JPH0782187A - Production of 1,4-butanediol - Google Patents

Abstract

PURPOSE:To highly selectively produce 1,4-butanediol under mild reaction conditions by hydrogenating gamma-butyrolactone in the presence of a catalyst. CONSTITUTION:A method for producing 1,4-butanediol comprises hydrogenating C-butyrolactone in the presence of a catalyst comprising palladium metal and a rhenium compound and in the presence of an amine compound, an alkali type zeolite or water as an additive.

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-based paints, adhesives, etc., as a solvent for organic synthesis,
It is a very useful substance as a raw material for tetrahydrofuran, which is useful as a solvent for vinyl chloride resins and the like, and as an intermediate for polyurethane elastic fibers and polyester elastomers.

[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, in Japanese Patent Laid-Open No. 3-178943, copper-chromium-manganese-
Using barium catalyst, reaction temperature 210 ℃, pressure 60at
Although a method of hydrogenating with m has been described, there are problems of agglomeration of copper as a catalyst component and treatment of heavy metals in a used catalyst. Further, in Japanese Patent Laid-Open No. 1-290640, Ru is disclosed.
-Using an alkylphosphine complex catalyst, a reaction temperature of 200
A method of hydrogenating at 50 ° C and a pressure of 50 atm is described, but a satisfactory yield of 1,4-butanediol is not obtained (23%). Further, U.S. Pat. No. 4,550,185 describes a method of hydrogenating using a palladium-rhenium catalyst supported on activated carbon at a reaction temperature of 180 ° C. and a pressure of 170 atm. -Obtaining butanediol.

[0003]

Therefore, it is strongly desired to develop a method for producing 1,4-butanediol highly selectively under more mild reaction conditions by hydrogenating γ-butyrolactone using a catalyst. It was rare.

[0004]

Means for Solving the Problems As a result of intensive studies to solve the above problems, the present inventors have found that a metal of Group VIII of the periodic table in the presence of an amine compound, an alkaline zeolite or water. It has been found that hydrogenation of γ-butyrolactone using a catalyst composed of at least one metal selected from the group consisting of a rhenium compound and 1,4-butanediol can be highly selectively obtained under milder conditions. Has been completed.

That is, according to the present invention, when 1,4-butanediol is produced by hydrogenation of γ-butyrolactone,
A hydrogenation reaction is performed by using a catalyst composed of a rhenium compound and at least one metal selected from Group VIII metals of the periodic table, and coexisting with at least an amine compound, an alkaline zeolite or water as an additive. The present invention relates to a method for producing 1,4-butanediol. The present invention will be described in detail below.

In the present invention, an amine compound, an alkali type zeolite or water is used as an additive in the presence of a raw material and a catalyst.

The amine compounds usable in the present invention include primary amines, secondary amines, tertiary amines, pyridine compounds and the like.

The primary amines are monoamines represented by RNH ₂ , and R represents a substituent such as an alkyl group, an aryl group, a cycloalkyl group and a hydroxyalkyl group.
The primary amines include methylamine, ethylamine,
Examples thereof include n-propylamine, i-propylamine, n-butylamine, t-butylamine, cyclohexylamine and monoethanolamine. T-of these
Butylamine is preferably used.

The secondary amines are di-substituted monoamines represented by R ¹ R ² NH and R ¹ NH- (CH ₂ ) _n -NHR.
² is a di-substituted diamine represented by ² (n is an integer of 1 to 6), and R ¹ and R ² are substituents such as an alkyl group, an aryl group, a cycloalkyl group and a hydroxyalkyl group. Examples of the di-substituted monoamines include dimethylamine, diethylamine, dipropylamine, methylbenzylamine, methylcyclohexylamine, diethanolamine, piperidine and the like. The di-substituted diamines include N, N'-dimethylethylenediamine, N, N'-
Examples thereof include dimethylpropanediamine and piperazine. Of these, dipropylamine is preferably used.

The tertiary amines are tri-substituted monoamines represented by R ¹ R ² R ³ N, R ¹ R ² N- (CH ₂ ) _n -NR ³
Tetra-substituted diamines represented by R ⁴ (n is an integer of 1 to 6), and R ^{1 to} R ⁴ are substituents such as an alkyl group, an aryl group, a cycloalkyl group, and a hydroxyalkyl group. Examples of tri-substituted monoamines include trimethylamine, triethylamine, tripropylamine, dimethylbenzylamine, dimethylcyclohexylamine, methyldicyclohexylamine, dimethyloctylamine,
Dimethyldodecylamine, methyldiethanolamine,
Examples include triethanolamine, methyldiisopropanolamine, triisopropanolamine and the like. Examples of the tetra-substituted diamines include tetramethylethylenediamine, tetramethylpropanediamine, tetramethylhexamethylenediamine, triethylenediamine, bis (dimethylaminoethyl) ether, N, N'-dimethylpiperazine and tetramethyltoluenediamine. Of these, trimethylamine, triethylamine and tripropylamine are more preferably used.

The pyridine compound is a pyridine compound having a substituent such as pyridine or an alkyl group, an aryl group, a cycloalkyl group, a halogen, a hydroxyl group, an alkoxy group and a carboxyl group. Examples of these are
Examples thereof include pyridine, picoline, lutidine, phenylpyridine, nicotinic acid, picolinic acid and bipyridyl, and among these, pyridine is more preferred.

In the present invention, an alkali type zeolite can be used as an additive. Zeolite is M _{2 / n}
It is a crystalline silicate generally referred to as T ₂ O ₃ .xSiO ₂ . Here, T is an element in the zeolite skeleton, which is generally a trivalent metal such as aluminum, iron, or boron, and x is usually an integer of 2 or more. Zeolite is a crystalline compound in which the TO ₄ tetrahedron and the SiO ₄ tetrahedron are regularly and three-dimensionally arranged through oxygen atoms so that the O / (Si + T) ratio is 2. Since T is a trivalent cation, TO ₄ carries a negative charge, and thus M having a positive charge is required to neutralize this negative charge. Therefore, M need only be a cationic species to maintain the skeletal structure of zeolite, and a proton, an alkali metal, or an alkaline earth metal is common. 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.

When zeolite is used in the method of the present invention, it is essential only to use zeolite in which M is an alkali metal, and T and x are not particularly limited. Examples of alkali metals include lithium, sodium, potassium, rubidium and cesium. In the method of the present invention, the crystal structure of the zeolite used is not particularly limited. Specifically, Phillipsite, faujasite, erionite, offretite, mordenite,
Natural zeolite such as ferrierite, A type, X type, Y
Examples thereof include synthetic zeolites such as type, USY type, L type, ZSM-5, mordenite, and ferrierite.
In addition, although some of the known zeolites can be synthesized, it goes without saying that the synthesized ones can be used. Zeolite is generally obtained as an alkali type zeolite, and may be used as it is or may be ion-exchanged with a desired alkali cation in the present invention.

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 atoms to T atoms, which atomic ratio is preferably 0.05 to 1.0, more preferably Is 0.2 to 1.0
Is. If the amount of alkali atoms is too small, the effect of coexistence cannot be sufficiently exerted.

There are no particular restrictions on the ion exchange method for obtaining the desired alkali cation species and alkali cation amount, and any ordinary method can be used. For example, as the most general example, a desired salt or a salt containing two or more kinds of alkali metals is dissolved in a desired amount of water, ion exchange is performed at a predetermined temperature for a predetermined time, washed with water, and dried to form an alkali-type zeolite. can do. If necessary, a product that has been heat-treated under the flow of air or an inert gas can also be used.
The heat treatment temperature is not particularly limited as long as the alkaline zeolite does not cause structural destruction, and is generally performed up to 500 ° C. Further, there are zeolites having different skeletons of silicon / aluminum ratio even though they have the same crystal structure, but any of them can be used.

There are no particular restrictions on the method of adding the amine compound, the alkaline zeolite or the water used as an additive in the method of the present invention, and they may be added individually. However, more preferably, the amine compound and water, or the alkaline zeolite and water are added in combination.

The amounts of the amine compound, alkaline zeolite and water used are not particularly limited, but they are preferably 0.1 to 300% by weight, preferably 1 to 250% by weight, based on the raw materials. If it is more than this, the effect does not improve significantly,
If it is less than this range, sufficient activity may not be obtained.

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. Of these, VIII
Group metals include iron, cobalt, nickel, ruthenium,
One or a mixture of two or more selected from rhodium, palladium, osmium, iridium and platinum can be exemplified, and palladium and ruthenium are more preferably used.

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

In the case of the impregnation method among these preparation methods, the raw material of the Group VIII metal is dissolved in a suitable solvent, the carrier is added to this, and the mixture is mixed, and if necessary, left standing for a predetermined time and then dried. . After that, the reduction may be performed directly, or in some cases, the reduction may be performed after firing. The reduction method is not particularly limited, and may be reduced in the gas phase using hydrogen or the like, or 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 desired concentration of V
Ion exchange can be performed using the raw material of the group III metal, and thereafter, it can be prepared by a method similar to the impregnation method.

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

VI used as a catalyst in the present invention
The amount of the Group II 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 20% by weight, there is a cost disadvantage, and if it is less than 0.01% by weight, 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 a reduction reaction after being loaded on a carrier. For example, as the cobalt compound, cobalt chloride, cobalt bromide, cobalt iodide, cobalt nitrate,
Examples thereof include cobalt sulfate, cobalt carbonate, and hexaamminecobalt bromide, and examples of the nickel compound include nickel carbonate, nickel chloride, nickel hydroxide, nickel nitrate, nickel oxide, nickel sulfate, nickel acetate, nickel oxalate, and the like.

Examples of the ruthenium compound include ammonium ruthenate, potassium perruthenate, ruthenium bromide, ruthenium chloride, ruthenium iodide, nitrosyl ruthenium nitrate, ruthenium oxide, hexaammine ruthenium chloride, hexacarbonyltetrachlorozirthenium and tris. Examples thereof include ruthenium compounds such as (acetylacetonato) ruthenium, tricarbonylbis (triphenylphosphine) ruthenium and dichlorotris (triphenylphosphine) ruthenium.

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.

Further, as the iridium compound, ammonium hexachloroiridate, iridium bromide, iridium chloride, iridium oxide, potassium hexachloroiridate, chloropentaammineiridium chloride,
Dodecacarbonyl tetriridium and the like, and platinum compounds include ammonium tetrachloroplatinate, dinitrodiamine platinum, hexabromoplatinic acid, hexachloroplatinic acid, hexahydroxyplatinic acid, platinum bromide, platinum chloride, platinum iodide, platinum oxide. , Potassium hexabromoplatinate, potassium tetrabromoplatinate, tetraammine platinum chloride, tetraammine platinum hydroxide, tetrakis (triphenylphosphine) platinum and the like.

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, Examples thereof include 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. 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. For the suspension bed, powder or granules are preferably used, and for the fixed bed, tablet compression molded products, spherical or rod-shaped extrusion molded products and the like are preferably used.

In the present invention, the catalyst comprises a Group VIII metal and a rhenium compound. The rhenium compound that can be used here is a 0-valent metal itself, a known divalent to 7-valent oxide, and / or various salts of rhenium. Examples of rhenium metal include rhenium black, examples of rhenium oxide include rhenium heptoxide, rhenium trioxide, rhenium dioxide, and the like, and examples of known rhenium compounds include, for example, dirhenium heptasulfide, rhenium disulfide, and heptafluoride. Rhenium, rhenium hexafluoride, rhenium tetrafluoride, rhenium pentachloride, rhenium tetrachloride, rhenium trichloride, rhenium tribromide, rhenium chloride trioxide, perrhenic acid, ammonium perrhenate, tetrabutylammonium rhenium oxide, Examples thereof include potassium rhenate, 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 is not particularly limited, and the rhenium compound may be used alone or in admixture of two or more, if necessary. 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. In addition, like the Group VIII metal,
A rhenium compound supported on a carrier 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 a rhenium compound and a Group VIII metal are supported on a carrier, VIII
The group metal may be first formed on the carrier and then the rhenium compound may be supported, or conversely, the rhenium compound may be first supported and then the group VIII metal may be formed on the carrier. Further, the Group VIII metal and the rhenium compound may be simultaneously supported on the carrier.

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

In the present invention, the amount of the rhenium compound used as a catalyst is not particularly limited, but it is preferably 0.01 to 20% by weight, more 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.

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

In the method of the present invention, a solvent can be used if necessary. The solvent is not particularly limited as long as it is inert to the hydrogenation reaction and does not react with the product 1,4-butanediol, and examples thereof include diethyl ether, dimethoxyethane, diglyme, triglyme, tetrahydrofuran and dioxane. Ethers, methanol, ethanol, n-butanol, i-
Examples thereof include alcohols such as butanol, t-butanol, and 1,4-butanediol, aliphatic hydrocarbons such as n-hexane and cyclohexane, and acid amides such as 2-methylpyrrolidone and N-methylpyrrolidone. Of these, dimethoxyethane, tetrahydrofuran, which has a relatively low boiling point and is easy to recover, or a solvent which does not require recovery of 1,4-
Butanediol is preferably used.

The amount of solvent used is not particularly limited. Further, these solvents do not need to be particularly dried before use, and conversely water may coexist as long as it is about 1 mol% with respect to the raw materials. When water is used as an additive, the total amount of water used in the reaction, including the water in the solvent, may be 0.1 to 300% by weight based on the raw material, and preferably 1 ~ 250 wt%.

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 pressure of hydrogen is usually 1
0 to 150 kg / cm ² G, preferably 15 to 120 k
g / 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 method of setting the 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 necessary to take 1 hour or more. , Preferably 1 to 20 hours. 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. If it is longer than this, the reaction may proceed further and a by-product may be produced. On the other hand, for times shorter than this range,
High yields may not be obtained in some cases.

[0038]

The present invention will be described in more detail with reference to the following examples, but it goes without saying that the present invention is not limited to these examples.

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

BDO: 1,4-butanediol TH
F: Tetrahydrofuran BuOH: Butanol Pd: 5% Pd /
Activated carbon Ru: 5% Ru / activated carbon ReCO: Dyrhenium decacarbonyl TBRe: Tetrabutylammonium rhenium oxide (1): Triethylamine (2): Water (3): t-Butylamine (4): Di (n-
Propyl) amine (5): Pyridine (6): Tri (i)
-Butyl) amine (7): Molecular sieve 3A (8): Na-type mordenite Example 1 In a 10 ml autoclave made of stainless steel, γ-butyrolactone 86 mg (1 mmol), 5% Pd / activated carbon (made by Aldrich Chemical Co.) 21 mg, tetra Butyl ammonium rhenium oxide (Bu ₄ NReO ₄ ; manufactured by Aldrich Chemical Co.) 3 mg, triethylamine 10
mg and 1 ml of dimethoxyethane were charged, the system was sufficiently replaced with hydrogen, and then hydrogen was introduced under pressure to 50 Kg / cm ² G. While heating and stirring, raise the temperature to 180 ° C and
The hydrogenation reaction was carried out for 6 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 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 18 mg of water was used instead of triethylamine. 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 7 mg of t-butylamine was used instead of triethylamine. The reaction results are shown in Table 1.

Example 4 Reaction and analysis were carried out in the same manner as in Example 1 except that 10 mg of di (n-propyl) amine was used instead of triethylamine. 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 8 mg of pyridine was used instead of triethylamine. The reaction results are shown in Table 1.

Example 6 Reaction and analysis were carried out in the same manner as in Example 1 except that 18 mg of tri (i-butyl) amine was used instead of triethylamine. 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 triethylamine was not used. The reaction results are shown in Table 1.

[0048]

[Table 1]

Example 7 In a 10 ml autoclave made of stainless steel, γ-butyrolactone 86 mg (1 mmol), 5% Ru / activated carbon (manufactured by NE Chemcat Ltd.) 20 mg, dilenium decacarbonyl (Re ₂ (CO) ₁₀ ; N Chemcat Co., Ltd.) 3 mg, triethylamine 10 m
g 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, raise the temperature to 150 ° C, and
The hydrogenation reaction was carried out for an hour.

After completion of the reaction, the autoclave was cooled to room temperature, and then hydrogen was purged to take out the reaction solution. After removing the catalyst and the like by filtration, the filtrate was analyzed by gas chromatography. The reaction results are shown in Table 2.

Example 8 Molecular sieve 3A instead of triethylamine
Reaction and analysis were carried out in the same manner as in Example 7 except that 10 mg (potassium type A zeolite; manufactured by Aldrich Chemical Co.) was used. The reaction results are shown in Table 2.

Example 9 Reaction and analysis were carried out in the same manner as in Example 7 except that 10 mg of Na-type mordenite (manufactured by Tosoh Corp .; TSZ640NAA) was used instead of triethylamine. The reaction results are shown in Table 2.

Comparative Example 2 Reaction and analysis were carried out in the same manner as in Example 7 except that triethylamine was not used. The reaction results are shown in Table 2.

Example 10 The reaction and analysis were conducted in the same manner as in Example 7 except that 180 mg of water was used instead of triethylamine and the reaction temperature was 170 ° C. The reaction results are shown in Table 2. Example 11 Reaction and analysis were performed in the same manner as in Example 7 except that 180 mg of water was used in addition to triethylamine and the reaction temperature was 170 ° C. The reaction results are shown in Table 2.

Comparative Example 3 Reaction and analysis were carried out in the same manner as in Example 10 except that water was not used. The reaction results are shown in Table 2.

Example 12 In a 10 ml autoclave made of stainless steel, 86 mg (1 mmol) of γ-butyrolactone, 20 mg of 5% Ru / activated carbon (manufactured by NE Chemcat Ltd.), direnium decacarbonyl (Re ₂ (CO) ₁₀ ); N Chemcat Co., Ltd.) 3 mg, molecular sieve 3A
After charging 10 mg, 144 mg of water and 1 ml of dimethoxyethane, the inside of the system was sufficiently replaced with hydrogen, and then 100 Kg / c
Hydrogen was press-fitted so as to have m ² G. The temperature was raised to 160 ° C. with heating and stirring, and a hydrogenation reaction was carried out for 16 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 removing the catalyst and the like by filtration, the filtrate was analyzed by gas chromatography. The reaction results are shown in Table 2.

Comparative Example 4 The reaction and analysis were carried out in the same manner as in Example 12 except that the molecular sieve 3A and water were not used. The reaction results are shown in Table 2.

[0059]

[Table 2]

[0060]

According to the present invention, when hydrogenating γ-butyrolactone, hydrogenation is carried out in the presence of a catalyst composed of a Group VIII metal and a rhenium compound in the presence of an amine compound, an alkaline zeolite and / or water. By carrying out the reaction, 1,4-butanediol can be produced highly selectively under mild conditions as compared with conventional reaction conditions.

Claims (2)

[Claims] 1. Hydrogenation of γ-butyrolactone yields 1,4
-In the production of butanediol, VI of the Periodic Table
A catalyst comprising at least one metal selected from Group II metals and a rhenium compound is used, and at least an amine compound, an alkaline zeolite or water is coexistent as an additive to carry out a hydrogenation reaction. 4-
Butanediol manufacturing method. 2. The method for producing 1,4-butanediol according to claim 1, wherein an amine compound and water, or an alkaline zeolite and water are allowed to coexist as an additive.