Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/86—Chromium
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
  • C07B61/00—Other general methods
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
  • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
  • C07D207/18—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member
  • C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D207/24—Oxygen or sulfur atoms
  • C07D207/26—2-Pyrrolidones
  • C07D207/263—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms
  • C07D207/267—2-Pyrrolidones with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to the ring nitrogen atom
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D307/32—Oxygen atoms
  • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/10—Energy storage using batteries

Definitions

• 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.
• LIB batteries lithium-ion secondary batteries
• NMP N-methylpyrrolidone
• GBL gamma-butyrolactone
• 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.
• a catalyst represented by Cu-ZnO-Al 2 O 3- ZrO 2 in the gas phase to cause a dehydrogenation reaction.
• Patent Document 2 describes that a catalyst containing a platinum and a bismuth compound is used in a method for producing ⁇ -butyrolactone by oxidative dehydrogenation of 1,4-butanediol in the presence of molecular oxygen.
• 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.
• 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.
• 2HTHF 2-hydroxytetrahydrofuran
• 4-HBA 4-hydroxybutyraldehyde
• 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.
• 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.
• [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.
• GHSV gas space velocity
• [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.
• 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 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.
• a third aspect of the present invention is the following catalyst.
• 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.
• 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.
• 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.
• gamma-butyrolactone is produced using the method for producing gamma-butyrolactone of the present invention, so that N-methylpyrrolidone can be efficiently produced.
• 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 2-hydroxytetrahydrofuran
• 4-HBA 4-hydroxybutyraldehyde
• 2HTHF and 4-HBA are in equilibrium in solution.
• 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.
• 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.
• the ratio may be 0.01 to 50, 0.1 to 20, 0.5 to 5, or the like.
• a raw material production step In the present embodiment, it is preferable to carry out the raw material production step before the reaction step.
• a raw material (2HTHH, etc.) is produced by hydroformylating allyl alcohol (AAL) using a mixed gas of carbon monoxide and hydrogen (H 2).
• AAL allyl alcohol
• H 2 a mixed gas of carbon monoxide and hydrogen
• the hydroformylation reaction of allyl alcohol is preferably carried out in the presence of a catalyst.
• 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.
• CO carbon monoxide
• H 2 hydrogen
• AAL hydroformylating allyl alcohol
• the reaction vessel for example, a stainless steel pressure resistant reaction vessel can be used as the reaction vessel.
• 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.
• 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.
• the organophosphorus compound ligand is a bidentate diphosphine ligand.
• the bidentate diphosphine ligand include trans-4,5-bis (diphenylphosphinomethyl) -2,2-dimethyl-1,3-dioxolane (DIOP).
• DIOP trans-4,5-bis (diphenylphosphinomethyl) -2,2-dimethyl-1,3-dioxolane
• aromatic hydrocarbons saturated hydrocarbons, ethers, esters and the like can be preferably used.
• aromatic hydrocarbon 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 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.
• a 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.
• 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.
• a catalyst containing zinc, zirconium and aluminum oxides, and metallic copper 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.
• the reaction for producing gamma-butyrolactone can be further accelerated.
• the amount of the oxide or metallic copper can be arbitrarily selected.
• 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.
• zinc is 0.01 to 0.05 mol
• zirconium is 0.05 to 0.2 mol
• 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.
• 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 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.
• a chromium oxide is preferable.
• 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 (CuZnAlCrOx); zirconium, aluminum and chromium oxides,
• 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.
• 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.
• 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.
• 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.
• 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.
• the method for producing the catalyst is not particularly limited and may be arbitrarily selected.
• a coprecipitation method, a hydrothermal method, a sol-gel method and the like can be used, and the coprecipitation method is particularly preferable.
• the catalyst can be prepared by the following procedure.
• 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.
• the metal include copper, zinc, zirconium, aluminum, chromium and the like.
• the basic aqueous solution is added dropwise to the precursor aqueous solution while stirring the precursor aqueous solution to form a precipitate.
• 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.
• nitrate, acetate, carbonate, oxalate and the like can be used, and among them, nitrate is preferable.
• the basic aqueous solution an aqueous ammonia solution and / or an aqueous alkali hydroxide solution can be preferably used.
• 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.
• the pH at the end of the dropping is preferably 5 to 10, and the pH is 6 to 8. Is more preferable.
• 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.
• the precipitate may be formed by dropping the precursor aqueous solution onto the basic aqueous solution while stirring the basic aqueous solution.
• 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.
• 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.
• ICP inductively coupled plasma
• 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.
• 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.
• 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.
• 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.
• GHSV gas space velocity
• the catalyst more preferably from 30000 ⁇ 200000hr -1, more preferably 40000 ⁇ 100000hr - It is 1.
• 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.
• 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
• F represents the raw material supply rate.
• 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.
• a reaction temperature of 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.
• 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.
• 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.
• 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.
• a stainless steel reaction vessel can be preferably used as the reaction vessel.
• 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.
• 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.
• 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.
• 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.
• 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.
• the catalyst layer of the prepared catalyst (a) was set in the reaction apparatus.
• 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.
• a catalyst (b) of 0: 1.5: 4.5) was prepared.
• the catalyst (e) was prepared.
• CuZnZrAlOx catalyst (4)
• the catalyst (f) was prepared.
• 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.
• 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.
• the catalyst layer of the prepared catalyst (g) was set in the reaction apparatus.
• 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.
• the catalyst (h) which is 2.0) was prepared.
• 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.
• AAL allyl alcohol
• 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.
• reaction step Production of gamma-butyrolactone (GBL)
• GBL gamma-butyrolactone
• 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.
• Example 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.
• Example 3 (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.
• Example 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.
• 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.
• Example 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.
• hydrogen gas at 200 ° C. was circulated at a flow rate of 30 mL / min for 1 hour to reduce copper oxide with hydrogen.
• NMP N-Methylpyrrolidone
• GBL gamma-butyrolactone
• Fujifilm sum 40% monomethylamine aqueous solution
• 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.
• the conversion rate of GBL was 98.4%
• 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.

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