JPH09176080A - Production of acyl group-substituted aromatic compound and catalyst for production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To increase acylation activity in acylation reaction and obtain the above compound by reacting an aromatic compound with a carboxylic acid or its derivative in the presence of a catalyst containing a zeolite which is sub jected to dealumination treatment. SOLUTION: When (A) an aromatic compound is reacted with (B) a carboxylic aid which is an acylating agent or its derivative, the reaction is carried out in the presence of (C) a catalyst containing a zeolite which is subjected to dealumination treatment so that dealumination ratio does not exceed 50% based on total alumium amount before treatment. Moreover, dealumination treatment is carried out using a mineral acid, especially either one kind of hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid and an aromatic hydrocarbon, especially benzene or naphthalene is used as the component A and a carboxylic acid halide, especially carboxylic acid chloride is preferably used as the component B.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing an acyl group-substituted aromatic compound by reacting an aromatic compound with a carboxylic acid or a derivative thereof in the presence of a zeolite treated with a mineral acid.

[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.

On the other hand, regarding the treatment of the zeolite catalyst with a mineral acid, it is possible to remove aluminum as AlCl ₃ by treating with a gaseous chlorine compound, for example.
No. 0740 discloses a method of removing alumina from a crystalline aluminosilicate with an aqueous solution of a chromium salt of a mineral acid, and US Pat. No. 3,937,791 discloses a method of removing amorphous alumina with a dilute mineral acid after water treatment at high temperature. US Patent 3591
Japanese Patent Publication No. 3-41408 discloses a method for producing a highly siliceous zeolite beta by treating with hydrochloric acid, and relates to a method for increasing the silica / alumina ratio of zeolite. However, these dealuminated zeolites have a lower acidic activity than the starting material.

[0007]

When the zeolite catalyst is used in the acylation reaction, the reaction activity is not yet sufficient, though it is a recognized advantage that it is non-corrosive. There is a strong demand for the creation of active catalysts.

[0008]

Means for Solving the Problems As a result of intensive studies to solve the problems, the present inventors unexpectedly show that the reaction activity in the acylation reaction becomes large when the dealuminated zeolite catalyst is used. Therefore, the present invention has been achieved.

That is, according to 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, the dealumination ratio corresponds to the total amount of aluminum before treatment. To 50%
A method for producing an acyl group-substituted aromatic compound and a catalyst for producing the same, wherein the reaction is carried out in the presence of a catalyst containing a zeolite that has been dealuminated so as not to exceed the above.

[0010]

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

The zeolite used in the present invention may be either synthetic one or commercially available one. The method for synthesizing beta zeolite is described, for example, in US Pat.
No. 308,069.

The cations in the zeolite can be easily exchanged by ion exchange. 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 using an aqueous solution of ammonium ions,
Ion exchange produces ammonium type zeolite, which can be converted to acid type by firing.

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.

The dealumination treatment agent used in the present invention is not particularly limited, but a mineral acid is preferably used. Examples of the mineral acid include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and the like, and hydrochloric acid is preferable.

This treatment may be carried out on either the zeolite powder or the molded product using an alumina binder or the like, but it is preferably carried out on the zeolite powder.

It is important that the zeolite catalyst of the present invention is dealuminated, and the dealumination treatment is carried out by impregnating it with a solution containing a mineral acid, preferably an aqueous solution.

The treatment temperature at this time is not particularly limited,
From the viewpoint of easy operation, the temperature is preferably around room temperature to 100 ° C.

When the dealumination treatment is carried out with a solution containing a mineral acid, the concentration of this solution can be from 0.01 N to the maximum concentration, but is preferably 0.05 to 3 N, particularly preferably 0. It is 1 to 1N.

The dealumination treatment liquid may be used in any amount as long as it can be impregnated with the zeolite, but preferably, the solid-liquid ratio is 0.1 to 10 relative to the absolute dry weight of the zeolite. And particularly preferably 0.5 to 5
It is.

It is necessary that the dealumination ratio of the zeolite produced by the dealumination treatment does not exceed 50% with respect to the total amount of aluminum before the treatment, and if it exceeds this, the activity is reduced.

The dealumination rate is determined by the fluorescent X-ray method as Si.
The O ₂ / Al ₂ O ₃ ratio was measured and calculated according to the following formula.

[0022]

[Equation 1] In addition, the zeolite used in the present invention may include 2
You may use as a catalyst which mixed the zeolite of 1 or more types.

The amount of the zeolite catalyst used varies depending on the reaction method, but in batch operation or 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.
The ratio of 30h ^-1, preferably the ratio of 0.1~5h ^-1,
Commonly used.

The acylating agent used in the present invention is an aromatic or aliphatic carboxylic acid, or a derivative thereof such as a carboxylic acid halide, a carboxylic acid ester or a carboxylic acid anhydride, preferably an aliphatic carboxylic acid. , Or 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, n-methyl butyrate, isobutyric acid, isobutyric acid chloride, isobutyric acid bromide, isobutyric acid anhydride, methyl isobutyric acid, chloroacetic acid, chloroacetic acid chloride, dichloroacetic acid, dichloroacetic acid chloride, acrylic acid, acrylic acid chloride, methacrylic acid, Methacrylic acid chloride, phenylacetic acid chloride, malonic anhydride, succinic 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,
Examples thereof include o-toluic acid.

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, 2-amylbenzene, 3-amylbenzene, isoamylbenzene, t-amylbenzene, 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, bromobenzene, chloromethylbenzene, phenol, o-cresol, Examples thereof include m-cresol, p-cresol, o-chlorophenol, m-chlorophenol, p-chlorophenol, catechol, resorcinol, hydroquinone, pyrogallol, anisole, biphenyl ether and vanillin.
Of these, benzene and naphthalene are particularly preferable.

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 temperature used in the present invention is usually 2
The temperature is 0 to 500 ° C, preferably 20 to 350 ° C. At this time, the reaction time is usually 0.1 to 24 hours, preferably 0.5 to 10 hours in a batch operation or a 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.

[0031]

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 (SiO ₂ synthesized by the method described in US Pat. No. 3,308,069)
/ Al ₂ O ₃ molar ratio 24.0) was calcined at 550 ° C., and 10 g thereof was placed in a 100 ml eggplant-shaped flask containing 30 ml of 0.5N HCl aqueous solution and stirred at 90 ° C. for 1 hour. Then, the zeolite powder was taken out and washed with water three times, and then this catalyst was dried at 120 ° C. overnight and calcined at 500 ° C. for 3 hours. This zeolite powder was molded with an alumina binder to prepare a zeolite-containing catalyst (catalyst 1).

Catalyst 2 In the method for preparing Catalyst 1, 0.
A zeolite-containing catalyst (catalyst 2) was prepared in the same manner except that a 1N HCl aqueous solution was used instead of the 5N HCl aqueous solution.

Catalyst 3 In the method for preparing Catalyst 1,
1N HCl aqueous solution was used instead of 5N HCl aqueous solution,
A zeolite-containing catalyst (catalyst 3) was prepared in the same manner except that the mixture was stirred at room temperature for 1 hour.

(Evaluation of catalytic activity) Example 1 Molded product of zeolite powder treated with hydrochloric acid (Catalyst 1)
5.0 g was packed in a stainless steel pipe having an outer diameter of 1/2 inch and a wall thickness of 1.24 mm, and a 4: 1 (molar ratio) mixed solution of benzene and propionic acid was added thereto, and WHSV = 1.6 h ^−1.
A fixed bed flow reaction was carried out in which the solution was sent at. The system pressure is 9
The reaction temperature was initially maintained at 270 ° C. and the temperature was raised to 290 ° C. 44 hours after the start of the reaction. The reaction solution was analyzed by gas chromatography, and the reaction was initiated 12 and 48.
The yield of propiophenone produced after time (relative to propionic acid) was calculated and is shown in Table 1.

Comparative Example 1 In Example 1, the catalyst was an untreated zeolite-containing catalyst and the reaction was carried out under the same conditions as in Example 1. The yields of propiophenone produced 12 hours and 48 hours after the start of the reaction (vs. propionic acid) are shown in Table 1 together with the results of Examples 1 to 3.

Comparative Example 2 The catalyst 2 was used in place of the catalyst 1 used in Example 1, the experiment was conducted under the same conditions except that the same analysis was conducted. Table 1 shows the results
It was shown to.

COMPARATIVE EXAMPLE 3 Instead of the catalyst 1 used in Example 1, the catalyst 3 was used, the other conditions were the same, the experiment was conducted, and the same analysis was conducted. Table 1 shows the results
It was shown to.

[0039]

[Table 1]

From the above results, in producing an acyl group-substituted aromatic compound, a catalyst having a dealumination ratio of the dealuminated zeolite catalyst which does not exceed 50% of the total amount of aluminum before the treatment is used as the catalyst. Was found to increase the acylation activity.

[0041]

EFFECT OF THE INVENTION When the dealumination treatment is carried out within the dealuminated zeolite catalyst within the range where the dealumination amount of the zeolite does not exceed 50% of the total amount of aluminum, it is possible to increase the acylation activity. .

Claims (13)

[Claims] 1. When producing an acyl group-substituted aromatic compound by reacting an aromatic compound with a carboxylic acid or its derivative as an acylating agent, the dealumination rate is 50% with respect to the total amount of aluminum before treatment. A process for producing an acyl group-substituted aromatic compound, characterized in that the reaction is carried out in the presence of a catalyst containing a zeolite that has been dealuminated so as not to exceed the limit. 2. The method for producing an acyl group-substituted aromatic compound according to claim 1, wherein the dealumination treatment is performed with a mineral acid. 3. The method for producing an acyl group-substituted aromatic compound according to claim 1 or 2, wherein the aromatic compound is an aromatic hydrocarbon, an aromatic ether compound, a phenol compound or an aromatic halide. . 4. The method for producing an acyl group-substituted aromatic compound according to claim 3, wherein the aromatic hydrocarbon is benzene or naphthalene. 5. The carboxylic acid or its derivative is an aliphatic carboxylic acid or its derivative,
The method for producing an acyl group-substituted aromatic compound according to claim 1. 6. The production of an acyl group-substituted aromatic compound according to claim 1, wherein the carboxylic acid derivative is a carboxylic acid halide, a carboxylic acid ester or a carboxylic acid anhydride. Method. 7. The method for producing an acyl group-substituted aromatic compound according to claim 6, wherein the carboxylic acid halide is carboxylic acid chloride. 8. The production of an acyl group-substituted aromatic compound according to claim 1, wherein the mineral acid is at least one selected from hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid. Method. 9. The acyl-substituted aroma according to claim 1, wherein the zeolite has a structure selected from beta type, pentasil type, mordenite type and faujasite type. Method for producing group compound. 10. The method for producing an acyl group-substituted aromatic compound according to claim 1, wherein the zeolite is an acid type. 11. The reaction is carried out in a liquid phase,
The method for producing an acyl group-substituted aromatic compound according to claim 1. 12. A catalyst for producing an acyl group-substituted aromatic compound, characterized in that the dealuminated zeolite contains a zeolite in which the dealumination ratio does not exceed 50% with respect to the total amount of aluminum before the treatment. 13. The catalyst for producing an acyl group-substituted aromatic compound according to claim 12, wherein the zeolite has a structure selected from beta type, pentasil type, mordenite type and faujasite type.