KR101001332B1 - PROCESS FOR PREPARING OF ?-Butyrolactone - Google Patents

Abstract

The present invention relates to a process for producing gamma-butyrolactone (γ-Butyrolactone), and more specifically, gamma-butyrate by liquid-hydrogenation reaction of maleic acid dialkyl ester in a hydrogen atmosphere in the presence of a metal oxide solid phase catalyst. It relates to a method for producing the rock lactone.

The production process of gamma butyrolactone according to the present invention is a continuous production process using a metal oxide solid-phase catalyst, does not contain heavy metals such as chromium in the catalyst, there is no risk of environmental pollution, minimizing side reactions to gamma butyrolactone The selectivity of the catalyst is high, and the catalyst can be used for a long time by liquid phase reaction under mild reaction conditions such as low temperature, low pressure and low hydrogen molar ratio.

Gamma butyrolactone, metal oxide solid phase catalyst, continuous liquid phase reaction

Description

Production Method of Gamma Butyrolactone {PROCESS FOR PREPARING OF γ-Butyrolactone}

The present invention relates to a method for producing gamma butyrolactone, and more particularly, to a method for producing gamma butyrolactone, including a continuous production process using a solid catalyst containing a metal oxide as an active ingredient.

As gamma-butyrolactone is now becoming more environmentally regulated, it is an environmentally friendly product in the fields of polymer polymerization and processing solvents, paint manufacturing solvents, metal surface cleaners, pharmaceutical synthesis and refining solvents, semiconductor and electronic materials processing solvents, and lithium battery manufacturing solvents. It is an important intermediate used in the preparation of pyrrolidone derivatives such as N-methylpyrrolidone which is in increasing demand.

Gamma butyrolactone can be industrially classified into a method of dehydrogenating 1,4-butanediol, a method of hydrogenating maleic anhydride or succinic anhydride, a method of hydrogenating maleic acid dialkyl ester, and the like.

As a method for dehydrogenating 1,4-butanediol, a method of producing gamma butyrolactone in a yield of 95% by adding zinc or manganese to a copper / chromium catalyst is disclosed in Japanese Patent Application Laid-Open No. 4-17954. Was initiated.

Hydrogenation of maleic anhydride or succinic anhydride is a method for producing gammabutyrolactone from maleic anhydride using a CuO-Cr ₂ O ₃ catalyst, but the yield is low in US Patent No. 3,065,243. There is a problem in that a significant amount of succinic anhydride is generated and recycled. In addition, Korean Patent Publication No. 10-0326505 discloses gamma-buti by gas-hydrogenating maleic anhydride at 250-280 ° C. using a catalyst having a CuO—Cr ₂ O ₃ —SiO ₂ ratio of 78: 20: 2. A method for producing rockactone is disclosed. In addition, Korean Patent Publication No. 10-0532545 discloses a method for producing gamma-butyrolactone by vapor-hydrogenating maleic anhydride or succinic anhydride at 200-300 ° C. with a catalyst in which barium or manganese is added to copper / chromium. Started.

The manufacturing method of hydrogenating maleic acid dialkyl ester is disclosed in Korea Patent Publication No. 10-0582220, step 1 of hydrogenating a maleic acid dialkyl ester to a succinic acid dialkyl ester using a Pd / Al ₂ O ₃ catalyst, A two-step reaction using a hydrogenation reaction using CuO / ZnO or a CuO / CuCr ₂ O ₄ catalyst to produce gammabutyrolactone, and a three-step reaction using a silica-alumina type acid catalyst, which is a dehydrogenation catalyst to produce tetrahydrofuran. A method of preparing 53% gamma butyrolactone, 34% tetrahydrofuran, 7% 1,4-butanediol and 3% by-products has been disclosed.

However, the production method is a copper / chromium-based catalyst is mainly used for the risk of environmental pollution by heavy metals, the reaction temperature is higher than 250 ℃ mainly due to the large gas phase reaction, copper-based catalyst is low thermal stability, reactants There are various problems such as reduction of catalyst life due to reduction of the catalytic activity by tar generated during vaporization, multistage reaction and selectivity to gamma butyrolactone, and complexity of manufacturing process such as increase of separation and purification process.

The present invention increases the selectivity of gamma butyrolactone by using a metal oxide solid-phase catalyst that does not contain metals harmful to the environment such as chromium and is highly reactive, and the process can produce gamma butyrolactone in a simple one-step reaction. To provide a method.

The present invention provides a method for producing gamma butyrolactone comprising the step of liquid-hydrogenating maleic acid dialkyl ester in a hydrogen atmosphere in the presence of a metal oxide solid phase catalyst to produce gamma butyrolactone.

The present invention also provides a method for producing N-methylpyrrolidone comprising the step of reacting gammabutyrolactone prepared by the above method with monomethylamine in the presence of a metal oxide solid phase catalyst to produce N-methylpyrrolidone. To provide.

Hereinafter, the present invention will be described in more detail.

The inventors of the present invention continue to study the catalyst for producing gamma butyrolactone and the production process of gamma butyrolactone using the same, and as a catalyst, a solid metal oxide containing at least one active ingredient selected from Group 11 and Group 2 as a catalyst. When used, it shows excellent catalytic activity and is effective in producing gamma butyrolactone, and it is found that liquid phase reaction at low temperature, low pressure, and low hydrogen molar ratio is possible compared to the conventional gas phase reaction, and is easy to apply to continuous process. It was confirmed that the mass production of gamma butyrolactone, and completed the present invention based on this.

In particular, the present invention uses a catalyst that does not contain a metal harmful to the environment, such as chromium, there is no risk of environmental pollution, and the catalyst due to the low thermal stability and tar through the liquid phase reaction, which is a milder reaction condition than conventional gas phase reactions. Prolongs catalyst life by preventing activity reduction, minimizes side reactions with the use of highly reactive metal oxide solid phase catalysts, increases selectivity to gammabutyrolactone, simplifies the process through one-step reactions, It is a liquid at room temperature, so there are no process obstacles such as clogging during the reaction of maleic anhydride and succinic anhydride, and it is more convenient for commercialization. This method can provide a small amount of gamma butyrolactone.

The present invention uses a solid catalyst comprising at least one active ingredient selected from the group consisting of specific metal oxides in the process for producing gamma butyrolactone by hydrogenating maleic acid dialkyl esters. In addition, the present invention has a feature that can be produced gamma butyrolactone under mild reaction conditions than the conventional gas phase reaction because it is a liquid phase reaction.

Such a method for preparing gammabutyrolactone of the present invention includes a continuous one-step process using a metal oxide solid phase catalyst.

In the continuous process of the present invention, gamma-butyrolactone is prepared by liquid-hydrogenation of maleic acid dialkyl ester under mild conditions at low temperature, low pressure and low hydrogen molar ratio.

The solid phase catalyst used in the process includes at least one active ingredient selected from the group of oxides containing group 11 metal elements. Group 11 metal elements usable in the solid catalyst of the present invention include Cu, Ag, Au, and the like, and in view of improving reaction efficiency and selectivity to gamma butyrolactone, an oxide containing Cu is preferably used as an active ingredient.

In addition, in order to further improve the activity of the catalyst, the present invention may further include a promoter within a conventional content range. The promoter may be one or more selected from the group of oxides containing Group 2 metal elements. Group 2 metal elements that can be used as promoters in the present invention include Mg, Ca, and the like. It is preferable to use an oxide containing Ca as a promoter in minimizing side reactions and in terms of reaction efficiency.

The metal oxide solid phase catalyst may further include a carrier within a conventional content range in order to ensure structural stability. The type of the carrier is not particularly limited since it may be used in the art to which the present invention pertains. Preferably, the carrier may be one or more selected from the group of oxides containing metals of Groups 13 and 14.

In particular, in a preferred embodiment of the present invention, the copper-based oxide is contained in an active ingredient of 70 to 95% by weight, more preferably 80 to 90% by weight, calcium-based oxide as a promoter 1 to 20% by weight, more preferably Is 1 to 10% by weight, a solid metal catalyst containing 1 to 29% by weight, more preferably 3 to 15% by weight of silica may be used.

Since the metal oxide solid phase catalyst does not contain chromium that is harmful to the environment like the existing catalysts, there is no risk of environmental pollution by heavy metals during catalyst preparation and disposal, and the existing gas phase reaction vaporizes the reactants at a high temperature of 250 ° C. or higher. Since tar is generated to promote catalyst deactivation and copper catalyst has low thermal stability, catalyst life is shortened. A multi-step process for preventing catalyst reduction, prolonging catalyst life, minimizing side reactions by using highly reactive metal oxide solid-state catalysts, increasing selectivity to gamma butyrolactone, and hydrogenating existing maleic dialkyl esters; Compares the process with a one-step reaction Simplified, there are no process obstacles such as clogging during the reaction, because the reactants and products are liquid at room temperature and the reactants are solid in the conventional maleic anhydride and succinic anhydride processes. It has the advantage of low equipment investment for high pressure, complex reaction and purification process.

On the other hand, the production method of the metal oxide solid phase catalyst used in the continuous process according to the present invention is not particularly limited, and can be prepared by a person skilled in the art.

At this time, the molar ratio of maleic acid dialkyl ester: hydrogen in the process is added 1: 5 to 1: 100, preferably 1:10 to 1:50. That is, the molar ratio of maleic acid dialkyl ester: hydrogen is preferably 1: 5 or more in order to maintain the minimum hydrogen partial pressure and improve selectivity, and the maleic acid dialkyl ester: The molar ratio of hydrogen is preferably added at 1: 100 or less.

The maleic acid dialkyl ester and hydrogen, which are the reaction raw materials of the liquid-hydrogenation reaction step, are most preferably used purely without impurities, and even though those containing impurities do not affect the effects of the present invention, The purity is not particularly limited.

In particular, the maleic acid dialkyl ester may include at least one maleic acid monoalkyl ester or the like as a raw material, and the maleic acid dialkyl ester and maleic acid monoalkyl ester may be selected from the group consisting of succinic acid dialkyl ester and Since the reaction proceeds via the succinic acid monoalkyl ester, it is present in the reactor as succinic acid dialkyl ester and succinic acid monoalkyl ester, and the unreacted succinic acid dialkyl ester and succinic acid monoalkyl ester are recycled back to the liquid-hydrogenation reaction step. Maleic acid dialkyl esters may include recycled unreacted succinic acid dialkyl esters and succinic acid monoalkyl esters.

Further, the maleic acid dialkyl ester used in the reaction may be maleic acid dimethyl ester, maleic acid diethyl ester, maleic acid dipropyl ester, maleic acid diisopropyl ester, maleic acid dibutyl ester, maleic acid di, depending on the type of alkyl group. Isobutyl ester, maleic acid dipentyl ester, maleic acid dihexyl ester, maleic acid diisohexyl ester, maleic acid dioctyl ester, maleic acid diisooctyl ester, etc. are possible, The kind is not specifically limited.

In addition, maleic dialkyl esters were used which were prepared from maleic anhydride via a two step reaction via maleic monoalkyl ester.

For example, the molar ratio of maleic anhydride to alcohol is 1: 2 to 1:15, and the reaction is carried out in a batch reaction for 30 minutes to 3 hours at a reaction temperature of 50 to 120 ° C. It is preferable.

In addition, for the desired reaction conditions of maleic acid dialkyl ester for example, a catalyst using a strong acid cation exchange resin, and the fluid space velocity, indicating the retention time in the reactor of the reactant (Liquid Hourly Space Velocity, LHSV) from 0.1 to 1.5 hr ^{- 1} , the molar ratio of maleic acid monoalkyl ester: alcohol is 1: 2 to 1:15, the reaction temperature is 60 to 120 ℃, the reaction pressure is preferably carried out in a continuous process at 2 to 20 atm.

Taking the preferred reaction conditions of the present invention as an example, the fluid space velocity is preferably 0.05 to 5.0 hr ⁻¹ , more preferably 0.1 to 1.0 hr ⁻¹ . In other words, when the amount of reactant introduced into the reactor is small, it is difficult to achieve economic productivity, so the fluid space velocity is preferably 0.1 hr ^-1 or more, and the reaction rate is preferably 5.0 hr ^-1 or less in consideration of the maximum reaction efficiency. .

In addition, the flow of the reactant in the continuous process may use both a bottom-up and a top-down method, but is not particularly limited, but the channeling (Channeling) It is more preferable to use a bottom-up method that can prevent the phenomenon.

The liquid-hydrogenation reaction process is preferably carried out at a temperature of 150 to 250 ℃, more preferably carried out at 170 to 230 ℃. In other words, in order to supply the minimum reaction activation energy, the reaction temperature is preferably 150 ° C. or more. In consideration, it is preferable to carry out at a temperature of 250 ℃ or less.

In the liquid-hydrogenation reaction process, the reaction pressure is preferably maintained at atmospheric pressure to 15 atm. That is, it is preferable that it is above normal pressure in consideration of the minimum conversion rate, and it is preferable that it is 15 atmosphere or less in consideration of the economical efficiency of the reaction such as the cost for maintaining the high pressure, the effect of increasing the conversion rate, and the increase of side reactions.

In addition, in order to control the reaction heat of the liquid-hydrogenation reaction process, alcohol may be used as a solvent, and the weight ratio of maleic acid dialkyl ester: alcohol is preferably 1: 9 to 9: 1, and 3: 7 to 5: 5. More preferred.

The liquid-hydrogenation reaction process may further include an alcohol solvent to react the maleic acid dialkyl ester, and the alcohol used as the solvent in the present invention uses an alcohol having the same alkyl group as the alkyl group of the maleic acid dialkyl ester. It is preferable.

The present invention may be such that the selectivity of gamma butyrolactone is 80% or more, preferably 90% or more through a liquid-hydrogenation reaction which is a continuous process having the above configuration.

Each step of the present invention is carried out in a continuous manner, the continuous reaction steps may be combined with a typical step in the art to which the present invention belongs, but is not particularly limited thereto.

In addition, in the production method according to the present invention, the method for purifying the product obtained after the reaction is not particularly limited, and distillation or the like, which is a method commonly used in the art to which the present invention pertains, may be used.

On the other hand, the present invention can be prepared N-methylpyrrolidone using gamma butyrolactone prepared in the continuous process.

Taking the preferred reaction conditions of N-methylpyrrolidone as an example, the catalyst contains at least one active ingredient selected from the group of oxides containing metal elements of Groups 4, 6, 8, 11, 12, 13 and 14, Using a metal oxide solid-state catalyst further comprising a carrier having at least one active ingredient selected from the group of oxides containing metal elements of groups 13 and 14, the weight hourly space velocity (WHSV) is 0.1 to 5.0 hr ⁻¹ , the molar ratio of gammabutyrolactone: monomethylamine is 1: 0.5 to 1: 5, the reaction temperature is 150 to 400 ° C., and the reaction pressure is preferably performed in a continuous process at atmospheric pressure to 100 atm. .

The method for preparing gamma butyrolactone according to the present invention is a continuous one-step process using a highly reactive metal oxide solid-phase catalyst, there is no risk of environmental pollution by using a catalyst containing no metal harmful to the environment, such as chromium, Liquid phase reaction, which is a milder reaction condition than conventional gas phase reaction, prevents low thermal stability of catalyst and decrease of catalytic activity caused by tar, prolongs catalyst life and minimizes side reactions by using highly reactive metal oxide solid phase catalyst. Increases selectivity to rolactone, simplifies the process through one-step reaction, and handles and eliminates process disturbances such as clogging during the reaction of conventional maleic anhydride and succinic anhydride processes because the reactants and products are liquid at room temperature This is more convenient for commercialization due to its convenience, high temperature, high pressure, complex reaction and purification It is advantageous in that the investment in equipment for the process is low.

Hereinafter, preferred embodiments of the present invention will be described. However, the following examples are merely described for the purpose of more clearly expressing the present invention, but the content of the present invention is not limited thereto.

[Production example of maleic acid monoalkyl ester]

Example  One

The molar ratio of maleic anhydride and ethanol was mixed 1: 5, and 130.6 g was put into a round bottom flask (250 mL), and reacted for 1 hour with stirring at 60 ° C.

After the reaction was completed, the selectivity of maleic acid monoethyl ester was analyzed by gas chromatography. As a result, maleic acid monoethyl ester having a selectivity of 96.86% was obtained.

Example  2 to 9

As shown in Table 1, except for changing the reaction temperature and the molar ratio, maleic acid monoethyl ester was prepared in the same manner as in Example 1.

division Temperature (℃) Mole ratio Maleic acid monoethyl ester
Selectivity (%) Example 1 60 1: 5 97.35 Example 2 60 1: 7 96.86 Example 3 60 1:11 95.47 Example 4 70 1: 5 96.97 Example 5 70 1: 7 96.15 Example 6 70 1:11 94.22 Example 7 80 1: 5 96.31 Example 8 80 1: 7 95.38 Example 9 80 1:11 93.96

Note 1) molar ratio = maleic anhydride: ethanol

Example  10

The molar ratio of maleic anhydride and pentanol was mixed 1: 5, and 134.7 g was put into a round bottom flask (250 mL), and reacted for 1 hour with stirring at 80 ° C.

After the reaction, the selectivity of maleic acid monopentyl ester was analyzed by gas chromatography. As a result, maleic acid monopentyl ester having a selectivity of 95.38% was obtained.

Example  11

As shown in Table 2, except that the molar ratio was changed, maleic acid monopentyl ester was prepared in the same manner as in Example 10.

division Temperature (℃) Mole ratio Maleic acid monopentyl ester
Selectivity (%) Example 10 80 1: 5 95.38 Example 11 80 1: 7 94.92

* 1) molar ratio = maleic anhydride: pentanol

[Production example of maleic acid dialkyl ester]

Example  12

Fill a tubular reactor 2.54 cm in diameter and 25.4 cm in length with 140 cc of Amberlyst-15 (Rohm & Haas, strongly acidic cation exchange resin) and attach an electric heating tape to the outside of the reactor to raise the reaction temperature to 105 ° C. Maintained.

The maleic acid monoethyl ester prepared according to Example 1 was used, and the reactant maleic acid monoethyl ester: ethanol was mixed in a molar ratio of 1:10 to obtain a fluid space velocity (LHSV) = 0.5 hr ⁻¹ through a pressurized pump. The reactor was injected at the bottom of the reactor (bottom-up) at a rate of 10, and the reaction pressure was maintained at 10 atm.

After the reaction was completed, the selectivity of maleic acid diethyl ester was analyzed by gas chromatography. As a result, maleic acid diethyl ester having a selectivity of 98.69% was obtained.

Example  13 to 18

As shown in Table 3 below, maleic acid diethyl ester was prepared in the same manner as in Example 12 except that the fluid space velocity (LHSV), the reaction pressure, and the molar ratio were changed.

division Temperature (℃) LHSV (hr ^-1 ) Pressure (atmospheric pressure) Mole ratio DEM
Selectivity (%) Example 12 105 0.5 10 1:10 98.69 Example 13 105 0.5 10 1: 8 97.84 Example 14 105 0.5 10 1: 6 98.81 Example 15 105 0.5 4 1: 8 97.98 Example 16 105 0.3 15 1:10 97.97 Example 17 105 0.5 15 1:10 97.96 Example 18 105 0.7 15 1:10 97.62

Note 1) molar ratio = maleic acid monoethyl ester: ethanol

Note 2) DEM: Maleic acid diethyl ester

Example  19

A tubular reactor 2.54 cm in diameter and 15.24 cm in length was filled with 80 cc of SPC-180H (Samyang Corporation, strongly acidic cation exchange resin), and an electric heating tape was attached to the outside of the reactor to maintain the reaction temperature at 105 ° C.

The maleic acid monoethyl ester prepared according to Example 1 was used, and the reactant maleic acid monoethyl ester: ethanol was mixed in a molar ratio of 1: 6, and the fluid space velocity (LHSV) = 1.0 hr ^-1 through a pressure pump. The reactor was injected at the bottom of the reactor (bottom-up) at a rate of 10, and the reaction pressure was maintained at 10 atm.

After the reaction was completed, the selectivity of maleic acid diethyl ester was analyzed by gas chromatography. As a result, maleic acid diethyl ester having a selectivity of 98.17% was obtained.

Example  20

Fill a tubular reactor 1.9 cm in diameter and 25.4 cm in length with 45 cc of Amberlyst-15 (Rohm & Haas, strongly acidic cation exchange resin), and attach an electric heating tape to the outside of the reactor to raise the reaction temperature to 105 ° C. Maintained.

Use Example 10 The maleic acid mono-pentyl ester prepared in accordance with, and reaction of maleic acid mono-pentyl ester: butanol is about 1: a mixture of 6 molar ratio of = the fluid space velocity (LHSV) through the pressure pump 1.0 hr ^{- The} reactor was injected at the bottom of the reactor at a speed of ¹ , and the reaction pressure was maintained at 10 atm.

After the reaction was completed, the selectivity of maleic acid dipentyl ester was analyzed by gas chromatography. As a result, maleic acid dipentyl ester having a selectivity of 95.60% was obtained.

Example  21 to 22

As in Table 4, maleic acid dipentyl ester was prepared in the same manner as in Example 20 except that the fluid space velocity (LHSV) was changed.

division Temperature (℃) LHSV (hr ^-1 ) Pressure (atmospheric pressure) Mole ratio DPM
Selectivity (%) Example 20 105 1.0 10 1: 6 95.60 Example 21 105 0.75 10 1: 6 97.17 Example 22 105 0.5 10 1: 6 97.41

* 1) molar ratio = maleic acid monopentyl ester: pentanol

Note 2) DPM: Maleic Acid Dipentyl Maleate

[Production example of gamma butyrolactone]

Example  23

Fill a tubular reactor 2.54 cm in diameter and 15.24 cm in length with 80 cc of KL-2010T (Kata Leuna, CuO 89%, CaO 2%, SiO ₂ 9%), and attach an electrical heating tape to the outside of the reactor. To maintain the reaction temperature at 200 ° C.

The maleic acid diethyl ester prepared according to Example 12 was used, and the reactant maleic acid diethyl ester: ethanol was mixed at a weight ratio of 5: 5 to obtain a fluid space velocity (LHSV) = 0.4 hr ⁻¹ through a pressure pump. It was injected at the bottom of the reactor (bottom-up) at the speed of. At this time, the molar ratio of maleic acid diethyl ester and hydrogen was maintained at 1:30, and the reaction pressure was maintained at 3 atmospheres.

After the completion of the reaction, the selectivity of gamma butyrolactone was analyzed by gas chromatography. As a result, gamma butyrolactone having a selectivity of 95.32% was obtained.

Example  24 to 37

As shown in Table 5, except for changing the reaction temperature, the fluid space velocity (LHSV), the reaction pressure, the molar ratio, the weight ratio, gamma butyrolactone was prepared in the same manner as in Example 23 for about 500 hours.

division Temperature (℃) LHSV (hr ^-1 ) Pressure (atmospheric pressure) Mole ratio Weight ratio
(wt%) GBL
Selectivity (%) Example 23 200 0.4 3 1:30 5: 5 95.32 Example 24 200 0.3 3 1:30 5: 5 95.25 Example 25 200 0.25 3 1:30 5: 5 93.14 Example 26 200 0.4 5 1:30 5: 5 94.92 Example 27 200 0.3 5 1:30 5: 5 93.25 Example 28 200 0.15 5 1:30 5: 5 91.76 Example 29 200 0.3 8 1:30 5: 5 90.31 Example 30 200 0.35 3 1:30 3: 7 92.24 Example 31 190 0.3 5 1:30 5: 5 93.60 Example 32 210 0.3 3 1:30 5: 5 89.39 Example 33 210 0.4 5 1:30 5: 5 88.48 Example 34 220 0.4 5 1:30 5: 5 86.27 Example 35 220 0.3 3 1:30 5: 5 86.98 Example 36 220 0.5 3 1:10 5: 5 86.04 Example 37 220 0.4 3 1:15 5: 5 84.43

Note 1) molar ratio = maleic acid diethyl ester: hydrogen

Note 2) Weight ratio = maleic acid diethyl ester: ethanol

Note 3) GBL: gamma butyrolactone (γ-Butyrolactone)

Example  38

Fill a tubular reactor 2.54 cm in diameter and 15.24 cm in length with 80 cc of KL-2010T (Kata Leuna, CuO 89%, CaO 2%, SiO ₂ 9%), and attach an electrical heating tape to the outside of the reactor. The reaction temperature was maintained at 220 ° C.

The maleic acid diethyl ester (containing 6.63% maleic acid monoethyl ester) prepared according to Example 17 was used, and the maleic acid diethyl ester: ethanol was mixed at a weight ratio of 5: 5 to obtain a fluid space through a pressure pump. LHSV = 0.3 hr ⁻¹ at the bottom of the reactor (bottom-up) was injected. At this time, the molar ratio of maleic acid diethyl ester and hydrogen was maintained at 1:30, and the reaction pressure was maintained at 3 atmospheres.

After the completion of the reaction, the selectivity of gamma butyrolactone was analyzed by gas chromatography. As a result, gamma butyrolactone having a selectivity of 92.09% was obtained.

Example  39

Fill a tubular reactor 2.54 cm in diameter and 15.24 cm in length with 80 cc of KL-2010T (Kata Leuna, CuO 89%, CaO 2%, SiO ₂ 9%), and attach an electrical heating tape to the outside of the reactor. The reaction temperature was maintained at 220 ° C.

Use Example 20 The maleic acid dipentyl ester prepared in accordance with, and the reaction of maleic acid dipentyl ester pentanol is 4: 6, mixed in a weight ratio = liquid space velocity (LHSV) through the pressure pump 0.2 hr ^- Injected at the bottom of the reactor (bottom-up) at a speed of ¹ . At this time, the molar ratio of maleic acid dipentyl ester and hydrogen was maintained at 1:30, and the reaction pressure was maintained at 3 atmospheres.

After the completion of the reaction, the selectivity of gamma butyrolactone was analyzed by gas chromatography. As a result, gamma butyrolactone having 83.06% selectivity was obtained.

[Production example of N-methylpyrrolidone]

Example  40

A tubular reactor 2.54 cm in diameter and 15.24 cm in length was charged with 98 g of ZnO (Johnson Matty), and an electric heating tape was attached to the outside of the reactor to maintain the reaction temperature at 280 ° C.

Using gamma butyrolactone prepared according to Example 23, the reactant gamma butyrolactone and 40% by weight of a monomethylamine aqueous solution were maintained at a molar ratio of 1: 1.5 through a pressurized pump, respectively, and the mass space velocity (WHSV) = 0.2 hr ⁻¹ at the bottom of the reactor. At this time, the pressure was maintained at 50 atmospheres.

After completion of the reaction, the selectivity of N-methylpyrrolidone was analyzed by gas chromatography. As a result, N-methylpyrrolidone having a selectivity of 99.73% was obtained.

Example  41 to 52

As shown in Table 6, N-methylpyrrolidone was prepared in the same manner as in Example 40 except for changing the reaction temperature, reaction pressure, mass space velocity (WHSV), and molar ratio.

division Temperature (℃) Pressure (atmospheric pressure) WHSV (hr ^-1 ) Mole ratio NMP
Selectivity (%) Example 40 280 50 0.2 1: 1.5 99.73 Example 41 300 50 One 1: 1.5 99.44 Example 42 300 50 One 1: 2 97.95 Example 43 300 50 0.5 1: 1.5 99.43 Example 44 300 50 One 1: 3 98.80 Example 45 300 50 0.25 1: 1.5 99.55 Example 46 280 50 One 1: 1.5 97.60 Example 47 270 50 0.15 1: 1.5 99.26 Example 48 270 70 0.15 1: 1.5 99.37 Example 49 265 50 0.1 1: 1.5 99.66 Example 50 260 50 0.25 1: 1.5 99.52 Example 51 260 70 0.25 1: 1.5 99.33 Example 52 260 70 0.1 1: 1.5 99.48

* 1) molar ratio = gamma butyrolactone to monomethylamine

Note 2) NMP: N-Methyl Pyrrolidone

Note 3) GBL: gamma butyrolactone (γ-Butyrolactone)

Example  53

Fill a tubular reactor 2.54 cm in diameter and 15.24 cm in length with 65 g of KL-5717T (Kata Leuna, ZnO 40%, Al ₂ O ₃ 55%, CuO 4%), and an electric heating tape outside the reactor. Was attached to maintain the reaction temperature at 300 ℃.

Using gamma butyrolactone prepared according to Example 23, the reactant gamma butyrolactone and 40% by weight of monomethylamine aqueous solution were each maintained at a molar ratio of 1: 1.5 through a pressurized pump, and the mass space velocity (WHSV) = 1.0 hr ^-1 at the bottom of the reactor (bottom-up) was injected. At this time, the pressure was maintained at 50 atmospheres.

After completion of the reaction, the selectivity of N-methylpyrrolidone was analyzed by gas chromatography. As a result, N-methylpyrrolidone having a selectivity of 97.25% was obtained.

Example  54 to 58

As shown in Table 7, N-methylpyrrolidone was prepared in the same manner as in Example 53, except that the reaction temperature, reaction pressure, and mass space velocity (WHSV) were changed.

division Temperature (℃) Pressure (atmospheric pressure) WHSV (hr ^-1 ) Mole ratio NMP
Selectivity (%) Example 53 300 50 1.0 1: 1.5 97.25 Example 54 300 30 1.0 1: 1.5 97.27 Example 55 300 50 0.5 1: 1.5 97.37 Example 56 280 50 1.0 1: 1.5 98.95 Example 57 260 60 1.0 1: 1.5 98.60 Example 58 260 50 0.15 1: 1.5 97.53

* 1) molar ratio = gamma butyrolactone to monomethylamine

Note 2) NMP: N-Methyl Pyrrolidone

Note 3) GBL: gamma butyrolactone (γ-Butyrolactone)

Example  59

40.9 g of TS-A (Heesung-BASF, TiO ₂ 85%, SiO ₂ 5%, WO ₃ 10%) was charged into a tubular reactor 2.54 cm in diameter and 15.24 cm in length, and the electric heating tape outside the reactor ) And the reaction temperature was maintained at 280 ℃.

Using gamma butyrolactone prepared according to Example 23, the reactant gamma butyrolactone and 40% by weight of a monomethylamine aqueous solution were maintained at a molar ratio of 1: 1.5 through a pressurized pump, respectively, and the mass space velocity (WHSV) = 1.0 hr ^-1 at the bottom of the reactor (bottom-up) was injected. At this time, the pressure was maintained at 50 atmospheres.

After completion of the reaction, the selectivity of N-methylpyrrolidone was analyzed by gas chromatography. As a result, N-methylpyrrolidone having a selectivity of 99.45% was obtained.

Example  60 to 62

As shown in Table 8, N-methylpyrrolidone was prepared in the same manner as in Example 59 except for changing the reaction temperature, the reaction pressure, and the mass space velocity (WHSV).

division Temperature (℃) Pressure (atmospheric pressure) WHSV (hr ^-1 ) Mole ratio NMP
Selectivity (%) Example 59 280 50 1.0 1: 1.5 99.45 Example 60 280 30 1.0 1: 1.5 98.19 Example 61 280 50 0.5 1: 1.5 99.16 Example 62 260 30 1.0 1: 1.5 97.06

* 1) molar ratio = gamma butyrolactone to monomethylamine

Note 2) NMP: N-Methyl Pyrrolidone

Note 3) GBL: gamma butyrolactone (γ-Butyrolactone)

Example  63

Fill a tubular reactor 2.54 cm in diameter and 15.24 cm in length with 98 g of ceramic balls (SAMWHA, SiO ₂ 67.6%, Al ₂ O ₃ 28.2%, TiO ₂ 0.41%, Fe ₂ O ₃ 0.57%) An electrical heating tape was attached to maintain the reaction temperature at 280 ° C.

Using gamma butyrolactone prepared according to Example 23, the reactant gamma butyrolactone and 35 wt% monomethylamine aqueous solution were each maintained at a molar ratio of 1: 1.5 through a pressurized pump, and the mass space velocity (WHSV) = injected at the bottom of the reactor (bottom-up) at a rate of 0.15 hr ⁻¹ . At this time, the pressure was maintained at 50 atmospheres.

After completion of the reaction, the selectivity of N-methylpyrrolidone was analyzed by gas chromatography. As a result, N-methylpyrrolidone having a selectivity of 98.50% was obtained.

There was no problem in the progress of the reaction even when the content of the general 40% by weight of monomethylamine aqueous solution.

Gamma butyrolactone produced by the method of the present invention is economically capable of mass production, polymer polymerization and processing solvents, paint preparation solvents, metal surface cleaners, pharmaceutical synthesis and purification solvents, semiconductor and electronic materials processing solvents, lithium battery production It can be used as a raw material used in the manufacture of pyrrolidone derivatives such as N-methylpyrrolidone which is increasing in demand as an environment-friendly non-toxic product in the field of solvents and the like.

Claims (14)

A liquid-hydrogenation reaction of maleic acid dialkyl ester in a hydrogen atmosphere in the presence of a metal oxide solid phase catalyst to produce gammabutyrolactone, The solid catalyst comprises gamma-butyrolactone that comprises at least one active ingredient selected from the group of oxides containing metals of Group 11 and at least one active ingredient selected from the group of oxides containing metals of Group 2 Way. delete The method of claim 1, The solid catalyst is a method for producing gamma butyrolactone further comprises a carrier having at least one active ingredient selected from the group of oxides containing group 13 and 14 metal elements. delete The method of claim 1, The maleic acid dialkyl ester is reacted by mixing with at least one selected from the group consisting of succinic acid dialkyl ester, maleic acid monoalkyl ester, and succinic acid monoalkyl ester. The method of claim 1, Maleic acid dialkyl ester: hydrogen in the above process is a method for producing gamma butyrolactone is added in a molar ratio of 1: 5 to 1: 100. The method of claim 1, Method of producing a gamma butyrolactone of the liquid hourly space velocity (Liquid Hourly Space Velocity) in the process of 0.05 to 5.0 hr ^-1 . The method of claim 1, In the above process, the reaction temperature is 150 to 250 ℃ the production method of gamma butyrolactone. The method of claim 1, In the above process, the reaction pressure is a method for producing gamma butyrolactone at normal pressure to 15 atm. The method of claim 1, The process is a method for producing gamma butyrolactone to react the maleic acid dialkyl ester further comprising an alcohol solvent. The method of claim 10, Wherein said process adds maleic acid dialkyl ester: alcohol in the presence of an alcohol catalyst in a weight ratio of 1: 9 to 9: 1. A method for producing N-methylpyrrolidone, comprising the step of reacting gammabutyrolactone prepared by the method according to claim 1 with monomethylamine in the presence of a metal oxide solid phase catalyst to produce N-methylpyrrolidone. The method of claim 12, The metal oxide solid-phase catalyst contains at least one active ingredient selected from the group of oxides containing metal elements of Groups 4, 6, 8, 11, 12, 13, and 14, and contains metal elements of Groups 13 and 14. A method for producing N-methylpyrrolidone further comprising a carrier having at least one active ingredient selected from the group of oxides. The method of claim 12, In the above process, the weight hourly space velocity is 0.1 to 5.0 hr ⁻¹ , and the molar ratio of gamma butyrolactone to monomethylamine is 1: 0.5 to 1: 5, the reaction temperature is 150 to 400 ° C., and the reaction. The pressure is a method for producing N-methylpyrrolidone at normal pressure to 100 atm.