JP2003026623A - Method for producing dihydric phenol - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a dihydric phenol in high yield by a highly active acid catalyst causing no corrosion, and oxidizing a monohydric phenol with a peroxide (e.g. hydrogen peroxide or a ketone peroxide) in the presence of a ketone and phosphoric acid. SOLUTION: The dihydric phenol is produced in high yield by using β-zeolite as the catalyst by oxidizing the monohydric phenol with the oxide (e.g. the hydrogen peroxide or the ketone peroxide) in the presence of the ketone and the phosphoric acid.

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 ketone and phosphoric acid.

[0002]

2. Description of the Related Art 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 catalyst. For example, a method in which hydrogen peroxide is used as a peroxide and sulfuric acid is used as a catalyst in the presence of a ketone and phosphoric acid is described in JP-A-52-65232 and JP-A-52-65233. . Sulfuric acid used as a catalyst in this method is corrosive, and there is a demand for the development of an alternative catalyst. As catalysts to replace sulfuric acid, for example, phosphotungstic acid and silicotungstic acid are disclosed in JP-A-52-78843, various sulfates are disclosed in JP-A-50-130727, and clay minerals are disclosed in JP-A-52-78723. It is described in Japanese Patent No. 142026, respectively. However, these methods have low yields on the basis of peroxides, and the development of higher activity catalysts has been awaited.

[0003]

The object of the present invention is to develop a highly active acid catalyst which is not corrosive, and oxidizes a monohydric phenol with a peroxide in the presence of a ketone and phosphoric acid to produce a high yield of dicarboxylic acid. It is to provide a method for producing a dihydric phenol.

[0004]

Means for Solving the Problems As a result of investigations for solving the above problems, the present inventors have found that a monohydric phenol is oxidized with a peroxide in the presence of a ketone and phosphoric acid to produce a dihydric phenol. The present invention was completed by finding that a dihydric phenol can be produced at a high yield by using β-zeolite that is not corrosive as a catalyst during production.

[0005]

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 include m- or p-ethylphenol, o-propylphenol, p-isopropylphenol, m-butylphenol, p-isobutylphenol, pt-butylphenol, m-isobutylphenol, p-pentylphenol, 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 linear or branched alkyl groups 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-trimethylphenol, 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, 2-isopropyl-5-methylphenol, 2-pentyl-6-methylphenol, 3-
Hexyl-5-methylphenol may be mentioned.

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 linear aliphatic monoketones 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 branched aliphatic monoketones include 3-methyl-2-butanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 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 cyclic monoketones include cycloalkyl monoketones 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 0.2: 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 preferably such that the weight ratio of phosphoric acid to monohydric phenol (phosphoric acid: monohydric phenol) is 0.0001: 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 ketone peroxides 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%.

The peroxide used in the present invention is preferably hydrogen peroxide or ketone peroxide. 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, and alkaline earth metal-supported proton-type β-zeolite is particularly preferable. The aluminum content in β zeolite is 1: 1 Al: Si (atomic ratio).
The ratio is preferably 0 to 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.

As the alkaline earth metal-supporting proton type β zeolite, the above-mentioned proton type β zeolite on which an alkaline earth metal is supported and fired can be used. Examples of alkaline earth metals include beryllium, magnesium, calcium, strontium, and barium.
Preferred are magnesium, calcium, strontium and barium. As a metal supporting method, a metal supporting method such as an ordinary ion exchange method, an impregnation method, a chemical vapor deposition (CVD) method, or a mechanical kneading method can be applied, but the ion exchange method is preferable.

The preparation of the alkaline earth metal-supported proton type β-zeolite by the ion exchange method was carried out according to the production research, 21,
7, (1969) 453-454 and the like. For example, the proton-type β zeolite is added to an alkaline earth metal nitrate-containing aqueous solution (alkaline earth metal salt concentration: 0.1 to 40% by weight) of an alkaline earth metal at 20 to 120 ° C. And 1-2
Heat treatment for 0 hours, wash with deionized water, etc.
After drying at ~ 150 ° C for 5 minutes to 24 hours, 300 to 650
It is obtained by baking at 1 ° C. for 1 to 10 hours. The alkaline earth metal ions introduced into the proton-type β zeolite have M ²⁺ / Al of 0.0001 to 10, more preferably 0.
01 to 1 (M ²⁺ represents an alkaline earth metal ion)
The ratio is preferably in the range (atomic ratio).

The β zeolite used in the present invention may be in the form of powder, granules, pellets or the like.
The shape according to the method for producing the dihydric phenol, for example, powder when produced using a liquid phase batch reactor,
Granules and the like are preferably used, and pellets and the like are preferable when a liquid phase flow reactor is used.

In the production of the dihydric phenol of the present invention, the reaction temperature is preferably 20 to 250 ° C, more preferably 40 to 150 ° 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.

In the present invention, a complexing agent for metal ions (for example, a phosphoric acid type complexing agent such as phosphoric acid monoalkyl ester or phosphoric acid dialkyl ester) may be used in combination.

As the reaction in the present invention, for example, monohydric phenol, hydrogen peroxide, ketone and phosphoric acid are fed to a reactor containing β-zeolite to oxidize the monohydric phenol to produce dihydric phenol. , A reaction of discharging the reaction mixture from the reactor, and the like.

The dihydric phenol produced by the present invention corresponds to the structure of the starting monohydric phenol, and is 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.

[0029]

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. As the reagents used in Examples and Comparative Examples, special grade products made by Wako Pure Chemical Industries, Ltd. were used. The yield of dihydric phenol is obtained according to the following equation. The analysis was performed by gas chromatography.

[0030]

[Equation 1]

Reference Example 1 (Preparation of Strontium Ion-Supporting Proton-Type β Zeolite) 0.47 g of strontium nitrate was dissolved in 20 ml of ultrapure water to prepare an aqueous solution 2 containing strontium ions.
0 ml was prepared. 2 g of a proton type β zeolite manufactured by Zeolyst International was immersed in the obtained aqueous solution,
Ion exchange between protons and strontium ions was performed at 85 ° C for 14 hours while keeping the temperature. The obtained suspension was suction filtered, dried at 110 ° C., and then calcined at 550 ° C. for 2.5 hours to obtain 1.9 g of strontium ion-supporting proton type β zeolite. The atomic ratio (Sr ²⁺ / Al) of strontium ions and Al introduced into the β zeolite by ICP emission analysis was 0.31.

Reference Example 2 (Preparation of Barium Ion-Supporting Proton-Type β Zeolite) The procedure of Reference Example 1 was repeated except that 0.58 g of barium nitrate was used. As a result, 1.9 g of barium ion-supporting proton type β zeolite was obtained. Barium ions and Al introduced into the β zeolite by ICP emission analysis
The atomic ratio (Ba ²⁺ / Al) was 0.34.

Reference Example 3 (Preparation of Proton-Type β Zeolite Bearing Magnesium Ion) The same preparation as in Reference Example 1 was carried out except that 0.57 g of magnesium nitrate hexahydrate was used. As a result, 1.9 g of magnesium ion-supported proton type β zeolite was obtained.
The atomic ratio (Mg ²⁺ / Al) of magnesium ions and Al introduced into the β zeolite was 0.29 by ICP emission spectrometry.

Reference Example 4 (Preparation of Calcium Ion-Supporting Proton Type β Zeolite) Except that 0.52 g of calcium nitrate tetrahydrate was used,
It was prepared in the same manner as in Reference Example 2. As a result, 1.9 g of calcium ion-supporting proton type β zeolite was obtained. ICP
The atomic ratio (Ca ²⁺ / Al) between the introduced calcium ion and Al in the β zeolite was 0.28 by optical emission analysis.
Met.

Example 1 0.20 g of proton type β zeolite manufactured by Zeolyst International, 10.00 g of phenol, 0.60 g of 4-methyl-2-pentanone and 0.03 g of 85% by weight phosphoric acid aqueous solution were placed in a 300 ml flask, After replacing with a nitrogen atmosphere, the temperature was raised to 80 ° C. with stirring. Then, at this temperature, 30 wt% hydrogen peroxide water 0.6
After dropping 2 g, the temperature was maintained for 30 minutes to carry out the reaction. As a result, the yield of dihydric phenol was 58% for catechol and 40% for hydroquinone, and the total yield of hydroquinone and catechol was 98%. The reaction solution was only colored in pale yellow, and almost no accumulation of tar content was observed.

Example 2 The reaction was performed in the same manner as in Example 1 except that the reaction temperature was 60 ° C. The yield of dihydric phenol was 5 for catechol.
5%, hydroquinone was 38%, and the total yield of hydroquinone and catechol was 93%. The reaction solution was only colored in a very pale yellow color, and almost no accumulation of tar content was observed.

Comparative Example 1 95% by weight sulfuric acid 0.04 g, phenol 10.00 g,
0.60 g of 4-methyl-2-pentanone and 0.03 g of 85% by weight phosphoric acid aqueous solution were placed in a 300 ml flask, the atmosphere was replaced with nitrogen, and the temperature was raised to 80 ° C. with stirring. Next, at this temperature, 0.63 g of 30 wt% hydrogen peroxide solution was added dropwise, and the temperature was maintained for 30 minutes to carry out the reaction. As a result, the yield of dihydric phenol was
Catechol was 50%, hydroquinone was 33%, and the total yield of hydroquinone and catechol was 83%.
The reaction solution was strongly colored in blackish brown, and accumulation of tar content was observed.

Comparative Example 2 The reaction was performed in the same manner as in Comparative Example 1 except that the reaction temperature was 60 ° C. As a result, the yield of dihydric phenol was 52% for catechol and 34% for hydroquinone, and the total yield of hydroquinone and catechol was 86%. The reaction solution was strongly colored in blackish brown, and accumulation of tar content was observed.

Comparative Example 3 The reaction was performed in the same manner as in Example 1 except that 0.20 g of the proton type ZSM-5 zeolite was used as the catalyst. As a result, the yield of dihydric phenol was 15% for catechol and 8% for hydroquinone, and the total yield of hydroquinone and catechol was 23%. The reaction solution was strongly colored in blackish brown, and accumulation of tar content was observed.

Example 3 0.20 g of proton type β zeolite manufactured by Zeolyst International, 10.00 g of phenol, 0.27 g of 3-pentanone, and 0.02 g of 85% by weight phosphoric acid aqueous solution were added.
After putting in a 00 ml flask and replacing the atmosphere with nitrogen,
The temperature was raised to 60 ° C with stirring. At this temperature,
0.10 g of 60% by weight hydrogen peroxide solution was added dropwise to 1.5.
After another 0.10 g, 3 minutes later 0.10 g was dropped,
The reaction was continued for 5 minutes from the first dropping. as a result,
The yield of dihydric phenol was 50% for catechol and 35% for hydroquinone, and the total yield of hydroquinone and catechol was 85%. The reaction solution was only colored in a very pale yellow color, and almost no accumulation of tar content was observed.

Example 4 The reaction was performed in the same manner as in Example 3 except that the reaction temperature was 100 ° C. The yield of dihydric phenol was 51% for catechol and 34% for hydroquinone, and the total yield of hydroquinone and catechol was 85%. 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 3 except that 0.20 g of the proton-type β zeolite carrying strontium ions in Reference Example 1 was used as the catalyst. As a result, the yield of dihydric phenol was 51% for catechol and 38% for hydroquinone,
The total yield of hydroquinone and catechol was 89%. The reaction solution was only colored in a very pale yellow color, and almost no accumulation of tar content was observed.

Example 6 The reaction was performed in the same manner as in Example 5 except that the reaction temperature was 100 ° C. As a result, the yield of dihydric phenol was 53% for catechol and 39% for hydroquinone, and the total yield of hydroquinone and catechol was 92%. 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 3 except that 0.20 g of the barium ion-supporting proton type β zeolite of Reference Example 2 was used as the catalyst. As a result, the yield of dihydric phenol was 49% for catechol and 37% for hydroquinone, and the total yield of hydroquinone and catechol was 86%. The reaction solution was only colored in a very pale yellow color, and almost no accumulation of tar content was observed.

Example 8 The reaction was carried out in the same manner as in Example 7 except that the reaction temperature was 100 ° C. As a result, the yield of dihydric phenol was 55% for catechol and 39% for hydroquinone, and the total yield of hydroquinone and catechol was 94%. The reaction solution was only colored in a very reddish brown color, and almost no accumulation of tar content was observed.

Example 9 Magnesium ion-supported proton type β of Reference Example 3 was used as a catalyst.
The reaction was performed in the same manner as in Example 8 except that 0.20 g of zeolite was used. As a result, the yield of dihydric phenol was
Catechol was 54%, hydroquinone was 39%, and the total yield of hydroquinone and catechol was 93%.
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 3 except that 0.20 g of the calcium ion-supporting proton type β zeolite of Reference Example 4 was used as the catalyst. As a result, the yield of dihydric phenol was 48% for catechol and 36% for hydroquinone, and the total yield of hydroquinone and catechol was 84%. The reaction solution was only colored in a very pale yellow color, and almost no accumulation of tar content was observed.

Example 11 The reaction was performed in the same manner as in Example 10 except that the reaction temperature was 100 ° C. As a result, the yield of dihydric phenol was
Catechol was 56%, hydroquinone was 40%, and the total yield of hydroquinone and catechol was 96%.
The reaction solution was only colored in a very reddish brown color, and almost no accumulation of tar content was observed.

Comparative Example 4 The reaction was carried out in the same manner as in Example 3 except that the catalyst was 0.04 g of 95% by weight sulfuric acid. As a result, the yield of dihydric phenol was catechol 44% and hydroquinone 29%,
The total yield of hydroquinone and catechol was 73%. The reaction solution was strongly colored in blackish brown, and accumulation of tar content was observed.

Comparative Example 5 The reaction was carried out in the same manner as in Example 4 except that 0.20 g of proton type Y zeolite (Si: Al = 10: 1) manufactured by JGC Universal Co., Ltd. was used as the catalyst. As a result, the yield of dihydric phenol was 3% catechol and 1% hydroquinone,
The total yield of hydroquinone and catechol was 4%. The reaction solution was strongly colored in blackish brown, and accumulation of tar content was observed.

Comparative Example 6 The reaction was carried out in the same manner as in Example 4 except that 0.20 g of a proton-type Y zeolite (Si: Al = 24: 1) manufactured by JGC Universal Co., Ltd. was used as the catalyst. As a result, the yield of dihydric phenol was 11% for catechol and 5% for hydroquinone.
The total yield of hydroquinone and catechol was 16%. The reaction solution was strongly colored in blackish brown, and accumulation of tar content was observed. The results of Examples 1 to 11 and Comparative Examples 1 to 6 are shown in Table 1.

[0052]

[Table 1]

By the method of using the non-corrosive β zeolite of the present invention as a catalyst, in the presence of ketone and phosphoric acid,
When oxidizing a monohydric phenol with a peroxide, a dihydric phenol can be obtained in a high yield without causing accumulation of a tar component.

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 4H006 AA02 AC42 BA06 BA71 BE32                       DA10 FC50 FE13                 4H039 CA60 CC30

Claims (5)

[Claims] 1. In the presence of β zeolite, ketone and phosphoric acid,
A process for producing a dihydric phenol, which comprises oxidizing a monohydric phenol with a peroxide. 2. The method for producing a dihydric phenol according to claim 1, wherein a proton type β zeolite is used as the β zeolite. 3. The method for producing a dihydric phenol according to claim 2, wherein the proton type β zeolite is an alkaline earth metal-supported proton type β zeolite. 4. The method for producing a dihydric phenol according to claim 1, wherein the peroxide is hydrogen peroxide or ketone peroxide. 5. A monohydric phenol, hydrogen peroxide, a ketone and phosphoric acid are fed to a reactor containing β-zeolite to oxidize the monohydric phenol to produce a dihydric phenol. Phenol manufacturing method.