JPH06135953A - Production of lactones by hydrogenation - Google Patents

Abstract

PURPOSE:To provide a method for producing a lactone in a high yield under a mild condition by using a saturated and/or unsaturated dicarboxylic acid derivative as the raw material. CONSTITUTION:In this method for producing a lactone, hydrogenation of a saturated and/or unsaturated dicarboxylic acid derivative is carried out characteristically by using a catalyst composed of palladium and lead supported on a carrier in the presence of an alkaline metal salt.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing lactones, and more particularly to a method for producing .gamma.-butyrolactone. γ-Butyrolactone is a compound useful as a raw material for the synthesis of various solvents and pyrrolidones.

[0002]

2. Description of the Related Art Conventionally, many proposals have been made regarding a method for producing a lactone by hydrogenating a saturated and / or unsaturated dicarboxylic acid derivative in a liquid phase.

For example, as an example of using a noble metal catalyst, a method using a palladium catalyst supported on activated carbon (hereinafter abbreviated as Pd / C) (US Pat. No. 3,113,138),
A method using a catalyst composed of palladium and gold or silver supported on diatomaceous earth (US Pat. No. 4,096,156), and a method using a catalyst composed of palladium and rhenium supported on zirconia (JP-A-63-218636). Etc. are known. On the other hand, as an example of using a base metal catalyst, a method using a nickel-based catalyst (for example, Japanese Patent Publication No.
6947), a method using a cobalt-palladium catalyst (for example, Japanese Patent Publication No. 58-29142).

However, in the method using Pd / C (US Pat. No. 3,113,138), when succinic anhydride is used as a raw material, γ-butyrolactone is obtained in a relatively high yield, but maleic anhydride is used as a raw material. When used, there is a problem in that it requires a two-step reaction, and that a catalyst must be added when carrying out the second-step reaction, and the operation is complicated. In the case of using a catalyst composed of Pd and silver supported on diatomaceous earth (US Pat. No. 4,096,156), the reaction condition is 225 to 230 ° C. and 210 to 215 atm, and in addition to being extremely severe, noble metal The supporting rate exceeds 10%, and there is a problem that a catalyst cost is required. In an example using a catalyst composed of palladium and rhenium supported on zirconia (Japanese Patent Laid-Open No. 63-218636), when the conversion rate of the raw material is increased, by-products such as butanediol and tetrahydrofuran increase, while the purpose and In order to increase the selectivity of γ-butyrolactone, the conversion rate must be lowered.

On the other hand, the method using a nickel-based catalyst or a cobalt-palladium-based catalyst has the advantage that the cost of the catalyst is relatively low, but the reaction conditions are 250 ° C. and 100 ° C.
It is extremely severe at kg / cm ² G. Therefore, side reactions such as formation of cyclic ether and decarboxylation proceed, and the selectivity of lactones is not always satisfactory.

[0006]

The object of the present invention is to provide a milder condition than a conventionally known catalyst in a one-step hydrogenation reaction, regardless of whether a saturated or unsaturated dicarboxylic acid derivative is used as a raw material. Below, lactones in high yield,
Particularly, it is to provide a method for producing γ-butyrolactone.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the inventors of the present invention have used a novel catalyst consisting of specific components and saturated it in the presence of an alkali metal salt. It was found that lactones can be produced in high yield under mild conditions by hydrogenating an unsaturated dicarboxylic acid derivative and / or the present invention has been completed.

That is, in the present invention, when hydrogenating a saturated and / or unsaturated dicarboxylic acid derivative, a hydrogenation reaction is carried out in the presence of an alkali metal salt using a catalyst composed of palladium and lead supported on a carrier. The present invention relates to a method for producing a characteristic lactone.

The present invention will be described in detail below.

The raw materials used in the present invention are saturated and / or
Alternatively, it is an unsaturated dicarboxylic acid derivative. Here, the saturated and / or unsaturated dicarboxylic acid derivative means an anhydride of a saturated and / or unsaturated dicarboxylic acid such as maleic anhydride, succinic anhydride, itaconic anhydride, citraconic anhydride, methylsuccinic anhydride and glutaric anhydride. , Maleic acid, succinic acid, fumaric acid, itaconic acid, citraconic acid,
Mesaconic acid, methyl succinic acid, glutaric acid and the like can be mentioned. Of these, maleic anhydride, maleic acid, succinic anhydride, succinic acid, and fumaric acid are more preferable, and in this case, γ-butyrolactone can be obtained in high yield.

These starting materials, saturated or unsaturated dicarboxylic acid derivatives, may be mixed in any ratio if the hydrogenation products are the same.

In the method of the present invention, the saturated and / or unsaturated dicarboxylic acid derivative is preferably dissolved in a solvent and then subjected to the reaction. The solvent is inert to the hydrogenation reaction, and is not particularly limited as long as it does not react with the product lactone, for example, diethyl ether, dimethoxyethane, diglyme, triglyme,
Ethers such as tetrahydrofuran and dioxane, esters such as methyl acetate, ethyl acetate, methyl benzoate and ethyl benzoate, methanol, ethanol, n-butanol, iso-butanol, tert-butanol,
Alcohols such as 1,4-butanediol, aliphatic hydrocarbons such as n-hexane and cyclohexane, acidic solvents such as acetic acid, lactones such as γ-butyrolactone, and acid amides such as 2-pyrrolidone and N-methylpyrrolidone. Etc. Among them, preferable examples include dimethoxyethane and tetrahydrofuran, which have a relatively low boiling point and are easily recovered, or γ-butyrolactone which does not require solvent recovery.

The amount of the solvent used is not limited as long as the raw materials are dissolved at the reaction temperature. These solvents do not have to be particularly dried before use, and conversely water may coexist as long as they are about 1 molar equivalent to the raw materials.

The catalyst used in the present invention is a catalyst composed of palladium and lead supported on a carrier. The raw material that can be used in preparing this catalyst is not particularly limited as long as it can be converted into metallic palladium and lead during the hydrogenation reaction or before being used in the reaction. For example, as the palladium raw material, ammonium hexachloropalladate, ammonium tetrachloropalladate, dinitrodiamine palladium, palladium bromide, chlorocarbonylpalladium, palladium chloride, palladium iodide, palladium nitrate, palladium oxide, palladium sulfate, palladium acetate, dinitro. Potassium sulfite palladate, potassium hexachloropalladate, potassium tetrabromopalladate, potassium tetrachloropalladate, sodium hexachloropalladate,
Sodium tetrachloropalladate, tetraamminepalladium chloride, tetraamminepalladium nitrate,
cis-dichlorodiaminepalladium, trans-dichlorodiaminepalladium, dichloro (ethylenediamine) palladium, potassium tetracyanopalladate, etc. can be exemplified, and as the lead raw material, lead acetate, lead bromide, lead carbonate, lead chloride, lead iodide, Lead nitrate, lead oxalate, lead oxide,
Examples thereof include lead perchlorate, lead sulfate and lead tartrate.

The carrier used in the catalyst of the present invention may be a porous substance, for example, silica, alumina, magnesia, titania, silica-alumina, zeolite, diatomaceous earth,
Examples thereof include crystalline or non-crystalline metal oxides such as silica magnesia or composite oxides, layered clay compounds such as teniolite and hectorite, and activated carbon. The shape of the catalyst is not particularly limited, and it can be used in the form of powder as it is or according to the reaction mode. Powders or granules are preferably used in the suspension bed, and tablet compression molded products, spherical or rod-shaped extrusion molded products and the like are preferably used in the fixed bed.

The method for producing the catalyst used in the present invention is not particularly limited, and a catalyst produced by a known method can be used. For example, it can be prepared by a precipitation method, a kneading method, an impregnation method, an ion exchange method, a deposition method or the like. When preparing by the impregnation method,
For example, a palladium compound and a lead compound are dissolved in an appropriate solvent, a carrier is added thereto, and if necessary, the mixture is allowed to stand for a predetermined time and then dried. Palladium and lead do not necessarily have to be loaded at the same time, and either of them may be loaded first, and the rest may be loaded later, so-called a two-step loading method. In the case of production by the ion exchange method, it can be prepared by the same method as the impregnation method after ion exchange using a palladium compound and a lead compound at desired concentrations. Further, in the case of preparation by the deposition method, for example, a palladium compound and a lead compound are dissolved in a suitable solvent such as water, the above-mentioned carrier is added, and the precipitating agent is gradually or all at once added with stirring to obtain a palladium compound. The lead component may be deposited and the resulting mixture may be dried. The catalyst raw material thus supported on the carrier is then reduced to a metal.

The reduction method is not particularly limited, and the reduction may be carried out directly, or in some cases, it may be reduced after firing. Of course, it may be reduced in the reaction system. Once metallic palladium and lead are obtained, they may be reduced in the gas phase using, for example, hydrogen, or in the liquid phase using hydrazine. The reduction temperature is not particularly limited as long as at least palladium and lead are reduced to metals, but generally a temperature up to 600 ° C is sufficient.

The amount of palladium supported on the catalyst to be used is 0.
1 to 10% by weight, preferably 0.5 to 7% by weight,
In addition, the amount of lead carried is based on the atomic ratio (Pb
/ Pd) is preferably 0.001 to 0.5, and more preferably 0.01 to 0.3.

The amount of the catalyst used is not particularly limited, but is preferably 0.5 to 200% by weight, more preferably 1 to 150% by weight based on the raw material.

The present invention is characterized in that a catalyst composed of palladium and lead supported on a carrier is used, and an alkali metal salt is made to coexist as an additive. The alkali metal in the present invention is an alkali metal of Group Ia of the periodic table, for example, lithium, sodium, potassium, rubidium and cesium. As alkali metal salts, various inorganic,
Organic alkali metal salts can be used. For example,
Examples of the inorganic salt include alkali metal chlorides, nitrates, carbonates, sulfates, phosphates, hydroxides and the like. Further, a layered compound represented by clay containing an alkali metal and various zeolites ion-exchanged with an alkali metal can also be used.

Specifically, chlorides such as lithium chloride, sodium chloride, potassium chloride, rubidium chloride and cesium chloride, nitrates such as lithium nitrate, sodium nitrate, potassium nitrate, rubidium nitrate and cesium nitrate, lithium nitrite and nitrite. Sodium, potassium nitrite, rubidium nitrite, nitrite such as cesium nitrite, lithium carbonate, sodium carbonate, potassium carbonate, rubidium carbonate,
Carbonate such as cesium carbonate, lithium sulfate, sodium sulfate, potassium sulfate, rubidium sulfate, sulfate such as cesium sulfate, lithium phosphate, sodium phosphate, potassium phosphate, rubidium phosphate, cesium phosphate and other phosphates Hydroxides such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide and cesium hydroxide.

Further, clay such as sodium-type, potassium-type, rubidium-type or cesium-type montmorillonite and carionite, and ion-exchangeable cations are
Various zeolites which are alkali cations such as potassium, rubidium and cesium can be mentioned. For example, philippite, harmotome, merlinoites, jismondin, amisite, gallonite, govinsite, anal sim, wairakite, poringite, lomontite, yugawaralite, shabasite, willhendersonite, gmelinite, faujasite, erionite, offretite, levin mazzite, Natrolite, Tetrasoda Fluorite, Parasoda Fluorite, Mesolite, Scholesite, Tomsonite, Gonaldite,
Natural zeolites such as edingtonite, mordenite, duckardite, episulile bite, ferrierite, bikitite, hurlandite, clinotyrolite, stillbite, tutererite, barlarite, brewsterite, kohrensite, boothcreekite, and type A, X type, Y type, USY type (US-
(Also referred to as Y type), L type, HS type, ZK-5 type, B
Type, R type, S type, G type, D type, T type, W type, C type, Ze
Olon type, ZSM-5, mordenite, ferrierite and the like.

Examples of the organic salts include alkali metal carboxylates and sulfonates. As carboxylates, carboxylates such as formate, acetate, propionate, dicarboxylates such as maleate and succinate, dicarboxylates such as monomethyl maleate and monoethyl succinate. Acid monoester salts, hydroxybutyrate, hydroxycarboxylates such as salicylate, aminobenzoates, aminocarboxylates such as aminoisobutyrate, formylbenzoate, formylcinnamate, formylpropionic acid Examples thereof include formyl carboxylate such as salt, sulfoacetate, and sulfocarboxylate such as 5-sulfoisophthalate. Examples of sulfonate include benzenesulfonate and sulfone such as p-toluenesulfonate. Acid salts, hydroxy sulfonates such as hydroxybenzene sulfonate, 2-
Amino sulfonates such as aminoethane-1-sulfonate, formyl sulfonates such as formylbenzene sulfonate, salts of sulfocarboxylic acid esters such as salts of methyl sulfoacetate, ethyl sulfoisophthalate, Examples thereof include disulfonates such as m-benzenedisulfonate, sulfohydroxycarboxylates such as sulfosalicylates, and hydroxyaminocarboxylates such as 2-hydroxy-4-aminobenzoate.

Specifically, acetates such as lithium acetate, sodium acetate, potassium acetate, rubidium acetate, and cesium acetate, lithium trifluoroacetate, sodium trifluoroacetate, potassium trifluoroacetate, rubidium trifluoroacetate, and cesium trifluoroacetate. Such as trifluoroacetate, lithium propionate, sodium propionate, potassium propionate, rubidium propionate, cesium propionate, lithium 3-hydroxypropionate, sodium 3-hydroxypropionate, potassium 3-hydroxypropionate, 3- Rubidium hydroxypropionate, propionates such as cesium 3-hydroxypropionate, lithium benzoate,
Benzoic acid salts such as sodium benzoate, potassium benzoate, rubidium benzoate and cesium benzoate, lithium maleate, sodium maleate, potassium maleate, rubidium maleate, cesium maleate, monomethyllithium maleate, monomethyl sodium maleate. , Maleic acid salts such as monomethyl potassium maleate, monomethyl rubidium maleate and monomethyl cesium maleate, succinates such as lithium succinate, sodium succinate, potassium succinate, rubidium succinate, cesium succinate, monomethyl lithium succinate , Oxalates such as lithium oxalate, sodium oxalate, potassium oxalate, rubidium oxalate, cesium oxalate, monomethyllithium oxalate, lithium salicylate, salicylic acid Thorium, potassium salicylate, rubidium, salicylates such as salicylic acid cesium, 3-formyl lithium propionic acid, 3-
Carboxylates such as sodium formylpropionate, potassium 3-formylpropionate, rubidium 3-formylpropionate, cesium 3-formylpropionate, and the like, lithium methylsulfonate, sodium methylsulfonate, methylsulfone. Methyl sulfonates such as potassium acidate, rubidium methyl sulfonate and cesium methyl sulfonate, sodium benzene sulfonate, potassium benzene sulfonate, rubidium benzene sulfonate, benzene sulfonate such as cesium benzene sulfonate, p-toluene sulfonic acid Sodium, potassium p-toluenesulfonate, p-
Rubidium toluenesulfonate, p-toluenesulfonates such as cesium p-toluenesulfonate, lithium 5-sulfosalicylate, sodium 5-sulfosalicylate, potassium 5-sulfosalicylate, rubidium 5-sulfosalicylate, cesium 5-sulfosalicylate, etc. Examples include sulfonates such as sulfosalicylates.

These additives are sufficiently effective when used alone, but may be used as a mixture of two or more if necessary.

The amount of the additive used is not particularly limited, but is 0.1 to 100% by weight, preferably 1 to 100% by weight based on the raw materials.
50% by weight is good. If the amount is larger than this, the reaction device is unnecessarily enlarged, and in the suspension bed, the removal operation after the reaction is burdened, and if the amount is smaller, the effect may be diminished.

In the present invention, the reaction can be carried out in a batch system using a suspension bed, a semi-batch system, a continuous system, or a fixed bed flow system.

The reaction according to the method of the present invention is carried out under heating and hydrogen pressure. The reaction temperature is usually 50 to 250 ° C,
120-225 degreeC is selected preferably. Even if it is higher than this, side reaction products tend to increase. On the contrary, if the temperature is lower than this, the reaction rate becomes slow. The pressure of hydrogen is usually 10 to 150 kg / cm ² G, preferably 15
~ 120 kg / cm ² G is selected. In the method of the present invention, the reaction proceeds sufficiently within this range. A high pressure exceeding this is economically unnecessary for the apparatus, and a lower pressure lowers the reaction rate.

The reaction time varies depending on the setting method of temperature, pressure, amount of catalyst or the like or the reaction method, so that it is difficult to determine the range unconditionally, but in the batch system and the semi-batch system, it is usually 1 hour or more. It is necessary and preferably 1 to 20 hours. Although it may be longer than this, the reaction usually ends within this range. If it is shorter than this, a high conversion rate may not be obtained. In addition, in a continuous reaction using a suspension bed or a fixed bed flow reaction, the residence time is 0.1 to 1
0 hours is enough.

[0030]

EXAMPLES Hereinafter, this reaction will be described in more detail with reference to Examples, but it goes without saying that this reaction is not limited to these Examples.

Example 1 0.15 g of palladium chloride (PdCl ₂ manufactured by NE Chemcat) was dissolved in 10 ml of 4N aqueous hydrochloric acid. To this solution was added 2.85 g of silica crushed to 200 mesh or less (Carrieract 15 manufactured by Fuji Devison Co., Ltd.).

Water was removed under reduced pressure with a rotary evaporator, and the obtained paste was dried under reduced pressure at 80 ° C. for 2 hours and further at 110 ° C. for 2 hours.

This powder was put into a gas flow type reduction apparatus, and reduced using a gas mixed with nitrogen (135 ml / min) and hydrogen (15 ml / min) at 400 ° C. for 2 hours.
% Pd / silica catalyst was obtained.

Next, 0.016 g of lead nitrate (Pb (NO ₃ ) ₂ manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 3 ml of distilled water, and 1.00 g of the above Pd / silica catalyst was added to this solution.

Water was removed under reduced pressure with a rotary evaporator, and the obtained paste was dried at 120 ° C. for 3 hours under normal pressure.

This powder was placed in a gas flow type reduction apparatus and reduced at 200 ° C. for 1 hour using a gas mixed with nitrogen at 135 ml / min and hydrogen at 15 ml / min to obtain Pb / Pd.
/ Silica catalyst was obtained.

98 mg (1 mmol) of maleic anhydride and Pb / P were placed in a 10 ml autoclave made of stainless steel.
21 mg of d / silica, 10 mg of cesium carbonate and 1 ml of dimethoxyethane were charged, the system was sufficiently replaced with hydrogen, and then hydrogen was injected under pressure to 50 kg / cm ² G.
While heating and stirring, the temperature was raised to 180 ° C. and the hydrogenation reaction was carried out for 2 hours.

After completion of the reaction, the autoclave was cooled to room temperature, and subsequently, hydrogen was purged and the reaction solution was taken out. After filtering off the catalyst and the like, the filtrate was analyzed by gas chromatography. As a result, the yield of γ-butyrolactone was 94.3% based on the maleic anhydride as a raw material. At this time, formation of propionic acid, butanediol and tetrahydrofuran was not observed.

Example 2 A hydrogenation reaction and analysis were carried out in the same manner as in Example 1 except that monocesium succinate salt was used as an additive. As a result, the yield of γ-butyrolactone was 90.8% based on the maleic anhydride as a raw material. At this time, formation of propionic acid, butanediol and tetrahydrofuran was not observed.

Example 3 Hydrogenation reaction and analysis were carried out in the same manner as in Example 1 except that A-type zeolite (MS3A) whose ion-exchangeable cation was potassium was used as an additive. As a result, the yield of γ-butyrolactone was 98.4% based on the maleic anhydride as a raw material. At this time, formation of butanediol and tetrahydrofuran was not observed.

Example 4 The hydrogenation reaction and analysis were carried out in the same manner as in Example 1 except that the catalyst shown in Table 1 was used as the catalyst and the cesium succinate salt was used as the additive. As a result, the yield of γ-butyrolactone was 97.
It was 4%. At this time, propionic acid, butanediol,
The formation of tetrahydrofuran was not observed.

Example 5 The hydrogenation reaction and analysis were carried out in the same manner as in Example 1 except that the catalyst shown in Table 1 was used as the catalyst and cesium carbonate was used as the additive. As a result, the yield of γ-butyrolactone was 96.9% based on the raw material maleic anhydride. At this time, formation of propionic acid, butanediol and tetrahydrofuran was not observed. Comparative Example 1 98 mg (1 mmol) of maleic anhydride, Pb / Pd / silica 21 were placed in a stainless steel autoclave of 10 ml.
mg and 1 ml of dimethoxyethane were charged, the system was sufficiently replaced with hydrogen, and then hydrogen was injected under pressure to 50 kg / cm ² G. While heating and stirring, the temperature was raised to 180 ° C. and the hydrogenation reaction was carried out for 2 hours.

After completion of the reaction, the autoclave was cooled to room temperature, and then hydrogen was purged to take out the reaction solution. After the catalyst was filtered off, the filtrate was analyzed by gas chromatography. As a result, the yield of γ-butyrolactone was 86.1% based on the maleic anhydride as a raw material. At this time, butanediol and tetrahydrofuran were not produced except that 0.5% of propionic acid was produced.

Comparative Examples 2 to 3 The hydrogenation reaction and analysis were performed in the same manner as in Comparative Example 1 except that the catalysts shown in Table 1 were used. The results are shown in Table 1. Also in this comparative example, formation of butanediol and tetrahydrofuran was not observed.

[0045]

[Table 1]

[0046]

According to the present invention, when hydrogenating a saturated and / or unsaturated dicarboxylic acid derivative, a conventional heterogeneous catalyst is obtained by carrying out a hydrogenation reaction using palladium and lead supported on a carrier as a catalyst. It is possible to produce lactones in a high yield and a high selectivity under mild conditions as compared with.

Front page continuation (72) Inventor Takashi Okada 1-6-17 Hatsunaka, Yokkaichi-shi, Mie (72) Inventor Atsushi Fujimura Yokkaichi-shi, Mie 6-7-8 (72) Inventor Hiroyuki Sasakihara Yokkaichi, Mie 6618-12 Sakuramachi, Ichi (72) Takanori Miyake, Yokkaichi, Mie 3-5-1 (72) Inventor, Yoshiaki Kano, Mie Prefecture, Miyukigaoka, Yokkaichi, 1504-67 (72) Inventor, Toshihiro Saito, Mie Prefecture Yokkaichi City aka 4-14-22

Claims (2)

[Claims] 1. When hydrogenating a saturated and / or unsaturated dicarboxylic acid derivative, a hydrogenation reaction is carried out in the presence of an alkali metal salt using a catalyst composed of palladium and lead supported on a carrier. Method for producing lactones. 2. The method according to claim 1, wherein the saturated and / or unsaturated dicarboxylic acid derivative is succinic acid and / or maleic acid derivative, and the lactone is γ-butyrolactone.