JPH11199530A - Production of alcohol compound and carboxylic acid reduction catalyst used therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing an alcohol compound, capable of producing the alcohol compound in a high yield by directly hydrogenating the corresponding carboxylic acid compound under a relatively mild condition. SOLUTION: This method for producing an alcohol compound comprises hydrogenating a carboxylic acid in the presence of a catalyst comprising ruthenium metal and/or its compound and rhenium metal and/or its compound and at least one substance selected from alkali metals, alkaline earth metals and their compounds.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an alcohol compound by hydrogenating and reducing a carboxylic acid compound in the presence of a catalyst, and a catalyst used in the production method. The resulting alcohol compound is a surfactant, a fiber oil agent, a synthetic detergent, a plasticizer, a raw material for a deodorant lubricating oil additive,
It is widely used as a raw material for synthetic chemistry and as a solvent for organic synthetic products. Among alcohol compounds, diol compounds are used, for example, as an alcohol component of polyester-based resins, polyurethane-based resins, and polycarbonate-based resins, and impart excellent performance to the obtained resin, and are also used as synthetic raw materials such as pharmaceutical raw materials. Is a useful compound.

[0002]

2. Description of the Related Art Conventionally, methods for producing alcohol compounds include a method for reducing natural fats and oils or fatty acids, a method for synthesizing petrochemicals as a raw material, and a microbial fermentation method. Among these methods, as a method of producing an aliphatic alcohol from a fatty acid or a fatty acid ester, a method of hydrogenating and reducing using a catalyst such as copper chromium oxide is common. For example, German Offenlegungsschrift No. 1178045 discloses a method for hydrogenating fatty acids using a chromium-copper oxide catalyst, and German Offenlegungsschrift No. 117804.
No. 5 discloses a method of hydrogenating a carboxylic acid compound using an aluminum-chromium-copper-manganese catalyst, and JP-A-60-38333 discloses a method of hydrogenating a fatty acid ester using a copper-chromium catalyst. A method is described. However, these production methods use a catalyst containing harmful chromium, and thus have a very serious problem in terms of environmental protection.

[0003] Various methods have also been proposed for hydrogenating a carboxylic acid ester using a catalyst other than a copper-chromium catalyst. For example, JP-A-58-216131 discloses a method in which a carboxylic acid ester is hydrogenolyzed using a rhodium catalyst modified with tin, germanium or lead, and JP-A-61-56139 discloses nickel and tin,
A method for hydrocracking carboxylic esters in the presence of a catalyst containing germanium or lead is described. However, these methods cannot provide an alcohol compound in a satisfactory yield due to insufficient catalytic activity. Furthermore, in these methods, since a carboxylic acid ester is used as a raw material, a step of once esterifying the carboxylic acid is required, which is disadvantageous for industrial use.

[0004] Various methods have also been proposed for producing a polyol compound from a polycarboxylic acid compound, which is more difficult to hydrogenate than a monocarboxylic acid. For example, JP-A-6-228087 and JP-A-6-22802
No. 8 describes a method for hydrogenating and reducing dicarboxylic acid diesters using a ruthenium-tin supported catalyst. However, such a method has the same industrial disadvantages as described above because the diester compound is used as a raw material, and in addition to being bifunctional, performs the reaction under high temperature conditions. However, there is a disadvantage that the ester exchange reaction proceeds during the reaction to produce an ester compound as a by-product and the yield of diol is low.

Under these circumstances, there is a demand for a method capable of producing a polyol compound with high efficiency by directly hydrogenating and reducing a carboxylic acid compound, particularly a polycarboxylic acid compound, and various methods have been proposed. For example, as a method for producing a diol compound by hydrogenating and reducing a dicarboxylic acid compound, hydrogenation and reduction of glutaric acid with a rhenium heptaoxide catalyst is known [H. Smith Broadbent et al.
J. Org. Chem. , 24, 1847 (195
9)]. However, in order to obtain 1,5-pentanediol in good yield using this catalyst, it is necessary to carry out the reaction in a water solvent at a high temperature of 250 ° C. and a high pressure of 179 atm for a long time (50 hours). Also, a catalyst comprising rhenium and palladium is known (DE-OS 26051).
No. 07). However, even when this catalyst is used,
A high temperature of 300 ° C. or higher and a high pressure of 300 atm are required. JP-A-7-82190 describes a method for hydrogenating succinic anhydride under a relatively mild condition using a catalyst comprising a ruthenium metal and a rhenium compound. However, in these methods, the yield was not sufficient because the generated diol compound was decomposed by a side reaction.

[0006]

DISCLOSURE OF THE INVENTION The present invention suppresses a side reaction when directly reducing a carboxylic acid compound, particularly a polycarboxylic acid compound under relatively mild conditions, to reduce the corresponding alcohol compound. It is an object of the present invention to provide a method for producing in a yield.

[0007]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, in a reaction system using a catalyst comprising ruthenium metal and rhenium metal, an alkali metal and / or alkaline earth metal was used. By coexisting a metal or these metal compounds on a catalyst or in a reaction system, it has been found that a carboxylic acid compound can be directly hydrogenated and reduced under relatively mild conditions to produce an alcohol compound in high yield.

That is, the present invention provides a catalyst comprising a ruthenium metal and / or a metal compound thereof and a rhenium metal and / or a metal compound thereof, and at least one selected from alkali metals, alkaline earth metals and these metal compounds. Wherein the carboxylic acid compound is hydrogenated and reduced in the presence of, a ruthenium metal and / or a metal compound thereof and a rhenium metal used in the method for producing an alcohol compound. And / or a metal compound thereof, and a carboxylic acid hydrogenation / reduction catalyst in which at least one selected from an alkali metal, an alkaline earth metal, and these metal compounds is supported on a carrier.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The carboxylic acid compound used as a raw material in the present invention has at least one carboxyl group in the molecule.
Various compounds can be used. For example, as the monocarboxylic acid compound, a compound represented by the general formula (1): R ¹ —COO
H (wherein R ¹ represents a saturated, unsaturated or aromatic hydrocarbon group which may have a substituent having 1 to 40 carbon atoms, preferably having a lower limit of 3, more preferably 5 and an upper limit of 20) A carboxylic acid compound represented by the following formula: Specifically, acetic acid, propionic acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, hexanoic acid, heptanoic acid,
Octanoic acid, nonanoic acid, decanoic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, nonadecanoic acid, icosanoic acid, docosanoic acid, di-n-propyl acetic acid, cyclohexane Carboxylic acid, 1-adamantanecarboxylic acid, 4-methoxycyclohexanecarboxylic acid,
3-methoxypropionic acid, leucic acid, 4- (N, N
-Dimethylaminomethyl) cyclohexanecarboxylic acid,
Saturated carboxylic acids such as nipecotic acid and isonipecotic acid;
Unsaturated carboxylic acids such as acrylic acid, propiolic acid, methacrylic acid, crotonic acid, isocrotonic acid, hexenoic acid, tridecenoic acid, oleic acid, elaidic acid, icosapentaenoic acid and docosahexaenoic acid; benzoic acid, toluic acid, naphthoic acid, atropic acid And aromatic carboxylic acids such as cinnamic acid, phenylacetic acid, anisic acid, N, N-dimethylaminobenzoic acid and salicylic acid.

The polycarboxylic acid compound includes, for example, a compound represented by the general formula (2): HOOC-R ² —COOH (wherein R ² has 1 to 40 carbon atoms, preferably 3 at the lower limit, more preferably 5 at the upper limit, and 5 at the upper limit. Represents a saturated, unsaturated or aromatic divalent hydrocarbon group which may have 20 substituents.). Specifically, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, tridecandioic acid, tetradecandioic acid, pentadecandioic acid, hexadecandioic acid, heptadecandioic acid , Octadecandioic acid, nonadecandioic acid, icosandioic acid, docosandioic acid, cyclohexanedicarboxylic acid,
Saturated aliphatic or cycloaliphatic dicarboxylic acids such as succinic acid; unsaturated aliphatic or cycloaliphatic carboxylic acids such as pentenedioic acid, hexenedioic acid, tridecenedioic acid, icosadienedioic acid, docosatrienedioic acid, cyclopentenedicarboxylic acid Acids; phthalic acid, isophthalic acid, terephthalic acid, homophthalic acid, aromatic dicarboxylic acids such as naphthalenedicarboxylic acid and the like can be exemplified. Examples of the trifunctional or higher polycarboxylic acid compound include butane-1,2,3-tricarboxylic acid: 1,2,2-tetradecanetricarboxylic acid: 1,2,3,4-butanetetracarboxylic acid: 1,1
2,3,4-cyclopentatetracarboxylic acid and the like.

Further, the carboxylic acid compound is a methyl group,
It may be substituted with a lower alkyl group such as an ethyl group, a propyl group or an isobutyl group, or a lower alkoxy group such as an amino group, a hydroxyl group, a methoxy group, an ethoxy group, or an isopropyloxy group. Also, there is no problem even if the carboxylic acid compound used is a mixture thereof, such as a component obtained by hydrolyzing natural fats and oils.

In the production method of the present invention, when one of the above carboxylic acid compounds having an unsaturated bond (including an aromatized compound) is used, hydrogenation of the unsaturated bond is simultaneously performed. As the process proceeds, a saturated alcohol compound having the same carbon skeleton as the starting carboxylic acid compound is obtained.

In the present invention, a catalyst comprising a ruthenium metal and / or a metal compound thereof (hereinafter referred to as a ruthenium component) and a rhenium metal and / or a metal compound thereof (hereinafter referred to as a rhenium component) is used.

Examples of the ruthenium component include ruthenium zero-valent metal itself; various inorganic compounds such as ruthenium nitrate, acetate and chloride; various organic compounds such as acetylacetonate; various complex compounds such as amine complex and carbonyl complex. And the like. Specifically, ruthenium black, ruthenium powder, ruthenium oxide, ruthenium nitrosyl nitrate, ruthenium chloride, ruthenium bromide, ruthenium iodide, ammonium oxydecachlorodiruthenate, ammonium penachloroaquarthenate, ammonium ruthenate chloride, Potassium oxydecachlorodiruthenate, sodium oxydecachlorodiruthenate, potassium pentachloroaquarthenate, potassium perruthenate, hexaammineruthenium chloride, pentaamminechlororuthenium chloride,
Hexaammine ruthenium bromide, triruthenium dodecacarbonyl (ruthenium carbonyl), hexacarbonyltetrachlorozirthenium, tris (acetylacetonato) ruthenium, dichlorotricarbonylruthenium dimer, dichlorotris (triphenylphosphine) ruthenium, dichlorodicarbonylville Phenylphosphine) ruthenium, dicarbonylcyclopentadieruthenium dimer, bis (cyclopentadienyl) ruthenium and the like can be used, and these can be used alone or in combination of two or more.

Examples of the rhenium component include a zero-valent metal of rhenium itself; various inorganic compounds such as nitrate, acetate and chloride of rhenium; various organic compounds such as acetylacetonate; various complexes such as amine complex and carbonyl complex. Compounds. Specifically, there can be used, for example, dirhenium decacarbonyl (rhenium carbonyl), rhenium oxide, perrhenic acid, ammonium perrhenate, rhenium chloride, cyclopentadienylrhenium tricarbonyl and the like. Or two or more of them can be used in combination. Among these, a carbonyl compound is preferable in terms of the reaction rate of the hydrogenation reaction.

The catalyst comprising the ruthenium component and the rhenium component can be present in the reaction system as it is, but in the present invention, it is preferable to use the catalyst supported on a carrier. When the catalyst is used by being supported on a carrier, the carrier used is not particularly limited as long as it is a porous substance.
Specific examples include layered clay compounds such as alumina, silica, silica alumina, zeolite, diatomaceous earth, titania, zirconia, and other crystalline or non-crystalline metal oxides or composite oxides, teniolite, hectorite, and activated carbon. Can be Of these, alumina, silica and activated carbon are preferred, and activated carbon is more preferred. Also,
The shape of the catalyst is not particularly limited, and the catalyst can be used as it is or after being molded. The preparation of the carrier-supported catalyst is not particularly limited. For example, various methods such as an impregnation method, an ion exchange method, and a physical mixing method can be adopted. The ruthenium component and the rhenium component do not always need to be supported all at once, and after loading either one component first, the remaining components can be supported.

The method of activating the ruthenium-rhenium supported catalyst is not particularly limited, but is usually activated by reduction. For example, the ruthenium and rhenium components may be directly reduced after being loaded on a carrier, or may be reduced after being calcined. Of course, it may be reduced in the reaction system. The reduction method is not particularly limited, and the reduction is performed in a gas phase or a liquid phase. The valence of the metal of ruthenium and rhenium after the reduction operation is not particularly limited, and is 0.
It may be a valence metal or an oxidized state.

The amount of supported ruthenium metal in the catalyst supported on the carrier is 0.1 to 60% by weight, preferably 0.5% by weight at the lower limit and 50% by weight at the upper limit, based on the total weight of the catalyst. When the supported amount is more than 60% by weight, the activity of ruthenium per unit weight of metal tends to be small, and when it is less than 0.1% by weight, sufficient activity may not be obtained.

The amount of the catalyst in the present invention is based on the amount of the ruthenium metal, and the lower limit of the amount of the ruthenium metal used relative to the carboxylic acid compound as the raw material is usually 0.0%.
It is at least 05 mol% by metal, preferably at least 0.01 mol%, particularly preferably at least 2 mol%, and the upper limit is usually at most 25 mol%, preferably at most 10 mol%. If the content is less than 0.005 mol%, the reaction may not proceed sufficiently, or the difference between the rate at which the side reaction proceeds and the rate at which the main reaction proceeds may be small, and the yield of the alcohol compound may be reduced. In the present invention, when a relatively large amount of catalyst is used in order to increase the reaction rate, the rate of production of alcohol, which is the main reaction, can be selectively and markedly enhanced, and the rate of production, which is a side reaction, can be increased. Advantageously, the decomposition of alcohol is not promoted.

On the other hand, the amount of rhenium used is ruthenium:
The atomic ratio of rhenium is 100: 1 to 1:50, preferably 50: 1 to 1:20. Focusing on the yield of the alcohol compound, the atomic ratio of ruthenium to rhenium is 4: 1.
１ ： 1: 20, more preferably 1: 1１〜1: 10.

In the reaction system in the method for producing an alcohol compound of the present invention, in addition to the above-mentioned carboxylic acid compound and catalyst as raw materials, at least one kind selected from alkali metals, alkaline earth metals and these metal compounds (hereinafter referred to as “metallic compounds”). , An alkali (earth) metal component). Examples of the alkali metal include zero-valent metals such as lithium, sodium, potassium, rubidium, and cesium. Examples of the alkaline earth metal include zero-valent metals such as magnesium, calcium, strontium, and barium. Also alkali metal compounds,
As the alkaline earth metal compound, various compounds can be used. Among them, alkali metal and alkaline earth metal salts are preferable. For example, various inorganic salts such as nitrates, carbonates, chlorides, various complex salts, acetates, etc. And organic metal salts such as carboxylic acid metal salts. Also alkaline (earth)
The alkali metal species of the metal component are preferably sodium and potassium, and the alkaline earth metal species are preferably magnesium and calcium. Specific examples of the alkali (earth) metal component include sodium nitrate, potassium nitrate, calcium nitrate, magnesium nitrate, sodium carbonate, sodium chloride, sodium acetate, and the sodium salt of the starting carboxylic acid. These can be used alone or in combination of two or more.

As a method for allowing the alkali (earth) metal component to be present in the reaction system together with the carboxylic acid compound and the catalyst, for example, there is a method in which an alkali (earth) metal component is simply added to the reaction system and allowed to coexist. . In this case, as the alkali (earth) metal component, it is preferable to use a metal carboxylate salt among the above-mentioned examples, since a side reaction due to the decomposition of the alcohol is suppressed and the yield of the alcohol is largely increased. Particularly, a metal salt of a carboxylic acid compound as a raw material is preferable. The alkali (earth) metal component may be uniformly dissolved in the solvent or may be mixed heterogeneously depending on the form of the reaction.

The alkali (earth) metal component can also be introduced into the reaction system by using a catalyst in which the alkali (earth) metal component is supported on a carrier supporting the ruthenium component and the rhenium component. It can also be present. The same method as described above can be used for the method of loading on the carrier and the method of activating the catalyst.

The proportion of the alkali (earth) metal component used is such that the atomic ratio of ruthenium: alkali metal and / or alkaline earth metal is 100: 1 to 1:50, preferably 50: 1 to 1:20. . When focusing on the yield of the alcohol compound, the atomic ratio of ruthenium: alkali metal and / or alkaline earth metal is from 4: 1 to 1:20, more preferably from 1: 1 to 1:10.

The method for producing an alcohol compound according to the present invention comprises:
Usually, after dissolving the starting carboxylic acid compound in the solvent,
Provide for reaction. The solvent is not particularly limited as long as it dissolves the carboxylic acid compound, but is preferably a solvent that is inert to the hydrogenation reaction and does not react with the reactants or products. In the present invention, for example, ether solvents such as diethyl ether, dimethoxyethane, diethylene glycol dimethyl ether, triglyme, tetraglyme, tetrahydrofuran, dioxane, alcohol solvents such as ethanol and butanol, and aliphatic hydrocarbons such as hexane, heptane and octane , Cyclohexane,
Alicyclic hydrocarbons such as cycloheptane and cyclooctane can be used. Of these, ether solvents are preferred, and at least one selected from the group consisting of diisopropyl ether, dimethoxyethane and tetrahydrofuran is particularly preferred. Among them, diisopropyl ether is particularly preferred in terms of reaction rate, and the more the amount of the catalyst, the more remarkably excellent. The amount of the solvent used is not particularly limited as long as the raw materials are dissolved at the reaction temperature.

The reaction is carried out under heating and under hydrogen pressure.
The reaction method is not particularly limited, and may be, for example, a batch system, a semi-batch system, or a flow system.

The reaction temperature is usually about 50 to 230 ° C., preferably the lower limit is 100 ° C. and the upper limit is 170 ° C. When the temperature is higher than 230 ° C., the amount of side-reactive products due to the decomposition of the alcohol compound tends to increase, and when the temperature is lower than 50 ° C., the reaction rate is disadvantageous. In the present invention, the decomposition of the alcohol compound, which is a side reaction, can be remarkably suppressed by performing the reaction at a low temperature of 170 ° C. or less. In the present invention, it is particularly preferable to use a large amount of a catalyst and react at a low temperature in terms of accelerating the production rate of the alcohol compound and suppressing the decomposition of the alcohol compound.

The pressure of hydrogen is usually 10 to 150 k
g / cm ² , preferably 20 to 120 kg / cm ²
Is selected. Higher pressures are disadvantageous in terms of safety and economy, while lower pressures are disadvantageous because the reaction rate is slow.

Since the reaction time varies depending on the reaction conditions such as temperature, pressure and amount of catalyst, it is difficult to determine the range in a straightforward manner. Approximately 2 hours as the preferred lower limit
The preferred upper limit is 20 hours. The reaction time may be longer than 30 hours, but usually the reaction proceeds sufficiently within the range. On the other hand, if it is less than 0.5 hour, a high conversion rate may not be obtained.

[0030]

According to the present invention, by the action of the alkali metal (earth) metal component, the selectivity when hydrogenating and reducing a carboxylic acid compound in the presence of a ruthenium-rhenium catalyst is increased, and alcohol, which is a side reaction, is reduced. Since the decomposition of the compound can be suppressed, the yield of the alcohol compound can be increased. Further, according to the present invention, the reaction can be carried out under mild conditions.

[0031]

EXAMPLES The present reaction will be described in more detail with reference to the following examples, but the present reaction is not limited to these examples. The percentage in each example is based on the weight of the catalyst carried, and on a molar basis in the other cases.

Example 1 (Catalyst preparation method) 1.33 g of ammonium perrhenate was dissolved in 80 g of water, and 5% ruthenium-activated carbon powder K type (N.
Echemcat Co., Ltd., specific surface area 1200m ² /
g) 5 g was added and left overnight. Water was distilled off under reduced pressure using a rotary evaporator, and the obtained powder was reduced at 450 ° C. for 2 hours under a hydrogen stream to obtain 4.2% ruthenium-15.
6% rhenium-activated carbon powder (hereinafter referred to as catalyst (1))
4.7 g were obtained. (Hydrogenation reaction) 5 g (0.025 mol) of sebacic acid, 1 g of the catalyst (1), 0.5 g of disodium sebacate and 150 g of tetrahydrofuran (hereinafter referred to as THF) were charged into a 300 ml rotary stirring type autoclave, After fully replacing the inside of the system with hydrogen, 75 kg / cm
Hydrogen was injected so as to be ² . Raise the temperature while stirring,
When the reaction temperature reaches 160 ° C, the reaction pressure is increased to 100k.
g / cm ² . This time is defined as the reaction start time,
The hydrogenation reaction was performed for 6 hours. After the completion of the reaction, the autoclave was cooled to room temperature, subsequently purged with hydrogen, and the reaction solution was taken out. The reaction was analyzed by gas chromatography. The yield of 1,10-decanediol was 69%. Table 1 shows the results.

Example 2 (Hydrogenation reaction) A hydrogenation reaction of sebacic acid was carried out in the same manner as in Example 1 except that the amount of disodium sebacate added was changed to 0.1 g. The liquid was taken out. The reaction was analyzed by gas chromatography. 1,10
The yield of -decanediol was 64%. Table 1 shows the results
Shown in

Example 3 (Hydrogenation reaction) Sebacic acid was prepared in the same manner as in Example 1 except that the addition amount of disodium sebacate in Example 1 was changed to 0.25 g and the reaction time was changed to 5 hours. , And a reaction solution was taken out. The reaction was analyzed by gas chromatography. The yield of 1,10-decanediol was 69%. Table 1 shows the results.

Example 4 (Catalyst preparation method) 0.113 g of sodium acetate was dissolved in 40 g of water, and 2 g of the catalyst (1) prepared in Example 1 was added thereto.
Was added and left overnight. Water was distilled off under reduced pressure using a rotary evaporator, and the obtained powder was heated at 450 ° C. under a hydrogen stream.
For 2 hours to obtain 1.9 g of 4.1% ruthenium-15.3% rhenium-0.9% sodium-activated carbon powder (hereinafter referred to as catalyst (2)). (Hydrogenation reaction) 5 g (0.025 mol) of sebacic acid, 1 g of the catalyst (2), and tetrahydrofuran (hereinafter referred to as TH) were placed in a 300 ml rotary stirring autoclave.
After 150 g of the mixture (referred to as F) was charged and the inside of the system was sufficiently replaced with hydrogen, hydrogen was injected to a pressure of 75 kg / cm ² .
The temperature was increased while stirring, and when the reaction temperature reached 170 ° C., the reaction pressure was increased to 100 kg / cm ² . This time was set as the reaction start time, and the hydrogenation reaction was performed for 5 hours. After the completion of the reaction, the autoclave was cooled to room temperature, subsequently purged with hydrogen, and the reaction solution was taken out. The reaction was analyzed by gas chromatography. The yield of 1,10-decanediol was 65%. Table 1 shows the results.

Example 5 (Preparation method of catalyst) In the same manner as in Example 4, except that the amount of sodium acetate used was changed to 0.226 g, 4.1% ruthenium-15.3% rhenium was used. 1.9
% Sodium-activated carbon powder (hereinafter referred to as catalyst (3))
Was prepared. (Hydrogenation reaction) A hydrogenation reaction of sebacic acid was carried out in the same manner as in Example 4, except that the catalyst (3) was used instead of the catalyst (2), and the reaction time was changed to 8 hours. The reaction solution was taken out. The reaction was analyzed by gas chromatography. The yield of 1,10-decanediol is 65
%Met. Table 1 shows the results.

Example 6 (Catalyst preparation method) In the same manner as in Example 4, except that the amount of sodium acetate used was changed to 0.565 g, 4.0% ruthenium-14.9% rhenium- 4.6
% Sodium-activated carbon powder (hereinafter referred to as catalyst (4))
Was prepared. (Hydrogenation reaction) A hydrogenation reaction of sebacic acid was carried out in the same manner as in Example 4 except that the catalyst (4) was used instead of the catalyst (2) and the reaction time was changed to 8 hours. The reaction solution was taken out. The reaction was analyzed by gas chromatography. The yield of 1,10-decanediol is 63
%Met. Table 1 shows the results.

Example 7 (Catalyst preparation method) 40 g of 0.3535 g of sodium nitrate
Of the catalyst (1) 2 prepared in Example 1
g was added and left overnight. Water was distilled off under reduced pressure using a rotary evaporator, and the obtained powder was dried under a stream of hydrogen under a stream of hydrogen.
The mixture was reduced at a temperature of 2 ° C. for 2 hours to obtain 1.9 g of 4.0% ruthenium-14.9% rhenium-4.6% sodium-activated carbon powder (hereinafter referred to as catalyst (5)). (Hydrogenation reaction) 5 g (0.025 mol) of sebacic acid, 1 g of the catalyst (5) and 150 g of THF were charged into a 300 ml rotary stirring type autoclave, and after the system was sufficiently replaced with hydrogen, the pressure was reduced to 75 kg / cm ² . Hydrogen was injected. The temperature was raised while stirring, and the reaction temperature was 170 ° C.
When the reaction became, the reaction pressure was increased to 100 kg / cm ² . This time was defined as the reaction start time, and the hydrogenation reaction was performed for 8 hours. After the completion of the reaction, the autoclave was cooled to room temperature, subsequently purged with hydrogen, and the reaction solution was taken out. The reaction was analyzed by gas chromatography. 1,10
The yield of -decanediol was 65%. Table 1 shows the results
Shown in

Example 8 (Catalyst preparation method) 40 g of 0.2205 g of sodium carbonate
Of the catalyst (1) 2 prepared in Example 1
g was added and left overnight. Water was distilled off under reduced pressure using a rotary evaporator, and the obtained powder was dried under a stream of hydrogen under a stream of hydrogen.
The mixture was reduced at 40 ° C. for 2 hours to prepare 1.9 g of 4.0% ruthenium-14.9% rhenium-4.6% sodium-activated carbon powder (hereinafter referred to as catalyst (6)). The rotating stirring type autoclave (hydrogenation reaction) 300 ml, sebacic acid 5 g (0.025 mol), the catalyst (6) was charged 1g and THF150g, and after sufficiently replacing the inside of the system with hydrogen, the 75 kg / cm ² Hydrogen was injected. The temperature was raised while stirring, and the reaction temperature was 170 ° C
When the reaction became, the reaction pressure was increased to 100 kg / cm ² . This time was defined as the reaction start time, and the hydrogenation reaction was performed for 8 hours. After the completion of the reaction, the autoclave was cooled to room temperature, subsequently purged with hydrogen, and the reaction solution was taken out. The reaction was analyzed by gas chromatography. 1,10
The yield of -decanediol was 64%. Table 1 shows the results
Shown in

Example 9 (Catalyst preparation method) In the same manner as in Example 4, except that 0.168 g of potassium nitrate was used in place of sodium acetate, 4.1% ruthenium-15.1% rhenium was used. A 3.1% potassium-activated carbon powder (hereinafter referred to as catalyst (7)) was prepared. (Hydrogenation reaction) A hydrogenation reaction of sebacic acid was carried out in the same manner as in Example 4 except that the catalyst (8) was used instead of the catalyst (2) and the reaction time was changed to 8 hours. The reaction solution was taken out. The reaction was analyzed by gas chromatography. The yield of 1,10-decanediol is 66
%Met. Table 1 shows the results.

Example 10 (Catalyst preparation method) In the same manner as in Example 4, except that 0.3925 g of calcium nitrate was used instead of sodium acetate, 4.1% ruthenium-15.1%
Rhenium-3.1% calcium-activated carbon powder (hereinafter referred to as catalyst (8)) was prepared. (Hydrogenation reaction) A hydrogenation reaction of sebacic acid was carried out in the same manner as in Example 4 except that the catalyst (8) was used instead of the catalyst (2) and the reaction time was changed to 8 hours. The reaction solution was taken out. The reaction was analyzed by gas chromatography. The yield of 1,10-decanediol is 61
%Met. Table 1 shows the results.

Example 11 (Catalyst preparation method) The procedure of Example 4 was repeated, except that 0.4260 g of magnesium nitrate was used instead of sodium acetate, and 4.0% ruthenium-15.3 was used.
% Rhenium-2.0% magnesium-activated carbon powder (hereinafter referred to as catalyst (9)) was prepared. (Hydrogenation reaction) A hydrogenation reaction of sebacic acid was carried out in the same manner as in Example 4 except that the catalyst (9) was used instead of the catalyst (2) and the reaction time was changed to 8 hours. The reaction solution was taken out. The reaction was analyzed by gas chromatography. The yield of 1,10-decanediol is 54
%Met. Table 1 shows the results.

Example 12 (Hydrogenation reaction) 5 g of 1,4-cyclohexanedicarboxylic acid (0.0 g) was placed in a 300 ml rotary stirring type autoclave.
29 mol), 1 g of the catalyst (2) and THF 150
g, and the system is sufficiently purged with hydrogen.
Hydrogen was injected so as to be cm ² . The temperature was raised while stirring, and when the reaction temperature reached 160 ° C, the reaction pressure was increased to 10
The pressure was increased to 0 kg / cm ² . This time was set as the reaction start time, and the hydrogenation reaction was performed for 10 hours. After the completion of the reaction, the autoclave was cooled to room temperature, subsequently purged with hydrogen, and the reaction solution was taken out. The reaction was analyzed by gas chromatography. The yield of 1,4-cyclohexanedimethanol was 93%. Table 1 shows the results.

Example 13 (Hydrogenation reaction) 5 g (0.034 mol) of adipic acid, 1 g of the above-mentioned catalyst (3) and 150 g of THF were charged into a 300 ml rotary stirring type autoclave, and the system was sufficiently purged with hydrogen. , And 75 kg / cm ² of hydrogen. The temperature was increased while stirring, and when the reaction temperature reached 160 ° C., the reaction pressure was increased to 100 kg / cm ² . This time was defined as the reaction start time, and the hydrogenation reaction was performed for 8 hours. After the completion of the reaction, the autoclave was cooled to room temperature, subsequently purged with hydrogen, and the reaction solution was taken out. The reaction was analyzed by gas chromatography. The yield of 1,6-hexanediol was 92%. Table 1 shows the results.

Example 14 (Hydrogenation reaction) 5 g (0.029 mol) of suberic acid, 1 g of the above catalyst (3) and 150 g of THF were charged into a 300 ml rotary stirring type autoclave, and the system was sufficiently replaced with hydrogen. , And 75 kg / cm ² of hydrogen. The temperature was increased while stirring, and when the reaction temperature reached 160 ° C., the reaction pressure was increased to 100 kg / cm ² . This time was defined as the reaction start time, and the hydrogenation reaction was performed for 8 hours. After the completion of the reaction, the autoclave was cooled to room temperature, subsequently purged with hydrogen, and the reaction solution was taken out. The reaction was analyzed by gas chromatography. The yield of 1,8-octanediol was 78%. Table 1 shows the results.

Comparative Example 1 (Hydrogenation reaction) 5 g (0.025 mol) of sebacic acid, 1 g of the above-mentioned catalyst (1) and 150 g of THF were charged into a 300 ml rotary stirring type autoclave, and the system was sufficiently purged with hydrogen. , And 75 g / cm ² . The temperature was increased while stirring, and when the reaction temperature reached 170 ° C., the reaction pressure was increased to 100 kg / cm ² . This time was defined as the reaction start time, and the hydrogenation reaction was performed for 6 hours. After the completion of the reaction, the autoclave was cooled to room temperature, subsequently purged with hydrogen, and the reaction solution was taken out. The reaction was analyzed by gas chromatography. 1,10
The yield of -decanediol was 22%. Table 1 shows the results
Shown in

[0047]

[Table 1]

In Table 1, Ru represents ruthenium, Re represents rhenium, C represents carbon (activated carbon), Na represents sodium, Ca represents calcium, and Mg represents magnesium. The addition amount or Ru metal atom ratio indicates the addition amount of the alkali (earth) metal component or the atomic ratio of alkali (earth) metal to Ru atoms in the catalyst.

Claims (6)

[Claims] 1. A catalyst comprising a metal of ruthenium and / or a metal compound thereof and a metal of rhenium and / or a metal compound thereof, and at least one selected from an alkali metal, an alkaline earth metal and these metal compounds. And a carboxylic acid compound is hydrogenated and reduced. 2. At least one selected from an alkali metal, an alkaline earth metal and a metal compound thereof,
The production method according to claim 1, wherein the production method is an alkali metal salt and / or an alkaline earth metal salt. 3. The method according to claim 2, wherein the alkali metal salt and / or alkaline earth metal salt is an alkali metal carboxylate and / or alkaline earth metal salt. 4. A catalyst comprising a metal of ruthenium and / or a metal compound thereof and a metal of rhenium and / or a metal compound thereof is a supported catalyst.
Or the production method according to 3. 5. At least one selected from an alkali metal, an alkaline earth metal and a metal compound thereof,
5. The method according to claim 4, wherein the metal of ruthenium and / or its metal compound and the metal of rhenium and / or its metal compound are supported on a carrier. 6. A ruthenium metal and / or ruthenium used in the method for producing an alcohol compound according to claim 5.
Or a catalyst for hydrogenation and reduction of carboxylic acid, wherein the metal compound and a metal of rhenium and / or a metal compound thereof, and at least one selected from an alkali metal, an alkaline earth metal and these metal compounds are supported on a carrier.