JP2001163830A - Method for producing phenyl ester and catalyst - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for keeping activity of a catalyst and stably producing a phenyl ester when reacting benzene with a carboxylic acid and molecular oxygen in the presence of the specific catalyst in a liquid phase. SOLUTION: The benzene is reacted with the carboxylic acid and the molecular oxygen in the presence of the catalyst comprising palladium, at least one kind of element selected from the groups consisting of IIIb group, IVb group, Vb group and VIb group in periodic table and at least one kind of element selected from the groups consisting of IIIa group and IVa group in the periodic table to produce the phenyl ester.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to the reaction of benzene, carboxylic acid and molecular oxygen in the presence of a specific catalyst,
The present invention relates to a method for producing a phenyl ester with good yield and more stability.

[0002] Phenyl esters are useful as starting compounds for phenol.

[0003]

2. Description of the Related Art A method for producing phenyl ester by reacting benzene, carboxylic acid and molecular oxygen in the presence of a specific catalyst is well known, and uses a noble metal as a catalyst in a gas or liquid phase. Considered examples have been reported. Palladium is best known as the main catalyst, and a method of adding a metal which is not effective by itself as a cocatalyst is also known.

For example, as an example using a metal catalyst, Japanese Patent Publication No. 46-33024 discloses a mixture of benzene, a saturated aliphatic carboxylic acid and molecular oxygen selected from the group consisting of palladium and platinum. A method for reacting in the presence of at least one metal is disclosed. Japanese Patent Publication No. 48-18219 discloses a method using a catalyst in which elemental bismuth or tellurium is mixed and coexisted with at least one metal selected from the group consisting of palladium and platinum. Furthermore, in Japanese Patent Publication No. 55-15455,
A method of performing a liquid phase reaction in the presence of nitric acid using a catalyst comprising palladium or a palladium compound and one or more of cadmium, zinc, uranium, tin, lead, antimony, bismuth, tellurium, and thallium compounds is disclosed. ing.

Further, Japanese Patent Publication No. 56-21463, Japanese Patent Application Laid-Open No. 52-27089, and Japanese Patent Application Laid-Open No.
JP-A-52-130494 discloses a catalyst obtained by adding an alkali metal salt as an activity promoter to palladium and antimony.

Further, as an example of using a metal compound as a catalyst, Japanese Patent Publication No. 34544/1976 discloses platinum,
Oxides and hydroxides of noble metals selected from palladium, rhodium, ruthenium, iridium and osmium,
A method using a catalyst in which at least one of acetate or nitrate and at least one of alkali metal nitrate are combined is disclosed. JP-A-48-4439 discloses that (a) at least one kind of palladium metal or a compound thereof, (b) at least one kind of nitric acid, nitrous acid or a metal salt thereof, or (a), (b) A method using a catalyst in which at least one metal carboxylate is added to a component is disclosed. Furthermore, Japanese Patent Publication No. 2-13653 discloses a method using a catalyst comprising palladium acetate, antimony acetate, and at least one acetate salt selected from the group consisting of chromium, nickel, manganese, and iron.

However, in these conventional methods, when benzene, carboxylic acid and molecular oxygen are reacted in the liquid phase in the presence of a specific catalyst to produce a phenyl ester, palladium metal is eluted into the raw material liquid and the catalyst is dissolved. There is a problem that the activity decreases with time. Since palladium is an expensive noble metal, its loss is economically burdensome. In addition, when a palladium recovery step is provided at a subsequent stage, the process becomes complicated. Furthermore, from an industrial point of view, a decrease in activity over time means that an operation must be performed to compensate for this, which is a serious problem.

On the other hand, the method of using a metal salt soluble in a reaction solution as a catalyst requires a step of recovering the metal salt at a later stage. Further, as the reaction proceeds, for example, in the case of a palladium compound, the palladium compound Is deposited as a metal in the reactor. Even in this case, the catalyst activity decreases with time, and the loss of palladium becomes an economic burden.

Japanese Patent Application Laid-Open No. Sho 63-174950 discloses that a soluble bismuth or lead compound coexists in a reaction system in a liquid phase reaction using palladium, bismuth and / or lead as a catalyst. Have been. According to the publication, a soluble bismuth or lead compound prevents the elution of bismuth or lead in a metal state supported on a catalyst, and the elution of palladium as a main catalyst is suppressed. As a result, the effect on maintaining activity is reduced. It is stated that there is.

However, also in this method, the amount of soluble bismuth or lead compound added to the reaction system is large, and in the step of separating and purifying phenyl ester, a step of recovering these compounds as crystals is necessary. Is complicated and not practical.

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and an object of the present invention is to produce a phenyl ester by reacting benzene, a carboxylic acid and molecular oxygen in the presence of a palladium catalyst. An object of the present invention is to provide a method for producing a phenyl ester more stably while maintaining the activity.

[0012]

Means for Solving the Problems The present inventor has made intensive studies in order to solve the above-mentioned problems of the prior art. As a result, they have found that by reacting benzene, carboxylic acid and molecular oxygen in the presence of a specific catalyst, it is possible to suppress a decrease in catalytic activity over time as compared with the conventional method, and completed the present invention.

That is, according to the present invention, benzene, carboxylic acid, and molecular oxygen are converted into (A) palladium and (B) I of the periodic table.
At least one element selected from the group consisting of group IIb, group IVb, group Vb and group VIb, and (C) I of the periodic table
A method for producing a phenyl ester, characterized by reacting in the presence of a catalyst containing at least one element selected from the group consisting of Group IIa and Group IVa, and a catalyst thereof.

Hereinafter, the present invention will be described in more detail.

[0015] The main catalyst of the catalyst used in the process of the present invention is palladium, and furthermore, group IIIb of the periodic table,
At least one element selected from the group consisting of groups IVb, Vb and VIb, and groups IIIa and I of the periodic table;
At least one element selected from the group consisting of Va group is used.

In the method of the present invention, the catalyst component is
It can also be used by being supported on a carrier inert to the reaction itself. Preferred carriers include activated carbon and silica.

In the method of the present invention, palladium and at least one element selected from the group consisting of groups IIIb, IVb, Vb and VIb of the periodic table are preferably used in a metal state. Palladium and at least one element selected from the group consisting of groups IIIb, IVb, Vb and VIb of the periodic table may form an intermetallic compound with each other.

In the method of the present invention, the periodic table IIIb
The at least one element selected from the group consisting of Group IVb, Group Vb and Group VIb is not particularly limited, but is usually an element of the fourth to sixth periods, and among these, it is preferable. Are lead, bismuth, antimony and tellurium. Also, the periodic table IIIb group, IVb group, Vb
The at least one element selected from the group consisting of Group VIb and Group VIb is preferably a Group VIb element. The molar ratio of palladium to these elements is usually from 0.01 to 20, preferably from 0.02 to 2, with respect to palladium 1. If the amount is too large or too small, the effect of addition may be reduced.

In the method of the present invention, III of the periodic table
at least one selected from the group consisting of group a and group IVa
The seed elements are preferably used in the form of a metal oxide, but some of them may be in a metal state, and palladium and / or group IIIb, group IVb or group Vb of the periodic table may be used.
And at least one element selected from the group consisting of Group VIb and Group VIb.

In the process of the present invention, when the catalyst is supported on a carrier which is inert to the reaction itself, the catalyst of the present invention can be obtained by
At least one element selected from the group consisting of Group IIa and Group IVa may be present in the form of a composite oxide with the carrier. When the catalyst is used without being supported on a carrier inert to the reaction, palladium and group IIIb of the periodic table, I
At least one element selected from the group consisting of Vb group, Vb group and VIb group,
It may be used by being supported on a metal oxide formed by at least one element selected from the group consisting of group a.

In the method of the present invention, III of the periodic table
at least one selected from the group consisting of group a and group IVa
The seed element is not particularly limited, but is usually an element of the fourth to sixth periods. Of these, yttrium, a lanthanoid element, titanium, zirconium, hafnium, and more preferably cerium,
Praseodymium, neodymium, titanium, zirconium and hafnium. The addition amount of these elements is usually 0.1% by weight to 99.99% by weight, preferably 1% by weight to 99.9% by weight based on the total weight of the catalyst. II of the periodic table
If the addition amount of at least one element selected from the group consisting of Group Ia and Group IVa is too small, the effect of addition is reduced,
If it is too large, palladium as the main catalyst will decrease,
Again, the effect of addition decreases.

In the method of the present invention, the source of palladium is not particularly limited. For example, palladium metal, ammonium hexachloropalladate, potassium hexachloropalladate, sodium hexachloropalladate, ammonium tetrachloropalladate, potassium tetrachloropalladate, sodium tetrachloropalladate, potassium tetrabromopalladate, palladium oxide, palladium chloride, Palladium bromide, palladium iodide, palladium nitrate, palladium sulfate, palladium acetate, potassium dinitrosulfite palladium, chlorocarbonyl palladium, dinitrodiammine palladium, tetraamminepalladium chloride, tetraamminepalladium nitrate, cis-dichlorodiaminepalladium, trans-dichloro Diamine palladium, dichloro (ethylenediamine) palladium Potassium tetracyano palladium acid, palladium acetylacetonate and the like.

In the method of the present invention, the periodic table IIIb
The raw material of at least one element selected from the group consisting of group IV, group IVb, group Vb and group VIb is not particularly limited. Specifically, as a raw material of lead, lead metal, lead acetate,
Examples thereof include lead chloride, lead fluoride, lead iodide, lead nitrate, lead oxide, lead sulfate, lead oxalate, lead naphthenate, and lead stearate. Examples of bismuth raw materials include bismuth metal, bismuth chloride, bismuth nitrate, bismuth oxychloride, bismuth acetate, bismuth oxide, and the like. Antimony materials include antimony metal, antimony fluoride, antimony chloride, antimony bromide, antimony iodide, antimony acetate, antimony methoxide, antimony ethoxide, antimony isopropoxide, antimony butoxide, antimony ethylene. Examples thereof include glycosides, antimonypotassium tartrate, antimony oxide, antimony sulfide, and complex compounds with organic acids such as tartaric acid and oxalic acid. Examples of tellurium raw materials include tellurium metal, tellurium chloride, tellurium oxide, tellurium iodide, telluric acid, and the like.

In the method of the present invention, the periodic table IIIa
The raw material of at least one element selected from the group consisting of Group IVa and Group IVa is not particularly limited. Specifically, as a raw material of cerium, cerium metal, cerium fluoride, cerium chloride, cerium bromide, cerium iodide, cerium acetate, cerium nitrate, cerium ammonium nitrate, diammonium cerium nitrate, cerium oxide, cerium sulfate, Cerium ammonium sulfate, quaternary ammonium cerium sulfate, cerium carbonate, cerium oxalate, cerium acetylacetonate and the like are exemplified. Examples of the raw material of praseodymium include praseodymium metal, praseodymium acetate, praseodymium fluoride, praseodymium chloride, praseodymium nitrate, praseodymium oxide, praseodymium oxalate and the like. Neodymium raw materials include neodymium metal, neodymium acetate, neodymium fluoride, neodymium chloride, neodymium nitrate, neodymium oxide, neodymium carbonate, neodymium oxalate,
Neodymium acetylacetonate and the like are exemplified. As a raw material of titanium, titanium metal, titanium carbide, titanium chloride, titanium oxide, titanium sulfate, titanium potassium oxalate, titanium tetraethoxide, titanium tetraisopropoxide, titanium tetrabutoxide, titanium-2-ethyl-hexanolate, etc. Is exemplified. Examples of zirconium raw materials include zirconium metal, zirconium chloride, zirconium oxychloride, zirconium oxide, zirconium oxynitrate, zirconium tetraisopropoxide, zirconium tetrabutoxide, zirconium acetylacetonate, and zirconium naphthenate.
Examples of the hafnium raw material include hafnium metal, hafnium chloride, hafnium oxide and the like.

The amount of palladium used is 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the total weight of the catalyst.
% By weight. If the amount of palladium is less than 0.01% by weight, a substantial reaction rate may not be obtained,
Adding more than 10% by weight has less effect,
Economically disadvantageous.

The method for preparing the catalyst used in the method of the present invention is not particularly limited. When the catalyst component is supported on a carrier, a conventionally known method, for example, a so-called impregnation method,
Examples thereof include an ion exchange method, a deposition method, and a kneading method.

In the method of the present invention, the carrier can be prepared by a conventionally known method. In the process of preparing the carrier, at least one element selected from the group consisting of Group IIIa and Group IVa of the periodic table may be introduced in advance.
For example, a co-precipitation is performed by hydrolyzing a solution containing a raw material of at least one element selected from the group consisting of Group IIIa and Group IVa of the periodic table with a precursor compound of a carrier. According to the method, it can be obtained as a composite oxide. Palladium and at least one element selected from the group consisting of Group IIIb, Group IVb, Group Vb and Group VIb of the periodic table may be supported on this composite oxide.

When an inert carrier is not used in the reaction itself, at least one element selected from the group consisting of groups IIIa and IVa of the periodic table is converted into a metal oxide by a conventionally known method, The oxide can also carry palladium and at least one element selected from the group consisting of groups IIIb, IVb, Vb and VIb of the periodic table.

When the impregnation method is used in the process of supporting each component, the raw materials of each component may be dissolved simultaneously and impregnated and supported. After impregnating and supporting one of the components, the remaining material is impregnated and supported. You may.

After the loading, the solvent is removed by an operation such as decantation, filtration, heating, or heating under reduced pressure according to a known method in an impregnation method or an ion exchange method. For drying after removing the solvent, drying by heating, drying under reduced pressure, or the like can be used.

After drying, reduction is performed, but baking may be performed before the reduction. When baking is performed, it is preferable to perform baking at 200 to 700 ° C. using oxygen or oxygen diluted with nitrogen, helium, argon, or the like, and further using air.

A known method is used for the reduction to the catalyst. For example, a gas phase reduction method using hydrogen, carbon monoxide, ethylene, methanol, or the like as a reducing agent, or a liquid phase reduction method using hydrazine hydrate, formalin, formic acid, or the like can be used. In the case of the gas phase reduction method, the reduction temperature is 100
To 700 ° C., preferably 100 to 600 ° C.

The carboxylic acid used in the method of the present invention includes those having 10 or less carbon atoms. Specific examples thereof include monocarboxylic acids such as acetic acid, propionic acid and butyric acid, and dicarboxylic acids such as adipic acid.
Among them, lower carboxylic acids having 6 or less carbon atoms, such as acetic acid and propionic acid, are preferred.

The ratio between benzene and carboxylic acid can be freely changed. The preferred benzene / carboxylic acid ratio may be in the range of 1 / 0.1 to 1/100 in molar ratio.

The molecular oxygen used in the method of the present invention may be pure oxygen, or may be diluted with an inert gas such as nitrogen, helium, argon or the like. Air can also be used. The optimum supply amount of oxygen varies depending on the reaction temperature, the amount of the catalyst, and the like.

In the method of the present invention, the reaction with benzene, carboxylic acid and molecular oxygen is carried out in the presence of a catalyst in a gas phase, a liquid phase or a gas-liquid mixed phase. The reactor is not particularly limited, and a conventionally known method, for example, a fixed bed flow reactor, a batch reactor, a suspension bed, or the like can be used.

The amount of the catalyst to be used varies depending on the reaction method, and cannot be specified uniformly.
For example, in the case of a fixed bed, the unit catalyst volume and the total supply amount of benzene and carboxylic acid per unit time (LHSV) are in the range of 0.1 to 50 h ^-1 , preferably 0.1 to 30 h ^-1.
h- ¹ is preferable, and in the case of a suspension bed, the catalyst concentration is preferably in the range of 0.05 to 30% by weight based on the raw material.

[0038] The reaction temperature is usually 100 to 300 ° C, preferably 100 to 250 ° C.

The reaction pressure may be any pressure above normal pressure.
Usually, it is normal pressure to 200 atm, preferably normal pressure to 100 atm.

The reaction time varies depending on the method of setting the reaction temperature, pressure, amount of catalyst, and the like, or the reaction method, so that it is difficult to determine the range in a straightforward manner. In the case of, 0.5 hours or more is required. In a continuous reaction using a suspension bed or a fixed bed continuous reaction, the residence time may be 0.03 to 10 hours.

The phenyl ester obtained by the method of the present invention can easily produce phenol by a conventional method such as a hydrolysis reaction or a transesterification reaction.

[0042]

According to the method of the present invention, in producing phenyl ester by reacting benzene with carboxylic acid and molecular oxygen, palladium and group IIIb, group IVb, group Vb and group IIIb of the periodic table are used as cocatalysts. At least one element selected from the group consisting of group VIb and III of the Periodic Table
at least one selected from the group consisting of group a and group IVa
By using the catalyst containing the element of the kind, the phenyl ester can be produced more stably while maintaining the activity as compared with the conventional method.

Further, the phenyl ester is useful as a raw material compound of phenol, and the method of the present invention which can produce phenyl ester more stably with good yield, selectivity and inexpensive raw materials such as benzene and acetic acid is as follows: It is extremely significant industrially.

[0044]

EXAMPLES The present invention will be described below in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 Preparation of catalyst: 1.3 g of zirconyl nitrate was dissolved in distilled water to make the total volume of the solution 21 ml. 20 g of Caractact Q-30 manufactured by Fuji Silysia Ltd. was added to the aqueous solution and impregnated. Then, it dried under reduced pressure, dried at 110 degreeC overnight, and air-fired at 350 degreeC for 5 hours.

2.1 g of an 8.4 wt% aqueous solution of palladium dinitrodiamine nitrate and 0.03 g of telluric acid were weighed into a round-bottomed flask, and distilled water was added to make a total volume of 6 ml.
5.4 g of zirconia-supported silica prepared above was added to this solution.
Was added for impregnation. After that, drying under reduced pressure
After drying overnight at 600 ° C. for 5 hours,
Hydrogen reduction at 0 ° C. for 16 hours.

Reaction: 10 m of catalyst prepared as above
was packed in a SUS316 reaction tube having an inner diameter of 13 mm, and at a catalyst layer temperature of 190 ° C. and a reaction pressure of 20 atm, an equimolar mixture of benzene and acetic acid was 2.2 g / min, and oxygen was 27 Nm.
The reaction was performed by continuously supplying 1 / min and nitrogen at 183 Nml / min.

The reaction products were collected at 100 hours and 400 hours after the start of the reaction, separated into gas components and liquid components, and analyzed by gas chromatography. As a result, 1
Ratio of phenyl acetate STY at 400 hours to phenyl acetate STY at 00 hours (400 hr / 100 hr)
Was 0.99.

Example 2 Preparation of catalyst: zirconium tetraisopropoxide 5
g and 25 g of tetramethoxysilane were dissolved in 500 ml of methanol. 50 ml of distilled water was gradually dropped into this solution while stirring. After aging for 24 hours with stirring, the mixture was filtered. The filtered precipitate was added to 500 ml of distilled water, stirred for 10 minutes, and then filtered. Wash this water for a total of 3
After performing the steps twice, the precipitate washed with water was dried at 110 ° C. overnight. Then, it was air-fired at 500 ° C. for 5 hours.

2.1 g of a 8.4 wt% aqueous solution of palladium dinitrodiamine nitrate and 0.03 g of telluric acid were weighed into a round bottom flask, and distilled water was added to make a total volume of 6 ml.
The solution was impregnated with 5.4 g of the zirconia-silica composite oxide prepared above. Then, dried under reduced pressure,
After vacuum drying at 100 ° C. for 3 hours, baking in air at 400 ° C. for 5 hours, hydrogen reduction was performed at 400 ° C. for 5 hours. Catalyst radius 2
The tablet was formed into a column having a height of 3 mm and a height of 3 mm.

Reaction: The reaction was carried out in the same manner as in Example 1.
Ratio of phenyl acetate STY at 0 hour (400 hr / 10
0 hr) was 0.90.

Example 3 Preparation of catalyst: 50 g of zirconyl nitrate was dissolved in 1000 ml of distilled water. 25% aqueous ammonia 4
0 ml was gradually added dropwise with stirring. The pH of the solution at the end of the dropping of the aqueous ammonia was 9. After aging for 24 hours with stirring, the mixture was filtered. The filtered precipitate was added to 500 ml of distilled water, stirred for 10 minutes, and then filtered. After performing the washing three times in total, the washed sediment is removed for 1 hour.
Dried at 10 ° C. overnight.

8.26 wt% aqueous solution of palladium nitrate
27 g was weighed into an eggplant-shaped flask, and telluric acid 0.13
g and distilled water to make a total volume of 21 ml. The aqueous solution was impregnated with 20 g of the previously prepared zirconia. Then, it is dried under reduced pressure and vacuum dried at 100 ° C. for 3 hours.
After air calcination at 00 ° C for 5 hours, hydrogen reduction was performed at 400 ° C for 5 hours. The catalyst was tablet-shaped into a column having a radius of 2 mm and a height of 3 mm.

Reaction: The reaction was carried out in the same manner as in Example 1.
Ratio of phenyl acetate STY at 0 hour (400 hr / 10
0 hr) was 0.97.

Example 4 Preparation of Catalyst 1.5 g of cerium nitrate was dissolved in distilled water to make the total volume of the solution 21 ml. 20 g of Caractact Q-30 manufactured by Fuji Silysia Ltd. was added to the aqueous solution and impregnated. Then, it is dried under reduced pressure, dried at 110 ° C. overnight,
Air calcination was performed at 400 ° C. for 5 hours.

2.1 g of an 8.4 wt% palladium dinitrodiamine nitric acid aqueous solution and 0.03 g of telluric acid were weighed into an eggplant-shaped flask, and distilled water was added to make a total volume of 6 ml.
Cerium oxide-supported silica 5.4 prepared above was added to this solution.
g was added for impregnation. Then, it is dried under reduced pressure to obtain 110
After drying overnight at 600 ° C, air calcination was performed at 600 ° C for 5 hours.
Hydrogen reduction was performed at 00 ° C. for 5 hours.

Reaction: The reaction was carried out in the same manner as in Example 1.
Ratio of phenyl acetate STY at 0 hour (400 hr / 10
0 hr) was 0.95.

Example 5 Preparation of catalyst: 2.1 g of tetraisopropoxytitanium was dissolved in isopropanol to make the total volume of the solution 21 ml. This solution was added to Carrieract Q-3 manufactured by Fuji Silysia.
0 was added and impregnated. Then, dried under reduced pressure,
After drying at 110 ° C. overnight, it was calcined in air at 400 ° C. for 5 hours.

2.1 g of an 8.4 wt% aqueous solution of palladium dinitrodiamine nitrate and 0.03 g of telluric acid were weighed into an eggplant-shaped flask, and distilled water was added to make a total volume of 6 ml.
To this solution, 5.4 g of titania-supported silica prepared above was added and impregnated. Thereafter, the resultant was dried under reduced pressure, dried at 110 ° C. overnight, and air-baked at 450 ° C. for 5 hours.
Hydrogen reduction for 5 hours at ° C.

Reaction: The reaction was carried out in the same manner as in Example 1.
Ratio of phenyl acetate STY at 0 hour (400 hr / 10
0 hr) was 0.90.

Example 6 Preparation of Catalyst: 1.5 g of proseodymium nitrate was dissolved in distilled water to make the total amount of the solution 21 ml. 20 g of Caractact Q-30 manufactured by Fuji Silysia Ltd. was added to the aqueous solution and impregnated. Then, it dried under reduced pressure, dried at 110 degreeC overnight, and air-fired at 400 degreeC for 5 hours.

An 8.4 wt% aqueous solution of palladium dinitrodiamine nitric acid (2.1 g) and telluric acid (0.03 g) were weighed in an eggplant-shaped flask, and distilled water was added to make a total volume of 6 ml.
To this solution, 5.4 g of silica prepared on proseodymium oxide prepared above was added and impregnated. Then, dried under reduced pressure,
After drying at 110 ° C. overnight, the mixture was calcined in air at 600 ° C. for 5 hours and then hydrogen reduced at 400 ° C. for 5 hours.

Reaction: The reaction was carried out in the same manner as in Example 1.
Ratio of phenyl acetate STY at 0 hour (400 hr / 10
0 hr) was 0.96.

Comparative Example 1 A catalyst was prepared in the same manner as in Example 1 except that zirconia was not supported.

The reaction was carried out in the same manner as in Example 1.
Ratio of phenyl acetate STY at 400 hours to phenyl acetate STY at 00 hours (400 hr / 100 hr)
Was 0.51.

Example 7 Preparation of catalyst: Tartaric acid (11.3 g) was dissolved in distilled water.
1.6 g of antimony oxide was dissolved while warming. Thereafter, 4.6 g of zirconyl nitrate was dissolved to make the total amount of the solution 50 ml. The aqueous solution was impregnated with 50 g of Caractact Q-30 manufactured by Fuji Silysia. Then, it is dried under reduced pressure, dried under vacuum at 100 ° C for 3 hours, and dried at 110 ° C for 1 hour.
After drying overnight, it was calcined in air at 500 ° C. for 5 hours.

5.6 g of an 8.4 wt% palladium dinitrodiamine nitric acid aqueous solution and 0.1 g of telluric acid were weighed into an eggplant-shaped flask, and distilled water was added to make a total volume of 15 ml.
This solution was impregnated with the previously prepared antimony oxide and 15 g of zirconia-supported silica. Thereafter, the resultant was dried under reduced pressure, dried at 110 ° C. overnight, fired in air at 500 ° C. for 5 hours, and reduced with hydrogen at 50 ° C. for 5 hours.

The reaction was carried out in the same manner as in Example 1.
Ratio of phenyl acetate STY at 400 hours to phenyl acetate STY at 00 hours (400 hr / 100 hr)
Was 0.86.

Comparative Example 2 Preparation of Catalyst 0.6 g of tartaric acid was dissolved in 2.7 ml of distilled water, and 0.07 g of antimony oxide was dissolved while warming. Thereafter, 2.1 g of 8.4 wt% palladium dinitrodiamine nitric acid aqueous solution, 0.03 g of telluric acid and distilled water were added to make the total amount of the solution 6 ml. 5.4 g of Caractact Q-30 manufactured by Fuji Silysia Ltd. was added to this aqueous solution to impregnate it. Thereafter, the resultant was dried under reduced pressure, vacuum-dried at 100 ° C. for 3 hours, dried at 110 ° C. overnight, calcined at 400 ° C. for 5 hours, and hydrogen reduced at 400 ° C. for 5 hours.

The reaction was carried out in the same manner as in Example 1.
Ratio of phenyl acetate STY at 400 hours to phenyl acetate STY at 00 hours (400 hr / 100 hr)
Was 0.60.

Example 8 Preparation of Catalyst: 32 g of an 8.4 wt% aqueous solution of palladium dinitrodiamine nitric acid and 0.5 g of telluric acid were weighed into an eggplant-shaped flask. Add SAINT-GOBAIN to this solution
-80% zirconia XZ-16052 manufactured by NORTON
g was added for impregnation. After that, drying under reduced pressure
After drying overnight at 500 ° C. for 5 hours,
Hydrogen reduction was performed at 0 ° C. for 5 hours.

Reaction: 10 m of catalyst prepared as above
was packed in a SUS316 reaction tube having an inner diameter of 13 mm, and at a catalyst layer temperature of 190 ° C. and a reaction pressure of 40 atm, an equimolar mixture of benzene and acetic acid was 2.2 g / min, and oxygen was 34 Nm.
The reaction was carried out by continuously supplying 1 / min and nitrogen at 176 Nml / min.

The ST of phenyl acetate 5 hours after the start of the reaction
Y was 300 g / l · h. The STY of phenyl acetate at 100 hours was 205 g / l · h, and the STY of phenyl acetate at 400 hours was 190 g / l · h. 10
The ratio of phenyl acetate STY at 400 hours to phenyl acetate STY at 0 hours (400 hr / 100 hr) was 0.93.

Comparative Example 3 A catalyst was prepared in the same manner as in Example 1 except that zirconia was not supported.

When the reaction was carried out in the same manner as in Example 8, the STY of phenyl acetate 100 hours after the start of the reaction was 73 g.
/ L · h, STY of phenyl acetate after 400 hours is 40
g / l · h. Phenyl acetate ST for 100 hours
Ratio of phenyl acetate STY at 400 hours to Y (4
(00 hr / 100 hr) was 0.55.

Comparative Example 4 A catalyst was prepared in the same manner as in Example 8 except that tellurium was not supported.

When the reaction was carried out in the same manner as in Example 8, the STY of phenyl acetate at the third hour after the start of the reaction was 83 g /
It was 1 · h, but it decreased to 4 g / l · h in the 24th hour, and did not substantially react in 50 hours.

Claims (12)

[Claims] (1) benzene, carboxylic acid and molecular oxygen,
(A) palladium and (B) group IIIb of the periodic table, I
A catalyst comprising at least one element selected from the group consisting of Vb group, Vb group and VIb group, and (C) at least one element selected from the group consisting of IIIa group and IVa group of the periodic table; A method for producing a phenyl ester, characterized by reacting in the presence. (C) Group IIIa and IVa of the periodic table
2. The method according to claim 1, wherein at least one element selected from the group consisting of groups is included in the catalyst in the form of a metal oxide. (A) palladium; (B) at least one element selected from the group consisting of groups IIIb, IVb, Vb and VIb of the periodic table; and (C) a compound of the periodic table. The method according to claim 1, wherein at least one element selected from the group consisting of Group IIIa and Group IVa is supported on a carrier. (B) Group IIIb, IVb of the periodic table
The method according to claim 1, wherein at least one element selected from the group consisting of Group Vb, Group VIb, and Group VIb is a Group VIb element of the periodic table. 5. A palladium, (B) at least one element selected from the group consisting of group IIIb, group IVb, group Vb and group VIb of the periodic table, and (C) a compound of the periodic table. A catalyst for producing a phenyl ester by reacting benzene containing at least one element selected from the group consisting of Group IIIa and Group IVa, carboxylic acid and molecular oxygen. (C) Group IIIa and IVa of the periodic table
The catalyst according to claim 5, wherein at least one element selected from the group consisting of a group is included in the catalyst in the form of a metal oxide. 7. (A) palladium; (B) at least one element selected from the group consisting of groups IIIb, IVb, Vb and VIb of the periodic table; and (C) a compound of the periodic table. The catalyst according to claim 5, wherein at least one element selected from the group consisting of Group IIIa and Group IVa is supported on a carrier. (B) Group IIIb, IVb of the periodic table
The catalyst according to claim 5, wherein at least one element selected from the group consisting of Group Vb, Group VIb, and Group VIb is a Group VIb element of the periodic table. 9. A benzene, carboxylic acid and molecular oxygen,
(A) palladium and (B) group IIIb of the periodic table, I
A catalyst comprising at least one element selected from the group consisting of Vb group, Vb group and VIb group, and (C) at least one element selected from the group consisting of IIIa group and IVa group of the periodic table; A method for producing phenol, comprising reacting in the presence of a phenol ester and subjecting the obtained phenyl ester to hydrolysis or transesterification. 10. (C) Group IIIa and IV of the periodic table
at least one element selected from the group consisting of group a,
The method according to claim 9, wherein the catalyst is contained in a state of a metal oxide. 11. (A) palladium, (B) at least one element selected from the group consisting of groups IIIb, IVb, Vb and VIb of the periodic table, and (C) a compound of the periodic table. The method according to claim 9, wherein at least one element selected from the group consisting of Group IIIa and Group IVa is supported on a carrier. (B) Group IIIb, IVb of the periodic table
The method according to claim 9, wherein at least one element selected from the group consisting of Group Vb, Group VIb, and Group VIb is a Group VIb element of the periodic table.