JPH054935A - Production of phenols - Google Patents

Abstract

PURPOSE:To produce phenols which are very important in chemical industry as an intermediate for aniline, bisphenols, alkyl phenols and phenol resin. CONSTITUTION:An aromatic compound is reacted with a mixed gas consisting of an oxygen-containing gas and hydrogen-containing gas or alternately reacted therewith using a catalyst obtained by supporting a noble metal of the group VIII of periodic table and oxide of base metal consisting of one or more kinds of substances selected from these groups IIIa, IVa, Va, VIa, VIIa, IIb, IVb and Vb to produce phenols.

Description

Detailed Description of the Invention

[0001]

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

[0002]

BACKGROUND OF THE INVENTION Most of phenols, which are the most representative compounds among phenols having a hydroxyl group on an aromatic ring, are produced by the cumene method. However, the cumene phenol manufacturing process is alkylated,
It is composed of multiple steps such as oxidation and decomposition, and it has a problem that acetone of equimolar amount to phenol is produced as a by-product.

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 the equipment, increase of equipment cost due to multi-step process, and complexity of handling solids and slurries.

Regarding the polycyclic aromatic compound having a hydroxyl group on the aromatic ring, diphenyl, which is a non-condensed cyclic compound, or naphthalene, which is a condensed cyclic compound, is sulfonated to give naphthol and phenylphenol, respectively. The manufacturing method is industrially established. However, in this process as well, there is corrosion of the device due to acid and alkali.

As described above, since the existing process of the aromatic compound having a hydroxyl group has many problems, it is attempted to directly oxidize the corresponding aromatic compound to obtain a desired phenol. Has been done. 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 or phosphate such as phosphorus and zinc or phosphorus, silver and zinc as a catalyst. Also, JP-A-61-2533
No. 8 discloses that in a liquid phase, metal porphyrin, imidazole,
A method for producing phenol by reacting benzene with oxygen in the presence of platinum and hydrogen is disclosed.

[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.

[0007]

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

That is, the present invention relates to noble metals of Group VIII of the periodic table and IIIa, IVa, Va, VIa, VIIa, I.
An aromatic compound is reacted with a mixed gas consisting of an oxygen-containing gas and a hydrogen-containing gas using a catalyst in which a base metal oxide consisting of one or more selected from the group Ib, IVb and Vb is supported on a carrier, or an oxygen-containing gas And a hydrogen-containing gas are alternately reacted to produce a phenol.

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 used together as a catalyst is palladium, rhodium, ruthenium, platinum, iridium,
And mixtures thereof. When supporting these metals, examples of the raw material include halides, nitrates, sulfates, inorganic complex salts, organic acid salts and the like. 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, and organic acid salts such as palladium acetate can be used. The loading amount of these noble metal components is usually 0.01 to 20 as a metal based on the total weight of the catalyst.
% By weight, preferably 0.01 to 15% by weight. 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, when the content of the noble metal is less than 0.1% by weight, the reaction rate becomes slow and the economical efficiency in the industrial process is lost. When using these noble metals as catalysts, reduction treatment is necessary. This reduction treatment may be carried out before the reaction or may be activated by reduction during the reaction. This reduction method is not particularly limited, but a conventional method, for example, a wet reduction method using 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 using 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.

In the method of the present invention, the base metal oxide, which is the other catalyst component used together, is the periodic table IIIa, IVa, Va, VIa, VIIa, IIb,
It is composed of one or more selected from the group IVb and Vb group base metal oxides. As an example of a base metal oxide, the periodic table III
Group a yttrium oxide, lanthanum oxide, cerium oxide, group IVa zirconium oxide, group Va vanadium pentoxide, group VIa chromium oxide, molybdenum oxide, tungsten oxide, group VIIa manganese oxide, group IIb zinc oxide, IVb. Examples thereof include a single-component base metal oxide such as tin oxide of group I and bismuth oxide of group Vb, and two or more base metal oxides such as molybdenum oxide-bismuth oxide and molybdenum oxide-phosphorus oxide. The amount of the base metal oxide component supported is usually 1 to 99% by weight, preferably 5 to 20% by weight, based on the total weight of the catalyst.
Is.

In the case of supporting the base metal oxide, as the raw material thereof, for example, ammonium salt, nitrate, chloride, inorganic acid salt, acetate, oxide and the like can be used. Examples of these are ammonium metavanadate, ammonium molybdate, ammonium paratungstate, yttrium nitrate, lanthanum nitrate, zinc nitrate, bismuth nitrate,
Examples thereof include zirconium oxynitrate, chromium chloride, tin chloride, manganese acetate, niobium oxide and the like. The raw materials for these base metal oxides are supported by a conventional method and then heat-treated to obtain the corresponding base metal oxides. The method of heat treatment is not particularly limited as long as the base metal oxide is finally obtained. For example, when heat treatment is performed with or without circulation of an oxygen-containing gas,
The heat treatment may be performed at a temperature of 0 to 1000 ° C.

In the method of the present invention, the noble metal and base metal oxide are used by being supported on a carrier. Examples of the carrier include silica, alumina, titania or composite oxides thereof, and activated carbon, which are generally used as carriers. Some of the carriers that can be used are the same as the above-mentioned base metal oxides, but there is no problem even if the same base metal oxide as the carrier is carried. The method for supporting the catalyst component on these carriers is not particularly limited, and any known method may be used. For example, it can be prepared by a so-called impregnation method in which a carrier is immersed in an aqueous solution, suspension, acidic solution, alkaline solution, or organic solution of a noble metal raw material and / or a base metal oxide raw material. When the catalyst component is loaded on the carrier, all the catalyst components may be loaded simultaneously or sequentially.

When the reaction is carried out continuously, the amount of the catalyst used in the reaction is determined by the reaction rate and the heat balance, so it is difficult to unconditionally specify. When the reaction is performed in a batch system or a semi-batch system, 0.01% of the reaction solution is used.
The amount may be up to 30% by weight, and if it is used in excess, it may hinder the stirring of the reactor.

In the method of the present invention, the aromatic compound which 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. May be. 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, and a solvent may be used if necessary. As the solvent, the aromatic compound itself which is the raw material may be used as the 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, and for example, the reaction is a batch system in which an aromatic compound as a raw material, a catalyst, an oxygen-containing gas, a hydrogen-containing gas and, if necessary, a solvent are charged into a reaction apparatus at once. Even if it is a semi-batch method in which oxygen-containing gas and / or hydrogen-containing gas is continuously blown into the reaction apparatus, or aromatic compounds, oxygen-containing gas, hydrogen-containing gas, etc. are continuously supplied. In addition, it may be a continuous type in which the unreacted gas and the reaction liquid are continuously extracted. Further, the supplied gas may be diluted with an inert gas such as nitrogen, helium, argon, carbon dioxide or the like. Air can also be used as the oxygen-containing gas. The amount of oxygen-containing gas supplied varies depending on the reaction method and reaction conditions, so it cannot be determined unconditionally, but the amount of oxygen gas supplied per unit weight (g) of the catalyst is 0.01 ml / mi.
It may be n to 1000 ml / min. 0.01 ml / mi
If it is less than n, the productivity will be insufficient and 1000 ml
If it exceeds / min, the effect of supplying more than that is small. 1
If it exceeds 000 ml / min, the gas conversion rate becomes small, which is not economical. The ratio of oxygen and hydrogen in the oxygen-containing gas and the hydrogen-containing gas is not particularly limited and can be arbitrarily changed, but the hydrogen / oxygen (molar ratio) is preferably 0.1 to 10.
Is. When the aromatic compound is continuously supplied, the aromatic compound supply rate per unit weight (g) of the catalyst is 1 × 10.
It is a ^{-5 g / min~10 2 g / min} . 1 x 10
^If it is less than ^-5 g / min, the productivity will be insufficient, and
If it exceeds 10 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 raised to increase the reaction rate, the reaction may be performed under pressure. As a practical temperature range, room temperature to 20
It is 0 ° C. If the reaction temperature is lower than room temperature, the conversion rate of the aromatic compound will be low. On the other hand, if the reaction temperature is higher than 200 ° C, the selectivity of the product may be lowered. The pressure is usually from normal pressure to 200 Kg / cm ² ,
It is preferably normal pressure to 50 Kg / cm ² .

[0018]

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

Example 1 3.16 g of ammonium metavanadate and oxalic acid 1.
Dissolve 77 g in 40 ml of distilled water and add silica (CA
RIACT-15; FUJI-DAVISON)
9.81 g was added. After evaporating to dryness on a hot water bath, it is decomposed by heating at 400 ° C. for 1 hour under air flow to give 20 wt% -V.
₂ O ₅ / silica was prepared.

Tetraamminedichloropalladium 79.
20 mg of the above was prepared by dissolving 0 mg in 25 ml of distilled water.
After dipping t% -V ₂ O ₅ /6.31 g of silica and evaporating to dryness on a hot water bath, the mixture was reduced at 150 ° C. for 1 hour under hydrogen flow to 0.5 wt% -Pd / 20 wt% -V ₂ O ₅ / A silica catalyst was prepared.

In a 100 ml glass reactor equipped with a reflux condenser, 20 ml of benzene and 25 m of acetic acid were used as a reaction solution.
1 of the above catalyst was added thereto. The temperature of the solution was set to 60 ° C., and 40 ml / min of hydrogen was supplied for 30 min while stirring with a magnetic stirrer to activate the catalyst. Subsequently, 24 ml / min of hydrogen and 38 ml / min of air were simultaneously supplied, and 1 hour later, the products in the solution were analyzed by gas chromatography. As a result, 0.302 mmol of phenol and a very small amount (<0.010 mmol) of benzoquinone were formed. After the reaction, when the amount of water was measured by a Karl Fischer water content meter, 1.58 mmol of water was produced.

Example 2 In Example 1, 58.5 mg of tetraamminedichloroplatinum was used instead of tetraamminedichloropalladium, and the reduction temperature was 250 ° C. and 0.5 wt-Pt.
The reaction was performed in exactly the same manner as in Example 1 except that a / 20 wt5-V ₂ O ₅ / silica catalyst was prepared. Table of results
Shown as 1.

Examples 3 to 4 In Example 2, rhodium chloride or iridium chloride was used in place of tetraamminedichloroplatinum to give a pH value of 0.
_{5wt% -Rh / 20wt% -V 2} O 5 / silica and _{0.5wt% -Ir / 20wt% -V 2} O 5 / silica catalyst was prepared. The reaction was carried out in exactly the same manner as in Example 2 except that these were used as catalysts. The results are shown in Table 1.

Example 5 In Example 2, a ruthenium chloride ethanol solution was used in place of the tetraamminedichloroplatinum aqueous solution to give a 0.1.
The _{5wt% -Ru / 20wt% -V 2} O 5 / silica catalyst was prepared. The reaction was carried out in exactly the same manner as in Example 2 except that this was used as a catalyst. The results are shown in Table 1.

Example 6 Exactly the same as Example 1 except that 0.5 wt-Pd / 20 wt% WO ₃ / silica catalyst prepared by using ammonium paratungstate in place of ammonium metavanadate was used. The reaction was carried out.
The results are shown in Table-2.

Examples 7 to 14 In Example 1, instead of ammonium metavanadate oxalic acid solution, yttrium nitrate aqueous solution, lanthanum nitrate aqueous solution, ammonium molybdate aqueous solution, zirconium oxynitrate aqueous solution, chromium (III) chloride aqueous solution,
0.5 wt% -Pd prepared using cerium nitrate aqueous solution, manganese acetate aqueous solution or zinc nitrate aqueous solution, respectively
/ 20wt% _-Y 2 _{O 3} / silica, 0.5 wt% -Pd
/ 20wt% _-La 2 _{O 3} / silica, 0.5 wt% -P
d / 20wt% -MoO ₃ / silica, 0.5 wt% -P
d / 20wt% -ZrO ₂ / silica, 0.5 wt% -P
_{d / 20wt% -Cr 2 O 3} / silica, 0.5 wt% -
Pd / 20wt% -CeO ₂ / silica, 0.5 wt% -
_{Pd / 20wt% -Mn 2 O 3} / silica or, 0.5
The reaction was performed in exactly the same manner as in Example 1 except that the wt% -Pd / 20 wt% -ZnO / silica catalyst was used. The results are shown in Table-2.

Examples 15 to 16 In Example 1, 0.5 wt% Pd / 20 wt prepared by using a bismuth nitrate nitric acid solution and a bismuth nitrate-ammonium molybdate nitric acid solution instead of the ammonium metavanadate oxalic acid solution, respectively. % -Bi ₂ O
₃ / silica or 0.5 wt% -Pd / 20 wt% -B
The reaction was carried out in exactly the same manner as in Example 1 except that i ₂ O ₃ .2MO ₃ / silica catalyst was used. The results are shown in Table-2.

Example 17 In Example 1, tin (II) chloride solution was used instead of ammonium metavanadate oxalic acid solution.
The reaction was performed in exactly the same manner as in Example 1 except that 5 wt% -Pd / 20 wt% -SnO ₂ / silica catalyst was used. The results are shown in Table-2.

Example 18 A catalyst was prepared and reacted in exactly the same manner as in Example 1 except that the loading ratio of palladium was 2.5% by weight. When the reaction was carried out, phenol was 0.516 mmol and benzoquinone was 0.1.
017 mmol and 2.73 mmol of water were produced.

Example 19 The reaction was carried out in the same manner as in Example 1 except that a catalyst prepared by using a solution of palladium acetate in acetone was used instead of the aqueous solution of tetraamminedichloropalladium in Example 1, and the phenol was 0. .421 mmol,
Benzoquinone 0.041mmol, water 1.88mm
ol generated.

Examples 20 to 23 The loading rates of vanadium pentoxide were 5, 8, 50, and 99.
The amount was changed to 5% by weight and each catalyst was prepared. The reaction was carried out in the same manner as in Example 1 except that these were used as catalysts. The results are shown in Table-3.

Example 24 Instead of silica as a carrier, alumina (Neobead-
C; manufactured by Mizusawa Chemical Co., Ltd.) was used to prepare a catalyst and carry out the reaction in exactly the same manner as in Example 1. As a result, phenol was 0.155 mmol and benzoquinone was 0.011 mmo.
1, 0.12 mmol of water was produced.

Examples 25 to 28 Reactions were carried out in exactly the same manner as in Example 1 except that the feed ratios of hydrogen and air (oxygen amount was fixed at 21 mmol / hr) were changed. The results are shown in Table-4.

Examples 29 to 30 Example 1 except that the reaction temperature was changed to 20 ° C. and 80 ° C.
The reaction was carried out in exactly the same manner as. The results are shown in Table-5.

Example 31 The reaction was carried out in the same manner as in Example 1 except that only 20 ml of benzene was used as the reaction solvent.
0.109 mmol for benzoquinone and 0.075 m for benzoquinone
4.15 mmol of water and water were produced.

Examples 32 to 33 In Example 1, the reaction pressure was 2 or 4 kg / cm ² −.
The reaction was carried out in exactly the same manner as in Example 1 except that G was changed. The results are shown in Table-6.

Example 34 The reaction was carried out in exactly the same manner as in Example 2 except that the amount of catalyst was changed from 1 g to 0.1 g, but phenol was 0.224 mmol and water was 0.59 mmo.
l produced.

Examples 35 to 36 In Example 34, the reaction pressure was set to 2 or 4 kg / cm ^2.
The reaction was carried out in exactly the same manner as in Example 34 except that -G was changed. The results are shown in Table-7.

Example 37 A reaction was carried out in exactly the same manner as in Example 34 except that toluene was used instead of benzene in Example 34. As a result, 0.086 mmol of benzaldehyde, 0.012 mmol of benzyl alcohol and o-cresol were obtained. 0.
172 mmol, 0.178 mmo of m, p-cresol
1, cresyl acetate 0.011 mmol, water 2.3 m
mol produced.

Example 38 A reaction was carried out in exactly the same manner as in Example 37 except that the reaction pressure was changed to 4 kg / cm ² -G in Example 37, and 0.277 mmol of benzaldehyde and 0. 076 mmol, 0-cresol 0.537 mmol, m, p-cresol 0.546
mmol, cresyl acetate 0.035 mmol, and water 9.4 mmol.

Example 39 In Example 34, 12.5 mmo was used instead of benzene.
When the reaction was carried out in exactly the same manner as in Example 34 except that 1 diphenyl was used, o-hydroxydiphenyl was 0.0.
69 mmol, 0.0 of m, p-hydroxydiphenyl
71 mmol and 2.4 mmol of water were produced.

Example 40 In Example 34, 12.5 mmo was used instead of benzene.
When the reaction was carried out in the same manner as in Example 34 except that 1 naphthalene was used, 1-naphthol was 0.049 m.
mol, naphthoquinone 0.029 mmol, water 0.
60 mmol was produced.

Comparative Examples 1 to 3 20 wt% -V ₂ O ₅ / silica prepared without supporting a noble metal and prepared with ammonium metavanadate oxalic acid solution from ammonium metavanadate hydrochloric acid solution, chromium chloride aqueous solution or manganese acetate aqueous solution, respectively. Two
0wt% _-Cr 2 _{O 3} / silica or 20 wt% -Mn
_The reaction was carried out in exactly the same manner as in Example 1 except that ₂ O ₃ / silica was used. The results are shown in Table-8.

Comparative Example 4 0.1595 g of iron (III) chloride was dissolved in 20 ml of distilled water to prepare a solution of silica (CARIACT-50; FUJI).
-Manufactured by DAVISON) 5.40 g was immersed, evaporated to dryness in a hot water bath, and reduced at 450 ° C for 1 hour under hydrogen flow to prepare 1.0 wt% -Fe / silica, and the reaction temperature was 20.
The reaction was carried out in exactly the same manner as in Example 1 except that the temperature was changed to ° C. The results are shown in Table-9.

Comparative Examples 5 to 7 1.0 wt% -Ni / silica, 2.5 wt% prepared respectively from an aqueous solution of nickel nitrate, an aqueous solution of silver nitrate and an aqueous solution of tetrachloroauric acid (III) instead of the aqueous solution of iron (III) chloride. -Ag / silica and 2.5 wt%-
The reaction was carried out in exactly the same manner as in Example 1 except that Au / silica was used. The results are shown in Table-9.

Comparative Examples 8 to 10 0.5 wt% -Ru / silica, 0.5 wt% -prepared from a ruthenium chloride hydrochloric acid solution, a rhodium chloride hydrochloric acid solution, and a palladium chloride hydrochloric acid solution instead of the iron (III) chloride aqueous solution. Rh / silica and 0.5 wt%-
The reaction was carried out in exactly the same manner as in Example 1 except that Rd / silica was used. The results are shown in Table-10.

Comparative Examples 11 to 12 0.5 wt% -Ir / silica prepared from an iridium chloride aqueous solution and a tetraamminedichloroplatinum aqueous solution instead of the iron (III) chloride aqueous solution, and 0.5 w, respectively.
The reaction was carried out in exactly the same manner as in Example 1 except that t% -Rt / silica was used. The results are shown in Table-10.

[0048]

EFFECTS OF THE INVENTION According to the method of the present invention, phenols can be produced by liquid-phase oxidation of an aromatic compound with an oxygen-containing gas and a hydrogen-containing gas under mild conditions.

[Table 1]

[Table 2]

[Table 3]

[Table 4]

[Table 5]

[Table 6]

[Table 7]

[Table 8]

[Table 9]

[Table 10]

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location B01J 23/64 X 8017-4G C07C 37/58 9159-4H 39/07 9159-4H // C07B 61 / 00 300

Claims (2)

[Claims] 1. A method for producing a phenol by reacting an aromatic compound with a mixed gas comprising an oxygen-containing gas and a hydrogen-containing gas, or alternately reacting an oxygen-containing gas and a hydrogen-containing gas, to produce a phenol. Group VIII noble metals and IIIa, I
A process for producing phenols, which comprises using a catalyst in which a base metal oxide comprising at least one selected from the group consisting of Va, Va, VIa, VIIa, IIb, IVb and Vb is supported on a carrier. 2. A method for producing phenols according to claim 1, wherein the reaction is carried out at atmospheric pressure or higher.