CN102070501A - Method for preparing n-methylpyrrolidone from 1,4-butanediol - Google Patents
Method for preparing n-methylpyrrolidone from 1,4-butanediol Download PDFInfo
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- 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
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- 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
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- 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
- C07D207/27—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with substituted hydrocarbon radicals directly attached to the ring nitrogen atom
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Abstract
The invention provides a method for preparing gamma-butyrolactone (GBL) and N-methylpyrrolidone (NMP), more specifically, a method for preparing NMP, comprising introducing 1,4-butanediol in a reactor, performing dehydrogenation in the presence of metallic oxide catalyst to provide GBL; supplying monomethyl amine (MMA) aqueous solution and GBL to the reactor; separating the NMP generated by the reaction of the MMA and the GBL from the water; mixing the separated water with the MMA to provide the MMA aqueous solution; and leading the MMA aqueous solution back into the reactor. Since the GBL is prepared from the butanediol in the presence of the catalyst, the water generated from the reaction of the MMA and the GBL is collected to provide the MMA aqueous solution, and the MMA aqueous solution is returned to the reactor, the prepared NMP has the advantages that energy is saved and simple separation of the product NMP is realized.
Description
Technical field
The present invention relates to a kind of method for preparing N-Methyl pyrrolidone (NMP), more specifically, relate to the method for preparing N-Methyl pyrrolidone as described below, wherein with 1,4-butyleneglycol (BDO) imports in the reactor, and carries out dehydrogenation so that gamma-butyrolactone (GBL) to be provided in the presence of metal oxide catalyst; Supply with Monomethylamine (MMA) aqueous solution and gamma-butyrolactone to reactor; The N-Methyl pyrrolidone and the water sepn that will generate by the reaction of Monomethylamine and gamma-butyrolactone; Isolated water is mixed with Monomethylamine so that monomethylamine aqueous solution to be provided, again described monomethylamine aqueous solution is led back in the reactor.
Background technology
Knownly prepare the certain methods of gamma-butyrolactone (GBL) by butanediol dehydrogenation, described gamma-butyrolactone is as the intermediate of preparation such as N-N-methyl-2-2-pyrrolidone N-pyrrolidone such as (NMP).
Special fair 2-27349 communique of Japan and Japanese kokai publication sho 61-212577 communique disclose in the presence of the catalyzer that comprises one or more metals that are selected from palladium (Pd), platinum (Pt) and silver (Ag), use the method that makes butanediol dehydrogenation such as oxygenants such as oxygen.
Use such as oxygenants such as oxygen make the method write up of butanediol dehydrogenation in special fair 2-27349 communique of Japan and Japanese kokai publication sho 61-212577 communique.According to aforesaid method, use relatively costly palladium metal and silver that butyleneglycol is carried out dehydrogenation.Because catalyst life is short, and transformation efficiency and selectivity are low, and this method is only at low weight hourly space velocity (h
-1) be suitable for down, and do not have commercial practicality.
Described in the Japanese kokai publication hei 2-255668 communique by add to copper-zinc class catalyzer catalyzer that basic metal makes in the presence of, make the method for butanediol dehydrogenation.According to present method, used the catalyzer that makes through reductive copper and basic metal by adding to zinc oxide carrier.Though obtained the productive rate of 93.6 moles of %～99.8 mole % by about 8 hours reaction, this method does not have commercial practicality, because reaction has only continued 8 hours.
N-Methyl pyrrolidone is a kind of colourless, nontoxic and have an organic solvent of low viscosity and excellent heat resistance.As a kind of chemically stable and high polar solvent, N-Methyl pyrrolidone is very useful in the various chemical reactions that need inert media.Along with the rules of environment aspect become severe day by day, environmental friendliness and nontoxic N-Methyl pyrrolidone polymkeric substance synthetic with processing, coating manufacturing, metallic surface cleaning, medicine is synthetic and purification, semi-conductor and Application for Field such as electron device processing or lithium cell manufacturing increase day by day.
Industrial, to use or do not using under the condition of catalyzer, the dehydrogenation by Monomethylamine (MMA) and gamma-butyrolactone prepares N-Methyl pyrrolidone.
As not using the Preparation of catalysts method, following method is disclosed, make gamma-butyrolactone and Monomethylamine in batch reactor, react 4 hours with preparation N-Methyl pyrrolidone (productive rate: 90%～93%) (J.Amer.Chem.Soc., 71 (1949), 896) by described method in 280 ℃.And Japanese kokai publication hei 1-190667 communique discloses and has made the reaction 3 hours and prepare the method (productive rate: 94.3%) of N-Methyl pyrrolidone under 240 ℃～265 ℃ and 50 normal atmosphere in the high pressure batch reactor of gamma-butyrolactone, water and Monomethylamine.
As using the Preparation of catalysts method, following method is disclosed, by described method in the presence of the y-type zeolite catalyzer of Copper Ion Exchange, make gamma-butyrolactone and Monomethylamine under 280 ℃ and normal pressure successive reaction with preparation N-Methyl pyrrolidone (productive rate: (Bull.Chem.Soc.Japan 98%), 50 (10) (1977), 2517).In addition, following method is disclosed, wherein the ZSM-5 type zeolite catalyst by using the chromium ion exchange prepares N-Methyl pyrrolidone (productive rate: 98.2%) (J.Org.Chem., 50 (1994), 3998) by gamma-butyrolactone and Monomethylamine through 300 ℃ successive reaction.In addition, Japanese Patent Publication 49-20582 communique discloses catalyzer such as a kind of use such as aluminum oxide, silica-alumina, gac, silica gel or silica-magnesia are prepared N-Methyl pyrrolidone by gamma-butyrolactone and Monomethylamine method (productive rate: 63%～93%).Recently, Akzo Noble is at United States Patent (USP) the 5th, 478, reported that the X type zeolite catalyst that uses the sodium ion exchange prepares N-Methyl pyrrolidone (productive rate: 96%) by 275 ℃ successive reaction in No. 950.Recently in Korea S, SK Corp. reported (korean patent application discloses 10-0404579 number) with such as the beta-zeolite catalyzer of cationic exchange such as copper or calcium in the presence of, under 235 ℃ low temperature, produce N-Methyl pyrrolidone with the ground of the high yield long-time continuous more than 96%.Isu Chemical Co. has reported that also (Korean Patent communique 10-2009-0010864 number) produce N-Methyl pyrrolidone with high yield in the presence of metal oxide catalyst under 280 ℃～300 ℃ temperature.
Yet because catalyst activity reduces, above-mentioned catalysis process need often carry out the regeneration of catalyzer and separating of product.As a result, be difficult to use catalyzer for a long time, and the method for catalyst-free is more effective economically.Therefore, need develop in the new reaction system that under mild conditions, can produce desired product under the situation of not using catalyzer with high yield long-term and stably.
Summary of the invention
Technical problem
One object of the present invention is to provide a kind of and passes through 1 in the presence of metal oxide catalyst, the successive reaction of 4-butyleneglycol (BDO) prepares the method for gamma-butyrolactone, described method has shown higher transformation efficiency and selectivity, has higher catalyst life and provide excellent cost benefit by the hydrogen that recovery/sale generates in reaction.Another object of the present invention is to provide the method that under amount that needs are purified and the minimized situation of wastewater flow rate, under mild conditions, prepares N-Methyl pyrrolidone (NMP) by following step on a large scale: make gamma-butyrolactone and Monomethylamine mutually reactive generate N-Methyl pyrrolidone and water to reactor supply Monomethylamine (MMA) aqueous solution and gamma-butyrolactone with high purity, high yield and expensive benefit; Utilize temperature of reaction to need not extra indirect heating and separate the N-Methyl pyrrolidone and the water of generation with pressure; Isolated water is mixed with Monomethylamine to form monomethylamine aqueous solution, and described monomethylamine aqueous solution imports reactor again.
Technical scheme
One total aspect, comprising with the method for high purity and high yield mass preparation N-Methyl pyrrolidone (NMP): make 1 in the presence of the metal oxide catalyst under atmosphere of hydrogen, 4-butyleneglycol (BDO) dehydrogenation is to provide gamma-butyrolactone (GBL); In reactor, supply with Monomethylamine (MMA) aqueous solution and gamma-butyrolactone, make gamma-butyrolactone and Monomethylamine mutually reactive generate N-Methyl pyrrolidone and water, separate N-Methyl pyrrolidone and the water that generates then, and isolated water mixed with Monomethylamine to form monomethylamine aqueous solution, described monomethylamine aqueous solution is imported reactor again.
In the presence of catalyzer of the present invention,, when the dehydrogenation of 4-butyleneglycol prepares gamma-butyrolactone, can prolong catalyst life, suppress the generation of by product and improve 1, the productive rate of the transformation efficiency of 4-butyleneglycol and selectivity and gamma-butyrolactone by 1.
The metal oxide catalyst that is used for preparing gamma-butyrolactone comprises at least a activeconstituents that is selected from the group of being made up of the oxide compound that contains the 11st family's metallic element.
In addition, in order further to improve the catalytic activity in the gamma-butyrolactone preparation, also can there be the additional promotor of standard range amount in the catalyzer.For example, catalyzer can also comprise following carrier and promotor, described carrier has at least a activeconstituents that is selected from the group of being made up of the oxide compound that contains the 13rd family, the 14th family's metallic element, and described promotor has at least a activeconstituents that is selected from the group of being made up of the oxide compound that contains the 1st family, the 2nd family, the 3rd family, the 4th family, the 6th family, the 7th family, the 12nd family's metallic element.
Preferably, the solid-phase catalyst that is used to prepare gamma-butyrolactone is represented with Chemical formula 1:
M
1 aM
2 bM
3 cO
xChemical formula 1
In Chemical formula 1, M
1For being selected from least a element in the 11st family's metallic element, M
2For being selected from least a element in the 13rd family and the 14th family's metallic element, M
3For being selected from least a element in the 1st family, the 2nd family, the 3rd family, the 4th family, the 6th family, the 7th family and the 12nd family's metallic element, the composition a of wherein said element: b: c is 1: 0～1.1: 0～4.6, and x is the stoichiometric number that depends on the valency and the composition of other element.
More specifically, M
1Be Cu, M
2For being selected from least a element among Al and the Si, M
3For being selected from least a element among Na, Mg, Ce, Cr, Mn and the Zn.
The hydrogen that generates in can the preparation benefit that raises the cost by recovery/sale gamma-butyrolactone.
Simultaneously, consider economy and efficient, the optimum reaction condition in the reaction of Monomethylamine and gamma-butyrolactone can be 260 ℃～320 ℃ the temperature and the pressure of 50 crust～120 crust, the pressure of preferred 270 ℃～310 ℃ temperature and 70 crust～110 crust.
In addition, can collect and the isolating water of N-Methyl pyrrolidone, to provide monomethylamine aqueous solution also and then provide it to reactor by being operated in 100 ℃～300 ℃ temperature and pressure one or more separators down of 0 crust～70 crust.When making isolated water enter reactor by the pipeline circulation, can with the temperature that prevents inside reactor any variation take place by the heater heats pipeline of pipeline outer setting, and thereby reduce the reaction times.
Monomethylamine unnecessary in the reactor can be mixed so that monomethylamine aqueous solution to be provided with isolated water, described monomethylamine aqueous solution is supplied to reactor again.
The monomethylamine aqueous solution that is used to prepare N-Methyl pyrrolidone can contain the Monomethylamine of 25 weight %～65 weight % and the water of 35 weight %～75 weight %, and Monomethylamine can have 81%～100% purity, and the Trimethylamine 99 (TMA) that contains 0%～19% dimethylamine (DMA) and 0%～19% is as impurity.
In the method for preparing N-Methyl pyrrolidone of the present invention, raw material Monomethylamine and gamma-butyrolactone can be by gamma-butyrolactones: the mol ratio of Monomethylamine is 1: 1.001～1.05 to provide, described mol ratio is preferably 1: 1.005～and 1.015.
The gamma-butyrolactone that is used to prepare N-Methyl pyrrolidone can be not purify or the gamma-butyrolactone through purifying, and can be by previous operation via 1, and the catalyzed reaction of 4-butyleneglycol makes.Do not purify or purity that the gamma-butyrolactone through purifying can have is 80.000%～99.999%, and can contain 0.001%～10.000% be selected from C3 alcohol, C4 alcohol, tetrahydrofuran (THF), C3 aldehyde, hydroxyl tetrahydrofuran and 1, one or more materials in the 4-butyleneglycol are as impurity.Particularly, do not purify or the gamma-butyrolactone through purifying can contain 1 of 0.001%～1.000% C3 alcohol, 0.001%～2.000% C4 alcohol, 0.001%～10.000% tetrahydrofuran (THF), 0.001%～5.000% C3 aldehyde, 0.001%～5.000% hydroxyl tetrahydrofuran and 0.001%～10.000%, the 4-butyleneglycol is as impurity.
Can use distiller that the reaction product N-Methyl pyrrolidone that reacts the back acquisition is purified, make then N-Methyl pyrrolidone by ion exchange resin so that high purity N-methyl-2-pyrrolidone to be provided, described high purity N-methyl-2-pyrrolidone contains the following metal of 1ppb, and does not contain the above particle of 0.2 μ m.
Beneficial effect
The method for preparing N-Methyl pyrrolidone (NMP) of the present invention comprises preparation gamma-butyrolactone (GBL) and preparation N-Methyl pyrrolidone.By 1, the method that the successive reaction of 4-butyleneglycol (BDO) prepares gamma-butyrolactone demonstrates higher transformation efficiency and selectivity in the presence of metal oxide catalyst, and provides excellent cost benefit by the hydrogen that generates in the recovery/sale reaction.In addition, the method for preparing N-Methyl pyrrolidone comprises: supply with Monomethylamine (MMA) aqueous solution and gamma-butyrolactone to reactor, make gamma-butyrolactone and Monomethylamine mutually reactive to generate N-Methyl pyrrolidone and water; Separate the N-Methyl pyrrolidone and the water that generate; And isolated water and Monomethylamine mixed to form monomethylamine aqueous solution, described monomethylamine aqueous solution is imported reactor again.Like this, the amount that will purify after can using gentle reaction conditions and making reaction minimizes, thereby makes the production efficiency maximization.And because collected and reclaimed the water that uses in the reaction, institute is so that the waste water generation minimizes, and this has just improved cost benefit and has prevented environmental pollution.Compare with the known method for preparing N-Methyl pyrrolidone, this is remarkable improvement.When isolated water enters reactor by the pipeline circulation, can with the temperature that prevents inside reactor any variation take place by the heater heats pipeline of pipeline outer setting, thereby reduce the reaction times.In addition, minimize with restriction working condition raw material by limiting the content of the impurity that comprises in raw material Monomethylamine and the gamma-butyrolactone, making.Compare with existing method, the method for preparing N-Methyl pyrrolidone of the present invention need not under the condition of complicated procedures of forming, can easily produce desirable product with high yield at short notice, and can simplify working process, and improves the productive rate in the industrial-scale production.
Description of drawings
Above and other objects of the present invention, feature and advantage will become apparent by the following explanation to the preferred implementation that provides in conjunction with the accompanying drawings, wherein:
Fig. 1 is for preparing the synoptic diagram (R: reactor, S: separator) of the method for N-Methyl pyrrolidone according to an embodiment; With
Fig. 2 is for preparing the synoptic diagram (R: reactor, S: separator, D: distiller) of the method for N-Methyl pyrrolidone according to another embodiment.
Description of reference numerals
F1: gamma-butyrolactone (GBL)
F2: Monomethylamine (MMA)
F3: mix the monomethylamine aqueous solution that makes with the water that F6 supplies with by the Monomethylamine that F2 is supplied with
The mixture of F4:N-methyl-2-pyrrolidone (NMP) and water
The F5:N-methyl-2-pyrrolidone
F6: by collecting the monomethylamine aqueous solution that isolated water prepares F3
F7: ion exchange resin
Embodiment
Hereinafter describe embodiments of the present invention with reference to the accompanying drawings in detail.
As shown in Figure 1, Monomethylamine (MMA) aqueous solution F3 and gamma-butyrolactone (GBL) F1 are supplied to reactor R, and under the pressure of 260 ℃～320 ℃ temperature and 50 crust～120 crust, react.The N-Methyl pyrrolidone of Sheng Chenging (NMP) F4 separates by separator S with water F4 thus.Collect isolated water F6 by the one or more separators under the pressure that are operated in 100 ℃～300 ℃ temperature and 0 crust～70 crust, and mix so that monomethylamine aqueous solution F3 to be provided with Monomethylamine F2, monomethylamine aqueous solution F3 circulates again and enters among the reactor R.
In another embodiment as shown in Figure 2, Monomethylamine (MMA) aqueous solution F3 and gamma-butyrolactone (GBL) F1 are supplied to reactor R, and under the pressure of 260 ℃～320 ℃ temperature and 50 crust～120 crust, react.The N-Methyl pyrrolidone F4 of Sheng Chenging separates by separator S with water F4 thus.Collect isolated water F6 by the one or more separators under the pressure that are operated in 100 ℃～300 ℃ temperature and 0 crust～70 crust, and mix so that monomethylamine aqueous solution F3 to be provided with Monomethylamine F2, monomethylamine aqueous solution F3 circulates again and enters among the reactor R.By distiller D to purifying by the isolated N-Methyl pyrrolidone F5 of separator S, and make its by ion exchange resin F7 the metal that contains below the 1ppb to be provided and not to contain particulate high purity N-methyl-2-pyrrolidone more than the 0.2 μ m.
Embodiment
Now embodiment and experimental example will be described.Embodiment hereinafter and experimental example are not intended to limit scope of the present invention only for descriptive purpose.
Embodiment 1
Cupric nitrate, zinc nitrate and aluminum nitrate are dissolved in the distilled water (500mL),, carry out vacuum-drying at 70 ℃ subsequently so that metal precursor solutions to be provided.Then, under air atmosphere, dried powder was fired 4 hours in 500 ℃.Here, so that each metal nitrate meets mode weighing and each metal nitrate of dissolving of the composition of the final metal oxide of firing the back acquisition.
As a result, obtained the catalyzer of oxide form, the gained catalyzer has following elementary composition: CuO 51 weight %, ZnO 31 weight % and Al
2O
318 weight %.
Be in 3/4 inch the fixed-bed reactor with catalyzer (5g) with the Powdered internal diameter made by SUS of packing into that generates.Then, at 4kg/cm
2Use hydrogen to reduce under the temperature of the pressure of G and 250 ℃ 4 hours.After the reduction reaction of catalyzer, be 240 ℃ in temperature of reaction, the weight hourly space velocity of butyleneglycol (WHSV) is 3.12h
-1, reaction pressure is 4kg/cm
2G and flow hydrogen gas speed are to begin reaction under the condition of 1162sccm.By being furnished with the gas chromatographic analysis reaction product of flame ionization detector.Show the result in table 1 and the table 2.
Be to supply with gamma-butyrolactone (GBL) F1 and Monomethylamine (MMA) aqueous solution F3 that generates to flow reactor R under 1.0 the condition in liquid hourly space velocity (LHSV), and under the pressure of 300 ℃ temperature and 100 crust, react.Separated from one another by N-Methyl pyrrolidone (NMP) F4 and water F4 that the separator S that is positioned at reactor R rear will generate thus.Collect isolated water F6 by being operated in 200 ℃ temperature and the one or more separators under 40 pressure that cling to, and mix with preparation monomethylamine aqueous solution F3, monomethylamine aqueous solution F3 is circulated again enter among the reactor R with Monomethylamine F2.To provide excessive Monomethylamine for 1.01 mol ratio with respect to gamma-butyrolactone.Table 1 has provided and concentration dependent transformation efficiency of reactant Monomethylamine and productive rate.
Embodiment 2
Preparing N-Methyl pyrrolidone with mode identical described in the embodiment 1, difference be so that final catalyzer have consist of CuO 53 weight %, ZnO 32 weight %, Al
2O
312.5 weight %, Ce
2O
32 weight % and Na
2The mode of O 0.5 weight % takes by weighing and uses each metal nitrate.
Embodiment 3
Preparing N-Methyl pyrrolidone with mode identical described in the embodiment 1, difference be so that final catalyzer have consist of CuO 76 weight %, SiO
219.5 weight %, MgO3 weight % and Cr
2O
31.5 the mode of weight % takes by weighing and uses each metal nitrate.
Embodiment 4
Preparing N-Methyl pyrrolidone with mode identical described in the embodiment 1, difference be so that final catalyzer have consist of CuO 42 weight %, ZnO 47 weight % and Al
2O
3The mode of 11 weight % takes by weighing and uses each metal nitrate.
Embodiment 5
Preparing N-Methyl pyrrolidone with mode identical described in the embodiment 1, difference be so that final catalyzer have consist of CuO 45 weight %, CrO 51 weight % and MnO
2The mode of 4 weight % takes by weighing and uses each metal nitrate.
Embodiment 6
Preparing N-Methyl pyrrolidone with mode identical described in the embodiment 1, difference be so that final catalyzer have consist of CuO 18 weight %, ZnO 35 weight % and Cr
2O
3The mode of 47 weight % takes by weighing and uses each metal nitrate.
Embodiment 7
Preparing N-Methyl pyrrolidone with mode identical described in the embodiment 1, difference be so that final catalyzer have consist of CuO 54 weight %, ZnO 33 weight % and Al
2O
3The mode of 13 weight % takes by weighing and uses each metal nitrate.
Table 1
Table 2
Embodiment 8
Preparing N-Methyl pyrrolidone with mode identical described in the embodiment 1, difference is that the concentration of the monomethylamine aqueous solution that uses fades to 99.9% by 10%.Table 3 shows the result.
Table 3
As can be seen from Table 3, when non-pneumatic provides with the aqueous solution, higher transformation efficiency and productive rate have been obtained at Monomethylamine.Particularly, the Monomethylamine concentration in the aqueous solution is 30.6% or 41.9% o'clock, and transformation efficiency is 99.9%, and productive rate is respectively 99.8% or 99.9%.
Embodiment 9
Prepare N-Methyl pyrrolidone under the reaction conditions identical with embodiment 1, difference is that the raw material Monomethylamine has different Monomethylamine content.Table 4 provided with monomethylamine aqueous solution in the relevant result of impurity that contains.
Table 4
aMMA: Monomethylamine,
bDMA: dimethylamine,
cTMA: Trimethylamine 99
As can be seen from Table 4, though the content of Monomethylamine only be the content of 80% o'clock and impurity dimethylamine and Trimethylamine 99 up to 30% o'clock, transformation efficiency is 99.9%, productive rate is more than 99.7%.
Embodiment 10
Use obtains under the reaction conditions identical with embodiment 1 does not purify or the gamma-butyrolactone through purifying prepares N-Methyl pyrrolidone.Table 5 has provided the result.
Table 5
In the table 5, experimental example 9 has used the gamma-butyrolactone through purifying, and experimental example 10 and experimental example 11 have used without any purification by 1, the preparation of 4-butyleneglycol and gamma-butyrolactone.Transformation efficiency and productive rate under all situations are 99.9%.
Embodiment 11
Use the preparation and the reaction product F5 that gets purifies down of the identical reaction conditions of D pair of distiller and embodiment 1, and make it pass through ion exchange resin F7.Table 6 has provided the result.
Table 6
In experimental example 12, N-Methyl pyrrolidone is not by ion exchange resin, and in experimental example 13, N-Methyl pyrrolidone has passed through ion exchange resin.Make metal and anion-content be reduced to the degree that is applicable to electron device by ion exchange resin.
The application contains the 10-2009-0114652 number relevant subject content of korean patent application that is committed to Korea S Department of Intellectual Property with on November 25th, 2009, and the full content of this application is incorporated herein with way of reference.
One of skill in the art will appreciate that can be easily with disclosed design in the aforementioned specification and the basis of embodiment with other embodiment that makes improvements or design the purpose that realizes that the present invention is identical.It will also be appreciated by those of skill in the art that such embodiment that is equal to does not break away from the spirit and scope of the invention of being set forth as in the appended claims.
Claims (15)
1. method for preparing N-Methyl pyrrolidone (NMP), described method comprises:
Make 1 in the presence of metal oxide catalyst under atmosphere of hydrogen, 4-butyleneglycol (BDO) dehydrogenation is to provide gamma-butyrolactone (GBL); With
In reactor, supply with Monomethylamine (MMA) aqueous solution and gamma-butyrolactone, make gamma-butyrolactone and Monomethylamine to react to each other and generate N-Methyl pyrrolidone and water, then the N-Methyl pyrrolidone that generates is mixed with Monomethylamine to form monomethylamine aqueous solution with water sepn and with isolated water, described monomethylamine aqueous solution is imported into described reactor again.
2. the method for preparing N-Methyl pyrrolidone as claimed in claim 1, wherein, the described metal oxide catalyst that is used for preparing gamma-butyrolactone comprises at least a activeconstituents that is selected from the group of being made up of the oxide compound that contains the 11st family's metallic element.
3. the method for preparing N-Methyl pyrrolidone as claimed in claim 2, wherein, the described metal oxide catalyst that is used to prepare gamma-butyrolactone also comprises carrier, and described carrier has at least a activeconstituents that is selected from the group of being made up of the oxide compound that contains the 13rd family, the 14th family's metallic element.
4. the method for preparing N-Methyl pyrrolidone as claimed in claim 2, wherein, the described metal oxide catalyst that is used to prepare gamma-butyrolactone also comprises promotor, and described promotor has at least a activeconstituents that is selected from the group of being made up of the oxide compound that contains the 1st family, the 2nd family, the 3rd family, the 4th family, the 6th family, the 7th family, the 12nd family's metallic element.
5. the method for preparing N-Methyl pyrrolidone as claimed in claim 1, wherein, the described metal oxide catalyst that is used to prepare gamma-butyrolactone is represented with Chemical formula 1:
M
1 aM
2 bM
3 cO
xChemical formula 1
In Chemical formula 1, M
1For being selected from least a element in the 11st family's metallic element, M
2For being selected from least a element in the 13rd family and the 14th family's metallic element, M
3For being selected from least a element in the 1st family, the 2nd family, the 3rd family, the 4th family, the 6th family, the 7th family and the 12nd family's metallic element, the composition a of wherein said element: b: c is 1: 0～1.1: 0～4.6, and x is the stoichiometric number that depends on the valency and the composition of other element.
6. the method for preparing N-Methyl pyrrolidone as claimed in claim 5, wherein, M
1Be Cu, M
2For being selected from least a element among Al and the Si, M
3For being selected from least a element among Na, Mg, Ce, Cr, Mn and the Zn.
7. the method for preparing N-Methyl pyrrolidone as claimed in claim 2 wherein, reclaims the hydrogen that generates in the preparation by gamma-butyrolactone.
8. the method for preparing N-Methyl pyrrolidone as claimed in claim 1, wherein, the temperature and pressure that is used to prepare the described inside reactor of N-Methyl pyrrolidone is respectively 260 ℃～320 ℃ and 50 crust～120 crust.
9. the method for preparing N-Methyl pyrrolidone as claimed in claim 1, wherein, by be operated in 100 ℃～300 ℃ temperature and 0 the crust～70 the crust pressure under one or more separators collect isolated water, so that described monomethylamine aqueous solution to be provided, described monomethylamine aqueous solution is supplied to described reactor again.
10. the method for preparing N-Methyl pyrrolidone as claimed in claim 1, wherein, described monomethylamine aqueous solution contains the Monomethylamine of 25 weight %～65 weight % and the water of 35 weight %～75 weight %.
11. the method for preparing N-Methyl pyrrolidone as claimed in claim 1, wherein, described Monomethylamine has 81%～100% purity, and the Trimethylamine 99 (TMA) that contains 0%～19% dimethylamine (DMA) and 0%～19% is as impurity.
12. the method for preparing N-Methyl pyrrolidone as claimed in claim 1, wherein, described Monomethylamine and described gamma-butyrolactone provide with 1.001～1.05 mol ratio.
13. the method for preparing N-Methyl pyrrolidone as claimed in claim 1, wherein, the described gamma-butyrolactone that is used to prepare N-Methyl pyrrolidone is not the purifying or the gamma-butyrolactone through purifying of catalyzed reaction that derives from the preparation gamma-butyrolactone.
14. the method for preparing N-Methyl pyrrolidone as claimed in claim 13, wherein, the purity that described not purification or the gamma-butyrolactone through purifying have is 80.000%～99.999%, and contain 0.001%～10.000% be selected from C3 alcohol, C4 alcohol, tetrahydrofuran (THF), C3 aldehyde, hydroxyl tetrahydrofuran and 1, one or more materials in the 4-butyleneglycol are as impurity.
15. the method for preparing N-Methyl pyrrolidone as claimed in claim 1, wherein, use distiller that isolated N-Methyl pyrrolidone is purified, and make described N-Methyl pyrrolidone by ion exchange resin so that high purity N-methyl-2-pyrrolidone to be provided, described high purity N-methyl-2-pyrrolidone contains the following metal of 1ppb, and does not contain the above particle of 0.2 μ m.
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| KR1020090114652A KR101103512B1 (en) | 2009-11-25 | 2009-11-25 | Process for preparing of n-methyl pyrrolidone from 1,4-butanediol |
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Cited By (8)
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| CN103204764A (en) * | 2012-01-17 | 2013-07-17 | 中国石油化学工业开发股份有限公司 | Heterogeneous catalyst and method for co-production of 1, 4-butanediol, gamma-butyrolactone and tetrahydrofuran |
| 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 |
| CN105085361A (en) * | 2015-09-08 | 2015-11-25 | 江苏恒祥化工有限责任公司 | System for synthesizing N-methyl-2-pyrrolidone |
| CN105175306A (en) * | 2015-08-13 | 2015-12-23 | 张铨望 | Synthetic method of N-methylpyrrolidone |
| CN105237456A (en) * | 2015-10-19 | 2016-01-13 | 北京石油化工学院 | Production method of pyrrolidone products |
| CN108026041A (en) * | 2015-07-31 | 2018-05-11 | 科学与工业研究委员会 | The improved method that n-methyl-2-pyrrolidone (NMP) is produced for selectivity |
| CN113563247A (en) * | 2021-08-11 | 2021-10-29 | 安徽晟捷新能源科技有限公司 | Method for preparing N-methyl pyrrolidone by using 1, 4-butanediol |
| CN115819311A (en) * | 2022-05-17 | 2023-03-21 | 重庆市中润化学有限公司 | GBL heavy component recycling method |
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| WO2021045153A1 (en) * | 2019-09-06 | 2021-03-11 | 昭和電工株式会社 | Method for producing gamma-butyrolactone and method for producing n-methylpyrrolidone |
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| CN103204764A (en) * | 2012-01-17 | 2013-07-17 | 中国石油化学工业开发股份有限公司 | Heterogeneous catalyst and method for co-production of 1, 4-butanediol, gamma-butyrolactone and tetrahydrofuran |
| CN103204764B (en) * | 2012-01-17 | 2015-09-02 | 中国石油化学工业开发股份有限公司 | Heterogeneous catalyst and method for co-production of 1, 4-butanediol, gamma-butyrolactone and tetrahydrofuran |
| 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 |
| 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 |
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| CN105175306A (en) * | 2015-08-13 | 2015-12-23 | 张铨望 | Synthetic method of N-methylpyrrolidone |
| CN105085361A (en) * | 2015-09-08 | 2015-11-25 | 江苏恒祥化工有限责任公司 | System for synthesizing N-methyl-2-pyrrolidone |
| CN105237456A (en) * | 2015-10-19 | 2016-01-13 | 北京石油化工学院 | Production method of pyrrolidone products |
| CN105237456B (en) * | 2015-10-19 | 2017-12-22 | 北京石油化工学院 | A kind of production method of pyrrolidinone compounds product |
| CN113563247A (en) * | 2021-08-11 | 2021-10-29 | 安徽晟捷新能源科技有限公司 | Method for preparing N-methyl pyrrolidone by using 1, 4-butanediol |
| CN113563247B (en) * | 2021-08-11 | 2022-03-25 | 安徽晟捷新能源科技股份有限公司 | Method for preparing N-methyl pyrrolidone by using 1, 4-butanediol |
| CN115819311A (en) * | 2022-05-17 | 2023-03-21 | 重庆市中润化学有限公司 | GBL heavy component recycling method |
| CN115819311B (en) * | 2022-05-17 | 2023-11-07 | 重庆中润新材料股份有限公司 | GBL heavy component recycling method |
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| KR101103512B1 (en) | 2012-01-09 |
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