JP2003062468A - Oxidation catalyst and method for manufacturing phenols using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an oxidation catalyst of an aromatic compound. SOLUTION: The oxidation catalyst of an aromatic compound in the presence of hydrogen is obtained by being subjected to reduction treatment after having at least one or more of metals among groups VIII, IB or IIB metal supported on a carrier selected from zeolite, an ion exchange resin having a sulfonic acid group or a complex of a fluororesin having a sulfonic acid group and a silica gel. The method is characterized by performing the reduction treatment of the catalyst under a nitrogen gas stream, a hydrogen gas stream or a mixed gas stream of nitrogen and hydrogen after having at least one or more of metals among groups VIII, IB or IIB metal supported on a carrier selected from zeolite, an ion exchange resin having a sulfonic acid group or a complex of a fluororesin having a sulfonic acid group and a silica gel.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a novel oxidation catalyst, a method for producing the same, and a method for producing phenols by oxidizing an aromatic compound with oxygen in the presence of hydrogen using the catalyst.

[0002]

2. Description of the Related Art Among the phenols produced by the method of the present invention, for example, phenol is an industrially very important compound as a raw material for a phenol resin or bisphenol A. Presently, as a main method for producing phenol industrially, there are a cumene method and a toluene oxidation method. The cumene method uses benzene as a raw material by propylene alkylation, oxidation and decomposition.
The method of oxidizing toluene is a method of producing phenol by oxidation of toluene or oxidative decarboxylation. However, the above-mentioned two methods have many reaction steps, and further, there is a problem that acetone is by-produced in the cumene method, and a more rational method for producing phenol has been desired.

Therefore, many studies have been made so far to produce phenols by the direct oxidation of benzene, and hydrogen peroxide (Japanese Patent Laid-Open No. 03-17894) is used as an oxidizing agent.
6, US6188083, DE198553491, EP
919531, EP861688, SU109759
8, J. Mol. Catal. A: Chem. 2000, 164, 181. J.Mo.
l. Catal. A: Chem. 2000, 156, 143. Angew. Chem. I
nt. Ed., 2000, 39, 23, 4321. Can. J. Chem., 1998,
76, 6, 955. J. Mol. Catal. A: Chem. 1996, 111, 8
1. J. Mol. Catal. A: Chem. 1996, 108, 135. Chem.
Commun., 1996, 8, 979. J. Mol. Catal. A: Chem. 1
996, 114, 181. J. Chem. Eng. Jpn., 1994, 27, 307.
Catal. Lett., 1993, 22, 239. J. Mol. Catal. A:
Chem., 1993, 78, 201. Appl. Catal., A 1990, 57, 1, L
1. Catal. Lett., 1989, 3, 1, 31.Bull. Chem. Soc.
Jpn., 1989, 62, 1, 148. Bull. Chem. Soc. Jpn., 19
89, 62, 1, 153. Tetrahedron Lett., 1983, 24, 484
7. Chem., Lett., 1981, 6, 789.), dinitrogen monoxide (US5110995, EP1052242, DE19).
829515, JP-A-2000-26347, US58.
74646, US5324702, Stud. Surf. Sci. C
atal. 2000, 130A, 881. Stud. Surf. Sci. Catal., 2
000, 130B, 1679. Appl. Catal., A 2000, 487. Cata
l. Lett., 1998, 56, 145. Appl. Catal., A 1996, 14
1, 185. Catal. Lett., 1994, 29, 299. Appl. Cata
l., A 1994, 117, 1. Appl. Catal., A 1992, 82, 31.
), An organic peroxide (Japanese Patent Laid-Open No. 2000-310627,
JP-A 07-258146), electrolytic reaction (JP-A 07-258146)
305187, JP-A 03-122296, JP-A 60
−9889, Catalyst 1997 Vol. 39, page 360, Sutd. Surf. Sci.
Catal., 1994, 82, 703. Chem. Lett., 1994, 10, 186
1. J. Chem. Soc., Faraday Trans. 1994, 90, 451.
Tetrahedron Lett., 1991, 47, 841. Chem. Lett., 19
90, 4, 509. Tetrahedron Lett., 1989, 30, 205. An
gew. Chem., 1983, 95, 504. Chem. Ber., 1977,110,
3561.), nitric acid (JP-A 2000-34246, JP-A 61-236738), enzyme (JP-A 58-19369).
1), Photoreaction (Stud. Surf. Sci. Catal., 2000, 130B,
1979. Catal. Lett., 2000, 66, 4, 251. Chem. Let
t., 1997, 12, 1209.) and the like are known. However, hydrogen peroxide, organic peroxides, and dinitrogen monoxide are generally expensive as oxidizers, special equipment is required for electrolytic reactions and photoreactions, and enzymes are expensive and economically disadvantageous. However, none of these methods are industrially advantageous. Therefore, conventionally, it has been desired to develop a method of using oxygen, which is cheaper and has less environmental load, as an oxidant, and among them, the following method has been known as an oxidation method in the coexistence of hydrogen. 1) Pd salt-Cu salt supported silica gel catalyst system, oxidation in the presence of hydrogen (ChemistryExpress, 1989, 4, 201. Stud.
Surf. Sci. Catal., 1994, 451. J. Chem. Soc., Pe
rkin Trans. 2, 1990, 1991. J. Chem. Soc. Perkin Tr
ans. 2, 1993, 981. Catalyst Lett., 1991, 11, 11.
JP-A-04-178341) 2) Pd / carbon-dihydrodihydroxyanthracene sulfonate system (US4992600) 3) Pt-metalloporphyrin-imidazole catalyst system, oxidation in the presence of hydrogen (JP-A-61-85338) 4) Pd salt -Pt salt-heteropolyacid catalyst system, oxidation in the presence of hydrogen (J. Mol. Catal. A: Chem., 1996, 131.) 5) Fe salt-Pd salt-phenazine methosulfate catalyst system, oxidation in the presence of hydrogen (Chemistry Express, 198
9, 4, 617.) 6) A catalyst system in which Pd-Ti-anthraquinone is supported on zeolite, oxidation in the presence of hydrogen (WO996412)
9) 7) Eu (OTf) ₃ -PtO-supported silica gel, TiO
(Acac) ₂ catalyst system, oxidation in the coexistence of hydrogen (rare earth 2000 vol. 36, p. 66) 8) Catalyst system in which group VIII metal and any one of V, W, Y, Bi and Sn are co-supported on a carrier , Oxidation in the presence of hydrogen (JP-A-05-4935, JP-A-05-3106)
22, JP 05-310623 A, JP 06-409 A.
76, JP 06-256241, JP 06-25624.
242)

[0004]

However, in any of the above methods, the conversion of benzene and the selectivity / yield of phenols cannot be said to be sufficient, and the catalyst amount and catalyst life are industrially used. Wasn't happy to be.
Further, in 2), 3), 5), 6), and 7), expensive dihydrodihydroxyanthracene sulfonate, metalloporphyrin, phenazine methosulfate, anthraquinone, E
There are problems such as the use of u (OTf) ₃ , which is not always an industrially advantageous method.

[0005]

The inventors of the present invention have made extensive studies to solve the above-mentioned problems, and as a result, the conversion rate of aromatic compounds and the yield of phenols have been significantly improved. The inventors have found a catalyst capable of industrially producing phenols and have completed the present invention.

That is, the present invention provides a carrier selected from zeolite, an ion exchange resin having a sulfonic acid group or a fluorinated resin having a sulfonic acid group and a silica gel composite, and at least one of Group VIII, IB or IIB metals. A catalyst obtained by carrying out a reduction treatment after supporting at least one kind of metal compound, and using the catalyst in the presence of oxygen and hydrogen,
The present invention provides a method for producing phenols, which comprises oxidizing an aromatic compound in water, alcohol or a mixed solvent of water and alcohol.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The oxidation catalyst of the present invention can be produced by supporting at least one metal compound of Group VIII, Group IB or Group IIB metal on a carrier, and then performing reduction treatment. As the carrier, a solid acid is preferable, and examples thereof include an ion exchange resin having a sulfonic acid group, a fluorinated resin, a complex of a fluorinated resin and silica, zeolite (including mesoporous silicates), and the like. As the ion exchange resin having a sulfonic acid group, there are Amberlyst-15 and Amberlite IR-11.
8, IR-120B, IR-122, IR-124, 2
00-C, 201B, 252 (registered trademark Rohm and Haas); Duolite C-3, C-20S, C-
20, ES-291, C-26, C-26TR, C-2
0HC (registered trademark Rohm and Haas); Dowex MWC-1-H, Dowex 88, 50W, H
CR-W2, HGR, HGR-W2, HCR-S (registered trademark Dow Chemical); Diaion SK 1B, S
K102, SK104, SK106, SK110, SK
112, SK116, PK208, PK212, PK2
16, PK220, PK228 (Mitsubishi Chemical); Sumikaion KC-470 (registered trademark, Sumitomo Chemical Co., Ltd.); Nafion-H (registered trademark DuPont) and the like. Known natural / synthetic zeolite can be used as the zeolite, but in order to effectively use the reaction field in the pores, it is preferable that the substrate has a pore size capable of diffusing into the pores, and usually, Those having pores of 10-membered rings or more are used. Such zeolites include MFI, MEL, FA
Examples thereof include zeolites (aluminosilicate, aluminophosphate) having a crystal structure such as U, FEA, BEA, MOR and MWW. The Al content in zeolite is not particularly limited because the amount that can be introduced varies depending on the crystal structure, but the Si / Al ratio is usually in the range of 5 to 20000, preferably 5 to 300 in terms of molar ratio. Metals belonging to the IVA and VA groups such as Ti and V are not particularly required, but zeolites containing these metals in the crystal lattice can be used without any problems. In addition, mesoporous silicates (zeolites) having mesopores can also be used. Since the pore diameter is larger than that of zeolite, it is preferably used depending on the size of the substrate. Such compounds include MCM-41 and MCM-4
8, MCM-50, FSM-16 and the like. The fluorinated resin having a sulfonic acid group is usually represented by the general formula (1) (In the formula, n, m, and x represent integers.). Preferably, Nafion-H (registered trademark
DuPont).

The fluorinated resin having a sulfonic acid group and the silica gel composite can be produced according to the method of WO9906145.

The content of the fluorinated resin having a sulfonic acid group is usually in the range of 1 to 80% by weight, preferably 8 to 25% by weight, based on the composite.

The Group VIII, IB, and IIB metals to be supported are usually the metals listed in the periodic table, and by supporting at least one of these metals, the catalyst can be formed. Although obtained, it preferably contains one or more Group VIII metals. More preferably, a co-supporting system of palladium and platinum is used. The supported catalyst is then subjected to a reduction treatment to obtain the desired catalyst, but a compound belonging to Group IIIB, IVB or VB of the Periodic Table can also be co-supported on the catalyst as an additive in order to adjust the catalyst activity.

The carrying method is not particularly limited as long as a known method may be used, but an ion exchange method is preferably used. Usually, it can be carried out by bringing a carrier and an aqueous solution of a metal salt into solid-liquid contact, and the method of contacting the solid-liquid is not particularly limited, and either a flow system or a batch system can be adopted. Two
When carrying more than one kind of metal compound, the carrier may be carried simultaneously by treating the carrier with the mixed aqueous solution,
Alternatively, they may be carried sequentially.

The metal raw material to be supported may be either organic or inorganic salt and is not particularly limited. Examples of such compounds include halides, sulfates, nitrates, phosphates, organic acid salts, and inorganic complex salts. Examples of the Group VIII metal raw material include palladium chloride, palladium nitrate, palladium sulfate, palladium acetate, tetraammine palladium chloride, tetraammine palladium nitrate, platinum chloride,
Tetraammine platinum chloride, tetraammine platinum nitrate, chlorotriammine platinum chloride, hexaammine platinum chloride, hexaammine platinum sulfate, chloropentaammine platinum chloride, cis-tetrachlorodiammine platinum, trans-tetrachlorodiammine platinum, chloride Rhodium, rhodium acetate, hexaammine rhodium chloride,
Hexaammine rhodium bromide, hexaammine rhodium sulfate, pentaammine aqua rhodium chloride, pentaammine aqua rhodium nitrate, cis-dichlorotetraammine rhodium chloride, trans-dichlorotetraammine rhodium chloride, ruthenium chloride, hexaammine ruthenium chloride, hexa Ammine ruthenium bromide, hexaammine ruthenium iodide, chloropentaammine ruthenium chloride, pentaammine (dinitrogen)
Ruthenium chloride, cis-dichlorotetraammine ruthenium chloride, ferrous chloride, ferric chloride, ferrous nitrate,
Ferric nitrate, hexaammine iron bromide, cobalt chloride,
Cobalt nitrate, cobalt sulfate, cobalt phosphate, cobalt acetate, hexaamminecobalt chloride, fluoropentaamminecobalt nitrate, chloropentaamminecobalt chloride, bromopentaamminecobalt bromide, iodopentaamminecobalt nitrate, pentaammineaquacobalt chloride, Hydroxopentaamminecobalt chloride, Nitritopentaamminecobalt chloride, Nitropentaamminecobalt chloride, Sulfide pentaamminecobalt sulfite, Thiosulfide pentaamminecobalt chloride, Isothiocyanatopentaamminecobalt sulphate, Dichlorotetraamminecobalt salt , Cis-Tetraamminediaquacobalt chloride, dinitrotetraamminecobalt chloride, nickel chloride, nickel nitrate, nickel sulfate Le, hexamminenickel chloride, iridium chloride (III), iridium chloride (IV),
Hexaammine iridium chloride, hexaammine iridium nitrate, chloropentaammine iridium chloride, chloropentaammine iridium bromide, hexaammine osmium chloride, hexaammine osmium iodide, pentaammine (dinitrogen) osmium chloride and the like can be mentioned. Examples of Group IB metal raw materials include copper (I) chloride, copper (II) chloride, copper nitrate, copper sulfate, and copper phosphate (I
I), copper acetate, tetraammine copper (II) sulfate, tetraammine copper (II) nitrate, tetraammine copper (II) chloride, bisethylenediamine copper (II) sulfate, bisethylenediamine copper (II) nitrate, trisethylenediamine copper ( II) Sulfate, trisethylenediamine copper nitrate, silver chloride, silver nitrate, silver acetate, dipyridine silver (I) perchlorate,
Tetrachloroauric (III) acid tetrahydrate, dichloro (1,1
0-phenanthroline) gold (III) chloride and the like. Examples of Group IIB metal raw materials include zinc chloride, zinc nitrate, zinc sulfate, zinc acetate, trisethylenediamine zinc (II) chloride dihydrate, cadmium chloride, cadmium nitrate, cadmium sulfate, cadmium acetate, mercury chloride, and nitric acid. Examples thereof include mercury, mercury sulfate, mercury acetate, diammine mercury (II) chloride, and bisethylenediamine mercury (II) nitrate. Preferably, tetraammine palladium chloride, tetraammine palladium nitrate, tetraammine platinum chloride, tetraammine platinum nitrate, chlorotriammine platinum chloride, hexaammine platinum chloride, hexaammine platinum sulfate, chloropentaammine platinum chloride, cis-tetra Chlorodiammine platinum and trans-tetrachlorodiammine platinum are used. The amount used is, in terms of each metal, usually 0.01 to 15% by weight, based on the carrier.
Preferably 0.1 to 5% by weight, more preferably 0.3 to
It is in the range of 1% by weight. In this reaction system, compounds belonging to Group IIIB, IVB, and VB of the Periodic Table for the purpose of adjusting the catalytic activity,
It can be added together or to the reaction system. The elements belonging to groups IIIB, IVB and VB of the periodic table which can be co-supported or added are not particularly limited, but preferably Sn or P
b, As, Sb, Bi, S and the like. As a form of sharing or addition, inorganic salts such as nitrates and sulfates, organic salts such as acetates and oxalates, or thiophene,
An organic compound such as tetraethyl lead can be exemplified. The carrying method may be carried out as a mixed solution with a group VIII, IB, or IIB metal compound, or may be carried sequentially. The supported amount is not particularly limited, but is usually 0.001 to 5% by weight, preferably 0.01 to
The amount is 2% by weight, more preferably 0.05 to 0.7% by weight.

The supported metal compound used in the method of the present invention needs to be subjected to a reduction treatment before use.
Usually, this reduction treatment is carried out during the catalyst preparation step after carrying out the treatment and after separating the solid-liquid by filtration, but it can also be carried out in the reaction system.

The reduction treatment can be carried out under a stream of nitrogen, hydrogen, carbon monoxide, methane gas, or a stream of a mixed gas thereof. The mixing ratio is not particularly limited.

The gas flow rate is not particularly limited.

The reduction treatment temperature is usually -50 to 300 ° C,
It is preferably in the range of 0 to 200 ° C.

The content of each metal in the oxidation catalyst produced as described above is usually 0.01 to 15% by weight, preferably 0.1 to 5% by weight, more preferably 0.3 to 1% by weight. weight%
Is the range.

Phenols are produced by oxidizing an aromatic compound in the presence of oxygen and hydrogen in water, alcohol or a mixed solvent of water and alcohol using the oxidation catalyst produced by the method described above. be able to.

The aromatic compound which can be used as a raw material in the method of the present invention is a compound having at least one aromatic ring, and the aromatic ring may be substituted with an alkyl group or a hydroxyl group. Examples of such compounds include benzene, toluene, xylene, phenol, cresol,
Examples thereof include biphenyl and naphthalene.

The phenols produced by the method of the present invention are compounds in which at least one of carbon atoms forming an aromatic ring is substituted with a hydroxyl group, and examples of monovalent phenols include phenol, cresol, Examples of xylenol, naphthol, and divalent phenols include catechol and hydroquinone.

It is difficult to unconditionally specify the amount of the oxidation catalyst to be used when the reaction is continuously carried out, but in the case of a batch system or a semi-batch system in which only gas is continuously supplied, it is supported. In terms of metals, relative to the raw material aromatic compound,
Usually, it is at least 0.001% by weight, preferably at least 0.01% by weight. The upper limit is not particularly limited, but for economic reasons, usually with respect to the aromatic compound as a raw material in terms of metal,
It is 1% by weight or less.

Oxygen and hydrogen may be used as a mixed gas of an inert gas. As the inert gas, for example, usually, nitrogen, helium, argon, carbon dioxide, methane,
Examples include ethane, with nitrogen being preferred for economic reasons. Air can also be used as the oxygen-containing gas, and the concentration of oxygen in the mixed gas is usually 1 to 90% by volume, preferably
The concentration of hydrogen is usually in the range of 20 to 40% by volume.
It is in the range of 1 to 90% by volume, preferably 20 to 40% by volume. The concentration of the inert gas is usually 0 to 98% by volume,
The preferred range is 20 to 60% by volume. Such oxygen, hydrogen and inert gas may be mixed in advance and supplied, or may be supplied separately.

The ratio of oxygen to hydrogen (oxygen / hydrogen) is not particularly limited, but is usually 0.1 to 90, preferably 0.1 to 90.
The range is 10.

As the solvent, usually water, alcohol or a mixed solvent of alcohol and water can be used, and preferably a mixed solvent of alcohol and water is used. As the alcohol, for example, methanol, ethanol,
Lower alcohols such as 2-propanol can be mentioned, and preferably methanol is used. The ratio of alcohol to water (alcohol / water) is usually in the range of 0.01 to 50, preferably 0.1 to 5. The amount used is usually in the range of 1 to 100 times by weight, preferably 5 to 20 times by weight, the amount of the aromatic compound as the raw material.

Inorganic acids such as hydrochloric acid, sulfuric acid and phosphoric acid, and alkali metal or alkaline earth metal salts can be added to the solvent as reaction accelerators, and alkali metal or alkaline earth halides are preferably used. As these halides, chlorides, bromides and iodides of sodium, potassium, rubidium, cesium, magnesium, calcium, strontium and barium can be used, and sodium bromide is preferably used. The addition amount is not particularly limited, but when an inorganic acid is used, it is usually preferable to add it to a concentration of 0.5 N or less due to problems such as elution of catalyst components. When an alkali metal or alkaline earth metal is used, Is usually 0.1 to 10 mol%, preferably 1 to 5 with respect to the aromatic compound.
It is used in the range of mol%.

The order of preparation is not particularly limited.

The reaction temperature is usually -50 to 450 ° C, preferably 0 to 150 ° C, more preferably 20 to 70 ° C.
It is in the range of ° C.

The reaction system may be either gas phase / liquid phase and is not particularly limited. Further, it is possible to employ any of a batch type, a semi-batch type in which only gas is continuously supplied, and a continuous type (flow type).

In the case of a semi-batch system or a continuous system in which a mixed gas is continuously supplied, the gas supply rate is usually 0.1 to 1
0 liter / min. 1 mol of aromatic compound, preferably 1
The range is from 5 liters / minute to 1 mol of the aromatic compound.
The reaction can be carried out under normal pressure or under increased pressure, usually from normal pressure to 100 Kg / cm2 (10 MPa), preferably from normal pressure to 50 Kg / cm2 (5 MPa), more preferably from 1 to 30 Kg / cm2 (3 MPa). Is the range. It is also possible to select supercritical conditions from the composition of the charged gas.

The reaction time is not particularly limited. For example, when benzene is oxidized, the reaction time (continuous time) is determined by grasping the tendency that the production amount of divalent phenols such as catechol and hydroquinone which are sequential oxides increases with the reaction time. In the case of using the formula, the residence time of the reaction solution) may be set to a condition that is advantageous for the desired product. Usually 0.5
-24 hours, preferably 2-10 hours.

After completion of the reaction, the catalyst, the phenols as the product and the aromatic compound as the raw material can be separated by combining known separation techniques such as distillation, extraction and filtration.

[0032]

According to the production method of the present invention, phenols can be produced industrially advantageously.

[0033]

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

(Example 1) SAC13 (manufactured by DuPont)
Nafion-containing 13% by weight of Nafion-H
To a suspension of 2 g of silica complex) and 20 g of water, an aqueous solution of tetraammineplatinum chloride hydrate containing 250 mg of 50 mg of platinum and tetraammineplatinum chloride hydrate containing 50 mg of platinum is added, and this suspension is added. 80
The mixture was vigorously stirred at ℃ for 24 hours. The cake obtained after filtration and washing was dried at 110 ° C. overnight. Elemental analysis revealed that the palladium content was 0.5% and the platinum content was 0.5%. Furthermore, 2 g of this dry cake was filled in a baking tube,
First, purge with 10 liters / hour of nitrogen for 30 minutes,
Next, in a mixed gas containing 5% hydrogen and 95% nitrogen at a flow rate of 2 liter / hour, the temperature was raised to 150 ° C. at 1 ° C./minute,
As it was, treatment was carried out at 150 ° C. for 1 hour to obtain palladium-platinum co-supporting SAC13.

(Example 2) In Example 1, 5% hydrogen, 95
Example 1 except that the reduction treatment is performed in a hydrogen gas stream instead of the reduction treatment in a mixed gas gas stream containing nitrogen.
By carrying out in the same manner as above, SA supporting palladium-platinum SA
C13 was obtained. The palladium content was 0.5% and the platinum content was 0.5%.

(Example 3) In Example 1, 5% hydrogen, 95
Example 1 except that the reduction treatment is performed under a nitrogen stream instead of the reduction treatment under a mixed gas stream containing nitrogen.
By carrying out in the same manner as above, SA supporting palladium-platinum SA
C13 was obtained. The palladium content was 0.5% and the platinum content was 0.5%.

Example 4 In Example 1, SAC13 (Nafion-H manufactured by DuPont, containing 13% by weight of Na was used).
fion-silica composite) instead of using SAC
No. 8 (Nafion-silica composite containing 8% by weight of Nafion-H manufactured by DuPont) was used, and the same procedure as in Example 1 was carried out, and palladium-platinum co-supported SAC8 was used.
Got Palladium content is 0.5%, platinum content is 0.5%
Met.

(Example 5) In Example 1, SAC13 (Nafion-H manufactured by DuPont, containing 13% by weight of Na was used.
fion-silica composite) instead of using SAC
Palladium-platinum co-supported SA was carried out in the same manner as in Example 1 except that 15 (Nafion-silica composite containing 15% by weight of Nafion-H manufactured by DuPont) was used.
C15 was obtained. The palladium content was 0.5% and the platinum content was 0.5%.

(Example 6) In Example 1, SAC13 (Nafion-H manufactured by DuPont, containing 13% by weight of Na) was used.
fion-silica composite) instead of using SAC
Palladium-platinum co-supported SA was carried out in the same manner as in Example 1 except that 80 (Nafion-silica composite containing 80% by weight of Nafion-H manufactured by DuPont) was used.
C80 was obtained. The palladium content was 0.5% and the platinum content was 0.5%.

Reference Example 1 A palladium-platinum co-supporting SAC13 was obtained in the same manner as in Example 1 except that no reduction treatment was performed in Example 1. The palladium content was 0.4% and the platinum content was 0.4%.

(Example 7) In Example 1, SAC13 (Nafion-H manufactured by DuPont, containing 13% by weight of Na) was used.
fion-silica complex) instead of using H type β
-All were carried out in the same manner as in Example 1 except that zeolite (BEA, Si / Al = 12.5) was used, and palladium-platinum co-supported B
EA was obtained. Palladium content 0.4%, platinum content 0.4%.
It was 4%.

(Example 8) SAC13 in Example 1 (Na containing 13% by weight of Nafion-H manufactured by DuPont)
fion-silica composite), H-type ferriolite (FER, Si / Al = 9) was used in the same manner as in Example 1, except that palladium-platinum co-supported F was used.
I got ER. Palladium content 0.6%, platinum content 0.0.
It was 4%.

(Example 9) SAC13 in Example 1 (Na containing Dufon's Nafion-H 13% by weight) was used.
(fion-silica composite), H-type mordenite (MOR, Si / Al = 7.5) was used in the same manner as in Example 1, except that palladium-platinum co-supported M was used.
I got an OR. Palladium content is 1.6%, platinum content is 0.1%.
It was 5%.

(Example 10) In Example 1, SAC13 (Nfion-H manufactured by DuPont, N containing 13% by weight) was used.
afion-silica composite)
The procedure of Example 1 was repeated except that berlyst-15 was used, and palladium-platinum co-loaded Amberlys was used.
t-15 was obtained. The palladium content was 2.4% and the platinum content was 1.2%.

(Example 11) In a 200 ml stainless steel autoclave, 0.2 g of the palladium-platinum co-supported SAC13 obtained in Example 1, 20 g of water, and benzene 2 were added.
g, 0.05 g of sodium bromide, hydrogen partial pressure 10K
g / cm2 (1 MPa), nitrogen partial pressure 10 kg / cm2 (1M
Pa) and oxygen partial pressure was increased to 10 kg / cm 2 (1 MPa), and the reaction solution was heated to 43 ° C. with stirring in a closed system and then kept warm for 3 hours. After cooling, the pressure was released and the reaction mixture was analyzed by gas chromatography. The results are shown in Table 1.
Shown in.

Example 12 The same procedure as in Example 11 was carried out except that 25% by weight methanol water was used instead of using water as a solvent in Example 11. The results are shown in Table 1.
Shown in.

Example 13 The same procedure as in Example 11 was carried out except that 75% by weight methanol water was used instead of using water as a solvent in Example 11. The results are shown in Table 1.
Shown in.

Example 14 The procedure of Example 11 was repeated except that methanol was used instead of water as the solvent in Example 11. The results are shown in Table 1.

(Example 15) Instead of using the palladium-platinum co-supporting SAC13 obtained in Example 1 in Example 11, the palladium-platinum co-supporting B obtained in Example 7 was used.
The same procedure as in Example 11 was carried out except that EA was used. The results are shown in Table 2.

Example 16 Instead of using the palladium-platinum co-supporting SAC13 obtained in Example 1 in Example 11, the palladium-platinum co-supporting F obtained in Example 8 was used.
The same procedure as in Example 11 was performed except that ER was used. The results are shown in Table 2.

(Example 17) Instead of using the palladium-platinum co-supported SAC13 obtained in Example 1 in Example 11, the palladium-platinum co-supported M obtained in Example 9 was used.
The procedure of Example 11 was repeated except that OR was used. The results are shown in Table 2.

(Example 18) In place of using the palladium-platinum co-supporting SAC13 obtained in Example 1 in Example 11, the palladium-platinum co-supporting Amberlyst-15 obtained in Example 10 is used. Were all performed in the same manner as in Example 11. The results are shown in Table 2.

Example 19 Instead of using the palladium-platinum co-supporting SAC13 obtained in Example 1 in Example 13, the palladium-platinum co-supporting S obtained in Example 4 was used.
The same procedure as in Example 13 was carried out except that AC8 was used. The results are shown in Table 3.

Example 20 Instead of using the palladium-platinum co-supporting SAC13 obtained in Example 1 in Example 13, the palladium-platinum co-supporting S obtained in Example 5 was used.
The same procedure as in Example 13 was carried out except that AC15 was used. The results are shown in Table 3.

(Example 21) Instead of using the palladium-platinum co-supporting SAC13 obtained in Example 1 in Example 13, the palladium-platinum co-supporting S obtained in Example 6 was used.
The same procedure as in Example 13 was carried out except that AC80 was used. The results are shown in Table 3.

(Embodiment 22) Hydrogen partial pressure of 10 in Embodiment 11
Kg / cm2 (1 MPa), nitrogen partial pressure 10 Kg / cm2 (1
(MPa), oxygen partial pressure was increased to 10 Kg / cm 2 (1 MPa), and the total pressure was maintained at 14 Kg / cm 2 (1.4 MPa) instead of performing the reaction in a closed system, and hydrogen was 1.3%.
The same procedure as in Example 11 was carried out except that liter / Hr, oxygen (1.3 liter / Hr) and nitrogen (1.4 liter / Hr) were continuously supplied. The results are shown in Table 4.

(Example 23) Instead of using the palladium-platinum co-supporting SAC13 obtained in Example 1 in Example 22, the palladium-platinum co-supporting S obtained in Example 2 was used.
The same procedure as in Example 22 was performed except that AC13 was used. The results are shown in Table 4.

(Example 24) Instead of using the palladium-platinum co-supporting SAC13 obtained in Example 1 in Example 22, the palladium-platinum co-supporting S obtained in Example 3 was used.
The same procedure as in Example 22 was carried out except that CA13 was used. The results are shown in Table 4.

Comparative Example 1 Instead of using the palladium-platinum co-supporting SAC13 obtained in Example 1 in Example 22, the palladium-platinum co-supporting SC obtained in Reference Example 1 was used.
The same procedure as in Example 22 was carried out except that A13 was used. The results are shown in Table 4.

(Example 25) In Example 22, the total pressure was 14K.
The same procedure as in Example 22 was carried out except that the total pressure was set to 7 Kg / cm2 (0.7 MPa) instead of being maintained at g / cm2 (1.4 MPa). The results are shown in Table 5.

(Example 26) In Example 25, the reaction temperature was changed to 4
The same procedure as in Example 25 was performed except that the procedure was performed at 30 ° C instead of at 3 ° C. The results are shown in Table 5.

Example 27 In Example 25, the reaction temperature was changed to 4
The same procedure as in Example 25 was performed except that the procedure was performed at 20 ° C instead of at 3 ° C. The results are shown in Table 5.

(Example 28) In Example 25, the reaction temperature was changed to 4
The same procedure as in Example 25 was performed except that the procedure was performed at 10 ° C instead of at 3 ° C. The results are shown in Table 5.

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[Table 1]

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[Table 2]

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[Table 3]

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[Table 4]

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[Table 5]

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Claims (21)

[Claims] 1. A carrier selected from zeolite, an ion-exchange resin having a sulfonic acid group, or a complex of a fluorinated resin having a sulfonic acid group and silica gel, containing at least one metal selected from Group VIII, IB or IIB metals. A catalyst for oxidizing an aromatic compound in the presence of hydrogen, which is obtained by carrying out a reduction treatment after supporting a metal. 2. The catalyst according to claim 1, wherein the content of the fluorinated resin having a sulfonic acid group is 8 to 25% with respect to the composite of the fluorinated resin having a sulfonic acid group and silica gel. 3. A fluorinated resin having a sulfonic acid group is represented by the following general formula (1): The catalyst according to claim 1 or 2, which is a compound represented by the formula (n, m, and x are integers). 4. The catalyst according to claim 1, wherein the metal is palladium and / or platinum. 5. The catalyst according to claim 4, which has a palladium content of 0.3 to 1% by weight and a platinum content of 0.3 to 1% by weight. 6. A carrier selected from zeolite, an ion-exchange resin having a sulfonic acid group or a complex of a fluorinated resin having a sulfonic acid group and silica gel, and at least one metal selected from the group VIII, IB or IIB metals. After carrying
The method for producing a catalyst according to claim 1, wherein the reduction treatment is carried out under a nitrogen stream, a hydrogen stream or a mixed gas stream of nitrogen and hydrogen. 7. The method for producing a catalyst according to claim 6, wherein the content of the fluorinated resin having a sulfonic acid group is 8 to 25% with respect to the composite of the fluorinated resin having a sulfonic acid group and silica gel. 8. A fluorinated resin having a sulfonic acid group is represented by the following general formula (1): The method for producing a catalyst according to claim 6 or 7, which is a compound represented by the formula (n, m, and x are integers). 9. The method for producing a catalyst according to claim 6, wherein the metal is palladium and / or platinum. 10. The palladium and platinum are tetraammine nitrate or tetraammine chloride.
10. The method for producing the catalyst according to any one of 9 to 9. 11. The method for producing a catalyst according to claim 9, wherein the palladium content is 0.3 to 1% by weight and the platinum content is 0.3 to 1% by weight. 12. A carrier selected from a complex of silica gel, an ion exchange resin having a sulfonic acid group or a fluorinated resin having a sulfonic acid group and silica gel, and at least one metal selected from Group VIII, IB or IIB metals. The production of phenols characterized by oxidizing an aromatic compound in the presence of oxygen and hydrogen in water, alcohol or a mixed solvent of water and alcohol using a catalyst obtained by carrying out reduction treatment after supporting Method. 13. The method for producing phenols according to claim 12, wherein the content of the fluorinated resin having a sulfonic acid group is 8 to 25% with respect to the composite of the fluorinated resin having a sulfonic acid group and silica gel. . 14. A fluorinated resin having a sulfonic acid group is represented by the following general formula (1): The method for producing a phenol according to claim 12 or 13, which is a compound represented by the formula (n, m, and x are integers). 15. The aromatic compound is benzene.
The method for producing a phenol according to any one of 2 to 14. 16. The method for producing phenols according to claim 12, which is carried out in the presence of an alkali metal or alkaline earth metal halide. 17. The method for producing a phenol according to claim 16, wherein the alkali metal halide is sodium bromide. 18. The method according to claim 1, wherein the alcohol is methanol.
The method for producing a phenol according to any one of 2 to 17. 19. The metal according to claim 1, which is palladium and platinum.
The method for producing a phenol according to any one of 2 to 18. 20. The method for producing phenols according to claim 12, wherein the palladium content is 0.3 to 1% by weight and the platinum content is 0.3 to 1% by weight. 21. The method for producing phenols according to claim 12, wherein a mixed gas of oxygen, hydrogen and nitrogen is continuously supplied.