JPH07247233A - Production of aromatic hydroxy compound - Google Patents

Abstract

PURPOSE:To provide a method for producing an aromatic hydroxy compound such as phenol by one process from an aromatic compound such as benzene. CONSTITUTION:An aromatic compound such as benzene is oxidized by using an oxidizing agent such as oxygen in the presence of at least one selected from a group consisting of monohydroxy aromatic compounds to produce an aromatic hydroxy compound such as phenol. This process is a production method having extremely low corrosive properties, a small amount of by- products and high economic efficiency.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a novel process for producing an aromatic hydroxy compound, which comprises producing at least one aromatic hydroxy compound from an aromatic compound in one step.

[0002]

2. Description of the Related Art Conventionally, as a method for producing phenol from benzene and oxygen in one step, a method of reacting benzene and oxygen in a gas phase or a liquid phase in the presence of a catalyst is known.
However, in the case of a gas phase reaction, complete oxidation of benzene occurs and the selectivity of phenol is very low (Japanese Patent Laid-Open No. 56-87).
527). In the case of the liquid phase reaction, there is a method of oxidizing benzene using copper salt and oxygen, but the conversion rate of benzene is low and the yield of phenol is low (Organic Synthetic Chemistry 41
Vol. 839 (1983)).

Further, using a palladium-based catalyst, 1,1
Although there is a method of oxidizing benzene in the presence of 0-phenanthroline and carbon monoxide, the yield of phenol is low (JP-A-2-19809). Therefore, a method for producing phenol by direct oxidation of benzene has been desired,
It has not been industrialized yet.

Further, JP-A-3-236338 discloses a method for producing phenol from benzene using a metal phosphate catalyst. According to this method, the yield of phenol is around 6%, which is an unprecedentedly high yield.
The reaction temperature is as high as about 500 ° C., and a sufficiently economical production method has not yet been reached.

[0005]

Therefore, an object of the present invention is to obtain a high yield of aromatic hydroxy compounds represented by phenols from aromatic compounds represented by benzene and benzene derivatives under mild and low corrosive conditions. It is to provide a method of manufacturing at a rate.

[0006]

Means for Solving the Problems As a result of intensive studies on the above problems, the present inventors have shown that aromatic compounds represented by benzene and benzene derivatives are represented by phenols and the like in the presence of an oxidizing agent such as oxygen. The present invention has been completed by finding a method for producing an aromatic hydroxy compound according to the present invention in a high yield under mild and low corrosive conditions. That is, the present invention is a method for producing an aromatic hydroxy compound, which comprises reacting the aromatic compound with an oxidizing agent in the presence of at least one selected from the group consisting of monohydroxy aromatic compounds. As a result, by carrying out the present invention, a method for producing an aromatic hydroxy compound, which is excellent in terms of economy with extremely high efficiency and low corrosiveness, is provided.

The aromatic compound used in the present invention is a 6-carbon ring condensed compound such as benzene, substituted benzenes, naphthalene, substituted naphthalene, anthracene, substituted anthracenes, durene and substituted durenes, thiophene,
Substituted thiophenes, furans, substituted furans, pyridine,
Heteroaromatic compounds such as substituted pyridines, quinolines, and substituted quinolines. Substituents which these aromatic compounds have include alkyl groups such as methyl, ethyl, propyl and butyl groups, carboxyl groups, nitro groups, amino groups, cyano groups, acetyl groups, alkoxy groups, hydroxyl groups, acetoxy groups, halogens. Examples include elements and thioalkoxy groups. These are used alone or in combination of two or more.
Specific examples of the substituted benzenes include toluene, ethylbenzene, xylene, propylbenzene, butylbenzene, benzoic acid, nitrobenzene, aniline, benzonitrile, acetophenone, anisole, phenol, catechol, resorcin, hydroquinone, phenyl acetate,
Fluorobenzene, chlorobenzene, bromobenzene,
Examples include iodobenzene and thioanisole.

The aromatic hydroxy compound defined in the present invention is a compound in which at least one hydroxyl group is directly bonded to the carbon forming the aromatic ring of the above aromatic compound, and more specifically, the above aromatic compound. The carbon-hydrogen bond at the carbon forming the aromatic ring is converted to at least one carbon-hydroxy bond. For example, from benzene, phenol, catechol,
Hydroquinone, resorcin, etc. are produced, naphthols, dihydroxynaphthalenes, etc. are produced from naphthalene, mono- and polyhydroxytoluenes are produced from toluene, and methoxyphenol, methoxyresorcin, etc. are produced from anisole. Similarly, a compound having one or more hydroxyl groups directly bonded to aromatic carbon is produced from the aromatic compound. Depending on the reaction conditions, quinones such as benzoquinone, naphthoquinone or anthraquinone are simultaneously formed together with the aromatic hydroxy compound.

The monohydroxy aromatic compound used in the present invention is a compound in which one hydroxyl group is directly bonded to the carbon forming the aromatic ring, and specific examples thereof include phenol, o-aminophenol and m. -Aminophenol, p-aminophenol, o-nitrophenol, m-nitrophenol, p-nitrophenol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, 3,4-dimethylphenol, 3,5
-Dimethylphenol, 2,3,5-trimethylphenol, 2,4,5-trimethylphenol, 2,4,6
-Trimethylphenol, o-methoxyphenol, m
-Methoxyphenol, p-methoxyphenol, o-
Ethylphenol, m-ethylphenol, p-ethylphenol, o-hydroxybenzoic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, o-chlorophenol, m-chlorophenol, p-chlorophenol,
4-nitro-m-cresol, 2-nitro-p-cresol, 1-naphthol, 2-naphthol, 1-anthrol, 2-anthrol and the like can be mentioned. In the present invention, the amount of the monohydroxyaromatic compound used in the reaction is not particularly limited, but when phenol is used, the amount of benzene used in the batch reaction is, for example, an amount that is easy to implement. 0.00 for 100g
The amount is 1 to 500 g, more preferably 0.1 to 50 g.

The oxidant used in the present invention is a substance capable of supplying oxygen molecules, oxygen atoms, oxygen ions and oxygen radicals in the reaction state in the reaction system. Specifically, oxygen gas, oxygen gas diluted with an inert gas, air,
Examples include diluted air, hydrogen peroxide, organic peroxides, inorganic peroxides, and the like. Preferred is oxygen gas, oxygen gas diluted with an inert gas, or air. Use one or more of these.

In the present invention, the yield of an aromatic hydroxy compound such as phenol can be improved by adding water to the reaction system in a gas or liquid state. The reaction system is preferably acidic. This acidity is achieved by adding an acidic substance to the reaction system. Examples of the acidic substance added to the reaction system include Bronsted acid and Lewis acid. Examples of the Bronsted acid include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and boric acid,
Examples thereof include organic acids such as acetic acid, benzoic acid, formic acid, trichloroacetic acid, trifluoromethanesulfonic acid and sulfonic acid, and inorganic acids such as heteropolyacid, zeolites and mixed oxides. As the Lewis acid, aluminum chloride,
Examples thereof include ferric chloride, boron chloride compound, antimony chloride compound, stannic chloride, antimony fluoride, zeolites and mixed oxides. Furthermore, inorganic and organic acid salts are also used as the acidic substance. Preferably heteropolyacid is added to the reaction system.

The heteropolyacid referred to in the present invention is generally a composite metal oxide acid composed of two or more different metal oxide composites and those in which some or all of the protons of these acids are replaced with metal cations. is there. As a preferable heteropoly acid, a heteropoly acid containing vanadium as a metal is recommended, and as a more easily available heteropoly acid, a general formula H _{(3 + n)} PV _n Mo _(12-n) O ₄₀ , H _{(4 + n) is used. )} Si
V _n Mo _(12-n) O ₄₀ , H _{(3 + n)} PV _n W _(12-n) O ₄₀ , H
_{(4 + n)} SiV _n W _(12-n) O ₄₀ (where n is 0 or 6
The following positive integers, H is a hydrogen atom, P is a phosphorus atom,
Si represents a silicon atom, V represents a vanadium atom, Mo represents a molybdenum atom, W represents a tungsten atom, and O represents an oxygen atom. ) And heteropoly acids obtained by exchanging a part or all of the protons of these heteropoly acids with metal ions.

The metal to be exchanged with the proton of the heteropolyacid in the present invention may be a metal ion of a typical metal or a transition metal, but is preferably an ion of a typical metal, more preferably an alkali metal or an alkaline earth metal. It is a heteropoly acid that has been exchanged for at least one type of ion. The method for exchanging a proton with a metal ion is not particularly limited in the present invention, and any method may be used as long as a substantially metal ion-exchanged form is obtained, but as a method that is easy to carry out As an example, a method of stirring and mixing an aqueous solution of a metal hydroxide, a metal carbonate, a metal acetate and the like and an aqueous solution of a heteropolyacid, and then isolating by evaporating to dryness and the like can be mentioned.

Specific examples of the heteropolyacid in the present invention
If shown, H can be expressed as a molecular formula or a rational formula._FourPVMo₁₁O
₄₀, H_FivePV₂Mo_TenO₄₀, H₆PV₃Mo₉O₄₀, H₇PV_FourMo₈O₄₀, H₈PV_FiveM
o₇O₄₀, NaH₃PVMo₁₁O₄₀, Na₂H₂PVMo₁₁O₄₀, Na₃HPVMo₁₁O
₄₀, Na_FourPVMo₁₁O₄₀, KH₃PVMo₁₁O₄₀, K₂H₂PVMo₁₁O₄₀, K₃H
PVMo₁₁O₄₀, K_FourPVMo₁₁O₄₀, LiH₃PVMo₁₁O₄₀, Li₂H₂PVMo₁₁
O₄₀, Li₃HPVMo₁₁O₄₀, Li_FourPVMo₁₁O₄₀, RbH₃PVMo₁₁O₄₀, R
b₂H₂PVMo₁₁O₄₀, Rb₃HPVMo₁₁O₄₀, Rb_FourPVMo₁₁O₄₀, CsH₃PV
Mo₁₁O₄₀, Cs₂H₂PVMo₁₁O₄₀, Cs₃HPVMo₁₁O₄₀, Cs_FourPVMo₁₁O
₄₀, MgH₃PVMo₁₁O₄₀, Mg₂H₂PVMo₁₁O₄₀, Mg₃HPVMo₁₁O₄₀,
Mg_FourPVMo₁₁O₄₀, CaH₃PVMo₁₁O₄₀, Ca₂H₂PVMo₁₁O₄₀, Ca₃HP
VMo₁₁O₄₀, Ca_FourPVMo₁₁O₄₀, NaH_FourPV₂Mo_TenO₄₀, Na₂H₃PV₂Mo
_TenO₄₀, Na₂H₃PV₂Mo_TenO₄₀, Na₃H₂PV₂Mo_TenO₄₀, Na_FourHPV₂Mo
_TenO₄₀, Na_FivePV₂Mo_TenO₄₀, KH_FourPV₂Mo_TenO₄₀, K₂H₃PV₂Mo_TenO
₄₀, K₂H₃PV₂Mo_TenO₄₀, K₃H₂PV₂Mo_TenO₄₀, K_FourHPV₂Mo
_TenO₄₀, K_FivePV₂Mo_TenO₄₀, LiH_FourPV₂Mo_TenO₄₀, Li₂H₃PV₂Mo_TenO
₄₀, Li₂H₃PV₂Mo_TenO₄₀, Li₃H₂PV₂Mo_TenO₄₀, Li_FourHPV₂Mo_TenO
₄₀, Li_FivePV₂Mo_TenO₄₀, RbH_FourPV₂Mo_TenO₄₀, Rb₂H₃PV₂Mo
_TenO₄₀, Rb₂H₃PV₂Mo_TenO₄₀, Rb₃H₂PV₂Mo_TenO₄₀, Rb_FourHPV₂Mo
_TenO₄₀, Rb_FivePV₂Mo_TenO₄₀, CsH_FourPV₂Mo_TenO₄₀, Cs₂H₃PV₂Mo_Ten
O₄₀, CsRb₂H₃PV₂Mo_TenO₄₀, Cs₃H₂PV₂Mo_TenO₄₀, Cs_FourHPV₂Mo
_TenO₄₀, Cs_FivePV₂Mo_TenO₄₀, H_FourPVW₁₁O₄₀, H_FivePV2W_TenO₄₀, H₆P
V₃W₉O₄₀, H₇PV_FourW₈O₄₀, H₈PV_FiveW₇O₄₀, NaH₃PVW₁₁O₄₀, Na₂
H₂PVW₁₁O₄₀, Na₃HPV2W₁₁O₄₀, Na_FourPVW₁₁O₄₀, KH₃PV2W₁₁O
₄₀, K₂H₂PVW₁₁O₄₀, K₃HPVW₁₁O₄₀, K_FourPVW₁₁O₄₀, LiH₃PVW
₁₁O₄₀, Li₂H₂PVW₁₁O₄₀, Li₃HPVW₁₁O₄₀, Li_FourPVW₁₁O₄₀, R
bH₃PVW₁₁O₄₀, Rb₂H₂PVW₁₁O₄₀, Rb₃HPVW₁₁O₄₀, Rb_FourPVW₁₁
O₄₀, CsH₃PVW₁₁O₄₀, Cs₂H₂PVW₁₁O₄₀, Cs₃HPVW₁₁O₄₀, Cs_Four
PVW₁₁O₄₀, MgH₂PVW₁₁O40, Mg₂PVW₁₁O₄₀, CaH₂PVW₁₁O₄₀,
Ca₂PVW₁₁O₄₀, NaH₂PV₂W_TenO₄₀, Na₂H₃PV₂W_TenO₄₀, Na₃H₂P
V₂W_TenO₄₀, Na_FourHPV₂W_TenO₄₀, Na_FivePV2W_TenO₄₀, KH_FourPV₂W_TenO
₄₀, K₂H₃PV₂W_TenO₄₀, K₃H₂PV₂W_TenO₄₀, K_FourHPV₂W_TenO₄₀, K_Five
PV₂W_TenO₄₀, LiH_FourPV₂W_TenO₄₀, Li₂H₃PV₂W_TenO₄₀, Li₃H₂PV₂
W_TenO₄₀, Li_FourHPV₂W_TenO₄₀, Li_FivePV₂W_TenO₄₀, RbH_FourPV₂W
_TenO₄₀, Rb₂H₃PV₂W_TenO₄₀, Rb₃H₂PV₂W_TenO₄₀, Rb_FourHPV₂W_TenO
₄₀, Rb_FivePV₂W_TenO₄₀, CsH_FourPV₂W_TenO₄₀, Cs₂H₃PV₂W_TenO₄₀, C
s₃H₂PV₂W_TenO₄₀, Cs_FourHPV₂W_TenO₄₀, Cs_FivePV₂W_TenO₄₀, MgH₃PV
₂W_TenO₄₀, Mg₂HPV₃W_TenO₄₀, Mg_2.5PV₂W_TenO₄₀, CaH₃PVW_TenO
₄₀, Ca₂HPV₂W_TenO₄₀, Ca_2.5PV₂W_TenO₄₀, NaH_FivePV₃W₉O₄₀, N
a₂H_FourPV₃W₉O₄₀, Na₃H₃PV₃W₉O₄₀, Na_FourH₂PV₃W₉O₄₀, Na_FiveHPV
₃W₉O₄₀, Na₆PV₃W₉O₄₀, KH_FivePV₃W₉O₄₀, K₂H_FourPV₃W₉O₄₀, K₃
H₃PV₂W₉O₄₀, K_FourH₂PV₃W₉O₄₀, K_FiveHPV₃W₉O₄₀, K₆HPV₃W
₉O₄₀, LiH_FivePV₃W₉O₄₀, Li₂H_FourPV₃W₉O₄₀, Li₃H₃PV₃W₉O₄₀,
Li_FourH₂PV₃W₉O₄₀, Li_FiveHPV₃W₉O₄₀, Li₆PV₃W₉O₄₀, RbH_FivePV₃W
₉O₄₀, Rb₂H_FourPV₃W₉O₄₀, Rb₃H₃PV₃W₉O₄₀, Rb_FourH₂PV₃W
₉O₄₀, Rb_FiveHPV₃W₉O₄₀, Rb₆PV₃W₉O₄₀, CsH_FivePV₃W₉O₄₀, C
s₂H_FourPV₃W₉O₄₀, Cs₃H₃PV₃W₉O_{Four 0}, Cs_FourH₂PV₃W₉O₄₀, Cs_FiveHPV
₃W₉O₄₀, Cs₆PV₃W₉O₄₀, MgH_FourPV₃W₉O₄₀, Mg₂H₂PV₃W₉O₄₀,
Mg₃PV₃W₉O₄₀, CaH_FourPV₃W₉O₄₀, Ca₂H₂PV₃W₉O₄₀, Ca₃PV₃W₉
O₄₀, NaH₆PV_FourW₈O₄₀, Na₂H_FivePV_FourW₈O₄₀, Na₃H_FourPV_FourW₈O₄₀, N
a_FourH₃PV_FourW₈O₄₀, Na_FiveH₂PV_FourW₈O₄₀, Na₆HPV_FourW₈O₄₀, Na₇PV_FourW
₈O₄₀, KH₆PV_FourW₈O₄₀, K₂H_FivePV_FourW₈O₄₀, K₃H_FourPV_FourW₈O₄₀, K_FourH
₃PV_FourW₈O₄₀, K_FiveH₂PV_FourW₈O₄₀, K₆HPV_FourW₈O₄₀, K₇PV_FourW₈O₄₀,
LiH₆PV_FourW₈O₄₀, Li₂H_FivePV_FourW₈O₄₀, Li₃H_FourPV_FourW₈O₄₀, Li_FourH₃P
V_FourW₈O₄₀, Li_FiveH₂PV_FourW₈O₄₀, Li₆HPV_FourW₈O₄₀, Li₇PV_FourW
₈O₄₀, RbH₆PV_FourW₈O₄₀, Rb₂H_FivePV_FourW₈O₄₀, Rb₃H_FourPV_FourW₈O₄₀,
Rb_FourH₃PV_FourW₈O₄₀, Rb_FiveH₂PV_FourW₈O₄₀, Rb₆HPV_FourW₈O₄₀, Rb₇PV_Four
W₈O₄₀, CsH₆PV_FourW₈O₄₀, Cs₂H_FivePV_FourW₈O₄₀, Cs₃H_FourPV_FourW
₈O₄₀, Cs_FourH₃PV_FourW₈O₄₀, Cs_FiveH₂PV_FourW₈O₄₀, Cs₆HPV_FourW₈O₄₀,
Cs₇PV_FourW₈O₄₀, MgH_FivePV_FourW₈O₄₀, Mg₂H₃PV_FourW₈O₄₀, Mg₃HPV_FourW
₈O₄₀, Mg_3.5PV_FourW₈O₄₀, CaH_FivePV_FourW₈O₄₀, Ca₂H₃PV_FourW₈O_{Four 0},
Ca₃HPV_FourW₈O₄₀, Cs_3.5PV_FourW₈O₄₀, NaH₇PV_FiveW₇O₄₀, Na₂H₆PV
_FiveW₇O₄₀, Na₃H_FivePV_FiveW₇O ₄₀, Na_FourH_FourPV_FiveW₇O₄₀, Na_FiveH₃PV_FiveW₇O
₄₀, Na₆H₂PV_FiveW₇O₄₀, Na₇HPV_FiveW₇O₄₀, Na₈PV_FiveW₇O ₄₀, KH₇P
V_FiveW₇O₄₀, K₂H₆PV_FiveW₇O₄₀, K₃H_FivePV_FiveW₇O₄₀, K_FourH_FourPV_FiveW
₇O₄₀, K_FiveH₃PV_FiveW₇O₄₀, K₆H₂PV_FiveW₇O₄₀, K₇HPV_FiveW₇O₄₀, K₈P
V_FiveW₇O₄₀, LiH₇PV_FiveW₇O₄₀, Li₂H₆PV_FiveW₇O₄₀, Li₃H_FivePV_FiveW₇O
₄₀, Li_FourH_FourPV_FiveW₇O₄₀, Li_FiveH₃PV_FiveW₇O₄₀, Li₆H₂PV_FiveW₇O₄₀, L
i₇HPV_FiveW₇O₄₀, Li₈PV_FiveW₇O₄₀, RbH₇PV_FiveW₇O₄₀, Rb₂H₆PV_FiveW₇
O₄₀, Rb₃H_FivePV_FiveW₇O₄₀, Rb_FourH_FourPV_FiveW₇O₄₀, Rb_FiveH₃PV_FiveW₇O₄₀,
Rb₆H₂PV_FiveW₇O₄₀, Rb₇HPV_FiveW₇O₄₀, Rb₈PV_FiveW₇O₄₀, CsH₇PV_FiveW
₇O₄₀, Cs₂H₆PV_FiveW₇O₄₀, Cs₃H_FivePV_FiveW₇O₄₀, Cs_FourH_FourPV_FiveW
₇O₄₀, Cs_FiveH₃PV_FiveW₇O₄₀, Cs₆H₂PV_FiveW₇O₄₀, Cs₇HPV_FiveW₇O₄₀,
Cs₈PV_FiveW₇O₄₀, MgH₆PV_FiveW₇O₄₀, Mg₂H_FourPV_FiveW₇O₄₀, Mg₃H₂PV_Five
W₇O₄₀, Mg_FourPV_FiveW₇O₄₀, CaH₆PV_FiveW₇O₄₀, Ca₂H_FourPV_FiveW₇O₄₀, C
a₃H₂PV_FiveW₇O₄₀, Ca_FourPV_FiveW₇O₄₀ Etc.

When the present invention is carried out in the liquid phase, the reaction solution is usually used in the range of PH7 or less, preferably PH5 or less. However, the present invention is not necessarily limited to these ranges.

In carrying out the present invention, a monohydroxyaromatic compound and an acid (the monohydroxyaromatic compound and acid are hereinafter abbreviated as a catalyst) and an inert compound with respect to the aromatic compound in the reaction system, It is also possible to add a solvent or gas and perform the dilution. Specifically, methane, ethane, propane, butane, hexane,
Examples thereof include aliphatic saturated hydrocarbons such as cyclohexane and inert gases such as nitrogen, argon and helium.

The reaction temperature is not particularly limited, but is preferably 0 ° to 400 ° C, more preferably 10 ° to 300 ° C.
Is the range. If the reaction temperature is extremely low, the conversion rate of the aromatic compound is low, in other words, the reaction rate is extremely low, and the productivity of the reaction product is low. On the other hand, if the reaction temperature is 400 ° C. or higher, undesirable side reactions and the like progress and increase in by-products, aromatic compounds as raw materials,
Further, the stability of the aromatic hydroxy compound as a product is not preferable, and the selectivity of the reaction is lowered, which is not economical.

The reaction can be carried out under any of reduced pressure, increased pressure and normal pressure. From the viewpoint of reaction efficiency (reaction efficiency per unit volume), it is not preferable to carry out at a too low pressure. In addition, it is not preferable to carry out the reaction at an excessively high pressure from the viewpoint of the economical efficiency of the equipment such as a reactor. Normally preferred operating pressure range is 0.05-300 kg / c
m ² G, and more preferably 0.5 to 200 kg / cm ² G. However, the invention is not limited to only these pressure ranges.

The reaction can be carried out in any of a liquid phase, a gas-liquid phase and a gas phase. Furthermore, the catalyst can be used in either a uniform or non-uniform form. These catalysts can be used in any of a solution state, a two-layer separated state, a two-layer mixed layer state, a slurry state, a fixed bed, a moving bed, a fluidized bed and the like.

The present invention can be carried out in any reaction method of a normal batch reaction, a semi-batch reaction in which a part of raw materials or catalysts are continuously supplied, or a continuous flow reaction. In addition, the addition order and addition method of each component such as the aromatic compound, the oxidizing agent, and the catalyst are not particularly limited.

Furthermore, it is also possible to carry out in a semi-batch form, such as adding an oxidizing agent such as oxygen continuously or sequentially or intermittently over several steps depending on the consumption thereof. The yield of aromatic hydroxy compound is improved.

The reaction time (residence time or catalyst contact time in flow reaction) is not particularly limited, but is usually 0.
It is 1 second to 30 hours, preferably 0.5 seconds to 15 hours. After the reaction, if necessary, the reaction product can be separated and recovered from the catalyst or the like by a method such as filtration separation, extraction, and distillation. The aromatic hydroxy compound which is the target product is a sequential treatment method such as solvent extraction, distillation, alkali treatment, acid treatment or the like from the separated and recovered material, or a usual separation or purification method such as an operation in which these are appropriately combined. Can be separated, purified and obtained. Further, the unreacted raw material can be recovered and recycled to the reaction system for use.

In the case of a batch reaction, the catalyst recovered by separating the reaction product after the reaction can be used as it is, or after regenerating a part or all of it, it can be repeatedly used as a catalyst in the reaction again. When carried out in a fixed bed or fluidized bed flow continuous reaction system, by subjecting it to the reaction, a part or all of the catalyst is deactivated or activity-reduced,
After the reaction is interrupted, it can be regenerated for use in the reaction, or a part of the catalyst can be continuously or intermittently withdrawn, regenerated, recycled to the reactor and reused. Further, fresh catalyst can be continuously or intermittently fed to the reactor. When the reaction is carried out in a moving bed flow continuous reaction or a homogeneous catalyst flow reaction system, the catalyst can be separated, regenerated and reused as in the batch reaction.

[0024]

EXAMPLES The present invention will be described in more detail below with reference to examples. However, the invention is not limited to only these examples. In addition, the yield of the hydroxy compound which is the product described in each of the examples and the table was based on the aromatic compound which was the raw material for the charging.

Example 1 Benzene was added to 50 ml of Hastelloy C autoclave.
After charging 15.0 g, 10.0 g of water, phenol and 0.19 g, the inside of the autoclave was replaced with a mixed gas of oxygen 9% and nitrogen 91%, and then pressure was further increased to 110 kg / cm ² G. After reacting for 1.0 hour with stirring at a reaction temperature of 150 ° C, it was cooled and the reaction solution was analyzed by gas chromatography.As a result, it was confirmed that phenol was produced in a yield of 1.8% based on the charged benzene. It was

Example 2 In the method carried out in Example 1, H ₇ PV ₄ M was added to the reaction solution.
o ₈ O ₄₀ · 30H ₂ O, all under the same conditions and methods as in Example 1 except that 0.42 g was added. As a result, the phenol yield was 4.0%.

Example 3 The reaction and analysis were carried out under the same conditions and methods as in Example 2 except that the heteropolyacid was replaced by H ₆ PV ₃ Mo ₉ O ₄₀ · 30H ₂ O, 0.43 g. As a result, the yield of phenol was 4.1%.

Comparative Example 1 The reaction and analysis were carried out under the same conditions as in Example 3 except that phenol was not added by the method carried out in Example 3. As a result, the yield of phenol was 1.5%.

Example 4 The reaction and analysis were carried out under the same conditions as in Example 2 except that the heteropolyacid was replaced by H ₅ PV ₂ Mo ₁₀ O ₄₀ · 30H ₂ O, 0.44 g. As a result, the yield of phenol was 3.5%.

Example 5 The reaction and analysis were carried out under the same conditions as in Example 2 except that the heteropolyacid was replaced by H ₄ PVMo ₁₁ O ₄₀ .30H ₂ 0, 0.45 g.
The result was a phenol yield of 2.8%.

Example 6 The reaction and analysis were carried out under the same conditions as in Example 2 except that the heteropolyacid was replaced with H ₅ PV ₂ W ₁₀ O ₄₀ · 30H ₂ O (0.61 g). As a result, the yield of phenol was 2.6%.

Example 7 The reaction and analysis were carried out under the same conditions as in Example 2, except that H ₇ PV ₄ W ₈ O ₄₀ · 29H ₂ O (0.55 g) was used in place of the heteropolyacid. As a result, the yield of phenol was 3.2%.

Example 8 The reaction and analysis were carried out under the same conditions as in Example 2 except that the heteropolyacid was Na ₃ H ₃ PV ₃ Mo ₉ O ₄₀ · 29H ₂ O, 0.42 g. As a result, the yield of phenol was 3.4%.

Example 9 The reaction and analysis were carried out under the same conditions as in Example 1 except that 10.0 g of 0.1N sulfuric acid was used in place of water in the method carried out in Example 1. As a result, the yield of phenol is 2.
It was 3%.

Example 10 The procedure of Example 1 was repeated except that 0.1N phosphoric acid 1 was used instead of water.
The reaction and analysis were carried out under the same conditions as in Example 1 except that 0.0 g was used. As a result, the yield of phenol was 2.4%.

Example 11 The procedure of Example 3 was repeated except that m- was used instead of phenol.
The reaction and analysis were carried out under the same conditions as in Example 3 except that 0.22 g of aminophenol was used. As a result, the yield of phenol was 4.2%.

Example 12 The procedure of Example 3 was repeated except that p- was used instead of phenol.
The reaction and analysis were carried out under the same conditions as in Example 3 except that 0.22 g of aminophenol was used. As a result, the yield of phenol was 3.9%.

Example 13 The reaction and analysis were carried out under the same conditions as in Example 3 except that 0.22 g of o-aminophenol was used instead of phenol in the method carried out in Example 3. As a result, the yield of phenol was 3.2%.

Example 14 The procedure of Example 3 was repeated except that m- was used instead of phenol.
The reaction and analysis were carried out under the same conditions as in Example 3 except that 0.28 g of nitrophenol was used. As a result, the yield of phenol was 3.8%.

Example 15 The procedure of Example 3 was repeated except that m- was used instead of phenol.
The reaction and analysis were carried out under the same conditions as in Example 3 except that 0.22 g of cresol was used. As a result, the yield of phenol was 3.7%.

Example 16 In the method carried out in Example 3, p- was used instead of phenol.
The reaction and analysis were carried out under the same conditions as in Example 3 except that 0.26 g of chlorophenol was used. As a result, the yield of phenol was 3.1%.

Example 17 The reaction and analysis were carried out under the same conditions as in Example 3 except that 0.25 g of m-methoxyphenol was used instead of phenol in the method carried out in Example 3. As a result, the yield of phenol was 3.8%.

Example 18 The reaction and analysis were carried out under the same conditions as in Example 3 except that 0.28 g of m-hydroxybenzoic acid was used instead of phenol in the method carried out in Example 3. As a result, the yield of phenol was 3.1%.

Examples 19 to 21 The results of the same procedures and methods as in Example 3 were carried out except that the reaction temperatures were changed to 110 °, 130 ° and 170 ° C., respectively. Listed in Table 1. The results of Example 3 are also shown.

[0045]

[Table 1] Table 1 ──────────────────────────────────── Reaction temperature (℃) Phenol yield (%) ──────────────────────────────────── Example 19 110 1.1 1.1 Example 20 130 2.8 Example 3 150 4.1 Example 21 170 3.7 ────────────────────────────────── ───

Examples 22 to 25 In Example 3, instead of benzene, toluene, naphthalene, anisole and p-xylene were each used in an amount of 1 each.
Reaction and analysis were carried out under the same conditions and methods as in Example 3 except that the amount was 5.0 g. As a result, as shown in Table 2, the production of aromatic hydroxy compounds was recognized in good yields. The aromatic dihydroxy compound in the product is shown as the total of all isomers.

[0047]

[Table 2] Table 2 ──────────────────────────────────── Aromatic compound Yield (%) Hydroxy Compound Dihydroxy Compound ──────────────────────────────────── Example 22 Toluene 2.4 0.1 Example 23 Naphthalene 1.6 0.1 Example 24 Anisole 1.3 Trace amount Example 25 p-xylene 2.2 Trace amount ─────────────────────── ──────────────

[0048]

According to the present invention, the following effects can be obtained. (1) Phenol can be produced in good yield by directly oxidizing benzene. (2) Phenol can be directly oxidized and produced under mild conditions of low temperature and low pressure as compared with the conventional method. In addition, it can be carried out under the condition that the reactor or the like is hardly corroded. (3) In terms of safety, process, and phenol, which are industrially important,
It is possible to produce a significant economic advantage. As described above, the present invention can provide a novel industrially excellent method for producing phenol.

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Claims (10)

[Claims] 1. A method for producing an aromatic hydroxy compound, which comprises reacting an aromatic compound with an oxidizing agent in the presence of at least one selected from the group consisting of monohydroxy aromatic compounds. 2. The method according to claim 1, wherein the monohydroxyaromatic compound is a phenol. 3. The method according to claim 1, wherein the aromatic compound is a 6-carbon ring condensed compound. 4. The method according to claim 3, wherein the 6-membered condensed carbon compound is benzene, substituted benzenes, naphthalene or substituted naphthalene. 5. The method according to claim 1, wherein the oxidant is a substance capable of supplying an oxygen molecule, an oxygen atom, an oxygen ion or an oxygen radical. 6. The method according to claim 1, 2, 3 or 4, wherein the oxidant is oxygen gas, oxygen gas diluted with an inert gas, or air. 7. The method according to claim 1, wherein the reaction is carried out in the presence of water.
The method according to 3 or 4. 8. The method according to claim 1, wherein the reaction is performed in the presence of an acid.
The method according to 3 or 4. 9. The method of claim 8 wherein the acid is a heteropoly acid. 10. The method according to claim 1, 2, 3 or 4, wherein the oxidizing agent is inserted continuously or intermittently.