WO2021045153A1

WO2021045153A1 - Method for producing gamma-butyrolactone and method for producing n-methylpyrrolidone

Info

Publication number: WO2021045153A1
Application number: PCT/JP2020/033432
Authority: WO
Inventors: 勇輝奈村; 塚本　真也; 内田　博
Original assignee: 昭和電工株式会社
Priority date: 2019-09-06
Filing date: 2020-09-03
Publication date: 2021-03-11
Also published as: TW202124368A; JPWO2021045153A1; TWI776225B

Abstract

Provided is a method for producing gamma-butyrolactone, said method including a reaction step in which a raw material composed of one or both of 2-hydroxytetrahydrofuran and 4-hydroxybutyraldehyde and a catalyst containing copper and an oxide of at least one metal element selected from the group consisting of zinc, zirconium, and aluminum are brought into contact with each other at a reaction temperature higher than 200°C to generate gamma-butyrolactone.

Description

Method for producing gamma-butyrolactone and method for producing N-methylpyrrolidone

The present invention relates to a method for producing gamma-butyrolactone and a method for producing N-methylpyrrolidone.
The present application claims priority based on Japanese Patent Application No. 2019-162951 filed in Japan on September 6, 2019, the contents of which are incorporated herein by reference.

In recent years, the use of lithium-ion secondary batteries (LIB batteries) has been on the rise. Along with this, the demand for N-methylpyrrolidone (NMP) used as a binder solvent in LIB batteries is increasing. Therefore, it is desired to efficiently produce gamma-butyrolactone (GBL) used as a raw material for NMP at low cost.

Conventionally, as a method for producing gamma-butyrolactone, a method using a dehydrogenation reaction of 1,4-butanediol (1,4-BDO) has been widely used industrially. As a method for producing gamma-butyrolactone by a dehydrogenation reaction of 1,4-butanediol, there is a method described in Patent Document 1 or Patent Document 2.

In Patent Document 1, 1,4-butanediol (1,4-BDO) is brought into contact with a catalyst represented by Cu-ZnO-Al ₂ O _3- ZrO _{2 in the gas phase to cause a dehydrogenation reaction.} The manufacturing method is described.
Patent Document 2 describes that a catalyst containing a platinum and a bismuth compound is used in a method for producing γ-butyrolactone by oxidative dehydrogenation of 1,4-butanediol in the presence of molecular oxygen.

Further, as another method for producing gamma butyrolactone, there is a method of hydrogenating a dicarboxylic acid diester with hydrogen in a gas phase in the presence of a carrier catalyst supporting a copper metal and a silver metal.

Japanese Unexamined Patent Publication No. 2002-371075 Japanese Unexamined Patent Publication No. 5-286959

However, in the conventional method for producing gamma-butyrolactone, it has been required to improve the productivity. In particular, when gamma-butanediol is produced using the dehydrogenation reaction of 1,4-butanediol, the reactivity of 1,4-butanediol is low, so that a long-term reaction is required to sufficiently produce gamma-butanediol. I needed to let you. Therefore, the productivity was insufficient.

In addition, 1,4-butanediol used as a raw material for gamma-butyrolactone is generally obtained by a reaction for producing a mixture of 2-hydroxytetrahydrofuran (2HTHF) and 4-hydroxybutyraldehyde (4-HBA) from allyl alcohol. It is produced using two reactions, the reaction of reducing the resulting mixture. Therefore, when gamma-butyrolactone is produced using 1,4-butanediol as a raw material, there is a problem that it takes time and effort to produce the raw material.

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a method for producing gamma-butyrolactone having good productivity.
Another object of the present invention is to provide a method for producing N-methylpyrrolidone, which efficiently produces N-methylpyrrolidone using gamma-butyrolactone produced by using the method for producing gamma-butyrolactone of the present invention.

The present inventors have diligently studied to solve the above problems.
As a result, a raw material composed of 2-hydroxytetrahydrofuran and / or 4-hydroxybutyraldehyde and a specific catalyst are brought into contact with each other at a reaction temperature of more than 200 ° C. to produce gamma-butyrolactone, thereby efficiently producing gamma-butyrolactone. Found that it can be manufactured.
That is, the first aspect of the present invention is the following method for producing gamma-butyrolactone.

[1] A catalyst containing a raw material composed of one or both of 2-hydroxytetrahydrofuran and 4-hydroxybutyraldehyde, an oxide of at least one metal element selected from the group consisting of zinc, zirconium and aluminum, and copper. A method for producing gamma-butyrolactone, which comprises a reaction step of producing gamma-butyrolactone by contacting them at a reaction temperature of more than 200 ° C.

The method for producing gamma-butyrolactone according to the first aspect of the present invention can preferably include the following characteristics as described below. The following features may preferably be a combination of two or more.
[2] The method for producing gamma-butyrolactone according to [1], wherein in the reaction step, an aqueous solution containing 1 to 30% by mass of the raw material is vaporized and brought into contact with the catalyst.
[3] The method for producing gamma-butyrolactone according to [1] or [2], wherein in the reaction step, the raw material is vaporized and the catalyst is ^{brought into contact with the catalyst at a gas space velocity (GHSV) of 20000 to 300,000 hr-1.}

[4] The method for producing gamma-butyrolactone according to any one of [1] to [3], wherein in the reaction step, the raw material and the catalyst are brought into contact with each other at a reaction temperature of 400 ° C. or lower.
[5] The method for producing gamma-butyrolactone according to any one of [1] to [4], wherein the catalyst contains zinc, zirconium, and aluminum oxides, and metallic copper.
[6] The method for producing gamma-butyrolactone according to any one of [1] to [5], wherein the catalyst further contains an oxide of chromium.

[7] Before the reaction step,
Any of [1] to [6], which has a raw material producing step of producing the raw material by hydroformylating allyl alcohol using a mixed gas of carbon monoxide and hydrogen (H _2). The method for producing gamma butyrolactone according to the above.
[8] The method for producing a gamma butyrolactone according to [7], wherein in the raw material production step, the allyl alcohol is hydroformylated in the presence of a catalyst composed of an organophosphorus compound ligand and a rhodium complex.

[9] The method for producing gamma-butyrolactone according to [7] or [8], wherein the mixed gas has a molar ratio of hydrogen to carbon monoxide of 0.1 to 10.
[10] The method for producing gamma-butyrolactone according to any one of [7] to [9], wherein the hydroformylation reaction of allyl alcohol is carried out at a reaction pressure of 0.1 to 10 MPa.

[11] The method for producing gamma-butyrolactone according to any one of [7] to [10], wherein the hydroformylation reaction of allyl alcohol is carried out at a reaction temperature of 0 to 150 ° C.
[12] Of [1] to [11], the catalyst contains 0.01 to 0.2 mol of zinc, 0.01 to 1 mol of zirconium, and 0.05 to 3 mol of aluminum with respect to 1 mol of copper. The method for producing gamma butyrolactone according to any one.
[13] The catalyst contains 0.01 to 0.5 mol of zinc, 0.01 to 1 mol of zirconium, 0.05 to 3 mol of aluminum, and 0.01 to 0.3 mol of chromium with respect to 1 mol of copper. The method for producing gamma butyrolactone according to any one of [6] to [11], which comprises.

The second aspect of the present invention is the following method for producing N-methylpyrrolidone.
[14] A step of producing gamma-butyrolactone using the method for producing gamma-butyrolactone according to any one of [1] to [13], and
A method for producing N-methylpyrrolidone, which comprises a step of reacting the produced gamma-butyrolactone with monomethylamine.
A third aspect of the present invention is the following catalyst.
[15] A catalyst for producing gamma-butyrolactone, which comprises an oxide of at least one metal element selected from the group consisting of zinc, zirconium and aluminum, and copper.
The catalyst of the third aspect of the present invention can preferably include the following features, as described below. The following features may preferably be a combination of two or more.
[16] The catalyst according to [15], which is used in the production of producing gamma-butyrolactone from a raw material consisting of one or both of 2-hydroxytetrahydrofuran and 4-hydroxybutyraldehyde.
[17] The catalyst according to [15] or [16], wherein the catalyst contains zinc, zirconium and aluminum oxides, and metallic copper.
[18] The catalyst according to any one of [15] to [17], wherein the catalyst further contains an oxide of chromium.
[19] The catalyst of [15] to [18], wherein the catalyst contains 0.01 to 0.2 mol of zinc, 0.01 to 1 mol of zirconium, and 0.05 to 3 mol of aluminum with respect to 1 mol of copper. The catalyst according to any.
[20] The catalyst contains 0.01 to 0.5 mol of zinc, 0.01 to 1 mol of zirconium, 0.05 to 3 mol of aluminum, and 0.01 to 0.3 mol of chromium with respect to 1 mol of copper. The catalyst according to [18].

In the method for producing gamma-butyrolactone of the present invention, a raw material consisting of 2-hydroxytetrahydrofuran and / or 4-hydroxybutyraldehyde is used. This raw material can be easily produced using only one reaction of hydroformylating allyl alcohol, has good reactivity, and oxidizes at least one metal element selected from the group consisting of zinc, zirconium and aluminum. Gamma butyrolactone is rapidly produced by contacting a catalyst containing a substance and copper at a reaction temperature of more than 200 ° C. Therefore, the method for producing gamma-butyrolactone of the present invention is excellent in productivity.

Further, according to the method for producing N-methylpyrrolidone of the present invention, gamma-butyrolactone is produced using the method for producing gamma-butyrolactone of the present invention, so that N-methylpyrrolidone can be efficiently produced.

Hereinafter, preferred examples of the method for producing gamma-butyrolactone and the method for producing N-methylpyrrolidone of the present invention will be described in detail. The present invention is not limited to the embodiments shown below. Within the scope of the present invention, numbers, positions, types, quantities, ratios, combinations, numerical values, etc. can be omitted, changed, and / or added as necessary.

<Manufacturing method of gamma-butyrolactone>
The method for producing gamma-butyrolactone of the present embodiment is from 2-hydroxytetrahydrofuran (2HTHF) represented by the following formula (1) and / or 4-hydroxybutyraldehyde (4-HBA) represented by the following formula (2). It has a reaction step of producing gamma-butyrolactone (GBL) represented by the following formula (3) by contacting the raw material to be described below with a catalyst described later at a reaction temperature of more than 200 ° C.

2HTHF and 4-HBA are in equilibrium in solution. As a result of confirming the structure of the aqueous solution containing 2HTHH and 4-HBA using a nuclear magnetic resonance (NMR) device, it was confirmed that 2HTHF was present as a main component. Therefore, 2HTHF and / or 4-HBA may be referred to as "2HTHF and the like" below.
Since 4-HBA is an unstable compound, it is unlikely to be used as a raw material (starting material) when producing gamma-butyrolactone or the like.

As the 2HTHF or the like used as a raw material in the production method of the present embodiment, a commercially available product may be used, or a product produced by hydration reaction of 2,3-dihydrofuran may be used, as shown below. Those produced by performing a raw material production step may be used. The raw material such as 2HTHH can be easily produced by using only one reaction by performing the following raw material production step before the reaction step.
The ratio of 2HTHF to 4-HBA in 2HTHF and the like used as a raw material is not particularly limited. Due to the equilibrium relationship, 2HTHF may be the majority. When both 2HTHF and 4-HBA are contained, the ratio (molar ratio) of 2HTHF and 4-HBA in an organic solvent such as water or chloroform may be, for example, 2HTHF / 4-HBA = 1 to 50. , 2HTHF / 4-HBA = 1 to 30, and 2HTHF / 4-HBA = 1 to 10. The ratio may be 0.01 to 50, 0.1 to 20, 0.5 to 5, or the like.

(Raw material production process)
In the present embodiment, it is preferable to carry out the raw material production step before the reaction step. In the raw material production step, a raw material (2HTHH, etc.) is produced by hydroformylating allyl alcohol (AAL) using a mixed gas of _{carbon monoxide and hydrogen (H 2).} The hydroformylation reaction of allyl alcohol is preferably carried out in the presence of a catalyst.

In the raw material production step, for example, allyl alcohol and a catalyst and / or solvent used as needed are placed in a reaction vessel, and a mixed gas _{of carbon monoxide (CO) and hydrogen (H 2) is placed in the reaction vessel.} Can be used as a step of hydroformylating allyl alcohol (AAL).
In this case, as the reaction vessel, for example, a stainless steel pressure resistant reaction vessel can be used.

Further, as the mixed gas of carbon monoxide and hydrogen, it is preferable to use a gas in which the molar ratio of hydrogen to carbon monoxide is in the range of 0.1 to 10, and more preferably in the range of 0.5 to 5. Yes, more preferably in the range of 0.8-2. When the molar ratio of hydrogen to carbon monoxide is in the range of 0.1 to 10, the hydroformylation reaction is promoted, and 2HTHF and the like can be produced in a higher yield.

As the catalyst, it is preferable to use an organophosphorus compound ligand and a rhodium complex, and it is more preferable that the organophosphorus compound ligand is a bidentate diphosphine ligand. Examples of the bidentate diphosphine ligand include trans-4,5-bis (diphenylphosphinomethyl) -2,2-dimethyl-1,3-dioxolane (DIOP). By hydroformylating allyl alcohol in the presence of a catalyst composed of an organic phosphorus compound ligand and a rhodium complex, that is, a catalyst in which the rhodium complex is coordinated with the organic phosphorus compound ligand, 2HTHF and the like are obtained. Can be produced in high yield.
The amount of the catalyst added is not particularly limited, but is preferably 0.01 to 100 mmol, more preferably 0.1 to 50 mmol, still more preferably 1 to 5 mmol per liter of the reaction solution.

As the solvent, aromatic hydrocarbons, saturated hydrocarbons, ethers, esters and the like can be preferably used. As the solvent, it is particularly preferable to use an aromatic hydrocarbon, and specifically, toluene is preferably used.

The hydroformylation reaction of allyl alcohol is preferably carried out at an absolute pressure of 0.1 to 10 MPa, more preferably 0, in order to promote the hydroformylation reaction and produce 2HTHH and the like in a higher yield. It is .5 to 8 MPa, more preferably 1 to 4 MPa.

The hydroformylation reaction of allyl alcohol is preferably carried out at a reaction temperature of 0 to 150 ° C., more preferably 20 to 100 ° C. in order to promote the hydroformylation reaction and produce 2HTHH and the like in a higher yield. Yes, more preferably 40-80 ° C.
The reaction time of the hydroformylation reaction of allyl alcohol is preferably 0.5 to 10 hours, more preferably 1 to 7 hours, still more preferably 3 to 5 hours.

2HTHF and the like produced by the hydroformylation reaction of allyl alcohol are preferably used as a raw material in the reaction step after being extracted with water or purified by distillation.

(Reaction process)
Next, in the present embodiment, the raw material (2HTHF or the like) produced in the raw material production step and the catalyst are brought into contact with each other at a reaction temperature of more than 200 ° C. to carry out a dehydrogenation reaction of 2HTHF or the like, and gamma-butyrolactone (2HTHF or the like) GBL) is generated.
As the reaction device used in the reaction step, for example, a fixed bed type gas phase reaction device can be used.

"catalyst"
As the catalyst to be brought into contact with the raw material in the reaction step, a catalyst containing an oxide of at least one metal element selected from the group consisting of zinc, zirconium and aluminum and copper is used. Copper is essential, but one or two of zinc oxides, zirconium oxides, and aluminum oxides may not be contained in the catalyst. However, it is preferable to include all of the above oxides. Specific examples of the catalyst include a catalyst containing zinc oxide and metallic copper (CuZnOx); a catalyst containing zirconium oxide and metallic copper (CuZrOx); a catalyst containing aluminum oxide and metallic copper (CuAlOx); Zinc and aluminum oxides and catalysts containing metallic copper (CuZnAlOx); Zirconium and aluminum oxides and catalysts containing metallic copper (CuZrAlOx); Zinc and zirconium oxides and catalysts containing metallic copper (CuZnZrOx); examples thereof include oxides of zinc, zirconium and aluminum, and a catalyst containing metallic copper (CuZnZrAlOx). X in the above equation may be a number arbitrarily selected, but for example, x may be 0.01 to 18.5, 0.01 to 10.0, or 0. It may be 0.03 to 6.0, or 0.05 to 2.0. As the catalyst, since the reaction for producing gamma-butyrolactone can be further promoted, it is preferable to use a catalyst containing zinc, zirconium and aluminum oxides, and metallic copper. The catalyst may consist only of copper, at least one selected from the group consisting of zinc, zirconium and aluminum, and oxygen.

When the catalyst contains zinc, zirconium and aluminum oxides, and metallic copper, the reaction for producing gamma-butyrolactone can be further accelerated. The amount of the oxide or metallic copper can be arbitrarily selected. In order to further promote the reaction, the content of each metal in the catalyst is preferably 1 mol or less of zinc, 5 mol or less of zirconium, and 5 mol or less of aluminum with respect to 1 mol of copper. The lower limit of each of zinc, zirconium, and aluminum may be 0 mol. The content of each metal in the catalyst is more preferably 0.01 to 0.1 mol of zinc, 0.01 to 1 mol of zirconium, and 0.05 to 3 mol of aluminum with respect to 1 mol of copper. Preferably, zinc is 0.01 to 0.05 mol, zirconium is 0.05 to 0.2 mol, and aluminum is 0.1 to 1 mol with respect to 1 mol of copper.
The amount of zinc in the catalyst is preferably 1.0 mol or less, more preferably 0.005 to 0.3 mol, and 0.01 to 0.2 mol with respect to 1 mol of copper. Is even more preferable, 0.01 to 0.1 mol is more preferable, and 0.01 to 0.05 mol is particularly preferable.
The amount of zirconium in the catalyst is preferably 5.0 mol or less, more preferably 0.01 to 1 mol, and further preferably 0.05 to 0.4 mol with respect to 1 mol of copper. It is more preferably 0.05 to 0.3 mol, and particularly preferably 0.10 to 0.2 mol.
The amount of aluminum in the catalyst is preferably 5.0 mol or less, more preferably 0.01 to 3.0 mol, and 0.05 to 1.0 mol with respect to 1 mol of copper. Is even more preferable, 0.1 to 0.8 mol is more preferable, and 0.2 to 0.6 mol is particularly preferable.
However, the content of each metal in the catalyst can be arbitrarily selected and is not limited to the above range.

The catalyst in contact with the raw material may further contain other metal oxides in addition to the oxide and copper of at least one metal element selected from the group consisting of zinc, zirconium and aluminum. As the other metal oxide, a chromium oxide is preferable. When the catalyst used in the production method of the present invention contains a chromium oxide, specific examples of the catalyst include zinc and chromium oxides, and a catalyst containing metallic copper (CuZnCrOx); zirconium and chromium oxides, and Catalysts containing metallic copper (CuZrCrOx); oxides of aluminum and chromium, and catalysts containing metallic copper (CuAlCrOx); oxides of zinc, zirconium and chromium, and catalysts containing metallic copper (CuZnZrCrOx); zinc, aluminum And chrome oxides, and catalysts containing metallic copper (CuZnAlCrOx); zirconium, aluminum and chromium oxides, and catalysts containing metallic copper (CuZrAlCrOx); zinc, zirconium, aluminum, and chromium oxides, In addition, a catalyst containing metallic copper (CuZnZrAlCrOx) and the like can be mentioned. X in the above equation may be a number arbitrarily selected, but for example, x may be 0.025 to 13.5, 0.045 to 10.5, or 0. It may be .065 to 6.5, or 0.085 to 2.25. The catalyst preferably comprises only copper, at least one selected from the group consisting of zinc, zirconium, and aluminum, chromium, and oxygen.

When the catalyst contains oxides of zinc, zirconium and aluminum, and metallic copper, and also oxides of chromium, activation of the reaction can be expected by lowering the active barrier of the dehydrogenation reaction. Therefore, it is more preferable as a catalyst to be used. Since the reaction for producing gamma butyrolactone can be further promoted, the content of each metal in the catalyst is 1 mol or less of zinc, 2 mol or less of zirconium, 5 mol or less of aluminum, and 0.5 mol of chromium with respect to 1 mol of copper. The following is preferable. The content of each metal in the catalyst is 0.01 to 0.5 mol of zinc, 0.01 to 1 mol of zirconium, 0.05 to 3 mol of aluminum, and 0.01 to 0 mol of chromium with respect to 1 mol of copper. It is more preferably 3 mol, more preferably 0.05 to 0.2 mol of zinc, 0.05 to 0.3 mol of zirconium, 0.1 to 1 mol of aluminum and 0. It is 05 to 0.2 mol.
The amount of zinc in the catalyst is preferably 1.0 mol or less, more preferably 0.005 to 0.3 mol, and 0.01 to 0.2 mol with respect to 1 mol of copper. Is even more preferable, 0.01 to 0.1 mol is more preferable, and 0.01 to 0.05 mol is particularly preferable.
The amount of zirconium in the catalyst is preferably 5.0 mol or less, more preferably 0.01 to 1 mol, and further preferably 0.05 to 0.4 mol with respect to 1 mol of copper. It is more preferably 0.05 to 0.3 mol, and particularly preferably 0.10 to 0.2 mol.
The amount of aluminum in the catalyst is preferably 5.0 mol or less, more preferably 0.01 to 3.0 mol, and 0.05 to 1.0 mol with respect to 1 mol of copper. Is even more preferable, 0.1 to 0.8 mol is more preferable, and 0.2 to 0.6 mol is particularly preferable.
The amount of chromium in the catalyst is preferably 0.5 mol or less, more preferably 0.01 to 0.4 mol, and 0.03 to 0.3 mol with respect to 1 mol of copper. It is more preferably 0.05 to 0.2 mol, more preferably 0.07 to 0.15 mol.
However, the content of each metal in the catalyst can be arbitrarily selected and is not limited to the above range.
Selectivity by suppressing the production of 1,4-butanediol caused by reduction of 2HTHH and the side reaction that causes 1,4-butanediol and other impurities by containing an oxide of chromium in the catalyst. The effect of improvement can be expected.

[Catalyst manufacturing method]
The method for producing the catalyst is not particularly limited and may be arbitrarily selected. For example, a coprecipitation method, a hydrothermal method, a sol-gel method and the like can be used, and the coprecipitation method is particularly preferable. When the coprecipitation method is used, for example, the catalyst can be prepared by the following procedure.

First, a metal precursor of the type and amount corresponding to the composition of the target catalyst is dissolved in water to prepare an aqueous precursor solution. Examples of the metal include copper, zinc, zirconium, aluminum, chromium and the like. Next, the basic aqueous solution is added dropwise to the precursor aqueous solution while stirring the precursor aqueous solution to form a precipitate. Then, the precipitate is collected by filtration, washed with water, and dried. The dried precipitate is calcined to form an oxide, and then hydrogen reduction, specifically, hydrogen reduction of the obtained copper oxide is performed. Oxides of zinc, zirconium, aluminum, and chromium are difficult to reduce with hydrogen, so copper oxide is mainly reduced to metallic copper. A catalyst is obtained by the above steps.

As an example of the precursor of each metal used in the above-mentioned method for producing a catalyst, nitrate, acetate, carbonate, oxalate and the like can be used, and among them, nitrate is preferable. As the basic aqueous solution, an aqueous ammonia solution and / or an aqueous alkali hydroxide solution can be preferably used. Above all, it is preferable to use an alkaline hydroxide aqueous solution as the basic aqueous solution. Specific examples of the alkaline hydroxide aqueous solution include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and the like, and it is preferable to use sodium hydroxide.

In the above method for producing a catalyst, in the step of dropping a basic aqueous solution into a precursor aqueous solution to form a precipitate, the pH at the end of the dropping is preferably 5 to 10, and the pH is 6 to 8. Is more preferable. When the pH at the end of the dropping is within the above range, all the metals contained in the precursor aqueous solution can be made into a precipitate. In the step of forming a precipitate, the precipitate may be formed by dropping the precursor aqueous solution onto the basic aqueous solution while stirring the basic aqueous solution.

For filtration and washing with water in the above production method, general methods can be used.
The drying temperature for drying the precipitate is preferably 40 to 200 ° C, more preferably 60 to 100 ° C. The drying time is preferably 3 to 48 hours, more preferably 12 to 24 hours. The drying of the precipitate is preferably carried out by putting the precipitate in a container and setting the pressure in the container to 1 to 101.3 kPa, and more preferably to set the pressure in the container to 3 to 10 kPa.

The firing temperature when firing the dried precipitate in air is preferably 200 to 700 ° C, more preferably 300 to 600 ° C, and even more preferably 400 to 500 ° C. The firing time is preferably 1 to 10 hours, more preferably 2 to 7 hours, still more preferably 4 to 6 hours. The temperature at which the oxide obtained after calcination is hydrogen-reduced is preferably 100 to 500 ° C, more preferably 150 ° C to 450 ° C, still more preferably 200 to 400 ° C, and particularly preferably 250 to 300 ° C. The time for hydrogen reduction is preferably 0.5 to 5 hours, more preferably 0.5 to 3 hours, and even more preferably 1 to 3 hours. When performing hydrogen reduction, a mixed gas of hydrogen gas and nitrogen gas can be used as the hydrogen supply gas. The hydrogen gas content contained in the hydrogen supply gas is preferably 10 to 100 mol%, more preferably 50 to 100 mol%, still more preferably 90 to 100 mol%.

The composition of the metal component of the catalyst thus obtained can be calculated, for example, by the method shown below.
The mass of the precursor of each metal used as the raw material of the catalyst is measured. Inductively coupled plasma (ICP) measurement is also performed on the filtrate produced by filtration to determine the content of each metal contained in the filtrate. Then, the composition of the catalyst is calculated using the mass of the precursor of each metal used as a raw material and the content of each metal contained in the filtrate.

[Reaction process for producing gamma-butyrolactone]
In the reaction step, it is preferable to vaporize the aqueous solution of the raw material to bring the raw material into contact with the above catalyst. As the aqueous solution of the raw material, it is preferable to use an aqueous solution containing 1 to 30% by mass of the raw material, more preferably 5 to 25% by mass, and further preferably 10 to 20% by mass. By vaporizing an aqueous solution containing 1 to 30% by mass of the raw material and bringing the raw material into contact with the above-mentioned catalyst, the reaction for producing gamma-butyrolactone can be further promoted.
When an aqueous solution containing 30% by mass or more of the raw material is used as the aqueous solution of the raw material, it is preferable to adjust the liquid space velocity (LHSV) converted to the raw material. For example, when an aqueous solution containing 30 to 50% by mass of a raw material is used, the liquid space velocity (LHSV) converted to the raw material ^{is preferably 1.6 hr -1} or less in order to maintain the yield of gamma-butyrolactone. It is more preferably 0.4 hr ^{-1 or less.} The lower limit of the liquid space velocity (LHSV) can be selected as needed, and may be, for example, 0.1 hr ^-1 or more, but is not limited thereto.

In the reaction step, the raw material is vaporized, it is preferred to contact with a gas space velocity (GHSV) 20000 ~ 300000hr ^-1 the catalyst, more preferably from 30000 ~ 200000hr ^-1, more preferably 40000 ~ 100000hr ^- It is ^1. When GHSV is 20000 hr ^-1 or more, the decrease in the productivity of gamma-butyrolactone can be suppressed. When GHSV is 300,000 hr ^-1 or less, the reaction for producing gamma-butyrolactone proceeds sufficiently.

In the reaction step, the contact time (W / F) between the raw material and the catalyst can be arbitrarily selected, but is preferably 0.05 hr · g / mL or more, more preferably 0.1 hr · g / mL or more. More preferably, it is 0.4 hr · g / mL or more. When the W / F is 0.05 hr · g / mL or more, the reaction for producing gamma-butyrolactone proceeds sufficiently. The upper limit of the contact time (W / F) can be selected as needed, and may be, for example, 3.2 hr · g / mL or less, but is not limited thereto. W represents the weight of the catalyst, and F represents the raw material supply rate.

In the reaction step, the raw material and the catalyst are brought into contact with each other at a reaction temperature of over 200 ° C. to produce gamma-butyrolactone. In the present embodiment, since the reaction temperature is over 200 ° C., 2HTHF and the like in the reaction are present in the gas phase, the reaction for producing gamma-butyrolactone is promoted, and gamma-butyrolactone can be produced in a higher yield. The reaction temperature is preferably 400 ° C. or lower because the safety of the reaction produced by gamma-butyrolactone is further increased. The reaction temperature is more preferably 210 to 370 ° C, further preferably 230 to 360 ° C, and particularly preferably 260 to 350 ° C.

The gamma-butyrolactone obtained in the reaction step may be purified by a general method such as vacuum distillation. The gamma-butyrolactone obtained in the reaction step can be preferably used as a raw material for N-methylpyrrolidone.

In the method for producing gamma butyrolactone of the present embodiment, a raw material made of 2HTHH or the like and a catalyst containing an oxide of at least one metal element selected from the group consisting of zinc, zirconium and aluminum and copper are used at more than 200 ° C. It has a reaction step of producing gamma butyrolactone by contacting at the reaction temperature of. 2HTHF and the like have good reactivity, and gamma-butyrolactone is rapidly produced by contacting the catalyst at a reaction temperature of more than 200 ° C. Moreover, for 2HTHF and the like, before the reaction step, a raw material production step using only one reaction of hydroformylating allyl alcohol using a mixed gas of _{carbon monoxide and hydrogen (H 2) is performed.} Easy to manufacture. Therefore, the method for producing gamma-butyrolactone of the present embodiment is excellent in productivity.

<Manufacturing method of N-methylpyrrolidone>
The method for producing N-methylpyrrolidone (NMP) of the present embodiment includes a step of producing gamma-butyrolactone using the method for producing gamma-butyrolactone of the present embodiment and a step of reacting the produced gamma-butyrolactone with monomethylamine. including.
The step of reacting gamma-butyrolactone and monomethylamine can be, for example, a step of producing N-methylpyrrolidone by putting gamma-butyrolactone, monomethylamine and a solvent in a reaction vessel and causing a liquid phase reaction.

In this case, a stainless steel reaction vessel can be preferably used as the reaction vessel.
As the solvent, alcohols or water can be used, and water is preferable.
The molar ratio of monomethylamine to gamma-butyrolactone used as a raw material is preferably in the range of 1 to 10, more preferably in the range of 1 to 5, and even more preferably in the range of 1 to 1.5.

The reaction between gamma-butyrolactone and monomethylamine may be carried out in the air, in an inert gas atmosphere such as a nitrogen gas atmosphere or an argon atmosphere, and preferably in a nitrogen gas atmosphere.
The reaction between gamma-butyrolactone and monomethylamine is preferably carried out at a temperature of 100 to 400 ° C, more preferably 150 to 350 ° C, still more preferably 200 to 300 ° C. The reaction time is preferably 0.1 to 10 hours, more preferably 0.5 to 7 hours, still more preferably 1 to 5 hours.

N-methylpyrrolidone obtained in the step of reacting gamma-butyrolactone and monomethylamine may be purified by a general method such as vacuum distillation.

In the method for producing N-methylpyrrolidone of the present embodiment, gamma-butyrolactone is produced by using the method for producing gamma-butyrolactone of the present embodiment. Therefore, N-methylpyrrolidone can be efficiently produced.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to the following examples.

(1) Preparation of catalyst (a) CuZnZrAlOx catalyst (1)
Copper nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 5.03 g, zinc nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 0.622 g, aluminum nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as metal precursors in the beaker 3.56 g and 0.836 g of zinc nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were added and dissolved in 100 g of water to prepare an aqueous precursor solution. Next, while stirring the precursor aqueous solution, a 3N sodium hydroxide aqueous solution was added dropwise to the precursor aqueous solution until the pH reached 5, and a precipitate was obtained by the coprecipitation method. The precipitate was collected by filtration and washed with water. The water-washed precipitate was placed in a container and dried under reduced pressure at a pressure of 6.3 kPa in an air atmosphere at a temperature of 80 ° C.

The dried precipitate was placed in an electric furnace and calcined in air at 500 ° C. for 3 hours to obtain an oxide. 0.2 g of the obtained oxide was filled in a cylindrical reaction vessel (reaction vessel of a fixed-bed vapor phase reactor) having a diameter of 4.5 mm and a height of 10 mm. Before the reaction (3) below (production of GBL) is carried out, hydrogen gas at 300 ° C. is circulated in the reaction vessel filled with oxide at a flow rate of 30 mL / min for 1 hour to reduce copper oxide by hydrogen. went. Through the above steps, the catalyst layer of the prepared catalyst (a) was set in the reaction apparatus. The composition of the obtained catalyst was calculated by the above-mentioned method using the mass of the precursor of each metal used as a raw material and the content of each metal contained in the filtrate obtained after filtration. As a result, the composition of the catalyst was CuZnZrAlOx (molar ratio Cu: Zn: Zr: Al = 10: 0.2: 1.9: 5.5 (based on Zn = 1, Cu: Zn: Zr: Al = 46). It was 1: 8.6: 25)).

(B) CuZnZrAlOx catalyst (2)
The composition was CuZnZrAlOx (molar ratio Cu: Zn: Zr: Al = 10: 1) according to the same procedure as in (a) above, except that a 3N aqueous sodium hydroxide solution was added dropwise to the precursor aqueous solution until the pH reached 7. A catalyst (b) of 0: 1.5: 4.5) was prepared.

(C) CuZrAlOx catalyst The above (a) except that the ratio of the precursor of the metal was changed and the aqueous precursor solution was added dropwise to the pH of 7 while stirring the 3N aqueous sodium hydroxide solution in a beaker. ), A catalyst (c) having a composition of CuZrAlOx (molar ratio Cu: Zr: Al = 10: 1.5: 4.5) was prepared.

(D) CuZnAlOx catalyst A catalyst having a composition of CuZnAlOx (molar ratio Cu: Zn: Al = 10: 1.0: 4.5) according to the procedure of (c) above by changing the ratio of metal precursors. (D) was prepared.

(E) CuZnZrAlOx catalyst (3)
The composition is CuZnZrAlOx (molar ratio Cu: Zn: Zr: Al = 10: 1.0: 1.5: 2.5) according to the procedure (c) above by changing the ratio of the metal precursor. The catalyst (e) was prepared.

(F) CuZnZrAlOx catalyst (4)
The composition is CuZnZrAlOx (molar ratio Cu: Zn: Zr: Al = 15: 1.0: 1.5: 4.5) according to the procedure (c) above by changing the ratio of the metal precursor. The catalyst (f) was prepared.

(G) CuZnZrAlCrOx catalyst (1)
Copper nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 5.03 g, zinc nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) 0.622 g, aluminum nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) as metal precursors in the beaker 3.56 g, 0.836 g of zinc nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and 0.836 g of chromium nitrate (manufactured by Kanto Kagaku) were added and dissolved in 106 g of water to prepare an aqueous precursor solution. Next, 30 g of a 3N aqueous sodium hydroxide solution was placed in a beaker, and the precursor aqueous solution was added dropwise until the pH reached 7, while stirring to obtain a precipitate by the coprecipitation method. The precipitate was collected by filtration and washed with water. The water-washed precipitate was placed in a container and dried under reduced pressure at a pressure of 6.3 kPa in an air atmosphere at a temperature of 80 ° C.

The dried precipitate was placed in an electric furnace and calcined in air at 500 ° C. for 3 hours to obtain an oxide. 0.2 g of the obtained oxide was filled in a cylindrical reaction vessel (reaction vessel of a fixed-bed vapor phase reactor) having a diameter of 4.5 mm and a height of 10 mm. Before the reaction (3) below (production of GBL) is carried out, hydrogen gas at 300 ° C. is circulated in the reaction vessel filled with oxide at a flow rate of 30 mL / min for 1 hour to reduce copper oxide by hydrogen. went. Through the above steps, the catalyst layer of the prepared catalyst (g) was set in the reaction apparatus. The composition of the obtained catalyst was calculated by the above-mentioned method using the mass of the precursor of each metal used as a raw material and the content of each metal contained in the filtrate obtained after filtration. As a result, the composition of the catalyst was CuZnZrAlCrOx (molar ratio Cu: Zn: Zr: Al: Cr = 10: 1.0: 1.5: 4.5: 1.0).

(H) CuZnZrAlCrOx catalyst (2)
By changing the ratio of the metal precursor, the composition is CuZnZrAlCrOx (molar ratio Cu: Zn: Zr: Al: Cr = 10: 1.0: 1.5: 4.5: 4.5: according to the procedure of (g) above. The catalyst (h) which is 2.0) was prepared.

(2) Raw material production process (manufacturing of 2HTHF, etc.)
1.89 g of allyl alcohol (AAL) and 30 g of toluene as a solvent were placed in a reaction vessel of an autoclave having a capacity of 100 mL made of stainless steel, and RhH (CO) (PPh ₃ ) ₃ 0.0536 g as a catalyst was added. 0.116 g of trans-4,5-bis (diphenylphosphinomethyl) -2,2-dimethyl-1,3-dioxolane (DIOP), which is a counterdiphosphin ligand, was added. Then, the reaction vessel is filled with a mixed gas of carbon monoxide and hydrogen gas to a pressure of 2 MPa (partial pressure CO / H ₂ = 1), and the inside of the reaction vessel is stirred with a mechanical stirrer at a reaction temperature of 65 ° C. for 3 hours. I made it react while. The reaction solution obtained after the reaction was extracted with 30 g of water to obtain the desired 2HTHF or the like as an aqueous solution.

The obtained aqueous solution containing 2HTHH and the like was analyzed by liquid chromatography to determine the conversion rate of allyl alcohol (AAL) and the yield of 2HTHF and the like. As a result, the conversion rate of AAL was 100%, and the yield of 2HTHH and the like was 87.6%. The yield of 2HTHF and the like is based on the total number of moles of 2HTHF and 4-HBA.
From this, 2HTHF and the like can be easily produced with a high conversion rate and yield by using only one reaction of hydroformylating allyl alcohol using a mixed gas of carbon monoxide and hydrogen gas. It could be confirmed.

(3) Reaction step (Production of gamma-butyrolactone (GBL))
As a fixed-bed gas phase reactor, a reaction solution is provided with a vaporizer at the top of the reaction vessel, a carrier gas inlet and a raw material inlet at the top of the vaporizer, and a gas outlet at the bottom of the reaction vessel. The one provided with a collection container (cooling) was used.

(Examples 1 to 7, Comparative Example 1)
In Examples 1 to 7 and Comparative Example 1, the catalyst (a) was used. Using a fixed-bed gas phase reactor in which the catalyst layer obtained in (1) above is set in the reaction vessel, a vaporizer contains an aqueous solution containing 2HTHF and the like produced in (2) above at the concentrations shown in Table 1. From the upper part of the reaction vessel, the gas was supplied together with nitrogen gas as a carrier gas under the conditions shown in Table 1 and brought into contact with the catalyst (a) under the conditions shown in Table 1 to produce gamma butyrolactone. ..

(Comparative Example 2)
The catalyst (a) was also used in Comparative Example 2. An aqueous solution of 1,4-butanediol (1,4-BDO) having a concentration shown in Table 1 was used in a fixed-bed gas phase reactor in which the catalyst layer obtained in (1) above was set in the reaction vessel. Is vaporized by a vaporizer and supplied from the upper part of the reaction vessel together with nitrogen gas as a carrier gas under the conditions shown in Table 1 and brought into contact with the catalyst (a) under the conditions shown in Table 1 to obtain gamma butyrolactone. It was generated.

Concentration of 2HTHF and the like in an aqueous solution of raw materials, 2HTHF and the like used in Examples 1 to 7 and Comparative Examples 1 and 2 (in Comparative Example 2, the concentration of 1,4-BDO in an aqueous solution of 1,4-BDO). , Reaction temperature, 2THTH and other aqueous solutions (1,4-BDO aqueous solution in Comparative Example 2), nitrogen gas flow velocity, raw material equivalent liquid space velocity (LHSV), gas space velocity (GHSV). ) Is shown in Table 1.
Further, the gamma-butyrolactone obtained in Examples 1 to 7 and Comparative Examples 1 and 2 was analyzed by using liquid chromatography, and the conversion rate of the raw material (2HTHF, etc.) and the yield and selection of gamma-butyrolactone (GBL) were selected. I asked for the rate. The results are shown in Table 1.

As shown in Table 1, Examples 1 to 7 in which gamma-butyrolactone was produced by contacting 2HTHF or the like as a raw material with a catalyst (a) composed of CuZnZrAlOx at a reaction temperature of more than 200 ° C. It was confirmed that the rate, the yield and selectivity of gamma-butyrolactone (GBL) were high, and the productivity was good.
Further, in Example 1 and Example 2, the reaction concentration and the reaction temperature were the same, but the GHSV was different, but the raw material conversion rate and the yield of gamma-butyrolactone (GBL) were about the same. From this, it was shown that a good raw material conversion rate and a yield of gamma-butyrolactone (GBL) can be maintained even if the productivity is improved by carrying out the reaction at a high GHSV of ^{30,000 hr-1 or more.}

On the other hand, in Comparative Example 1 in which gamma-butyrolactone was produced by contacting a raw material such as 2HTHH and a catalyst (a) made of CuZnZrAlOx at a reaction temperature of 200 ° C., the reaction temperature was over 200 ° C. Compared with Examples 1 to 7, the raw material conversion rate, the yield and selectivity of gamma-butyrolactone (GBL) were lower.
Further, in Comparative Example 2 in which 1,4-butanediol (1,4-BDO) was used as the raw material and the catalyst (a) was used, the raw material conversion rate and gamma-butyrolactone (gamma-butyrolactone) were higher than those in Examples 1 to 7. The yield and selectivity of GBL) was low. This is because the reactivity of 1,4-butanediol is lower than that of 2HTHF and the like.

(Examples 8 to 14)
The reaction was carried out in the same manner as in Example 1 except that the catalysts and reaction conditions shown in Table 2 were used. The results are shown in Table 2.

From the comparison of the results of Examples 8 to 10 in which only the reaction temperature was different, it was confirmed that the raw material conversion rate, the yield of gamma-butyrolactone (GBL) and the selectivity were the highest in Example 9 in which the reaction temperature was 300 ° C. It was. Further, from the comparison of the results of Examples 9 and 11 to 14 in which the types of catalysts are different, the catalyst composition is CuZnZrAlOx (molar ratio Cu: Zn: Zr: Al = 10: 1.0: 1.5: 4.5). ), It was confirmed that the raw material conversion rate, the yield of gamma-butyrolactone (GBL), and the selectivity were the highest.

(Examples 15 to 19, Comparative Example 3)
The reaction was carried out in the same manner as in Example 1 except that the catalysts and reaction conditions shown in Table 3 were used. The results are shown in Table 3.
(Comparative Example 4)
The reaction was carried out in the same manner as in Comparative Example 2 except that the catalysts and reaction conditions shown in Table 3 were used. The results are shown in Table 3.

From the comparison of the results of Examples 15 and 16 or the comparison of the results of Examples 17 and 18, which differ only in the reaction temperature, when the reaction temperature is 300 ° C. as compared with the case where the reaction temperature is 270 ° C. It was confirmed that the raw material conversion rate, the yield and selectivity of gamma-butyrolactone (GBL) were improved. Further, from the comparison of the results of Examples 15 and 17 in which only the types of catalysts are different, or the comparison of the results of Examples 16 and 18, the catalyst composition is CuZnZrAlCrOx (molar ratio Cu: Zn: Zr: Al = 10: 1. It was confirmed that when the ratio was 0: 1.5: 4.5: 1.0), the raw material conversion rate, the yield of gamma-butyrolactone (GBL), and the selectivity were improved.
In Comparative Example 3 in which the reaction temperature was 200 ° C., the raw material conversion rate, the yield and selectivity of gamma-butyrolactone (GBL) were lower than those in Example 19 in which the reaction temperature was over 200 ° C. Further, in Comparative Example 4 in which 1,4-butanediol (1,4-BDO) was used as the raw material, the conversion rate of the raw material, the yield of gamma-butyrolactone (GBL) and the selectivity were low.

(Examples 20 to 23)
The reaction was carried out in the same manner as in Example 1 except that the catalysts and reaction conditions shown in Table 4 were used. In Examples 20 to 23, the amount (flow rate) of the aqueous solution such as 2HTHH and the flow rate of the nitrogen gas are changed, these ratios are fixed, and the contact time (W / F) between the raw material and the catalyst is changed. did. The results are shown in Table 4.
(Examples 24-26)
The reaction was carried out in the same manner as in Example 1 except that the catalysts and reaction conditions shown in Table 4 were used. In Examples 24 to 26, the concentration of 2HTHF and the like in an aqueous solution of 2HTHF and the like was set to 50% by mass, and the contact time (W / F) between the raw material and the catalyst was changed. The results are shown in Table 4.
In the preparation of the catalyst used in Examples 24 to 26, hydrogen gas at 200 ° C. was circulated at a flow rate of 30 mL / min for 1 hour to reduce copper oxide with hydrogen.

From the results of Examples 20 to 23, when the ratio of the liquid feed amount (flow rate) of an aqueous solution such as 2HTHF to the flow rate of nitrogen gas is fixed, the larger the contact time (W / F) between the raw material and the catalyst, the more. It was confirmed that the yield of gamma-butyrolactone (GBL) was improved. Further, from the results of Examples 24 to 26, even if the concentration of 2HTHF or the like is as high as 50% by mass, gamma-butyrolactone (GBL) can be obtained by increasing the contact time (W / F) between the raw material and the catalyst. ) Was confirmed to be improved.

(4) Production of N-Methylpyrrolidone (NMP) 12.92 g of gamma-butyrolactone (GBL) obtained in Example 4 and a 40% monomethylamine aqueous solution (Fujifilm sum) were placed in a stainless steel autoclave reaction vessel having a capacity of 100 mL. 12.89 g (manufactured by Kojun Yakuhin Co., Ltd.) and 51.66 g of water as a solvent were added. Then, in a nitrogen gas atmosphere, the reaction starting pressure was set to 101.3 kPa, and the reaction was carried out at 240 ° C. for 3 hours with stirring to generate N-methylpyrrolidone.

The obtained reaction solution containing N-methylpyrrolidone was analyzed by liquid chromatography to determine the conversion rate of gamma-butyrolactone (GBL) and the yield of N-methylpyrrolidone. As a result, the conversion rate of GBL was 98.4%, and the yield of NMP was 97.9%.
From this, it was confirmed that N-methylpyrrolidone can be efficiently produced by using the gamma-butyrolactone (GBL) obtained in Example 4.

The present invention provides a method for producing gamma-butyrolactone having good productivity.
The method for producing gamma-butyrolactone of the present invention has good productivity and is therefore suitable as an industrial method for producing gamma-butyrolactone.

Claims

A catalyst containing a raw material consisting of one or both of 2-hydroxytetrahydrofuran and 4-hydroxybutyraldehyde, an oxide of at least one metal element selected from the group consisting of zinc, zirconium and aluminum, and copper. A method for producing gamma-butyrolactone, which comprises a reaction step of producing gamma-butyrolactone by contacting the mixture at a reaction temperature exceeding ° C.
The method for producing gamma-butyrolactone according to claim 1, wherein in the reaction step, an aqueous solution containing 1 to 30% by mass of the raw material is vaporized and brought into contact with the catalyst.
The method for producing gamma-butyrolactone according to claim 1 or 2, wherein in the reaction step, the raw material is vaporized and brought into contact with the catalyst at a gas space velocity (GHSV) of 20000 to 300,000 hr- 1.
The method for producing gamma-butyrolactone according to any one of claims 1 to 3, wherein in the reaction step, the raw material and the catalyst are brought into contact with each other at a reaction temperature of 400 ° C. or lower.
The method for producing gamma butyrolactone according to any one of claims 1 to 4, wherein the catalyst contains zinc, zirconium, and aluminum oxides, and metallic copper.
The method for producing gamma-butyrolactone according to any one of claims 1 to 5, wherein the catalyst further contains an oxide of chromium.
Before the reaction step,
Any one of claims 1 to 6, which comprises a raw material producing step of producing the raw material by hydroformylating allyl alcohol using a mixed gas of carbon monoxide and hydrogen (H 2). The method for producing gamma butyrolactone according to the section.
The method for producing a gamma butyrolactone according to claim 7, wherein in the raw material production step, the allyl alcohol is hydroformylated in the presence of a catalyst composed of an organophosphorus compound ligand and a rhodium complex.
The method for producing gamma-butyrolactone according to claim 7 or 8, wherein the mixed gas has a molar ratio of hydrogen to carbon monoxide of 0.1 to 10.
The method for producing gamma-butyrolactone according to any one of claims 7 to 9, wherein the hydroformylation reaction of the allyl alcohol is carried out at a reaction pressure of 0.1 to 10 MPa.
The method for producing gamma-butyrolactone according to any one of claims 7 to 10, wherein the hydroformylation reaction of the allyl alcohol is carried out at a reaction temperature of 0 to 150 ° C.
Any one of claims 1 to 11, wherein the catalyst contains 0.01 to 0.2 mol of zinc, 0.01 to 1 mol of zirconium, and 0.05 to 3 mol of aluminum with respect to 1 mol of copper. The method for producing gamma butyrolactone according to the item.
Claimed that the catalyst comprises 0.01 to 0.5 mol of zinc, 0.01 to 1 mol of zirconium, 0.05 to 3 mol of aluminum and 0.01 to 0.3 mol of chromium with respect to 1 mol of copper. The method for producing gamma butyrolactone according to any one of items 6 to 11.
A step of producing gamma-butyrolactone using the method for producing gamma-butyrolactone according to any one of claims 1 to 13.
A method for producing N-methylpyrrolidone, which comprises a step of reacting the produced gamma-butyrolactone with monomethylamine.
A catalyst for producing gamma-butyrolactone containing an oxide of at least one metal element selected from the group consisting of zinc, zirconium and aluminum and copper.
The catalyst for producing gamma-butyrolactone according to claim 15, which is used for producing gamma-butyrolactone from a raw material composed of one or both of 2-hydroxytetrahydrofuran and 4-hydroxybutyraldehyde.
The catalyst for producing gamma butyrolactone according to claim 15 or 16, wherein the catalyst contains zinc, zirconium, and aluminum oxides, and metallic copper.
The catalyst for producing gamma-butyrolactone according to any one of claims 15 to 17, wherein the catalyst further contains an oxide of chromium.
The catalyst according to any one of claims 15 to 18, wherein the catalyst contains 0.01 to 0.2 mol of zinc, 0.01 to 1 mol of zirconium, and 0.05 to 3 mol of aluminum with respect to 1 mol of copper. The catalyst for producing gamma butyrolactone according to the above.
The catalyst comprises 0.01 to 0.5 mol of zinc, 0.01 to 1 mol of zirconium, 0.05 to 3 mol of aluminum and 0.01 to 0.3 mol of chromium with respect to 1 mol of copper. Item 18. The catalyst for producing gamma butyrolactone according to Item 18.