JPH0640976A - Production of phenols - Google Patents

Abstract

PURPOSE:To produce a phenolic compound in high selectivity by efficiently oxidizing an aromatic compound. CONSTITUTION:A phenolic compound is produced by the liquid-phase oxidization of an aromatic compound in the presence of a catalyst produced by supporting a noble metal of the group VIII and the oxide of one or more base metals selected from the groups III a, IV a, Va, VIa, VIIa, IIb, IVb and Vb of the periodic table on a carrier in a system containing a vanadium compound in dissolved state.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing phenols which is very important in the chemical industry as an intermediate for aniline, bisphenols, alkylphenols and phenol resins.

[0002]

2. Description of the Related Art Most of phenols having a hydroxyl group in an aromatic ring are phenols, most of which are produced by the cumene method. However, the cumene method phenol production process has a problem that it is composed of multiple steps such as alkylation, oxidation, and decomposition, and that acetone of the same mole as phenol is by-produced.

As an alternative to the cumene method, there are processes such as the Raschig method in which benzene is converted to chlorobenzene and the toluene oxidation method in which toluene is converted to benzoic acid, which have been industrialized. However, these existing processes also have problems such as corrosion of equipment, increase in equipment cost due to multi-step process, and complexity of handling solids and slurries.

Regarding polycyclic aromatic compounds having a hydroxyl group on the aromatic ring, diphenyl, which is a non-condensed cyclic compound, and naphthalene, which is a condensed cyclic compound, are sulfonated to produce phenylphenol and naphthol, respectively. The manufacturing method is industrially established. However, this process also has problems such as corrosion of the device due to acid and alkali.

As described above, the existing processes for the aromatic compound having a hydroxyl group have many problems. Therefore, it has been attempted to directly oxidize the corresponding aromatic compound to obtain the desired phenols. It has been. For example, as a method of obtaining phenol, which is the most representative compound of phenols, a method of oxidizing benzene at a high temperature of about 600 ° C. and a reaction of oxidizing it under mild conditions near room temperature have been reported. For example, in JP-A-56-87527, phenol is produced by direct oxidation in the presence of methanol using a metal oxide such as phosphorus and zinc or a metal oxide such as phosphorus, silver and zinc or a phosphate as a catalyst. In addition, JP-A-61-8
Japanese Patent No. 5338 discloses a method for producing phenol by reacting benzene with oxygen in the presence of metal porphyrin, imidazole, platinum and hydrogen in a liquid phase.

[0006]

As described above, various methods for producing phenols by directly oxidizing aromatic compounds instead of existing processes have been proposed in the past. There are still many points that need to be improved regarding the conversion rate and selectivity of.

Therefore, it is an object of the present invention to provide a method for efficiently oxidizing aromatics to produce phenols with high selectivity.

[0008]

[Means for Solving the Problems] In view of such a current situation,
The present inventors have conducted intensive studies on a method of efficiently oxidizing aromatic compounds, and have completed the present invention.

That is, according to the present invention, when an aromatic compound is reacted with a mixed gas containing oxygen and hydrogen or alternately with an oxygen-containing gas and a hydrogen-containing gas to produce phenols in a liquid phase, A catalyst in which a noble metal of Group VIII of the Periodic Table is supported on a carrier, or a noble metal of Group VIII of the Periodic Table and IIIa, IVa, Va, VIa, VIIa, I
A method for producing phenols, characterized in that a vanadium compound is dissolved in the system in the presence of a catalyst in which a base material oxide composed of one or more selected from the group consisting of Ib, IVb and Vb is supported on a carrier, and The present invention relates to a method for producing phenols in which a liquid phase flow reaction is performed.

The present invention will be described in more detail below.

In the method of the present invention, the noble metal of Group VIII of the Periodic Table to be supported on the carrier is ruthenium,
Mention may be made of rhodium, palladium, iridium, platinum and mixtures thereof. Of these, palladium and platinum are preferable. These noble metals are supported on a carrier and prepared into a catalyst. The method of supporting these noble metals on the carrier is not particularly limited, but they can be supported by, for example, an impregnation method. In this case, various inorganic and organic compounds such as halides, nitrates, sulfates, inorganic complex salts and organic acid salts can be used as the raw material of the Group VIII noble metal.

For example, in the case of palladium, various inorganic acid salts such as palladium chloride, palladium nitrate and palladium sulfate, inorganic complexes such as tetraamminedichloropalladium,
Organic acid salts such as palladium acetate may be mentioned.

Examples of the solvent used for supporting these noble metal raw materials include water, hydrochloric acid aqueous solution, ammonia aqueous solution, sodium hydroxide aqueous solution, acetic acid, benzene, alcohol and acetone.

In the method of the present invention, the noble metal of Group VIII supported on the carrier needs to be in a metallic state during the phenol-forming reaction. Therefore, the raw material of the noble metal supported on the carrier is subjected to a reduction treatment before being used. This reduction treatment may be carried out in the catalyst preparation step or in the reaction system. This reduction method is not particularly limited, but a conventional method, for example, a wet reduction method performed with a solution of sodium formate, formaldehyde, hydrazine, or the like, or hydrogen or carbon monoxide or the like diluted with an inert gas such as nitrogen or helium A dry reduction method performed in a gas phase with a reducing gas can be used. The reduction temperature is not particularly limited as long as the noble metal of Group VIII of the periodic table is reduced, but it is usually 0 to 200 ° C. in the wet reduction method and 0 to 500 ° C. in the dry reduction method.

The amount of these noble metals supported is usually 0.01 to 20% by weight, preferably 0.1 to 10% by weight, as metal, based on the total weight of the catalyst. When the amount of the noble metal to be supported exceeds 20% by weight, the reaction rate tends to increase, but a large amount of expensive noble metal is used, resulting in an increase in manufacturing cost. On the other hand, the precious metal is 0.0
If it is less than 1% by weight, the reaction rate becomes slow and the economical efficiency in the industrial process is lost.

In the method of the present invention, a noble metal of Group VIII of the periodic table and IIIa and IV of the periodic table are further added.
a, Va, VIa, VIIa, IIb, IVb and V
A catalyst in which one or more kinds selected from group b base metal oxides are supported on a carrier can be used.

Examples of the base metal oxide to be supported include yttrium oxide, lanthanum oxide, cerium oxide, group IVa zirconium oxide and Va of the periodic table.
Group Vanadium Pentoxide, Niobium Oxide, Group VIa Chromium Oxide, Molybdenum Oxide, Tungsten Oxide, Group VIIa Manganese Oxide, Group IIb Zinc Oxide, Group IVb Tin Oxide, Group Vb Bismuth Oxide, etc. Examples include base metal oxides, those composed of two or more base metal oxides such as molybdenum oxide-bismuth oxide, and those composed of base metal oxides such as molybdenum oxide-phosphorus oxide and other oxides. Of these base metal oxides, vanadium oxide,
Yttrium oxide, lanthanum oxide, zirconium oxide,
Molybdenum oxide, tungsten oxide, and niobium oxide are more preferably used.

The method of supporting the base metal oxide on the carrier is not particularly limited, and it can be carried by, for example, an impregnation method. Examples of base metal oxide raw materials include ammonium salts,
Nitrate, chloride, inorganic acid salt, acetate, oxide and the like can be used. Examples of these include ammonium metavanadate, ammonium molybdate, ammonium paratungstate, yttrium nitrate, lanthanum nitrate, zinc nitrate, bismuth nitrate, zirconium oxynitrate, chromium chloride, tin chloride, manganese acetate, niobium oxide and the like. .

These base metal oxide raw materials are supported by a conventional method, for example, by using the solvent used for supporting the above-mentioned noble metal raw materials, and then heat treated to form the corresponding base metal oxide. The method of the heat treatment is not particularly limited as long as a base metal oxide is finally obtained, but it is usually 200 to 1000 under the circulation or non-circulation of an oxygen-containing gas.
The heat treatment is performed at a temperature of ° C. When the base metal oxide is supported on the carrier, the supported amount is usually 0.1 to 99% by weight, preferably 0.3% as the base metal oxide based on the total weight of the catalyst.
Is about 20% by weight.

In the method of the present invention, the order of loading the above-mentioned noble metal and base metal oxide is not particularly limited, and either of them can be loaded first or simultaneously. In that case, when the Group VIII noble metal is loaded first or simultaneously, heat treatment is first performed, and then reduction treatment is performed. The method can be performed in the manner described above. In the method of the present invention, a method in which the base metal compound is supported on a predetermined carrier, a heat treatment is carried out, and then a noble metal compound is carried thereon, and a reduction treatment is carried out is more preferable.

A carrier is used in the method of the present invention, but any carrier generally used can be used without particular limitation. For example, silica, alumina, titania, zirconia or a composite oxide thereof, zeolite, and a carbon-based carrier such as coconut husk activated carbon can be exemplified. The base metal oxide may be used as the carrier, but the same base metal oxide as the carrier may be supported.

In the method of the present invention, the catalyst is used by dissolving the vanadium compound in the reaction system. There is no particular limitation on the method for allowing the vanadium compound to coexist in the reaction system.For example, the vanadium compound is dissolved in a solvent or a reaction raw material and supplied into the reaction solution, or the vanadium compound is gradually suspended in the reaction solution. The vanadium compound may be eluted in the reaction solution. In this reaction, the vanadium compound dissolved in the reaction system acts as a so-called co-catalyst in the presence of the prepared catalyst, and dramatically increases the phenol-forming activity. Further, in the liquid phase flow reaction, in the catalyst supporting the noble metal and the base metal oxide, the supported base metal oxide is often eluted in the reaction solution, and the catalytic activity may deteriorate, but in this case, the vanadium compound is continuously added. By effectively supplying into the reaction system, deterioration of the catalytic activity can be suppressed.

An oxide is used as a raw material for the vanadium compound,
Examples thereof include halides, nitrates, sulfates, oxalates, ammonium salts, inorganic complex salts and organic acid salts. For example,
Examples thereof include vanadium pentoxide, vanadium trichloride, vanadium oxytrichloride, ammonium metavanadate, vanadium (III) acetylacetonate, vanadium oxide acetylacetonate, vanadyl sulfate and vanadyl oxalate. The concentration of vanadium dissolved in the reaction system varies depending on the reaction mode, but is usually 1 ppm to 5% as vanadium, and preferably 5 ppm to 2%. When the amount of dissolved vanadium is less than 1 ppm, the reaction rate becomes slow and the addition effect of the vanadium compound becomes significantly small. On the other hand, if the vanadium content is 5% or more, the manufacturing cost will increase.

The amount of the catalyst used in the reaction varies depending on the reaction mode, but in the case of continuous reaction, it is difficult to unconditionally specify it, because it is determined by the reaction rate and heat balance. Also, when performing the reaction in a batch system or a semi-batch system,
It may be 0.01 to 30% by weight with respect to the reaction solution, and if it is used in excess of this range, stirring of the reaction solution may be hindered.

In the method of the present invention, the aromatic compound that can be used as a raw material is an aromatic compound having at least one aromatic ring, which is substituted with a substituent such as an alkyl group or a hydroxyl group. Good. Examples of such aromatic compounds include monocyclic aromatic compounds such as benzene, toluene, xylene, and anisole, non-condensed polycyclic aromatic compounds such as diphenyl, diphenylmethane, diphenyl ether, and condensed polycyclic compounds such as naphthalene and indene. Mention may be made of cyclic aromatic compounds.

In the method of the present invention, the reaction is carried out in the liquid phase, but a solvent may be used if necessary. As a solvent,
The aromatic compound itself as a raw material may be used as a solvent, or another suitable solvent may be used. Examples of the solvent that can be used as the solvent include pentane, saturated hydrocarbons such as cyclohexane, nitriles such as acetonitrile, ethers such as methyl ether and ethyl ether, ketones such as acetone and methyl ethyl ketone, and ethyl acetate as the organic solvent. , Esters such as butyl acetate, amides such as acetamide and N, N-dimethylacetamide, and organic acids such as formic acid, acetic acid, and propionic acid. Any one or a mixture of two or more of these may be used as a solvent. You can also do it. In addition, water can be used as a solvent in this reaction. Of course, water may be mixed with the above-mentioned organic solvents.

If necessary, an inorganic acid may be added to these reaction solvents. Examples of the acid that can be added include inorganic acids such as phosphoric acid, sulfuric acid and nitric acid. When an inorganic acid is added, it is preferable to use it at a concentration of 0.5 N or less in view of problems such as elution of catalyst components and apparatus corrosion. The amount of the solvent is not particularly limited, but if it is too large, the reaction rate will be slow, so the amount added is preferably adjusted so that the solvent concentration is 1 to 60% by weight of the entire reaction solution.

In the method of the present invention, the reaction method is not particularly limited. For example, the reaction is an aromatic compound as a raw material,
A batch system in which a catalyst, oxygen, hydrogen and, if necessary, a solvent are charged to a reactor at one time, a semi-batch system in which oxygen and / or hydrogen are continuously blown into the reactor, or an aroma A continuous system in which the group compound, oxygen, hydrogen and the like are continuously supplied and the unreacted gas and the reaction liquid are continuously extracted may be used.

The oxygen and hydrogen gases supplied in this reaction may be diluted with an inert gas such as nitrogen, helium, argon or carbon dioxide. Air can also be used as oxygen. The amount of oxygen supplied varies depending on the reaction method and reaction conditions, so it cannot be determined unconditionally, but normally the amount of oxygen supplied per unit weight (g) of the catalyst is 0.
It is performed at 01 ml / min to 1000 ml / min. If it is less than 0.01 ml / min, the productivity will be insufficient, and if it exceeds 1000 ml / min, the gas conversion rate will be small and it will be uneconomical. The ratio of oxygen and hydrogen is not particularly limited and can be arbitrarily changed, but hydrogen / oxygen (molar ratio) is preferably 0.1 to 10.

When the aromatic compound is continuously supplied, the aromatic compound supply rate per unit weight (g) of the catalyst is 1 × 1.
0 be a ^{-5 g / min~10 2 g / min} . 1 x 10 ^-5
If it is less than g / min, the productivity will be insufficient and 10
If it exceeds ² g / min, the amount of unreacted aromatic compound increases, which may be economically inconvenient.

The reaction temperature and pressure are not particularly limited as long as the reaction solution as a raw material is in the liquid phase during the reaction. When the reaction temperature is increased to increase the reaction rate, the reaction may be performed under pressure. The practical temperature range is room temperature to 2
It is 00 ° C. If the reaction temperature is lower than room temperature, the conversion of the aromatic compound will be low, while if the reaction temperature is higher than 200 ° C., the selectivity of the product may be low. The pressure is usually from atmospheric pressure to 200 Kg / cm ² ,
It is preferably normal pressure to 50 Kg / cm ² .

[0032]

The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

Example 1 Tetraamminedichloroplatinum (41.5 mg) was added to distilled water (18).
Dissolve it in ml and add silica (CARiACT-15,
100-200 mesh; manufactured by Fuji Davison Co., Ltd.
4.51 g was added. After evaporating to dryness on a hot water bath, 10
% -Hydrogen (remaining nitrogen) was passed through at 150 ° C. for 1 hour for reduction to prepare a 0.5 wt% -Pt / silica catalyst.

In a 100 ml glass reactor equipped with a reflux condenser, 20 ml of benzene and 25 ml of acetic acid were used as a reaction solution.
ml, vanadium (III) acetylacetonate 5.
9 mg was added, and 0.10 g of the above 0.5 wt% Pt / silica catalyst was added thereto. The temperature of the solution is set to 60 ° C, and 40 m of hydrogen is stirred with a magnetic stirrer.
The catalyst was activated by supplying 1 / min for 30 minutes. Subsequently, hydrogen 24 ml / min, air 38 ml / m
In was simultaneously supplied, and after 1 hour, the product in the solution was analyzed by gas chromatography. The results are shown in Table 1.

Example 2 In Example 1, 6.0 mg of vanadium oxytrichloride was used instead of vanadium (III) acetylacetonate.
A catalyst was prepared and a reaction was performed in exactly the same manner as in Example 1 except that was used. The results are shown in Table 1.

Example 3 In Example 1, ammonium metavanadate 3.8 was used instead of vanadium (III) acetylacetonate.
A catalyst was prepared and a reaction was carried out in the same manner as in Example 1 except that mg was used. The results are shown in Table 1.

Example 4 A catalyst was prepared and a reaction was carried out in the same manner as in Example 1 except that 5.6 mg of vanadium trichloride was used instead of vanadium (III) acetylacetonate. The results are shown in Table 1.

Example 5 A catalyst was prepared and the reaction was carried out in the same manner as in Example 1 except that 9.2 mg of vanadium oxide acetylacetonate was used instead of vanadium (III) acetylacetonate. It was The results are shown in Table 1.

Example 6 A catalyst was prepared and a reaction was carried out in the same manner as in Example 1 except that 7.9 mg of vanadyl sulfate was used instead of vanadium (III) acetylacetonate. The results are shown in Table 1.

Example 7 A catalyst was prepared and reacted in exactly the same manner as in Example 1 except that 8.2 mg of vanadyl oxalate was used instead of vanadium (III) acetylacetonate. The results are shown in Table 1.

Example 8 19.2 mg of rhodium (III) chloride trihydrate was dissolved in 6 ml of distilled water, and silica (CARiACT-1) was added thereto.
5,100-200 mesh; Fuji Devison Co., Ltd.
1.50 g) was added. After evaporating to dryness on a hot water bath,
Reduction was carried out at 150 ° C. for 2 hours under a flow of 10% -hydrogen (remaining nitrogen) to prepare a 0.5 wt% -Rh / silica catalyst.

In Example 1, vanadium (III)
Acetylacetonate 5.8 mg, 0.5 wt% -P
t / silica catalyst instead of 0.5 wt% -Rh /
The reaction was carried out in exactly the same manner as in Example 1 except that 0.10 g of the silica catalyst was used. The results are shown in Table 1.

Example 9 Tetraamminedichloroplatinum (18.2 mg) was added to distilled water (8 m).
1 and dissolved in alumina (Neobead-C, 2
00 mesh or less; Mizusawa Chemical Co., Ltd.) 2.00 g
Was added. After evaporating to dryness on a hot water bath, reduction was carried out at 250 ° C. for 1 hour under a flow of 10% -hydrogen (remaining nitrogen) to prepare a 0.5 wt% -Pt / alumina catalyst.

In Example 1, vanadium (III)
Acetylacetonate 6.0 mg, 0.5 wt% -P
t / silica catalyst instead of 0.5 wt% -Pt /
The reaction was carried out in exactly the same manner as in Example 1 except that 0.10 g of the alumina catalyst was used. The results are shown in Table 1.

[0045]

[Table 1]

In the table, acac represents an acetylacetonate group.

Example 10 Tetraamminedichloroplatinum (20.9 mg) was added to distilled water (9 m).
It was dissolved in 1, and 2.28 g of titania (200 mesh or less; manufactured by Sakai Chemical Industry Co., Ltd.) was added thereto. After evaporating to dryness on a hot water bath, 250% with 10% hydrogen (remaining nitrogen) flowing
A 0.5 wt% Pt / titania catalyst was prepared by reducing at 0 ° C. for 1 hour.

In Example 1, vanadium (III)
Acetylacetonate 6.1 mg, 0.5 wt% -P
t / silica catalyst instead of 0.5 wt% -Pt /
The reaction was carried out in exactly the same manner as in Example 1 except that 0.10 g of the titania catalyst was used. The results are shown in Table 2.

Example 11 Tetraamminedichloroplatinum (12.5 mg) was added to distilled water (5 m).
It is dissolved in 1, and zirconia (90 m ² / g, 200
1.36 g of less than mesh; manufactured by Norton Co., Ltd. was added. After evaporating to dryness on a hot water bath, the product was reduced at 250 ° C for 1 hour under a flow of 10% -hydrogen (remaining nitrogen) to give 0.5% by weight-P.
A t / zirconia catalyst was prepared.

In Example 1, vanadium (III)
Acetylacetonate 6.3 mg, 0.5 wt% -P
t / silica catalyst instead of 0.5 wt% -Pt /
The reaction was carried out in exactly the same manner as in Example 1 except that 0.10 g of the zirconia catalyst was used. The results are shown in Table 2.

Example 12 Tetraamminedichloroplatinum (18.2 mg) was added to distilled water (8 m).
It was melt | dissolved in 1, and H-ZSM-5 (200 mesh or less; Tosoh Corporation make) 1.99g was added here. After evaporating to dryness on a hot water bath, under 10% -hydrogen (remaining nitrogen) flow 25
0.5 wt% -Pt / H-ZSM reduced at 0 ° C for 1 hour
-5 catalyst was prepared.

In Example 1, vanadium (III)
Acetylacetonate 6.2 mg, 0.5 wt% -P
t / silica catalyst instead of 0.5 wt% -Pt /
Example 1 except that 0.10 g of H-ZSM-5 catalyst was used.
The reaction was carried out in exactly the same manner as. The results are shown in Table 2.

Example 13 22.9 mg of tetraamminedichloroplatinum was added to 10 parts of distilled water.
Dissolve it in ml and add Macropore Carbon (200me
sh or less; 2.49 g of Mitsubishi Kasei Co., Ltd.) was added. After evaporating to dryness on a hot water bath, the product was reduced at 250 ° C for 1 hour under a flow of 10% -hydrogen (remaining nitrogen) to give 0.5% by weight-P.
A t / macropore carbon catalyst was prepared.

In Example 1, vanadium (III)
Acetylacetonate 6.0 mg, 0.5 wt% -P
t / silica catalyst instead of 0.5 wt% -Pt /
The reaction was carried out in exactly the same manner as in Example 1 except that 0.10 g of macropore carbon catalyst was used. The results are shown in Table 2.

Example 14 Tetraamminedichloroplatinum (41.5 mg) was added to distilled water (18).
Dissolve it in ml and add silica (CARiACT-15,
100-200 mesh; manufactured by Fuji Davison Co., Ltd.
4.51 g was added. After evaporating to dryness on a hot water bath, 10
% -Hydrogen (remaining nitrogen) was passed through at 150 ° C. for 1 hour for reduction to prepare a 0.5 wt% -Pt / silica catalyst.

In a 100 ml glass reactor equipped with a reflux condenser, 20 ml of benzene and 25 ml of acetic acid were used as a reaction solution.
ml, vanadium (III) acetylacetonate 1.
0 mg was added, and 0.10 g of the above 0.5 wt% Pt / silica catalyst was added thereto. The temperature of the solution is set to 60 ° C., while stirring with a magnetic stirrer, 40 ml of hydrogen /
The catalyst was activated by supplying min for 30 minutes. Subsequently, 24 ml / min of hydrogen and 38 ml / min of air were simultaneously supplied, and after 1 hour, the product in the solution was analyzed by gas chromatography. The results are shown in Table 2.

Example 15 A catalyst was prepared and the reaction was carried out in the same manner as in Example 14 except that 118 mg of vanadium (III) acetylacetonate was used. The results are shown in Table 2.
Shown in.

Example 16 Tetraamminedichloroplatinum (12.5 mg) was added to distilled water (5 m).
It is dissolved in 1, and zirconia (90 m ² / g, 200
1.36 g of less than mesh; manufactured by Norton Co., Ltd. was added. After evaporating to dryness on a hot water bath, the product was reduced at 250 ° C for 1 hour under a flow of 10% -hydrogen (remaining nitrogen) to give 0.5% by weight-P.
A t / zirconia catalyst was prepared.

In a 100 ml glass reactor equipped with a reflux condenser, 20 ml of benzene and 25 ml of acetic acid were used as a reaction solution.
ml, vanadium (III) acetylacetonate 1.
0 mg was added thereto, and 0.10 g of the above 0.5 wt% Pt / zirconia catalyst was added thereto. The temperature of the solution is set to 60 ° C., and hydrogen is stirred while stirring with a magnetic stirrer.
The catalyst was activated by supplying ml / min for 30 minutes. Subsequently, hydrogen 24 ml / min, air 38 ml /
min was simultaneously supplied, and after 1 hour, the product in the solution was analyzed by gas chromatography. The results are shown in Table 2.

Example 17 A catalyst was prepared and the reaction was carried out in the same manner as in Example 16 except that 118 mg of vanadium (III) acetylacetonate was used. The results are shown in Table 2.
Shown in.

Comparative Example 1 A catalyst was prepared and a reaction was carried out in the same manner as in Example 1 except that vanadium (III) acetylacetonate was not used. The results are shown in Table 2.

[0062]

[Table 2]

In the table, acac represents an acetylacetonate group.

Example 18 Tetraamminedichloroplatinum (45.5 mg) was added to distilled water (20).
Dissolve it in ml and add silica (CARiACT-15,
10-20 mesh; manufactured by Fuji Davison Co., Ltd.) 5.0
0 g was added. After evaporating to dryness on a hot water bath, reducing it to 150 ° C. for 2 hours under a flow of 10% hydrogen (remaining nitrogen), and reducing it to 0.5.
A wt% -Pt / silica catalyst was prepared.

A glass reaction tube having an inner diameter of 8 mm was charged with 1.50 g of the above catalyst, and at a reaction temperature of 60 ° C., a 40 wt% benzene / acetic acid solution in which 38 ppm of ammonium metavanadate in terms of vanadium was dissolved from the bottom of the reaction tube. 0.25 ml / min, hydrogen 24 ml /
min and air 38 ml / min were simultaneously supplied to carry out the reaction. The products in the solution above the reaction tube were analyzed by gas chromatography. The results are shown in Table 3.

[0066]

[Table 3]

Example 19 0.13 g of ammonium metavanadate and 0.1% of oxalic acid.
Dissolve 13 g in 40 ml of distilled water and add silica (CA
RiACT-15, 10 to 20 mesh; Fuji Devison Chemical Co., Ltd. product) 10.00 g was added. After evaporating to dryness on a hot water bath, it was thermally decomposed at 500 ° C. for 3 hours under air flow to prepare 1 wt% V ₂ O ₅ / silica.

Tetraamminedichloroplatinum 18.2 mg
Was dissolved in 8 ml of distilled water and added to the above 1 wt% V ₂ O ₅
/2.00 g of silica was evaporated and evaporated to dryness on a hot water bath, and then reduced at 250 ° C. for 2 hours under a flow of 10% -hydrogen (remaining nitrogen) to give 0.5% by weight-Pt / 1% by weight V ₂ O. _{A 5} / silica catalyst was prepared.

A glass reaction tube having an inner diameter of 8 mm was charged with 1.50 g of the above catalyst, and at a reaction temperature of 60 ° C., 40% by weight of benzene / acetic acid solution was added from the bottom of the reaction tube at 0.25.
ml / min, hydrogen 24 ml / min, air 38
The reaction was performed by simultaneously supplying ml / min. Reaction is 2
After 5 hours, instead of the 40 wt% -benzene / acetic acid solution, 40 wt% -benzene / ammonium metavanadate dissolved 38 ppm in terms of vanadium was dissolved.
The acetic acid solution was supplied and the reaction was carried out. The products in the solution above the reaction tube were analyzed by gas chromatography. The results are shown in Table 4.

[0070]

[Table 4]

Example 20 In Example 18, vanadium (III) acetylacetonate was dissolved in an amount of 3.4 ppm in terms of vanadium in place of the 40 wt% benzene / acetic acid solution in which ammonium metavanadate was dissolved in an amount of 38 ppm in terms of vanadium 40. A catalyst was prepared and the reaction was carried out in the same manner as in Example 18 except that a wt% -benzene / acetic acid solution was used. The results are shown in Table 5.

[0072]

[Table 5]

Comparative Example 2 In Example 19, ammonium metavanadate 4 was added.
A catalyst was prepared and the reaction was carried out in the same manner as in Example 19 except that the catalyst was not dissolved in a 0 wt% -benzene / acetic acid solution. The results are shown in Table 6.

[0074]

[Table 6]

[0075]

According to the present invention, it is possible to efficiently oxidize aromatic compounds to produce phenols with high selectivity.

Claims (3)

[Claims] 1. An aromatic compound is reacted with a mixed gas containing oxygen and hydrogen, or is alternately reacted with an oxygen-containing gas and a hydrogen-containing gas to produce a phenol in a liquid phase. A method for producing phenols, characterized in that a vanadium compound is dissolved in the system in the presence of a catalyst in which a noble metal of Group III is supported on a carrier. 2. An aromatic compound is reacted with a mixed gas containing oxygen and hydrogen, or is alternately reacted with an oxygen-containing gas and a hydrogen-containing gas to produce a phenol in a liquid phase. Group noble metals and IIIa, IVa, V
a, VIa, VIIa, IIb, IVb and Vb, a vanadium compound dissolved in the system in the presence of a catalyst having a base metal oxide consisting of at least one selected from the group consisting of a, VIa, VIIa, IIb, IVb and Vb. Manufacturing method. 3. The reaction method is a liquid phase flow reaction.
Or the manufacturing method according to 2.