JPH06157490A - Production of tetrahydrofuran - Google Patents

Abstract

PURPOSE:To obtain a method for producing tetrahydrofuran in high yield by hydrogenating maleic anhydride, succinic anhydride or gamma-butyrolactone which is a raw material under milder conditions using a catalyst. CONSTITUTION:This method for producing tetrahydrofuran is characterized by carrying out the hydrogenating reaction in the coexistence of an acidic substance using a catalyst composed of at least one or more metals selected from group VIII of the periodic table and a rhenium compound in hydrogenating at least one or more compounds selected from the group consisting of maleic anhydride, succinic anhydride and gamma-butyrolactone.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing tetrahydrofuran. Tetrahydrofuran is a very useful substance as an organic synthesizing solvent, a solvent such as a vinyl chloride resin, and an intermediate such as a polyurethane elastic fiber and a polyester elastomer.

[0002]

2. Description of the Related Art Hitherto, many proposals have been made regarding a method for producing tetrahydrofuran by hydrogenating a maleic acid derivative, a succinic acid derivative or γ-butyrolactone using a catalyst.

For example, Japanese Examined Patent Publication (Kokoku) No. Sho 49-9464 uses a nickel-based catalyst and a reaction temperature of 90 ° C. (inlet) to
A method for continuously hydrogenating maleic anhydride at 260 ° C. (outlet) and a hydrogen pressure of 400 atm is described. In this method, tetrahydrofuran is obtained in a high yield by partly producing γ-butyrolactone, but it requires very high temperature and pressure as described above.

In Japanese Patent Publication No. 47-42832, a cobalt-rhenium type catalyst is used, and the reaction temperature is 280
A method for hydrogenating maleic anhydride at a temperature of 130 to 150 kg / cm ² G and a pressure of 130 ° C. is described. This method also requires considerable high temperature and high pressure, and the yield of tetrahydrofuran is 8
By-products such as propanol and butanol are produced at 4%.

In US Pat. No. 4,550,185, a method of hydrogenating maleic acid or its anhydride using a palladium-rhenium catalyst supported on activated carbon at a reaction temperature of 180 ° C. and a pressure of 17 MPa (about 170 atm) is disclosed. In JP-A-3-500657, a palladium alloy-rhenium-based catalyst is used, and the reaction temperature is 230 ° C. and the pressure is 80 bar.
A method for hydrogenating γ-butyrolactone at g (about 80 atm) is described. All of these methods obtain tetrahydrofuran under severe conditions of high temperature and high pressure.

[0006] Therefore, in the method for producing tetrahydrofuran by hydrogenating a maleic acid derivative, a succinic acid derivative or γ-butyrolactone using a catalyst, development of a method which gives a sufficient yield under milder reaction conditions has been strongly pursued. Was wanted.

[0007]

The object of the present invention is to hydrogenate maleic anhydride, succinic anhydride, or γ-butyrolactone as a raw material under a milder condition using a catalyst to give tetrahydrofuran in a high yield. A method of manufacturing is provided.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that maleic anhydride is produced by a catalyst composed of a Group VIII metal and a rhenium compound in the presence of an acidic substance. In the reaction for hydrogenating at least one compound selected from the group consisting of succinic anhydride and γ-butyrolactone, a process for producing tetrahydrofuran which gives a sufficient yield under milder conditions is found, and the present invention is completed. I arrived.

That is, in the present invention, in hydrogenating at least one compound selected from the group consisting of maleic anhydride, succinic anhydride and γ-butyrolactone, at least one metal selected from Group VIII of the periodic table. The present invention relates to a method for producing tetrahydrofuran, which comprises carrying out a hydrogenation reaction in the presence of an acidic substance using a catalyst composed of a rhenium compound.

The present invention will be described in detail below.

The raw material used in the present invention is at least one compound selected from maleic anhydride, succinic anhydride and γ-butyrolactone. The mixing ratio at that time may be any ratio.

According to the invention, acidic substances are used as additives in the presence of raw materials and catalysts. The acidic substance of the present invention is a substance having a Bronsted acid, which is generally defined as an acid, or a Lewis acid, and is a heterogeneous solid phase even if it is a homogeneous liquid phase in the reaction system, that is, a so-called solid acid. It may be present, and its properties are not particularly limited. Further, the acidic substance that can be used in carrying out the present invention is not particularly limited, except that it is thermally stable depending on the reaction conditions.

Examples of the acidic substance that can be used in the present invention include mineral acids and organic sulfonic acids. Here, examples of the mineral acid include phosphoric acid, hydrochloric acid, nitric acid, sulfuric acid and the like. Examples of the organic sulfonic acid include alkyl sulfonic acids, aromatic sulfonic acids having a substituent and polymer compounds having a sulfonic acid group.

Specific examples include alkyl sulfonic acids such as methane sulfonic acid, ethane sulfonic acid, propane sulfonic acid and trifluoromethane sulfonic acid, and aromatic sulfonic acids having a substituent include those of aromatic nucleus. Examples of the substituent being hydrogen are benzene sulfonic acid, naphthalene sulfonic acid, etc., Examples of the substituent being an alkyl group are para-toluene sulfonic acid, para-butyl toluene sulfonic acid, mesitylene sulfonic acid, methyl naphthalene sulfonic acid, etc. Examples in which hydrogen or an alkyl group of an aromatic nucleus is substituted with a halogen group, an alkoxy group, a carboxyl group, an ester group, a nitrile group, a nitro group or the like include paramethoxybenzenesulfonic acid, parasulfobenzoic acid t-butyl ester, paracyanobenzenesulfonic acid. , Nitroben Etc. Nsuruhon acid. Examples of the polymer compound having a sulfonic acid group, polyethylene sulfonic acid, polystyrene sulfonic acid, poly-naphthalene sulfonic acid and the like.

Further, as the acidic substance usable in the present invention, a sulfuric acid-supported metal oxide can also be used. The sulfuric acid-supported metal oxide is generally known as a solid acid having a strong acid strength, and is also called a solid superacid. The sulfuric acid-supported metal oxide can be prepared by immersing sulfuric acid in a metal hydroxide of Group IV metal of the periodic table, a metal such as iron or aluminum, or an amorphous metal oxide, followed by firing.
For example, Japanese Examined Patent Publication No. 59-6181 discloses periodic table I
A technique is disclosed in which a Group V metal hydroxide or oxide is brought into contact with a sulfate group-containing solution, and then an excessive sulfate group-containing solution is removed, followed by firing to obtain a solid superacid. The sulfuric acid-supported metal oxide used in the present invention is not particularly limited as long as it is a solid acid prepared by a known method represented by the above. Examples of the metal oxide used at this time include oxides of titanium, zirconium, hafnium, tin and lead which are metals of Group IV of the periodic table, oxides of iron, aluminum, silicon and the like and oxides thereof. Examples thereof include metal oxides, so-called complex oxides, which are composed of a combination of two or more selected.

Further, the acidic substance usable in the present invention is
Proton exchange zeolite can be used. Zeolites commonly known as solid acids are M _{2 / nT 2} O ₃
It is a crystalline silicate represented by xSiO ₂ . Here, T is an element in the zeolite skeleton, aluminum,
Trivalent metals such as iron and boron are common, and x is usually an integer of 2 or more. Zeolite is a crystalline compound in which TO ₄ tetrahedra and SiO ₄ tetrahedra are regularly and three-dimensionally arranged through oxygen atoms so that the O / (Si + Al) ratio is 2. Since T is a trivalent cation, TO ₄ carries a negative charge, and therefore, M having a positive charge is required to neutralize this negative charge. Therefore, M needs only to be a cation species in order to maintain the skeletal structure of zeolite, and is generally a proton, an alkali metal, or an alkaline earth metal, and is called M-exchanged zeolite.

In the method of the present invention, as the zeolite that can be used, the cation species of M are exchanged for protons. Zeolites are generally capable of ion-exchange with cation species, so that the proton-exchanged zeolite used may be proton-exchanged in a used state. The method for proton exchange is not particularly limited, and proton exchange can be performed by a known method. Examples of the zeolite capable of performing proton exchange include natural zeolites such as Phillipsite, faujasite, erionite, offretite, mordenite, and ferrierite, and A-type, X-type, Y-type, USY-type, L-type, ZSM-
5, synthetic zeolites such as mordenite and ferrierite can be mentioned.

In the method of the present invention, the method of adding the acidic substance to be used is not particularly limited, and it may be added singly or as a mixture of two or more kinds if necessary. Further, depending on the reaction form, depending on the acidic substance to be added, it may be uniformly dissolved in the raw material and / or the solvent, or may be mixed nonuniformly. In addition, when a solid acid such as a metal oxide supporting sulfuric acid or a proton exchange zeolite is added, there is no particular limitation on the shape thereof. For example, a molded body can be used in the fixed bed reaction method, and a powder or granules can be used in the suspension bed reaction method.

The amount of the acidic substance 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, the effect is not remarkably improved, and there is a possibility that a problem may remain in the step of separating and purifying the target product from the reaction solution after the reaction. Conversely, if it is less than this, the effect tends to be diminished.

The catalyst used in the present invention is a catalyst composed of a Group VIII metal and a rhenium compound. Examples of the Group VIII metal include one or a mixture of two or more metals such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum. Of these, palladium and / or ruthenium are more preferably used.

According to the present invention, the Group VIII metal can 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 method for preparing the carrier is not particularly limited, and those prepared by a known method such as a physical mixing method, an impregnation method, or an 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 an appropriate solvent, the carrier is added to this, and the mixture is allowed to stand for a predetermined time, if necessary, 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 for example, hydrogen or the like may be used for the gas phase reduction, or hydrazine or the like may be used for the liquid phase reduction. 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 the Group VIII metal is used by supporting it on a carrier, the amount supported is 0.01 to 5 relative to the total weight of the catalyst.
It is 0% by weight, preferably 0.1 to 20% by weight. If the supported amount exceeds 50% by weight, the catalytic activity per unit weight of metal tends to be small, and if it is less than 0.01%, 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 supported on a carrier.

For example, as the palladium compound, 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 tetrachloropalladate, sodium hexachloropalladate, Sodium tetrachloropalladate, tetraamminepalladium chloride, tetraamminepalladium nitrate, cis-dichlorodiaminepalladium, trans-dichlorodiaminepalladium, dichloro (ethylenediamine) palladium, potassium tetracyanopalladate, dichlorobis (triphenylphosphine) palladium, bis (acetyl) Acetonato) palladium, tetrakis (triphenylphosphine) pa Indium, and the like.

Examples of the ruthenium compound include ammonium oxydecachlorodiruthenate, ammonium pentachloroaquoruthenate, ammonium ruthenate chloride, potassium oxydecachlorodiruthenate, potassium pentachloroaquoruthenate, potassium perruthenate, and bromide. Ruthenium, ruthenium chloride, ruthenium iodide, nitrosyl ruthenium nitrate, ruthenium oxide, sodium oxydecachlorodiruthenate, hexaammineruthenium chloride, pentaamminechlororuthenium chloride, hexaammineruthenium bromide, dodecacarbonyltriruthenium, hexacarbonyltetra Chlorodilthenium, cesium tricarbonyltrichlororuthenate, tris (acetylacetonato) ruthenium, tricarb Bis (triphenylphosphine) ruthenium, dichloro-tris (triphenylphosphine) ruthenium and the like.

As the cobalt compound, cobalt chloride,
Examples thereof include cobalt bromide, cobalt iodide, cobalt nitrate, cobalt sulfate, cobalt carbonate, and hexaamminecobalt bromide.

As the nickel compound, nickel carbonate,
Examples thereof include nickel chloride, nickel hydroxide, nickel nitrate, nickel oxide, nickel sulfate, nickel acetate and nickel oxalate.

Examples of the iridium compound include ammonium hexabromoiridate, ammonium hexachloroiridate, hexachloroiridium acid, iridium bromide, iridium chloride, iridium oxide, potassium hexachloroiridate, sodium hexachloroiridate, chloropentaammineiridium chloride, Dodecacarbonyl tetriridium and the like can be mentioned.

Examples of the platinum compound include ammonium hexabromoplatinate, ammonium tetrachloroplatinate, dinitrodiamine platinum, dinitrosulfite platinic acid, hexabromoplatinic acid, hexachloroplatinic acid, hexahydroxyplatinic acid, platinum bromide, platinum chloride and iodine. Platinum oxide, platinum oxide, potassium hexabromoplatinate, potassium hexachloroplatinate, potassium hexahydroxoplatinate, potassium hexaiodoplatinate, potassium tetrabromoplatinate, potassium tetrachloroplatinate, sodium hexabromoplatinate, sodium hexachloroplatinate, hexahydroxo Sodium platinate, sodium tetrachloroplatinate,
Examples include tetraammine platinum chloride, tetraammine platinum hydroxide, sodium tetracyanoplatinate, and the like.

According to the present invention, when a Group VIII metal is used by supporting it on a carrier, the carrier may be a porous substance, for example, silica, alumina, silica-alumina, zeolite, diatomaceous earth, silica magnesia, silica zirconia. ,
Magnesia, zirconia, titania and other crystalline or non-crystalline metal oxides or composite oxides thereof, layered clay compounds such as teniolite and hectorite, activated carbon, etc.
Further, the above-mentioned solid acid such as a metal oxide supported by sulfuric acid or a proton-exchanged zeolite may be 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.

According to the invention, the catalyst of the invention comprises VIII
It consists of group metals and rhenium compounds. The rhenium compound that can be used here is a 0-valent metal itself, a known divalent to 7-valent oxide, or various salts of rhenium. For example, the rhenium metal may be rhenium black, the rhenium oxide may be dirhenium heptoxide, rhenium trioxide, rhenium dioxide or the like, and the known rhenium compounds may be, for example, dirhenium heptasulfide, rhenium disulfide or heptafluoride. Rhenium, rhenium hexafluoride, rhenium tetrafluoride, rhenium pentachloride, rhenium tetrachloride, rhenium trichloride, rhenium tribromide, rhenium chloride trioxide, perrhenic acid, ammonium perrhenate, tetrabutylammonium perrhenate, Examples thereof include potassium perrhenate, sodium perrhenate, dirhenium decacarbonyl, chloropentacarbonylrhenium, pentacarbonylmethylrhenium, rhenium carbonyl iodide, rhenium ethoxide, and dirhenium heptoxide ether complex.

According to the present invention, the method of adding the rhenium compound to be used is not particularly limited, and the rhenium compound may be added alone or, if necessary, as a mixture of two or more kinds. Further, the rhenium compound added depending on the reaction form may be uniformly dissolved in the raw material and / or the solvent or may be mixed nonuniformly. Further, as in the case of the Group VIII metal, a rhenium compound supported on a carrier may be added. 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. Rhenium compound alone or VI and rhenium compound
When the Group II metal is supported on the carrier, the supporting method is not particularly limited. For example, the rhenium compound may be the VI
It can be supported in the same manner as the group II metal. Also,
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, 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.

According to the present invention, the addition amount of the rhenium compound used as a 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 there is more than this, it is disadvantageous in cost,
On the contrary, if the amount is small, the effect of the catalyst may be reduced. When the rhenium compound is used by being supported on a carrier,
The supported amount 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 metal including the carrier.

A solvent can be used if desired in the process of the present invention. As a solvent, it is inert to the hydrogenation reaction,
In addition, there is no particular limitation as long as it does not react with the product tetrahydrofuran, for example, ethers such as diethyl ether, dimethoxyethane, diglyme, triglyme, tetrahydrofuran, dioxane, methanol, ethanol, n-butanol, iso-butanol. , Tert-butanol, alcohols such as 1,4-butanediol, aliphatic hydrocarbons such as n-hexane and cyclohexane, and acid amides such as 2-methylpyrrolidone and N-methylpyrrolidone. Preferred are dimethoxyethane, which has a relatively low boiling point and is easily recovered, or tetrahydrofuran, which does not require solvent recovery. When γ-butyrolactone or a mixture containing γ-butyrolactone is used as a raw material, the reaction can be advantageously performed in the process without the need of the solvent.

The amount of the solvent used is not particularly limited as long as the raw materials are dissolved depending on the reaction temperature. It is not necessary to dry these solvents before use, and conversely, water may coexist as long as they are about 1 molar equivalent to the raw materials.

In the present invention, the reaction can be carried out in a batch system 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 hydrogen pressure. The reaction temperature is usually 50 to 300 ° C,
120-250 degreeC is selected preferably. If it is higher than this, the progress of side reactions may increase, and if it is lower than this, the reaction rate tends to be disadvantageous. The pressure of hydrogen is usually 10 to 150 kg / cm ² G, preferably 15
~ 120 kg / cm ² G is selected, and in the method of the present invention,
The desired reaction proceeds sufficiently within this range.

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. However, in the batch system and the semi-batch system, one hour or more is usually required. Therefore, it is preferably 1 to 20 hours. If it is longer than this, the reaction may proceed further and a by-product may be produced. On the other hand, in a shorter time than this range,
High yields may not be obtained in some cases. 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.

[0040]

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.

Example 1 98 mg (1 mmol) of maleic anhydride, 21 mg of 5% Pd / C (manufactured by Aldrich Chemical), 3 mg of dirhenium decacarbonyl (Re ₂ (CO) ₁₀ ), and proton exchange mordenite were placed in a 10 ml stainless steel autoclave. (Manufactured by Tosoh Corporation; trade name HSZ-620HO
A) 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. 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 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 5% Ru / C (manufactured by Aldrich Chemical) 20 mg instead of 5% Pd / C, proton exchange ZSM-5 (manufactured by Tosoh Corp .; trade name HSZ-870HOA) instead of proton exchange mordenite. The hydrogenation reaction and analysis were performed in the same manner as in Example 1 except that 10 mg was used and the reaction time was 8 hours. The reaction results are shown in Table 1.

Comparative Example 1 Proton exchange mordenite (manufactured by Tosoh Corp .; trade name)
Example 1 except that HSZ-620HOA) was not used.
The hydrogenation reaction and analysis were performed in the same manner as in. Table 1 shows the reaction results
Shown in.

Comparative Example 2 Proton Exchange ZSM-5 (manufactured by Tosoh Corporation; trade name H)
The hydrogenation reaction and analysis were performed in the same manner as in Example 2 except that SZ-870HOA) was not used. The reaction results are shown in Table 1.

[0046]

[Table 1]

Example 3 In a 10 ml autoclave made of stainless steel, 100 mg (1 mmol) of succinic anhydride, 21 mg of 5% Pd / C,
Direnium decacarbonyl 3 mg, proton exchange mordenite (manufactured by Tosoh Corporation; trade name HSZ-620HO)
A) 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. 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 liquid. 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 4 Instead of dirhenium decacarbonyl, 5% Re / C
The hydrogenation reaction and analysis were performed in the same manner as in Example 3 except that 41 mg (manufactured by Aldrich Chemical) was used. The reaction results are shown in Table 2.

Comparative Example 3 Proton exchange mordenite (manufactured by Tosoh Corporation; trade name)
Example 3 except that HSZ-620HOA) was not used.
The hydrogenation reaction and analysis were performed in the same manner as in. Table 2 shows the reaction results
Shown in.

Comparative Example 4 Proton exchange mordenite (manufactured by Tosoh Corporation; trade name)
Example 4 except that HSZ-620HOA) was not used.
The hydrogenation reaction and analysis were performed in the same manner as in. Table 2 shows the reaction results
Shown in.

[0052]

[Table 2]

Example 5 5% Ru / C 20 mg instead of 5% Pd / C, methanesulfonic acid 10 m instead of proton exchange mordenite
Hydrogenation reaction and analysis were carried out in the same manner as in Example 3 except that g was used and the reaction time was 8 hours. Table 3 shows the reaction results
Shown in.

Example 6 10 g of zirconium hydroxide (Zr (OH) ₄ ) was gradually added to 250 ml of a 1N aqueous sulfuric acid solution at room temperature (25 ° C.) with stirring. After soaking for 24 hours, it was filtered with suction to sufficiently remove water, and then dried at 110 ° C. for 24 hours. The dried sulfuric acid-treated product was placed in an electric furnace and calcined at 500 ° C. for 3 hours under air flow to obtain sulfuric acid-supported zirconium oxide (SO ₄ / zirconia).

The hydrogenation reaction and analysis were carried out in the same manner as in Example 5 except that 10 mg of SO ₄ / zirconia prepared above was used as the acidic substance. The reaction results are shown in Table 3.

Example 7 The hydrogenation reaction and analysis were carried out in the same manner as in Example 5 except that the acidic substance was replaced by 10 mg of proton-exchanged USY type zeolite (manufactured by Tosoh Corp .; trade name HSZ-330HUA). The reaction results are shown in Table 3.

Comparative Example 5 The hydrogenation reaction and analysis were carried out in the same manner as in Example 5 except that methanesulfonic acid was not used. The reaction results are shown in Table 3.

[0058]

[Table 3]

Example 8 In a 10 ml stainless steel autoclave, γ-butyrolactone 86 mg (1 mmol), 5% Pd / C21m was added.
g, 3 mg of dirhenium decacarbonyl, 12 mg of phosphoric acid 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. The temperature was raised to 180 ° C. with heating and stirring, and a hydrogenation reaction was carried out for 8 hours.

After completion of the reaction, 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 4.

Example 9 Hydrogenation reaction and analysis were carried out in the same manner as in Example 8 except that 10 mg of methanesulfonic acid was used as the acidic substance. The reaction results are shown in Table 4.

Example 10 The hydrogenation reaction and analysis were carried out in the same manner as in Example 8 except that 17 mg of toluenesulfonic acid was used as the acidic substance. The reaction results are shown in Table 4.

Example 11 The hydrogenation reaction and analysis were carried out in the same manner as in Example 8 except that 10 mg of SO ₄ / zirconia prepared in the same manner as in Example 6 was used as the acidic substance. The reaction results are shown in Table 4.

Example 12 Titanium tetraisopropoxide (Ti (OPr-
i) ₄ ) 134 g and tetraethyl orthosilicate (S
41 g of n-propanol was added to 42 g of i (OEt) _{4 and the} mixture was refluxed for 4 hours under a nitrogen atmosphere. After standing to cool, distilled water 9
7 g was added and the mixture was further refluxed for 1 hour. After that, the precipitate was filtered, washed with water, and then dried at 110 ° C. for 15 hours. 10 g of the obtained white powder was gradually added to 250 ml of a 1N sulfuric acid aqueous solution at room temperature (25 ° C.) with stirring. After soaking for 24 hours, filter with suction to remove sufficient water,
It was dried at 110 ° C. for 24 hours. The dried sulfuric acid-treated product is put into an electric furnace and fired at 500 ° C. for 3 hours under air flow.
Sulfuric acid-supported silica titania (SO ₄ / silica titania) was obtained.

The hydrogenation reaction and analysis were carried out in the same manner as in Example 8 except that 10 mg of SO ₄ / silica titania prepared above was used as the acidic substance. The reaction results are shown in Table 4.

Example 13 An acidic substance was used as a proton exchange Y-type zeolite (HSZ-32).
The hydrogenation reaction and analysis were performed in the same manner as in Example 8 except that 10 mg of 0HOA Tosoh Corp. was used. The reaction results are shown in Table 4.

[0067]

[Table 4]

Example 14 The hydrogenation reaction and analysis were carried out in the same manner as in Example 8 except that the acidic substance was changed to 10 mg of proton-exchanged USY type zeolite (manufactured by Tosoh Corp .; trade name HSZ-330HUA). The reaction results are shown in Table 5.

Example 15 An acidic substance was used as a proton exchange mordenite (Tosoh Corporation).
Manufactured; product name: HSZ-620HOA) was replaced with 10 mg, and the hydrogenation reaction and analysis were performed in the same manner as in Example 8.
The reaction results are shown in Table 5.

Example 16 Dirhenium decacarbonyl was converted to dirhenium heptoxide (Re ₂
0 ₇₎ was replaced 3mg made a hydrogenation reaction and analyzed as in Example 15. The reaction results are shown in Table 5.

Example 17 An acidic substance was used as a proton exchange mordenite (Tosoh Corp.).
Manufactured; product name HSZ-620HOA) 10 mg, reaction temperature 160 ° C., reaction time 16 hours Example 8
The hydrogenation reaction and analysis were performed in the same manner as in. Table 5 shows the reaction results
Shown in.

Comparative Example 6 The hydrogenation reaction and analysis were carried out in the same manner as in Example 8 except that phosphoric acid was not used. The reaction results are shown in Table 5.

Comparative Example 7 Proton Exchange Mordenite (manufactured by Tosoh Corporation; trade name)
Example 1 except that HSZ-620HOA) was not used.
The hydrogenation reaction and analysis were performed in the same manner as in 7. The reaction results are shown in Table 5.

[0074]

[Table 5]

Example 18 Hydrogenation reaction was carried out in the same manner as in Example 8 except that 5 mg Ru / C (20 mg) was used instead of 5% Pd / C, and methanesulfonic acid (10 mg) was used instead of phosphoric acid, and the reaction time was 8 hours. And analysis was performed. The reaction results are shown in Table 6.

Example 19 An acidic substance was prepared in the same manner as in Example 12 SO ₄ /
The hydrogenation reaction and analysis were carried out in the same manner as in Example 18 except that 10 mg of silica-titania was used. The reaction results are shown in Table 6.

Example 20 An acidic substance was used as a proton exchange Y-type zeolite (Tosoh Corp.).
(Manufactured; HSZ-320HOA, trade name) was replaced with 10 mg, and the hydrogenation reaction and analysis were performed in the same manner as in Example 18. The reaction results are shown in Table 6.

Comparative Example 8 The hydrogenation reaction and analysis were performed in the same manner as in Example 18 except that methanesulfonic acid was not used. The reaction results are shown in Table 6.

[0079]

[Table 6]

Example 21 An acidic substance was used as a proton exchange ZSM-5 (manufactured by Tosoh Corp .;
Brand name HSZ-870HOA) 10 mg, reaction temperature 1
The hydrogenation reaction and analysis were performed in the same manner as in Example 18 except that the reaction time was changed to 60 ° C. and the reaction time was 4 hours. The reaction results are shown in Table 7.

Example 22 The hydrogenation reaction and analysis were carried out in the same manner as in Example 21 except that the acidic substance was changed to 10 mg of proton-exchanged USY type zeolite (manufactured by Tosoh Corp .; trade name HSZ-330HOA). The reaction results are shown in Table 7.

Example 23 An acidic substance was used as a proton exchange mordenite (Tosoh Corp.).
(Manufactured: HSZ-620HOA, trade name) 10 mg was used, and the hydrogenation reaction and analysis were performed in the same manner as in Example 21. The reaction results are shown in Table 7.

Comparative Example 9 The hydrogenation reaction and analysis were carried out in the same manner as in Example 21 except that the proton exchange Y-type zeolite was not used. The reaction results are shown in Table 7.

[0084]

[Table 7]

[0085]

According to the present invention, in hydrogenating at least one compound selected from the group consisting of maleic anhydride, succinic anhydride and γ-butyrolactone,
By carrying out a hydrogenation reaction in the presence of an acidic substance in the presence of a catalyst composed of a Group VIII metal and a rhenium compound, it is possible to highly selectively produce tetrahydrofuran under mild conditions as compared with conventional reaction conditions. it can.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification number Internal reference number FI Technical display location B01J 29/06 X 9343-4G // C07B 61/00 300 (72) Inventor Makoto Hanatani Yokkaichi, Mie Prefecture 129 Izumi Hanatsu Otsu (72) Inventor Akira Sato 6-7-5, also known as Yokkaichi, Mie (72) Takanori Miyake Other names 3-5-1 Yokkaichi, Mie

Claims (2)

[Claims] 1. When hydrogenating at least one compound selected from the group consisting of maleic anhydride, succinic anhydride and γ-butyrolactone, the periodic table VIII is used.
A method for producing tetrahydrofuran, characterized in that a hydrogenation reaction is carried out in the presence of an acidic substance using a catalyst composed of at least one metal selected from the group and a rhenium compound. 2. The method for producing tetrahydrofuran according to claim 1, wherein the acidic substance is at least one selected from the group consisting of a mineral oxide, an organic sulfonic acid, a metal oxide supporting sulfuric acid and a proton exchange zeolite.