JPH01301646A - Production of carboxylic acid aryl esters and catalyst used in said production process - Google Patents

Abstract

PURPOSE:To obtain the subject compound in high yield and selectivity, at a low cost, keeping excellent catalytic activity, by reading an aromatic hydrocarbon with a carboxylic acid and molecular oxygen in the presence of a specific catalyst containing a palladium component and an arsenic component. CONSTITUTION:The objective compound is produced by reacting an aromatic hydrocarbon (preferably benzene or naphthalene) with a carboxylic acid and molecular oxygen at 100-350 deg.C in the presence of a catalyst produced by supporting a catalyst component containing a palladium component and an arsenic component on a carrier. Preferably, the amount of the arsenic component to the palladium component is 0.1-5,000 and the amount of the palladium component supported on the carrier is 0.001-10wt.%, especially 0.01-5wt.% in terms of palladium metal. The molar ratio of the aromatic hydrocarbon to the carboxylic acid is preferably 1/(0.1-10).

Description

[Detailed description of the invention] Nine skin left cunning dog! The present invention relates to a method for producing carboxylic acid aryl esters, and more specifically, the present invention relates to a method for producing carboxylic acid aryl esters, and more specifically, a method for producing carboxylic acid aryl esters with high selectivity and high yield by reacting aromatic hydrocarbons, carboxylic acids, and molecular oxygen in the presence of a specific catalyst. The present invention relates to a method for producing carboxylic acid aryl esters.

The present invention also relates to a palladium-based catalyst used in the method for producing carboxylic acid aryl esters as described above.

Technical Background of the Invention and One Problem Conventionally, as a method for producing aryl carboxylic esters, aryl carboxylic esters are obtained by reacting an aromatic hydrocarbon, a carboxylic acid, and molecular oxygen in the presence of a catalyst. There is a way. As the catalyst used in the above reaction, noble metals of group Ⅰ of the periodic table of elements, especially palladium or its compounds are effective, and palladium or its compounds are salts of metals of group 1A and nB of the periodic table of elements. Catalysts containing these are already known.

In addition, various attempts have been made to produce carboxylic acid aryl esters by blending co-catalysts with noble metals such as palladium and platinum to obtain catalysts with higher activity than the catalyst described in 1 above. .

For example, Japanese Patent Publication No. 48-18219 discloses that benzene, a saturated aliphatic carboxylic acid, and molecular oxygen are reacted in the presence of a catalyst prepared by adding metal Bi, Te, Sb, or Se to palladium as a promoter. JP-A No. 51-8188 teaches a method for producing phenyl esters and phenol using palladium as a co-catalyst. Catalysts for the production of carboxylic acid esters are taught which are added and supported on a carrier.

Furthermore, JP-A-52-77892 discloses a method for producing phenylnisder carboxylate in which antimony as a promoter and an alkali metal sulfonate as an activator are added to palladium and supported on a carrier. A catalyst is taught, and JP-A-61-212527 discloses a method in which benzene, carbonic acid, and molecular oxygen are reacted in the presence of a catalyst consisting of palladium carboxylate, antimony carboxylate, and carboxylic acid. A method for producing phenyl esters and phenols is taught. Furthermore, Japanese Patent Publication No. 119-34973 discloses that benzene, a saturated carboxylic acid, and molecular oxygen are reacted in the presence of a catalyst consisting of palladium, zinc, cadmium, or a neutral or basic carboxylate of a rare earth element. A method for producing carboxylic acid phenyl esters is taught.

The present inventors have found that aromatic hydrocarbons, carboxylic acids, and molecular oxygen can be reacted with high selectivity and yield using a catalyst in which a catalyst component containing a palladium component and an arsenic component is supported on a carrier. The present inventors have discovered that carboxylic acid aryl esters can be obtained at a relatively low temperature, and have completed the present invention.

Further, the present invention provides high selectivity and high yield by using a specific catalyst when producing carboxylic acid aryl esters by reacting aromatic hydrocarbons, carboxylic acids, and molecular oxygen. An object of the present invention is to provide a method for producing aryl carboxylic acid esters, which can produce aryl carboxylic acid esters.

Furthermore, the present invention is particularly preferably used in the reaction of producing carboxylic acid aryl esters by reacting aromatic hydrocarbons, carboxylic acids, and molecular oxygen, and can produce carboxylic acid aryl esters with high selectivity and high yield. The objective is to provide a highly active palladium-based catalyst that can produce .

9th group left and star = 5- The method for producing carboxylic acid aryl esters according to the present invention comprises: an aromatic hydrocarbon; It is characterized by reacting carboxylic acid with molecular oxygen.

Further, the catalyst for producing aryl carboxylic acid esters according to the present invention is characterized in that a catalyst component containing a palladium component and an arsenic component is supported on a carrier.

Below, V of the carboxylic acid aryl esters according to the present invention
The method and catalyst used in this method will be explained in detail.

Specifically, the aromatic hydrocarbons used in the present invention include benzene, 1-toluene, xylene, ethylbenzene, t-butylbenzene, p-di-t-hexylbenzene, naphthalene, 2-methylnaphthalene, anthracene, etc. are used, and benzene and naphthalene are particularly preferably used.

[kJ] The carboxylic acid used in the present invention has a carbon number of 10.
The following carbonic acids are used, specifically acetic acid,
Lower carboxylic acids such as propionic acid are preferably used.

In the production method of the present invention, the aromatic hydrocarbon/carboxylic acid molar ratio used can vary over a wide range, but the preferred aromatic hydrocarbon/carboxylic acid molar ratio is usually 110.
1 to], /100.

The molecular oxygen used in the present invention includes pure oxygen,
Alternatively, oxygen diluted with an inert gas such as nitrogen or argon is used.

In the production method of the present invention, the amount of molecular oxygen in the reaction system can be changed arbitrarily.

Catalyst The catalyst used in the present invention contains a palladium component as a main component.

The starting material for the palladium component is not particularly limited, and any palladium compound that is normally used in preparing a supported palladium catalyst may be used. Specifically, palladium acetate, palladium chloride, etc. palladium,
Palladium nitrate, palladium sodium chloride, etc. are used.

In the present invention, the palladium compound as described above is supported on a carrier by a conventional method, and the palladium component supported on the carrier is 0.001 to 10% by weight, preferably 0.01 to 10% by weight in terms of palladium metal. It is used in an amount of 5%.

Specifically, the carrier used in the present invention includes alumina, silica, silica/alumina, carbon, diatomaceous earth, clay, macnesia, anionic clay (hydrotalcites), zeolite, etc. Among them, alumina , silica, zeolite, etc. are preferably used.

The catalyst used in the present invention contains an arsenic component as a promoter in addition to the palladium component.

The starting material for the arsenic component is not particularly limited, and metals, salts such as oxygen acids, oxygen acid salts, oxides, halides, complex salts, organometallic compounds, and mixtures thereof are used.

The arsenic component constituting the catalyst used in the present invention is used in an amount of 0.1 to 5000 mol, preferably 1 to 2000 mol, in terms of arsenic metal, per 100 mol of palladium component (palladium metal equivalent). .

In addition to the palladium component and the arsenic component, the catalyst used in the present invention includes components conventionally used as catalysts in the reaction related to the present invention, such as potassium acetate, sodium acetate, sodium phosphate, potassium hydrogen sulfate, and methane. Alkali metal salts such as potassium sulfonate and lithium propionate, carboxylic acid salts such as zinc acetate, cadmium acetate, and chromium acetate may be appropriately included as additional components.

The above-mentioned additional components are equivalent to 0.01 mole of palladium component (palladium metal equivalent value) in gold R equivalent value.
It is used in an amount of ~5000 mol, preferably 1-2000 mol.

- In the present invention, it is preferable to add a potassium component as an additional component.

The method for preparing the catalyst used in the present invention is not particularly limited, and conventionally known methods of supporting catalyst components on a carrier, such as the so-called impregnation method (immersion method), ion exchange method, etc., are preferably used.

As the solvent used in the above-mentioned impregnation method or ion exchange method, a solvent capable of dissolving the starting arsenic component but not dissolving the carrier is used.

After the catalyst component is supported on the carrier by the above method, the solvent is distilled off by performing operations such as tecantation, filtration, heating or heating under reduced pressure according to a conventional method.

In the production method of the present invention, the reaction between aromatic hydrocarbons, carboxylic acids, and molecular oxygen is carried out in the gas phase or in a gas-liquid mixed phase in the presence of the above-mentioned catalyst. In the present invention, a reactor such as a fixed bed flow reactor or a fluidized bed flow reactor that can carry out a continuous reaction in a gas phase or a gas-liquid mixed state is used.

-1,0- By using the above reactor, the total failure rate of the target reaction product can be increased.

The reaction temperature is usually 100 to 350°C2, preferably 129°C.
~250°C, and the reaction pressure may be normal pressure or increased pressure, preferably normal pressure to 100 atm.

Further, the contact time between the raw materials and the catalyst in the reaction system is not particularly limited, but it depends on the load of the reactant flow and the size of the reactor, and is usually within the range of 0.01 to 1000 seconds.

In the method for producing aryl carboxylic acid esters according to the present invention, when producing aryl carboxylic esters by reacting aromatic hydrocarbons, carboxylic acids, and molecular oxygen, in addition to the palladium component, Since a specific palladium-based catalyst in which a catalyst component containing an arsenic component is supported on a carrier is used, there is an effect that carboxylic acid aryl esters can be produced with high selectivity and high yield.

Hereinafter, the present invention will be explained by examples, or The invention is not limited to these examples.

"1%" - [Preparation of catalyst] 1 to 3.0 rifhenylarsine in 50 ml of acetic anhydride
After dissolving 6 g (10 mmol) at room temperature, approx.
50ml was added and the temperature of the mixture was maintained at 60-70°C. Add dried activated alumina (#8 to #
14 mesh particle size) was added, and then 0.45 f (2 mmol) of palladium acetate was added to 70 ml of glacial acetic acid.
A fresh solution was added and stirred at 60-70°C for 4 hours.

Next, this solution was allowed to stand overnight at room temperature, and then volatile components were distilled off at 80°C under reduced pressure to obtain a mixture.

Next, 0.59 g of potassium acetate (6
After adding a solution in which 1 mmol) was dissolved to the above mixture and stirring for 2 hours, volatile components were distilled off at 80 °C under reduced pressure, and the obtained solid was further dissolved at 115 °C and 80 ru
Volatiles were removed under conditions of m HQ.

Next, this solid was passed through a #42 mesh sieve to remove powder components, yielding 39.51 g of a solid catalyst.

The results of elemental analysis of the obtained solid catalyst were as follows.

Pd: 0.4.0% by weight, As: 1.72% by weight: 0
．． 46% by weight As/Pd (molar ratio): 6. I K/Pd (molar ratio): 3.1 [Synthesis of phenyl acetate and phenol] Above catalyst 30
Phenyl acetate and phenol were synthesized in the same manner as in Example 1, except that ml (30.07 g) was used, and their yields were determined.

The results are shown in Table 1.

Comparative Example 1 [Catalyst Preparation] 0.45 g (2 mmol) of palladium acetate was added to 60 mL of a mixture of glacial acetic acid 200011 and acetic anhydride 50 ml.
Activated alumina (dissolved at ~70°C and dried)
#8~#14 mesh particle size) Add 30g to 60~
Stirred at 70°C for 4 hours. Next, this solution was allowed to stand overnight at room temperature, and then volatile components were distilled off at 80°C under reduced pressure to obtain a mixture.

Next, 100 ml of a solution of glacial acetic acid in which 0.59 f (6 mmol) of potassium acetate was dissolved was added to the above mixture, and after stirring for 2 hours, volatile components were distilled off at 80 ° C. under reduced pressure. Furthermore, from the obtained solid, 115°C58011
Volatile components were removed under mHiJ conditions.

Next, this solid was passed through a #42 mesh sieve to remove powder components, yielding 36.96 g of a solid catalyst.

The results of elemental analysis of the obtained solid catalyst were as follows.

Pd: 0.43% by weight, K: 0.47% by weight/Pd
(Molar ratio): 3.0 [Synthesis of phenyl acetate and phenol] The above catalyst fJX
Except that 30 ml (23,78 g) was used.
Phenyl acetate and phenol were synthesized in the same manner as in Example 1, and their yields were determined.

−14= The results are shown in Table 1.

Lukasa Hiromata [Catalyst preparation ice i! ! t: Dissolve 0.45 g (2 mmol) of palladium acetate in a mixed solution of about 200 ml of acid and 50 ml of acetic anhydride at 60 to 70°C, and then add dried activated alumina (#8 to #14 mesh particles). 30 g (diameter) was added and stirred at 60-70°C for 4 hours. Next, this solution was allowed to stand overnight at room temperature, and then volatile components were distilled off at 60° C. under reduced pressure to obtain 34.5 g of a solid catalyst.

The results of elemental analysis of the obtained solid catalyst were as follows.

Pd: 0.26% by weight [Synthesis of phenyl acetate and phenol] Above catalyst 30
Phenyl acetate and phenol were synthesized in the same manner as in Example 1, except that ml (22.20 g) was used and the contact time was 4.3 seconds, and the yields thereof were determined.

The results are shown in Table 1.

= 15 = No: 1

Claims (1)

[Scope of Claims] 1) An aromatic hydrocarbon, a carboxylic acid, and molecular oxygen are reacted in the presence of a catalyst in which a catalyst component containing a palladium component and an arsenic component is supported on a carrier. A method for producing a carboxylic acid aryl ester. 2) The molar ratio of the palladium component and the arsenic component constituting the catalyst in terms of metal value is 0.1 to 5000 mol of the arsenic component to 100 mol of the palladium component, and
2. The method for producing carboxylic acid aryl esters according to claim 1, wherein the amount of the palladium component supported on the carrier is 0.001 to 10% by weight in terms of palladium metal. 3) A catalyst for producing aryl carboxylic acid esters, characterized in that a catalyst component containing a palladium component and an arsenic component is supported on a carrier. 4) The molar ratio of the palladium component and the arsenic component based on the metal equivalent value is 0.1 to 5000 mol of the arsenic component to 100 mol of the palladium component, and the amount of the palladium component supported on the carrier is palladium 0 in metal equivalent value.
Claim 3, characterized in that the amount is 0.001 to 10% by weight.
Catalyst for producing carboxylic acid aryl esters as described in 2.