JP6268892B2 - Method for producing alcohol compound - Google Patents

Description

  The present invention relates to a method for producing an alcohol compound.

  Conventionally, as a method for producing a corresponding alcohol compound from a carboxylic acid compound, a method in which the carboxylic acid is esterified and then reduced is widely known. However, it was necessary to esterify the carboxyl group prior to the reduction. Therefore, a method for directly producing an alcohol compound without esterifying the carboxylic acid compound is desired.

As a method for producing an alcohol compound directly from a carboxylic acid compound, for example, the following methods (1) to (3) are known.
(1) A method for producing 1,4-butanediol by reducing maleic acid in the presence of a catalyst in which palladium / silver / rhenium is supported on carbon oxidized by peroxide (see, for example, Patent Document 1) ).
(2) A method for producing 1,4-butanediol by reducing maleic acid in the presence of a catalyst in which palladium / silver / rhenium / metal (M) is supported on carbon (see, for example, Patent Document 2).
(3) A method for producing a corresponding diol by reducing a mixture of succinic acid, glutaric acid and adipic acid in the presence of a catalyst in which ruthenium / tin / platinum is supported on activated carbon treated with hydrogen peroxide ( For example, see Patent Document 3).

Japanese Patent Laid-Open No. 11-12207 JP 2001-46871 A JP 2000-355562 A

However, in the method of Patent Document 1 described above, a carbon support that has been oxidized by bringing a carbon support into contact with an oxidizing agent must be used prior to the production of the catalyst. Is clearly disclosed in the comparative example (for example, comparison between Example 2 and Comparative Example B). Therefore, there has been a problem that the manufacture of the catalyst becomes complicated.
Furthermore, in the catalyst, since the product greatly varies depending on LHSV (liquid space velocity) and reaction temperature, it is necessary to set reaction conditions in a limited manner (Contrast between paragraph numbers [0045] and [0046]). )

  Further, in the method of Patent Document 2, the fourth component metal (M; aluminum, iron, cobalt) is an indispensable constituent requirement for the catalytic activity (comparison of Reference Example 1, Example 1 and Comparative Example), Even if Reference Examples 1 and 2 (treatment before using the catalyst) are taken into account, there is a problem that the production of the catalyst is complicated.

  On the other hand, in Patent Document 3, there is a problem similar to Patent Document 1 in addition to the problem that activated carbon must be previously treated with hydrogen peroxide or the like.

  In the reduction reaction using any of the above-mentioned catalysts proposed above, for example, when a dicarboxylic acid compound is reduced, the hydroxycarboxylic acid compound that is an incompletely reduced form remains, a cyclic ester compound, a cyclic ether compound, etc. There was still a problem of generating.

  Therefore, the present invention makes it possible to produce an alcohol compound with high yield and high selectivity at a high reaction rate using a carboxylic acid compound as a starting material by using a catalyst comprising specific constituent components. It is an object of the present invention to provide a method for producing an alcohol compound that can be applied to industrial production.

An object of the present invention is to provide a carboxylic acid compound in the presence of a hydrogen source,
At least two selected from the group consisting of rhodium, iridium, platinum, ruthenium, tantalum, rhenium, palladium, lanthanum, cerium, samarium, ytterbium, lutetium, zirconium, hafnium, niobium, molybdenum, tungsten, cobalt, nickel, copper and gold A metal compound (A) of
A metal oxide (B1) or metal carbonyl compound (B2) containing a metal of Group 5, 6 or 7 of the periodic table;
This is solved by a method for producing an alcohol compound, which comprises contacting the catalyst with a catalyst obtained by reduction and mixing.

  The present invention provides a catalyst capable of reducing a carboxylic acid compound to produce an alcohol compound corresponding to the carboxylic acid compound with high reaction rate and high yield, and a method for producing the catalyst. can do. Further, in the present invention, by using the above-mentioned catalyst, it is possible to produce an alcohol compound with high reaction rate, high yield and high selectivity, and a method for producing an alcohol compound that can be applied to industrial production. I will provide a.

Hereinafter, the present invention will be specifically described.
(catalyst)
The catalyst of the present invention comprises
At least two selected from the group consisting of rhodium, iridium, platinum, ruthenium, tantalum, rhenium, palladium, lanthanum, cerium, samarium, ytterbium, lutetium, zirconium, hafnium, niobium, molybdenum, tungsten, cobalt, nickel, copper and gold A metal compound (A) of
A metal oxide (B1) or metal carbonyl (B2) compound containing a metal of Group 5, 6 or 7 of the periodic table;
Is a catalyst obtained by mixing and reducing.
Hereafter, the component at the time of manufacturing the catalyst of this invention is demonstrated. In addition, hereinafter, a mixture of each component may be referred to as a “mixture”.

(At least 2 selected from the group consisting of rhodium, iridium, platinum, ruthenium, tantalum, rhenium, palladium, lanthanum, cerium, samarium, ytterbium, lutetium, zirconium, hafnium, niobium, molybdenum, tungsten, cobalt, nickel, copper and gold. Seed metal compound (A))
At least two selected from the group consisting of rhodium, iridium, platinum, ruthenium, tantalum, rhenium, palladium, lanthanum, cerium, samarium, ytterbium, lutetium, zirconium, hafnium, niobium, molybdenum, tungsten, cobalt, nickel, copper and gold As the metal compound (A), for example,
Rhodium trichloride, Rhodium triammonium chloride, Tripotassium hexachloride, Trisodium hexachloride, Rhodium trinitrate, Rhodium trinitrate, Trisodium hexahydroxyrhodium (III), Tripotassium hexahydroxyrhodium (III), Hexahydroxyrhodium ( IV) Rhodium compounds such as disodium acid, dihydroxy potassium hexahydroxyrhodium (IV);
Iridium trichloride, iridium tribromide, iridium tetrachloride, iridium tetrabromide, ammonium iridate, hexaammine iridium trichloride, pentaammine chloroiridium dichloride, iridium hexachloride triammonium hexachloride iridium trichloride, Trisodium iridium hexachloride, diammonium iridium tetrachloride, diammonium iridium hexachloride, iridium hexachloride, dipotassium hexachloride, iridium hexachloride, iridium hexachloride disodium, disodium hexahydroxyiridium (IV), hexahydroxyiridium (IV ) Iridium compounds such as dipotassium acid;
Platinum dichloride, platinum tetrachloride, hexachloroplatinic acid, platinum dibromide, platinum tetrabromide, platinum hexabromide acid, platinum diiodide, platinum tetraiodide, diammonium platinum dichloride, diammonium platinum hexachloride , Platinum hexachloride diammonium, platinum diammonium tetrachloride, platinum disodium hexachloride, dipotassium tetrachloride, dipotassium hexachlorochloride, diammonium platinum dibromide, dipotassium tetrabromide tetrachloride, platinum dibromide Platinum compounds such as ammonium, sodium hexaiodide platinate, potassium hexaiodide platinate, platinum oxide, hydrogen hexahydroxoplatinate, platinum hydroxide, sodium hexahydroxyplatinate, potassium hexahydroxyplatinate (IV);
Ruthenium trichloride, ruthenium tribromide, ruthenium diammonium pentachloride, ruthenium triammonium hexachloride, ruthenium hexachloride dipotassium, ruthenium hexachloride disodium, ruthenium hexabromide tripotassium, ruthenium hexabromide dipotassium perruthenate Ruthenium such as potassium, perruthenic acid (tetrapropylammonium), perruthenic acid (tetrabutylammonium), dipotassium tetraoxoruthenium (VI), disodium tetraoxoruthenium (VI), tetrahydroxyruthenium (IV) compounds Compound;
Tantalum compounds such as tantalum pentachloride, tantalum pentabromide, tantalum pentaiodide, tantalum pentaethylate, sodium tantalate, potassium tantalate;
Rhenium compounds such as rhenium trichloride, rhenium pentachloride, rhenium triiodide, ammonium perrhenate, potassium perrhenate, sodium perrhenate, tripotassium hexachlororhenium, dipotassium rhenium hexachloride, dirhenium heptoxide;
Palladium dichloride, palladium dibromide, palladium diiodide, palladium diacetate, palladium dinitrate, palladium sulfate, palladium oxide, disodium hexahydroxypalladium (IV), dipotassium hexahydroxypalladium (IV), hydroxylated Palladium compounds such as palladium;
Lanthanum compounds such as lanthanum trichloride, lanthanum tribromide, lanthanum triiodide, lanthanum trinitrate, lanthanum phosphate, dilanthanum trisulfate, dilanthanum tricarbonate, lanthanum formate;
Cerium chloride, cerium bromide, cerium trioxalate, cerium trinitrate, cerium tetrahydroxide, cerium tricarbonate, cerium ammonium nitrate, cerium ammonium nitrate, cerium ammonium nitrate, cerium phosphate, primary sulfate Cerium compounds such as cerium and ceric sulfate;
Samarium compounds such as samarium trichloride, samarium triacetate, samarium trioxalate, samarium trinitrate, samarium tricarbonate, samarium triiodide, samarium sulfate;
Ytterbium compounds such as ytterbium trichloride, ytterbium tribromide, ytterbium trinitrate, diytterbium trisulfate, ytterbium triacetate, ytterbium trioxalate, ytterbium triiodide, ytterbium phosphate;
Lutetium compounds such as lutetium trichloride, lutetium triacetate, dilutetium trioxalate, lutetium trinitrate, lutetium sulfate;
Zirconium compounds such as zirconium tetrachloride, zirconium tetrabromide, zirconium tetraiodide, zirconium tetranitrate, zirconium disulfate;
Hafnium compounds such as hafnium tetrachloride, hafnium tetrabromide, hafnium tetraiodide, hafnium tetranitrate, hafnium disulfate;
Niobium compounds such as niobium pentachloride, niobium pentabromide, niobium pentaiodide, niobium penta (hydrogen oxalate), niobium pentaethylate, niobium penta-n-butyrate, sodium niobium trioxide;
Molybdenum compounds such as molybdenum trichloride, molybdenum pentachloride, molybdenum tribromide, ammonium tetracosaoxoheptamolybdate (VI), potassium tetraoxomolybdenum (VI), sodium tetraoxomolybdate (VI);
Tungsten compounds such as tungsten tetrachloride, tungsten hexachloride, tungsten pentabromide, silicotungstic acid, potassium silicotungstate, sodium silicotungstate, ammonium paratungstate, potassium tungstate;
Cobalt dichloride, cobalt dibromide, cobalt diiodide, cobalt difluoride, cobalt dinitrate, cobalt oxide, cobalt phosphate, cobalt diacetate, trihydroxycobalt (III), cobaltous formate, citric acid first Cobalt compounds such as cobalt;
Nickel compounds such as nickel dichloride, nickel dibromide, nickel diiodide, nickel oxalate, nickel dinitrate, nickel dihydroxide;
Copper monochloride, copper dichloride, copper diammonium dichloride, cupric formate, copper monobromide, copper dibromide, copper nitrate, copper phosphate, copper sulfate, copper acetate, copper carbonate, copper oxalate, etc. Copper compounds;
Gold compounds such as gold monochloride, gold trichloride, gold tetrachloride, gold tribromide, gold triiodide, gold hydroxide, gold tetrachloride, sodium tetrabromide, sodium tetrabromide, etc .;
And preferably,
Rhodium trichloride, rhodium trinitrate, iridium trichloride, iridium tetrachloride, ammonium iridate, iridium hexachloride, trisodium iridium tetrachloride, diammonium iridium hexachloride, diammonium iridium hexachloride, dipotassium iridium hexachloride, iridium hexachloride, Iridium hexachloride disodium, platinum dichloride, platinum tetrachloride, hexachloroplatinic acid, hydrogen hexahydroxoplatinate, platinum hydroxide, sodium hexahydroxyplatinate, potassium hexahydroxyplatinate (IV), ruthenium trichloride, pentachloride Ruthenium diammonium, ruthenium hexachloride triammonium, ruthenium hexachloride dipotassium, ruthenium hexachloride disodium, potassium perruthenate, perruthenate (tetrapropylammonium), perruthenate (tetrabutylammonium) ), Tetraoxoruthenium (VI) dipotassium, tetraoxoruthenium (VI) disodium, tantalum pentachloride, potassium tantalate, rhenium trichloride, rhenium pentachloride, ammonium perrhenate, potassium perrhenate, Sodium rhenate, dirhenium heptoxide, palladium dichloride, palladium diacetate, palladium dinitrate, palladium hydroxide, lanthanum trichloride, lanthanum trinitrate, lanthanum phosphate, dilanthanum tricarbonate, lanthanum formate, cerium chloride, Cerium trinitrate, cerium tetrahydroxide, cerium tricarbonate, cerium phosphate, samarium trichloride, samarium triacetate, samarium trinitrate, ytterbium trichloride, ytterbium trinitrate, ytterbium triacetate, ytterbium phosphate, lutetium trichloride, Luteti triacetate Lutetium trinitrate, zirconium tetrachloride, zirconium tetranitrate, hafnium tetrachloride, hafnium tetranitrate, niobium pentachloride, niobium trioxide, molybdenum trichloride, molybdenum pentachloride, ammonium tetracosaoxoheptamolybdate (VI), Potassium tetraoxomolybdate (VI), sodium tetraoxomolybdate (VI), tungsten tetrachloride, tungsten hexachloride, silicotungstic acid, potassium silicotungstate, sodium paratungstate, ammonium paratungstate, potassium tungstate, di Cobalt chloride, cobalt dinitrate, cobalt phosphate, cobalt diacetate, nickel dichloride, nickel dinitrate, nickel dihydroxide, copper monochloride, copper dichloride, copper nitrate, copper phosphate, copper acetate, gold monochloride, Gold trichloride , Tetrachloroauric acid, gold hydroxide, and potassium tetrachloride. More preferably,
Rhodium trichloride, rhodium trinitrate, iridium trichloride, iridium tetrachloride, iridium chloride, platinum dichloride, platinum tetrachloride, hexachloroplatinic acid, platinum hydroxide, ruthenium trichloride, potassium perruthenate, perruthenic acid ( Tetrapropylammonium), tantalum pentachloride, potassium tantalate, rhenium trichloride, rhenium pentachloride, ammonium perrhenate, potassium perrhenate, dirhenium heptoxide, palladium dichloride, palladium diacetate, palladium dinitrate, trichloride Lanthanum, lanthanum trinitrate, cerium chloride, cerium trinitrate, samarium trichloride, samarium triacetate, samarium trinitrate, ytterbium trichloride, ytterbium trinitrate, ytterbium triacetate, lutetium trichloride, lutetium triacetate, lutetium trinitrate , Zirconium tetrachloride Zirconium tetranitrate, hafnium tetrachloride, hafnium tetranitrate, niobium pentachloride, niobium trioxide, molybdenum trichloride, molybdenum pentachloride, ammonium tetracosaoxoheptamolybdate (VI), potassium tetraoxomolybdate (VI) , Sodium tetraoxomolybdate (VI), tungsten tetrachloride, tungsten hexachloride, silicotungstic acid, potassium silicotungstate, sodium silicotungstate, ammonium paratungstate, cobalt dichloride, cobalt dinitrate, cobalt diacetate, two Nickel chloride, nickel dinitrate, nickel dihydroxide, copper monochloride, copper dichloride, copper nitrate, copper acetate, gold monochloride, gold trichloride, tetrachloroauric acid, and potassium tetrachloride are used.

  In the present invention, the metal compound (A) may be a metal compound such as scandium, yttrium, titanium, vanadium, titanium, manganese, and iron in addition to the above.

(Metal oxide (B1) or metal carbonyl compound (B2) containing a metal of Group 5, 6 or 7 of the periodic table)
Examples of the metal oxide (B1) or metal carbonyl compound (B2) containing a metal of Group 5, 6 or 7 of the periodic table include vanadium, niobium, tantalum, chromium, molybdenum, tungsten, manganese, rhenium. Of these, vanadium, molybdenum, tungsten, and rhenium are preferable.

  The form of the metal oxide (B1) 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. It may be in the form of a metal oxide salt. Furthermore, the metal oxide (B1) 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 (B1), at least one metal oxide selected from the group consisting of metal oxides, metal peroxide acids 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. Buden oxide; Tungsten oxide such as sodium tetraoxotungsten (VI), cadmium (II) tetraoxotungsten (VI), potassium tetraoxotungsten (VI), calcium tetraoxotungsten (VI); tetraoxo Examples include rhenium oxides such as ammonium rhenium (VII), potassium tetraoxorhenium (VII), sodium tetraoxorhenium (VII), rhenium dioxide, rhenium trioxide, and dirhenium heptoxide. Preferably, divanadium pentoxide, potassium trioxovanadate (V), sodium trioxovanadate (V), sodium pyrovanadate, sodium tetraoxotungstate (VI), silicomolybdic acid, tetracosaoxoheptamolybdenum (VI Ammonium acid, sodium tetraoxomolybdate (VI), ammonium tetraoxorhenium (VII), potassium tetraoxorhenium (VII), dirhenium heptoxide.

  The form of the metal carbonyl compound (B2) is not particularly limited as long as it is a compound having one metal and a carbonyl carbon bond (M-CO; M is a metal). For example, it is a hydrate or an adduct of an organic compound. It may be in the form of a metal peroxide acid or metal peroxide salt. Furthermore, the metal carbonyl compound (B2) 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.

  Examples of the metal carbonyl compound (B2) include hexacarbonyl vanadium, hexacarbonyl chromium, hexacarbonyl molybdenum, tricarbonylcyclopentadienyl molybdenum dimer, hexacarbonyl tungsten, decacarbonyl dimanganese, tricarbonylcyclopentadienyl manganese, penta Carbonyl hydride manganese, decacarbonyl dirhenium, pentacarbonyl chlororhenium, pentacarbonyl bromorhenium, pentacarbonyl hydrido rhenium are used.

  The amount of the metal oxide (B1) or metal carbonyl compound (B2) containing a metal of Group 5, Group 6 or Group 7 of the periodic table is preferably based on 1 mol of the total amount of the metal compound (A). It is 0.1-30 mol, More preferably, it is 0.5-20 mol. When the amount of the metal oxide (B1) or the metal carbonyl compound (B2) used is too large, the activity in the reaction is lowered, and when too small, the selectivity in the reaction is lowered.

(Carrier)
The catalyst of the present invention may be a catalyst supported on a carrier (supported catalyst). 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, graphene, carbon nanotube, zeolite, mesoporous material (mesoporous) -Alumina, mesoporous-silica, mesoporous-carbon), preferably silica, alumina, silica alumina (aluminosilicate), titania, zirconia and activated carbon, graphene, carbon nanotubes, zeolite, etc. are used, more preferably silica. , Alumina, and activated carbon are used. These carriers may be used alone or in combination of two or more.

  When the catalyst of the present invention is a supported catalyst, the composition containing the mixture and the support may be calcined. 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.

(Polyvalent acid salt)
In the catalyst of the present invention, a polyvalent acid salt may coexist in the mixture, and as such a polyvalent acid salt, a salt derived from a divalent or higher acid such as carbonic acid, sulfuric acid, phosphoric acid or the like is used. That means. As such polyvalent acid salt, if it is a polyvalent inorganic acid salt, for example, tripotassium phosphate, dipotassium monohydrogen phosphate, trisodium phosphate, disodium monohydrogen phosphate, triammonium phosphate, Phosphates such as diammonium phosphate monobasic; carbonates such as ammonium carbonate, ammonium hydrogen carbonate, potassium carbonate, potassium hydrogen carbonate, sodium carbonate, sodium hydrogen carbonate (as a broad meaning including hydrogen carbonate); potassium sulfate, Examples thereof include sulfates such as sodium sulfate and ammonium sulfate. Examples of the polyvalent organic acid salt include polyvalent carboxylates such as potassium oxalate and sodium oxalate. These polyvalent acid salts may be hydrates or adducts of organic compounds, or may be supported on a carrier.

  The polyvalent inorganic acid salt is preferably tripotassium phosphate, trisodium phosphate, triammonium phosphate, diammonium monohydrogen phosphate, ammonium carbonate, potassium carbonate, sodium carbonate, potassium sulfate, sodium sulfate, Ammonium sulfate, more preferably tripotassium phosphate, triammonium phosphate, ammonium carbonate, diammonium monohydrogen phosphate, potassium carbonate, potassium sulfate is used.

  The amount of the polyvalent inorganic acid salt used is preferably 0.1 to 30 mol, more preferably 0.5 to 10 mol, per 1 mol of the total amount of the metal compound (A). These values are in terms of metal atoms.

(Manufacture of catalyst)
In the production of the catalyst of the present invention, first, rhodium, iridium, platinum, ruthenium, tantalum, rhenium, palladium, lanthanum, cerium, samarium, ytterbium, lutetium, zirconium, hafnium, niobium, molybdenum, tungsten, cobalt, nickel, copper And at least two metal compounds (A) selected from the group consisting of gold and
A metal oxide (B1) or metal carbonyl compound (B2) containing a metal of Group 5, 6 or 7 of the periodic table;
However, the mixing form is not particularly limited (at this time, a mixture is formed).

  The reduction treatment of the mixture 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.

As a preferred embodiment of the catalyst of the present invention,
At least two selected from the group consisting of rhodium, iridium, platinum, ruthenium, tantalum, rhenium, palladium, lanthanum, cerium, samarium, ytterbium, lutetium, zirconium, hafnium, niobium, molybdenum, tungsten, cobalt, nickel, copper and gold Noble metal compound (A) of
A metal oxide (B1) or metal carbonyl compound (B2) containing a metal of Group 5, 6 or 7 of the periodic table;
A carrier;
If necessary, with polyvalent inorganic acid salt,
Are mixed and reduced.

  The catalyst of the present invention may be isolated once by, for example, filtration and washing, or may be used in the production of an alcohol compound as it is in a suspension state.

  The catalyst obtained by the above method can be used as a catalyst for producing an alcohol compound from a carboxylic acid compound. Next, a preferred embodiment of a method for producing an alcohol compound using the above-described catalyst will be described.

(Production of alcohol compounds)
The reaction of the present invention is to produce a corresponding alcohol compound by bringing a carboxylic acid compound into contact with the catalyst in the presence of a hydrogen source.

  The carboxylic acid compound is a compound having at least one carboxyl group, but the number of carboxyl groups is not particularly limited. Moreover, the said compound may have substituents, such as a hydroxyl group, an acyl group, an alkoxyl group, a halogen group, and a multiple bond, for example.

Specific examples of such compounds include the following monocarboxylic acids and polycarboxylic acids (compounds having a plurality of carboxyl groups).
Examples of monocarboxylic acids include acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, dodecanoic acid, tetradecane Acid, pentadecanoic acid, hexadecanoic acid, heptadecanoic acid, octadecanoic acid, nonadecanoic acid, eicosanoic acid, acrylic acid, propiolic acid, methacrylic acid, crotonic acid, isocrotonic acid, oleic acid, 9-hexadecenoic acid, 11-octadecenoic acid, linoleic acid , Cyclopropanecarboxylic acid, cyclobutanecarboxylic acid, cyclopentanecarboxylic acid, cyclohexanecarboxylic acid, tetrahydrofuran-2-carboxylic acid,
Examples of the polycarboxylic acid include oxalic acid, fumaric acid, maleic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, speric acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, itacone Acid aconitic acid, furandicarboxylic acid, malic acid, citric acid, glucaric acid, tartaric acid, tartronic acid, citramalic acid As aromatic carboxylic acids, benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, salicylic acid, 3-hydroxybenzoic acid 4-hydroxybenzoic acid, 2-furancarboxylic acid, gallic acid, furandicarboxylic acid, toluic acid (including positional isomer), xylyl acid (including positional isomer), α-toluic acid, cinnamic acid,
Other carboxylic acids include glycolic acid, lactic acid, 3-hydroxypropionic acid, glyceric acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, leucine acid, mevalonic acid, bantoic acid, ricinoleic acid, ricinaleic acid , Cerebronic acid, pyruvic acid, oxaloacetic acid, α-ketoglutaric acid, acetoacetic acid, oxaloacetic acid, acetone dicarboxylic acid, levulinic acid,
Etc. are used. These carboxylic acids may be a plurality of mixtures.

  The amount of the catalyst used in the reaction in the present embodiment is preferably 0.0005 to 0.1 mol, more preferably 0 with respect to 1 mol of the carboxylic acid, in terms of metal atoms of the total amount of the metal compound (A). 0.001 to 0.075 mol. By using this amount, an alcohol compound can be obtained with high yield and high selectivity while obtaining a sufficient reaction rate. In addition, a catalyst may prepare and use several types of catalysts separately.

  The hydrogen source used in the reaction in the present embodiment is not particularly limited as long as it is a compound that provides hydrogen. For example, it is diluted with a reducing gas such as hydrogen gas or ammonia gas (inert gas such as nitrogen, helium, or argon). Water; alcohols such as methanol, ethanol and isopropyl alcohol; organic acids such as formic acid, acetic acid and chloroformic acid; inorganic acids such as hydrochloric acid and sulfuric acid, preferably reducing gas, more preferably Hydrogen gas is used.

  The amount of the hydrogen source is preferably 5 to 200 mol, more preferably 10 to 160 mol, per 1 mol of the carboxylic acid compound. By using this amount, an alcohol compound can be obtained with high yield and high selectivity while obtaining a sufficient reaction rate. In addition, a catalyst may prepare and use several types of catalysts separately.

  The reaction in this embodiment is preferably performed in a solvent. The solvent used is not particularly limited as long as it does not inhibit the reaction. For example, water; alcohols such as methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, t-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, 1,2- Ethers such as dimethoxymethane, 1,2-diethoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, 1,4-dioxane; methylene chloride, dichloroethane, chlorocyclohexane, etc. Halogenated hydrocarbons. Of these, water, hydrocarbons, and ethers are preferable, and water, ethers, more preferably water, 1,2-diethoxymethane, 1,4-dioxane, and diethylene glycol dimethyl ether are more preferable. In addition, you may use these solvents individually or in mixture of 2 or more types.

  The amount of the solvent used is preferably 0.05 to 100 g, more preferably 0.1 to 20 g, relative to 1 g of the carboxylic acid compound. By setting it as this usage-amount, stirring can be performed rapidly and reaction can be advanced smoothly.

  As the reaction form in the present embodiment, either a batch type or a continuous type can be selected depending on the form of the catalyst. Depending on the nature of the catalyst, it 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 reaction in the present embodiment is performed by, for example, a method of mixing a carboxylic acid compound, a catalyst, and a solvent and reacting with stirring in the presence of a hydrogen source. The reaction temperature at that time is preferably 25 to 300 ° C., more preferably 50 to 200 ° C., and the reaction pressure is preferably a normal pressure to 20 MPa, more preferably 0.2 to 15 MPa as a hydrogen partial pressure. . By setting the reaction temperature and the reaction pressure, it is possible to obtain an alcohol compound as a target product with high yield and high selectivity at a high reaction rate while suppressing the formation of by-products. In order to accelerate the reaction, an acid such as hydrochloric acid, sulfuric acid, phosphoric acid or acetic acid or a base such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen carbonate, potassium carbonate or potassium hydrogen carbonate is used as necessary. May be present. The amount of such an acid or base is preferably 0.001 to 0.1 mol, more preferably 0.005 to 0.05 mol, per 1 mol of the carboxylic acid compound.

The target alcohol compound is obtained by the reaction in the present embodiment. After completion of the reaction, the alcohol compound can be isolated and purified from the resulting 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, although an Example is given and this invention is demonstrated concretely, this invention is not restrict | limited to these Examples. In addition, the abbreviation of the catalyst of this invention consists of the following structures.
(First metal of metal compound (A))-(Second metal of metal compound (A))-(Metal of Group 5 to Group 7 of the periodic table) / (Support) catalyst

Example 1 (Production of catalyst)
In an autoclave equipped with a 50 ml glass inner tube, 13.3 mg rhodium trichloride trihydrate (0.050 mmol rhodium), 16.9 mg platinum tetrachloride (0.050 mmol platinum), tripotassium phosphate 24.8 mg (0.12 mmol) and 3 ml of water were added, and the mixture was heated and stirred at 100 ° C. for 60 minutes. To the solution once cooled to room temperature, 18.2 mg of dirhenium heptoxide (0.075 mmol of rhenium) and 200 mg of activated carbon (AC, manufactured by Calgon Carbon Japan, MH4-8A) were added and stirred at room temperature for 5 minutes. Next, the mixture was pressurized to 8 MPa in a hydrogen atmosphere at room temperature, and heated and stirred at 120 ° C. for 1 hour to reduce the mixture. The obtained solution was cooled to room temperature, the aqueous layer was removed by centrifugation, and a catalyst in which rhodium was supported by 2.1% by mass, platinum by 4.3% by mass, and rhenium by 6.1% by mass was retained as activated carbon ( Hereinafter, “Rh—Pt—Re / AC catalyst (1)” may be obtained.

Example 2 (Production of catalyst)
Rhodium trichloride trihydrate (13.3 mg, rhodium is 0.050 mmol), platinum tetrachloride (16.9 mg, platinum is 0.050 mmol), tripotassium phosphate (24.8 mg, 0.12 mmol) and water (3 ml) are mixed. A homogeneous aqueous solution was prepared. The prepared aqueous solution was added to activated carbon (AC: Calgon Carbon Japan, trade name: MH4-8A) and concentrated under reduced pressure at 80 ° C., and the solvent was distilled off. Subsequently, an aqueous solution in which 18.2 mg of dirhenium heptoxide (0.075 mmol of rhenium) was dissolved in 2 ml of water was added and concentrated again under reduced pressure at 80 ° C., and the solvent was distilled off. The obtained residue was further dried under reduced pressure at 60 ° C. for 8 hours, and a solid in which activated carbon supported 2.2% by mass of rhodium, 4.1% by mass of platinum, and 5.5% by mass of rhenium (hereinafter referred to as “Rh”). 260 mg (sometimes referred to as -Pt-Re / AC (2) ").

Example 3 (Production of catalyst)
In Example 2, rhodium was 1.8% by mass in silica in the same manner as in Example 2 except that the activated carbon was changed to silica (SiO ₂ ; manufactured by Fuji Silysia Chemical Ltd., trade name: CARiACT G-6). 260 mg of a solid (hereinafter also referred to as “Rh—Pt—Re / SiO ₂ (1)”) on which 3.8% by mass of platinum and 4.9% by mass of rhenium were supported was obtained.

Example 4 (Production of catalyst)
In Example 1, rhodium was added to the activated carbon in the same manner as in Example 1 except that rhenium heptoxide was changed to sodium tetraoxomolybdate (VI) sodium (0.075 mmol of molybdenum) and the amount of activated carbon used was changed to 450 mg. A catalyst carrying 1.2% by mass, 2.2% by mass of platinum, and 1.6% by mass of molybdenum (hereinafter sometimes referred to as “Rh—Pt—Mo / AC catalyst (1)”) was obtained. .

Example 5 (Production of catalyst)
In Example 2, except that the dirhenium heptoxide was changed to sodium tetraoxomolybdate (VI) sodium (molybdenum was 0.075 mmol), rhodium was 1.9% by mass in activated carbon in the same manner as in Example 2, platinum Was 3.8% by mass and molybdenum was supported by 2.7% by mass (hereinafter, also referred to as “Rh—Pt—Mo / AC catalyst (2)”).

Example 6 (Production of catalyst)
In Example 1, except that platinum tetrachloride was changed to 9.0 mg (0.050 mmol) of palladium dichloride, rhodium was 2.1% by mass and palladium was 2.1% by mass in the same manner as in Example 1. Thus, a catalyst carrying 6.1% by mass of rhenium (hereinafter sometimes referred to as “Rh—Pd—Re / AC catalyst (1)”) was obtained.

Example 7 (Production of catalyst)
In Example 1, except that the platinum tetrachloride was changed to ruthenium trichloride n-hydrate (0.050 mmol), the activated carbon was 2.0% by mass of ruthenium and the rhodium was 2.1% in the same manner as in Example 1. A catalyst (hereinafter, also referred to as “Ru—Rh—Re / AC catalyst (1)”) on which mass% and rhenium were supported by 6.1 mass% was obtained.

Example 8 (Production of catalyst)
In Example 1, rhodium trichloride trihydrate was converted to iridium trichloride n hydrate (0.050 mmol), and the activated carbon was changed to activated carbon in the same manner as in Example 1 except that the amount of activated carbon used was changed to 450 mg. A catalyst carrying 2.2% by mass of iridium, 2.2% by mass of platinum and 3.1% by mass of rhenium (hereinafter sometimes referred to as “Ir-Pt-Re / AC catalyst (1)”) Obtained.

Example 9 (Production of catalyst)
In Example 1, rhodium trichloride trihydrate was converted to iridium trichloride n hydrate (0.050 mmol), dirhenium heptoxide was added to sodium tetraoxomolybdate (VI) sodium (0.075 mmol), Except that the amount of the activated carbon used was changed to 450 mg, a catalyst having 2.2% by mass of iridium, 2.2% by mass of platinum and 1.5% by mass of molybdenum supported on the activated carbon in the same manner as in Example 1 And “Ir—Pt—Mo / AC catalyst (1)”).

Example 10 (Production of catalyst)
In an autoclave equipped with a 50 ml glass inner tube, ruthenium chloride trihydrate 6.5 mg (ruthenium 0.025 mmol), rhodium trichloride trihydrate 6.6 mg (rhodium 0.025 mmol), 13.3 mg (0.063 mmol) of tripotassium phosphate and 4 ml of water were added, and the mixture was heated and stirred at 100 ° C. for 60 minutes. To this solution, which was once cooled to room temperature, 9.1 mg of dirhenium heptoxide (rhenium was 0.038 mmol) and 96.1 mg of activated carbon (AC, MH4-8A manufactured by Calgon Carbon Japan) were added and stirred at room temperature for 5 minutes. . Next, the mixture was pressurized to 8 MPa in a hydrogen atmosphere at room temperature, and heated and stirred at 120 ° C. for 1 hour to reduce the mixture. The resulting solution was cooled to room temperature, the aqueous layer was removed by centrifugation, and a catalyst in which rhodium 2.7% by mass, ruthenium 2.6% by mass, and rhenium 7.3% by mass were supported on activated carbon as a residue ( Hereinafter, “Ru—Rh—Re / AC catalyst (2)” may be obtained.

Example 11 (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 “Ru—Ir—” in which 2.1% by mass of ruthenium, 4.0% by mass of iridium and 3.9% by mass of rhenium were supported on silica. 588 mg (sometimes referred to as “Re / SiO ₂ catalyst (1)”) was obtained.

Example 12 (Production of catalyst)
In Example 1, rhodium is 2.2% by mass and platinum is 4.1% by mass in the same manner as in Example 1 except that rhenium heptoxide is changed to dodecacarbonyl dirhenium (rhenium is 0.075 mmol). Thus, a catalyst carrying 5.5% by mass of rhenium (hereinafter sometimes referred to as “Rh—Pt—Re / AC catalyst (3)”) was obtained.

Example 13 (Production of catalyst)
Example 1 Example 1 except that rhodium trichloride trihydrate was changed to ruthenium trichloride n hydrate (0.050 mmol) and platinum tetrachloride was changed to tantalum pentachloride (0.050 mmol). In the same manner as above, a catalyst (hereinafter referred to as “Ta-Ru-Re / AC catalyst (1)”) in which activated carbon is supported by 3.9% by mass of tantalum, 2.2% by mass of ruthenium, and 6.1% by mass of rhenium is supported. Sometimes called).

Example 14 (Production of catalyst)
Example 1 Example 1 except that rhodium trichloride trihydrate was changed to ruthenium trichloride n hydrate (0.050 mmol) and platinum tetrachloride was changed to rhenium pentachloride (0.050 mmol). In the same manner as described above, a catalyst (hereinafter referred to as “Re-Ru-Re / AC catalyst (1)”) in which activated carbon is supported by 4.0% by mass of rhenium, 2.2% by mass of ruthenium, and 6.1% by mass of rhenium. Sometimes called).

Example 15 (Production of catalyst)
In Example 1, except that rhodium trichloride trihydrate was changed to ruthenium trichloride n hydrate (0.050 mmol) and platinum tetrachloride was changed to tetrachloroauric acid (0.050 mmol). In the same manner as in No. 1, a catalyst having 2.2% by mass of ruthenium, 4.3% by mass of gold, and 6.1% by mass of rhenium supported on activated carbon (hereinafter referred to as “Ru—Au—Re / AC catalyst (1)”). May also be called).

Example 16 (Production of catalyst)
Example 1 Example 1 except that rhodium trichloride trihydrate was changed to ruthenium trichloride n hydrate (0.050 mmol) and platinum tetrachloride was changed to palladium dichloride (0.050 mmol). In the same manner as described above, a catalyst in which 2.2% by mass of ruthenium, 2.2% by mass of palladium and 6.1% by mass of rhenium are supported on activated carbon (hereinafter referred to as “Ru—Pd—Re / AC catalyst (1)”). Sometimes called).

Example 17 (Production of catalyst)
Example 1 except that rhodium trichloride trihydrate was changed to ruthenium trichloride n hydrate (0.050 mmol) and platinum tetrachloride was changed to zirconium tetrachloride (0.050 mmol). In the same manner as above, a catalyst in which 2.0% by mass of zirconium, 2.2% by mass of ruthenium, and 6.1% by mass of rhenium are supported on activated carbon (hereinafter referred to as “Zr-Ru—Re / AC catalyst (1)”). Sometimes called).

Example 18 (Production of catalyst)
Example 1 Example 1 except that rhodium trichloride trihydrate was changed to ruthenium trichloride n hydrate (0.050 mmol) and platinum tetrachloride was changed to hafnium tetrachloride (0.050 mmol). In the same manner as above, a catalyst (hereinafter referred to as "Hf-Ru-Re / AC catalyst (1)") in which activated carbon is supported with 3.9% by mass of hafnium, 2.2% by mass of ruthenium, and 6.1% by mass of rhenium. Sometimes called).

Example 19 (Production of catalyst)
In Example 1, except that the support was changed from activated carbon to graphene (manufactured by STREM), rhodium was 2.1% by mass, platinum was 4.3% by mass, rhenium was 6.1% by mass in the same manner as Example 1. A mass% supported catalyst (hereinafter sometimes referred to as “Rh—Pt—Re / graphene catalyst (1)”) was obtained.

Example 20 (Production of catalyst)
In Example 1, rhodium trichloride trihydrate is converted to ruthenium trichloride n hydrate (0.050 mmol), platinum tetrachloride is converted to palladium dichloride (0.050 mmol), and the carrier is graphene (made by STREM). Except for the above, the catalyst in which ruthenium was supported by 2.2% by mass, palladium by 2.2% by mass, and rhenium by 6.1% by mass was supported in the same manner as in Example 1 (hereinafter referred to as “Ru—Pd”). -Re / graphene catalyst (1) ”).

Example 1A (Synthesis of 1,4-butanediol from succinic acid)

In an autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 1 (Rh-Pt-Re / AC catalyst (1)), succinic acid 0.600 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of aqueous sodium hydroxide solution was added, and the volume was increased with water so that the succinic acid content was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the reaction was carried out at 120 ° C. for 12 hours while stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 69.8%. The yield was 69.8%, the yield of 1-butanol was 9.7%, the selectivity was 9.7%, the yield of γ-butyrolactone was 2.1%, and the selectivity was 2.1%. It was.

Example 1B (Synthesis of 1,6-hexanediol from adipic acid)

To the autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 1 (Rh—Pt—Re / AC catalyst (1)) and 1.460 g (10.0 mmol) of adipic acid were added, and adipic acid was added. The volume was adjusted to 15% with water. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 120 ° C. for 30 hours with stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
The obtained filtrate was analyzed by gas chromatography. The conversion of adipic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,6-hexanediol was 93.6%. The rate was 93.6%, the yield of 1-hexanol was 2.5%, and the selectivity was 2.5%.

Reference Example 1C (Synthesis of 1,4-pentanediol from levulinic acid)

In an autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 1 (Rh—Pt—Re / AC catalyst (1)), levulinic acid 1.75 g (15.0 mmol), 1.0 mol / l 0.30 g (0.30 mmol) of an aqueous sodium hydroxide solution was added, and the volume was increased with water so that levulinic acid was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 120 ° C. for 15 hours with stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
The obtained filtrate was analyzed by gas chromatography. The conversion of levulinic acid was 100%, the yield of 1,4-pentanediol was 63.6%, the selectivity was 63.6%, and γ- The yield of valerolactone is 1.7%, the selectivity is 1.7%, the yield of 2-methyltetrahydrofuran is 4.0%, the selectivity is 4.0%, and the yield of 2-pentanol is The selectivity was 4.3% and the selectivity was 4.3%.

Reference Example 1D (Synthesis of 1-hexanol from hexanoic acid)

In an autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 1 (Rh-Pt-Re / AC catalyst (1)), 1.16 g (10.0 mmol) of hexanoic acid, 1.0 mol / l 0.20 g (0.20 mmol) of an aqueous sodium hydroxide solution was added, and diluted with diethylene glycol dimethyl ether so that hexanoic acid was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 180 ° C. for 9 hours while stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of hexanoic acid was 97.3%, the yield of 1-hexanol was 58.6%, the selectivity was 57.0%, and hexyl hexanoate. The yield was 2.3%, and the selectivity was 2.2%.

Example 2A (Synthesis of 1,4-butanediol from succinic acid)

To an autoclave equipped with a 50 ml glass inner tube, 120 mg of the solid obtained in Example 2 (Rh-Pt-Re / AC catalyst (2)) and 2 ml of water were added, and the pressure was increased to 8 MPa with hydrogen gas at room temperature. The solid was reduced by heating and stirring at 120 ° C. for 1 hour. The resulting solution was cooled to room temperature and the aqueous layer was removed by centrifugation. To the obtained residue, 1.50 g (12.7 mmol) of succinic acid and 0.25 g (0.25 mmol) of a 1.0 mol / l aqueous sodium hydroxide solution were added, and the volume of the succinic acid was increased to 15%. . The pressure was increased to 8 MPa with hydrogen gas, and the mixture was reacted at 120 ° C. for 36 hours with stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 82.3%, the same selection. The yield was 82.3%, the yield of 1-butanol was 11.5%, the selectivity was 11.5%, the yield of γ-butyrolactone was 0.16%, and the selectivity was 0.16%. It was.

Example 3A (Synthesis of 1,4-butanediol from succinic acid)

To an autoclave equipped with a 50 ml glass inner tube, 120 mg of the solid (Rh—Pt—Re / SiO ₂ (1)) obtained in Example 3 and 2 ml of water were added and heated to 8 MPa with hydrogen gas at room temperature. The solid was reduced by heating and stirring at 120 ° C. for 1 hour. The resulting solution was cooled to room temperature and the aqueous layer was removed by centrifugation. To the obtained residue, 0.35 g (3.0 mmol) of succinic acid and 0.10 g (0.10 mmol) of a 1.0 mol / l aqueous sodium hydroxide solution were added, and the volume was adjusted to 15% with succinic acid. . The pressure was increased to 8 MPa with hydrogen gas, and the reaction was performed at 120 ° C. for 18 hours with stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 82.9%. The yield was 12.9%, the yield of 1-butanol was 15.5%, the selectivity was 15.5%, the yield of γ-butyrolactone was 3.9%, and the selectivity was 3.9%. It was.

Reference Example 3B (Synthesis of 1,3-propanediol from 3-hydroxypropionic acid)

To an autoclave equipped with a 50 ml glass inner tube, 128 mg of the solid (Rh—Pt—Re / SiO ₂ (1)) obtained in Example 3 and 2 ml of water were added, and hydrogen gas was added up to 8 MPa at room temperature. The solid was reduced by heating and stirring at 120 ° C. for 1 hour. The resulting solution was cooled to room temperature and the aqueous layer was removed by centrifugation. To the obtained residue, 1.50 g (5.0 mmol) of a 30% aqueous solution of 3-hydroxypropionic acid was added, and the volume was increased with water so that 3-hydroxypropionic acid became 10%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the reaction was carried out while stirring at 120 ° C. for 4 hours and further at 140 ° C. for 14 hours. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of 3-hydroxypropionic acid was 77.6%, the yield of 1,3-propanediol was 65.1%, and the selectivity was 83. The yield of 9%, 1-propanol was 12.2%, and the selectivity was 15.7%.

Example 4A (Synthesis of 1,4-butanediol from succinic acid)

In an autoclave equipped with a 50 ml glass inner tube, the residue (Rh—Pt—Mo / AC catalyst (1)) obtained in Example 4, succinic acid 0.600 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of NaOH aqueous solution was added, and the volume was increased with water so that succinic acid was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 120 ° C. for 18 hours while stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 70.1%. The yield was 70.1%, the yield of 1-butanol was 9.6%, the selectivity was 9.6%, the yield of γ-butyrolactone was 2.8%, and the selectivity was 2.8%. It was.

Example 5A (Synthesis of 1,4-butanediol from succinic acid)

To an autoclave equipped with a 50 ml glass inner tube, 120 mg of the solid (Rh—Pt—Mo / AC (2)) obtained in Example 5 and 2 ml of water were added, and the pressure was increased to 8 MPa with hydrogen gas at room temperature. The solid was reduced by heating and stirring at 120 ° C. for 1 hour. The resulting solution was cooled to room temperature and the aqueous layer was removed by centrifugation. To the obtained residue, 0.35 g (3.0 mmol) of succinic acid and 0.10 g (0.10 mmol) of a 1.0 mol / l aqueous sodium hydroxide solution were added, and the volume was adjusted to 15% with succinic acid. . The pressure was increased to 8 MPa with hydrogen gas, and the reaction was performed at 120 ° C. for 18 hours with stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 74.9%. The yield was 74.9%, the yield of 1-butanol was 4.0%, the selectivity was 4.0, the yield of γ-butyrolactone was 3.7%, and the selectivity was 3.7%. .

Example 6A (Synthesis of 1,4-butanediol from succinic acid)

In an autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 6 (Rh—Pd—Re / AC catalyst (1)), succinic acid 0.600 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of aqueous sodium hydroxide solution was added, and the volume was increased with water so that the succinic acid content was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the reaction was carried out at 120 ° C. for 12 hours while stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 61.7%. The yield was 61.7%, the yield of 1-butanol was 13.0%, the selectivity was 13.0%, the yield of γ-butyrolactone was 2.3%, and the selectivity was 2.3%. It was. Met.

Example 7A (Synthesis of 1,4-butanediol from succinic acid)

In an autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 7 (Ru-Rh-Re / AC catalyst (1)), succinic acid 0.600 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of aqueous sodium hydroxide solution was added, and the volume was increased with water so that the succinic acid content was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the reaction was carried out at 120 ° C. for 12 hours while stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 61.0%. The yield was 61.0%, the yield of 1-butanol was 9.3%, the selectivity was 9.3%, the yield of γ-butyrolactone was 2.1%, and the selectivity was 2.1%. It was.

Example 8A (Synthesis of 1,4-butanediol from succinic acid)

In an autoclave equipped with a 50 ml glass inner tube, the residue (Ir-Pt-Re / AC catalyst (1)) obtained in Example 8, succinic acid 1.20 g (10 mmol), 1.0 mol / l water Sodium oxide aqueous solution 0.20g (0.20mmol) was added, and it was made up with water so that succinic acid might be 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 100 ° C. for 60 hours with stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 57.5%. The yield was 57.5%, the yield of 1-butanol was 23.8%, the selectivity was 23.8%, the yield of γ-butyrolactone was 1.9%, and the selectivity was 1.9%. It was.

Example 9A (Synthesis of 1,4-butanediol from succinic acid)

In an autoclave equipped with a 50 ml glass inner tube, the residue (Ir-Pt-Mo / AC catalyst (1)) obtained in Example 9, succinic acid 1.20 g (10 mmol), 1.0 mol / l water 0.20 g (0.20 mmol) of an aqueous oxidation solution was added, and the volume was increased with water so that succinic acid was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 100 ° C. for 60 hours with stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 60.8%. The yield was 60.8%, the yield of 1-butanol was 10.8%, the selectivity was 10.8%, the yield of γ-butyrolactone was 6.9%, and the selectivity was 6.9%. It was.

Reference Example 10A (Synthesis of 1,3-propanediol from 3-hydroxypropionic acid)

In an autoclave equipped with a 50-ml glass inner tube, the residue obtained in Example 10 (Ru—Rh—Re / AC catalyst (2)), 1.50 g of a 30% aqueous solution of 3-hydroxypropionic acid (5. 0 mmol) was added, and the volume was made up with water so that 3-hydroxypropionic acid was 10%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the reaction was carried out while stirring at 120 ° C. for 4 hours and further at 140 ° C. for 14 hours. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of 3-hydroxypropionic acid was 88.0%, the yield of 1,3-propanediol was 76.3%, and the selectivity was 86. The yield of 7%, 1-propanol was 8.8%, and the selectivity was 10.0%.

Reference Example 10B (Synthesis of 1,2-propanediol from lactic acid)

In an autoclave equipped with a 50 ml glass inner tube, the residue (Rh-Ru-Re / AC catalyst (2)) obtained in the same manner as in Example 10 and 0.50 g of a 90.3% aqueous solution of lactic acid ( 5.0 mmol) was added, and the volume was increased with water so that the amount of lactic acid was 10%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the reaction was carried out with stirring at 100 ° C. for 22 hours. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of lactic acid was 97.5%, the yield of 1,2-propanediol was 77.4%, the selectivity was 79.4%, The yield of -propanol was 4.6%, the selectivity was 4.7%, the yield of 2-propanol was 1.5%, and the selectivity was 1.5%.

Reference Example 11A (Synthesis of 1,3-propanediol from 3-hydroxypropionic acid)

In an autoclave equipped with a 50 ml glass inner tube, 60 mg of the residue obtained in Example 11 (Ru—Ir—Re / SiO ₂ catalyst (1)), 1.50 g of a 30% aqueous solution of 3-hydroxypropionic acid ( 5.0 mmol) was added, and the volume was increased with water so that 3-hydroxypropionic acid was 10%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the reaction was carried out with stirring at 100 ° C. for 4 hours and further at 140 ° C. for 11 hours. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of 3-hydroxypropionic acid was 87.0%, the yield of 1,3-propanediol was 65.8%, and the selectivity was 75. The yield of 6%, 1-propanol was 18.9%, and the selectivity was 2.2%.

Reference Example 11B (Synthesis of 1,2-propanediol from lactic acid)

In an autoclave equipped with a 50 ml glass inner tube, 60 mg of the residue (Ru—Ir—Re / SiO ₂ catalyst (1)) obtained in Example 11 and 0.50 g of a 90.3% aqueous solution of lactic acid (5. 0 mmol) was added, and the volume of the lactic acid was increased to 10% with water. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the reaction was carried out with stirring at 100 ° C. for 15 hours. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of lactic acid was 95.2%, the yield of 1,2-propanediol was 85.3%, the selectivity was 89.6%, 1 The yield of -propanol was 5.1%, the selectivity was 5.3%, the yield of 2-propanol was 2.0%, and the selectivity was 2.1%.

Reference Example 11C (Synthesis of 1-propanol from propionic acid)

To an autoclave equipped with a 50 ml glass inner tube, 60 mg of the residue (Ru—Ir—Re / SiO ₂ catalyst (1)) obtained in Example 11 and 0.375 g (5.0 mmol) of propionic acid were added, The volume was increased with water so that the propionic acid was 10%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the reaction was carried out with stirring at 100 ° C. for 17 hours. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of propionic acid was 98.9%, the yield of 1-propanol was 93.2%, and the selectivity was 94.2%.

Example 12A (Synthesis of 1,4-butanediol from succinic acid)

In an autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 12 (Rh—Pt—Re / AC catalyst (3)), succinic acid 0.60 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of aqueous sodium hydroxide solution was added, and the volume was increased with water so that the succinic acid content was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 120 ° C. for 36 hours with stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 64.6%. The yield was 64.6%, the yield of 1-butanol was 11.6%, the selectivity was 11.6%, the yield of γ-butyrolactone was 5.9%, and the selectivity was 5.9%. It was.

Example 13A (Synthesis of 1,4-butanediol from succinic acid)

In an autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 13 (Ta-Ru-Re / AC catalyst (1)), succinic acid 0.60 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of aqueous sodium hydroxide solution was added, and the volume was increased with water so that the succinic acid content was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 120 ° C. for 36 hours with stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 87.2%, the same selection. The yield was 87.2%, the yield of 1-butanol was 7.8%, the selectivity was 7.8%, the yield of γ-butyrolactone was 4.7%, and the selectivity was 4.7%. It was.

Example 14A (Synthesis of 1,4-butanediol from succinic acid)

In an autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 13 (Re-Ru-Re / AC catalyst (1)), succinic acid 0.60 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of aqueous sodium hydroxide solution was added, and the volume was increased with water so that the succinic acid content was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 120 ° C. for 18 hours while stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 80.9%. The yield was 80.9%, the yield of 1-butanol was 4.9%, the selectivity was 4.9%, the yield of γ-butyrolactone was 2.2%, and the selectivity was 2.2%. It was.

Example 15A (Synthesis of 1,4-butanediol from succinic acid)

In an autoclave equipped with a 50 ml glass inner tube, the residue (Ru—Au—Re / AC catalyst (1)) obtained in Example 14, succinic acid 0.60 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of aqueous sodium hydroxide solution was added, and the volume was increased with water so that the succinic acid content was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 150 ° C. for 12 hours with stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 68.1%. The yield was 68.1%, the yield of 1-butanol was 6.4%, the selectivity was 6.4%, the yield of γ-butyrolactone was 3.0%, and the selectivity was 3.0%. It was.

Example 16A (Synthesis of 1,4-butanediol from succinic acid)

Into an autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 15 (Ru—Pd—Re / AC catalyst (1)), succinic acid 0.60 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of aqueous sodium hydroxide solution was added, and the volume was increased with water so that the succinic acid content was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 120 ° C. for 18 hours while stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 62.1%. The yield was 62.1%, the yield of 1-butanol was 11.0%, the selectivity was 11.0%, the yield of γ-butyrolactone was 0.25%, and the selectivity was 0.25%. It was.

Example 17A (Synthesis of 1,4-butanediol from succinic acid)

In an autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 17 (Zr-Ru-Re / AC catalyst (1)), succinic acid 0.60 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of aqueous sodium hydroxide solution was added, and the volume was increased with water so that the succinic acid content was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 120 ° C. for 18 hours while stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 90.4%. The rate was 90.4%, the yield of 1-butanol was 9.1%, the selectivity was 9.1%, and γ-butyrolactone was not observed.

Example 18A (Synthesis of 1,4-butanediol from succinic acid)

In an autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 18 (Hf-Ru-Re / AC catalyst (1)), succinic acid 0.60 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of aqueous sodium hydroxide solution was added, and the volume was increased with water so that the succinic acid content was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the reaction was carried out at 120 ° C. for 12 hours while stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 70.1%. The yield was 70.1%, the yield of 1-butanol was 8.5%, the selectivity was 8.5%, the yield of γ-butyrolactone was 5.0%, and the selectivity was 5.0%. It was.
Example 19A (Synthesis of 1,4-butanediol from succinic acid)

In an autoclave equipped with a 50 ml glass inner tube, the residue obtained in Example 19 (Rh—Pt—Re / graphene catalyst (1)), succinic acid 0.60 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of aqueous sodium hydroxide solution was added, and the volume was increased with water so that the succinic acid content was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 120 ° C. for 6 hours with stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 75.2%. The yield was 75.2%, the yield of 1-butanol was 12.4%, the selectivity was 12.4%, the yield of γ-butyrolactone was 5.5%, and the selectivity was 5.5%. It was.
Example 20A (Synthesis of 1,4-butanediol from succinic acid)

In an autoclave equipped with a 50 ml glass inner tube, the residue (Ru—Pd—Re / graphene catalyst (1)) obtained in Example 20, succinic acid 0.60 g (5.0 mmol), 1.0 mol / l 0.10 g (0.10 mmol) of aqueous sodium hydroxide solution was added, and the volume was increased with water so that the succinic acid content was 15%. The pressure was increased to 8 MPa with hydrogen gas at room temperature, and the mixture was reacted at 120 ° C. for 15 hours with stirring. After completion of the reaction, the resulting reaction solution was cooled to room temperature and then filtered with a syringe equipped with a membrane filter (0.45 μm).
When the obtained filtrate was analyzed by gas chromatography, the conversion of succinic acid was 100% (confirmed by esterification with trimethylsilyldiazomethane), and the yield of 1,4-butanediol was 80.8%. The yield was 10.8%, the selectivity was 11.0%, the yield of γ-butyrolactone was 2.4%, and the selectivity was 2.4%. It was.

From the above results,
(1) selected from the group consisting of rhodium, iridium, platinum, ruthenium, tantalum, rhenium, palladium, lanthanum, cerium, samarium, ytterbium, lutetium, zirconium, hafnium, niobium, molybdenum, tungsten, cobalt, nickel, copper and gold. At least two metal compounds (A)
(2) Metal oxide (B1) or metal carbonyl compound (B2) containing a metal of Group 5, 6 or 7 of the periodic table
The catalyst obtained by mixing and reducing the catalyst (the catalyst of the present invention) can be contacted in the presence of a carboxylic acid compound in the presence of a hydrogen source so that the reaction can be carried out at a high reaction rate with high yield and high selectivity. It was found to give an alcohol compound.

  According to the present invention, it is possible to provide a catalyst capable of reducing a carboxylic acid compound to give a corresponding alcohol compound with high reaction rate and high yield. If the carboxylic acid compound is a dicarboxylic acid, a corresponding diol compound can be produced. The obtained diol compound is useful as, for example, polymer raw materials such as polyester, polycarbonate, and polyurethane, resin additives, medical and agrochemical intermediate raw materials, various solvents, and the like.

Claims (5)

A polycarboxylic acid compound in water in the presence of hydrogen gas;
2 selected from the combination of rhodium and platinum, rhodium and palladium, rhodium and ruthenium, iridium and platinum, iridium and ruthenium, tantalum and ruthenium, rhenium and ruthenium, ruthenium and gold, ruthenium and palladium, zirconium and ruthenium, hafnium and ruthenium A seed metal compound (A);
Molybdenum or rhenium oxide (B1) or carbonyl compound (B2);
A method for producing an alcohol compound, comprising: bringing a catalyst into contact with a catalyst obtained by performing pressure reduction in a hydrogen atmosphere at room temperature and then heating and reducing the mixture.   The method for producing an alcohol according to claim 1, wherein the polycarboxylic acid compound is succinic acid or adipic acid.   The method for producing an alcohol according to any one of claims 1 to 2, wherein the catalyst is supported on a carrier. The method for producing alcohol according to claim 3 , wherein the carrier is at least one carrier selected from the group consisting of silica, alumina, silica alumina (aluminosilicate), titania, zirconia, activated carbon, graphene, carbon nanotubes, and zeolite. 2 selected from the combination of rhodium and platinum, rhodium and palladium, rhodium and ruthenium, iridium and platinum, iridium and ruthenium, tantalum and ruthenium, rhenium and ruthenium, ruthenium and gold, ruthenium and palladium, zirconium and ruthenium, hafnium and ruthenium A seed metal compound (A);
Molybdenum or rhenium oxide (B1) or carbonyl compound (B2);
A catalyst for producing an alcohol from a polycarboxylic acid compound by hydrogenation with hydrogen gas in water .