JPH0782190A - Production of 1,4-butanediol - Google Patents

Abstract

PURPOSE:To produce 1,4-butanediol in a high yield under mild reaction conditions by hydrogenating maleic anhydride or succinic anhydride in the presence of a catalyst. CONSTITUTION:When 1,4-butanediol is produced by hydrogenating maleic acid anhydride and/or succinic acid anhydride, the hydrogenation reaction is performed in the presence of a catalyst comprising palladium and a rhenium compound by using tert-butanol as a solvent.

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 maleic anhydride or succinic anhydride using a catalyst. For example, the Chemical Society of Japan, (7), 1195 (197).
In 4), a homogeneous rhenium catalyst is used, and the reaction temperature is 210
A method of hydrogenating at a temperature of 120 ° C. and a pressure of 120 atm is also disclosed in JP-A-2-233630.
Using barium catalyst, reaction temperature 230 ℃, pressure 40at
Further, JP-A-2-200648 describes a method of hydrogenating at m, using a homogeneous ruthenium-alkylphosphine complex catalyst at a reaction temperature of 200 ° C. and a pressure of 50 atm. However, the yields of 1,4-butanediol are low by these methods, and the yields are 58.8%, 61.1%, and 46.5%, respectively.

[0003]

Therefore, a method for producing 1,4-butanediol in high yield under milder reaction conditions by hydrogenating maleic anhydride or succinic anhydride with a catalyst is proposed. Development was strongly desired.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have selected a metal of Group VIII of the Periodic Table using a specific alcohol as a solvent. It was found that hydrogenation of maleic anhydride or succinic anhydride using a catalyst composed of at least one metal and a rhenium compound gives 1,4-butanediol highly selectively under milder conditions. The present invention has been completed.

That is, according to the present invention, when 1,4-butanediol is produced by hydrogenating maleic anhydride and / or succinic anhydride, at least one metal selected from metals of Group VIII of the periodic table is used. The present invention relates to a method for producing 1,4-butanediol, which comprises carrying out a hydrogenation reaction using a catalyst composed of a rhenium compound and a tertiary alcohol as a solvent. The present invention will be described in detail below.

In the present invention, hydrogenation reaction is carried out using a tertiary alcohol as a solvent. Alcohols are classified into primary, secondary and tertiary depending on the number of carbons to which the hydroxyl group is attached, but the solvent used in the present invention is a tertiary alcohol, and various solvents are used. Tertiary alcohols can be used. The tertiary alcohol usable in the present invention has a general formula R ¹ R ² R ³
It can be described as C-OH. Where R ¹ , R ² ,
R ³ is each independently an alkyl group such as a methyl group or an ethyl group, a phenyl group or the like, and typical tertiary alcohols include, for example, tert-butanol, tert-amyl alcohol and 1,1-dimethyl-1-. Examples thereof include phenyl carbinol and triphenyl carbinol. Of these, tert-butanol, which is inexpensive and easily available, is preferably used.

The amount of the tertiary alcohol used is not particularly limited as long as the raw materials are dissolved under the reaction conditions. Further, the tertiary alcohol as a solvent does not need to be particularly dried before use, and water may coexist at about 1 mol% with respect to the raw material.

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 method of using the rhenium compound to be used is not particularly limited, and a single compound may be used, or two or more compounds may be mixed and used as necessary. Further, the rhenium compound to be used may be uniformly dissolved in the raw material and / or the solvent or may be mixed nonuniformly depending on the reaction mode. Further, a carrier in which a rhenium compound is supported may be used. When supported on a carrier, only the rhenium compound may be supported, or the carrier on which the Group VIII metal is supported may further support a rhenium compound. in this case,
The method for supporting the rhenium compound is not particularly limited. For example, the rhenium compound can be supported in the same manner as the above-mentioned Group VIII metal. Rhenium compound and VIII
When the group metal is supported on the carrier, the group VIII metal and the rhenium compound may be simultaneously supported on the carrier, or VIII
The group metal may be loaded on the carrier first, and then the rhenium compound may be loaded, or conversely, the rhenium compound may be loaded first, and then the group VIII metal may be loaded. When the rhenium compound is used by supporting it on the carrier, the amount supported is not particularly limited, but is 0.01 to 20% by weight, preferably 0.1 to 10% by weight based on the total weight of the rhenium compound including the carrier.
% By weight.

The rhenium compound used in the present invention is a 0-valent metal itself, a known divalent to 7-valent oxide and / or various salts of 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 Potassium salt, sodium perrhenate, dirhenium decacarbonyl, chloropentacarbonyl rhenium,
Examples include pentacarbonylmethylrhenium, rhenium carbonyl iodide, rhenium ethoxide, and dirhenium heptoxide ether complex.

In the present invention, the amount of the rhenium compound used as a catalyst 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, there is a cost disadvantage, and conversely, if it is less, sufficient activity may not be obtained.

In the present invention, maleic anhydride and / or succinic anhydride are used as raw materials. When a mixture of maleic anhydride and succinic anhydride is used as a raw material, the mixing ratio is not particularly limited.

In the present invention, the reaction can be carried out in a batch mode 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 under pressure of hydrogen. 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.

The reaction time varies depending on the setting method of temperature, pressure and catalyst amount or the reaction system, so that it is difficult to determine the range unconditionally, but in the batch system and the semi-batch system, it is usually required at least 1 hour. , 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. Also,
In a continuous reaction using a suspension bed or a fixed bed flow reaction, the residence time may be 0.1 to 15 hours.

[0023]

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 TBRe: Tetrabutylammonium rhenium oxide THF: Tetrahydrofuran BuOH: Butanol Example 1 In a 10 ml stainless steel autoclave, 86 mg (1 mmol) of succinic anhydride, 5% Pd / activated carbon (Aldrich chemical. 21 mg, tetrabutylammonium rhenium oxide 4.9 mg and te which is a solvent
1 ml of rt-butanol was charged. Next, the system was sufficiently replaced with hydrogen, and then hydrogen was injected under pressure to 100 Kg / cm ² G. Then, 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.

Comparative Example 1 2-propanol secondary alcohol 1 ml as a solvent
Reaction and analysis were performed in the same manner as in Example 1 except that was used. The reaction results are shown in Table 1.

Comparative Example 2 Reaction and analysis were carried out in the same manner as in Example 1 except that 1 ml of dimethoxyethane which was an ether was used as the solvent. The reaction results are shown in Table 1.

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

[0030]

[Table 1]

[0031]

According to the present invention, when hydrogenating maleic anhydride and / or succinic anhydride, VIII
By carrying out the hydrogenation reaction using a tertiary alcohol as a solvent in the presence of a catalyst composed of a group metal and a rhenium compound, 1,4-butanediol can be produced in high yield under mild conditions as compared with conventional reaction conditions. It can be manufactured.

Claims (1)

[Claims] 1. When producing 1,4-butanediol by hydrogenation of maleic anhydride and / or succinic anhydride, at least one metal selected from metals of Group VIII of the periodic table and a rhenium compound are used. The method for producing 1,4-butanediol is characterized in that a hydrogenation reaction is carried out by using a catalyst as described above and a tertiary alcohol as a solvent.