JP3062327B2 - Production method of lactones - Google Patents

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 γ-butyrolactone. γ-butyrolactone is a compound useful as a solvent for organic electroconductive solutions and as a raw material for synthesis such as pyrrolidones.

[0002]

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

For example, a method using a palladium catalyst supported on activated carbon (hereinafter abbreviated as Pd / C) as a catalyst (US Pat. No. 3,113,138), a method using a nickel-based catalyst (for example, Japanese Patent Publication No. 43-6947). Using a cobalt-palladium catalyst (for example, Japanese Patent Publication No. 58-29)
No. 142 gazette).

However, the method using Pd / C is as follows.
When succinic anhydride is used as a raw material, γ-butyrolactone can be obtained in a relatively high yield, but when maleic anhydride is used, a two-stage reaction is required, and furthermore, a catalyst is added during the 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 / kg.
Since the reaction is severe at cm ² G, side reactions such as generation of cyclic ether and decarboxylation proceed, and the selectivity of lactones is not satisfactory.

[0006]

SUMMARY OF THE INVENTION An object of the present invention is to provide a catalyst which is milder than a conventionally known catalyst in a single-stage hydrogenation reaction even when a saturated or unsaturated dicarboxylic anhydride is used as a raw material. An object of the present invention is to provide a method for producing lactones, particularly γ-butyrolactone, with high selectivity under conditions.

[0007]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, the hydrogenation reaction was carried out in the presence of zeolite using a Group VIII noble metal supported on a carrier as a catalyst. It is found that lactones can be produced in a single-stage hydrogenation reaction even under the use of a saturated or unsaturated dicarboxylic anhydride as a raw material, and highly selectively under mild conditions. It was completed.

That is, in the present invention, when hydrogenating an anhydride of a saturated and / or unsaturated dicarboxylic acid, a hydrogenation reaction is carried out in the presence of an alkaline zeolite using a group VIII noble metal supported on a carrier as a catalyst. And a method for producing lactones.

Hereinafter, the present invention will be described in detail.

[0010] As anhydrides of saturated and / or unsaturated dicarboxylic acid raw material used in the present invention are maleic anhydride, succinic anhydride, itaconic anhydride, citraconic anhydride, methyl succinic, elevation is glutaric anhydride I can do it. Particularly, when γ-butyrolactone is intended, maleic anhydride and succinic anhydride can be used.

[0011] These raw materials of the saturated or unsaturated dicarboxylic anhydride may be mixed in any ratio as long as the hydrogenated product is the same, or may be mixed with the dicarboxylic anhydride. If the content is 20% by weight or less, a dicarboxylic acid compound obtained by hydrolyzing a dicarboxylic anhydride as a raw material may be contained.

The catalyst used in the present invention is a noble metal of Group VIII 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 is obtained by physically and chemically treating a noble metal compound and a carrier. 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, dinitrodiaminepalladium,
Palladium bromide, chlorocarbonyl palladium, palladium chloride, palladium iodide, palladium nitrate, palladium oxide, palladium sulfate, palladium acetate, potassium dinitrosulfite palladium, 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 pentachloroaquarhodate, potassium pentachloroaquarhodate, rhodium bromide, rhodium chloride, rhodium hydroxide, rhodium iodide, Rhodium nitrate, rhodium oxide, sodium hexabromorhodate, sodium hexachlororhodate, mer-trichlorotriamminerhodium, chloropentaamminerhodium 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 pentachloroaquaruthenate, ammonium chloride ruthenate, potassium oxydecachlorodiruthenate, potassium pentachloroaquaruthenate, potassium perruthenate, Ruthenium bromide, ruthenium chloride, ruthenium iodide, nitrosylruthenium nitrate, ruthenium oxide, sodium oxydecachlorodiruthenate, hexaammineruthenium chloride, pentaamminechlororuthenium chloride, hexaammineruthenium bromide, dodecacarbonyltriruthenium, hexa Ruthenium compounds such as carbonyltetrachlorodiruthenium, cesium tricarbonyltrichlororuthenate, hexabromo Ammonium iridate, 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 chloride, dodecacarbonyl tetriiridium, iridium compounds such as trans-octacarbonyloctachlorotetriiridic acid, ammonium hexabromoplatinate, ammonium tetrachloroplatinate, dinitrodiamine platinum, dinitr sulfite platinum acid, hexabromoplatinic acid, hexachloroplatinum 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 tetraammineplatinum chloride, tetraammineplatinum hydroxide and sodium tetracyanoplatinate are exemplified. Preferably, it is a palladium compound.

The amount of the noble metal of Group VIII carried 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 activity increase per unit weight of the noble metal of Group VIII becomes small, which is not preferable. On the other hand, if it is lower than 0.1%, sufficient activity cannot be obtained.

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 carrier may be a porous substance, and specific examples thereof include silica, alumina, silica alumina, zeolite, diatomaceous earth, silica magnesia, silica zirconia, magnesia, zirconia, titania, and other crystalline or non-crystalline metals. Examples include oxides or composite oxides, layered clay compounds such as teniolite and hectorite, activated carbon, and the like. Among them, activated carbon is particularly preferred. The shape of the catalyst is not particularly limited, and the catalyst can be used as it is or in the form of powder according to the reaction format. For the suspension bed, powder or granules are used, and for the fixed bed, tablet compression moldings, spherical or columnar extrusion moldings, and the like are used.

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 physical mixing method, an impregnation method, an ion exchange method, or the like. When preparing by the impregnation method, the noble metal compound of Group VIII is dissolved in an appropriate solvent, a carrier is added thereto, and if necessary, the mixture is left for a predetermined time and then dried. Reduction may be performed directly after drying, or in some cases, reduction may be performed after firing. Of course, reduction may be performed in the reaction system. There is no particular limitation on the reduction method.
If a 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 or the like. The reduction temperature is not particularly limited as long as the group VIII noble metal is reduced to a metal. Generally, temperatures up to 500 ° C. may be used. Further, in the case of producing by an ion exchange method, ion exchange can be performed using a desired concentration of a Group VIII noble metal compound, and thereafter, it can be prepared by a method similar to the impregnation method.

The present invention is characterized in that an alkali zeolite is used as an additive together with a Group VIII noble metal supported on a carrier. Zeolite is M2 _{/ n} · T
It is a crystalline silicate generally denoted as ₂ O ₃ .xSiO ₂ . Here, T is an element in the zeolite skeleton,
Trivalent metals such as aluminum, iron and boron are generally used, and x is usually an integer of 2 or more. Zeolites, TO ₄ tetrahedra and SiO ₄ tetrahedra, O / (Si +
Al) is a crystalline compound that is regularly and three-dimensionally arranged via oxygen atoms so that the ratio becomes 2. Because T is a trivalent cation, TO ₄ is negatively charged,
To neutralize this negative charge, M having a positive charge is required. Therefore, M only needs to be a cation in order to maintain the framework structure of zeolite, and hydrogen, an alkali metal, and an alkaline earth metal are generally used. n is 1 when M is a monovalent cation, and is 2 or 3 when M is a divalent or trivalent cation. Thus, the basic structure of zeolite is composed of TO ₄ and SiO ₄ tetrahedra, and M can be ion-exchanged. In the method of the present invention, it is only essential to use zeolite in which M is an alkali metal, and T and x are not particularly limited. Examples of the alkali metal include lithium, sodium, potassium, rubidium, and cesium. The zeolite used in the present invention may have any of the skeleton structures exemplified below. Illustrative examples of such zeolites include Phillipsite, Harmotome, Merlinoite, Dismondin, Amisite, Gallonite, Govinsite, Analcyme, Wairakite, Polingite, Lomontite, Yugawaralite, Shabasite, Willhendersonite, Gmelinite, Faujasite, Elionite, Offretite, levin, mazzite, natrolite, tetrasoda fluorite,
Parasoda fluorite, mesolite, scolecite, tomsonite, gonardite, eddonite, mordenite, dachaldite, episylite, ferrierite, biquitite, heurandite, clino-tylolite, stilbite, steterite, burlerite, brusterite, korencite Zeolites such as, goose creekite, A type, X type, Y
Type, USY type (also described as US-Y type), L type, H
S type, ZK-5 type, B type, R type, S type, G type, D type, T
Types, W type, C type, Zeolon type, ZSM-5, mordenite, ferrierite, and the like. In addition, among those known as natural zeolites,
Although some can be synthesized, it goes without saying that the synthesized one can be used. Preferably, it is a synthetic zeolite with few impurities. Since zeolite is generally obtained as an alkaline zeolite, in the method of the present invention, it may be used as it is, or may be used after ion exchange with a desired alkali cation. or,
In the case of an alkaline earth type zeolite, it may be used after ion exchange with an alkaline type zeolite. The amount of alkali in the alkaline zeolite used in the method of the present invention can be defined as the atomic ratio of alkali atom to T atom, and this atomic ratio is 0.05 to 1.0, preferably,
0.2 to 1.0. If the amount of the alkali atom is too small, the effect of coexistence becomes insufficient. There is no particular limitation on the method of ion exchange for obtaining the desired alkali cation species and the amount of alkali cation, and it can be carried out by a usual method. For example, as the most common example, a desired salt containing one or two or more alkali metals is dissolved in a desired amount of water, ion-exchanged at a predetermined temperature for a predetermined time, washed with water, dried, and washed with an alkali. It can be a type zeolite. If necessary, under air or inert gas flow,
Heat-treated ones can also be used. The temperature of the heat treatment is not particularly limited as long as the alkali-type zeolite does not cause structural destruction, and generally may be up to 500 ° C. Although some zeolites have the same crystal structure but different skeleton silicon / aluminum ratios, any of them can be used.

Although these additives are effective when used alone, they may be used as a mixture of two or more as necessary. The shape of the additive is not particularly limited, but depending on the reaction method, for example, the additive may be formed in a fixed bed, or may be used in the form of powder or granules in a suspension bed.

The amount of the additive to be used is not particularly limited, but is 0.1 to 100% by weight, preferably 1 to 100% by weight based on the raw material.
50% by weight is good. If the amount is larger than this, it is only necessary to increase the size of the reactor unnecessarily, and in the case of a suspension bed, only a burden is imposed on the removing operation after the reaction.

In the method of the present invention, the anhydride of the saturated and / or unsaturated dicarboxylic acid 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 product lactones.Examples include diethyl ether, dimethoxyethane, diglyme, triglyme, tetrahydrofuran, and dioxane. Ethers,
Acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, ketones such as acetophenone, methyl acetate, ethyl acetate, methyl benzoate, esters such as ethyl benzoate, methanol,
Ethanol, n-butanol, iso-butanol, t
alcohols such as tert-butanol and 1,4-butanediol; aliphatic hydrocarbons such as n-hexane and cyclohexane; aromatic hydrocarbons such as benzene, toluene, ethylbenzene and cumene; acidic solvents such as acetic acid; γ-butyrolactone And amides such as 2-pyrrolidone and N-methylpyrrolidone. Among them, preferred 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 to be used is not particularly limited as long as the raw materials are dissolved at the reaction temperature. These solvents do not need to be particularly dried before use, and conversely, water may be present if they are about 1 molar equivalent to the raw materials.

In the present invention, the reaction can be carried out batchwise, semi-batchwise, continuously with a suspension bed or in 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,
Preferably, 120 to 250 ° C is selected. If it is higher than this, the progress of side reactions only increases, and if it is lower, it is disadvantageous in terms of reaction speed. The pressure of hydrogen is usually 10
150 kg / cm ² G, preferably 15 to 120 kg
/ Cm ² G is selected. In the process of the present invention, the desired reaction proceeds sufficiently within this range, so that no higher pressure is necessary, and below this, there is a disadvantage in terms of reaction rate.

The reaction time varies depending on the setting method of the temperature, pressure, amount of catalyst, etc. or the reaction method, so it is difficult to determine the range in a straightforward manner. However, in a batch system or a semi-batch system, usually 1 hour or more is required. Required, preferably 1-16
Time is good. It may be longer than this, but it is meaningless since the reaction is completed within this range. Below this, a high conversion rate may not be obtained. In a continuous reaction using a suspension bed or a fixed bed flow reaction, the residence time may be 0.1 to 10 hours.

[0025]

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 and reference examples.

Reference Example (Preparation method of catalyst) A typical preparation method of the catalyst used in this example will be described using 5% Pd / C as an example. 0.44 g of palladium chloride (PdCl ₂ ) is dissolved in 40 ml of 2N hydrochloric acid. This solution is impregnated with 4.94 g of activated carbon ground to 200 mesh or less.

Excess water was removed under reduced pressure using a rotary evaporator, and the obtained paste was dried at 80 ° C. for 2 hours under reduced pressure, and further dried at 110 ° C. for 2 hours to obtain a catalyst powder. (Reduction of catalyst) The above-mentioned powder was put into a gas flow reduction device, and reduced at 400 ° C. for 2 hours using a gas mixed with 100 ml / min of nitrogen and 10 ml / min of hydrogen, and 5%
Pd / C activity was obtained. (Ion exchange of zeolite) A typical example of ion exchange will be described. Na-type mordenite (manufactured by Tosoh Corporation; TSZ64)
0NAA) 10 g, potassium chloride 21.8 g, distilled water 1
50 ml was placed in a three-necked flask equipped with a reflux condenser. The temperature was adjusted to 95 ° C. using a warm bath, and ion exchange was performed for 5 hours. The obtained slurry was filtered, washed with water, dried at 110 ° C. overnight, and then calcined at 500 ° C. for 3 hours under an air stream to obtain potassium mordenite. The atomic ratio of potassium to aluminum, K / Al, was 0.98. Na /
Al was 0.02.

The following examples used the above catalyst.

Example 1 In a 10 ml stainless steel autoclave, 98 mg (1 mmol) of maleic anhydride and 21 m of 5% Pd / C were added.
g, molecular sieve 3A (potassium form A-type zeolite; Aldrich Chemical Co.) was charged 10mg and dimethoxyethane 1 ml, was thoroughly purging the system with hydrogen, it was injected hydrogen to be 50 kg / cm ² G . The temperature was raised to 180 ° C. while heating and stirring, and a hydrogenation reaction was performed for 4 hours.

After the completion of the reaction, the autoclave was cooled to room temperature, then purged with hydrogen 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 99 mol% with respect to the starting material maleic anhydride. At this time, no by-products such as THF and 1,4-BDO were observed. Table 1 shows the results.

Example 2 A reaction was carried out in the same manner as in Example 1 except that 100 mg (1 mmol) of succinic anhydride was used as a raw material.

As a result of analysis in the same manner as in Example 1, the yield of γ-butyrolactone was 99 m with respect to the raw material succinic anhydride.
ol% or more. At this time, THF, 1,4-BDO
No by-products were seen at all. Table 1 shows the results.

Examples 3 and 4 The reaction and reaction were carried out in the same manner as in Example 1 except that the compounds shown in Table 1 were used instead of molecular sieve 3A (potassium type A zeolite) as an additive and the reaction time was changed to 16 hours. Analysis was carried out. Table 1 shows the results.

Example 5 A 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. Table 1 shows the results.

Example 6 Molecular sieve 3A (potassium type A) was used as an additive.
The reaction and analysis were conducted in the same manner as in Example 1 except that potassium-type mordenite was used instead of the zeolite (type zeolite). Table 1 shows the results.

Comparative Example 1 A reaction and analysis were carried out in the same manner as in Example 1 except that molecular sieve 3A (potassium type A zeolite) was not used. Table 1 shows the results.

Comparative Example 2 A reaction and analysis were carried out in the same manner as in Example 2 except that molecular sieve 3A (potassium type A zeolite) was not used. Table 1 shows the results.

Comparative Example 3 A reaction and analysis were carried out in the same manner as in Comparative Example 1 except that the reaction time was changed to 16 hours. Table 1 shows the results.

[0039]

[Table 1] Example 7 In a 10 ml stainless steel autoclave, 98 mg (1 mmol) of maleic anhydride and 21% of 5% Pd / C were added.
g, molecular sieve 3A (potassium type A zeolite A) 10 mg, dimethoxyethane 1 ml and water 1
After charging 8 mg and thoroughly replacing the inside of the system with hydrogen, 50 kg
/ Cm ² G was injected with hydrogen. The temperature was raised to 180 ° C. while heating and stirring, and a hydrogenation reaction was performed for 4 hours.

After the completion of the reaction, the autoclave was cooled to room temperature, then purged with hydrogen 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 95 mol% based on the starting material maleic anhydride. At this time, no by-products such as THF and 1,4-BDO were observed.

[0041]

According to the present invention, the hydrogenation of an anhydride of a saturated and / or unsaturated dicarboxylic acid is carried out using a noble metal of Group VIII supported on a carrier as a catalyst in the presence of an alkali type zeolite. By performing the reaction, lactones can be produced with high yield and high selectivity as compared with conventional heterogeneous catalysts.

Continuation of the front page Examiner Junko Uchida (56) References JP-A-4-16237 (JP, A) JP-A-3-98647 (JP, A) JP-A-2-9873 (JP, A) JP-A Sho51 -14187 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 307/33 B01J 29/10 B01J 29/20 CA (STN) REGISTRY (STN)

Claims (1)

(57) [Claims] (1) maleic anhydride, succinic anhydride, italic anhydride
Conic acid, citraconic anhydride, methyl succinic anhydride and
Hydrogenation of one or more saturated and / or unsaturated dicarboxylic acid anhydrides selected from aqueous glutaric acid is carried out by using a group VIII noble metal supported on a carrier as a catalyst in the presence of an alkaline zeolite. A method for producing lactones, which comprises carrying out a chlorination reaction.