chromatographic analysis gamma-butyrolactone content (weight) more than 90%, enters reactor 23 through pipeline 10;
Step 2: methyl alcohol and ammonia are dropped into reactor 15 with the speed of 16Kg/h, reactor heating 15 simultaneously, keep temperature of reaction at 300 DEG C, pressure keeps 1.5Mpa, waits for that tundish 20 have output object, enters reactor 23 through pipeline 21;
Step 3: 90Kg catalyst B is loaded reactor 23, and in this step, catalyst B is the mixture of three kinds of materials, and its composition is: ZnO40wt%, Al
2o
355wt% and CuO5wt%, reactor heating 23, keep temperature of reaction at 330 DEG C, pressure keeps 10Mpa, enters reactor 23, through condensation, degassed, rectifying respectively with transferpump line of pipes 10 and the logistics of pipeline 21, collect cut at 81 ~ 82 DEG C/mmHg post overhead product, this overhead product is N-Methyl pyrrolidone, and be 99.99% by analyzing the content (weight ratio) of N-Methyl pyrrolidone, moisture content (weight ratio) is 0.01%.
The method that method therefor of the present invention produces N-Methyl pyrrolidone with gamma-butyrolactone and methylamine is compared, often produce one ton of N-Methyl pyrrolidone and can save Renminbi 1000 yuan (calculating according to present market conditions), and the content (weight ratio) of the N-Methyl pyrrolidone that the present invention produces is higher than 99.95%, and moisture content (weight ratio) is lower than 0.05%.
Claims (8)
1. a synthetic method for N-Methyl pyrrolidone, is characterized in that:
Comprise the following steps
(1) gamma-butyrolactone is prepared, by gamma-butyrolactone standby not purified for BDO Oxidative Dehydrogenation under existing with catalyst A in a hydrogen atmosphere;
(2) mixed amine synthesis, becomes mixed methyl amine with ammonia with methanol conversion;
(3) the mixed methyl amine generation dehydration reaction that not purified gamma-butyrolactone step (1) obtained under catalyst B and step (2) obtain, the product be obtained by reacting is through condensation, degassed and rectifying, collect cut at 81 ~ 82 DEG C/mmHg post overhead product, this overhead product is N-Methyl pyrrolidone
The described catalyst A be wherein used in described step (1) can be selected from the oxide compound of the IIth A race, the Ith B race, group IIIA or the IVth A race metallic element one or more,
Wherein be used in that catalyst B described in described step (3) can be selected from the oxide compound of the IVth B race, group VIB, the VIIIth race, the Ith B race, II B-group, group IIIA or the IVth A race metallic element one or more.
2. method according to claim 1, is characterized in that: in described step (1), the mol ratio of BDO and hydrogen is 1:0.1 ~ 1:10.
3. method according to claim 1, is characterized in that: the methyl alcohol dropped in described step (2) and the mol ratio of ammonia are 1:1 ~ 1:5.
4. method according to claim 1, is characterized in that: the mol ratio of described mixed methyl amine and BDO is 1:1 ~ 1:5.
5. method according to claim 1, is characterized in that: described step (1) and step (2) are carried out at the temperature of 150 ~ 350 DEG C.
6. method according to claim 1, is characterized in that: described step (1) and step (2) are carried out under the pressure of 0.1 ~ 2Mpa.
7. method according to claim 1, is characterized in that: described step (3) is carried out at the temperature of 150 ~ 400 DEG C.
8. method according to claim 1, is characterized in that: described step (3) is carried out under the pressure of 7 ~ 15Mpa.
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| CN201510493500.8A CN105175306A (en) | 2015-08-13 | 2015-08-13 | Synthetic method of N-methylpyrrolidone |
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| CN201510493500.8A CN105175306A (en) | 2015-08-13 | 2015-08-13 | Synthetic method of N-methylpyrrolidone |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010018528A1 (en) * | 2000-02-04 | 2001-08-30 | Frank Ohlbach | Preparation of N-methy1-2-pyrrolidone (NMP) |
| CN1384820A (en) * | 1999-10-27 | 2002-12-11 | 巴斯福股份公司 | Process for production of N-methyl pyrrolidone using gamma butyrolactone and mixed methylamines as starting materials |
| CN101903344A (en) * | 2007-12-21 | 2010-12-01 | 梨树化学株式会社 | 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 |
-
2015
- 2015-08-13 CN CN201510493500.8A patent/CN105175306A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1384820A (en) * | 1999-10-27 | 2002-12-11 | 巴斯福股份公司 | Process for production of N-methyl pyrrolidone using gamma butyrolactone and mixed methylamines as starting materials |
| US20010018528A1 (en) * | 2000-02-04 | 2001-08-30 | Frank Ohlbach | Preparation of N-methy1-2-pyrrolidone (NMP) |
| CN101903344A (en) * | 2007-12-21 | 2010-12-01 | 梨树化学株式会社 | 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 |
Non-Patent Citations (1)
| Title |
|---|
| 张军等: "N-甲基吡咯烷酮合成技术分析", 《合成技术及应用》 * |
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Application publication date: 20151223 |
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