JPH09278705A - Production of acyl group-substituted aromatic compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing the subject compound, capable of improving catalytic activity, suppressing reduction activity with time and reducing the occurrence of waste, by using an inexpensive noncorrosive solid catalyst in the reaction. SOLUTION: An aromatic compound (at least one selected from an aromatic hydrocarbon, an aromatic ether compound, a phenol compound and an aromatic halide) and a carboxylic acid or its derivative as an acylating agent (e.g. an aliphatic carboxylic acid) are brought into contact with a catalyst containing a zeolite (β-type, pentasil type, faujasite type or mordenite type zeolite) in the presence of hydrogen and reacted to give the objective acyl group-substituted aromatic compound. The amount of hydrogen existing in the reaction system is preferably >=1×<-3> mol/mol based on the supply source.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to reacting an aromatic compound and a carboxylic acid or a derivative thereof by bringing them into contact with a catalyst containing zeolite in the presence of hydrogen,
The present invention relates to a method for producing an acyl group-substituted aromatic compound.

[0002]

2. Description of the Related Art Conventional methods for producing an acyl group-substituted aromatic compound generally include aluminum chloride as a catalyst,
A method in which a Lewis acid such as iron chloride or boron trifluoride or a protic acid such as hydrofluoric acid is used to carry out a Friedel-Crafts type acylation reaction between an aromatic compound and a carboxylic acid chloride or a carboxylic acid anhydride. It has been known. These catalysts are generally required in a stoichiometric amount or more, and when industrially carried out, the problem of high corrosiveness against equipment and after the reaction, when isolating an acyl compound, hydrochloric acid is used to hydrolyze hydrochloric acid. It is well known that there are many operational and environmental problems to be solved, such as the generation of large amounts of waste.

Therefore, finding non-corrosive, inexpensive solid acid catalysts to replace these catalysts has long been a research objective. Various types of zeolite catalysts have been proposed to achieve this end.

In particular, many methods relating to the acylation of aromatic ether compounds and phenol compounds, which are susceptible to Friedel-Crafts type reactions, have been disclosed (US Pat. No. 4,668,826, US Pat. No. 465268).
No. 3, European Patent No. 334096, Japanese Patent Laid-Open No.
-299246, Japanese Patent Laid-Open No. 4-235941, Japanese Patent Laid-Open No. 5-37975, Japanese Patent Laid-Open No. 4-221.
336 publication).

Regarding the acylation reaction of aromatic hydrocarbons, which have lower acylation reactivity than aromatic ether compounds and phenol compounds, European Patent 239383,
JP-A-4-279545 and French Patent 259203.
No. 9, JP-A-4-221336, JP-A-6
It is disclosed in JP-A-3-203642.

[0006]

Despite the recognized advantage of being non-corrosive when a zeolite catalyst is used in the acylation reaction, the catalytic activity is still insufficient and the reaction time There is a drawback that it decreases with time. For this reason, the reaction requires a long time or requires a large amount of catalyst, and therefore, it is not preferable as an industrial method for producing an acyl group-substituted aromatic.

[0007]

Means for Solving the Problems As a result of intensive studies to solve the problems, the present inventors have brought an aromatic compound and an acylating agent into contact with a catalyst containing zeolite in the presence of hydrogen to cause a reaction. By doing so, it was unexpectedly found that the catalytic activity can be improved, and further, the decrease of the activity with time can be remarkably suppressed, and the present invention has been completed.

That is, in the present invention, when an aromatic group-substituted aromatic compound is produced by reacting an aromatic compound with a carboxylic acid which is an acylating agent or a derivative thereof, a catalyst containing a zeolite is contacted in the presence of hydrogen. And a method for producing an acyl group-substituted aromatic compound.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The structure of the zeolite used in the present invention may be any structure, but is preferably beta type, pentasil type, faujasite type and mordenite type, and more preferably beta type and pentasil type. Type zeolite.

The zeolite used in the present invention may be a synthesized one or a commercially available one. Beta-type zeolite can be synthesized by, for example, USP 3,3.
08,069, the synthesis method of pentasil-type zeolite is described in, for example, USP 3,702,886, USP 4,511,5.
47, a method for synthesizing a mordenite type zeolite is disclosed in, for example, Japanese Patent Publication No. 47-46677, and a method for synthesizing a faujasite type zeolite is disclosed, for example, in Japanese Patent Publication No. 38-5806.

The cation in the zeolite is not particularly limited, but it is preferable that the cation introduces the zeolite into an acid form. . Preferred cations include protons, ammonium ions, alkaline earth metals, transition metals or rare earth metal ions. Examples of the alkaline earth metal include magnesium, calcium, strontium, and barium, examples of the transition metal include nickel, cobalt, copper, and iron, and examples of the rare earth metal include lanthanum, cerium, and praseodymium. More preferably, it is a proton. Ion exchange methods for cations are widely known to those skilled in the art having knowledge of the production of crystalline aluminosilicates and usually involve adding the zeolite to an aqueous solution of a soluble salt of one or more cations to be added to the zeolite. Can be carried out by contacting. This contact may be repeated several times if necessary. When an aqueous solution of ammonium ions is used, it is converted into ammonium type zeolite by ion exchange, but can be converted into proton type zeolite by calcining it.

Further, as the catalyst used in the present invention, pure zeolite may be used as it is or may be used as a molded body. The molding method is not particularly limited, and known methods such as an extrusion method and a compression method can be applied. If necessary at the time of molding, a binder such as silica, alumina, silica-alumina, magnesia or clay mineral may be used.

Further, the zeolite used in the present invention may be used as a catalyst in which two or more kinds of zeolite are mixed, if necessary.

The amount of the zeolite catalyst used varies depending on the reaction method, but in a batch operation or a semi-batch operation, 0.1 to 100 is used with respect to the total amount of the organic reactant to be reacted.
% By weight, preferably 1 to 50% by weight, and in continuous or intermittent operation, as a weight ratio of the organic reactant to be reacted to the reaction weight per catalyst weight, is 0.1 to 50% by weight.
It is generally used in a ratio of 30 h-1, preferably 0.1-5 h-1.

The acylating agent used in the present invention is an aromatic or aliphatic carboxylic acid, or a carboxylic acid halide, ester or carboxylic acid anhydride which is a derivative thereof, preferably an aliphatic carboxylic acid, or It is a derivative thereof.

Specific examples of the acylating agent are as follows. Acetic acid, acetic acid chloride, acetic acid bromide, acetic anhydride, methyl acetate, propionic acid, propionic acid chloride, propionic acid bromide, propionic anhydride, methyl propionate, n-butyric acid, n-butyric acid chloride, n-butyric acid bromide, anhydrous n- Butyric acid, methyl n-butyrate, isobutyric acid, isobutyric acid chloride, isobutyric acid bromide, isobutyric acid anhydride, methyl isobutyrate, valeric acid, valeric acid chloride, valeric anhydride, methyl valerate, caproic acid, caproic acid chloride, capronic anhydride Acid, methyl caproate, heptanoic acid, heptanoic acid chloride, heptanoic acid anhydride, methyl heptanoate, chloroacetic acid, chloroacetic acid chloride, dichloroacetic acid, dichloroacetic acid chloride, acrylic acid, acrylic acid chloride, methacrylic acid, methacrylic acid chloride, phenyl Acetic acid chloride, malonic acid, succinic acid, Water succinic acid, maleic acid,
Maleic anhydride, benzoic acid, benzoic acid chloride, benzoic anhydride, p-ethylbenzoic acid, m-ethylbenzoic acid, o
-Ethylbenzoic acid, p-chlorobenzoic acid, p-toluic acid, m-toluic acid, o-toluic acid and the like are exemplified.

The aromatic compound used in the present invention is not particularly limited, but is preferably an aromatic hydrocarbon, an aromatic ether compound or a phenol compound.

Representative examples of aromatic compounds are as follows. Benzene, toluene, ethylbenzene, n-propylbenzene, isopropylbenzene, n-butylbenzene, isobutylbenzene, t-butylbenzene, n-amylbenzene, isoamylbenzene, t-amylbenzene, 2-phenylpentane, 3-phenylpentane, o
-Xylene, m-xylene, p-xylene, o-ethyltoluene, m-ethyltoluene, p-ethyltoluene,
o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3-trimethylbenzene,
1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, naphthalene, α-methylnaphthalene, β
-Methylnaphthalene, biphenyl, styrene, fluorobenzene, chlorobenzene, o-dichlorobenzene, m
-Dichlorobenzene, p-dichlorobenzene, bromobenzene, chloromethylbenzene, phenol, o-cresol, m-cresol, p-cresol, o-chlorophenol, m-chlorophenol, p-chlorophenol, catechol, resorcinol, hydroquinone , Pyrogallol, anisole, biphenyl ether, vanillin and the like.

In the method for producing an acyl group-substituted aromatic compound of the present invention, hydrogen is present in the reaction system,
Required. The amount of hydrogen present is preferably 1 × 10 ⁻³ mol / mol or more with respect to the feedstock containing the aromatic compound and the acylating agent. More preferably 1 × 10 ^-2 mol / mo
1 or more. If it is too large, it will be disadvantageous in terms of economic efficiency, so the upper limit is determined in consideration of economic efficiency.

When carrying out the method of the present invention, a metal having hydrogen activating ability may be supported on the catalyst in order to enhance the effect of the presence of hydrogen. Examples of the metal having hydrogen activating ability include gold, platinum, palladium, rhenium, rhodium, ruthenium, silver, cobalt, nickel, tungsten, iron,
Examples include chrome, but not limited to this.

The acylation reaction is generally carried out only with the reaction product, but it is of course possible to use a solvent. Suitable solvents include those inert to the zeolites and acylating agents used under the reaction conditions, such as cyclohexane, petroleum ether, diethyl ether, tetrahydrofuran, nitrobenzene, and carbon disulfide. The amount of the solvent used is usually 1 to 10 times the total amount of the organic reactant to be reacted.

The present invention may be either gas phase reaction or liquid phase reaction. The reaction temperature is usually 20 to 500 ° C., preferably 2
0-350 ° C. The reaction pressure is not particularly limited, but it goes without saying that in the case of liquid phase reaction, the reaction pressure must be set in order to keep the reaction system in the liquid phase state. The reaction time is usually 0.1 to 24 hours, preferably 0.5 to 10 hours in batch operation or semi-batch operation. In a continuous operation or an intermittent operation, the space velocity (WHSV = weight space velocity per hour) is set to 0.
It is in the range of 1 to 30 h-1, preferably 0.1 to 5 h-1.

After completion of the reaction, the acyl group-substituted aromatic compound produced from the reaction mixture can be separated and purified by a conventional distillation method, crystallization method, chromatography method or the like. Further, when the unreacted raw material is recovered, it can be used again in the acylation reaction.

[0024]

EXAMPLES Examples of the present invention will be described below.
The present invention is not limited to this.

(Catalyst Preparation) Catalyst 1 Beta-type zeolite powder having a SiO 2 / Al 2 O 3 molar ratio of 24.0 was dried at 120 ° C. for about 12 hours, heated from room temperature to 350 ° C., and further heated to 550 ° C. in steps of 50 ° C. The temperature was raised at intervals of time, and finally the temperature was maintained at 550 ° C. for 3 hours for firing. This powder was tableted, crushed and sized to a particle size of 0.7 to 1.4 mm. Subsequently, 20 g of this catalyst was immersed in 60 g of a 10 wt% ammonium chloride aqueous solution at 85 ° C. for about 1 hour. Thereafter, the operation of putting the catalyst in 200 g of purified water, maintaining the temperature at 85 ° C. for 30 minutes, and washing with water was repeated 7 times. This was dried at 120 ° C. overnight and then calcined at 500 ° C. for 3 hours to prepare a proton-type zeolite-containing catalyst (catalyst 1).

Catalyst 2 SiO2 / Al2O3 molar ratio 5
0.0 Pentasil-type zeolite powder at 120 ℃ about 1
After drying for 2 hours, raise the temperature from room temperature to 350 ° C, and
The temperature was raised to 50 ° C. in steps of 50 ° C. every 1 hour, and finally, the temperature was kept at 550 ° C. for 3 hours for firing. This powder was tableted, crushed and sized to a particle size of 0.7 to 1.4 mm. Subsequently, 20 g of this catalyst was immersed in 60 g of a 10 wt% ammonium chloride aqueous solution at 85 ° C. for about 1 hour. Then, put the catalyst in 200 g of purified water,
The operation of maintaining at 85 ° C. for 30 minutes and washing with water was repeated 7 times. This was dried at 120 ° C. overnight and then calcined at 500 ° C. for 3 hours to prepare a proton-type zeolite-containing catalyst (catalyst 2).

(Evaluation of catalytic activity) Example 1 The above catalyst 1 (5.2 g) was used, having an outer diameter of 3/8 inch and a wall thickness of 1.
A 2 mm stainless steel pipe was packed, and a 4: 1 (molar ratio) mixture of benzene and propionic acid was fed as a feed material at WHSV = 1.5 h −1 to carry out a fixed bed flow reaction. Hydrogen gas was supplied into the reaction system at a rate of 0.18 mol / mol with respect to the feed material. The pressure in the system is kept at 9 MPa by the pressure regulating valve, and the reaction temperature is 270 ° C.
And The amount of propiophenone produced by the acyl-substituted aromatic compound as a reaction product was calculated as the yield based on propionic acid in the feedstock by gas chromatography analysis. The result is shown in FIG.

Comparative Example 1 In Example 1, the reaction was carried out under the same conditions as in Example 1 except that hydrogen gas was not supplied. The result is shown in FIG.

Example 2 The above catalyst 2 (5.2 g) was used with an outer diameter of 3/8 inch and a wall thickness of 1.
A 2 mm stainless steel pipe was packed, and a 4: 1 (molar ratio) mixture of benzene and propionic acid was fed as a feed material at WHSV = 1.5 h −1 to carry out a fixed bed flow reaction. Hydrogen gas was supplied into the reaction system at a rate of 0.18 mol / mol with respect to the feed material. The pressure in the system is kept at 9 MPa by the pressure regulating valve, and the reaction temperature is 250 ° C.
And The amount of propiophenone produced by the acyl-substituted aromatic compound as a reaction product was calculated as the yield based on propionic acid in the feedstock by gas chromatography analysis. The result is shown in FIG.

Comparative Example 2 In Example 2, the reaction was performed under the same conditions as in Example 2 except that hydrogen gas was not supplied. The result is shown in FIG.

From the above results, when the acyl group-substituted aromatic compound is produced, it is possible to improve the catalytic activity by bringing it into contact with the catalyst containing the zeolite in the presence of hydrogen to cause the reaction, and further, It was found that the reduction of various catalytic activities can be suppressed.

[0032]

INDUSTRIAL APPLICABILITY In the method for producing an acyl group-substituted aromatic compound using a zeolite catalyst, the presence of hydrogen in the reaction system can improve the catalytic activity and further suppress the deterioration of the catalytic activity over time. .

[Brief description of drawings]

FIG. 1 is a diagram showing a change with time of a propiophenone yield in a distribution experiment conducted in Example 1 and Comparative Example 1 of the present invention.

FIG. 2 is a diagram showing a change with time in the yield of propiophenone in the distribution experiment conducted in Example 2 and Comparative Example 2 of the present invention.

Claims (8)

[Claims] 1. When an aromatic compound is reacted with a carboxylic acid which is an acylating agent or a derivative thereof to produce an acyl group-substituted aromatic compound, the catalyst is brought into contact with a catalyst containing zeolite in the presence of hydrogen. And a method for producing an acyl group-substituted aromatic compound. 2. The aromatic group-substituted aroma according to claim 1, wherein the aromatic compound is at least one selected from aromatic hydrocarbons, aromatic ether compounds, phenol compounds and aromatic halides. Method for producing group compound. 3. The method for producing an acyl group-substituted aromatic compound according to claim 1 or 2, wherein the carboxylic acid or its derivative is an aliphatic carboxylic acid or its derivative. 4. The method for producing an acyl group-substituted aromatic compound according to claim 1 or 2, wherein the carboxylic acid or its derivative is an aromatic carboxylic acid or its derivative. 5. The method for producing an acyl group-substituted aromatic compound according to claim 1, wherein the zeolite is selected from beta type, pentasil type, faujasite type and mordenite type. . 6. The method for producing an acyl group-substituted aromatic compound according to claim 1, wherein the zeolite is an acid type. 7. The acyl group according to claim 1, wherein the amount of hydrogen present in the reaction system is 1 × 10 ⁻³ mol / mol or more relative to the feedstock. A method for producing a substituted aromatic compound. 8. The method for producing an acyl group-substituted aromatic compound according to claim 1, wherein the reaction is performed in a liquid phase.