JPH0641106A - Production of lactones - Google Patents

Abstract

PURPOSE:To produce lactones, especially gamma-butyrolactone useful as a solvent for an electrically conductive organic solution or a synthetic raw material for pyrrolidones in a high selectivity from a saturated and/or unsaturated dicarboxylic acid derivative under mild condition. CONSTITUTION:A saturated and/or unsaturated dicarboxylic acid derivative is hydrogenated in the presence of an inorganic alkali metal salt by using a capalyst composed of a group VIII noble metal supported on a carrier.

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. [gamma] -butyrolactone is a compound useful as a solvent for an organic electroconductive solution, a synthetic raw material for pyrrolidones and the like.

[0002]

2. Description of the Related Art Hitherto, 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 a catalyst, a method using an activated carbon-supported palladium catalyst (hereinafter abbreviated as Pd / C) (US Pat. No. 3,113,138) and a method using a nickel-based catalyst (for example, JP-B-43-6947). , A method using a cobalt-palladium-based catalyst (for example, JP-B-58-29).
No. 142) is known.

However, the method using Pd / C is
When succinic anhydride is used as a raw material, γ-butyrolactone is obtained in a relatively high yield, but when maleic anhydride is used, a two-step reaction is required, and in addition, a catalyst is added during operation. There's a problem.

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 kg /
Since it is as severe as cm ² G, side reactions such as formation of cyclic ether and decarboxylation proceed, and the selectivity of lactones is not 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. It is an object of the present invention to provide a method for producing lactones, particularly γ-butyrolactone, with high selectivity.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a noble metal of Group VIII supported on a carrier is used as a catalyst in the presence of an inorganic alkali metal salt. It was found that lactones can be produced highly selectively in a single-stage hydrogenation reaction under mild conditions regardless of whether a saturated or unsaturated dicarboxylic acid derivative is used as a raw material by carrying out a hydrogenation reaction. 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 inorganic alkali metal salt using a noble metal of Group VIII supported on a carrier as a catalyst. The present invention relates to a method for producing lactones characterized by:

The present invention will be described in detail below.

The raw materials used in the present invention are saturated and / or unsaturated dicarboxylic acid derivatives. Specifically, maleic anhydride, succinic anhydride, itaconic anhydride, citraconic anhydride, methylsuccinic anhydride, anhydrides of saturated and / or unsaturated dicarboxylic acids such as glutaric anhydride, maleic acid, succinic acid, fumaric acid. , Itaconic acid, citraconic acid,
Examples thereof include saturated and / or unsaturated dicarboxylic acids such as methylsuccinic acid and glutaric acid. Particularly when .gamma.-butyrolactone is intended, maleic anhydride, succinic anhydride, maleic acid, succinic acid and fumaric acid can be mentioned.

The saturated or unsaturated dicarboxylic acid derivatives which are the starting materials may be mixed in any proportion as long as 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 not particularly limited as long as it is inert to the hydrogenation reaction and does not react with the lactone that is a product, for example, diethyl ether, dimethoxyethane, diglyme, triglyme, tetrahydrofuran, ethers such as dioxane, Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, acetophenone and other ketones, methyl acetate, ethyl acetate, methyl benzoate, ethyl benzoate and other esters, methanol, ethanol, n
Alcohols such as -butanol, iso-butanol, tert-butanol, 1,4-butanediol, n-
Aliphatic hydrocarbons such as hexane and cyclohexane, aromatic hydrocarbons such as benzene, toluene, ethylbenzene and cumene, acidic solvents such as acetic acid, lactones such as γ-butyrolactone, acid amides such as 2-pyrrolidone and N-methylpyrrolidone And the like. 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 Group VIII noble metal supported on a carrier. In the present invention, a Group VIII noble metal supported on a carrier is used as a catalyst. Such a catalyst can be obtained by subjecting a noble metal compound and a carrier to physical and chemical treatments. V to use
The Group III noble metal compound is not particularly limited as long as it can be converted into a metallic Group VIII noble metal during or before the hydrogenation reaction. Specifically, ammonium hexachloropalladate, ammonium tetrachloropalladate, dinitrodiamine palladium,
Palladium bromide, chlorocarbonylpalladium, palladium chloride, palladium iodide, palladium nitrate, palladium oxide, palladium sulfate, palladium acetate, potassium dinitrosulfite palladate, potassium hexachloropalladate, potassium tetrabromopalladate, potassium tetrachloropalladate. , Sodium hexachloropalladate, sodium tetrachloropalladate, tetraamminepalladium chloride, tetraamminepalladium nitrate, cis-dichlorodiaminepalladium, trans-dichlorodiaminepalladium,
Palladium compounds such as dichloro (ethylenediamine) palladium, potassium tetracyanopalladate, ammonium hexachlororhodate, ammonium pentachloroacuorodate, potassium pentachloroacuorodate, rhodium bromide, rhodium chloride, rhodium hydroxide, rhodium iodide, Rhodium nitrate, rhodium oxide, sodium hexabromorhodate, sodium hexachlororhodate, mel-trichlorotriammine rhodium, chloropentaammine rhodium chloride, dichlorobis (ethylenediamine) rhodium nitrate, cis-dichlorobis (ethylenediamine) rhodium nitrate, tris (ethylenediamine) ) Rhodium chloride, trans-dichlorotetrapyridine rhodium chloride, dodecacarbonyltetrarhodium Rhodium compounds such as hexadecacarbonyl hexarhodium, ammonium oxydecachlorodiruthenate, ammonium pentachloroaquatheruthenate, ammonium ruthenate chloro, potassium oxydecachlorodiruthenate, potassium pentachloroaquathenate, potassium perruthenate, Ruthenium bromide, ruthenium chloride, ruthenium iodide, ruthenium nitrate, nitrosyl ruthenium nitrate, ruthenium oxide, sodium oxydecachlorodiruthenate, hexaammine ruthenium chloride, pentaammine chlorthenium chloride, hexaammine ruthenium bromide, dodecacarbonyl triruthenium, hexa Carbonyl tetrachlorodiruthenium, ruthenium compounds such as cesium tricarbonyltrichlororuthenate, hexabromo Ammonium dihydrate, ammonium hexachloroiridate, hexachloroiridate, iridium bromide, iridium chloride, iridium oxide, potassium hexabromoiridate, potassium hexachloroiridate, sodium hexabromoiridate, sodium hexachloroiridate, chloropentaammineiridium chloride Thing, c
is-dichlorobis (ethylenediamine) iridium chloride, trans-dichlorobis (ethylenediamine)
Iridium compounds such as iridium chloride, dodecacarbonyltetriridium, trans-octacarbonyloctachlorotetriridium acid, ammonium hexabromoplatinate, ammonium tetrachloroplatinate, dinitrodiamineplatinum, dinitrosulfiteplatinic acid, hexabromoplatinic acid, hexachloro Platinic acid, hexahydroxyplatinic acid, platinum bromide, platinum chloride, platinum iodide, platinum oxide, potassium hexabromoplatinate, potassium hexachloroplatinate, potassium hexahydroxoplatinate, potassium hexaiodoplatinate, potassium tetrabromoplatinate, tetrachloro Potassium platinate, sodium hexabromoplatinate, sodium hexachloroplatinate, sodium hexahydroxoplatinate, sodium tetrachloroplatinate,
Platinum compounds such as tetraammine platinum chloride, tetraammine platinum hydroxide and sodium tetracyanoplatinate can be mentioned. Preferred is a palladium compound.

The amount of the Group VIII noble metal supported on the catalyst used is 0.1 to 20% by weight, preferably 0.5 to 10% by weight, based on the total weight of the catalyst. Even if it is 20% by weight or more, the increase in activity per unit weight of the noble metal of Group VIII is small, which is not preferable. If it is less than 0.1%, sufficient activity cannot be obtained.

The amount of 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 carrier may be a porous substance, and specific examples include silica, alumina, silica-alumina, zeolite, diatomaceous earth, silica magnesia, silica zirconia, magnesia, zirconia, titania and other crystalline or non-crystalline metals. Examples thereof include oxides or complex oxides, layered clay compounds such as teniolite and hectorite, activated carbon and the like. 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 used for the suspension bed, and tablet compression molded products, spherical or rod-shaped extrusion molded products, and the like are used for the fixed bed.

The method of producing the catalyst used in the present invention is not particularly limited, and those produced by a known method can be used. For example, it can be prepared by a physical mixing method, an impregnation method, an ion exchange method or the like. In the case of the impregnation method, a noble metal compound of Group VIII is dissolved in a suitable solvent, a carrier is added thereto, and if necessary, the mixture is left standing for a predetermined time and then dried. The reduction may be performed directly after drying, or in some cases, reduction may be performed after firing. Of course, it may be reduced in the reaction system. There is no particular limitation on the reduction method, and metallic VI
Once the Group II noble metal is obtained, it 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 the noble metal of Group VIII is reduced to the metal. Generally, a temperature of up to 500 ° C is sufficient. In the case of production by the ion exchange method, ion exchange can be performed using a solution containing a noble metal compound of Group VIII at a desired concentration, and thereafter the same method as the impregnation method can be used.

The present invention is characterized in that an inorganic alkali metal salt is allowed to coexist as an additive with a noble metal catalyst of Group VIII supported on a carrier. As the inorganic alkali metal salt, various inorganic salts of alkali metals such as lithium, sodium, potassium, rubidium, and cesium can be used, and examples thereof include chloride, nitrate, carbonate, sulfate, phosphate, or hydroxide. Can be mentioned. Further, a layered compound represented by clay containing 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, sodium nitrite, and nitrite. Nitrite such as potassium nitrate, rubidium nitrite, 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, sodium-type, potassium-type, rubidium-type or cesium-type montmorillonite and carionite can be mentioned.

These additives are sufficiently effective when used alone, but may be used in combination of two or more kinds, if necessary.

The amount of additives 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. When the amount is larger than this range, the reaction device is only unnecessarily enlarged, and the removal operation after the reaction is burdened even in the suspension bed. On the contrary, if the amount is small, the effect may be diminished.

The inorganic alkali metal salt used as an additive can be coexisted by coexisting with a saturated and / or unsaturated dicarboxylic acid derivative which is a raw material or a solvent and suspended or dissolved in the carrier to carry a Group VIII noble metal catalyst. It may be used in the reaction.

In the present invention, the reaction can be carried out in a batch mode using a suspension bed, a semi-batch mode, 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 300 ° C,
120-250 degreeC is selected preferably. When the temperature is raised to 300 ° C. or higher, the progress of side reactions only increases, and when the temperature is lowered, it may be disadvantageous in terms of reaction rate. The hydrogen pressure is usually selected from 10 to 150 kg / cm ² G, preferably 15 to 120 kg / cm ² G. In the method of the present invention, the desired reaction proceeds sufficiently within this range, so that a higher pressure than this is unnecessary, and below this, there is a disadvantage in terms of reaction rate.

The reaction time is difficult to unconditionally determine because it varies depending on the setting method such as temperature, pressure, catalyst amount or the reaction method, but in the batch system and the semi-batch system, it is usually 1 hour or more. Necessary, preferably 1-20
Good time It may be longer than this, but it is meaningless since the reaction is completed within this range. Below this range, 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 may be 0.1 to 10 hours.

[0026]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples and reference examples.

Example 1 0.44 g of palladium chloride (PdCl ₂ ) is dissolved in 40 ml of 2N hydrochloric acid. To this solution is added 4.94 g of activated carbon crushed to 200 mesh or less.

Excess water was removed under reduced pressure by 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 to obtain a catalyst powder. Put the powder into a gas flow reduction device and add nitrogen 10
Using a gas mixed with 0 ml / min and 10 ml / min of hydrogen, reduction was performed at 400 ° C. for 2 hours to obtain a 5% activated carbon-supported palladium (hereinafter abbreviated as 5% Pd / C) catalyst.

98 mg (1 mmol) of maleic anhydride and 5% P in a 10 ml autoclave made of stainless steel.
d / C (21 mg), cesium sulfate (10 mg) and dimethoxyethane (1 ml) were charged, the system was sufficiently replaced with hydrogen, and then hydrogen was injected under pressure to 50 kg / cm ² G. The temperature was raised to 180 ° C. and the hydrogenation reaction was carried out for 16 hours.

After the reaction was completed, the autoclave was cooled to room temperature, and then hydrogen was purged to take out the reaction liquid. After the catalyst and the like were filtered off, the filtrate was analyzed by gas chromatography. As a result, the yield of γ-butyrolactone was 97 mol% based on the maleic anhydride as a raw material. At this time,
No by-products such as THF and 1,4-BDO were found. The results are shown in Table 1.

Examples 2 to 6 Reactions and analyzes were carried out in the same manner as in Example 1 except that the compounds in Table 1 were used instead of cesium sulfate as an additive. The results are shown in Table 1.

Example 7 Montmorillonite (manufactured by Kunimine Industries; trade name KUNI)
The reaction was performed in the same manner as in Example 1 except that K-type montmorillonite prepared by ion-exchanging PIA-G) with an aqueous potassium chloride solution was used as an additive. The results are shown in Table 1.

Example 8 A reaction was carried out in the same manner as in Example 1 except that 116 mg (1 mmol) of maleic acid was used as a raw material.

As a result of the same analysis as in Example 1, the yield of γ-butyrolactone was 86 mol with respect to the maleic acid as a raw material.
It was 1% or more. At this time, by-products such as THF and 1,4-BDO were not found at all. The results are shown in Table 1.

Examples 9 to 10 Reactions and analyzes were carried out in the same manner as in Example 7 except that the compounds shown in Table 1 were used instead of cesium sulfate as an additive. The results are shown in Table 1.

Examples 11 to 12 The reaction was carried out in the same manner as in Example 1 except that the compounds shown in Table 1 were used instead of maleic anhydride as a raw material. The results are shown in Table 1.

Example 13 The reaction and analysis were carried out in the same manner as in Example 1 except that THF was used instead of dimethoxyethane as a solvent. The results are shown in Table 1.

Comparative Example 1 Reaction and analysis were carried out in the same manner as in Example 1 except that cesium sulfate was not used.

The results are shown in Table 1.

Comparative Example 2 The reaction and analysis were carried out in the same manner as in Example 8 except that cesium sulfate was not used. The results are shown in Table 1.

Comparative Examples 3 to 4 Reactions and analyzes were carried out in the same manner as in Comparative Example 1 except that the compounds shown in Table 1 were used instead of maleic anhydride as a raw material. The results are shown in Table 1.

[0042]

[Table 1]

[0043]

INDUSTRIAL APPLICABILITY According to the present invention, when hydrogenating a saturated and / or unsaturated dicarboxylic acid derivative, a hydrogenation reaction is carried out in the presence of an organic alkali metal salt using a noble metal of Group VIII supported on a carrier as a catalyst. By carrying out the above, lactones can be produced in high yield and high selectivity as compared with the conventional heterogeneous catalyst.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Takashi Okada 1-6-17 Hanatsuka, Yokkaichi-shi, Mie (72) Inventor Hiroyuki Sasakihara 6618-12 Sakuracho, Yokkaichi-shi, Mie (72) Inventor Atsushi Fujimura, Mie Yokkaichi-shi Alias 6-7-8 (72) Inventor Takanori Miyake Others Yokkaichi-shi, Mie 3-5-1 (72) Inventor Yoshiaki Kano 2-150-67 Miyukigaoka, Yokkaichi-shi, Mie (72) Inventor Saito Kotobuki Yokkaichi-shi, Mie 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 inorganic alkali metal salt using a Group VIII noble metal supported on a carrier as a catalyst. A method for producing a lactone. 2. When hydrogenating a succinic acid and / or maleic acid derivative, a hydrogenation reaction is carried out in the presence of an inorganic alkali metal salt using a Group VIII noble metal supported on a carrier as a catalyst. Method for producing γ-butyrolactone.