JP3168548B2 - Method for producing tetrahydrofuran - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing tetrahydrofuran. Tetrahydrofuran is a very useful substance as a solvent for organic synthesis, a solvent such as a vinyl chloride resin, or an intermediate such as a polyurethane elastic fiber or a polyester elastomer.

[0002]

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

For example, Japanese Patent Publication No. 49-9664 discloses a method using a nickel-based catalyst at a reaction temperature of 90 ° C. (inlet).
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 high yield by partially co-producing γ-butyrolactone, but requires extremely high temperature and pressure as described above.

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

In US Pat. No. 4,550,185, a method for 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. JP-A-3-500657 discloses that a palladium alloy-rhenium catalyst is used at a reaction temperature of 230 ° C. and a pressure of 80 bar.
A method for hydrogenating gamma-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 a method for producing tetrahydrofuran by hydrogenating a maleic acid derivative, a succinic acid derivative or γ-butyrolactone using a catalyst, a method for giving a sufficient yield under milder reaction conditions has been strongly developed. Was desired.

[0007]

SUMMARY OF THE INVENTION An object of the present invention is to hydrogenate raw material maleic anhydride, succinic anhydride or γ-butyrolactone under milder conditions using a catalyst to obtain tetrahydrofuran in high yield. It provides a manufacturing method.

[0008]

Means for Solving the Problems The present inventors have conducted intensive studies to solve the above problems, and as a result, in the presence of an acidic substance, a catalyst comprising a Group VIII metal and a rhenium compound was used. In a reaction for hydrogenating at least one compound selected from the group consisting of succinic anhydride and γ-butyrolactone, a process for producing tetrahydrofuran that gives a sufficient yield under milder conditions has been found, and the present invention has been completed. Reached.

That is, the present invention relates to 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, wherein a hydrogenation reaction is carried out in the presence of an acidic substance using a catalyst comprising a compound of formula (II) and a rhenium compound.

Hereinafter, the present invention will be described in detail.

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 this time may be any ratio.

According to the invention, the acidic substance is used as an additive in the presence of a raw material and a catalyst. The acidic substance of the present invention is a substance having Bronsted acid, which is generally defined as an acid, or a substance having Lewis acidity. 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 for a condition that is thermally stable according to the reaction conditions.

The acidic substance usable in the present invention can be exemplified by mineral acids and organic sulfonic acids. Here, examples of the mineral acid include phosphoric acid, hydrochloric acid, nitric acid, and sulfuric acid. Examples of the organic sulfonic acid include alkylsulfonic acids, aromatic sulfonic acids having a substituent, and high molecular compounds having a sulfonic acid group.

Specifically, examples of the alkylsulfonic acids include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, and trifluoromethanesulfonic acid. The aromatic sulfonic acids having a substituent include aromatic nuclei having an aromatic nucleus. Examples where the substituent is hydrogen are benzenesulfonic acid, naphthalenesulfonic acid and the like, and examples where the substituent is an alkyl group are paratoluenesulfonic acid, parabutyltoluenesulfonic acid, mesitylenesulfonic acid and methylnaphthalenesulfonic acid. Examples of the aromatic nucleus in which hydrogen or an alkyl group is substituted with a halogen group, an alkoxy group, a carboxyl group, an ester group, a nitrile group, a nitro group, etc. include paramethoxybenzenesulfonic acid, parasulfobenzoic acid t-butyl ester, and 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 that can be used in the present invention, a metal oxide carrying sulfuric acid can also be used. Sulfuric acid-supported metal oxides are generally known as solid acids having strong acid strength, and are also called solid superacids. A method for preparing a metal oxide loaded with sulfuric acid is obtained by immersing sulfuric acid in a metal hydroxide such as a metal belonging to Group IV of the periodic table, iron, aluminum or the like, or an amorphous metal oxide, followed by firing.
For example, Japanese Patent Publication No. 59-6181 discloses periodic table I
There is disclosed a technique in which a group V metal hydroxide or oxide is brought into contact with a sulfate group-containing solution, an excess sulfate group-containing solution is removed, and then calcined to obtain a solid superacid. The metal oxide supported on sulfuric acid used in the present invention is not particularly limited as long as it is a solid acid prepared by a known method as represented above. Examples of the metal oxide used at this time include oxides of titanium, zirconium, hafnium, tin, and lead that are metals belonging to Group IV of the periodic table, and oxides of iron, aluminum, and silicon, and oxides of these. An oxide of a metal composed of a combination of two or more selected so-called composite oxides can be used.

Further, the acidic substance that can be used in the present invention includes:
Proton exchanged zeolites can be used. It is generally zeolite known as a solid _{acid, M 2 / n · T 2} O 3 ·
It is a crystalline silicate denoted as xSiO ₂ . Here, T is an element in the zeolite skeleton, and aluminum,
Trivalent metals such as iron and boron are generally used, and x is usually an integer of 2 or more. Zeolite is a crystalline compound in which TO ₄ tetrahedron and SiO ₄ tetrahedron are regularly and three-dimensionally arranged via oxygen atoms so that the O / (Si + Al) ratio becomes 2. Since T is a trivalent cation, TO ₄ is negatively charged, and therefore, a positively charged M is required to neutralize the negative charge. Therefore, M need only be a cationic species in order to maintain the framework structure of the zeolite, and protons, alkali metals, and alkaline earth metals are generally used and are called M-exchanged zeolites.

In the method of the present invention, the usable zeolite is obtained by exchanging a cationic species of M for proton. Since zeolite can generally ion-exchange cation species, the proton-exchanged zeolite to be used only needs to be proton-exchanged in the state of use. The method for proton exchange is not particularly limited, and proton exchange can be performed by a known method. Examples of zeolites capable of performing proton exchange include, for example, 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.

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 alone or, if necessary, as a mixture of two or more kinds. Further, depending on the form of the reaction, 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 heterogeneously. When a solid acid such as a metal oxide supported on sulfuric acid or a proton-exchanged zeolite is added, the shape is not particularly limited. For example, in the reaction method using a fixed bed, a molded product can be used, and in the reaction method using a suspension bed, a powdery or granular material can be used.

The amount of the acidic substance to be used is not particularly limited, but is 0.1 to 100% by weight, preferably 1 to 100% by weight based on the raw material.
50% by weight is good. If the amount is more than this, the effect is not remarkably improved, and a problem may be left in the step of separating and purifying the target product from the reaction solution after the reaction. Conversely, if the amount is less than this, the effect tends to be weakened.

The catalyst used in the present invention is a catalyst comprising 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, in the practice of the present invention, the Group VIII metal can be used by suspending a powdery or pasty metal as it is, but is preferably used by being supported on a carrier. When used on a carrier, the preparation method is not particularly limited, and those prepared by a known method, for example, a physical mixing method, an impregnation method, an ion exchange method, or the like can be used.

When preparing by the impregnation method among these preparation methods, the raw material of the Group VIII metal is dissolved in an appropriate solvent, a carrier is added thereto, mixed, and if necessary, allowed to stand for a predetermined time and then dried. . Thereafter, reduction may be performed directly, or in some cases, reduction may be performed after firing. The reduction method is not particularly limited, and may be, for example, reduction in a gas phase using hydrogen or the like, or reduction in a liquid phase using hydrazine or the like. The reduction temperature is not particularly limited as long as the raw material is reduced to metal, but is generally performed at a temperature of 150 to 500 ° C. In the case of preparing by an ion exchange method, ion exchange is performed using a raw material of a desired concentration of a Group VIII metal, and thereafter, it can be prepared by a method similar to the impregnation method.

When the Group VIII metal is used by being supported on a support, the amount of the supported metal is 0.01 to 5 parts by weight based on the total weight of the catalyst.
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 the metal tends to be small, and if it is lower 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 by the hydrogenation reaction of the present invention or by a reduction reaction after being supported on a carrier.

For example, palladium compounds include 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 pentachloroaquaruthenate, ammonium ruthenate, potassium oxydecachlorodiruthenate, potassium pentachloroaquaruthenate, potassium perruthenate, and potassium perruthenate. Ruthenium, ruthenium chloride, ruthenium iodide, nitrosylruthenium nitrate, ruthenium oxide, sodium oxydecachlorodiruthenate, hexaammineruthenium chloride, pentaamminechlororuthenium chloride, hexaammineruthenium bromide, dodecacarbonyltriruthenium, hexacarbonyltetra Chlorodilthenium, cesium tricarbonyltrichlororuthenate, tris (acetylacetonato) ruthenium, tricarbo Bis (triphenylphosphine) ruthenium, dichloro-tris (triphenylphosphine) ruthenium and the like.

As the cobalt compound, cobalt chloride,
Cobalt bromide, cobalt iodide, cobalt nitrate, cobalt sulfate, cobalt carbonate, hexaammine cobalt bromide and the like can be mentioned.

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

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

Examples of the platinum compound include ammonium hexabromoplatinate, ammonium tetrachloroplatinate, dinitrodiamineplatinum, dinitrosulfiteplatinate, hexabromoplatinate, hexachloroplatinate, hexahydroxyplatinate, platinum bromide, platinum chloride, 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 thereof include tetraammine platinum chloride, tetraammine platinum hydroxide, and sodium tetracyanoplatinate.

According to the present invention, when the Group VIII metal is used by being supported on a carrier, the carrier may be a porous substance such as 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, teniolite, layered clay compounds such as hectorite, activated carbon, etc.
Further, solid acids such as the above-mentioned metal oxides supported on sulfuric acid and proton-exchanged zeolites may be mentioned. Among these, activated carbon is particularly preferred. The shape of the carrier is not particularly limited, and it can be used as it is or in a powder form according to the reaction mode. Powders or granules are preferably used in the suspension bed, and tablet compression moldings, spherical or columnar extrusion moldings and the like are preferably used in the fixed bed.

According to the present invention, the catalyst of the present invention comprises VIII
It consists of a group metal and a rhenium compound. The rhenium compound that can be used here is a zero-valent metal itself, a known divalent to heptavalent oxide, or various salts of rhenium. For example, rhenium metal includes rhenium black, and rhenium oxide includes rhenium heptaoxide, rhenium trioxide, rhenium dioxide, and the like, and known rhenium compounds include, for example, rhenium heptasulfide, rhenium disulfide, and heptafluoride. Rhenium, rhenium hexafluoride, rhenium tetrafluoride, rhenium pentachloride, rhenium tetrachloride, rhenium trichloride, rhenium tribromide, rhenium trioxide, perrhenic acid, ammonium perrhenate, tetrabutylammonium perrhenate, Examples include potassium perrhenate, sodium perrhenate, zirhenium decacarbonyl, chloropentacarbonylrhenium, pentacarbonylmethylrhenium, rhenium carbonyl iodide, rhenium ethoxide, and rhenium heptaoxide 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 as a mixture of two or more as needed. The rhenium compound added depending on the form of the reaction may be uniformly dissolved in the raw materials and / or the solvent or may be mixed heterogeneously. In addition, as in the case of the Group VIII metal, a rhenium compound supported on a carrier may be added. When supported on a carrier, the rhenium compound may be supported alone, or the rhenium compound may be supported on the same carrier on which the Group VIII metal is supported. Rhenium compound alone or rhenium compound and VI
When a Group II metal is supported on a carrier, there is no particular limitation on the method of supporting the metal. For example, the rhenium compound may be replaced with VI as described above.
It can be carried 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 is first formed on the carrier, and then the rhenium compound may be supported, or conversely, after supporting the rhenium compound first, A Group VIII metal may be formed on the support. Further, the group VIII metal and the rhenium compound may be simultaneously supported on the carrier.

According to the present invention, the amount of the rhenium compound used as a catalyst is not particularly limited, but is preferably 0.01 to 20% by weight, and more preferably 0.1 to 10% by weight, based on the raw materials. Any more than this is disadvantageous in terms of cost,
Conversely, if the amount is small, the effect of the catalyst may be reduced. Further, when the rhenium compound is used by being supported on a carrier,
The loading 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.

In the method of the present invention, a solvent can be used if necessary. As a solvent, it is inert to the hydrogenation reaction,
There is no particular limitation as long as it does not react with the product, tetrahydrofuran.Examples include ethers such as diethyl ether, dimethoxyethane, diglyme, triglyme, tetrahydrofuran, dioxane, methanol, ethanol, n-butanol, and iso-butanol. And alcohols such as tert-butanol and 1,4-butanediol; aliphatic hydrocarbons such as n-hexane and cyclohexane; and acid amides such as 2-methylpyrrolidone and N-methylpyrrolidone. Preferably, dimethoxyethane, which has a relatively low boiling point and can be easily recovered, or tetrahydrofuran which does not require solvent recovery can be used. When γ-butyrolactone or a mixture containing γ-butyrolactone is used as a raw material, the reaction can be advantageously performed without the need for 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 be present as long as it is about 1 molar equivalent to the raw materials.

In the present invention, the reaction can be carried out batchwise, semi-batchwise, continuously with a suspension bed or in a fixed bed flow system.

The reaction according to the method of the present invention is carried out under heating and under hydrogen pressure. The reaction temperature is usually 50 to 300 ° C,
Preferably, 120 to 250 ° C is selected. If it is higher than this, the progress of side reactions may increase, and if it is lower, the reaction rate tends to be disadvantageous. The pressure of hydrogen is usually 10 to 150 kg / cm ² G, preferably 15
１２０120 kg / cm ² G is selected, and in the method of the present invention,
The desired reaction sufficiently proceeds within this range.

The reaction time varies depending on the setting method of the temperature, the pressure, the amount of the catalyst and the reaction system, so that it is difficult to determine the range in a straightforward manner. However, in the case of a batch system or a semi-batch system, usually one hour or more is required. And preferably for 1 to 20 hours. If the length is longer than this, the reaction further proceeds, and a by-product may be generated. On the other hand, for shorter time than this range,
High yields may not be obtained. In a continuous reaction using a suspension bed or a fixed bed flow reaction, the residence time may be 0.1 to 15 hours.

[0040]

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

Example 1 In a 10 ml stainless steel autoclave, 98 mg (1 mmol) of maleic anhydride, 21 mg of 5% Pd / C (manufactured by Aldrich Chemical), 3 mg of zilenium decacarbonyl (Re ₂ (CO) ₁₀ ), and proton exchange mordenite (Manufactured by Tosoh Corporation; trade name: HSZ-620HO)
A) 10 mg and 1 ml of dimethoxyethane were charged, and the inside of 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. while heating and stirring, and a hydrogenation reaction was performed for 16 hours.

After the completion of the reaction, the autoclave was cooled to room temperature, and subsequently, hydrogen was purged to take out the reaction solution. After filtering off the catalyst and the like, the filtrate was analyzed by gas chromatography. Table 1 shows the reaction results.

Example 2 20 mg of 5% Ru / C (manufactured by Aldrich Chemical) instead of 5% Pd / C, and proton exchange ZSM-5 (manufactured by Tosoh Corporation; trade name: HSZ-870HOA) instead of proton exchange mordenite 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 changed to 8 hours. Table 1 shows the reaction results.

Comparative Example 1 Proton exchange mordenite (manufactured by Tosoh Corporation; trade name)
Example 1 except that HSZ-620HOA) was not used.
Hydrogenation reaction and analysis were carried out in the same manner as described above. Table 1 shows the reaction results.
Shown in

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

[0046]

[Table 1]

Example 3 In a 10 ml stainless steel autoclave, 100 mg (1 mmol) of succinic anhydride, 21 mg of 5% Pd / C,
3 mg of gilenium decacarbonyl, proton exchange mordenite (manufactured by Tosoh Corporation; trade name: HSZ-620HO)
A) 10 mg and 1 ml of dimethoxyethane were charged, and the inside of 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. while heating and stirring, and a hydrogenation reaction was performed for 16 hours.

After the completion of the reaction, the autoclave was cooled to room temperature, then purged with hydrogen and the reaction solution was taken out. After filtering off the catalyst and the like, the filtrate was analyzed by gas chromatography. Table 2 shows the reaction results.

Example 4 Instead of dirhenium decacarbonyl, 5% Re / C
Hydrogenation reaction and analysis were performed in the same manner as in Example 3 except that 41 mg (manufactured by Aldrich Chemical) was used. Table 2 shows the reaction results.

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

[0052]

[Table 2]

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

Example 6 To 250 ml of a 1N aqueous sulfuric acid solution, 10 g of zirconium hydroxide (Zr (OH) ₄ ) was gradually added at room temperature (25 ° C.) with stirring. After immersion for 24 hours, the mixture 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 an air flow to obtain sulfuric acid-supported zirconium oxide (SO ₄ / zirconia).

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

Example 7 A hydrogenation reaction and analysis were carried out in the same manner as in Example 5 except that the acidic substance was changed to 10 mg of proton-exchanged USY zeolite (manufactured by Tosoh Corporation; trade name: HSZ-330HUA). Table 3 shows the reaction results.

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

[0058]

[Table 3]

Example 8 In a 10 ml stainless steel autoclave, 86 mg (1 mmol) of γ-butyrolactone, 5% Pd / C21m
g, 3 mg of direnium decacarbonyl, 12 mg of phosphoric acid, and 1 ml of dimethoxyethane, and the system was sufficiently purged with hydrogen, and then hydrogen was injected to 50 kg / cm ² G. The temperature was raised to 180 ° C. while heating and stirring, and a hydrogenation reaction was performed for 8 hours.

After the completion of the reaction, the autoclave was cooled to room temperature, then purged with hydrogen and the reaction solution was taken out. After filtering off the catalyst and the like, the filtrate was analyzed by gas chromatography. Table 4 shows the reaction results.

Example 9 A 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 methanesulfonic acid. Table 4 shows the reaction results.

Example 10 A hydrogenation reaction and analysis were carried out in the same manner as in Example 8 except that the acidic substance was changed to 17 mg of toluenesulfonic acid. Table 4 shows the reaction results.

Example 11 A 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 SO ₄ / zirconia prepared in the same manner as in Example 6. Table 4 shows the reaction results.

Example 12 Titanium tetraisopropoxide (Ti (OPr-
i) ₄ ) 134 g of 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. Thereafter, the precipitate was filtered, washed with water, and dried at 110 ° C. for 15 hours. 10 g of the obtained white powder was gradually added to 250 ml of a 1N aqueous sulfuric acid solution at room temperature (25 ° C.) with stirring. After immersion for 24 hours, filter while suctioning to remove enough water,
Dry 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 an 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 the acidic substance was changed to 10 mg of SO ₄ / silica titania prepared above. Table 4 shows the reaction results.

Example 13 An acidic substance was converted to a proton-exchanged Y-type zeolite (HSZ-32).
Hydrogenation reaction and analysis were carried out in the same manner as in Example 8 except that 10 mg of 0HOA (manufactured by Tosoh Corporation) was used. Table 4 shows the reaction results.

[0067]

[Table 4]

Example 14 A 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 zeolite (manufactured by Tosoh Corporation; trade name: HSZ-330HUA). Table 5 shows the reaction results.

Example 15 An acidic substance was replaced with proton exchange mordenite (Tosoh Corporation)
Hydrogenation reaction and analysis were performed in the same manner as in Example 8 except that the product was changed to 10 mg (trade name: HSZ-620HOA).
Table 5 shows the reaction results.

Example 16 Dilene decacarbonyl was replaced with rhenium heptaoxide (Re ₂
0 ₇₎ was replaced 3mg made a hydrogenation reaction and analyzed as in Example 15. Table 5 shows the reaction results.

Example 17 An acidic substance was replaced with proton-exchanged mordenite (Tosoh Corporation)
Example 8 except that 10 mg of the product, trade name HSZ-620HOA), the reaction temperature was 160 ° C., and the reaction time was 16 hours.
Hydrogenation reaction and analysis were carried out in the same manner as described above. Table 5 shows the reaction results.
Shown in

Comparative Example 6 A hydrogenation reaction and analysis were carried out in the same manner as in Example 8 except that no phosphoric acid was used. Table 5 shows the reaction results.

Comparative Example 7 Proton exchange mordenite (manufactured by Tosoh Corporation; trade name)
Example 1 except that HSZ-620HOA) was not used.
Hydrogenation reaction and analysis were performed as in Example 7. Table 5 shows the reaction results.

[0074]

[Table 5]

Example 18 A hydrogenation reaction was carried out in the same manner as in Example 8 except that 20 mg of 5% Ru / C was used instead of 5% Pd / C, and 10 mg of methanesulfonic acid was used instead of phosphoric acid, and the reaction time was changed to 8 hours. And analysis. Table 6 shows the reaction results.

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

Example 20 An acidic substance was converted to a proton-exchanged Y-type zeolite (Tosoh Corporation)
Hydrogenation reaction and analysis were carried out in the same manner as in Example 18, except that the product was changed to 10 mg (trade name: HSZ-320HOA). Table 6 shows the reaction results.

Comparative Example 8 A hydrogenation reaction and analysis were carried out in the same manner as in Example 18 except that methanesulfonic acid was not used. Table 6 shows the reaction results.

[0079]

[Table 6]

Example 21 The acidic substance was replaced with proton-exchanged ZSM-5 (manufactured by Tosoh Corporation;
Trade name HSZ-870HOA) 10 mg, reaction temperature 1
A hydrogenation reaction and analysis were carried out in the same manner as in Example 18 except that the temperature was changed to 60 ° C. and the reaction time was changed to 4 hours. Table 7 shows the reaction results.

Example 22 A 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 Corporation; trade name: HSZ-330HOA). Table 7 shows the reaction results.

Example 23 An acidic substance was replaced with proton exchange mordenite (Tosoh Corporation)
Hydrogenation reaction and analysis were carried out in the same manner as in Example 21 except that the product was changed to 10 mg (trade name: HSZ-620HOA). Table 7 shows the reaction results.

Comparative Example 9 A hydrogenation reaction and analysis were carried out in the same manner as in Example 21 except that no proton exchanged Y-type zeolite was used. Table 7 shows the reaction results.

[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 performing a hydrogenation reaction in the presence of a catalyst comprising a Group VIII metal and a rhenium compound in the presence of an acidic substance, tetrahydrofuran can be produced with high selectivity under mild conditions compared to conventional reaction conditions. it can.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI B01J 29/06 B01J 29/06 X // C07B 61/00 300 C07B 61/00 300 (72) Inventor Takanori Miyake Yokkaichi, Mie Prefecture Synonym 3-5-1 Examiner Shinichi Naito (56) References Tables of International Publication No. 3-500657 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07D 307/08 B01J 23/14 B01J 23/36 B01J 23/46 301 B01J 23/46 311 B01J 29/06 C07B 61/00 300 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] (1) In hydrogenating at least one compound selected from the group consisting of maleic anhydride, succinic anhydride, and γ-butyrolactone, the periodic table VIII
A method for producing tetrahydrofuran, comprising performing a hydrogenation reaction in the presence of an acidic substance using a catalyst comprising at least one metal selected from the group consisting of a rhenium compound. 2. The method for producing tetrahydrofuran according to claim 1, wherein the acidic substance is at least one selected from mineral acids, organic sulfonic acids, metal oxides supporting sulfuric acid, and proton exchanged zeolites.