JP6561506B2 - Method for producing gamma-butyrolactone - Google Patents

Description

  In the present invention, gamma-butyrolactone (hereinafter referred to as “succinic acid”) by hydrogenation reaction of any one or more compounds selected from succinic acid, succinic anhydride and succinic acid ester (hereinafter may be collectively referred to as “succinic acids”). GBL ”may be described). Specifically, the present invention relates to a method for producing a corresponding GBL by a hydrogenation reaction of succinic acids in which the concentration of the metal coordinating dicarboxylic acid in the reaction mixture during the hydrogenation reaction is controlled within a predetermined range.

  GBL is useful as a reaction intermediate for industrial solvents, cleaning agents, and polymer chemicals. GBL is also used as a raw material for N-methylpyrrolidone, which is useful as a solvent and an electrolytic solution in the production of electronic materials, or polyvinylpyrrolidone, which is widely used as a water-soluble polymer.

As a method for producing GBL, a method for obtaining GBL by hydrogenating succinic acid such as succinic anhydride in the presence of a ruthenium-based catalyst is known (for example, Patent Document 1).
As an industrial production method of the raw material succinic acid used in such a reaction, any one or more compounds selected from maleic acid, maleic anhydride and maleic acid esters produced from fossil fuels such as petroleum (hereinafter referred to as “ The method using hydrogenation (hereinafter referred to as “maleic acid”) (hereinafter, a method for producing succinic acid from such a fossil fuel as a raw material is abbreviated as “the fossilization method”) is generally used. May contain trace amounts of maleic acid.

  In addition, in view of the recent rise in the price of petroleum resources and consideration for the environment, the use of biomass has attracted attention as a raw material to replace petroleum resources, and a method for producing dicarboxylic acids and derivatives thereof by fermentation of saccharides contained therein ( Hereinafter, a method of producing succinic acids by fermentation using such biomass as a raw material is abbreviated as “bio-method”) (for example, Patent Document 2). In bio-methods, due to the nature of the reaction, a wide variety of products are often produced at the same time, so the resulting succinic acid contains fumaric acid, malic acid and other dicarboxylic acids that are different from the target product. (For example, Patent Document 3).

  In the GBL production process using succinic acid as a raw material, the reaction activity may decrease due to impurities in the raw material derived from the above production method, and the yield of the target product GBL becomes unstable. There is a point.

Japanese Patent Laid-Open No. 64-25771 JP 2010-1007007 A US Patent Application Publication No. 2012/0238722

  The present invention has been made to solve the above problems. That is, the subject of this invention is preventing the fall of a catalyst activity in the manufacturing method of GBL by hydrogenation of succinic acid, and preventing the fluctuation | variation (decrease) of the yield of GBL which is a product. By using the method of the present invention, an industrially advantageous process capable of stably obtaining GBL with a high yield is provided.

As a result of intensive studies to solve the above problems, the present inventors have found that dicarboxylic acids other than succinic acid in the raw material, particularly dicarboxylic acids having a metal-coordinating functional group (hereinafter referred to as “metal-coordinating dicarboxylic acid”). However, it has been found that it greatly affects the activity and stability of the hydrogenation catalyst, and thus greatly affects the yield of GBL.
That is, it has been found that by setting the concentration of the dicarboxylic acid having a metal-coordinating functional group in the reaction mixture in the hydrogenation reaction within a predetermined range, GBL can be obtained in a high yield, It was confirmed that the presence of the metal-coordinating dicarboxylic acid can prevent the deterioration of the metal catalyst as the hydrogenation catalyst while maintaining the GBL yield, and the present invention has been completed based on these findings. .

That is, the gist of the present invention resides in the following [1] to [7].
[1] In the method for producing gamma-butyrolactone by hydrogenating succinic acid, the concentration of the dicarboxylic acid having a metal-coordinating functional group in the reaction mixture during the hydrogenation reaction is 10 mass ppm or more and less than 10000 mass ppm. A process for producing gamma-butyrolactone.
[2] The method for producing gamma-butyrolactone according to the above 1, wherein the concentration of the dicarboxylic acid having a metal coordinating functional group in the reaction mixture during the hydrogenation reaction is 30 mass ppm or more and 5000 mass ppm or less.
[3] The gamma-butyrolactone according to 1 or 2 above, wherein the dicarboxylic acid having a metal-coordinating functional group in the reaction mixture during the hydrogenation reaction is at least one selected from the group consisting of fumaric acid and malic acid. Production method.
[4] The method for producing gamma-butyrolactone according to any one of the above items 1 to 3, wherein the catalyst used in the hydrogenation reaction contains ruthenium or copper.
[5] The method for producing gamma-butyrolactone according to any one of the above 1 to 4, wherein the catalyst used in the hydrogenation reaction is a ruthenium complex having a tertiary organophosphorus compound as a ligand.
[6] The succinic acid is succinic acid and / or succinic anhydride, the dicarboxylic acid having the metal coordinating functional group is fumaric acid and / or malic acid, and a catalyst used for the hydrogenation reaction is provided. 6. The method for producing gamma-butyrolactone according to any one of 1 to 5 above, which is a ruthenium complex having a tertiary organic phosphorus compound as a ligand.
[7] The above 1-6, wherein the succinic acid is produced by hydrogenating maleic anhydride obtained by a petrochemical method using a fossil fuel as a raw material, or produced by a fermentation method using a biomass raw material. A method for producing gamma-butyrolactone according to any one of the above.

  According to the present invention, when GBL is produced by hydrogenation of succinic acid, the concentration of the dicarboxylic acid having a metal coordinating functional group other than succinic acid in the reaction mixture is set within a predetermined range. Provided is an industrially advantageous process that enables stable operation over a period of time, can produce GBL with a high yield, and can prevent deterioration of a metal catalyst used as a hydrogenation catalyst.

Hereinafter, the present invention will be described in detail with respect to reaction raw materials, dicarboxylic acids having a metal coordinating functional group, hydrogenation reaction, and application to industrial processes.
1. Reaction raw materials (excluding dicarboxylic acids having metal-coordinating functional groups)
1-1. Raw Succinic Acids In the present invention, succinic acid and / or succinic acid derivatives (succinic acids) are used as raw materials for producing GBL. Here, as the raw material, individual compounds included in the succinic acid may be used alone, or a plurality of them may be used in any combination.

As the succinic acid used in the present invention, a method using the above-mentioned fossil fuel such as petroleum as a raw material (
A method produced by any method of a petrochemical method) or a method of producing a biomass resource through a fermentation process (bio method) can be used without particular limitation.
Among succinic acids, when a succinic acid ester is used as a raw material, a linear dialkyl ester having 1 to 4 carbon atoms is preferable, and dimethyl ester or diethyl ester is particularly preferable.
In addition, succinic acid salts (including acidic ester salts) such as ammonium salts, sodium salts, potassium salts, and calcium salts can also be used as raw materials, and among them, ammonium salts are preferable.

1-2. Petrochemical succinic acid The succinic acid production method by the petrochemical method includes, for example, petroleum fractionation by distillation and / or extraction, catalytic cracking (eg fluid catalytic cracking), thermal cracking or hydrocracking. A method using the obtained petroleum-derived hydrocarbon fraction as a raw material is often used. As an industrial succinic acid raw material, C4, C5 and C6 fractions are preferred. These succinic acid raw materials may be directly converted to succinic acid, or, for example, benzene or butane may be oxidized to produce maleic anhydride or maleic acid ester and then hydrogenated to produce succinic acid. .

1-3. Bio-method succinic acid In the bio-method succinic acid production method, examples of biomass resources that can be suitably used include wood, rice straw, rice husk, rice bran, old rice, corn, sugar cane, cassava, sago palm, okara, corn cob, There are plant-derived resources such as tapiocacass, bagasse, vegetable oil residue, rice cake, buckwheat, soybeans, fats and oils, waste paper, papermaking residues, animal-derived resources such as marine product residues, livestock excrement, mixed resources such as sewage sludge and food waste Among them, plant resources are preferable. Among plant resources, wood, rice straw, rice husk, old rice, corn, sugar cane, cassava, sago palm, straw, oil and fat, waste paper, and papermaking residue are preferable, and corn, sugar cane, cassava, and sago palm are particularly preferable.

  Examples of carbon sources derived from biomass resources as described above include hexoses such as glucose, mannose, galactose, fructose, sorbose and tagatose; pentoses such as arabinose, xylose, ribose, xylulose and ribulose; maltose, sucrose, lactose and trehalose Disaccharides and polysaccharides such as starch and cellulose; butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, palmitoleic acid, stearic acid, oleic acid, linoleic acid, linolenic acid, monoctinic acid, Fatty acids such as arachidic acid, eicosenoic acid, arachidonic acid, behenic acid, erucic acid, docosapentaenoic acid, docosahexaenoic acid, lignoceric acid, ceracolic acid; glycerin, mannitol, xylitol, ribitol, etc. Examples include fermentable sugars such as polyalcohols, among which hexoses such as glucose, mannose, galactose, fructose, sorbose, tagatose; pentoses such as arabinose, xylose, ribose, xylulose, ribulose; maltose, sucrose, lactose Disaccharides and polysaccharides such as trehalose, starch, and cellulose are preferable. Among these, glucose, maltose, fructose, sucrose, lactose, trehalose, and cellulose are preferable.

Succinic acids can be obtained from the above-mentioned various carbon sources by fermentation using microbial conversion using, for example, coryneform bacteria, Bacillus bacteria, Rhizobium bacteria, Mycobacterium bacteria, and the like. As such a microorganism, coryneform bacteria are preferable.
The reaction temperature, pressure, and other reaction conditions during microbial conversion by the fermentation method depend on the activity of microorganisms such as selected cells and molds, and may be appropriately selected according to the purpose.

2. Dicarboxylic acids having metal-coordinating functional groups (metal-coordinating dicarboxylic acids)
2-1. Types of dicarboxylic acids having metal-coordinating functional groups The succinic acid produced from the fossil fuel is present in the succinic acid as a reaction by-product, and can be removed in the succinic acid purification process. Missing dicarboxylic acids may be included. For example, in the process of producing succinic anhydride by hydrogenating maleic anhydride, unreacted maleic anhydride may be mixed in succinic anhydride.

On the other hand, bio-processed succinic acid produced from biomass resources is produced as a by-product of fermentation, or is produced as a compound before or after succinic acid in the metabolic pathway for producing succinic acid, α-ketoglutaric acid, fumaric acid, apple Dicarboxylic acids such as acids may be included without being removed in the succinic acid purification step.
Many of such dicarboxylic acid compounds behave as dicarboxylic acids having a metal coordinating functional group.

Specifically, the dicarboxylic acid having a metal coordinating functional group refers to a dicarboxylic acid represented by the general formula (1), and this is collectively referred to as “dicarboxylic acids having a metal coordinating functional group”.
_HOOC-R 1 -COOH formula (1)
In the formula, R ₁ is a linear or branched alkylene group having 1 to 17 carbon atoms, an alkenylene group, an alkynylene group, or a divalent aromatic group, preferably an alkenyl group.

Also, R ₁ may have a substituent R ₂ 1 or more, the alkenyl group as a substituent R _2, an alkynyl group, a chlorine, a halogen atom such as bromine, methoxy group, an ethoxy group, a propoxy group, a butoxy Functional groups containing oxygen such as alkoxy groups such as groups, hydroxyl groups, epoxy groups, carbonyl groups, carboxyl groups, aromatic ring-containing groups such as phenyl groups, (α- / β-) naphthyl groups, phenoxy groups, oxyphenyl groups, Functional groups containing phosphorus such as amide groups, amino groups, isocyanate groups, pyridyl groups, pyrrolidone groups, etc., phosphoric acid groups, phosphonic acid groups, phosphinic acid groups, phosphine groups, sulfuric acid groups, sulfonic acid groups, sulfines A functional group containing sulfur such as an acid group or a mercapto group, preferably an alkoxy group, a hydroxyl group, a carbonyl group, a carboxyl group, an amino group, or a sulfone group More preferred are a hydroxyl group, a carbonyl group, and a carboxyl group. These substituents R ₂ may each have one or more of a plurality of substituents on R ₁ , or a part or all of them may be anionized.

Incidentally, R ₁ is unsaturated carbon - is a group having a carbon bond includes the case in R ₂ is hydrogen or an alkyl group having 1 to 17 carbon atoms.
Specific examples of the aliphatic dicarboxylic acid represented by the general formula (1) include maleic acid, malic acid, fumaric acid, itaconic acid, epoxy succinic acid, oxaloacetic acid, aspartic acid, 3-hydroxyaspartic acid, tartaric acid, Mercaptosuccinic acid, tetrafluorosuccinic acid, 2-oxoglutaric acid, acetone dicarboxylic acid, glutamic acid, N-methylglutamic acid, isocitric acid-γ lactone, propanetricarboxylic acid, homophthalic acid, 3-butenetricarboxylic acid, pentanetricarboxylic acid, cyclohexanetricarboxylic acid Acid, cyclobutanetetracarboxylic acid, 2-aminoadipic acid, 1,2-phenylenediacetic acid, naphthalenedicarboxylic acid, galactaric acid, pyridinedicarboxylic acid, pyrazinedicarboxylic acid, aconitic acid, tricarballylic acid, phenylmalo Acid, benzylmalonic acid, phenylsuccinic acid, methylphthalic acid, hydroxyphthalic acid, fluorophthalic acid, phthalic acid, 2,3-naphthalenedicarboxylic acid, 1,2-naphthalenedicarboxylic acid, 4-methylphthalic acid, 3-methylphthalic acid, Trimellitic acid is exemplified, among which maleic acid, malic acid, fumaric acid, aspartic acid, epoxyacetic acid, tartaric acid, and phthalic acid are preferred, and malic acid and fumaric acid are particularly preferred.

In addition, the dicarboxylic acids having the metal-coordinating functional group described above are acid anhydrides in which the two carboxyl groups of the formula (1) are dehydration-cyclized, or at least one of the carboxyl groups forms an ester. It does not matter. ("Metal-coordinating dicarboxylic acids" above
Includes such things. )
These dicarboxylic acids having a metal-coordinating functional group may be used alone or in combination of two or more.

2-2. Effect on Reaction of Dicarboxylic Acids Having Metal Coordinating Functional Group The reason why GBL can be stably obtained at a high yield according to the present invention is not clear, but is estimated as follows.
Dicarboxylic acids having a metal coordinating functional group coordinate to a hydrogenation catalyst more strongly than succinic acids, and hydrogenation of succinic acids on the hydrogenation catalyst is suppressed.

At the same time, when a portion of the dicarboxylic acid having a metal-coordinating functional group is hydrogenolyzed under hydrogenation conditions to produce carbon monoxide, it is considered that this also coordinates with the catalyst more strongly than succinic acids.
If there are too many dicarboxylic acids having a metal-coordinating functional group, it is considered that many of the coordination sites of the hydrogenation catalyst are occupied by these, making it difficult to coordinate the succinic acid to the hydrogenation catalyst.

On the other hand, if the concentration of the dicarboxylic acid having a metal-coordinating functional group is excessively low, many of the coordination sites of the catalyst metal are emptied, the active sites are exposed, and the catalyst is liable to deteriorate. In order to reduce the concentration of dicarboxylic acids having a coordinated functional group, a purification step such as activated carbon treatment or hydrogenation treatment is required, which is not economically advantageous.
The suitable concentration of the dicarboxylic acids having a metal coordinating functional group in the present invention is considered to depend on the coordinating bond strength between the metal coordinating functional group and the catalytic metal of the coordinating dicarboxylic acid. For example, malic acid has a hydroxyl group having a strong bonding force with a metal as a metal-coordinating functional group, so that the GBL yield is reduced unless malic acid in the reaction mixture is less than 3000 ppm by mass. Further, since maleic acid is converted into maleic anhydride having a strong metal coordinating power in the reaction mixture, the concentration of maleic acid and / or maleic anhydride in the reaction mixture must be kept low as well. On the other hand, fumaric acid has only a carbon-carbon double bond having a weak bonding force with a metal as a metal coordinating functional group, and the upper limit of the fumaric acid concentration in the reaction mixture in which the GBL yield does not decrease is 10,000 masses. Less than about ppm.

2-3. Dicarboxylic Acid Concentration / Control Method The content of the metal coordinating dicarboxylic acids in the reaction mixture in the production method of the present invention is 10 mass ppm or more and less than 10,000 mass ppm. The concentration of the metal-coordinating dicarboxylic acids is preferably 30 ppm to less than 5000 ppm, more preferably 50 ppm to less than 3000 ppm, and particularly preferably 100 ppm to less than 1500 ppm.

By setting the metal coordinating dicarboxylic acid concentration in the reaction mixture within the above range, it is possible to produce GBL with high yield while suppressing deterioration of the hydrogenation catalyst. If this concentration is too high, the hydrogenation catalyst tends to deteriorate, and the yield of GBL may decrease. On the other hand, if the concentration is too low, the activity and stability of the hydrogenation catalyst may also be lowered.
Furthermore, the presence of a predetermined amount of the above-mentioned metal coordinating dicarboxylic acid can prevent deterioration of the metal catalyst that is a hydrogenation catalyst while maintaining the GBL yield, so that it is stable in the GBL production method using a metal catalyst. Continuous operation is possible. In addition, in the production method of the present invention, the smaller the amount of carbon monoxide produced, the more stable the catalyst is and the GBL can be produced stably.

The concentration of the metal coordinating dicarboxylic acid can be measured using an analytical method such as gas chromatography, gas chromatography mass spectrometer, or high performance liquid chromatography.
When the concentration of the metal coordinating dicarboxylic acids in the reaction mixture exceeds the above range, for example, taking the continuous process described later (4.) as an example,
i) A large amount of high boiling point components are discharged out of the system in the circulation process.
ii) thermally decomposing metal-coordinating dicarboxylic acids in the process,
iii) separating metal coordinating dicarboxylic acids in the circulating liquid by crystallization or extraction;
iv) using succinic acids containing lower concentrations of metal coordinating dicarboxylic acids as raw materials,
iv) dilute the reaction system by adding purified lactones or solvent,
Etc. can be used to return to the predetermined concentration range of the present application.

On the other hand, when the concentration falls below the concentration range defined in the present invention, the same as described above. For example, the continuous process described in
i) Reduce the amount of high boiling point components discharged outside the system in the circulation process.
ii) adding metal coordinating dicarboxylic acids to the reaction system,
iii) using succinic acid containing a higher concentration of metal coordinating dicarboxylic acid as a raw material,
iv) Concentrate the reaction system by distilling off the solvent,
Or the like.

3. 3. Reaction conditions for hydrogenation reaction 3-1. Catalyst As a hydrogenation catalyst that can be used for hydrogenation of succinic acid, a catalyst containing at least one metal selected from transition metals belonging to Groups 8 to 11 of the periodic table is preferable. Examples of the Group 8-11 transition metals include iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, and gold. Ruthenium, copper, and palladium are preferable in terms of catalytic activity. In particular, copper and ruthenium having high catalytic activity are preferable. The catalyst may be a solid catalyst or a complex catalyst, but a complex catalyst is preferred in order to obtain a higher quality GBL.

3-2. Solid catalyst As the solid catalyst, a compound containing the above metal may be used as it is, or the metal may be supported on a carrier.
When a carrier is used, the carrier is preferably carbon, alumina, silica, silica-alumina, silica-titania, titania, titania-alumina, barium sulfate, calcium carbonate, or strontium carbonate, or a combination thereof. The shape of the carrier is not particularly limited, such as powder, granule, pellet and the like. Use of a carrier is preferable because it is effective in that it can simultaneously adsorb and remove odor components, coloring components and organic impurities in the raw succinic acid. The amount of metal supported is usually 0.1 to 10% by weight of the support.

Such a supported catalyst uses at least one of copper oxide, palladium, platinum, iridium, rhodium, nickel, rhenium, and ruthenium as a metal component, and alumina, silica, carbon, titania as a carrier, and any metal component. What is necessary is just to select the thing combined with (1) in consideration of use conditions and strength.
Preferred supported catalysts include, for example, alumina supported copper oxide, silica supported copper oxide, carbon supported ruthenium, alumina supported ruthenium, carbon supported palladium, alumina supported palladium, titania supported palladium, carbon supported platinum, alumina supported platinum, carbon supported rhodium, And alumina-supported rhodium.

3-3. Complex catalyst A complex catalyst is formed from a catalytic metal and a ligand coordinated thereto.
Hereinafter, a complex catalyst using ruthenium as a metal component as a complex catalyst will be described as an example.
As a raw material for the metal component, both metal ruthenium and ruthenium compounds can be used.

As the ruthenium compound, oxide, hydroxide, inorganic acid salt, organic acid salt or complex compound can be used, for example, ruthenium dioxide, ruthenium tetroxide, ruthenium dihydroxide, ruthenium chloride, ruthenium bromide, iodide. Ruthenium, ruthenium nitrate, ruthenium acetate, etc. Ruthenium acid salts such as phonium, pentacarbonylruthenium, tris (acetylacetonato) ruthenium, cyclopentadienyldicarbonylruthenium, dibromotricarbonylruthenium, chromium Tris (triphenylphosphine) hydridoruthenium, tetra (triphenylphosphine) dihydridoruthenium, tetra (trimethylphosphine) dihydridolthenium, bis (tri-n-butylphosphine) tricarbonylruthenium, tetrahydridododecacarbonyltetraruthenium, dodecacarbonyl Examples include ruthenium complexes such as triruthenium. Among them, ruthenium chloride, tris (acetylacetonato) ruthenium, and ruthenium acetate, which are easily available in high purity, are preferably used.

  The ligand of the ruthenium complex catalyst used in the method of the present invention is preferably a phosphorus ligand. As the phosphorus ligand, those having an aryl group such as triphenylphosphine, diphenylmethylphosphine and dimethylphenylphosphine can be used, but trialkylphosphine, particularly trialkyl having a phosphorus atom bonded to a primary alkyl group. Phosphine or a decomposition product thereof is preferable. This alkyl group may have other substituents.

The carbon number of the alkyl group of such a trialkylphosphine is preferably about 1 to 12, and all three alkyl substituents need not be the same, all of which may be the same or different. One may be the same and one may be different.
Examples of phosphines that form ligands include tridecanylphosphine, trinonylphosphine, trioctylphosphine, triheptylphosphine, trihexylphosphine, tripentylphosphine, tributylphosphine, tripropylphosphine, triethylphosphine, trimethylphosphine, Dimethyloctylphosphine, dioctylmethylphosphine, dimethylheptylphosphine, diheptylmethylphosphine, dimethylhexylphosphine, dihexylmethylphosphine, dimethylcyclohexylphosphine, dicyclohexylmethylphosphine, dimethylpentylphosphine, dipentylmethylphosphine, dimethylbutylphosphine, dibutylmethylphosphine, tri Heptylphosphine, tricyclohexylphosphite , Trihexylphosphine, tripentylphosphine, tribenzylphosphine, 1,1,2,2-dimethylphosphinoethane, 1,1,2,2-dimethylphosphinopropane, 1,1,2,2-dimethylphosphino Butane, 1,1,2,2-dioctylphosphinoethane, 1,1,2,2-dioctylphosphinopropane, 1,1,2,2-dioctylphosphinobutane, 1,1,2,2-dihexyl Phosphinoethane, 1,1,2,2-dihexylphosphinopropane, 1,1,2,2-dihexylphosphinobutane, 1,1,2,2-dibutylphosphinoethane, 1,1,2,2 -Dibutylphosphinopropane, 1,1,2,2-dibutylphosphinobutane, 1,1-diphosphinane, 1,4-dimethyl-1,4-diphosphane, 3-dimethylphosphorinane, 1,4-dimethylphosphorinane, 8-methyl-8-phosphinobicyclooctane, 4-methyl-4-phosphatetracyclooctane, 1-methylphosphorane, 1-methylphosphonan Examples of the shape include monodentate ligands, bidentate ligands, and cyclic ligands.

As the phosphorus ligand, not only the above phosphine but also phosphite, phosphinate, phosphine oxide, aminophosphine, phosphinic acid and the like can be used.
These phosphorus ligands are used in an amount of 0. 1 mole per 1 mole of ruthenium metal. It is 1-1000 mol, Preferably it is the range of 1-100 mol.
In addition, the ruthenium complex catalyst for hydrogenation of succinic acid may be used in the reaction in the form of a cationic complex using a conjugate base of an acid having a pKa of less than 2, which may improve the activity and stabilize the catalyst. It is preferable in terms. Such a conjugate base of an acid having a pKa smaller than 2 may be any acid as long as it forms such a conjugate base during catalyst preparation or in the reaction system. Salt or the like is used.
Acids and salts thereof that can be used for such purposes include inorganic acids such as nitric acid, perchloric acid, borofluoric acid, hexafluorophosphoric acid, fluorosulfonic acid, trichloroacetic acid, dichloroacetic acid, trifluoroacetic acid, Bronsted acid such as organic acid such as dodecyl sulfonic acid, octadecyl sulfonic acid, trifluoromethane sulfonic acid, benzene sulfonic acid, paratoluene sulfonic acid, tetra (pentafluorophenyl) boronic acid, sulfonated styrene-divinylbenzene copolymer, or These include alkali metal salts, alkaline earth metal salts, ammonium salts, silver salts, and the like of these acids.

Moreover, you may add in the form of the acid derivative considered that the conjugate base of said acid produces | generates in a reaction system. For example, the same effect can be expected even if it is added to the reaction system in the form of acid halide, acid anhydride, ester, acid amide or the like.
The amount of these acids or salts thereof used is 1000 mol or less, preferably 100 mol or less, based on the ruthenium metal. 10 mol or less is particularly preferable.

3-4. Solvent The production of gamma-butyrolactone by the method of the present invention can be carried out using the reaction raw material and the reaction product mixture as a solvent, but various solvents can also be used as long as the purpose and progress of the reaction are not inhibited.
Examples of such solvents include ethers such as diethyl ether, anisole, tetrahydrofuran, ethylene glycol dimethyl ether, and dioxane; alcohols such as methanol, ethanol, n-butanol, benzyl alcohol, phenol, ethylene glycol, and diethylene glycol; formic acid, Carboxylic acids such as acetic acid, propionic acid and toluic acid; esters such as methyl acetate, butyl acetate and benzyl benzoate; aromatic hydrocarbons such as benzene, toluene, ethylbenzene and tetralin; n-hexane, n-octane and cyclohexane Aliphatic hydrocarbons such as dichloromethane, halogenated hydrocarbons such as dichloromethane, trichloroethane and chlorobenzene; nitro compounds such as nitromethane and nitrobenzene; N, N-dimethylformua De, N, N- dimethylacetamide, N- carboxylic acid amides such as methylpyrrolidone; hexamethylphosphoric triamide other amides; N,
Ureas such as N-dimethylimidazolidinone; sulfones such as dimethylsulfone; sulfoxides such as dimethylsulfoxide; lactones such as caprolactone; polyethers such as tetraglyme and triglyme; carbonates such as dimethyl carbonate and ethylene carbonate Etc., preferably ethers, polyethers, and lactones.

3-5. Reaction conditions The hydrogenation reaction carried out by the method of the present invention can be carried out either continuously or batchwise. The reaction temperature is usually 50 to 250 ° C, preferably 100 to 250 ° C, more preferably 150 to 220 ° C. The hydrogen partial pressure in the reaction system is not particularly limited, but is industrially usually 0.01 to 10 MPa · G (gauge pressure), preferably 0.03 to 5 MPa · G.

The target product GBL can be separated from the reaction product solution by ordinary separation means such as distillation and extraction.
The water content in the reaction system is preferably 0.01 to 5% by mass, more preferably 0.1 to 1% by mass. If there is too much moisture, the equilibrium between succinic acid and its anhydride shifts to the succinic acid side, so that the succinic anhydride concentration decreases and the GBL production rate tends to decrease. On the other hand, if the water content is too small, the concentration of succinic acid that is the counter anion of the ruthenium catalyst is lowered, and the cationicity of the catalyst is lowered, so that the hydrogenation reaction activity of the catalyst tends to be lowered.
As a method for removing water from the reaction system, a gas stripping method or the like can be used. Depending on the reaction process, water may be distilled off by distillation or a dehydrating agent may be added. When hydrogen is used as the gas for gas stripping, it is efficient because the succinic acid can be converted to GBL simultaneously with the removal of water in the reaction solution.

4). Example of industrial process to which the method of the present invention is applied The present invention can be suitably applied to a continuous reaction process comprising a hydrogenation step, a purification step, and a circulation step. In this case, in order to stably maintain the preferred range defined by the method of the present invention, a part of the circulating liquid containing the metal coordinating dicarboxylic acids is discharged out of the system and at least a part thereof is circulated to the reaction system. Thus, the concentration of the metal coordinating dicarboxylic acids in the reaction mixture can be controlled.

GBL obtained by the reaction method of the present invention can be purified GBL with high purity by a general purification method such as extraction, distillation, crystallization and the like after completion of the reaction.
In the method of the present invention, it is preferable to circulate the residual liquid (hereinafter sometimes referred to as “catalyst liquid”) containing the hydrogenation catalyst after separation of the product GBL to the reaction process by the above-described circulation process.

As the components to be circulated, in addition to the active components such as the catalyst and the unreacted succinic acid medium, a solvent and other components may be included as long as they do not adversely affect the reaction process, but components having a higher boiling point than the target product. Is preferably circulated.
For example, when at least a part of the high-boiling component containing the catalyst separated from the GBL in the distillation column after the hydrogenation reaction step is circulated to the reaction step, the metal coordinating dicarboxylic acids contained in the reaction raw material are also It circulates with the catalyst as a high boiling point component and accumulates in the process. For this reason, in order to make the concentration of the metal coordinating dicarboxylic acids in the reaction mixture within the concentration range defined in the present invention, usually, a part of the high-boiling components containing the metal coordinating dicarboxylic acids are excluded from the system. It is necessary to discharge (purge).

  There is no particular limitation on the method for purging such a high-boiling component to the outside of the system. For example, a method of purging a part of the catalyst liquid in which the high-boiling component is accumulated as a high-boiling-component-containing liquid in the purification process. Can be illustrated.

EXAMPLES Hereinafter, although this invention is demonstrated further in detail using an Example, this invention is not limited by a following example, unless the summary is exceeded.
1. Raw material Succinic acid: Special grade reagent (Wako Pure Chemical Industries, Ltd.)
Succinic anhydride: reagent grade (Wako Pure Chemical Industries, Ltd.)
Malic acid: reagent grade (Wako Pure Chemical Industries, Ltd.)
Fumaric acid: Special grade for reagent (Wako Pure Chemical Industries, Ltd.)
Maleic acid: Special reagent grade (manufactured by Wako Pure Chemical Industries, Ltd.)

2. Analysis [Gas chromatography analysis]
GBL was analyzed using a DB-1 column (nonpolar) manufactured by Agilent with a gas chromatography analyzer (GC-17A model manufactured by Shimadzu Corporation).
[Inductively coupled plasma optical emission spectrometry (ICP-OES)]
Ru analysis was carried out by an organic solvent direct introduction method using an ICP emission spectrometer (iCAP6500Duo manufactured by Thermo Fisher Scientific Co., Ltd., Peltier cooled organic solvent introduction system).
[Absorbance analysis]
The sample was put into a 10 mm quartz cell, and the absorbance at a wavelength of 500 nm was measured with a spectrophotometer (UV-2000 type manufactured by Hitachi High-Technologies Corporation).

3. Examples and Comparative Examples <Reference Example 1>
In a 100 ml autoclave (material: SUS316), 5.9 g (11.8% by mass) of succinic acid and 5.0 g (Ru: 400) of a ruthenium complex having trioctylphosphine as a ligand dissolved in triglyme. Mass ppm) and 39.1 g of triglyme as a solvent were charged. The total concentration of dicarboxylic acids (malic acid, maleic acid, fumaric acid) having a metal coordinating functional group in the reaction mixture was less than 1 ppm by mass.

After putting the magnetic rotating stirrer into the autoclave, the system was sufficiently replaced with hydrogen. The temperature was raised while stirring using a magnetic stirrer, and hydrogen was injected so that the internal pressure became 0.9 MPa · G (gauge pressure) when the internal temperature of the autoclave reached 205 ° C. This time was set as the reaction start time, and hydrogenation reaction was performed for 2 hours after that.
After completion of the reaction, the obtained reaction product liquid and reaction product gas were collected and analyzed by gas chromatography. As a result, the yield of gamma butyrolactone was 29.6%, and the amount of carbon monoxide produced was 18 ppm by volume. . The reaction results are shown in Table 1.

< Reference Example 5 >
In addition to the raw material of Reference Example 1, a hydrogenation reaction was carried out in the same manner as Reference Example 1 except that 0.025 g (500 ppm by mass) of fumaric acid was charged into the autoclave, and the resulting reaction product liquid And the reaction product gas was analyzed.
The yield of gamma butyrolactone was 30.0%, and the amount of carbon monoxide produced was 7 ppm by volume. The reaction results are shown in Table 1.

< Example 3, Reference Examples 6-9 >
In addition to the raw material of Reference Example 1 above, 0.05 g of fumaric acid ( Reference Example 6 ), 0.15 g ( Reference Example 8 ), 0.499 g ( Reference Example 9 ) and 0.05 g of malic acid (implemented) were added to the autoclave. Example 3) A hydrogenation reaction was carried out in the same manner as in Reference Example 5 except that 0.05 g of maleic acid ( Reference Example 7 ) was charged. The resulting reaction product solution and reaction product gas were collected and gas chromatographed. Analyzed graphically. The reaction results are summarized in Table 1.

<Comparative Example 1>
A hydrogenation reaction was carried out in the same manner as in Reference Example 5 except that the amount of malic acid added was 0.5 g (10000 mass ppm), and the reaction product solution and the reaction product gas were analyzed. As a result, the yield of gamma butyrolactone was 0.9%, and the amount of carbon monoxide produced was 18013 volume ppm. The reaction results are shown in Table 1.

<Comparative example 2>
A hydrogenation reaction was carried out in the same manner as in Reference Example 6 except that the amount of maleic acid added was changed to 0.5 g (10000 mass ppm), and the reaction product solution and the reaction product gas were analyzed. As a result, the yield of gamma butyrolactone was 4.0%, and the amount of carbon monoxide produced was 14904 ppm by mass. The reaction results are shown in Table 1.

<Reference Example 2>
The hydrogenation reaction was carried out in the same manner as in Reference Example 1 except that the reaction raw material was changed to 5.9 g (11.8% by mass) of succinic acid and 5.0 g (10.0% by mass) of succinic anhydride. It was. The maleic anhydride concentration in the reaction mixture was less than 1 ppm by mass.
After completion of the reaction, the obtained reaction product solution was analyzed. As a result, the yield of gamma butyrolactone was 60.7%. The reaction results are shown in Table 2.

< Reference Example 10 >
A hydrogenation reaction was carried out in the same manner as in Reference Example 2 except that 0.005 g (100 ppm by mass) of maleic anhydride was charged into the autoclave in addition to the raw material of Reference Example 2 above.
After completion of the reaction, the resulting reaction product solution was collected and analyzed by gas chromatography. As a result, the yield of gamma butyrolactone was 59.0%. The reaction results are shown in Table 2.

<Comparative Example 3>
A hydrogenation reaction was carried out in the same manner as in Reference Example 2 except that the amount of maleic anhydride added was changed to 0.5 g (10000 mass ppm), and after completion of the reaction, the reaction product solution was analyzed. As a result, the yield of gamma butyrolactone was 17.9%. The reaction results are shown in Table 2.

<Reference Example 3>
Instead of 5.0 g (Ru400 mass ppm) of a ruthenium complex having trioctylphosphine as a ligand as a catalyst, a ruthenium-platinum-tin supported activated carbon catalyst (Ru6 mass%, Pt3 mass%, Sn7 mass%) 0.4 g (Ru500 mass ppm) and 44.1 g of the solvent triglyme were charged. The concentration of the dicarboxylic acid having a metal coordinating functional group in the reaction mixture was less than 1 ppm by mass.
Except for the above, the hydrogenation reaction was carried out for 4 hours in the same manner as in Reference Example 1, and after completion of the reaction, the resulting reaction product solution was analyzed in the same manner as in Reference Example 1. As a result, the yield of gamma butyrolactone was 12.2%. Met. The reaction results are shown in Table 3.

<Example 8>
A hydrogenation reaction was carried out in the same manner as in Reference Example 3 except that 0.05 g (1000 ppm by mass) of malic acid was charged into the autoclave in addition to the raw material of Reference Example 3 above.
After completion of the reaction, the obtained reaction product solution was collected and analyzed by gas chromatography. As a result, the yield of gamma butyrolactone was 10.3%. The reaction results are shown in Table 3.

<Comparative Example 4>
A hydrogenation reaction was carried out in the same manner as in Reference Example 3 except that 0.5 g (10000 ppm by mass) of malic acid was charged into the autoclave in addition to the raw material of Reference Example 3 above.
As a result of analyzing the resulting reaction product after completion of the reaction, the yield of gamma butyrolactone was 6.1%. The reaction results are shown in Table 3.

<Example 9>
As a catalyst, 1 g of copper oxide-zinc oxide supported alumina catalyst (Cu 0.33 mass%. Zn 0.38 mass%), 5.9 g (5.9 mass%) of succinic acid, 0.05 g (1000 mass ppm) of malic acid, 94.1 g of solvent triglyme was charged.
After putting the magnetic rotating stirrer into the autoclave, the system was sufficiently replaced with hydrogen. The temperature was increased while stirring using a magnetic stirrer, and hydrogen was injected so that the internal pressure became 7.5 MPa · G (gauge pressure) when the internal temperature of the autoclave reached 270 ° C. This time was set as the reaction start time, and hydrogenation reaction was performed for 0.5 hour after that. After completion of the reaction, the obtained reaction product solution was analyzed in the same manner as in Reference Example 1. As a result, the yield of gamma butyrolactone was 18.0%. The reaction results are shown in Table 4.

<Comparative Example 5>
A hydrogenation reaction was carried out in the same manner as in Example 9 except that the malic acid charge in Example 9 was changed to 0.5 g (10000 mass ppm).
As a result of analyzing the obtained reaction product after completion of the reaction, the yield of gamma butyrolactone was 15.5%. The reaction results are shown in Table 4.

<Example 10>
A solution prepared by dissolving a ruthenium complex having trioctylphosphine as a ligand in triglyme to 0.25 g (Ru 2000 mass ppm), malic acid 0.1 mg (10 mass ppm) and a solvent triglyme 9.75 g is mixed. Prepared. When these solutions were stored in an open state in a 100 mL glass vial for 72 hours in the atmosphere, the solution that had been pale yellow before storage had turned pale red. The amount of change in absorbance at 500 nm of the obtained solution was 0.043.

<Example 11>
When stored in the air in the same manner as in Example 10 except that the amount of malic acid used was 1.0 mg (100 mass ppm), the color changed to light red. Table 5 shows the measurement results of absorbance. A hydrogenation raw material was prepared by mixing 45 g of the discolored catalyst and 5 g of succinic acid. Except for the above, the hydrogenation reaction was carried out for 2 hours in the same manner as in Reference Example 1. After the reaction was completed, the resulting reaction product solution was analyzed in the same manner as in Reference Example 1. As a result, the yield of gamma butyrolactone was 12.5%. Met. The reaction results are shown in Table 5.

<Comparative Example 6>
Except that malic acid was not added (dicarboxylic acid content having a metal coordinating functional group: less than 1 ppm by mass), it was stored in the air in the same manner as in Example 10 and changed to red. . Table 5 shows the measurement results of absorbance. A hydrogenation raw material was prepared by mixing 45 g of the discolored catalyst and 5 g of succinic acid. Except for the above, the hydrogenation reaction was carried out for 2 hours in the same manner as in Reference Example 1. After the reaction was completed, the resulting reaction product solution was analyzed in the same manner as in Reference Example 1. As a result, the yield of gamma butyrolactone was 10.0%. Met. The reaction results are shown in Table 5.

4). Evaluation of Results (1) When comparing Example 3 and Reference Examples 5-10 shown in Tables 1 and 2 with Comparative Examples 1 to 3, the concentration of the dicarboxylic acid having a metal coordinating functional group during the hydrogenation reaction was In the examples within the prescribed range of the present application, the GBL yield is the same level as Reference Examples 1 and 2 (raw materials not containing dicarboxylic acid having a metal coordinating functional group). It can be seen that in Comparative Examples 1 to 3 whose concentration exceeds the range of the present application, the yield is significantly reduced. It can also be seen that fumaric acid and malic acid produce less carbon monoxide than maleic acid at concentrations of dicarboxylic acids having the same metal coordinating functional group.
(2) In the examples using the solid catalysts shown in Tables 3 and 4, the GBL yield was almost the same in Example 8 and Reference Example 3, Example 9 and Reference Example 4, while the metal coordinating functional group Compared with Comparative Examples 4 and 5 in which the amount of the dicarboxylic acid having a group is excessive, the yield is significantly higher.
(3) In Example 11 of Table 5, by adding a dicarboxylic acid having a metal coordinating functional group, the degree of change in absorbance at a wavelength of 500 nm is reduced, resulting in a high GBL yield. On the other hand, in Comparative Example 56, this concentration was less than the range specified in this application, or the stability of the catalyst was lowered, and the absorbance at a wavelength of 500 nm was greatly changed, resulting in a low GBL yield.
(4) From the above, in the method for producing gamma-butyrolactone by hydrogenation of succinic acid, the concentration of metal coordinating dicarboxylic acid in the reaction mixture at the time of hydrogenation reaction is set within the range specified in the present invention, so that the yield of GBL can be reduced. It can be seen that the rate can be improved and the deterioration of the metal catalyst can be prevented.

Claims (6)

In a method for producing gamma-butyrolactone by hydrogenating succinic acid and / or a derivative thereof (hereinafter collectively referred to as “succinic acid”), the concentration of malic acid in the reaction mixture during the hydrogenation reaction is 10 mass ppm or more, A method for producing gamma-butyrolactone, characterized by being less than 10,000 ppm by mass. The method for producing gamma-butyrolactone according to claim 1, wherein the concentration of malic acid in the reaction mixture during the hydrogenation reaction is 30 mass ppm or more and 5000 mass ppm or less. The method for producing gamma-butyrolactone according to claim 1 or 2 , wherein the catalyst used in the hydrogenation reaction contains ruthenium or copper. The method for producing gamma-butyrolactone according to any one of claims 1 to 3 , wherein the catalyst used in the hydrogenation reaction is a ruthenium complex having a tertiary organophosphorus compound as a ligand. Claim wherein the succinic acid is a succinic acid and / or succinic anhydride, the catalyst used in either One the hydrogenation reaction, characterized in that a ruthenium complex having a tertiary organic phosphorus compound as a ligand The manufacturing method of the gamma butyrolactone of any one of 1-4 . The succinic acid is one produced by hydrogenating maleic anhydride obtained by a petrochemical method using a fossil fuel as a raw material, or produced by a fermentation method using a biomass raw material. gamma butyrolactone production method of the lactone according to any one of 1-5.