CN101903344B - Process for preparing of N-methyl pyrrolidone - Google Patents
Process for preparing of N-methyl pyrrolidone Download PDFInfo
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- CN101903344B CN101903344B CN200880121682.4A CN200880121682A CN101903344B CN 101903344 B CN101903344 B CN 101903344B CN 200880121682 A CN200880121682 A CN 200880121682A CN 101903344 B CN101903344 B CN 101903344B
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- butyrolactone
- gamma
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- methyl pyrrolidone
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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 relates to a process for preparation of N-methyl pyrrolidone, and more particularly to a process for preparing high purity, high yield N-methyl pyrrolidone, comprising a first step of dehydrogenating 1,4-butandiol under a hydrogen atmosphere in the presence of a metal oxide solid catalyst to prepare Gamma-butyrolactone, and a second step of subjecting the Gamma-butyrolactone obtained in the first step without purification to a dehydration with monomethylamine under a metal oxide solid catalyst. The process for preparation of N-methyl pyrrolidone according to the present invention is a continuous two-step process using a metal oxide catalyst, wherein the second step continuously progresses without purification of the reaction product of the first step, Gamma-butyrolactone. According to the present invention, little of a reaction intermediate Gamma-butyrolactone, which is difficult to separate because of a small difference in boiling point (about 2 DEG C) from the final product, N-methyl pyrrolidone, remains after reaction, and thus separation and purification are easy. Further, its simple process enables mass production and lowers purification equipment cost.
Description
Technical field
The present invention relates to the preparation method of N-Methyl pyrrolidone, relate more specifically to the preparation method of high purity and high yield N-Methyl pyrrolidone, described method is to use the continuous two-step approach of containing metal oxide as the solid catalyst of active ingredient, wherein two-step reaction can carry out and continuously without the reaction product gamma-butyrolactone of the purifying the first step, and be easy to separate and purifying because reacting rear reactionless intermediate product gamma-butyrolactone residue, and can prepare in a large number N-Methyl pyrrolidone because of its simple method, described intermediate product gamma-butyrolactone is difficult to Fen Li because of its boiling point very little with end product N-Methyl pyrrolidone difference (approximately 2 ℃).
Background technology
At polymerization and solvent, coating preparation solvent for processing, metallic surface stain remover, medicine synthetic and purifying for solvent, semi-conductor and electronic material processing solvent, lithium cell prepare with fields such as solvents, because the concern of environmentally friendly technique increases, the demand of the nontoxic N-Methyl pyrrolidone of former environment is increased.
N-Methyl pyrrolidone is standby at the industrial Dehydration by MMA and gamma-butyrolactone, and its preparation method method being used the method for catalyzer and do not use catalyzer by being roughly divided into.
As the method for not using catalyzer, disclose by gamma-butyrolactone and MMA are reacted to the method (J.Amer.Chem.Soc., 71 (1949) 896) of preparing the N-Methyl pyrrolidone of 90～93% productive rates for 4 hours at 280 ℃ in batch reactor.In addition, Japanese Patent Publication discloses for No. 1-190667 by gamma-butyrolactone, water and MMA are added to autoclave, and they are reacted to the method for preparing the N-Methyl pyrrolidone of 94.3% productive rate for 3 hours under 240～265 ℃ and 50atm pressure.
As the method for using catalyzer, disclose by by gamma-butyrolactone and MMA under 280 ℃ and normal atmosphere, and the y-type zeolite catalyzer of Copper Ion Exchange exists lower successive reaction to prepare the method (Bull.Chem.Soc.Japan, 50 (10) (1977) 2517) of the N-Methyl pyrrolidone of 98% productive rate.In addition, method (J.Org.Chem., 50 (1994) 3998) by gamma-butyrolactone and MMA are prepared with the ZSM-5 zeolite catalyzer of chromium ion exchange to the N-Methyl pyrrolidone of 98.2% productive rate 300 ℃ of successive reactions is disclosed.In addition, Japanese Patent Publication discloses the method for catalyzer such as aluminum oxide, silica-alumina, activated carbon, silica gel, silicon oxide-magnesium oxide, gamma-butyrolactone and MMA being reacted to the N-Methyl pyrrolidone of preparing 63～93% productive rates by using clear No. 49-20582.
But these methods have defect, as low in productive rate, and still remain unreacted reactant with the gamma-butyrolactone of product N-Methyl pyrrolidone boiling-point difference little (approximately 2 ℃), therefore make separation and purification difficult and increase impurity.
The method of most prior art is used gamma-butyrolactone as starting raw material, and it is first prepared by BDO or maleic anhydride, and through separate and purifying to prepare N-Methyl pyrrolidone.
Known N-Methyl pyrrolidone is prepared the intermediate product gamma-butyrolactone of use by 1,4-butyleneglycol is prepared by following certain embodiments, dehydrogenation under existing by the catalyzer of preparing under existing at Cu/Cr catalyzer or in Zn and Mn are added to Cu/Cr catalyzer, by using oxygenant as oxygen dehydrogenation under existing containing one or more the catalyzer such as Pt, Pd, Ag, or dehydrogenation under existing by the catalyzer of preparing in basic metal or Al are added to Cu/Zn catalyzer.
Generally, gamma-butyrolactone is prepared by the BDO dehydrogenation with Cu/Cr catalyzer.But this method has defect, as Cu/Cr catalyzer, because use heavy metal chromium can cause environmental pollution, and there is side reaction and produces by products such as tetrahydrofuran (THF), therefore reduce selectivity and be converted into the transformation efficiency of gamma-butyrolactone.Therefore, Japanese Patent Laid discloses flat No. 4-17954 zinc or magnesium is added in Cu/Cr catalyzer to overcome above defect, but this method still has problem, and if productive rate is 95%, and catalyst life is short approximately 1 month.
No. 2-27349, Japanese Patent Publication and Japanese Patent Laid disclose clear disclosing for No. 61-212577 and by use, contain the catalyzer such as palladium, silver are prepared gamma-butyrolactone under oxygenant exists as oxygen method by BDO dehydrogenation.But according to this method, catalyst life is very short, and selectivity and transformation efficiency very low.
GB1066979 discloses by using and has added catalyzer prepared by Cu/Zn catalyzer by BDO dehydrogenation, to be prepared the method for gamma-butyrolactone in aluminium.But according to this method, productive rate is very low and catalyst life is very short.
Summary of the invention
In order to solve the problems referred to above of prior art, one aspect of the present invention provides the preparation method of N-Methyl pyrrolidone, described preparation method by using metal oxide solid catalyzer to carry out continuous two-step approach without purification reaction intermediate product gamma-butyrolactone, can prepare in a large number the N-Methyl pyrrolidone of high purity and high yield, described metal oxide solid catalyzer has excellent reactive, after making reaction, reactionless intermediate product gamma-butyrolactone remains, described intermediate product gamma-butyrolactone is difficult to Fen Li because of very little with the boiling point difference of end product N-Methyl pyrrolidone (approximately 2 ℃).Another aspect of the present invention provides gamma-butyrolactone preparation method, described preparation method in the first step by 1,4-butyleneglycol is used the catalyzer that does not comprise the poisonous metal such as such as chromium environment during preparing gamma-butyrolactone, therefore do not cause environmental pollution, can at utmost reduce side reaction, therefore increase output, can during reaction by flow hydrogen gas reducing catalyst, increase catalytic activity, and by reducing the burnt formation speed extending catalyst life-span of catalyzer, and can prepare in a large number high yield gamma-butyrolactone by described continuation method.
In order to reach above object, the invention provides the preparation method of high purity and high yield N-Methyl pyrrolidone, comprise the first step under hydrogen atmosphere and under the existence of metal oxide solid catalyzer by 1,4-butanediol dehydrogenation is to prepare gamma-butyrolactone, and second step is directly introduced the not purified gamma-butyrolactone of the first step acquisition under metal oxide solid catalyzer and the dehydration reaction of MMA.
Embodiment
Now will explain in detail the present invention.
The inventor has been found that, as the result with the N-Methyl pyrrolidone preparation method's of the described catalyzer of use painstaking research to N-Methyl pyrrolidone catalyst for preparing, if metal oxide solid catalyzer is used in gamma-butyrolactone and N-Methyl pyrrolidone preparation, it demonstrates excellent catalytic activity, and react continuously and do not demonstrate without the synthetic gamma-butyrolactone of purifying and have any difference with purifying gamma-butyrolactone, therefore successive reaction can be used for preparing N-Methyl pyrrolidone, therefore can make it produce in a large number, and complete the present invention.
Therefore, according to the present invention, with comprising the solid catalyst that is selected from one or more active ingredients in special metal oxide compound group, by BDO dehydrogenation, prepare gamma-butyrolactone, and dewater to prepare N-Methyl pyrrolidone by gained gamma-butyrolactone and MMA.In addition, the present invention is characterised in that gamma-butyrolactone can directly react with MMA, and without the purifying process that carries out carrying out in art methods.
According to the present invention, the preparation method of N-Methyl pyrrolidone comprises two consecutive steps that use metal oxide solid catalyzer.
In the first step, by BDO under flow hydrogen gas dehydrogenation to prepare gamma-butyrolactone.In second step, the reaction product gamma-butyrolactone of the first step and MMA are dewatered and without purifying, to prepare N-Methyl pyrrolidone.
The present invention uses dissimilar solid catalyst for the first step (dehydrogenation) and second step (dehydration).
The solid catalyst being used in the first step comprises one or more active ingredients, and described active ingredient is selected from the oxide compound containing the 11st family's metallic element.
In order further to improve catalytic activity, the catalyzer being used in the first step can further comprise the promotor in conventional content range.Described promotor can be and is selected from containing one or more in the oxide compound of group II metal element.
In order to ensure the structural stability of catalyzer, the catalyzer being used in the first step can further comprise the carrier in conventional content range.The type of described carrier is not specifically limited, and can use those that commonly use in prior art.Preferably, described carrier can be and is selected from containing one or more in the oxide compound of the 13rd family or the 14th family's metallic element.
Because the metal oxide solid catalyzer being used in the first step does not contain chromium, these are different from existing catalyzer, so can not produce in catalyzer preparation with in discarding process the environmental pollution that heavy metal causes.In addition, the described metal oxide solid catalyzer being used in the first step has at utmost reduced side reaction to suppress by product as the generation of tetrahydrofuran (THF), therefore increase selectivity and the transformation efficiency that is converted into gamma-butyrolactone, therefore realized the high yield preparation of gamma-butyrolactone.
In the first step, although there is dehydrogenation reaction, during reaction add hydrogen with reducing catalyst, with this, increase catalyst activity and reduce the burnt formation speed of catalyzer, therefore extending catalyst life-span.
The solid catalyst being used in second step comprises one or more active ingredients, and described active ingredient is selected from the oxide compound containing the 4th family, the 6th family, the 8th family, the 11st family, the 12nd family, the 13rd family or the 14th family's metallic element.
In order to ensure the structural stability of catalyzer, the metal oxide solid catalyzer being used in second step can further comprise the carrier in conventional content range.The type of described carrier is not specifically limited, and can use those that commonly use in prior art.Preferably, described carrier is selected from one or more in the oxide compound that contains the 13rd family or the 14th family's metallic element.
The metal oxide solid catalyzer being used in second step has useful effect, the not purified gamma-butyrolactone obtaining in the first step as used does not demonstrate and uses the gamma-butyrolactone of purifying to have any difference with using in the existing technique of catalyzer, therefore make technique simple, and without gamma-butyrolactone, remain after reaction, therefore can prepare high yield, highly purified N-Methyl pyrrolidone, described gamma-butyrolactone is difficult to Fen Li because of very little with the boiling point difference of end product N-Methyl pyrrolidone (approximately 2 ℃).
Meanwhile, being used in metal oxide solid catalyzer in the present invention's the first and second steps can be by method preparation conventional in prior art, and to its preparation method without concrete restriction.
In the first step, the mol ratio of BDO and hydrogen is 1: 0.1～1: 5, preferably 1: 10～1: 3.5.In order to realize maximum catalyst life, extend effect and keep hydrogen partial pressure to improve selectivity with this, 1, the mol ratio of 4-butyleneglycol and hydrogen is 1: 0.1 or higher, and consider that catalyst life extends the increase of effect and optionally improves, and the economic benefit aspect circulating hydrogen cost, the mol ratio of BDO and hydrogen preferably 1: 5 or lower.
Most preferably, the reaction raw materials of dehydrogenation, BDO and hydrogen do not comprise impurity, but to purity without concrete restriction, this be because use impure reaction raw materials do not affect effect of the present invention.
In second step, the mol ratio of gamma-butyrolactone and MMA is 1: 0.5～1: 5, and preferably 1: 1.0～1: 3.5.In order to prevent to the reduction of the transformation efficiency of N-Methyl pyrrolidone, the mol ratio of gamma-butyrolactone and MMA preferably 1: 0.5 or higher, and consider that transformation efficiency increases and economic return, the mol ratio of gamma-butyrolactone and MMA preferably 1: 5 or lower.
In the reaction raw materials of dehydration, after the first step, can use unpurified reaction intermediate gamma-butyrolactone.Preferably use the MMA of aqueous solution form, and conventionally use MMA solution (the 40wt% aqueous solution), but to its concentration without concrete restriction, and can use the MMA of lower aq.
Method of the present invention is comprised of consecutive steps, and successive reaction step can be this area general procedure, and to it without concrete restriction.
For reaction conditions, preferably 0.1～5.0hr of weight hourly space velocity (WHSV, the residence time of reactant in expression reactor)
-1.Because add a small amount of reactant cannot realize economic manufacture in reactor, so preferably 0.1hr of weight hourly space velocity
-1or larger, and consider maximum reaction efficiency, it is 5.0hr preferably
-1or lower.
For the reagent flow in continuous processing, can use formula from bottom to up, or by upper to end formula and unrestricted.But, in order to prevent channel, more preferably use formula from bottom to up.
The dehydrogenation of the first step is preferably carried out under the temperature range of 150～350 ℃.For minimum reaction activity is provided, preferably 150 ℃ or higher of temperature of reaction, and consider gain in yield effect and economic benefit while heating, and the by product that under high temperature, sintering causes increases and catalyst life reduces, preferably 350 ℃ or lower of temperature of reaction.
Reaction pressure preferred atmosphere pressure～20atm that dehydrogenation is used.In order to realize minimum transformation efficiency, reaction pressure preferred atmosphere is pressed or is higher, and considers that transformation efficiency increases and economic benefit, as maintains the cost of high pressure, the preferred 20atm of reaction pressure or lower.
According to the first step dehydrogenation of the invention described above, can obtain BDO 95% or higher transformation efficiency, and 98% or higher gamma-butyrolactone selectivity.
Second step dehydration is preferably carried out under the temperature range of 150～400 ℃.For minimum reaction activity is provided, preferably 150 ℃ or higher of temperature of reaction, and consider economic benefit and gain in yield while heating, and the by product that under high temperature, sintering causes increases and catalyst life reduces, preferably 400 ℃ or lower of temperature of reaction.
The reaction pressure preferred atmosphere pressure～100atm of dehydration use.In order to realize minimum transformation efficiency, reaction pressure preferred atmosphere is pressed or is higher, and considers that transformation efficiency increases and economic benefit, as maintains the cost of high pressure, the preferred 100atm of reaction pressure or lower.
According to the second step dehydration of the invention described above, can obtain 99% or higher gamma-butyrolactone transformation efficiency, and 97% or higher N-Methyl pyrrolidone selectivity.
In N-Methyl pyrrolidone preparation method according to the present invention, can will between the reaction period, add the water in the MMA aqueous solution to remove from reaction product by the common method such as such as distillation, and to this method without concrete restriction.
According to the present invention, the preparation method of N-Methyl pyrrolidone uses the continuous two-step approach with excellent reactive metal oxide solid catalyzer.The gamma-butyrolactone preparation method of the first step uses the metal oxide catalyst containing the 11st family's metallic element, wherein use the not catalyzer containing the poisonous metal such as such as chromium environment, therefore do not worry environmental pollution, and can at utmost reduce side reaction to increase selectivity and the transformation efficiency to gamma-butyrolactone, therefore prepare high yield gamma-butyrolactone, and catalyzer during reaction reduces by hydrogen stream, with this, increase catalytic activity and reduce the burnt formation therefore extending catalyst life-span of speed of catalyzer.
The N-Methyl pyrrolidone preparation method of second step uses containing being selected from the 4th family, the 6th family, the 8th family, the 11st family, the 12nd family, the metal oxide catalyst of the 13rd family or the 14th family's metallic element, wherein use unpurified the first step reaction product gamma-butyrolactone, therefore make technique simple, after reaction, reactionless intermediate product gamma-butyrolactone remains and contributes to separate and purifying, and therefore realize high purity, the preparation of high yield N-Methyl pyrrolidone and extensive preparation, described intermediate product gamma-butyrolactone is difficult to Fen Li because of its boiling point very little with N-Methyl pyrrolidone difference (approximately 2 ℃).
Hereinafter, by embodiment, be described in further detail the present invention.But following examples are only for understanding the present invention, and the invention is not restricted to this and be not limited.
embodiment 1: the first step reaction
Packing 8g catalyst A into diameter is the tubular reactor that 1.27cm and length are 25.4cm, and the outside that heat tape is attached to reactor is to keep temperature of reaction at 240 ℃.
By reactant BDO by transferpump with 1.0hr
-1wHSV join the bottom (bottom-up) of reactor.The mol ratio of BDO and hydrogen is remained on to 1: 2, and reaction pressure is remained on to 5atm.
After reaction completes, by the selectivity of gas chromatographic analysis gamma-butyrolactone and the transformation efficiency of BDO.Therefore, obtain 99.20% gamma-butyrolactone selectivity, and the transformation efficiency of BDO is 99.33%
embodiment 2～5: the first step reaction
By the step identical with embodiment 1, prepare gamma-butyrolactone, difference is to change reaction pressure, temperature of reaction and WHSV described according to the form below 1.
[table 1]
Note 1) GBL: gamma-butyrolactone
Note 2) THF: tetrahydrofuran (THF)
Note 3) catalyst A: CuO64%, MgO1.3%, SiO
215%
comparative example 1: the comparison (intermittent reaction) of catalyzer
By 20g1,4-butyleneglycol adds in autoclave (250ml), by 2g (10wt%, with the weighing scale of BDO) E-113TU (CALSICAT company, copper chromite catalyst) adds wherein, and be filled with wherein subsequently hydrogen, make reaction pressure reach 5atm, and make mixture reaction, at 210 ℃, stir 3 hours simultaneously.
Subsequently, catalyzer is removed by filtration, used gas chromatographic analysis residue.Therefore, obtain 96.00% gamma-butyrolactone selectivity, and the transformation efficiency of BDO is 86.00%, and tetrahydrofuran (THF) makes with 1.43% selectivity.
comparative example 2: the comparison (intermittent reaction) of catalyzer
By the step identical with comparative example 1, prepare gamma-butyrolactone, difference is to change catalytic amount and reaction pressure described according to the form below 2.
[table 2]
Note 1) catalytic amount: wt%, with the weighing scale of BDO
embodiment 6: the first step reaction
Packing 90g catalyst B into diameter is the tubular reactor that 2.54cm and length are 15.24cm, and the outside that heat tape is attached to reactor is to keep temperature of reaction at 220 ℃.
By reactant BDO by transferpump with 1.0hr
-1wHSV join the bottom (bottom-up) of reactor.The mol ratio of BDO and hydrogen is remained on to 1: 2, and reaction pressure is remained to normal atmosphere.
After reaction completes, by the selectivity of gas chromatographic analysis gamma-butyrolactone and the transformation efficiency of BDO.Therefore, obtain 99.32% gamma-butyrolactone selectivity, and the transformation efficiency of BDO is 99.21%.
embodiment 7～13: the first step reaction
By the step identical with embodiment 6, prepare gamma-butyrolactone, difference is to change reaction pressure, temperature of reaction, WHSV and mol ratio described according to the form below 3.
[table 3]
Note 1) mol ratio=BDO: hydrogen
Note 2) GBL: gamma-butyrolactone
Note 3) THF: tetrahydrofuran (THF)
Note 4) catalyst B: CuO86～92%, CaO2～4%, SiO
23～9%
comparative example 3: the comparison (intermittent reaction) of catalyzer
20g1.4-butyleneglycol is added in autoclave (250ml), by 4g (20wt%, with 1, the weighing scale of 4-butyleneglycol) DEH-7 (Uop Inc., Pt catalyzer) add wherein, and be filled with wherein nitrogen subsequently, make reaction pressure reach 30atm, and make mixture reaction, at 220 ℃, stir 3 hours simultaneously.
Subsequently, by filtration, remove catalyzer, use gas chromatographic analysis residue.Therefore, obtain 16.00% gamma-butyrolactone selectivity, and the transformation efficiency of BDO is 63.28%, and prepares tetrahydrofuran (THF) with 79.00% selectivity.
comparative example 4: the comparison (intermittent reaction) of catalyzer
By the step identical with comparative example 3, prepare gamma-butyrolactone, difference is to change reaction pressure and gas described according to the form below 4.
[table 4]
embodiment 14: second step reaction
Packing 98g catalyzer C into diameter is the tubular reactor that 2.54cm and length are 15.24cm, and the outside that heat tape is attached to reactor is to keep temperature of reaction at 280 ℃.
By in embodiment 6 preparation reactant gamma-butyrolactone and MMA solution (the 40wt% aqueous solution) with 0.2hr
-1wHSV join the bottom (supreme the end of by) of reactor, the mol ratio that simultaneously keeps gamma-butyrolactone and MMA is 1: 1.5.Reaction pressure is remained on to 50atm.In addition, be used as the first step product obtain gamma-butyrolactone and without purifying.
After reaction completes, by the selectivity of gas chromatographic analysis N-Methyl pyrrolidone and the transformation efficiency of gamma-butyrolactone.Therefore, obtain 99.73% N-Methyl pyrrolidone selectivity, and the transformation efficiency of gamma-butyrolactone is 100%.
embodiment 15～26: second step reaction
By the step identical with embodiment 14, prepare N-Methyl pyrrolidone, difference is to change temperature of reaction, reaction pressure, WHSV and mol ratio described according to the form below 5.
[table 5]
Note 1) mol ratio=gamma-butyrolactone: MMA
Note 2) NMP:N-methyl-2-pyrrolidone
Note 3) GBL: gamma-butyrolactone
Note 4) catalyzer C:ZnO
Note 5) purity of unpurified GBL: GBL99.32% after the first step
embodiment 27: second step reaction
Packing 65g catalyzer D into diameter is the tubular reactor that 2.54cm and length are 15.24cm, and the outside that heat tape is attached to reactor is to keep temperature of reaction at 300 ℃.
By in embodiment 6 preparation reactant gamma-butyrolactone and MMA solution (the 40wt% aqueous solution) with 1.0hr
-1wHSV join the bottom (supreme the end of by) of reactor, the mol ratio that simultaneously keeps gamma-butyrolactone and MMA is 1: 1.5.Reaction pressure is remained on to 50atm.And, be used as the first step product obtain gamma-butyrolactone and without purifying.
After reaction completes, by the selectivity of gas chromatographic analysis N-Methyl pyrrolidone and the transformation efficiency of gamma-butyrolactone.Therefore, obtain 97.25% N-Methyl pyrrolidone selectivity, and the transformation efficiency of gamma-butyrolactone is 99.94%.
embodiment 28～32: second step reaction
By the step identical with embodiment 27, prepare N-Methyl pyrrolidone, difference is to change temperature of reaction, reaction pressure and WHSV described according to the form below 6.
[table 6]
Note 1) mol ratio=gamma-butyrolactone: MMA
Note 2) NMP:N-methyl-2-pyrrolidone
Note 3) GBL: gamma-butyrolactone
Note 4) catalyzer D:ZnO40%, Al
2o
355%, CuO4%
Note 5) purity of unpurified GBL: GBL99.32% after the first step
embodiment 33: second step reaction
Packing 40.9g catalyzer E into diameter is the tubular reactor that 2.54cm and length are 15.24cm, and the outside that heat tape is attached to reactor is to keep temperature of reaction at 280 ℃.
By in embodiment 6 preparation reactant gamma-butyrolactone and MMA solution (the 40wt% aqueous solution) with 1.0hr
-1wHSV join the bottom (supreme the end of by) of reactor, the mol ratio that simultaneously keeps gamma-butyrolactone and MMA is 1: 1.5.Reaction pressure is remained on to 50atm.In addition, be used as the first step product obtain gamma-butyrolactone and without purifying.
After reaction completes, by the selectivity of gas chromatographic analysis N-Methyl pyrrolidone and the transformation efficiency of gamma-butyrolactone.Therefore, obtain 99.45% N-Methyl pyrrolidone selectivity, and the transformation efficiency of gamma-butyrolactone is 99.87%.
embodiment 34～36: second step reaction
By the step identical with embodiment 33, prepare N-Methyl pyrrolidone, difference is to change temperature of reaction, reaction pressure and WHSV described according to the form below 7.
[table 7]
Note 1) mol ratio=gamma-butyrolactone: MMA
Note 2) NMP:N-methyl-2-pyrrolidone
Note 3) GBL: gamma-butyrolactone
Note 4) catalyzer E:TiO
285%, SiO
25%, WO
310%
Note 5) purity of unpurified GBL: GBL99.32% after the first step reaction
embodiment 37: second step reaction
This experiment is presented at uses the second reaction of metal oxide catalyst of the present invention to carry out, and uses the low-purity GBL of preparation separately and the high purity GBL for preparing according to the first step embodiment not to have any problem.
Packing 98g catalyzer C into diameter is the tubular reactor that 2.54cm and length are 15.24cm, and the outside that heat tape is attached to reactor is to keep temperature of reaction at 280 ℃.
Reactant gamma-butyrolactone and MMA solution (the 40wt% aqueous solution) are with 0.2hr
-1wHSV join the bottom (supreme the end of by) of reactor, the mol ratio that simultaneously keeps gamma-butyrolactone and MMA is 1: 1.5.Reaction pressure is remained on to 50atm.In addition, be used as the first step product obtain gamma-butyrolactone and without purifying.
After reaction completes, by the selectivity of gas chromatographic analysis N-Methyl pyrrolidone and the transformation efficiency of gamma-butyrolactone.Therefore, obtain 98.05% N-Methyl pyrrolidone selectivity, and the transformation efficiency of gamma-butyrolactone is 100%.
embodiment 38～39: second step reaction
By the step identical with embodiment 37, prepare N-Methyl pyrrolidone, difference is to change temperature of reaction and WHSV described according to the form below 8.
[table 8]
Note 1) mol ratio=gamma-butyrolactone: MMA
Note 2) NMP:N-methyl-2-pyrrolidone
Note 3) GBL: gamma-butyrolactone
Note 4) catalyzer C:ZnO
Note 5) purity of unpurified GBL: GBL97.54% after the first step reaction
embodiment 40: second step reaction
This experiment is presented at uses the second reaction of metal oxide catalyst of the present invention to carry out, and uses the low-purity GBL of preparation separately and the high purity GBL for preparing according to the first step embodiment not to have any problem.Demonstrating in second step reaction is carried out, there is not any problem in the MMA aqueous solution that working concentration is less than 40wt% yet.
Packing 98g catalyzer C into diameter is the tubular reactor that 2.54cm and length are 15.24cm, and the outside that heat tape is attached to reactor is to keep temperature of reaction at 280 ℃.
Reactant gamma-butyrolactone and MMA solution (the 35wt% aqueous solution) are with 0.15hr
-1wHSV join the bottom (supreme the end of by) of reactor, the mol ratio that simultaneously keeps gamma-butyrolactone and MMA is 1: 1.3.Reaction pressure is remained on to 50atm.In addition, be used as the first step product obtain gamma-butyrolactone and without purifying.
After reaction completes, by the selectivity of gas chromatographic analysis N-Methyl pyrrolidone and the transformation efficiency of gamma-butyrolactone.Therefore, obtain 98.54% N-Methyl pyrrolidone selectivity, and the transformation efficiency of gamma-butyrolactone is 100.00%.
embodiment 41～42: second step reaction
By the step identical with embodiment 40, prepare N-Methyl pyrrolidone, difference is to change temperature of reaction, reaction pressure and mol ratio described according to the form below 9.
[table 9]
Note 1) mol ratio=gamma-butyrolactone: MMA
Note 2) NMP:N-methyl-2-pyrrolidone
Note 3) GBL: gamma-butyrolactone
Note 4) catalyzer C:ZnO
Note 5) purity of unpurified GBL: GBL97.54% after the first step reaction
embodiment 43: second step reaction
This experiment is presented at uses the second reaction of metal oxide catalyst of the present invention to carry out, and uses the low-purity GBL of preparation separately and the high purity GBL for preparing according to the first step embodiment not to have any problem.Demonstrating in second step reaction is carried out, there is not any problem in the MMA aqueous solution that working concentration is less than 40wt% yet.
Packing 98g catalyzer F into diameter is the tubular reactor that 2.54cm and length are 15.24cm, and the outside that heat tape is attached to reactor is to keep temperature of reaction at 280 ℃.
Reactant gamma-butyrolactone and MMA solution (the 35wt% aqueous solution) are with 0.15hr
-1wHSV join the bottom (supreme the end of by) of reactor, the mol ratio that simultaneously keeps gamma-butyrolactone and MMA is 1: 1.5.Reaction pressure is remained on to 50atm.In addition, be used as the first step product obtain gamma-butyrolactone and without purifying.
After reaction completes, by the selectivity of gas chromatographic analysis N-Methyl pyrrolidone and the transformation efficiency of gamma-butyrolactone.Therefore, obtain 98.50% N-Methyl pyrrolidone selectivity, and the transformation efficiency of gamma-butyrolactone is 100.00%.
[table 10]
Note 1) mol ratio=gamma-butyrolactone: MMA
Note 2) NMP:N-methyl-2-pyrrolidone
Note 3) GBL: gamma-butyrolactone
Note 4) catalyzer F:SiO
267.6%, Al
2o
328.2%, TiO
20.41%, Fe
2o
30.57%
Note 5) purity of unpurified GBL: GBL97.54% after the first step reaction
embodiment 44: second step reaction
This experiment is also presented at uses the second reaction of metal oxide catalyst of the present invention to carry out, and uses the low-purity GBL of preparation separately and the high purity GBL for preparing according to the first step embodiment not to have any problem.Demonstrating in second step reaction is carried out, there is not any problem in the MMA aqueous solution that working concentration is less than 40wt% yet.
Packing 98g catalyzer C into diameter is the tubular reactor that 2.54cm and length are 15.24cm, and the outside that heat tape is attached to reactor is to keep temperature of reaction at 280 ℃.
Reactant gamma-butyrolactone and MMA solution (the 30wt% aqueous solution) are with .2hr
-1wHSV join the bottom (supreme the end of by) of reactor, the mol ratio that simultaneously keeps gamma-butyrolactone and MMA is 1: 1.5.Reaction pressure is remained on to 50atm.In addition, be used as the first step product obtain gamma-butyrolactone and without purifying.
After reaction completes, by the selectivity of gas chromatographic analysis N-Methyl pyrrolidone and the transformation efficiency of gamma-butyrolactone.Therefore, obtain 98.40% N-Methyl pyrrolidone selectivity, and the transformation efficiency of gamma-butyrolactone is 99.94%.
[table 11]
Note 1) mol ratio=gamma-butyrolactone: MMA
Note 2) NMP:N-methyl-2-pyrrolidone
Note 3) GBL: gamma-butyrolactone
Note 4) catalyzer C:ZnO
Note 5) purity of unpurified GBL: GBL90.15% after the first step reaction
Claims (8)
1. a preparation method for high purity, high yield N-Methyl pyrrolidone, comprising:
The first step under hydrogen atmosphere and metal oxide solid catalyzer exist under by BDO dehydrogenation to prepare gamma-butyrolactone; With
The not purified gamma-butyrolactone that second step obtains the described the first step under metal oxide solid catalyzer is introduced the dehydration reaction with the MMA aqueous solution,
Wherein be used in described solid catalyst in the described the first step by CuO, MgO and SiO
2composition; Or by CuO, CaO and SiO
2composition,
The described solid catalyst being wherein used in described second step is comprised of ZnO; Or by ZnO, Al
2o
3form with CuO; Or by TiO
2, SiO
2and WO
3composition; Or by SiO
2, Al
2o
3, TiO
2and Fe
2o
3composition.
2. the method for claim 1, wherein, in the described the first step, the mol ratio of BDO and hydrogen is 1:0.1～1:5.
3. the method for claim 1, wherein, in described second step, the mol ratio of gamma-butyrolactone and MMA is 1:0.5～1:5.
4. the method for claim 1, wherein, in the described the first step and second step, weight hourly space velocity is 0.1～5.0hr
-1.
5. the method for claim 1, the wherein said the first step is carried out at the temperature of 150～350 ℃.
6. the method for claim 1, wherein said second step carries out at the temperature of 150～400 ℃.
7. the method for claim 1, the wherein said the first step is pressed onto at atmosphere under the reaction pressure of 20atm carries out.
8. the method for claim 1, wherein said second step is pressed onto at atmosphere under the reaction pressure of 100atm and carries out.
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| KR1020070134910A KR100943528B1 (en) | 2007-07-23 | 2007-12-21 | Process for preparing of n-methyl pyrrolidone |
| PCT/KR2008/005790 WO2009082086A1 (en) | 2007-12-21 | 2008-10-01 | Process for preparing of n-methyl pyrrolidone |
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| 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) |
| CN105175306A (en) * | 2015-08-13 | 2015-12-23 | 张铨望 | Synthetic method of N-methylpyrrolidone |
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| JPS61246173A (en) * | 1985-04-23 | 1986-11-01 | Idemitsu Petrochem Co Ltd | Productionof gamma-butyrolactone |
| WO2001046169A1 (en) * | 1999-12-21 | 2001-06-28 | Mitsubishi Chemical Corporation | Process for producing carbonyl compounds by dehydrogenation of alcohols |
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| Title |
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| Yarlagadda V. et al.Modified ZSM-5 Catalysts for the Synthesis of Five- and Six-Membered Heterocyclics.《J. Org. Chem.》.1994,第59卷第3998页第2栏倒数第4－10，第3999页Table 2. * |
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