JP2005230672A - METHOD FOR ACTIVATING MOLDED BODY PROTON TYPE beta ZEOLITE - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for activating a molded body proton type β zeolite, the highly activated molded body proton type β zeolite prepared by this method and a method for producing divalent phenols by oxidizing monovalent phenols with peroxides by using the prepared molded body proton type β zeolite. <P>SOLUTION: The molded body proton type β zeolite is activated by dipping into an acidic aqueous solution with pH of 0-6, drying and baking after washing by water. Production of the divalent phenols by oxidizing the monovalent phenols with the peroxides is efficiently performed in a flow system by using the molded body proton type β zeolite activated by this method. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a method for activating a shaped body proton type β zeolite, a shaped body proton type β zeolite obtained by the activation method, and further converting a monohydric phenol into a peroxide using the obtained shaped body proton type β zeolite. The present invention relates to a method for producing dihydric phenols that are oxidized at the same time.

Patent Document 1 and Patent Document 2 describe a method for producing dihydric phenols by oxidizing monohydric phenols using β zeolite as a catalyst. The β zeolites described in these documents are powders. However, it is not described that β zeolite (molded β zeolite) is used as a molded product in the flow reaction system in the production.
When the molded product β zeolite is used in the flow reaction system for the same production, the yield is reduced as compared to the batch reaction using powdered β zeolite (see Reference Example 1 and Comparative Example 2).
In order to solve such a problem, there has been a demand for a method for activating the molded β zeolite.
As a method for activating a molded zeolite, for example, Patent Document 3 discloses a method of activating a molded X-type zeolite by a calcium ion exchange method.

US Pat. No. 6,441,250 Japanese Patent Laid-Open No. 2003-26623 Japanese Patent Laid-Open No. 10-81511 Studies in Surface Science and Catalysis 143 (2002) p217-225 Journal of Physical Chemistry, 104 (2000), p. 2853-2859 Catalyst Preparation Chemistry, Kodansha (1980) p. 61-73 Microporous and Mesoporous Materials, 40 (2000) p. 271-281 Keulemans, “Gas Chromatography”, Reinhold, New York, 1957, p. 39

  An object of the present invention is to provide a method for activating a shaped body proton type β zeolite, a highly active shaped body proton type β zeolite obtained by the activation method, and further using the obtained shaped body proton type β zeolite. It is to provide a method for producing dihydric phenols by oxidizing monohydric phenols with a peroxide.

As a result of investigations to solve the above problems, the inventors of the present invention have obtained a method for activating a molded proton-type β zeolite, a highly active molded proton-type β zeolite obtained by this activation method, and further obtaining The present invention was completed by finding a production method for producing dihydric phenols in high yield by oxidizing monohydric phenols with peroxides using the molded proton-type β zeolite.
That is, the present invention is as follows.

  In the first invention, Al: Si (atomic ratio) of 1: 5 to 1: 10000 shaped proton proton-type zeolite is immersed in an acidic aqueous solution having a pH of 0 to 6, then washed with water and dried. Further, the present invention relates to a method for activating the molded proton-type β zeolite to be fired.

  The second invention relates to the shaped proton-type β zeolite obtained by the first invention.

  3rd invention is related with the manufacturing method of the bihydric phenol which oxidizes monohydric phenol with a peroxide using the shaping | molding body proton-type beta zeolite of 2nd invention in presence of a ketone.

  The method for activating the shaped body proton type β zeolite of the present invention is a simple method of immersing the shaped body β zeolite in an acidic aqueous solution, and the obtained shaped body β zeolite oxidizes monohydric phenols with a peroxide. A dihydric phenol can be produced in a high yield by using it for the production of a distribution system of dihydric phenols. Further, the time until a steady reaction yield is obtained in the production can be shortened.

The present invention is described in detail below.
The shaped proton β-zeolite used in the first invention is obtained by immersing the shaped β-zeolite in an acidic aqueous solution having a pH of 0 to 6, followed by washing with water, drying, and further firing.

  Here, as the molded β zeolite, a molded β zeolite in which Al: Si (atomic ratio) of the β zeolite is 1: 5 to 1: 10000 is preferably used. This ratio can be controlled by the composition of Si compound and Al compound, which are raw materials for β zeolite, such as sodium silicate and sodium aluminate.

  As this molded product β zeolite, a molded product proton type β zeolite, a molded product ammonium ion exchange type β zeolite, or a molded product alkali metal ion exchange type β zeolite which has not been treated with the acidic aqueous solution of the present invention is used. be able to.

  Here, as the molded proton-type β zeolite that has not been treated with an acidic aqueous solution, a commercially available product may be used, but a commercially available powdered proton-type β zeolite may be obtained by a general method such as that described in Non-Patent Document 4. You may shape | mold by the method. As the raw material powder proton type β zeolite itself, for example, powder proton type β zeolite prepared by the method described in Non-Patent Document 5 can be used.

  Moreover, as a molded object ammonium ion exchange type | mold beta zeolite, a commercially available thing can be used. Further, as a molded product alkali metal ion exchange type β zeolite, non-patented is to immerse proton type β zeolite in an aqueous solution (alkali metal ion-containing aqueous solution) of alkali metal nitrate, hydrochloride or sulfate such as sodium and potassium. It can be prepared by the method described in Document 6.

  Of these molded β zeolites, a molded proton β zeolite that has not been treated with the acidic aqueous solution of the present invention is preferably used.

  Alumina, silica, montmorillonite and the like are preferably used as the molding agent used for the molded β zeolite, and the weight ratio of β zeolite to the molding agent is 1: 100 to 1: 1.

  The acid used in the acidic aqueous solution of the present invention is not particularly limited, but aliphatic carboxylic acids (formic acid, acetic acid, propionic acid, citric acid, etc.), aromatic carboxylic acids (benzoic acid, etc.), amino acids (aspartic acid, Organic acids such as glutamic acid) or sulfonic acids (such as trifluoromethylsulfonic acid), or inorganic acids (such as nitric acid, phosphoric acid, hydrofluoric acid, hydrochloric acid, sulfuric acid). Of these, inorganic acids are preferable, and nitric acid is more preferable.

  As the acidic aqueous solution, one adjusted to pH 0-6 is used. Further, the amount used is not particularly limited as long as the molded body β zeolite is sufficiently immersed.

The immersion temperature of the molded β zeolite in the acidic aqueous solution is in the range of room temperature to 120 ° C, preferably 40 to 90 ° C.
The immersion time is 1 to 12 hours.

  Next, the molded β zeolite immersed in the acidic aqueous solution is taken out and washed with water until the washing solution becomes neutral. Here, the extraction method is not particularly limited, and for example, it is performed by a method such as filtration or decantation. Moreover, as water used for water washing, ion-exchange water is preferable.

The water-washed molded β zeolite is dried.
The temperature range for drying is 90 to 150 ° C. The drying time is 1 hour to 2 days, depending on the amount of the molded β zeolite.

After the drying, the molded β zeolite is calcined. Although the temperature range of baking is 350-950 degreeC, 450-850 degreeC is preferable.
The firing time is 1 to 24 hours.

FIG. 2 shows the spectrum of diffuse reflection IR of the shaped proton type β zeolite obtained by the above activation method. It is observed that the absorption at 3780 cm ⁻¹ is weaker than the spectrum of diffuse reflection IR of the molded proton-type β zeolite not subjected to the activation treatment (FIG. 3).

  The shaped proton-type β zeolite obtained by the activation method of the first invention is suitably used in the production of dihydric phenols that oxidize monohydric phenols with peroxides in the presence of ketones.

  Examples of the monohydric phenol used here include phenol, monovalent monoalkylphenol, monovalent halogenated phenol, and monovalent polyalkylphenol.

  Examples of the alkyl group possessed by the monovalent monoalkylphenol include linear or branched alkyl groups 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. These compounds include, for example, o-, m- or p-cresol, o-, 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 possessed by 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 are not involved in the reaction. These compounds include, for example, o-, m- or p-fluorophenol, o-, m- or p-chlorophenol, o-, m- or p-bromophenol, o-, m- or p-iodination. Phenol, 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-dibromophenol, 2,3,4-, 2,3,5-, 2,3,6-, 2,4,5-, 2,4,6 -Or 3,4,5-trichlorophenol.

  Examples of the alkyl group that the monovalent polyalkylphenol has 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, 2-isopropyl-5-methylphenol, 2-pentyl-6-methylphenol, 3-hexyl-5-methylphenol.

  Examples of the ketone used in the method for producing a dihydric phenol using the molded proton-type β zeolite of the present invention include monoketones and diketones. Monoketones include acyclic or cyclic monoketones. Examples of the acyclic monoketone include linear or branched aliphatic monoketone and aromatic monoketone having 3 to 20 carbon atoms, preferably 3 to 10 carbon atoms. The hydrogen atom of these compounds may be substituted with a halogen atom (fluorine atom, chlorine atom, bromine atom or iodine atom). The number and position of halogen atoms are not particularly limited as long as they are not involved 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, and 3-decanone. 6-undecanone, 2-tridecanone, 7-tridecanone, 2-tetradecanone, 2-pentadecanone, 2-hexadecanone, 2-heptadecanone, 3-octadecanone, 4-nonadecanone, 1-chloro-2-propanone, 1-chloro-3 -Heptanone, 1-bromo-3-heptanone.

  Examples of the branched aliphatic monoketone include 3-methyl-2-butanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 3,3-dimethyl-2-butanone, 2,4-dimethyl- Examples include 3-pentanone, 6-methyl-2-heptanone, 2,6-dimethyl-4-heptanone, and 2,2,4,4-tetramethyl-3-heptanone. Examples of the aromatic monoketone include acetophenone, benzophenone, 1-phenyl-3-propanone, 1-phenyl-1-butanone, 1-phenyl-3-butanone, 1-phenyl-3-pentanone, 1,3-diphenyl- 2-propanone is mentioned.

  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 (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), 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.

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

  Examples of the cyclic diketone include cyclic diketones having 5 to 12 carbon atoms. The hydrogen atom of these compounds may be substituted with a halogen atom (a fluorine atom, a chlorine atom, a bromine atom or an iodine atom), 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 as the ketone used in the production method of the dihydric phenol using the proton type β zeolite obtained by the activation method of the present invention is a linear or branched aliphatic monoketone, or a cyclic monoketone, and more preferred. Those are linear or branched aliphatic monoketones, among which 4-methyl-2-pentanone and 3-pentanone are particularly preferred.

  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.

  In the method for producing a dihydric phenol using the molded proton-type β zeolite of the present invention, a small amount of phosphoric acid is added in order to avoid the adverse effect of dissolved metal ions such as iron ions on the reaction. It doesn't matter. Examples of phosphoric acid include orthophosphoric acid, pyrophosphoric acid, metaphosphoric acid, triphosphoric acid, tetraphosphoric acid, polyphosphoric acid, phosphoric anhydride, and phosphoric acid aqueous solution, and a phosphoric acid aqueous solution is preferable. The concentration of the phosphoric acid aqueous solution is preferably 0.001 to 100% by weight.

  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 production method of the dihydric phenol using the shaped body proton type β zeolite obtained by the activation method of the present invention is an inorganic peroxide such as hydrogen peroxide, or a ketone peroxide, an aliphatic. Organic peroxides such as percarboxylic acid can be mentioned.

  Examples of the ketone peroxide include dialkyl ketone peroxide having 3 to 20 carbon atoms, 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% by weight or more, preferably 0.1 to 90% by weight of hydrogen peroxide water can be used, but 30 to 80% by weight is more preferable.

  As the peroxide used in the process for producing a dihydric phenol using the molded proton-type β zeolite obtained by the activation method of the first invention, hydrogen peroxide or ketone peroxide is preferable. 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 such that the molar ratio of peroxide to monohydric phenol (peroxide: monohydric phenol) is 1: 1 to 1: 100, more preferably 1: 5 to 1:20. It is preferable that

  Examples of the shape of the proton-type β zeolite obtained by the activation method of the present invention used in the production of the dihydric phenol include granules, extruded molded products, and tableted molded products.

  As a method for producing a dihydric phenol using the shaped body proton type β zeolite obtained by the activation method of the first invention, for example, monohydric phenol, hydrogen peroxide, ketone and phosphoric acid are pre-filled with β zeolite. For example, a reaction in which a monohydric phenol is oxidized to produce a dihydric phenol and the reaction mixture is discharged from the reactor.

  In the production of the dihydric phenol, the amount of the shaped proton type β zeolite used is such that the weight ratio of the proton type β zeolite to the monohydric phenol (β zeolite: monohydric phenol) is 1: 1 to 1: 500, The range is preferably 1: 5 to 1: 100.

  The reaction temperature in the production of the dihydric phenol is preferably 20 to 300 ° C, more preferably 40 to 200 ° C. The reaction time varies depending on, for example, the difference in Al: Si (atomic ratio) of the proton type β zeolite and the reaction temperature, but is not particularly limited. The reaction can be performed at atmospheric pressure, but may be performed under reduced pressure or increased pressure.

  The dihydric phenol obtained by the production of the dihydric phenol can be obtained as one kind or a mixture of several kinds corresponding to the structure of the monohydric phenol of the raw material. These dihydric phenols can be obtained by separation and purification by a conventional method.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, this invention is not restrict | limited by these Examples.

  The yield of dihydric phenol is determined according to the following formula. The analysis was performed by gas chromatography.

Example 1. (Preparation of H / βHNO ₃ (38))
Eggplant flask containing 5.0 g of a molded proton-type β zeolite (hereinafter referred to as H / β (38)) made by Zeolis with Al: Si = 1: 38, and 40 ml of an aqueous nitrate solution (pH = 0.96). The mixture was heated to 80 ° C. in an oil bath and stirred. After 2 hours, the zeolite was filtered, washed with ion-exchanged water, dried at 110 ° C., and then air calcined at 550 ° C. for 2.5 hours (the obtained molded proton-type β zeolite was hereinafter referred to as H / βHNO _3. (Described as (38)).
The spectrum of the diffuse reflection IR of the obtained molded proton-type β zeolite (H / βHNO ₃ (38)) is shown in FIG.

Comparative Example 1
After putting 0.20 g of powder obtained by pulverizing H / β (38), 10.0 g of phenol, 0.27 g of 3-pentanone, and 0.02 g of 85 wt% phosphoric acid aqueous solution into a 300 ml flask, and substituting the nitrogen atmosphere, Heat to 100 ° C. with stirring. Next, at this temperature, 0.10 g of 60% by weight hydrogen peroxide water was dropped, and further 0.10 g after 1.5 minutes, further 0.10 g was dropped after 3 minutes, and reacted for 5 minutes from the first drop. .
As a result, the yield of dihydric phenol was 86.6%.

Reference Example 1 (Batch reaction using powdered proton type β zeolite)
Put 0.20 g of powdered proton type β zeolite made by Zeolis with Al: Si = 1: 38, 10.0 g of phenol, 0.27 g of 3-pentanone, 0.02 g of 85 wt% phosphoric acid aqueous solution in a 300 ml flask, After replacing with a nitrogen atmosphere, the temperature was raised to 100 ° C. with stirring. Next, at this temperature, 0.10 g of 60% by weight hydrogen peroxide water was dropped, and further 0.10 g after 1.5 minutes, further 0.10 g was dropped after 3 minutes, and reacted for 5 minutes from the first drop. .
As a result, the yield of dihydric phenol was 86.7%.

  From Comparative Example 1 and Reference Example 1, it can be seen that when the molded body is pulverized and used as a powder, it has almost the same activity as that of an unmolded powder proton type β zeolite.

Comparative Example 2
A glass reaction tube having a diameter of 10.0 mm was filled with H / β (38) having a particle diameter of 0.5 mm to 1 mm. The catalyst volume at this time was adjusted to 2.4 cm ³ and the height to 3 cm. The reactant components were circulated through the reaction tube heated to 100 ° C. The composition of the reaction product was phenol: 3-pentanone: 60% hydrogen peroxide solution: phosphoric acid (H ₃ PO ₄ ) = 100: 2.7: 3.0: 0.01 (mass ratio), and the space velocity was 10 ˜12 h ⁻¹ .
The yield was calculated every hour and the reaction was carried out for a total of 7 hours. As a result, the dihydric phenol yield was almost constant from 78.7% to 80.1% from the 3rd hour after the start of the reaction until the end of the reaction. (FIG. 1).

Example 2
The reaction was conducted in the same manner as in Comparative Example 1 except that the catalyst used was H / βHNO ₃ (38).
As a result, the dihydric phenol yield was almost constant from 84.7% to 86.6% from the second hour after the start of the reaction to the end of the reaction (FIG. 1).

The time transition of the dihydric phenol yield in a distribution system when H / β (38) and H / βHNO ₃ (38) are used as catalysts (Example 2 and Comparative Example 2). Diffuse reflection IR spectrum of H / βHNO ₃ (38). Diffuse reflection IR spectrum of H / β (38).

Claims (4)

  A shaped proton type β zeolite having an Al: Si (atomic ratio) ratio of 1: 5 to 1: 10000 is immersed in an acidic aqueous solution having a pH of 0 to 6, then washed with water, dried, and further calcined. A method for activating molded proton-type β zeolite, characterized in that:   2. A shaped proton-type zeolite obtained by the activation method according to claim 1.   A process for producing a dihydric phenol, which comprises oxidizing a monohydric phenol with a peroxide using the β zeolite according to claim 2. The method for producing a dihydric phenol according to claim 3, wherein the peroxide is hydrogen peroxide or ketone peroxide.

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