JP2003246761A - Method for producing dihydric phenol - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing dihydric phenol in a high yield by oxidizing monohydric phenol with a peroxide in the presence of a ketone and phosphoric acid by developing a highly activated acid catalyst having no corrosive properties. <P>SOLUTION: When dihydric phenol is produced by oxidizing monohydric phenol with a peroxide in the presence of a ketone and phosphoric acid, a β-zeolite catalyst is used as the catalyst, in which a transition metal, a group 2B metal, a group 3B metal from the third period to the sixth period, a group 4B metal from the fifth period to the sixth period, or a lanthanide metal each having no corrosive properties is supported. By using this method, dihydric phenol is obtained in a high yield without causing the accumulation of a tar component, when monohydric phenol is oxidized with a peroxide in the presence of a ketone and phosphoric acid. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a dihydric phenol by oxidizing a monohydric phenol with a peroxide in the presence of a zeolite catalyst, a ketone and phosphoric acid.

[0002]

The following method is known as a method for producing a dihydric phenol by oxidizing a monohydric phenol with a peroxide in the presence of a zeolite catalyst. For example, US Pat. No. 3,580,956 reports an oxidation reaction of monohydric phenol using a catalyst such as mordenite containing rare earth metals such as lanthanum and cerium and faujasite as a catalyst. However, it is described in the specification that tar and the like are produced as by-products, and the amount of dihydric phenol in all reaction products was as low as 42% by weight.

US Pat. No. 4,578,521 reports a para-selective oxidation technique of monohydric phenol using a proton type ZSM-5 as a catalyst. However, in the additional test conducted by the inventors of the present invention using phenol as a raw material, it was not observed that hydroquinone, which is a para-position oxide, was selectively produced, and the yield was not sufficient. French patent 2693
No. 457 discloses a production method in which a proton-type acidic zeolite and a ketone compound are allowed to coexist to oxidize a monohydric phenol with hydrogen peroxide. However, as the proton type acidic zeolite, ZSM-5, Y type zeolite (US-
Y, etc.), ferrierite, X-type zeolite (faujasite), L-type zeolite, mordenite, ZSM-1
1, Mazzite, and offretite are mentioned, but nothing is mentioned about the proton type β zeolite of the present invention. According to the specification, US-Y and ZSM-5 are particularly preferable as the proton-type acidic zeolite, but even in a system using 2-pentanone in US-Y, which is the combination with the highest yield, The yield based on hydrogen peroxide was about 74%, and a sufficient yield could not be obtained even in the additional test by the present inventors. US-Y used has a multi-step and complicated preparation process such as dealumination of Y-zeolite once prepared and further treatment with silicon chloride.

As a technique for utilizing a zeolite catalyst containing a metal in a crystal lattice, for example, US Pat. No. 4,396,783 is used.
Benzene having a substituent such as monohydric phenol, monoalkylbenzene or the like using titanosilicate-1 (TS-1) which is a ZSM-5 type zeolite containing titanium in the crystal lattice as a catalyst. A technique of oxidizing with hydrogen peroxide has been reported. According to this manufacturing method,
Although it is described that dihydric phenol is produced at a higher yield than conventional aluminosilicate zeolites,
The yield based on hydrogen peroxide was about 54%. Also, A
dvancesin Catalysis, 41 (19
96), 253-334, the same reaction using TS-1 as a catalyst is accompanied by a by-product such as tar, and the yield based on hydrogen peroxide is about 84% even under optimized conditions. Although stated, this yield is not satisfactory.

Japanese Unexamined Patent Publication Nos. 7-2714 and 6
No. -40977 discloses 1,4 with TS-1 as a catalyst.
-A technique is disclosed in which a cyclic ether such as dioxane and a polar solvent such as water or methanol are coexistent to selectively produce a mainly para-oriented product, that is, hydroquinone. This technology has a hydroquinone / catechol ratio of 4
Although dihydric phenol was obtained in the range of up to 5, the yield based on hydrogen peroxide was about 70%, which is not sufficient. The technology using these TS-1 is the Accounts of
Chemical Research, 31 (8), (1
998) 485-493, as shown in TS-
Reproducibility of preparation of 1 catalyst is a problem, which is an obstacle to industrial use of TS-1.

[0006] In addition, as a prior art using zeolite in which a metal is introduced into a crystal lattice, Chem. Comm
Un, (1996) 2707 to 2708 describes a method for producing a dihydric phenol by oxidizing a monohydric phenol with hydrogen peroxide using β-zeolite containing chromium as a catalytically active component in a crystal lattice. The yield based on hydrogen peroxide is about 72%, which is not sufficient.

As described above, the conventional method for producing a dihydric phenol using a zeolite catalyst does not disclose the proton type β zeolite carrying the metal of the present invention. Further, these dihydric phenol production methods have problems as industrial production methods such as low yield due to generation of by-products such as tar and complicated preparation of the zeolite catalyst to be used.

[0008]

The problem to be solved by the present invention is to provide a method for producing a dihydric phenol in a high yield by oxidizing a monohydric phenol using a highly active zeolite-based catalyst which is easy to prepare. Is to provide.

[0009]

Means for Solving the Problems As a result of studies for solving the above-mentioned problems, the present inventors have carried out an ion exchange treatment on a proton-type β zeolite, which is a proton-type acidic zeolite which has not been studied so far. By using a catalyst supporting the metal by a simple method such as, for example, a monohydric phenol is oxidized with a peroxide in the presence of a ketone and phosphoric acid to produce a dihydric phenol without producing a by-product such as tar. They have found that they can be produced in high yield and have completed the present invention.

[0010]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
Examples of the monohydric phenol used in the present invention include:
Phenol, monohydric monoalkylphenol, monohydric halogenated phenol, monohydric polyalkylphenol may be mentioned.

Examples of the alkyl group contained in the monovalent monoalkylphenol include a linear or branched alkyl group having 1 to 6 carbon atoms. The position of the alkyl group is not particularly limited as long as it does not participate in the reaction. Examples of these compounds include o-, m- or p-cresol, o-,
Examples thereof include m- or p-ethylphenol, o-propylphenol, p-isopropylphenol, m-butylphenol, p-isobutylphenol, pt-butylphenol, m-isobutylphenol, p-pentylphenol and p-hexylphenol. .

Examples of the halogen atom contained in the monovalent halogenated phenol include fluorine, chlorine, bromine and iodine. The number and position of halogen atoms are not particularly limited as long as they do not participate in the reaction. Examples of these compounds include o-, m- or p-fluorophenol, o-, m
-Or p-chlorophenol, o-, m- or p-bromophenol, o-, m- or p-iodophenol,
2,3-, 2,4-, 2,5-, 2,6-, 3,4- or 3,5-dichlorophenol, 2,3-, 2,4-,
2,5-, 2,6-, 3,4- or 3,5-dibromolophenol, 2,3,4-, 2,3,5-, 2,3,6
-, 2,4,5-, 2,4,6- or 3,4,5-trichlorophenol may be mentioned.

Examples of the alkyl group contained in the monovalent polyalkylphenol include a linear or branched alkyl group having 1 to 6 carbon atoms. The number and position of alkyl groups are not particularly limited as long as they do not participate in the reaction. Examples of these compounds include 2,3-, 2,4-, 2,5
-, 2,6-, 3,5- or 3,4-dimethylphenol, 2,3,4-, 2,3,5-, 2,3,6- or 3,4,5-trimethylphenol, 2 , 4,5-Trimethylphenol, 2,3,4,5- or 2,3,5
6-tetramethylphenol, 2-ethyl-3-methylphenol, 3-t-butyl-4-methylphenol,
Examples include 2-isopropyl-5-methylphenol, 2-pentyl-6-methylphenol, and 3-hexyl-5-methylphenol.

Examples of the ketone used in the present invention include monoketone and diketone. Monoketones include acyclic or cyclic monoketones. The acyclic monoketone has, for example, 3 to 20 carbon atoms.
One, preferably 3 to 10, linear or branched aliphatic monoketone or aromatic monoketone may be mentioned. The hydrogen atom of these compounds is a halogen atom (fluorine, chlorine,
Bromine or iodine). The number and position of halogen atoms are not particularly limited as long as they do not participate in the reaction.

Examples of the linear aliphatic monoketone include acetone, methyl ethyl ketone, 2-pentanone,
3-pentanone, 2-hexanone, 2-heptanone, 3
-Heptanone, 4-heptanone, 2-octanone, 2-
Nonanone, 3-decanone, 6-undecanone, 2-tridecanone, 7-tridecanone, 2-tetradecanone,
2-pentadecanone, 2-hexadecanone, 2-heptadecane, 3-octadecanone, 4-nonadecanone, 1
-Chloro-2-propanone, 1-chloro-3-heptanone, 1-bromo-3-heptanone.

Examples of the branched aliphatic monoketones include 3-methyl-2-butanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 3,3-dimethyl-2-butanone and 2,4. -Dimethyl-3-pentanone, 6-methyl-2-heptanone, 2,6-dimethyl-
4-heptanone, 2,2,4,4-tetramethyl-3-
Heptanone can be mentioned. As an aromatic monoketone,
For example, acetophenone, benzophenone, 1-phenyl-3-propanone, 1-phenyl-1-butanone, 1
-Phenyl-3-butanone, 1-phenyl-3-pentanone, 1,3-diphenyl-2-propanone.

Examples of the cyclic monoketone include cycloalkyl monoketone having 5 to 12 carbon atoms. The hydrogen atom of these compounds may be substituted with a halogen atom (fluorine, chlorine, bromine or iodine) or a substituent such as a linear or branched alkyl group having 1 to 6 carbon atoms. The number and position of the substituents are not particularly limited as long as they do not participate in the reaction. Examples of these compounds include cyclopentanone, cyclohexanone, cyclododecanone, 2-chlorocyclohexanone, 2-ethyl-1-cyclopentanone, and 2-methyl-1-cyclohexanone.

The diketone includes acyclic or cyclic diketones. Examples of the acyclic diketone include linear or branched aliphatic diketone and aromatic diketone having 5 to 21 carbon atoms, preferably 5 to 12 carbon atoms. The hydrogen atom of these compounds may be replaced by a halogen atom (fluorine, chlorine, bromine or iodine). The number and position of halogen atoms are not particularly limited as long as they do not participate in the reaction. Examples of the linear aliphatic diketone include 2,3-butanedione, 2,4-pentanedione,
2,5-hexanedione can be mentioned. Examples of the branched aliphatic diketone include 2,5-dimethyl-3,4-
Hexanedione may be mentioned. Examples of the aromatic diketone include 1,2-diphenylethane-1,2-dione.

Examples of cyclic diketones include cyclic diketones having 5 to 12 carbon atoms. The hydrogen atom of these compounds is a halogen atom (fluorine, chlorine,
(Bromine or iodine), or a substituent such as a linear or branched alkyl group having 1 to 6 carbon atoms. The number and position of the substituents are not particularly limited as long as they do not participate in the reaction. Examples of the cyclic diketone include 1,4
-Cyclohexanedione.

Preferred ketones used in the present invention are linear or branched aliphatic monoketones or cyclic monoketones, and more preferred are linear or branched aliphatic monoketones. Among them, 4-methyl-2-pentanone and 3-pentanone are particularly preferable. The amount of ketone used is preferably such that the molar ratio of ketone to peroxide (ketone: peroxide) is 0.05: 1 to 5: 1.

Examples of the phosphoric acid used in the present invention include orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid, triphosphoric acid, tetraphosphoric acid, polyphosphoric acid, phosphoric anhydride, and phosphoric acid aqueous solution, and phosphoric acid aqueous solution is preferable. The concentration of the phosphoric acid aqueous solution is 0.001 to
100% by weight is preferred. The amount of phosphoric acid used is such that the weight ratio of phosphoric acid to peroxide (phosphoric acid: peroxide) is 0.000.
The ratio is preferably 1: 1 to 0.05: 1.

The peroxide used in the present invention is an inorganic peroxide such as hydrogen peroxide, or a ketone peroxide,
Examples thereof include organic peroxides such as aliphatic percarboxylic acids.

Examples of the ketone peroxide include:
Examples thereof include dialkyl ketone peroxides having 3 to 20 carbon atoms, and preferably 3 to 10 carbon atoms. Examples of these compounds include dimethyl ketone peroxide, diethyl ketone peroxide, methyl ethyl ketone peroxide, methyl-n-propyl ketone peroxide, methyl isopropyl ketone peroxide,
And methyl isobutyl ketone peroxide. Examples of the aliphatic percarboxylic acid include peracetic acid and perpropionic acid. As hydrogen peroxide, 0.
1 wt% or more, preferably can be used hydrogen peroxide water 0.1 to 90% by weight, more preferably from 30 to 80 wt%.

Hydrogen peroxide or ketone peroxide is preferable as the peroxide used in the present invention. This ketone peroxide can be synthesized by contacting a ketone with hydrogen peroxide, and the ketone used here is the same as described above. The amount of peroxide used is in a range such that the molar ratio of peroxide to monohydric phenol (peroxide: monohydric phenol) is 1: 1 to 1: 100, and further 1: 5 to 1:20. Is preferred.

In the present invention, β zeolite is used as a catalyst. As β-zeolite, proton-type β-zeolite is preferable, but among them, transition metal, Group 2B metal, third group
Periodic to 6th period 3B group metal, 5th to 6th period 4B group metal, or lanthanoid metal-supported proton type β
Zeolites are particularly preferred (the names of the groups and periods of these elements are "Rikagaku Jiten", Iwanami Shoten, 4th Edition, 199).
3, Periodic Table of Elements in Appendix II (a) Based on long period type). The content of aluminum (aluminum in the skeleton) in β-zeolite is Al: Si (atomic ratio) of 1:10.
The ratio is preferably 1: 10000. The amount of β zeolite used is such that the weight ratio of β zeolite to monohydric phenol (β zeolite: monohydric phenol) is 1: 1 to 1: 500, and further 1: 5 to 1: 100.
The range is preferably such that

Β-zeolite is Journal of P
physical Chemistry, 104 (200
0), 2853 to 2859, or a commercially available product can be preferably used. The proton-type β zeolite is prepared by the method described in the above literature or the like. For example, β zeolite is ammonium nitrate,
20 in an aqueous solution containing ammonium ions such as ammonium chloride (ammonium salt concentration: 0.1 to 40% by weight)
Heat treatment at ~ 120 ° C for 1 to 20 hours, wash with ion exchanged water, etc., and dry at 20 to 150 ° C, then 300 to 65
It is obtained by firing at 0 ° C. for 1 to 10 hours. Also, soak in 0.01N to 1N hydrochloric acid solution at room temperature to 1
After treatment at 00 ° C for several minutes to several days, washing with ion-exchanged water, etc., drying at room temperature to 150 ° C, 150 ° C to 650 ° C
The proton-type β zeolite obtained by calcination in the above can also be suitably used.

As the metal-supported proton type β zeolite, a transition metal, a 2B group metal, a 3B group metal of the 3rd to 6th periods, a 4B group metal of the 5th to 6th periods, or A lanthanoid metal supported and fired can be used. As the transition metal, 3A group such as scandium and yttrium, 4A group such as titanium and zirconium, 5A such as vanadium and niobium
Group 6A, such as chromium, molybdenum, and tungsten,
Examples thereof include 7A group such as manganese, 8 group such as iron, cobalt, and nickel, and 1B group such as copper, silver, and gold. Among them, yttrium, niobium, tantalum, manganese, cobalt, nickel, and silver are preferable. Zinc is preferable as the 2B group metal. As the Group 3B metal in the fourth to sixth periods, gallium and indium are preferable. As the lanthanoid metal, lanthanum, cerium, praseodymium, samarium and ytterbium are preferable. Further, tin and lead, which are Group 4B metals in the fifth to sixth periods, are preferable. As a metal supporting method, a usual ion exchange method, an impregnation method,
A metal supporting method such as a chemical vapor deposition (CVD) method or a mechanical kneading method can be applied, but an ion exchange method or an impregnation method is preferable.

Preparation of the above-mentioned metal-supported proton type β zeolite by the ion exchange method is described in Catalyst Preparation Chemistry, Kodansha (19
80) 61-73. For example, 20 to 1 of the proton-type β zeolite in the metal ion-containing aqueous solution (the metal salt concentration: 0.1 to 40% by weight) of the metal nitrate, hydrochloride, or sulfate.
After heat treatment at 20 ° C for 1 to 20 hours, washing with ion-exchanged water, etc., and drying at 20 to 150 ° C for 5 minutes to 24 hours, 3
It is obtained by baking at 00 to 650 ° C. for 1 to 10 hours. The metal ion supported on the proton type β zeolite is M ^{δ +} / Al (δ represents 1, 2 or 3).
Is 0.0001 to 10, more preferably 0.01 to 1 (M ^{δ +} represents the metal ion, and Al represents aluminum in the skeleton of the proton-type β zeolite) within a ratio (atomic ratio). Preferably there is.

The metal-supported proton type β-zeolite prepared by the impregnation method is described in Catalyst Preparation Chemistry, Kodansha (1980) 49-60.
It can be performed by the method described in the above. For example, it can be prepared by the following method. A predetermined amount of a solution prepared by dissolving an inorganic salt such as a metal nitrate, a hydrochloride, a sulfate or an organic salt such as an alkoxide in an arbitrary solvent is impregnated into β-zeolite which has been subjected to a pre-calcination treatment. 90 ℃ ~ 1
After stirring and heating at 40 ° C. to evaporate the solvent, 300 to 6
Baking at 50 ° C. for 1 to 10 hours. At this time, a method using a beaker or a magnetic crucible is preferably used for the impregnation operation, but a method may also be used in which a carrier is put in the solution using a rotary evaporator, the solvent is removed under reduced pressure, and the solid is dried. The metal supported on the proton-type β zeolite is M
/ Al is 0.01 to 1000, more preferably 0.1 to 100
The ratio (atomic ratio) of (M is a metal to be supported and Al is aluminum introduced into the skeleton) is preferably in the range.

The β-zeolite used in the present invention may be in the form of powder, granules, pellets, honeycomb-shaped compact or the like. As the shape corresponding to the production method of the dihydric phenol, for example, when producing using a liquid phase batch reactor, it is preferable to use powder, granules, etc., when using a liquid phase flow reactor Pellets, honeycomb-shaped molded products and the like are preferable.

In the production of the dihydric phenol of the present invention, the reaction temperature is preferably 20 to 300 ° C, more preferably 40 to 200 ° C. The reaction time varies depending on the type of catalyst and reaction temperature, but is not particularly limited. The reaction can be carried out at atmospheric pressure, but may be carried out under reduced pressure or increased pressure. The reaction can be performed in a liquid phase by a batch system, a flow system, a trickle bed system, or the like.

As the reaction in the present invention, for example, monohydric phenol, hydrogen peroxide, ketone and phosphoric acid are supplied to a reactor pre-filled with β-zeolite to oxidize the monohydric phenol to give dihydric phenol. Reactions in which the reaction mixture is produced and the reaction mixture is discharged from the reactor.

The dihydric phenol produced by the present invention corresponds to the structure of the starting monohydric phenol and can be obtained as a mixture of one kind or several kinds. In addition, these dihydric phenols can be obtained by separating and purifying by a conventional method.

[0034]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. The present invention is not limited to these examples. The yield of dihydric phenol is obtained according to the following equation. The analysis was performed by gas chromatography.

[0035]

[Equation 1]

Reference Example 1 (Preparation of yttrium ion-supporting proton type β zeolite) Yttrium nitrate trihydrate (0.85 g) manufactured by Kanto Kagaku
Was dissolved in ultrapure water to prepare 20 cc of an aqueous solution containing yttrium ions. A to the obtained aqueous solution
Ion exchange of protons and yttrium ions was performed by immersing proton type β-zeolite (2 g) manufactured by Zeolist, in which 1: Si = 1: 37.5, and keeping the temperature at 85 ° C. for 14 hours. The suspension obtained is suction filtered and
After drying at 0 ° C. and calcining at 550 ° C. for 2.5 hours, 1.9 g of yttrium ion-supporting proton type β zeolite was obtained. ICP emission analysis showed that the β
The ratio (atomic ratio) of yttrium ions and Al supported on the zeolite was Y ³⁺ /Al=0.23.

Reference Example 2 (Preparation of Zinc Ion-Supporting Proton Type β Zeolite) Reference Example 1 was prepared except that zinc nitrate hexahydrate (0.66 g) manufactured by Kanto Kagaku was used. As a result, a zinc ion-supported proton type β zeolite (1.9 g) was obtained.
When ICP emission analysis was performed, the ratio (atomic ratio) of zinc ions and Al supported on the β zeolite was Zn ²⁺ /
Al = 0.28.

Reference Example 3 (Preparation of Proton Type β Zeolite Bearing Nickel Ion) The same preparation as in Reference Example 1 was carried out except that nickel nitrate hexahydrate (0.65 g) manufactured by Kanto Kagaku was used. As a result, nickel ion-supported proton type β zeolite (1.9 g)
Got ICP emission analysis revealed that the ratio of nickel ions and Al supported on the β zeolite (atomic ratio)
Was Ni ²⁺ /Al=0.27.

Reference Example 4 (Preparation of Manganese Ion-Supporting Proton Type β Zeolite) Reference Example 1 was prepared except that manganese nitrate hexahydrate (0.64 g) manufactured by Wako Pure Chemical Industries, Ltd. was used. As a result, manganese ion-supported proton type β zeolite (1.9 g)
Got ICP emission analysis revealed that the ratio of manganese ions and Al supported on the β zeolite (atomic ratio)
Was Mn ²⁺ /Al=0.27.

Reference Example 5 (Preparation of Cobalt Ion-Supporting Proton β Beta Zeolite) Reference Example 1 was prepared except that cobalt nitrate hexahydrate (0.65 g) manufactured by Kanto Chemical Co., Ltd. was used. As a result, cobalt ion-supported proton type β zeolite (1.9 g)
Got When ICP emission analysis was performed, the ratio of cobalt ions and Al supported on the β zeolite (atomic ratio)
Was Co ²⁺ /Al=0.26.

Reference Example 6 (Preparation of Proton-Type β Zeolite Bearing Silver Ion) The same preparation as in Reference Example 1 was carried out except that silver nitrate (0.38 g) manufactured by Kanto Kagaku was used. As a result, a silver ion-supported proton type β zeolite (1.9 g) was obtained. When ICP emission analysis was carried out, the ratio (atomic ratio) of silver ions and Al supported on the β zeolite was Ag ⁺ /Al=0.23.

Reference Example 7 (Preparation of tin ion-supporting proton type β zeolite) The same preparation as in Reference Example 1 was carried out except that tin chloride (0.50 g) manufactured by Kanto Kagaku was used. As a result, tin ion-supported proton type β zeolite (1.9 g) was obtained. ICP emission analysis showed that the ratio (atomic ratio) of tin ions and Al supported on the β zeolite was Sn ²⁺ /Al=2.10.
Met.

Reference Example 8 (Preparation of Lead Ion-Supporting Proton Type β Zeolite) The same preparation as in Reference Example 1 was carried out except that lead nitrate (0.74 g) manufactured by Kanto Kagaku was used. As a result, lead ion-supported proton type β zeolite (1.9 g) was obtained. ICP emission analysis showed that the ratio (atomic ratio) of lead ions and Al supported on the β zeolite was Pb ²⁺ /Al=0.30.
Met.

Reference Example 9 (Preparation of Proton-Type β Zeolite Bearing Lanthanum Ion) Preparation was carried out in the same manner as in Reference Example 1 except that lanthanum nitrate hexahydrate (0.96 g) manufactured by Wako Pure Chemical Industries, Ltd. was used. As a result, lanthanum ion-supported proton type β zeolite (1.9 g)
Got ICP emission analysis showed that the ratio of lanthanum ions and Al supported on the β zeolite (atomic ratio)
Was La ³⁺ /Al=0.08.

Reference Example 10 (Preparation of Cerium Ion-Supporting Proton Type β Zeolite) A reference example 1 was prepared except that cerium nitrate hexahydrate (0.96 g) manufactured by Wako Pure Chemical Industries, Ltd. was used. As a result, cerium ion-supported proton type β zeolite (1.9 g)
Got When ICP emission analysis was performed, the ratio of cerium ion and Al supported on the β zeolite (atomic ratio)
Was Ce ³⁺ /Al=0.09.

Reference Example 11 (Preparation of praseodymium ion-supporting proton type β zeolite) Praseodymium nitrate n hydrate (n = 4 to 6) manufactured by Wako Pure Chemical Industries, Ltd.
It was prepared in the same manner as in Reference Example 1 except that (0.93 g) was used. As a result, praseodymium ion-supported proton type β
Zeolite (1.9 g) was obtained. When ICP emission analysis was performed, the ratio (atomic ratio) of praseodymium ions and Al supported on the β zeolite was Pr ³⁺ /Al=0.1.
It was 0.

Reference Example 12 (Preparation of Ytterbium Ion-Supporting Proton Type β Zeolite) Ytterbium nitrate tetrahydrate (0.96 manufactured by Wako Pure Chemical Industries, Ltd.)
It was prepared in the same manner as in Reference Example 1 except that g) was used. As a result, ytterbium ion-supported proton type β zeolite (1.9 g) was obtained. When ICP emission analysis was performed, the ratio (atomic ratio) of ytterbium ions and Al supported on the β zeolite was Yb ³⁺ /Al=0.12.

Reference Example 13 (Preparation of samarium ion-supporting proton type β-zeolite) A reference example 1 was prepared except that samarium nitrate hexahydrate (0.99 g) manufactured by Kanto Kagaku was used. as a result,
Samarium ion-supported proton-type β zeolite (1.9
g) was obtained. When ICP emission analysis was carried out, the ratio (atomic ratio) of samarium ions and Al supported on the β zeolite was Sm ³⁺ /Al=0.12.

Reference Example 14 (Preparation of gallium ion-supporting proton type β zeolite) Gallium nitrate n hydrate (n≈3) (0.6) produced by Wako Pure Chemical Industries, Ltd.
It was prepared in the same manner as in Reference Example 1 except that 9 g) was used. As a result, a gallium ion-supported proton type β zeolite (1.9 g) was obtained. When ICP emission analysis was performed,
The ratio (atomic ratio) of gallium ions and Al supported on the β zeolite was Ga ³⁺ /Al=0.56.

Reference Example 15 (Preparation of Proton Type β Zeolite Bearing Indium Ion) Indium nitrate n hydrate (n≈3) (0.
It was prepared in the same manner as in Reference Example 1 except that 79 g) was used.
As a result, indium ion-supported proton type β zeolite (1.9 g) was obtained. When ICP emission analysis was carried out, the indium ion and A
The ratio of 1 (atomic ratio) was In ³⁺ /Al=0.50.

Reference Example 16 (Preparation of Proton Type β Zeolite Bearing Niobium) Niobium ethoxide (0.14 g) manufactured by Aldrich was diluted with 20 ml of ethanol to prepare 20 ml of an Nb-containing ethanol solution. 2 g of Zeolist's proton-type β zeolite was immersed in the obtained solution, and the mixture was stirred and heated at 90 ° C. for 1 hr to evaporate ethanol, thereby impregnating and supporting Nb on the β zeolite.
The obtained powder was calcined at 550 ° C. for 2.5 hours to obtain a niobium-supported proton type β zeolite (1.9 g). ICP emission analysis revealed that the ratio (atomic ratio) of niobium and Al supported on the β zeolite was Nb / A.
1 = 0.55.

Reference Example 17 (Preparation of tantalum-supported proton type β zeolite) 20 ml of a Ta-containing ethanol solution was prepared by diluting 20 ml of ethanol with tantalum ethoxide (0.09 g) manufactured by Aldrich. 2 g of Zeolist's proton-type β-zeolite was immersed in the obtained solution, and the mixture was stirred and heated at 90 ° C. for 1 hr to evaporate ethanol to impregnate and support Ta on the β-zeolite.
The obtained powder was calcined at 550 ° C. for 2.5 hours to give a tantalum-supported proton type β zeolite (1.9 g).
Got ICP emission analysis showed that the ratio (atomic ratio) of tantalum and Al supported on the β zeolite was Ta.
/Al=0.29.

Reference Example 18 (Zinc ion-supporting proton type β
Preparation of Zeolite) Zinc nitrate hexahydrate (0.33 g) manufactured by Kanto Kagaku Co., Ltd. was dissolved in ultrapure water to give a zinc ion-containing aqueous solution of 20
cc prepared. Al: Si = 1: 75 in the obtained aqueous solution
The proton-type β zeolite (2 g) manufactured by Sud Chemie Catalyst Co., Ltd. was immersed and kept at 85 ° C. for 14 hours to perform ion exchange between protons and zinc ions. The suspension obtained is suction filtered, dried at 110 ° C. and then at 550 ° C.
The zinc ion-supported proton type β zeolite (1.9 g) was obtained by calcining for 2.5 hours. When ICP emission analysis was performed, the ratio (atomic ratio) of zinc ions and Al supported on the β zeolite was Zn ²⁺ /Al=0.2.
It was 7.

Reference Example 19 (Preparation of Nickel Ion-Supporting Proton Type β Zeolite) A reference example 18 was prepared in the same manner as in Reference Example 18 except that nickel nitrate hexahydrate (0.33 g) manufactured by Kanto Kagaku was used. as a result,
Nickel ion-supported proton type β zeolite (1.9
g) was obtained. As a result of ICP emission spectrometry, the ratio (atomic ratio) of nickel ions and Al supported on the β zeolite was Ni ²⁺ /Al=0.27.

Reference Example 20 (Preparation of Manganese Ion-Supporting Proton-Type β Zeolite) Reference Example 20 was prepared in the same manner as in Reference Example 18 except that manganese nitrate hexahydrate (0.32 g) manufactured by Wako Pure Chemical Industries, Ltd. was used. as a result,
Manganese ion-supported proton type β zeolite (1.9
g) was obtained. As a result of ICP emission spectrometry, the ratio (atomic ratio) of manganese ions and Al supported on the β zeolite was Mn ²⁺ /Al=0.26.

Reference Example 21 (Preparation of Cobalt Ion-Supporting Proton Type β Zeolite) A reference example 18 was prepared in the same manner as in Reference Example 18 except that cobalt nitrate hexahydrate (0.33 g) manufactured by Kanto Kagaku was used. as a result,
Proton type β zeolite supporting cobalt ion (1.9
g) was obtained. When ICP emission analysis was carried out, the ratio (atomic ratio) of cobalt ions and Al supported on the β zeolite was Co ²⁺ /Al=0.26.

Reference Example 22 (Preparation of Cobalt Ion-Supporting Proton Type US-Y) A cobalt ion-containing aqueous solution of 20 cc was prepared by dissolving cobalt nitrate hexahydrate (0.65 g) manufactured by Kanto Chemical Co., Inc. in ultrapure water. did. In the obtained aqueous solution, Al: Si =
1: 3.0 JGC Universal Proton Type US
-Y (2 g) was immersed and kept at 85 ° C for 14 hours to perform ion exchange between protons and cobalt ions. The suspension obtained is suction filtered and dried at 110 ° C.,
By firing at 550 ° C. for 2.5 hours, cobalt ion-supported proton type US-Y (1.9 g) was obtained. IC
When P emission analysis was performed, the ratio (atomic ratio) of cobalt ions and Al supported on the zeolite was found to be Co ²⁺ / A.
1 = 0.02.

Reference Example 23 (Preparation of Cobalt Ion-Supporting Proton Mordenite) Cobalt nitrate hexahydrate (0.65 g) manufactured by Kanto Chemical Co., Inc. was dissolved in ultrapure water to prepare 20 cc of a cobalt ion-containing aqueous solution. In the obtained aqueous solution, Al: Si =
Prototype mordenite 2 manufactured by Tosoh, which is 1: 6.0
g was immersed and kept at 85 ° C. for 14 hours to perform ion exchange between protons and cobalt ions. The obtained suspension was suction filtered, dried at 110 ° C., and then calcined at 550 ° C. for 2.5 hours to obtain a cobalt ion-supported proton type mordenite (1.9 g). When ICP emission analysis was carried out, the ratio (atomic ratio) of cobalt ions and Al supported on the zeolite was found to be Co ²⁺ / Al =
It was 0.09.

Reference Example 24 (Preparation of Cobalt Ion-Supporting Proton Type ZSM-5) Cobalt ion-containing aqueous solution was prepared to 20 cc by dissolving cobalt nitrate hexahydrate (0.65 g) manufactured by Kanto Kagaku in ultrapure water. did. In the obtained aqueous solution, Al: Si =
1:20 JGC Universal Proton ZSM
By immersing -5 (2 g) and keeping the temperature at 85 ° C. for 14 hours, proton exchange with cobalt ion was performed. The suspension obtained is suction filtered and dried at 110 ° C.,
By firing at 550 ° C. for 2.5 hours, cobalt ion-supported proton type ZSM-5 (1.9 g) was obtained. I
When CP emission analysis was performed, the ratio (atomic ratio) of cobalt ions and Al supported on the zeolite was found to be Co ²⁺ /
Al = 0.08.

Example 1 Proton type β zeolite carrying zinc ions (0.20 g) of Reference Example 2, phenol (10.00 g), 3-pentanone (0.27 g), 85 wt% phosphoric acid aqueous solution (0.
(02 g) was placed in a 300 ml flask, the atmosphere was replaced with nitrogen, and the temperature was raised to 60 ° C. with stirring. Next, at this temperature, 0.10 g of 60 wt% hydrogen peroxide solution was dropped, 1.5 minutes later, 0.10 g was dropped, 3 minutes later, 0.10 g was further dropped, and 5 minutes after the first dropping. It was made to react until it became. As a result, the yield of dihydric phenol was 48.1% for catechol and 36. for hydroquinone.
At 3%, the total yield of catechol and hydroquinone was 8
It was 4.4%. The reaction solution was only colored in a very pale yellow color, and almost no accumulation of tar content was observed.

Example 2 A reaction was carried out in the same manner as in Example 1 except that the nickel ion-supporting proton type β zeolite of Reference Example 3 (0.20 g) was used as the catalyst. As a result, the yields of dihydric phenol were 47.7% for catechol and 35.3% for hydroquinone,
The total yield of catechol and hydroquinone was 83.0%. The reaction solution was only colored in a very pale yellow,
Almost no accumulation of tar was observed.

Example 3 A reaction was performed in the same manner as in Example 1 except that the cerium ion-supporting proton type β zeolite (0.20 g) of Reference Example 10 was used as the catalyst. As a result, the yield of dihydric phenol was 47.9% for catechol and 30.9% for hydroquinone.
And the total yield of catechol and hydroquinone was 78.8.
%Met. The reaction solution was only colored in a very pale yellow color, and almost no accumulation of tar content was observed.

[0063]

[Table 1]

Example 4 Yttrium ion-supporting proton type β zeolite (0.20 g), phenol (10.00 g), 3 of Reference Example 1
-Pentanone (0.27 g) and 85% by weight phosphoric acid aqueous solution (0.02 g) were placed in a 300 ml flask, the atmosphere was replaced with nitrogen, and the temperature was raised to 100 ° C with stirring. Next, at this temperature, 0.10 g of 60 wt% hydrogen peroxide solution was dropped, 1.5 minutes later, 0.10 g was dropped, 3 minutes later, 0.10 g was further dropped, and 5 minutes after the first dropping. It was made to react until it became. As a result, the yield of dihydric phenol was 51.2% for catechol and 33.8% for hydroquinone, and the total yield of catechol and hydroquinone was 85.0%. The reaction solution was only colored in a very pale yellow color, and almost no accumulation of tar content was observed.

Example 5 A reaction was carried out in the same manner as in Example 1 except that the reaction temperature was 100 ° C. As a result, the yield of dihydric phenol was 54.7% for catechol and 38.6% for hydroquinone, and the total yield of catechol and hydroquinone was 93.3%. The reaction solution was only colored in a very pale reddish brown,
Almost no accumulation of tar was observed.

Example 6 A reaction was carried out in the same manner as in Example 4 except that the nickel ion-supporting proton type β zeolite of Reference Example 3 (0.20 g) was used as the catalyst. As a result, the yields of dihydric phenol were 53.1% for catechol and 38.1% for hydroquinone,
The total yield of catechol and hydroquinone was 91.2%. The reaction solution was only colored in a very reddish brown color, and almost no accumulation of tar content was observed.

Example 7 A reaction was carried out in the same manner as in Example 4 except that the manganese ion-supporting proton type β zeolite (0.20 g) of Reference Example 4 was used as the catalyst. As a result, the yield of dihydric phenol was 54.5% for catechol and 39.2% for hydroquinone,
The total yield of catechol and hydroquinone was 93.7%. The reaction solution was only colored in a very reddish brown color, and almost no accumulation of tar content was observed.

Example 8 A reaction was performed in the same manner as in Example 4 except that the cobalt ion-supported proton type β zeolite (0.20 g) of Reference Example 5 was used as the catalyst. As a result, the yields of dihydric phenol were 54.4% for catechol and 40.2% for hydroquinone,
The total yield of catechol and hydroquinone was 94.6%. The reaction solution was only colored in a very reddish brown color, and almost no accumulation of tar content was observed.

Example 9 A reaction was carried out in the same manner as in Example 4 except that the catalyst was the silver ion-supporting proton type β zeolite (0.20 g) of Reference Example 6. As a result, the yield of dihydric phenol was 49.9% for catechol and 39.9% for hydroquinone, and the total yield of catechol and hydroquinone was 89.8%. The reaction solution was only colored in a very reddish brown color, and almost no accumulation of tar content was observed.

Example 10 A reaction was carried out in the same manner as in Example 4 except that the tin ion-supported proton type β zeolite (0.20 g) of Reference Example 7 was used as the catalyst. As a result, the yield of dihydric phenol was 54.7% for catechol and 38.9% for hydroquinone, and the total yield of catechol and hydroquinone was 93.6%. The reaction solution was only colored in a very reddish brown color, and almost no accumulation of tar content was observed.

Example 11 A reaction was carried out in the same manner as in Example 4 except that the lead ion-supporting proton type β zeolite (0.20 g) of Reference Example 8 was used as the catalyst. As a result, the yield of dihydric phenol was 52.7% for catechol and 39.1% for hydroquinone, and the total yield of catechol and hydroquinone was 91.8%. The reaction solution was only colored in a very reddish brown color, and almost no accumulation of tar content was observed.

Example 12 A reaction was carried out in the same manner as in Example 4 except that the praseodymium ion-supporting proton type β zeolite (0.20 g) of Reference Example 11 was used as the catalyst. As a result, the yields of dihydric phenol were 52.9% for catechol and 32. for hydroquinone.
At 4%, the total yield of catechol and hydroquinone was 8
It was 5.3%. The reaction solution was only colored in a very pale yellow color, and almost no accumulation of tar content was observed.

Example 13 A samarium ion-supported proton type β of Reference Example 13 was used as a catalyst.
The reaction was performed in the same manner as in Example 4 except that zeolite (0.20 g) was used. As a result, the yield of dihydric phenol was
52.2% catechol and 33.8% hydroquinone
And the total yield of catechol and hydroquinone was 86.0.
%Met. The reaction solution was only colored in a very reddish brown color, and almost no accumulation of tar content was observed.

Example 14 A reaction was carried out in the same manner as in Example 4 except that the ytterbium ion-supporting proton type β zeolite (0.20 g) of Reference Example 12 was used as the catalyst. As a result, the yield of dihydric phenol was 54.3% for catechol and 36. for hydroquinone.
At 2%, the total yield of catechol and hydroquinone was 9
It was 0.5%. The reaction solution was only colored in a very pale yellow color, and almost no accumulation of tar content was observed.

Example 15 A reaction was performed in the same manner as in Example 4 except that the gallium ion-supporting proton type β zeolite (0.20 g) of Reference Example 14 was used as the catalyst. As a result, the yield of dihydric phenol was 52.3% for catechol and 32.7% for hydroquinone.
And the total yield of catechol and hydroquinone was 85.0.
%Met. The reaction solution was only colored in a very reddish brown color, and almost no accumulation of tar content was observed.

Example 16 Indium ion-supported proton type β of Reference Example 15 was used as a catalyst.
The reaction was performed in the same manner as in Example 4 except that zeolite (0.20 g) was used. As a result, the yield of dihydric phenol was
53.6% catechol and 39.3% hydroquinone
And the total yield of catechol and hydroquinone was 92.9.
%Met. The reaction solution was only colored in a very reddish brown color, and almost no accumulation of tar content was observed.

Example 17 A reaction was performed in the same manner as in Example 4 except that the niobium-supported proton type β zeolite (0.20 g) of Reference Example 16 was used as the catalyst. As a result, the yield of dihydric phenol was 49.0% for catechol and 30.5% for hydroquinone, and the total yield of catechol and hydroquinone was 79.5%. The reaction solution was only colored in a very reddish brown color, and almost no accumulation of tar content was observed.

Example 18 A reaction was carried out in the same manner as in Example 4 except that the tantalum-supported proton type β zeolite of Reference Example 17 (0.20 g) was used as the catalyst. As a result, the yield of dihydric phenol was 52.4% for catechol and 35.7% for hydroquinone, and the total yield of catechol and hydroquinone was 88.1%. The reaction solution was only colored in a very reddish brown color, and almost no accumulation of tar content was observed.

Example 19 A reaction was carried out in the same manner as in Example 4 except that the zinc ion-supporting proton type β zeolite (0.20 g) of Reference Example 18 was used as the catalyst. As a result, the yield of dihydric phenol was 55.9% for catechol and 38.9% for hydroquinone, and the total yield of catechol and hydroquinone was 94.8%. The reaction solution was only colored in a very pale reddish brown,
Almost no accumulation of tar was observed.

Example 20 A reaction was performed in the same manner as in Example 4 except that the nickel ion-supported proton type β zeolite (0.20 g) of Reference Example 19 was used as the catalyst. As a result, the yield of dihydric phenol was 55.8% for catechol and 39.6% for hydroquinone.
And the total yield of catechol and hydroquinone was 95.4.
%Met. The reaction solution was only colored in a very reddish brown color, and almost no accumulation of tar content was observed.

Example 21 A reaction was carried out in the same manner as in Example 4 except that the manganese ion-supported proton type β zeolite (0.20 g) of Reference Example 20 was used as the catalyst. As a result, the yields of dihydric phenol were 55.0% for catechol and 38.8% for hydroquinone.
And the total yield of catechol and hydroquinone was 93.8.
%Met. The reaction solution was only colored in a very reddish brown color, and almost no accumulation of tar content was observed.

Example 22 A reaction was performed in the same manner as in Example 4 except that the cobalt ion-supporting proton type β zeolite (0.20 g) of Reference Example 21 was used as the catalyst. As a result, the yield of dihydric phenol was 57.5% for catechol and 40.5% for hydroquinone.
And the total yield of catechol and hydroquinone was 98.0.
%Met. The reaction solution was only colored in a very reddish brown color, and almost no accumulation of tar content was observed.

Example 23 The reaction was performed in the same manner as in Example 22 except that the reaction temperature was 120 ° C. As a result, the yields of dihydric phenol were 56.5% for catechol and 40.4% for hydroquinone,
The total yield of catechol and hydroquinone was 96.9%. The reaction solution was only colored in a very reddish brown color, and almost no accumulation of tar content was observed.

Example 24 Using the catalyst as the cobalt ion-supporting proton type β zeolite (0.20 g) of Reference Example 21, phenol (10.00
g), 3-pentanone (0.54 g) and 85 wt% phosphoric acid aqueous solution (0.02 g) were put in a 300 ml flask,
After replacing with a nitrogen atmosphere, the temperature was raised to 100 ° C. with stirring. Then, at this temperature, 0.10 g of 60
% Hydrogen peroxide solution was added dropwise, 1.5 minutes later, 3 minutes later, 4.5
After 10 minutes, 6 minutes, and 7.5 minutes, 0.10 g of each was added dropwise, and the reaction was allowed to proceed for 10 minutes from the first addition.
As a result, the yield of dihydric phenol was 5 for catechol.
2.4%, 38.4% of hydroquinone, and the total yield of catechol and hydroquinone was 90.6%. The reaction solution was only colored in a light reddish brown color, and almost no accumulation of tar content was observed.

Comparative Example 1 Example 8 except that the catalyst was Proton Type US-Y (0.20 g) manufactured by JGC Universal Co., Ltd. having Si / Al = 3.0.
The reaction was performed in the same manner as in. As a result, the yield of dihydric phenol was 11.0% for catechol and 5.
At 4%, the total yield of catechol and hydroquinone was 1.
It was 6.4%.

Comparative Example 2 A reaction was carried out in the same manner as in Example 8 except that the catalyst was Co ion-supported proton type US-Y (0.20 g) prepared in Reference Example 22. As a result, the yields of dihydric phenol were 14.9% for catechol and 8.1% for hydroquinone,
The total yield of catechol and hydroquinone was 23.0%.

Comparative Example 3 The reaction was performed in the same manner as in Example 8 except that the catalyst was proton type mordenite (0.20 g) manufactured by Tosoh Co., Ltd. having Si / Al = 6.0. As a result, almost no dihydric phenol was obtained.

Comparative Example 4 A reaction was carried out in the same manner as in Example 8 except that the Co ion-supported proton type mordenite (0.20 g) prepared in Reference Example 23 was used as the catalyst. As a result, almost no dihydric phenol was obtained.

Comparative Example 5 The reaction was carried out in the same manner as in Example 8 except that the catalyst was proton type ZSM-5 (0.20 g) manufactured by JGC Universal Co., Ltd. having Si / Al = 20.0. As a result, the yield of dihydric phenol was 16.8% for catechol and 6.7% for hydroquinone, and the total yield of catechol and hydroquinone was 23.5%.

Comparative Example 6 A reaction was carried out in the same manner as in Example 8 except that the Co ion-supporting proton type ZSM-5 (0.20 g) prepared in Reference Example 24 was used as the catalyst. As a result, the yield of dihydric phenol was
Catechol is 8.7%, hydroquinone is 2.4%,
The total yield of catechol and hydroquinone was 11.1%.

Comparative Example 7 A reaction was carried out in the same manner as in Example 8 except that TS-1 (0.20 g) manufactured by NE Chemcat having Si / Ti = 38.0 was used as the catalyst. As a result, the yield of dihydric phenol was 17.1% for catechol and 7.4 for hydroquinone.
%, The total yield of catechol and hydroquinone is 24.
It was 5%.

[0092]

[Table 2]

[0093]

[Table 3]

[0094]

[Effects of the Invention] A β-zeolite carrying a transition metal of the present invention, a Group 2B metal, a Group 3B metal of the third to sixth periods, or a Group 4B metal of the fifth to sixth periods, or a lanthanoid metal is used as a catalyst. In the presence of ketone and phosphoric acid, the dihydric phenol can be obtained in a high yield without causing accumulation of the tar component when oxidizing the monohydric phenol with peroxide. .

Continued front page    F-term (reference) 4H006 AA02 AC42 BA07 BA08 BA09                       BA11 BA66 BE32 DA15 FC52                       FE13                 4H039 CA60 CC30

Claims (2)

[Claims] 1. A transition metal, a Group 2B metal, a third period to a sixth period.
Characterized by oxidizing a monohydric phenol with a peroxide in the presence of a proton-type β zeolite carrying a group 3B metal of a period, a group 4B metal of a fifth period to a sixth period, or a lanthanoid metal, a ketone and phosphoric acid. Method for producing dihydric phenol. 2. The method for producing a dihydric phenol according to claim 1, wherein the peroxide is hydrogen peroxide or ketone peroxide.