JPH0782189A - Method for producing 1,4-butanediol - Google Patents

Abstract

(57) [Summary] [Objective] γ-butyrolactone is hydrogenated using a catalyst under milder reaction conditions to produce 1,4-butanediol in high yield. When a 1,4-butanediol is produced by hydrogenation of γ-butyrolactone, a hydrogenation reaction is carried out using ethanol as a solvent and a catalyst composed of palladium and a rhenium compound.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing 1,4-butanediol. 1,4-Butanediol is used as a raw material for polybutylene terephthalate resin, urethane foam, urethane coatings, adhesives, etc., and is also used as a solvent for organic synthesis, vinyl chloride resin, etc., polyurethane elastic fibers, polyester elastomers, etc. It is a very useful substance as a raw material for tetrahydrofuran, which is useful as an intermediate of.

[0002]

2. Description of the Related Art Conventionally, many proposals have been made regarding a method for producing 1,4-butanediol by hydrogenating γ-butyrolactone using a catalyst. For example, JP-A-3
No. 178943, a copper-chromium-manganese-barium catalyst is used, a reaction temperature is 210 ° C., and a pressure is 60 atm.
However, there is a problem of aggregation of copper as a catalyst component. Further, in JP-A-1-290640, a Ru-alkylphosphine complex catalyst is used,
Although a method of hydrogenating at a reaction temperature of 200 ° C. and a pressure of 50 atm is described, a satisfactory 1,4-butanediol yield has not been obtained (23%). Furthermore, US Pat.
No. 0,185 describes a method of hydrogenating a palladium-rhenium catalyst supported on activated carbon at a reaction temperature of 180 ° C. and a pressure of 170 atm, but 1,4-butanediol is obtained under severe high pressure conditions. .

[0003]

Therefore, the development of a method for producing 1,4-butanediol in high yield under more mild reaction conditions by hydrogenating γ-butyrolactone using a catalyst is strongly desired. It was rare.

[0004]

As a result of intensive studies to solve the above problems, the present inventors have used alcohol as a solvent and have selected at least one metal selected from Group VIII metals of the periodic table. It was found that hydrogenation of γ-butyrolactone using the above-mentioned catalyst composed of a metal and a rhenium compound gives 1,4-butanediol highly selectively under milder conditions, and completed the present invention. It was

That is, according to the present invention, when 1,4-butanediol is produced by hydrogenation of γ-butyrolactone,
A method for producing 1,4-butanediol, characterized by carrying out a hydrogenation reaction using alcohol as a solvent, using a catalyst comprising at least one metal selected from Group VIII metals of the periodic table and a rhenium compound Is. The present invention will be described in detail below.

In the present invention, the hydrogenation reaction is carried out using alcohol as a solvent. There are no particular restrictions on the alcohol that can be used, and various alcohols can be used.
For example, alcohols having one hydroxyl group in the molecule such as methanol, ethanol, isopropanol, butanol, and diols and triols having two or more hydroxyl groups in the molecule such as ethylene glycol and butanediol can be used. Among them, methanol,
Ethanol and butanol and butanediol are preferred examples when considering the process.

The amount of alcohol used is not particularly limited as long as the raw materials are dissolved under the reaction conditions. Further, the alcohol which is a solvent does not need to be particularly dried before use, and conversely water may coexist at about 50%.

The catalyst used in the present invention is VII of the periodic table.
It is a catalyst composed of a group I metal (hereinafter simply referred to as a group VIII metal) and a rhenium compound. Examples of the Group VIII metal include one metal selected from iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, and platinum, or a mixture of two or more metals. Of these, palladium and ruthenium are more preferably used.

In the present invention, the Group VIII metal may be used by suspending powdery or pasty metal as it is in the practice of the present invention, but is preferably used by being carried on a carrier. When the carrier is used as a carrier, the preparation method is not particularly limited, and known methods such as physical mixing method, impregnation method and ion exchange method can be used.

When the impregnation method is used among these methods, the following method can be used. That is, the Group VIII metal raw material is dissolved in a suitable solvent, a carrier is added to this, and the mixture is allowed to stand for a predetermined time, if necessary.
dry. After that, the reduction may be performed directly, or in some cases, the reduction may be performed after firing. There is no particular limitation on the reduction method, and for example, reduction in a gas phase using hydrogen etc.
Alternatively, it may be reduced in the liquid phase using hydrazine or the like. The reduction temperature is not particularly limited as long as the raw material is reduced to a metal, but it is generally carried out at a temperature of 150 to 500 ° C. When the ion-exchange method is used, the raw material of Group VIII metal having a desired concentration can be used for ion-exchange, and thereafter the same method as the impregnation method can be used.

When a Group VIII metal is used by supporting it on a carrier, the amount to be supported is not particularly limited, but 0.01 to 20% by weight based on the total weight of the Group VIII metal including the carrier.
It is preferably 0.1 to 10% by weight.

In the present invention, V used as a catalyst
The amount of the group III metal used is not particularly limited, but is 0.01 to 20% by weight, preferably 0.1 to 10% by weight based on the raw material. If it is more than this, it is disadvantageous in cost, and if it is less than that, sufficient activity may not be obtained.

The raw material of the Group VIII metal used in the present invention is not particularly limited as long as it can be converted into a metal during the hydrogenation reaction of the present invention or by reduction after being supported on a carrier. For example, in the case of ruthenium, which is a preferred Group VIII metal, the ruthenium compound is ammonium ruthenate chloride, potassium perruthenate, ruthenium bromide, ruthenium chloride, ruthenium iodide, nitrosyl ruthenium nitrate, ruthenium oxide, hexaammine ruthenium chloride, hexa. Carbonyl tetrachlorodiruthenium, tris (acetylacetonato) ruthenium, tricarbonylbis (triphenylphosphine) ruthenium,
Ruthenium compounds such as dichlorotris (triphenylphosphine) ruthenium are used.

As the palladium compound, dinitrodiamine palladium, palladium bromide, chlorocarbonyl palladium, palladium chloride, palladium iodide, palladium nitrate, palladium oxide, palladium sulfate, palladium acetate, potassium tetrachloropalladate, sodium hexachloropalladate. Palladium compounds such as tetraammine palladium chloride, tetraammine palladium nitrate, dichlorobis (triphenylphosphine) palladium, and tetrakis (triphenylphosphine) palladium are used.

In the present invention, when the Group VIII metal is used by supporting it on the carrier, the carrier may be a porous substance such as silica, alumina, silica alumina, zeolite, diatomaceous earth, silica magnesia, silica zirconia,
Crystalline or amorphous metal oxides such as magnesia, zirconia, and titania or composite oxides thereof, layered clay compounds such as teniolite and hectorite, and activated carbon are used. Of these, activated carbon is particularly preferable. The shape of the carrier is not particularly limited, and it can be used as a powder or after being molded, depending on the reaction mode. Powder 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 catalyst used in the present invention is VIII.
It consists of group metals and rhenium compounds. The rhenium compound used here is a zero-valent metal itself, or a known divalent to 7-valent metal.
And various salts of valent oxide and / or rhenium. Examples of rhenium metals include rhenium black, rhenium oxides such as dirhenium heptoxide, rhenium trioxide, rhenium dioxide, and other rhenium compounds such as dirhenium heptasulfide, rhenium disulfide, rhenium heptafluoride. Rhenium hexafluoride, rhenium tetrafluoride, rhenium pentachloride, rhenium tetrachloride, rhenium trichloride, rhenium tribromide, rhenium chloride trioxide, perrhenic acid, ammonium perrhenate, tetrabutylammonium rhenium oxide, perrhenium Examples thereof include potassium acid salt, sodium perrhenate, dirhenium decacarbonyl, chloropentacarbonyl rhenium, pentacarbonylmethyl rhenium, rhenium carbonyl iodide, rhenium ethoxide, and dirhenium heptoxide ether complex.

In the present invention, the method of using the rhenium compound to be used is not particularly limited, and may be used alone or in combination of two or more as required. Further, the rhenium compound used depending on the reaction mode may be uniformly dissolved in the raw material and / or the solvent or may be mixed nonuniformly. Further, a carrier in which a rhenium compound is supported may be used. When the rhenium compound is loaded on the carrier, the rhenium compound may be loaded alone, or the rhenium compound may be loaded on the same carrier on which the Group VIII metal is loaded. When a rhenium compound alone or a rhenium compound and a Group VIII metal are supported on a carrier, the supporting method is not particularly limited. For example, a rhenium compound can be supported in the same manner as the above-illustrated Group VIII metal. When the rhenium compound and the Group VIII metal are supported on the carrier, the Group VIII metal may be formed on the carrier first, and then the rhenium compound may be supported, or conversely, after the rhenium compound is supported first, VI
A group II metal may be formed on the carrier. Furthermore V
The Group III metal and the rhenium compound may be supported on the carrier at the same time.

When the rhenium compound is used by supporting it on a carrier, the amount supported is not particularly limited, but 0.01 to 20% by weight based on the total weight of the rhenium compound including the carrier.
It is preferably 0.1 to 10% by weight.

In the present invention, the amount of the rhenium compound used as the catalyst is not particularly limited, but 0.01 to 20% by weight, preferably 0.1 to 10% by weight, relative to the raw material. If it is more than this, it is disadvantageous in cost, and if it is less than this, sufficient activity cannot be obtained.

In the present invention, γ-butyrolactone is used as a raw material.

Further, 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 230 ° C, preferably 120 to 220 ° C. If the temperature is higher than this, the progress of side reactions may increase, and if the temperature is lower than this, there is a disadvantage in the reaction rate. The hydrogen pressure is usually 10 to 150 kg / cm ² G, preferably 15 to 120.
kg / cm ² G is selected, and the desired reaction proceeds sufficiently within this range in the method of the present invention.

It is difficult to unconditionally determine the reaction time because the reaction time varies depending on the setting method of the temperature, pressure, catalyst amount or reaction method, but in the batch system and the semi-batch system, usually one hour or more is required. , Preferably 1 to 20 hours. If the reaction time is longer than 20 hours, the reaction may further proceed and a by-product may be produced. On the other hand, if the time is shorter than this range, a high yield 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 15 hours.

[0024]

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.

The symbols used in the tables of the examples are as follows.

BDO: 1,4-butanediol THF: Tetrahydrofuran BuOH: Butanol ReCO: Dilenium decacarbonyl TBRe: Tetrabutylammonium rhenium oxide Example 1 86 mg (1 mmol) of γ-butyrolactone in a 10 ml stainless steel autoclave, 5%. 21 mg of Pd / activated carbon (manufactured by Aldrich Chemical Co.), 3.3 mg of dirhenium decacarbonyl, and 1 ml of ethanol as a solvent were charged. Next, after thoroughly replacing the system with hydrogen,
Hydrogen was injected under pressure so that the pressure was 100 Kg / cm ² G. After hydrogen pressure was introduced, the temperature was raised to 180 ° C. with heating and stirring, and a 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 removing the catalyst and the like by filtration, the filtrate was analyzed by gas chromatography. The reaction results are shown in Table 1.

Example 2 Reaction and analysis were carried out in the same manner as in Example 1 except that 1 ml of ethanol and 1.8 mg of water were used as the solvent. The reaction results are shown in Table 1.

Example 3 Reaction and analysis were carried out in the same manner as in Example 1 except that 4.9 mg of tetrabutylammonium rhenium oxide was used instead of dirhenium decacarbonyl. The reaction results are shown in Table 1.

Example 4 Reaction and analysis were carried out in the same manner as in Example 2 except that 4.9 mg of tetrabutylammonium rhenium oxide was used instead of dirhenium decacarbonyl. The reaction results are shown in Table 1.

Example 5 Reaction and analysis were carried out in the same manner as in Example 1 except that 37.2 mg of 5% Re / alumina was used instead of dirhenium decacarbonyl, and the reaction temperature was 170 ° C.
The reaction results are shown in Table 1.

Example 6 Reaction and analysis were carried out in the same manner as in Example 2 except that 57.2% Re / alumina 37.2 mg was used instead of dirhenium decacarbonyl, and the reaction temperature was 170 ° C.
The reaction 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 1 ml of an ether compound, dimethoxyethane, was used as the solvent instead of ethanol. The reaction results are shown in Table 1.

Comparative Example 2 Reaction and analysis were carried out in the same manner as in Example 3 except that 1 ml of triglyme was used instead of ethanol as the solvent. The reaction results are shown in Table 1.

Comparative Example 3 Reaction and analysis were carried out in the same manner as in Example 1 except that 1 ml of dioxane was used instead of ethanol as the solvent. The reaction results are shown in Table 1.

[0036]

[Table 1]

[0037]

According to the present invention, when hydrogenating γ-butyrolactone, the hydrogenation reaction is carried out in the presence of a catalyst composed of a Group VIII metal and a rhenium compound using an alcohol as a solvent, whereby the conventional reaction conditions are used. 1,4-butanediol can be produced in a high yield under mild conditions as compared with.

Claims (1)

[Claims] 1. Hydrogenation of γ-butyrolactone yields 1,4
-In the production of butanediol, VI of the Periodic Table
A process for producing 1,4-butanediol, which comprises carrying out a hydrogenation reaction using an alcohol as a solvent and a catalyst comprising at least one metal selected from Group II metals and a rhenium compound.