JPH08141396A - Hydrogenation catalyst for carboxylic acid and method for hydrogenation of carboxylic acid using said catalyst - Google Patents

Abstract

PURPOSE: To provide a method of forming tetrahydrofuran by hydrogenating dicarboxylic acids, particularly maleic anhydride, using a hydrogenation catalyst with a carrier having an improved precious metal component and a Re component of the group VIII metals as the catalytic components. CONSTITUTION: A hydrogenation catalyst for carboxylic acids is provided with a silica carrier having supported thereon a precious metal component and a Re component of the group VIII metals in the periodic table and consisting of a meso-porous body having a BET surface area of at least 120m<2> /g and an average pore size of 2.0-45.0nm in diameter or a sharp distribution of the pore with a diameter of 2<D(pore diameter)<50nm. A method of hydrogenating dicarboxylic acids comprises hydrogenating at least a member selected from the dicarboxylic acids having 4 carbon atoms and the acid anhydrides at a temperature of 130-350 deg.C and at a hydrogen pressure of 5.0-20.0MPa in the presence of the hydrogenation catalyst in order to form the corresponding cyclic ethers and/or lactones.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention relates to the catalyst component VIII
The present invention relates to improvement of a hydrogenation reaction catalyst for dicarboxylic acids having a carbon number of 4 and containing a group-noble metal and Re, and a method for hydrogenating a dicarboxylic acid using the catalyst. For more information,
The present invention relates to a catalyst for hydrogenation reaction of maleic anhydride in which a Group VIII noble metal and Re are supported on a specific silica carrier, and a method for hydrogenating maleic anhydride using the catalyst to selectively produce tetrahydrofuran.

[0002]

2. Description of the Related Art Conventionally, carboxylic acids such as maleic acid, maleic anhydride, fumaric acid, succinic acid and succinic anhydride have been hydrogenated to give tetrahydrofuran,
Many proposals have been made regarding catalysts for producing 1,4-butanediol or γ-butyrolactone. Among these, as a method of using a catalyst prepared by supporting a noble metal component and a Re component of Group VIII of the Periodic Table on a carrier, DE 2715667 describes Pd-Re /
A method for producing 1,4-butanediol using SiO ₂ as a catalyst is described, but in this case, silica obtained by a complicated operation of treating a metal silicate with acetic acid is used.

Further, JP-A-51-133212 discloses that maleic anhydride is hydrogenated by using a catalyst in which palladium and rhenium are supported on diatomaceous earth to produce butanediol as a main product. Kaisho 52-979
No. 01 describes that an alcohol is produced by hydrogenating a carboxylic acid at high temperature and high pressure in the presence of a catalyst in which palladium and rhenium are supported on an acid-resistant carrier. However, in any method, alcohol selection is performed. However, the production of γ-butyrolactone or tetrahydrofuran from maleic anhydride is extremely low.

In Japanese Patent Publication No. 4-500813, a method for producing γ-butyrolactone using Pd-Re-Ag / TiO ₂ as a catalyst is further disclosed in US Pat.
No. 86 discloses a method of producing tetrahydrofuran by adding Rh, Co, Pt and the like to Pd and Re and using a catalyst supported on activated carbon. However, although these reaction catalysts have relatively high selectivity to the alcohols and ethers to be produced, they have not yet been sufficiently satisfactory in terms of reaction activity, and neither of them has a severe condition of high temperature and high pressure. It was necessary to carry out the reaction below.

[0005]

Therefore, when hydrogenating carboxylic acids in the presence of a catalyst, a hydrogenation catalyst capable of efficiently advancing the hydrogenation reaction under mild conditions and selectively producing a target compound is proposed. Development was desired. The inventors of the present invention have made earnest studies on the characteristics of the carrier of the hydrogenation catalyst with a carrier that carries a Group VIII noble metal component and a Re component as catalyst components, and as a result, when silica having specific physical property values was used, When a dicarboxylic acid, particularly maleic anhydride, is subjected to a hydrogenation reaction with a catalyst under relatively mild conditions, a highly active and selective cyclic compound such as tetrahydrofuran and / or γ-butyrolactone can be produced. The present invention has been achieved by obtaining new knowledge that

[0006]

The present invention is directed to a hydrogenation catalyst for a carboxylic acid with a carrier having an improved Group VIII noble metal component and Re component as catalyst components, and a dicarboxylic acid, particularly maleic anhydride, using the catalyst. The present invention provides a method for hydrogenating an acid, the gist of which is to carry a noble metal component and a Re component of Group VIII of the periodic table on a silica carrier, the silica carrier having a BET of 120 m ² / g or more.
A dicarboxylic acid compound having a surface area and an average pore diameter of 2.0 to 45.0 nm, or a mesoporous material having a sharp pore distribution in 2 <D (pore diameter) <50 nm. A hydrogenation catalyst and at least one carboxylic acid selected from a dicarboxylic acid having 4 carbon atoms, an acid anhydride thereof, a mono- or di-lower alkyl ester thereof or an intramolecular ester thereof, in the presence of the hydrogenation catalyst at a temperature of 13
A method for hydrogenating carboxylic acids comprises hydrogenating at 0 to 350 ° C. and a hydrogen pressure of 5.0 to 20.0 MPa to produce the corresponding desired hydride, that is, lactones and / or cyclic ethers.

Hereinafter, the present invention will be described in detail. The carrier of the hydrogenation catalyst of the present invention is silica having a BET surface area of 120 m ² / g or more and a pore size of 2.0 to 45.0 nm. BET surface area is preferably 120-1250 m ² /
g, more preferably 180 to 1250 m ² / g. In particular, in the hydrogenation reaction of maleic anhydride, the production of tetrahydrofuran generally increases as the surface area of the silica carrier increases, but the surface area of 230 m
^When maleic anhydride is hydrogenated using a silica carrier of ² / g or more, the yield of tetrahydrofuran is further increased as compared with the case where a silica carrier having a smaller surface area is used even if the average pore size is almost the same. Because you can
A carrier may be selected and used according to the purpose.

The average pore diameter is 2.0 to 45.0n.
m, preferably in the range of 2.0 to 30.0 nm. When silica in this range is used, the catalytic metal component is supported in a highly dispersed state and an effective reaction field can be formed. These silica carriers can be selected and used from commercial products as long as they satisfy the above requirements of surface area and average pore size.

Further, mesoporous silica having a hexagonal structure can be used as a carrier. The mesoporous material is a porous material located between macroporous and microporous and has a pore diameter (D) in the range of 2 <D (pore diameter) <50 nm, and has pores much larger than zeolite. Have As an example of the mesoporous material, the mesopore region (2 <
A mesoporous material FSM-16 having a sharp pore distribution at D <50 nm is known (“Catalyst” Vol. 36 No. 2).
p.131 1994 ； 73rd CATSJ Meeting Abstracts ； No.1
B12). These have a BET surface area of about 1000 m ² / g and have pores larger than zeolite, although they may vary depending on the production conditions. Therefore, when used as a carrier, it is possible to support metals inside the pores. Therefore, a highly dispersed catalyst can be obtained.

Such mesoporous silica is described, for example, in the above (“Catalyst” Vol. 36 No. 2 p. 131 1994; 73rd CATSJ).
It can be synthesized by a known method as described in Meeting Abstracts; No. 1B12). That is, Na between the layers
Single layer silicate sheet with ions [(Si ₂ O ₅ ) ^2-
₌ ] When the interlayer Na ion of kanemite (NaHSi ₂ O ₅ · 3H ₂ O), which is a layered compound composed of , A single layer silicate sheet and a stable composite are formed. Next, this is calcined to obtain a mesoporous material (FSM-16) having a hexagonal structure with a three-dimensional skeleton whose layers are crosslinked by dehydration condensation of silanol groups. This silica porous material has a BET surface area and a pore volume of 1220 m ^{2 /} g and 1.0 m, respectively.
1 / g, showing a uniform pore distribution centered on 3 nm. Further, in producing a mesoporous material by this method, it is possible to change the pore size by changing the type of alkyl of alkyltrimethylammonium and prepare a desired porous silica. About 8 to 20 are used.

The shape of the silica carrier is not limited and may be powder or
It may be in the form of granules, granules, pellets, tablets, rods, or the like, and is arbitrarily selected depending on the hydrogenation reaction system in which a catalyst is applied. In the hydrogenation catalyst of the present invention, particularly in the hydrogenation catalyst of maleic anhydride, it is effective to increase the surface area of the silica carrier in order to increase its reaction activity.
Increasing the surface area tends to increase the selectivity of tetrahydrofuran at the same time. In the present invention, in order to maintain high reaction activity and selectivity to tetrahydrofuran, the surface area and average pore diameter of the catalyst carrier are controlled within a specific range, and with the catalyst of the present invention, maleic anhydride is used at a high reaction rate. Can be hydrogenated, and its hydrogenated product is tetrahydrofuran in which the cyclic structure is maintained and γ-butyrolactone which is also an intermediate thereof, and the number of alcohols by the ring-opening reaction is extremely small.

The hydrogenation catalyst of the present invention can be produced by a method known per se using the above silica carrier.
For example, the following methods may be mentioned, and these methods may be appropriately adopted. 1) A method of impregnating silica with a solution containing a group VIII noble metal compound or rhenium compound that can be decomposed by heating, and drying and reducing the same. 2) Ion-exchange the noble metal compound of group VIII with silica, dry and reduce it, and then impregnate it with a rhenium compound solution,
How to dry and reduce. 3) A method of physically mixing a noble metal compound of Group VIII and a rhenium compound with silica, followed by drying and reduction.

The noble metal compound and rhenium compound of Group VIII of the periodic table used as a catalyst component in the hydrogenation catalyst of the present invention are not particularly limited as long as they can be decomposed by heat during catalyst preparation. Examples of the Group VIII noble metal compound include compounds of palladium, ruthenium, rhodium, platinum and iridium, and these may be used alone or in combination of two or more kinds. Specific examples of the palladium compound include inorganic salts such as palladium chloride, palladium nitrate and palladium sulfate, organic compounds such as palladium acetate and palladium acetylacetonate, and coordination compounds such as tetraammine palladium chloride. Examples of ruthenium compounds include inorganic salts such as ruthenium chloride and ruthenium nitrosyl nitrate, organic compounds such as ruthenium acetylacetonate, coordination compounds such as pentaammine ruthenium chloride and triruthenium dodecacarbonyl, and examples of rhodium compounds include rhodium chloride. Inorganic salts such as rhodium nitrate and rhodium sulfate, organic compounds such as rhodium acetylacetonate, and coordination compounds such as tetrarhodium dodecacarbonyl.

As the platinum compound, chloroplatinic acid,
Acids such as sodium chloroplatinate and inorganic salts, organic compounds such as platinum acetylacetonate, coordination compounds such as tetraammineplatinium chloride, and the like, examples of iridium compounds include iridium chloride, iridium chloride and other acids and inorganic salts. , Organic compounds such as iridium acetylacetonate, and coordination compounds such as tetriridium dodecacarbonyl. Among these precious metal compounds,
Particularly, a palladium compound is preferably used.

Examples of the rhenium compound include inorganic salts such as dirhenium heptaoxide, perrhenic acid, ammonium perrhenate and rhenium chloride, acids, and coordination compounds such as dirhenium decacarbonyl.

The amount of the metal catalyst component supported is not particularly limited, but if it is small, a sufficient catalytic effect cannot be achieved, while if it is larger than necessary, it is economically disadvantageous. Usually VIII
The group noble metal is 0.1 to 20% by weight, preferably 1 to 10% by weight, and the rhenium is 0.1 to 20% by weight, preferably 0.1 to 10% by weight. desirable.

The hydrogenation catalyst of the present invention is preferably VII.
Group I noble metal compound and rhenium compound in a suitable solvent,
For example, it is dissolved in water, methanol or the like, impregnated in the silica and then reduced. The reduction is usually hydrogen, methanol,
10 with gas such as formaldehyde or reducing vapor
It is carried out in a gas phase at 0 to 700 ° C., but when it is reduced with hydrazine or the like, it can also be carried out in a liquid layer. Industrially, hydrogen gas is used, but even if hydrogen is pure, nitrogen,
It may be diluted with an inert gas such as argon.

The hydrogenation reaction of carboxylic acids is carried out using the hydrogenation catalyst of the present invention. The carboxylic acids to be subjected to the hydrogenation reaction include dicarboxylic acids having 4 carbon atoms, their acid anhydrides, their mono or It is selected from di-lower alkyl esters and their intramolecular esters. Specific examples of the dicarboxylic acid having 4 carbon atoms and its acid anhydride include maleic acid, fumaric acid, fumaric anhydride, and maleic anhydride. Among them, maleic acid and its acid anhydride are particularly preferable. preferable. The alcohol constituting the ester of mono- or di-lower alkyl ester of dicarboxylic acid having 4 carbon atoms is not particularly limited, and lower alcohol having 1 to 5 carbon atoms such as methanol, ethanol, propanol and butanol is preferable. The intramolecular ester is a lactone, specifically, γ-butyrolactone. In the hydrogenation method of the present invention, a hydride having a cyclic structure can be produced without ring-opening the cyclic structure of the raw material. Therefore, among these carboxylic acids, maleic anhydride, which is an acid anhydride of dicarboxylic acid, is most effective. It is a good starting material.

The conditions of the hydrogenation reaction of the present invention vary depending on the kind of the starting carboxylic acid and the activity of the catalyst, but the temperature is usually 130 to 350 ° C., preferably 160 to 300.
C., hydrogen pressure 1.00 to 30.0 MPa, preferably 5.
It is selected in the range of 0 to 20.0 MPa. The amount of catalyst used in the hydrogenation reaction is 100% of the reaction raw material such as dicarboxylic acid.
The amount is preferably 0.1 to 100 parts by weight with respect to parts by weight, but is arbitrarily selected within the range where a practical reaction rate can be obtained according to various conditions such as reaction temperature or reaction pressure.

The hydrogen used in the hydrogenation reaction has a purity that is usually used industrially, but hydrogen diluted with an inert gas such as nitrogen may also be used as the case may be. Further, the amount used is generally in excess of the stoichiometric amount with respect to the raw material carboxylic acids.

As the reaction system, either a liquid phase suspension bed or a fixed bed can be adopted. In the case of a suspension bed, the separation of the catalyst and the reaction solution after completion of the reaction can be easily performed by a commonly used method such as decantation or filtration. In the continuous method, for example, a trickle bed method or the like is used, and the raw material dicarboxylic acid is melted or supplied to the reaction tank as a solution of a reaction solvent. The target product can be easily separated from the obtained reaction solution by a method generally used in industry, such as distillation.

The hydrogenation reaction may be carried out without a solvent,
A solvent may be used if necessary. When using a solvent,
The solvent is not particularly limited as long as it does not adversely affect the reaction, and specifically, water, alcohols such as methanol, ethanol, octanol, dodecanol and ethylene glycol; tetrahydrofuran,
Ethers such as dioxane and tetraethylene glycol dimethyl ether; and hydrocarbons such as hexane, cyclohexane and decalin.

The product obtained by the hydrogenation reaction of the present invention is mainly a lactone or a cyclic ether, although it depends on the kind of the starting dicarboxylic acid, and a small amount of alcohols can be obtained. INDUSTRIAL APPLICABILITY The hydrogenation method of the present invention is particularly effective for the hydrogenation reaction of maleic anhydride. According to the method of the present invention, the conversion rate of maleic acid is high, and tetrahydrofuran can be produced with a high selectivity. The production of alcohols such as and butyl alcohol is slight. Further, as a hydrogenation reaction catalyst, B of a silica carrier is used.
If the ET surface area is made relatively large and the average pore size is made smaller, γ-butyrolactone can be produced in a certain ratio together with the main product, tetrahydrofuran.

[0024]

EXAMPLES The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the gist thereof. In the following Examples and Comparative Examples,% means% by weight.

Examples 1 to 5 Preparation of Catalyst As a silica carrier, manufactured by Fuji Davisson Chemical Co .; GRAD
E # 12 (Example 1), Cariact Q-6 (Example 2), Dokai Chemical Co., Ltd .; D-150-200A (Example 3), D-150-300A (Example 4) were used.
As for mesoporous silica (“Catalyst” Vol.36 No.2
p.131 1994 ； 73rd CATSJ Meeting Abstracts ； N
O.1B12) was synthesized according to the method described below. That is, 50 g of kanemite was dispersed in 1000 ml of a 0.1 M hexadecyltrimethylammonium chloride aqueous solution and heated at 60 to 70 ° C. for 3 hours. After cooling to room temperature,
The solid product was filtered off and put into 1000 ml of water to adjust the pH to 8.5. After separating the solid, thoroughly washing and drying, 550
It was calcined at ℃ for 6 hours. This is FSM-16 (Example 5)
Used as. 33.3 mg of palladium chloride and 78 mg of dirhenium heptaoxide were dissolved in 0.86 ml of a 5N aqueous hydrochloric acid solution, and 1.92 g of each silica was added to the solution to impregnate it, and then water was distilled off with a rotary vacuum dryer. afterwards,
After drying in vacuum at 100 ° C. for 2 hours, it was reduced in a hydrogen atmosphere at 300 ° C. for 2 hours to obtain a catalyst of 1% Pd-3% Re / silica.

Hydrogenation reaction 2 g of maleic anhydride was dissolved in 8 g of water, and 0.2 g of each catalyst prepared by the above method was charged into a 70 ml spinner stirring autoclave.
The reaction was carried out at 40 ° C for 2 hours. The results of gas chromatography analysis of the reaction products are shown in Table 1 together with the physical properties of the carrier.

Comparative Examples 1-2 Silica carriers manufactured by Fuji Davisson Chemical Co .; Cari
Using act-30 (Comparative Example 1) and Cariact-50 (Comparative Example 2), a catalyst was prepared in the same manner as in Example, and a hydrogenation reaction was carried out. The results are shown in Table-1.

[0028]

[Table 1]

[0029]

INDUSTRIAL APPLICABILITY The noble metal component and rhenium component of Group VIII of the periodic table of the present invention have specific physical properties, that is, 120 m ²
BET surface area of / g or more and 2.0 to 45.0
have an average pore size of nm, or 2 <D (pore size)
If hydrogenation of dicarboxylic acids having 4 carbon atoms, especially maleic anhydride, is carried out using a solid catalyst supported on silica composed of a mesoporous material having a sharp pore distribution at <50 nm, milder conditions will be obtained than conventional methods. The desired tetrahydrofuran can be produced with high selectivity at high conversion.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C07B 61/00 300

Claims (10)

[Claims] 1. A noble metal component and a Re component of Group VIII of the periodic table are supported on a silica carrier, and the silica carrier has a BET surface area of 120 m ² / g or more and 2.0-4.
A hydrogenation catalyst for a carboxylic acid selected from a dicarboxylic acid having 4 carbon atoms, an acid anhydride thereof, a mono- or di-lower alkyl ester thereof or an intramolecular ester thereof, which has an average pore diameter of 5.0 nm. 2. The BET surface area of the silica carrier is 120 to 1.
^2. The range is 250 m ² / g.
The hydrogenation catalyst described. 3. The silica carrier has an average pore diameter of 2.0 to 3.
The hydrogenation catalyst according to claim 1 or 2, which has a range of 0.0 nm. 4. A noble metal component and a Re component of Group VIII of the Periodic Table are supported on a silica carrier, and the silica carrier has a BET surface area of 120 m ² / g or more and 2.0-4.
A catalyst for producing tetrahydrofuran by hydrogenating maleic acid or its acid anhydride, which has an average pore diameter of 5.0 nm. 5. A noble metal component and a Re component of Group VIII of the Periodic Table are supported on a silica carrier, and the silica carrier is 1
BET surface area of 20 m ² / g or more and 2 <D
(Pore diameter) <40 nm, which is a mesoporous material having a sharp pore distribution, and is selected from a dicarboxylic acid having 4 carbon atoms, an acid anhydride thereof, a mono- or di-lower alkyl ester thereof or an intramolecular ester thereof. Hydrogenation catalyst for carboxylic acids. 6. The BET surface area of the silica carrier is 120 to 1.
6. The range is 250 m ² / g.
The hydrogenation catalyst described. 7. A silica carrier exchanges intercalated Na ions of kanemite with alkyltrimethylammonium to form a stable composite of a monolayer silicate sheet and alkyltrimethylammonium, and then calcinates the composite. The hydrogenation catalyst according to claim 5, which is a mesoporous material having a sharp pore distribution in 2 <D (pore diameter) <50 nm obtained by the above. 8. A noble metal component and a Re component of Group VIII of the Periodic Table are supported on a silica carrier, and the silica carrier is 1
BET surface area of 20 m ² / g or more and 2 <D
A catalyst for producing tetrahydrofuran by hydrogenation of maleic acid or its acid anhydride, which is a mesoporous material having a sharp pore distribution in (pore diameter) <50 nm. 9. The hydrogenation catalyst according to claim 1, wherein at least one carboxylic acid selected from a dicarboxylic acid having 4 carbon atoms, an acid anhydride thereof, a mono- or di-lower alkyl ester thereof or an intramolecular ester thereof is used. A method for hydrogenating carboxylic acids, which comprises hydrogenating in the presence of a temperature of 130 to 350 ° C. and a hydrogen pressure of 5.0 to 20.0 MPa to produce lactones and / or cyclic ethers. 10. Maleic acid and / or maleic anhydride in the presence of the catalyst according to claim 4 or 8 at a temperature of 130-3.
A method for producing tetrahydrofuran, which comprises hydrogenating at 50 ° C. and a hydrogen pressure of 5.0 to 20.0 MPa.