JP2015003892A - Method for producing polyol compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polyol compound, in which method a catalyst, that can allow the polyol compound to be produced from a furan compound having a hydroxymethyl group or a formyl group at a high reaction rate, in high yield and with high selectivity and can be applied to industrial production, is used so that the polyol compound can be produced at the high reaction rate, in high yield and with high selectivity and which method can also be applied to industrial production.SOLUTION: The method for producing the polyol compound comprises the steps of: mixing a metal compound (A) containing at least one of metals belonging to group 3 to group 11 in the periodical table, a compound (B) containing at least one selected from the group consisting of oxidized ruthenium compounds (B1) and high-valent compounds (B2) each containing at least one of metals belonging to group 8 to group 11 in the periodical table, and a metal oxide (C) containing a metal of group 5, group 6 or group 7 in the periodic table; reducing an obtained mixture to obtain the catalyst for hydrocracking; bringing the furan compound into contact with the obtained catalyst for hydrocracking in the presence of a hydrogen source under a basic condition to obtain the polyol compound.

Description

  The present invention relates to a method for producing a polyol compound corresponding to a furan compound by reducing and opening a furan compound having a hydroxymethyl group or a formyl group in the presence of a catalyst.

  Conventionally, as a method for producing a corresponding polyol compound by reducing and ring-opening a furan compound having a formyl group, for example, furfural, for example, a method using a platinum oxide catalyst (see, for example, Non-Patent Document 1), nickel- A method using a copper-manganese catalyst (see, for example, Patent Document 1), a catalyst in which copper is supported on alumina (see, for example, Patent Document 2), and a method using a catalyst in which platinum and cobalt are supported on alumina (for example, non-patents) Patent Document 2) is known. In addition, as a method of producing a corresponding polyol compound by reducing and opening a furan compound having a hydroxymethyl group, for example, furfuryl alcohol, a method using a copper chromium catalyst (for example, see Non-Patent Document 3) is known. It has been.

U.S. Pat. No. 2,201,347 German Patent No. 828804

J. et al. Am. Chem. Soc. 1923, 45, p. 3029-044 Chem. Comm. 2011, 47, p. 3924-3926 J. et al. Am. Chem. Soc. , 1931, 53, p. 1091-1095

  However, in any of the above-described methods using the catalyst, a high temperature and high pressure are required, and the double bond in the furan compound ring or the formyl group of the furan compound is not completely reduced, and the intermediate is not ring-opened. Or a polymer, and / or a selective regioisomer (for example, 1,2-pentanediol) different from the intended purpose is produced without selective cleavage of the furan ring. In addition, in the following reaction formula, the reaction which used furfural as a starting material is illustrated. In the following reaction formula, furfuryl alcohol, 2-formylfuran, and 2-hydroxymethyltetrahydrofuran are generated as intermediates. In addition, in the prior art, in addition to the target 1,5-pentanediol, 1,2-pentanediol, which is a regioisomer, may also be generated.

  Therefore, it has been desired to provide a method for producing a polyol compound from a furan compound that can solve the above problems and is industrially suitable.

  Therefore, the present invention solves the above-described problems, and provides a method capable of producing a polyol compound with high yield and high selectivity from a furan compound having a hydroxymethyl group or a formyl group at a high reaction rate. The purpose is to provide.

  Therefore, in the first aspect, the present invention solves the above problems and produces a polyol compound from a furan compound having a hydroxymethyl group or a formyl group at a high reaction rate and with high yield. It is possible to produce a polyol compound with high reaction rate, high yield and high selectivity by using a catalyst that can be applied to industrial production, and can be applied to industrial production. It is an object to provide a method for producing a compound.

An object of the present invention is to provide at least one furan compound selected from the group consisting of the following general formulas (1a), (1b), (1c), (1d) and (1e) in the presence of a hydrogen source;
A metal compound (A) containing any one of metals of Groups 3 to 11 of the periodic table;
A compound (B) containing at least one selected from the group consisting of a ruthenium oxide compound (B1) and a high-valence compound (B2) containing any one of metals in Groups 8 to 11 of the periodic table;
A metal oxide (C) containing a metal of Group 5, Group 6 or Group 7 of the periodic table, and a hydrocracking catalyst obtained by reduction treatment,
Is contacted under basic conditions, and then is contacted under acidic conditions to obtain a polyol compound represented by the following general formula (2a) or (2b).

(In formulas (1a), (1b), (1c), (1d) and (1e), R ¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a formyl group or a hydroxymethyl group; ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁴ represents a formyl group or a hydroxymethyl group, R ¹ and R ² , and R ² and R ³ May be bonded to each other to form a ring independently.)

(In formulas (2a) and (2b), R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ^1a represents a hydrogen atom or 1 to 5 carbon atoms. And R ^1a and R ² , and R ² and R ³ may be bonded to each other to form a ring independently.)
Solved by.

(Catalyst for hydrocracking)
A preferred embodiment of the present invention will be described below.

The hydrocracking catalyst of the present embodiment is a catalyst obtained by mixing component (1), component (2) and component (3) and performing a reduction treatment. Such a hydrocracking catalyst can be obtained, for example, by mixing the component (1), the component (2) and the component (3) and then reducing the resulting mixture.
(1) Metal compound (A) containing any one of metals of Group 3 to Group 11 of the periodic table
(2) Compound (B) containing at least one selected from the group consisting of a ruthenium oxide compound (B1) and a high-valence compound (B2) containing any one of metals in Groups 8 to 11 of the periodic table
(3) Metal oxide (C) containing a metal of Group 5, 6 or 7 of the periodic table

(1) Metal compound (A)
Examples of metals of Group 3 to Group 11 of the periodic table in the metal compound (A) used in the present embodiment include scandium, yttrium, lanthanum, cerium, neodymium, samarium, ytterbium, lutetium, titanium, zirconium, hafnium, and vanadium. Niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold and the like. Of these, lanthanum, ytterbium, zirconium, hafnium, niobium, tantalum, molybdenum, tungsten, rhenium, ruthenium, cobalt, rhodium, iridium, palladium, platinum, copper, gold, and more preferably ruthenium, rhodium, iridium. , Platinum. That is, the metal compound (A) is a compound having any one of metal elements belonging to Groups 3 to 11 of the periodic table as a constituent element.

  The form of the metal compound (A) is not particularly limited, and may be any form such as a simple metal, a metal alloy, a metal salt, a metal complex, and a metal oxide, and addition of a hydrate or an organic compound. It may be a body. Further, the metal compound (A) may be supported on a carrier. In addition, you may use these metal compounds (A) individually by 1 type or in mixture of 2 or more types.

  Specific examples of the metal compound (A) include lanthanum compounds such as lanthanum trichloride, lanthanum tribromide, lanthanum triiodide, lanthanum trinitrate, lanthanum phosphate, dilanthanum trisulfate, and dilanthanum tricarbonate. Ytterbium compounds such as ytterbium trichloride, ytterbium tribromide, ytterbium trinitrate and diytterbium trisulfate; zirconium compounds such as zirconium tetrachloride, zirconium tetrabromide, zirconium tetraiodide, zirconium tetranitrate and zirconium disulfate; Hafnium compounds such as hafnium chloride, hafnium tetrabromide, hafnium tetraiodide, hafnium tetranitrate, hafnium disulfate; niobium compounds such as niobium pentachloride, niobium pentabromide, niobium pentaiodide; tantalum pentachloride, pentabromide Tantalum compounds such as tantalum and tantalum pentaiodide; trichloride Molybdenum compounds such as ribden, molybdenum pentachloride, molybdenum tribromide; tungsten compounds such as tungsten tetrachloride, tungsten hexachloride, tungsten pentabromide; rhenium compounds such as rhenium trichloride, rhenium pentachloride, rhenium triiodide, three Ruthenium compounds such as ruthenium chloride, ruthenium tribromide, ruthenium diammonium pentachloride, ruthenium triammonium hexachloride, ruthenium hexachloride dipotassium, ruthenium hexachloride disodium, ruthenium tribromide hexabromide, ruthenium hexabromide dipotassium; Cobalt compounds such as cobalt dichloride, cobalt dibromide, cobalt diiodide, cobalt difluoride, cobalt dinitrate, cobalt oxide, cobalt phosphate, cobalt diacetate; rhodium trichloride, rhodium triammonium chloride, hexachloride Rhodium tripotassium Rhodium compounds such as trisodium rhodium, trisodium hexachloride, rhodium trinitrate; iridium trichloride, iridium tribromide, iridium tetrachloride, iridium tetrabromide, ammonium iridate, hexaammineiridium trichloride, pentaamminechloroiridium Dichloride, iridium hexachloride triammonium, iridium hexachloride tripotassium, iridium hexachloride trisodium, iridium tetrachloride, iridium hexachloride diammonium, iridium hexachloride dipotassium hexachloride, iridium hexachloride, disodium iridium hexachloride Iridium compounds such as nickel dichloride, nickel dibromide, nickel diiodide, etc .; palladium dichloride, palladium dibromide, palladium diiodide, palladium diacetate, palladium dinitrate, palladium sulfate Palladium compounds such as palladium oxide; platinum dichloride, platinum tetrachloride, hexachloroplatinic acid, platinum dibromide, platinum tetrabromide, platinum hexabromide, platinum diiodide, platinum tetraiodide, platinum dichloride Diammonium, diammonium platinum hexachloride, diammonium platinum hexachloride, diammonium platinum tetrachloride, disodium platinum hexachloride, dipotassium platinum tetrachloride, dipotassium platinum hexachloride, diammonium platinum dibromide, platinum tetrabromide Platinum compounds such as dipotassium, platinum hexabromide diammonium, sodium hexaiodide platinate, potassium hexaiodide platinate, platinum oxide, hexahydroxoplatinate; copper monochloride, copper dichloride, copper diammonium dichloride, etc. A gold compound such as gold monochloride, gold trichloride, tetrachloroauric acid, gold tribromide, and gold triiodide. Of these, preferably ruthenium trichloride, cobalt dichloride, rhodium trichloride, iridium trichloride, iridium tetrachloride, iridium hexachloride, nickel dichloride, palladium dichloride, platinum dichloride, copper dichloride, gold tetrachloride Acid is used.

(2) Compound (B)
In the present embodiment, as the compound (B), a ruthenium oxide compound (B1) and a compound (B) containing a high valence compound (B2) containing any of metals in Groups 8 to 11 of the periodic table are used.

[Ruthenium oxide compound (B1)]
As the ruthenium oxide compound (B1) used in the present embodiment, at least one compound selected from the group consisting of ruthenium oxide and ruthenium peroxide is preferably used. Examples of ruthenium oxide include ruthenium dioxide, ruthenium trioxide, and ruthenium tetroxide. Of these, ruthenium tetroxide is preferably used. Examples of the ruthenium peroxide include potassium perruthenate, perruthenic acid (tetrapropylammonium), perruthenic acid (tetrabutylammonium), dipotassium tetraoxoruthenium (VI), and tetraoxoruthenium (VI) acid. Disodium and the like. Among these, potassium perruthenate, perruthenic acid (tetrapropylammonium), dipotassium tetraoxoruthenium (VI), disodium tetraoxoruthenium (VI), and the like are preferably used. These ruthenium oxide compounds (B1) may be any of hydrates, aqueous solutions and adducts of organic compounds, or may be supported on a carrier.

[High-valent metal compound (B2)]
Examples of the metals in Groups 8 to 11 of the periodic table in the high-valence metal compound (B2) used in the present embodiment include iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, Examples include silver and gold. Of these, ruthenium, rhodium, iridium, palladium, platinum, and gold are preferable. That is, the high-valent metal compound (B2) is a compound having any one of metal elements belonging to Groups 8 to 11 of the periodic table as a constituent element. Here, the high-valence metal compound (B2) having ruthenium as a metal of Groups 8 to 11 of the periodic table may correspond to the ruthenium oxide compound (B1). That is, when the ruthenium oxide compound (B1) is a compound having ruthenium having a high valence as a constituent element, the compound also corresponds to the high valent metal compound (B2). It goes without saying that even when such a compound is used, it can correspond to the hydrocracking catalyst of the present embodiment.

  The high valent metal in the present specification refers to a metal having a metal valence of 3 or more. The form of the high valent metal compound (B2) is not particularly limited, and may be, for example, a hydrate or an adduct of an organic compound. Further, it may be supported on a carrier. In addition, you may use these high valence metal compounds (B2) individually by 1 type or in mixture of 2 or more types.

  As the high valence metal compound (B2), at least one compound selected from the group consisting of hydroxy metals and hydroxy metal acid salts is preferably used. Specific examples thereof include trihydroxy iron (III), tetrahydroxylthenium (IV), tetrahydroxy osmium (IV), trihydroxy cobalt (III), trisodium hexahydroxyrhodium (III), hexahydroxyrhodium ( III) Tripotassium acid, disodium hexahydroxyrhodium (IV), dipotassium hexahydroxyrhodium (IV), disodium hexahydroxyiridium (IV), dipotassium hexahydroxyiridium (IV), hexahydroxypalladium ( IV) disodium acid, disodium hexahydroxypalladium (IV), hexahydroxyplatinum (IV) acid, disodium hexahydroxyplatinum (IV), dipotassium hexahydroxyplatinate (IV), Hydroxy gold (III), and the like. Preferably tetrahydroxyruthenium (IV), trisodium hexahydroxyrhodium (III), tripotassium hexahydroxyrhodium (III), disodium hexahydroxyrhodium (IV), dipotassium hexahydroxyrhodium (IV), hexa Hydroxyiridium (IV) disodium, hexahydroxyiridium (IV) dipotassium, hexahydroxypalladium (IV) disodium, hexahydroxypalladium (IV) dipotassium, hexahydroxyplatinum (IV) acid, hexahydroxyplatinum (IV) disodium acid, hexahydroxyplatinic acid (IV) dipotassium, trihydroxygold (III), more preferably hexahydroxyrhodium (III) trisodium, hexahydroxyirid Beam (IV) dipotassium, dipotassium hexa hydroxy palladium (IV) acid, hexahydroxyplatinic (IV) acid, hexahydroxyplatinic (IV) Disodium, trihydroxy gold (III) is used. These high-valent metal compounds (B2) may be adducts of hydrates or organic compounds, or may be supported on a carrier.

  The compound (B) is a compound different from the metal compound (A). That is, in order to obtain the hydrocracking catalyst of the present embodiment, a compound different from the metal compound (A) is used as the compound (B). However, the metal compound (A) and the metal compound (B) may contain the same metal.

(3) Metal oxide (C)
Examples of the metal of the metal oxide (C) containing a metal of Group 5, 6 or 7 of the periodic table used in the present embodiment include vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, technotium, Rhenium etc. are mentioned. Preferred metals are vanadium, molybdenum, tungsten and rhenium. That is, the metal compound (C) is a compound having any one of metal elements belonging to Group 5, Group 6, or Group 7 of the periodic table as a constituent element.

  The form of the metal oxide (C) is not particularly limited as long as it is a compound having one metal-oxygen bond, and may be, for example, a hydrate or an adduct of an organic compound. The metal oxide (C) may be supported on a carrier. In addition, you may use these metal oxides individually by 1 type or in mixture of 2 or more types.

  As the metal oxide (C), at least one compound selected from the group consisting of metal oxides and metal peroxide salts is preferably used. Specific examples thereof include, for example, vanadium oxide, divanadium trioxide, vanadium dioxide, divanadium pentoxide, vanadium tribromide, potassium pyrovanadate, potassium tetraoxovanadate (V), trioxovanadium (V). Potassium oxide, vanadium oxides such as sodium trioxovanadate (V), sodium pyrovanadate, lithium trioxovanadate (V); silicomolybdic acid, ammonium tetracosaoxoheptamolybdate (VI), tetraoxomolybdenum (VI ) Potassium oxide, calcium tetraoxomolybdate, sodium tetraoxomolybdate (VI), magnesium tetraoxomolybdenum (VI), lithium tetraoxomolybdate (VI), molybdenum dioxide, molybdenum trioxide, etc. Tungsten oxides such as sodium tetraoxotungsten (VI), cadmium (II) tetraoxotungsten (VI), potassium tetraoxotungsten (VI), calcium tetraoxotungsten (VI); Examples include rhenium oxides such as ammonium oxorhenate (VII), potassium tetraoxorhenate (VII), sodium tetraoxorhenate (VII), rhenium dioxide, rhenium trioxide, and dirhenium heptoxide. Preferably, divanadium pentoxide, potassium trioxovanadate (V), sodium trioxovanadate (V), sodium pyrovanadate, sodium tetraoxotungsten (VI), silicomolybdic acid, tetracosaoxoheptamolybdenum (VI Ammonium acid, sodium tetraoxomolybdate (VI), ammonium tetraoxorhenium (VII), potassium tetraoxorhenium (VII), dirhenium heptoxide.

  The specific example of the metal oxide (C) described above can also correspond to the metal compound (A). However, in order to obtain the hydrocracking catalyst of this embodiment, a component different from the metal compound (A) is used as the metal oxide (C). The metal compound (A) and the metal oxide (C) may contain the same metal. That is, the catalyst for hydrogenation culture of the present embodiment is produced using at least three kinds of compounds that may have a common metal element as a constituent element.

  The hydrocracking catalyst of the present embodiment can be obtained by a production method having a first step of mixing raw materials to obtain a mixture and a second step of reducing the mixture. In the first step, the metal compound (A), the compound (B), and the metal oxide (C) are mixed. The mixing order is not particularly limited, but a method of adding the metal oxide (C) after mixing the metal compound (A) and the compound (B) is suitably employed. As the compound (B), a ruthenium oxide compound (B1) and / or a high-valent metal compound (B2) can be used.

  As a more specific production method, in the first step, the metal compound (A) and the compound (B) are added to a solvent (for example, water) to obtain a solvent solution (for example, an aqueous solution). The obtained aqueous solution is preferably heated and stirred at 60 to 200 ° C, more preferably 100 to 150 ° C. Next, the metal oxide (C) is added to this aqueous solution, and the mixture is preferably heated and stirred at 60 to 200 ° C, more preferably 100 to 150 ° C.

  The amount of compound (B) used when mixing is preferably 0.1 to 30 mol, more preferably 0.2 to 20 mol, per 1 mol of metal compound (A). The amount of the metal oxide (C) to be used is preferably 0.5 to 30 mol, more preferably 1 to 20 mol, per 1 mol of the metal compound (A). In addition, these values are values when the metal compound (A) and the metal oxide (C) are converted into metal atoms, respectively.

  The mixture obtained in the first step can be used as a hydrocracking catalyst by reducing it as it is in the second step. The reduction treatment can be performed using a normal reducing agent capable of generating hydrogen. For example, a method of bringing the mixture into contact with hydrogen gas is suitably employed. The contact temperature when contacting the mixture with hydrogen gas is preferably 40 to 300 ° C., more preferably 50 to 200 ° C., and the contact pressure is preferably atmospheric pressure to 20 MPa, more preferably 0.2 to 15 MPa. In addition, you may perform a 1st process and a 2nd process simultaneously. That is, a hydrocracking catalyst may be produced by performing a reduction treatment while preparing a mixture.

  The hydrocracking catalyst obtained by the above-described reduction treatment may be once isolated by, for example, filtration and washing, or may be used in the production of a hydroxy compound as it is in a suspension state.

  The hydrogenation reaction catalyst may be a catalyst (supported catalyst) supported on a carrier. Such a supported catalyst can be produced by the presence of a support in obtaining the above-mentioned mixture. As the carrier used, a porous carrier is preferably used. Specifically, for example, silica, alumina, silica alumina (aluminosilicate), ceria, magnesia, calcia, titania, silica titania (titanosilicate), zirconia and activated carbon, zeolite, mesoporous material (mesoporous-alumina, mesoporous- (Silica, Mesporous-Carbon) are used. These carriers may be used alone or in combination of two or more.

  When the hydrocracking catalyst is a supported catalyst, a third step of calcining a composition containing the catalyst and the carrier may be performed after the second step. The firing temperature is preferably 50 to 800 ° C, more preferably 100 to 600 ° C. The firing time can be appropriately adjusted, and is preferably 0.1 to 20 hours, more preferably 0.25 to 15 hours.

(Method for producing polyol compound)
The method for producing a polyol compound of this embodiment is to obtain a polyol compound by contacting a furan compound having a hydroxymethyl group or a formyl group with the above hydrocracking catalyst in the presence of a hydrogen source and an inorganic base. .

  The method for producing a polyol compound of the present embodiment is specifically represented by the following general formulas (1a), (1b), (1c), (1d) and (1e) in the presence of a hydrogen source and an inorganic base. At least one furan compound selected from the group consisting of the following compounds and the hydrocracking catalyst are brought into contact under basic conditions and then brought into contact under acidic conditions to give the following general formula (2a) Or the process of obtaining the polyol compound represented by (2b) is provided.

In the formulas (1a), (1b), (1c), (1d) and (1e), R ¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a formyl group or a hydroxymethyl group, and R ² And R ³ each independently represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ⁴ represents a formyl group or a hydroxymethyl group. R ¹ and R ² , and R ² and R ³ may be bonded to each other to independently form a ring (eg, a cyclohexane ring).

In formula (2a) or formula (2b), R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ^1a represents a hydrogen atom or 1 to 5 carbon atoms. R ² and R ³ may be bonded to each other to form a ring independently. Examples of the alkyl group having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. These groups include various isomeric structures.

  Examples of the furan compound having a hydroxymethyl group or a formyl group represented by the general formulas (1a), (1b), (1c), (1d) and (1e) include furfural, 5-hydroxymethylfurfural, 5 -Formylfurfural, 5-methylfurfural, 5-ethylfurfural, 5-propylfurfural, 5-butylfurfural, 5-pentylfurfural, 2-hydroxymethyl-2,3-dihydrofuran, 2-hydroxymethyl-4,5- Dihydrofuran, 2-hydroxymethyl-2,5-dihydrofuran, furfuryl alcohol, 5-hydroxymethylfurfuryl alcohol, 5-formylfurfurfuryl alcohol, 5-methylfurfuryl alcohol, 5-ethylfurfuryl alcohol, 5- Propylfurfuryl al 5-butylfurfuryl alcohol, 5-pentylfurfuryl alcohol, tetrahydrofurfuryl alcohol, 5-hydroxymethyltetrahydrofurfuryl alcohol, 5-methyltetrahydrofurfuryl alcohol, 5-ethyltetrahydrofurfuryl alcohol, 5-propyl Examples include tetrahydrofurfuryl alcohol, 5-butyltetrahydrofurfuryl alcohol, 5-pentyltetrahydrofurfuryl alcohol, and 2-formylfuran. Preferably furfural, 5-hydroxymethylfurfural, 5-formylfurfural, 5-methylfurfural, furfuryl alcohol, 2-hydroxymethyl-2,5-dihydrofuran, tetrahydrofurfuryl alcohol, 5-hydroxymethyltetrahydrofurfuryl alcohol, 5-methyltetrahydrofurfuryl alcohol or 2-formylfuran is used, more preferably furfural, 5-methylfurfural, or furfuryl alcohol. Moreover, these furan derivatives may be used independently and may be used in combination of 2 or more type.

  A polyol obtained by bringing a furan compound having a hydroxymethyl group or a formyl group represented by the general formulas (1a), (1b), (1c), (1d) and (1e) into contact with a catalyst for hydrocracking The compound is a polyol compound represented by the general formula (2a) or (2b). Examples of the polyol compound include 1,5-pentanediol, 1,5-hexanediol, 1,5-heptanediol, 1,5-octanediol, 1,5-nonanediol, 1,5-decanediol, 1,6-hexanediol, 1,2,6-hexanetriol, etc. are mentioned, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, or 1,2,6-hexane Triol is preferred, and 1,5-pentanediol is more preferred.

  In the method for producing a polyol compound of the present embodiment, for example, the compound represented by the following general formula (1e) is passed through the compounds represented by the general formulas (1e-1) and (1e-2) to the general formula (1e-2). The compound represented by 2a) or (2b) is obtained. In the reaction step until the polyol compound represented by the general formula (2a) or (2b) is obtained, from the compound represented by the following general formula (1e-2), the general formula (2a) or (2b) As shown in the reaction formula for the compound represented, the bond between the carbon to which the hydroxymethyl group in the furan compound is bonded and the oxygen forming the ether group is cleaved to obtain the corresponding polyol compound. It is done.

In the ^{formula, R 1, R 2, R} 3, R 4, and ^{R 1a} are as defined above. According to the method for producing a polyol compound of the present embodiment, the compound represented by the general formula (2a) or the general formula (2b) is continuously added from the compound represented by the general formula (1e) or (1e-1). It can be obtained as a reaction.

  In the method for producing a polyol compound in the present embodiment, the amount of the hydrocracking catalyst used is preferably 0.00005 to 1 mol of the furan compound in terms of metal atoms of Groups 3 to 11 of the periodic table. 0.1 mol, more preferably 0.0001 to 0.05 mol. By setting the amount of the catalyst to be used within the above range, there is a tendency that a polyol compound can be obtained at a higher level with high yield and high selectivity while obtaining a sufficient reaction rate. In addition, the said catalyst may prepare and use several types of catalysts separately.

  In the method for producing a polyol compound of the present embodiment, the hydrogen source is not particularly limited as long as it is a compound that provides hydrogen. For example, a reducing gas such as hydrogen gas and ammonia gas (such as nitrogen, helium, and argon). Water; alcohols such as methanol, ethanol, and isopropyl alcohol; organic acids such as formic acid, acetic acid, and chloroformic acid; and inorganic acids such as hydrochloric acid and sulfuric acid. Of these, a reducing gas is preferably used, and more preferably hydrogen gas is used.

  The amount of the hydrogen source described above is preferably 5 to 200 mol, more preferably 10 to 160 mol, relative to 1 mol of the furan compound. By using this amount, the polyol compound tends to be obtained with high yield and high selectivity while obtaining a sufficient reaction rate.

  In the method for producing a polyol compound of this embodiment, it is preferable to contact the furan compound and the hydrocracking catalyst in a solvent, but the solvent may not be used. The solvent to be used is not particularly limited as long as it does not inhibit the reaction. For example, water; alcohol such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, tert-butyl alcohol, and ethylene glycol Hydrocarbons such as heptane, hexane, cyclohexane and toluene; amides such as N, N-dimethylformamide, N, N-dimethylacetamide and N-methyl-2-pyrrolidone; diethyl ether, diisopropyl ether, 1 Ethers such as 1,2-dimethoxyethane, 1,2-diethoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, and dioxane; methylene chloride, dichloroethane, and chlorosilane Halogenated hydrocarbons such as Rohekisan like. Of these, water, hydrocarbons, or ethers are preferable, and water is more preferable. In addition, you may use these solvents individually by 1 type or in mixture of 2 or more types.

  The amount of the solvent used is preferably more than 0 to 100 parts by mass, more preferably more than 0 to 50 parts by mass with respect to 1 part by mass of the furan compound. By making the usage-amount of a solvent into the said range, stirring is performed rapidly and reaction can be advanced smoothly.

  The solvent used in the method for producing a polyol compound of the present embodiment may be the same as the above hydrogen source or may be different from the hydrogen source. Examples of the compound corresponding to both the solvent and the hydrogen source include water and alcohols such as methanol and ethanol. The amount of the compound having the functions of both the solvent and the hydrogen source may be more than 0 parts by mass and less than 100 parts by mass with respect to 1 part by mass of the furan compound, and more than 0 parts by mass. It may be less than or equal to parts by mass.

  Examples of the inorganic base include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate and the like, and sodium hydroxide or potassium hydroxide is preferable. The amount of the inorganic base used is appropriately adjusted so that the pH of the reaction solution becomes basic, but is preferably an amount such that the pH of the reaction solution is 7.5 to 12, specifically, Preferably it is 0.0001-0.1 mol with respect to 1 mol of furan compounds, More preferably, it is 0.001-0.04 mol. By making the pH of the reaction solution basic, it becomes possible to reduce polymerization reactions and side reactions at high temperatures.

  Moreover, in the manufacturing method of the polyol compound of this embodiment, a furan compound and a catalyst are made into basic conditions by using the compounds represented by the general formulas (1b), (1c), (1d) and (1e) as starting materials. In order to promote the reaction for obtaining the compound represented by the above general formula (2a) or (2b) when contacted or when the compound represented by the above general formula (1a) is used as a starting material, In addition to the compound and the catalyst, an acid such as hydrochloric acid, sulfuric acid, phosphoric acid and acetic acid may be contacted as necessary. The amount of such acid used is preferably 0.0001 to 0.1 mol, more preferably 0.001 to 0.04 mol, per 1 mol of furan compound. After the contact under basic conditions, the contact under acidic conditions is followed by a decrease in the rate of furan ring-opening reaction and the progress of side reactions.

  In the method for producing a polyol compound of the present embodiment, the temperature at which the furan compound and the hydrocracking catalyst are brought into contact is preferably 10 to 200 ° C, more preferably 20 to 180 ° C. The reaction step may include a step of raising the temperature stepwise or continuously. The pressure at the time of contacting the furan compound and the catalyst is preferably a normal pressure to 20 MPa, more preferably 0.2 to 15 MPa as a hydrogen partial pressure. By controlling the temperature and pressure within the above ranges, the production of a polyol compound as a target product with high yield and high selectivity at a high reaction rate can be achieved to a higher degree while suppressing the formation of by-products. There is.

  The conversion rate of the furan compound used in the reaction step of the production method of the present embodiment is, for example, 30 to 100 mol%, 40 to 100 mol%, or 50 to 100 mol%. Moreover, the selectivity of the polyol compound synthesize | combined at the said reaction process is 5-98 mol%, 10-95 mol%, or 15-90 mol%, for example. Furthermore, the yield of the polyol compound synthesize | combined at the said reaction process is 5-98 mol%, 10-95 mol%, or 15-90 mol%, for example. In this specification, the conversion rate is the difference between the number of moles of the furan compound subjected to the reaction and the number of moles of the furan compound remaining after the reaction (number of moles of the converted furan compound). Calculated by multiplying the value divided by the number of moles of furan compound by 100. The selectivity is calculated by multiplying 100 by the value obtained by dividing the number of moles of the obtained polyol compound by the number of moles of the converted furan compound. Further, the yield is calculated by multiplying 100 by the value obtained by dividing the number of moles of the obtained polyol compound by the number of moles of the furan compound subjected to the reaction.

  As the method for producing the polyol compound of the present embodiment, either a batch method or a batch method can be selected depending on the form of the hydrocracking catalyst. Depending on the nature of the catalyst, the reaction can be carried out in either a homogeneous system or a heterogeneous system (suspension reaction). If the catalyst is supported on a carrier, the reaction can be carried out continuously in a fixed bed.

  The target polyol compound is obtained by the reaction in the present embodiment. After completion of the reaction, the polyol compound can be isolated and purified from the obtained reaction solution by general operations such as filtration, concentration, extraction, distillation, sublimation, recrystallization, column chromatography and the like.

  The preferred embodiments of the present invention have been described above, but the present invention is not limited to the above embodiments.

  EXAMPLES Next, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

Using the following raw materials (1) to (3), a catalyst was prepared and reacted as described below.
(1) Metal compound (A) containing any one of metals of Group 3 to Group 11 of the periodic table
(2) Ruthenium oxide compound (B1)
(3) Metal oxide (C) containing any of metals in Groups 5 to 7 of the periodic table

Example 1-1 (Production of catalyst)
Silica (Fuji Silysia Chemical Co., Ltd., trade name: CARiACT G-6) 0.50 g, tetraoxoruthenium (VI) dipotassium aqueous solution (Fluya Metal Co., Ltd., ruthenium concentration 4.3 mass%) 0.244 g It was impregnated in an aqueous solution obtained by adding 0.2 g of water (0.104 mmol in terms of ruthenium) and dried at 110 ° C. for 7 hours. Next, the obtained powder was placed in an aqueous solution in which 53.0 mg (0.104 mmol in terms of iridium) of hexachloroiridium acid (manufactured by Wako Pure Chemical Industries, Ltd., iridium concentration: 37.7 mass%) was dissolved in 0.4 g of water. Impregnation and drying at 110 ° C. for 7 hours. Furthermore, the obtained powder was impregnated in a solution in which 27.9 mg of ammonium tetraoxorhenate (VII) (0.104 mmol in terms of rhenium) was dissolved in 0.4 g of water, and dried at 110 ° C. for 7 hours. . This powder was dried at 250 ° C. for 4 hours, and a solid catalyst (hereinafter referred to as “Ir—Ru—Re /”) in which 4% by mass of iridium, 2.1% by mass of ruthenium and 3.9% by mass of rhenium were supported on silica. 588 mg) (sometimes referred to as “SiO ₂ catalyst (1)”).

Example 1-2 (Production of catalyst)
In an autoclave equipped with a glass inner tube having an internal volume of 50 mL, 25.0 mg of the catalyst (Ir-Ru-Re / SiO ₂ catalyst (1)) obtained in Example 1-1 and 4.75 g of water were placed. After pressurizing to 8 MPa with hydrogen gas, the reaction was carried out at 120 ° C. for 1 hour with stirring, and a catalyst in which 4% by mass of iridium, 2.1% by mass of ruthenium and 3.9% by mass of rhenium were supported on silica ( In the following, an aqueous dispersion of “Ir—Ru—Re / SiO ₂ catalyst (2)” may be obtained.

Example 2-1 (Synthesis of 1,5-pentanediol)

To the aqueous dispersion of the catalyst (Ir—Ru—Re / SiO ₂ catalyst (2)) obtained in Example 1-2, 0.250 g (2.60 mmol) of furfural and 0.2 mol / L hydroxylation were obtained at room temperature. 30.0 mg of sodium aqueous solution was added, pressurized to 8 MPa with hydrogen gas, and reacted with stirring at 40 ° C. for 2 hours and at 80 ° C. for 2 hours (furfural and furfuryl alcohol were converted to tetrahydrofurfuryl alcohol at this point). Then, it was once cooled to room temperature. 40.0 mg of 0.2 mol / L hydrochloric acid was added to the obtained reaction liquid, and after pressurizing to 8 MPa with hydrogen gas, the mixture was further reacted at 120 ° C. for 2 hours with stirring. The obtained reaction liquid was cooled to room temperature, and then filtered through a syringe equipped with a membrane filter (pore diameter: 0.45 μm). The filtrate was analyzed by gas chromatography. The conversion rate of furfural was 100 mol%, the yield of 1,5-pentanediol was 15.0 mol%, and the yield of tetrahydrofurfuryl alcohol was 83.5 mol%. there were. Incidentally, 1,2-pentanediol as a by-product was not produced at all.

Comparative Example 2-1 (Synthesis of 1,5-pentanediol)
To an aqueous dispersion of the catalyst (Ir—Ru—Re / SiO ₂ catalyst (2)) obtained in the same manner as in Example 1-2, 0.250 g (2.60 mmol) of furfural was added at room temperature, and hydrogen was added. Pressurize to 8 MPa with gas, react for 2 hours at 40 ° C. with stirring, and react for 2 hours at 80 ° C. (furfural is converted to furfuryl alcohol or tetrahydrofurfuryl alcohol at this point), and further for 2 hours at 120 ° C. Reacted. The obtained reaction liquid was cooled to room temperature, and then filtered through a syringe equipped with a membrane filter (pore diameter: 0.45 μm). The filtrate was analyzed by gas chromatography. The conversion rate of furfural was 100 mol%, the yield of 1,5-pentanediol was 2.8 mol%, the yield of tetrahydrofurfuryl alcohol was 45.0 mol%, The yield of 1,4-butanediol was 22.0%.

Example 2-2 (Synthesis of 1,5-pentanediol)
The synthesis was performed in the same manner as in Example 2-1, except that 0.250 g of furfural used in Example 2-1 was replaced with 0.250 g (2.55 mmol) of furfuryl alcohol. As a result, the conversion of furfuryl alcohol was 100 mol%, the yield of 1,5-pentanediol was 41.5 mol%, and the yield of tetrahydrofurfuryl alcohol was 51.4 mol%. Incidentally, 1,2-pentanediol as a by-product was not produced at all.

Example 1-3 (Production of catalyst)
In an autoclave equipped with a glass inner tube having an internal volume of 50 mL, 17.5 mg of iridium trichloride n hydrate (Ishizu Pharmaceutical Co., Ltd., iridium content 53 mass%) (0.0.482 mmol in terms of iridium), 16.3 mg (0.0475 mmol in terms of platinum) of disodium hexahydroxyplatinum (IV) and 5.0 g of water were added, and the mixture was heated and stirred at 120 ° C. for 30 minutes. The solution, once cooled to room temperature, was charged with 463 mg of activated carbon (trade name: Diasoap, manufactured by Calgon Carbon Japan Co., Ltd.), stirred for 30 minutes at 25 ° C., and then 21.1 mg of dirhenium heptoxide (0. 0870 mmol) was pressurized to 8 MPa with hydrogen gas and then reacted at 120 ° C. for 1 hour with stirring. The aqueous layer of the resulting slurry solution was removed with a centrifuge, and a solid catalyst (2.0% by mass of iridium, 2.0% by mass of platinum, and 3.5% by mass of rhenium supported on wet activated carbon ( Hereinafter, 1.45 g of “Ir—Pt—Re / C catalyst (1)” may be obtained.

Example 1-4 (Production of catalyst)
In an autoclave equipped with a glass inner tube having an internal volume of 50 mL, 147.0 mg of the catalyst (Ir-Pt-Re / C catalyst (1)) obtained in Example 1-4 and 4.75 g of water were placed, and hydrogen was added. After pressurizing to 8 MPa with gas, the reaction was carried out at 120 ° C. for 1 hour with stirring, and the activated carbon supported 2.0 mass% of iridium, 2.0 mass% of platinum, and 3.5 mass% of rhenium. An aqueous dispersion (hereinafter also referred to as “Ir—Pt—Re / C catalyst (2)”) was obtained.

Example 2-3 (Synthesis of 1,5-pentanediol)
To the aqueous dispersion of the catalyst (Ir-Pt-Re / C catalyst (2)) obtained in Example 1-4, 0.250 g (2.60 mmol) of furfural and 0.2 mol / L sodium hydroxide were added at room temperature. After adding 45.0 mg of aqueous solution, pressurizing to 8 MPa with hydrogen gas, and reacting at 40 ° C. for 2 hours and at 80 ° C. for 2 hours (furfural and furfuryl alcohol were converted to tetrahydrofurfuryl alcohol at this point) Once cooled to room temperature. After adding 60.0 mg of 0.2 mol / L hydrochloric acid to the obtained reaction liquid and pressurizing to 8 MPa with hydrogen gas, it was further reacted at 150 ° C. for 2 hours with stirring. The obtained reaction liquid was cooled to room temperature, and then filtered through a syringe equipped with a membrane filter (pore diameter: 0.45 μm). The filtrate was analyzed by gas chromatography. The conversion rate of furfural was 100 mol%, the yield of 1,5-pentanediol was 24.7 mol%, and the yield of tetrahydrofurfuryl alcohol was 52.8 mol%. there were. Incidentally, 1,2-pentanediol as a by-product was not produced at all.

Example 2-4 (Synthesis of 1,5-pentanediol)
The synthesis was performed in the same manner as in Example 2-3 except that 0.250 g of furfural used in Example 2-3 was replaced with 0.250 g (2.55 mmol) of furfuryl alcohol. As a result, the conversion of furfuryl alcohol was 100 mol%, the yield of 1,5-pentanediol was 44.7 mol%, and the yield of tetrahydrofurfuryl alcohol was 42.7 mol%. Incidentally, 1,2-pentanediol as a by-product was not produced at all.

Example 1-5 (Production of catalyst)
In an autoclave equipped with a glass inner tube having an internal volume of 50 mL, 17.5 mg of iridium trichloride n hydrate (Ishizu Pharmaceutical Co., Ltd., iridium content 53 mass%) (0.0.482 mmol in terms of iridium), 16.3 mg (0.0475 mmol in terms of platinum) of disodium hexahydroxyplatinum (IV) and 5.0 g of water were added, and the mixture was heated and stirred at 120 ° C. for 30 minutes. The solution, once cooled to room temperature, was charged with 463 mg of activated carbon (trade name: Diasoap, manufactured by Calgon Carbon Japan Co., Ltd.), stirred for 30 minutes at 25 ° C., and then 21.1 mg of dirhenium heptoxide (0. 0870 mmol) was pressurized to 8 MPa with hydrogen gas and then reacted at 120 ° C. for 1 hour with stirring. The aqueous layer of the resulting slurry solution was removed with a centrifuge, and a solid catalyst (2.0% by mass of iridium, 2.0% by mass of platinum, and 3.5% by mass of rhenium supported on wet activated carbon ( Hereinafter, 1.45 g of “Ir—Pt—Re / C catalyst (1)” may be obtained.

Example 1-6 (Production of catalyst)
882 mg of the catalyst (Ir-Pt-Re / C catalyst (1)) obtained in Example 1-5 and 10.0 g of water were placed in an autoclave equipped with a glass inner tube having an internal volume of 50 mL, and hydrogen gas was used. After pressurizing up to 8 MPa, the reaction was carried out at 120 ° C. for 1 hour with stirring, and a catalyst in which activated carbon supported 2.0 mass% iridium, 2.0 mass% platinum, and 3.5 mass% rhenium (Ir An aqueous dispersion of -Pt-Re / C catalyst (2)) was obtained.

Example 2-5 (Synthesis of 1,5-pentanediol)
From the aqueous dispersion of the catalyst (Ir-Pt-Re / C catalyst (2)) obtained in Example 1-6, water was removed by decantation at room temperature, and 1.5 g of water was again added to the residue, and furfural 1 .50 g (15.6 mmol) and 27.0 mg of 2 mol / L aqueous sodium hydroxide solution were added, pressurized to 8 MPa with hydrogen gas, and reacted with stirring at 40 ° C. for 2 hours and at 80 ° C. for 2 hours (furfural and Furfuryl alcohol was converted to tetrahydrofurfuryl alcohol) and then cooled to room temperature. 36.0 mg of 2 mol / L hydrochloric acid was added to the obtained reaction liquid, and after pressurizing to 8 MPa with hydrogen gas, the mixture was further reacted at 150 ° C. with stirring for 3 hours. The obtained reaction liquid was cooled to room temperature, and then filtered through a syringe equipped with a membrane filter (pore diameter: 0.45 μm). When the filtrate was analyzed by gas chromatography, the conversion rate of furfural was 100 mol%, the yield of 1,5-pentanediol was 31.7 mol%, and the yield of tetrahydrofurfuryl alcohol was 58.7 mol%. there were. Incidentally, 1,2-pentanediol as a by-product was not produced at all.

  From the above results, it is possible to efficiently produce the target polyol compound by bringing the furan compound and the hydrogen decomposition catalyst into contact with each other under basic conditions and then contacting them under acidic conditions. it can.

  The present invention can provide a method for reducing a furan compound having a hydroxymethyl group or a formyl group to produce a corresponding polyol compound with high reaction rate and high yield. The obtained polyol compound is useful, for example, as a polymer raw material such as polyester, polycarbonate, and polyurethane, a resin additive, a raw material for intermediates for medical and agricultural chemicals, and various solvents.

Claims (4)

In the presence of a hydrogen source, at least one furan compound selected from the group consisting of the following general formulas (1a), (1b), (1c), (1d) and (1e);
A metal compound (A) containing any one of metals of Groups 3 to 11 of the periodic table;
A compound (B) containing at least one selected from the group consisting of a ruthenium oxide compound (B1) and a high-valence compound (B2) containing any one of metals in Groups 8 to 11 of the periodic table;
A metal oxide (C) containing a metal of Group 5, Group 6 or Group 7 of the periodic table, and a hydrocracking catalyst obtained by reduction treatment,
Is contacted under basic conditions, and then is contacted under acidic conditions to obtain a polyol compound represented by the following general formula (2a) or (2b).

(In formulas (1a), (1b), (1c), (1d) and (1e), R ¹ represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a formyl group or a hydroxymethyl group; ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, R ⁴ represents a formyl group or a hydroxymethyl group, R ¹ and R ² , and R ² and R ³ May be bonded to each other to form a ring independently.)

(In formulas (2a) and (2b), R ² and R ³ each independently represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R ^1a represents a hydrogen atom or 1 to 5 carbon atoms. It indicates an alkyl group or a hydroxymethyl group, R ^1a and R ^2, and, R ² and R ³ may form a ring independently combined with each other.)   The process according to claim 1, wherein the pH of the reaction solution under basic conditions is 7.5 to 12. 3. The production method according to claim 1, wherein the metal of Group 3 to 11 of the periodic table is iridium, and the metal of Group 5, 6 or 7 of the periodic table is rhenium.   The manufacturing method according to any one of claims 1 to 3, wherein the metal of Group 8 to 11 of the periodic table is platinum.