JP3225946B2 - Method for producing lactone and catalyst thereof - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a lactone compound by hydrogenating and reducing a dicarboxylic acid compound in the presence of a catalyst, and a catalyst used in the production method. In particular, the production method of the present invention relates to γ-butyrolactone, which is used as a raw material for N-methylpyrrolidone useful as an industrial solvent and a detergent, and polyvinylpyrrolidone widely used as a water-soluble polymer, and alkyl gamma useful as a flavor. It is useful as a method for producing lactones.

[0002]

2. Description of the Related Art Many catalysts have been proposed for producing γ-butyrolactone by catalytic hydrogenation of a dicarboxylic acid compound in a liquid phase. For example, a method using a nickel-palladium / silica system as a catalyst (Japanese Unexamined Patent Publication No.
No. 10852), and a method using a palladium-rhenium-based catalyst (Japanese Patent Application Laid-Open No. 9-25253). However, the yield of γ-butyrolactone obtained by these methods is not satisfactory, being 50 to 60%. In addition, a method using a cobalt-palladium catalyst (for example, Japanese Patent Publication No. 58-29142) and a method using a nickel catalyst (for example, Japanese Patent Publication No.
-6947) and the like. However, in these methods, the reaction conditions are generally 250 ° C., 100 kg / c.
Since it is severe as m ² , side reactions such as generation of cyclic ether and decarboxylation proceed, and the selectivity of lactones is not satisfactory.

[0003]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a lactone compound in high yield by hydrogenating and reducing a dicarboxylic acid compound under relatively mild conditions.

[0004]

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 the dicarboxylic acid compound can be hydrogenated and reduced under relatively mild conditions to produce a lactone compound in high yield.

That is, the present invention provides a catalyst comprising a ruthenium metal and / or its metal compound and a rhenium metal and / or its metal compound, and at least one kind selected from alkali metals, alkaline earth metals and these metal compounds. Wherein a dicarboxylic acid compound is hydrogenated and reduced in the presence of a lactone compound, and further, a ruthenium metal and / or a metal compound thereof and a rhenium metal used in the lactone compound production method. And / or a metal compound thereof, and a catalyst in which at least one selected from alkali metals, alkaline earth metals, and these metal compounds is supported on a carrier.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION Examples of the dicarboxylic acid compound used as a raw material in the present invention include various saturated or unsaturated dicarboxylic acids, and derivatives of the dicarboxylic anhydride. The dicarboxylic acid compound is not limited to a linear compound, and may be an alkyl group such as a methyl group, an ethyl group, a propyl group, an isobutyl group, a butyl group, a pentyl group, a hexyl group, and an octyl group; an amino group; a hydroxyl group; It may be a branched one substituted with a lower alkoxy group such as a methoxy group, an ethoxy group and an isopropyloxy group. Among such dicarboxylic acid compounds, the dicarboxylic acid compound of the present invention includes a carboxylic acid of the dicarboxylic acid compound of 2
Those bonded through carbon atoms are preferred. In particular, succinic acid, succinic anhydride, maleic acid, maleic anhydride and phthalic acid, phthalic anhydride, fumaric acid, 1,2
It is preferable to use at least one selected from -cyclohexanedicarboxylic acid and 1,2-cyclohexanedicarboxylic anhydride.

[0007] The lactone compound obtained by the production method of the present invention has the same carbon skeleton as the starting dicarboxylic acid compound. For example, when a compound in which two carboxylic acids are bonded via two carbon atoms is used as the dicarboxylic acid compound, γ-butyrolactone or a derivative thereof is obtained. When a dicarboxylic acid compound having an olefinic unsaturated bond is used, hydrogenation of the unsaturated bond proceeds simultaneously.

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.

The ruthenium component includes 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 pentachloroaquaruthenate, potassium perruthenate, hexaammineruthenium chloride, pentaamminechlororuthenium chloride,
Hexaammine ruthenium bromide, triruthenium dodecacarbonyl (ruthenium carbonyl), hexacarbonyltetrachlorozirthenium, tris (acetylacetonato) ruthenium, dichlorotricarbonylruthenium dimer, dichlorotris (triphenylphosphine) ruthenium, dichlorodicarbonylville (trichloro) 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.

The rhenium component includes 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 for 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 the supported ruthenium metal in the catalyst supported on the support is 0.1 to 60% by weight, preferably the lower limit is 0.5% by weight and the upper limit is 50% by weight, 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.

In the present invention, the amount of the catalyst is based on the content of the ruthenium metal, and the lower limit of the amount of the ruthenium metal used relative to the starting dicarboxylic acid compound is usually 0.1.
005 mol metal% or more, preferably 0.01 mol metal%
The above is particularly preferably 2 mol% or more, and the upper limit is usually 25 mol% or less, preferably 10 mol% or less. 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 lactone compound may be reduced. In the present invention, when a relatively large amount of a catalyst is used to increase the reaction rate, the rate of lactone production, which is the main reaction, can be selectively and significantly enhanced, and the side reaction is not accelerated. This is advantageous.

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 a lactone compound of the present invention, in addition to the above-mentioned dicarboxylic 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. Various compounds can be used as the alkali metal compound and the alkaline earth metal compound. Among them, alkali metal and alkaline earth metal metal salts are preferable. For example, various inorganic salts such as nitrates, carbonates, chlorides, and various complex salts are preferable. And organic metal salts such as carboxylic acid metal salts such as acetic acid salts. The alkali metal species of the alkali (earth) metal component are sodium, potassium,
As the alkaline earth metal species, magnesium and calcium are preferable. Specific examples of the alkali (earth) metal component include sodium nitrate, potassium nitrate, calcium nitrate, magnesium nitrate, sodium carbonate, sodium chloride, sodium acetate, and sodium salts of dicarboxylic acid compounds. These can be used alone or in combination of two or more.

As a method of allowing the alkali (earth) metal component to be present in the reaction system together with the dicarboxylic acid compound and the catalyst, for example, there is a method in which the alkali (earth) metal component is simply added to the reaction system and allowed to coexist. . In this case, it is preferable to use a metal dicarboxylate among the above examples as the alkali (earth) metal component, since the side reaction is suppressed and the yield of the lactone compound is greatly increased. Particularly, an alkali (earth) metal salt of a dicarboxylic acid compound as a raw material is preferable. In addition, alkali (earth)
The metal component may be uniformly dissolved in the solvent or may be heterogeneously mixed 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 lactone 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.

In the method for producing a lactone compound of the present invention, usually, after dissolving a raw material dicarboxylic acid compound in a solvent,
Provide for reaction. The solvent is not particularly limited as long as it dissolves the dicarboxylic acid compound, but is preferably a solvent that is inert to the hydrogenation reaction and does not react with the reactants and 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. If the temperature is higher than 230 ° C., the amount of by-products tends to increase. Conversely, if the temperature is lower than 50 ° C., the reaction rate is disadvantageous. In the present invention, in particular, 17
By reacting at a low temperature of 0 ° C. or less, side reactions can be significantly suppressed. 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 lactone compound and suppressing side reactions.

The pressure of hydrogen is usually 10 to 150 k
g / cm ² , preferably 20 kg / cm ² or more, 12
0 kg / cm ² or less. 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 reaction conditions such as temperature, pressure and amount of catalyst, it is difficult to determine the range in a straightforward manner. About an hour. If the reaction time is short, a high conversion rate may not be obtained, so the reaction time is 1
It is preferable to set the time to at least 2 hours, more preferably at least 2 hours. The reaction time may be longer than 30 hours, and usually the reaction sufficiently proceeds within 30 hours. However, if the reaction time is long, side reactions are likely to occur.
It is preferable to set the time to 10 hours or less, and more preferably 7 hours or less.

[0025]

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

[0026]

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 a 5% ruthenium-activated carbon powder K type (N.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. 40 g of sodium acetate 0.226 g
Was dissolved in water, and 2 g of the catalyst (1) was added thereto 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 4.1% ruthenium-15.3% rhenium-1.9.
% Sodium-activated carbon powder (hereinafter referred to as catalyst (2))
1.9 g were obtained. (Hydrogenation reaction) 5 g (0.025 mol) of succinic acid and the catalyst (2) were placed in a 300 ml rotary stirring type autoclave.
And 1 g of tetrahydrofuran (hereinafter referred to as THF) were charged, and the system was sufficiently replaced with hydrogen.
Hydrogen was injected at 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 γ-butyrolactone was 83%.

Example 2 5 g (0.025 mol) of succinic anhydride, 1 g of the catalyst (2) prepared in Example 1 and tetrahydrofuran (hereinafter referred to as TH) were placed in a 300 ml rotary stirring type 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 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. The yield of γ-butyrolactone was 77%.

Example 3 Phthalic acid was added to a 15 ml rotary stirring type autoclave.
5 g (0.003 mol), 0.1 g of the catalyst (2) prepared in Example 1, and 5 g of isopropyl ether were charged, and the system was sufficiently purged with hydrogen.
Hydrogen was injected so as to be ² . Raise the temperature while stirring,
The point at which the reaction temperature reached 170 ° C. was 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 phthalide was 69%.

Example 4 A 15 ml rotary stirring type autoclave was charged with 0.5 g (0.003 mol) of phthalic anhydride, 0.1 g of the catalyst (2) prepared in Example 1, and 5 g of isopropyl ether. After fully replacing the inside with hydrogen, 75 kg / cm
Hydrogen was injected so as to be ² . Raise the temperature while stirring,
The point at which the reaction temperature reached 170 ° C. was 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 phthalide was 77%.

Example 5 0.5 g (0.003 mol) of 1,2-cyclohexanedicarboxylic acid was placed in a 15 ml rotary stirring type autoclave.
After 0.1 g of the catalyst (2) prepared in Example 1 and 5 g of isopropyl ether were charged, the inside of the system was sufficiently replaced with hydrogen, and then hydrogen was injected under pressure to 75 kg / cm ² . The temperature was raised while stirring, and the point at which the reaction temperature reached 170 ° C. 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. The yield of hexahydrophthalide was 65%.

Example 6 In a 15 ml rotary stirring type autoclave, 0.5 g (0.003 mol) of 1,2-cyclohexanedicarboxylic anhydride, 0.1 g of the catalyst (2) prepared in Example 1 and isopropyl After 5 g of ether 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 raised while stirring, and the point at which the reaction temperature reached 170 ° C. 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. The yield of hexahydrophthalide was 70%.

Comparative Example 1 Succinic acid 5 was added to a 300 ml rotary stirring type autoclave.
g (0.025 mol) of the catalyst (1) prepared in Example 1
And 1 g of tetrahydrofuran (hereinafter referred to as THF).
U) After charging 150 g and sufficiently replacing the inside of the system with hydrogen,
75kg / cm ^TwoHydrogen was injected so that Stir
The reaction temperature rises to 170 ° C.
Pressure 100kg / cm^TwoPressurized to React at this time
The hydrogenation reaction was performed for 5 hours as a start time. End of reaction
Afterwards, the autoclave is cooled to room temperature, and then hydrogen is purged.
And the reaction solution was taken out. Gas chromatog
Analyzed by Raffy. The yield of γ-butyrolactone is
56%.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) C07D 307/33 B01J 23/58 C07D 307/89 C07B 61/00 300 CA (STN) REGISTRY (STN)

Claims (8)

(57) [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 method for producing a lactone compound, which comprises hydrogenating and reducing a dicarboxylic acid compound. 2. The method according to claim 1, wherein the dicarboxylic acid compound is a compound in which two carboxylic acids are bonded via two carbon atoms. 3. The method of claim 1, wherein the dicarboxylic acid compound is succinic acid, succinic anhydride, maleic acid, maleic anhydride, fumaric acid, phthalic acid, phthalic anhydride, 1,2-cyclohexanedicarboxylic acid and 1,2-cyclohexanedicarboxylic anhydride. The method according to claim 1, wherein the compound is at least one compound selected from the group consisting of: 4. At least one selected from an alkali metal, an alkaline earth metal and a metal compound thereof,
The production method according to claim 1, 2 or 3, which is an alkali metal salt and / or an alkaline earth metal salt. 5. The method according to claim 1, wherein the alkali metal salt and / or the alkaline earth metal salt is an alkali metal salt of dicarboxylic acid and / or
5. The method according to claim 4, which is an alkaline earth metal salt. 6. 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 catalyst supported on a carrier.
The production method according to any one of the above. 7. At least one selected from an alkali metal, an alkaline earth metal and a metal compound thereof,
The production method according to claim 6, 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. 8. A metal of ruthenium and / or a metal compound thereof and a metal of rhenium and / or a metal compound thereof, and an alkali metal, an alkaline earth metal and a metal thereof, which are used in the method for producing a lactone compound according to claim 7. A catalyst in which at least one selected from metal compounds is supported on a carrier.