JP2002119863A - Hydrogen peroxide decomposition catalyst, hydrogen peroxide decomposition catalyst composition and method for cracking hydrogen peroxide - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a catalyst and catalyst composition which have excellent chemical stability, are inexpensively and easily usable and can surely convert hydrogen peroxide to a safe substance and a method for decomposing the hydrogen peroxide using such catalyst and the catalyst composition. SOLUTION: The cyclic phenol sulfide metal complex expressed by the general formula (1) (where X is a hydrogen atom, hydrocarbon group, acyl group, carboxyalkyl group or carbamoylalkyl group; Y is a hydrogen atom, hydrocarbon halide group, halogen atom, acyl group, hydroxyl group, carboxyl group, amide group, amino group, nitro group, cyano group, chlorosulfonic acid group, alkoxysulfonyloxy group, sulfonic acid group or metal salt, ammonium salt, lower alkyl ammonium salt, lower alkanol ammonium salt or pyridinium salt of the sulfonic acid group; a plurality of X and Y may be same or different; (n) is an integer from 4 to 8; M is a transition metal or group IIB metal; (p) and (q) are an integer of >=1 indicating composition ratios) is used as the catalyst.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a hydrogen peroxide decomposition catalyst and a hydrogen peroxide decomposition catalyst composition having a cyclic phenol sulfide metal complex as an active site. The present invention also relates to a method for decomposing hydrogen peroxide using the catalyst or the catalyst composition.

[0002]

2. Description of the Related Art Hydrogen peroxide is an oxidizing agent used in many industrial applications such as sterilization, bleaching, and chemical synthesis. However, when acting on the human body, it is a substance that triggers carcinogenicity and aging of biological components. And the residue is expected to be reliably decomposed. In addition, oxygen peroxide normally taken into the body also produces hydrogen peroxide due to the effects of stress, drugs, tobacco, alcohol and various foods, and in addition to aging,
It is thought to cause tumors and inflammation. In vivo, such enzymes are decomposed by various enzymes,
If it is removed, but it cannot be sufficiently decomposed due to an imbalance in physiological balance or the like, it is required that at least exogenous hydrogen peroxide be surely decomposed and removed so as not to be taken into a living body. For this purpose, when a reducing agent is used to decompose hydrogen peroxide, a harmful substance may be secondarily generated as a decomposition product, and thus alternative means have been required.

[0003]

That is, an object of the present invention is to provide a catalyst which has excellent chemical stability, is inexpensive and can be used easily, and which can surely convert hydrogen peroxide into a safe substance. It is to provide a catalyst composition. Another object of the present invention is to provide a method for decomposing hydrogen peroxide using the catalyst or the catalyst composition.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies on such problems, and as a result, the present inventors have already disclosed the production method thereof, and have disclosed 25, 26, 27, 28-tetrahydroxy. -2,8,14,20-tetrathia [1.
9.3.1.1 ^3,7 1 ^9,13 1 ^15,19] Okutakosa -1 (25), 3,5,7 (28), 9,11,1
3 (27), 15, 17, 19 (26), 21, 23
A cyclic alkylphenol sulfide metal complex formed by mixing and contacting a metal ion with a cyclic alkylphenol sulfide such as dodecaene-5,11,17,23-sodium tetrasulfonate has a hydrogen peroxide decomposition activity similar to that of the natural enzyme catalase. The inventors have found that hydrogen peroxide molecules can be easily, safely and efficiently converted into oxygen molecules and water, and have completed the present invention. That is, the present invention relates to the general formula (1)

[0005]

Embedded image (1)

Wherein X is a hydrogen atom, a hydrocarbon group, an acyl group, a carboxyalkyl group or a carbamoylalkyl group, and Y is a hydrogen atom, a hydrocarbon group, a halogenated hydrocarbon group, a halogen atom, an acyl group, Hydroxyl group, carboxyl group, amide group, amino group, nitro group, cyano group, chlorosulfonic acid group, alkoxysulfonyloxy group, sulfonic acid group, or sulfonic acid group metal salt, ammonium salt, lower alkyl ammonium salt, lower alkanol ammonium A salt or a pyridinium salt,
And Y may be the same or different. n is 4 ~
8 is an integer of 8, M is a transition metal or a Group IIB metal,
wherein p and q are integers of 1 or more representing the composition ratio). The present invention also provides a hydrogen peroxide decomposition catalyst composition characterized by mixing or supporting the above-mentioned cyclic phenol sulfide metal complex on a solid carrier. Further, the present invention provides a method for decomposing hydrogen peroxide, which comprises contacting the hydrogen peroxide decomposition catalyst or the hydrogen peroxide decomposition catalyst composition with hydrogen peroxide. Hereinafter, the present invention will be described in detail.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION In the general formula (1), X is a hydrogen atom,
Hydrocarbon group, acyl group, carboxyalkyl group, or
It is a rubamoylalkyl group. Carbon number of hydrocarbon group of X
Is not particularly limited as long as it is 1 or more, preferably 1 to
6. Hydrocarbon groups include methyl, ethyl, n-propyl
Ropyl, isopropyl, n-butyl, n-pentyl, n
-Alkyl groups such as hexyl, and alkene such as vinyl and allyl
Alicyclic hydrocarbon groups such as phenyl, cyclohexyl,
And aromatic hydrocarbon groups such as Also, X
The carbon number of the acyl group is not particularly limited as long as it is 1 or more.
However, it is preferably 1 to 7. Suitable examples of acyl groups
As formyl, acetyl, propionyl, butyric
, Valeryl, oxalyl, malonyl, succinyl,
Nzoyl, acryloyl, methacryloyl, crotonyl
And the like. Carbon number of the carboxyalkyl group of X
Is not particularly limited as long as it is 2 or more, preferably 2 to
Thirteen. Suitable examples of the carboxyalkyl group
-CH₂COOH, -CH₂CH ₂COOH,-
CH (CH₃) COOH, -C (CH₃)₂COOH
And so on. Carbon number of the carbamoylalkyl group of X
Is not particularly limited as long as it is 2 or more, preferably 2 to
Thirteen. Suitable examples of the carbamoylalkyl group include
Is -CH₂NH₂, -CH₂CH₂CONH₂,
-CH (CH₃) CONH ₂, -C (CH₃)₂CON
H₂, -CH₂CONH (CH₃), -CH₂CONH
CH (CH₃) Ph and the like.

When the number of carbon atoms of these hydrocarbon group, acyl group, carboxyalkyl group or carbamoylalkyl group increases, the ability to form a complex with a metal generally decreases. In the catalyst composition of the present invention, the metal complex moiety exhibits activity,
It is preferable that the ability to form a complex with a metal is high. In the general formula (1), 4 to 8 Xs exist in one molecule,
These Xs may be the same or different. When the abundance of X other than a hydrogen atom in a plurality of Xs is high, the ability to form a complex with a metal is reduced. When X other than a hydrogen atom has an average carbon number of 3 or more, the number of Xs other than a hydrogen atom is n-
X is preferably 2 or less, and X other than a hydrogen atom has an average carbon number of 3
When it is less than 1, the number of Xs other than a hydrogen atom is preferably n-1 or less. Y in the general formula (1) is a hydrogen atom, a hydrocarbon group,
Halogenated hydrocarbon group, halogen atom, acyl group, hydroxyl group, carboxyl group, amide group, amino group, nitro group,
Sulfonates such as a metal salt, an ammonium salt, a lower alkylammonium salt, a lower alkanolammonium salt or a pyridinium salt of a cyano group, a chlorosulfonic acid group, an alkoxysulfonyloxy group, a sulfonic acid group or a sulfonic acid group. Among these, Y is preferably a chlorosulfonic acid group, an alkoxysulfonyloxy group, a sulfonic acid group, or a metal salt, an ammonium salt, a lower alkylammonium salt, a lower alkanolammonium salt or a pyridinium salt of a sulfonic acid group. The carbon number of the hydrocarbon group of Y is not particularly limited as long as it is 1 or more, but is preferably 1 to 30, and more preferably 1 to 18. Examples of these hydrocarbon groups include a saturated aliphatic hydrocarbon group, an aromatic hydrocarbon group, an aromatic-aliphatic hydrocarbon group, and an alicyclic hydrocarbon group.

Suitable examples of the saturated aliphatic hydrocarbon group include, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-butyl
-Pentyl, neopentyl, n-hexyl, n-octyl, tert-octyl, n-nonyl, isononyl, n
-A group consisting of dodecyl and a polymer or copolymer of ethylene, propylene and butylene. Suitable specific examples of the unsaturated aliphatic hydrocarbon group include, for example, vinyl, allyl, isopropenyl, 2-butenyl, and a group of a polymer of acetylene, butadiene, isoprene, or a copolymer thereof. . Suitable specific examples of the alicyclic hydrocarbon group include, for example, cyclohexyl, methylcyclohexyl, ethylcyclohexyl and the like. Suitable specific examples of the alicyclic-aliphatic hydrocarbon group include, for example, cyclohexylmethyl, cyclohexylethyl and the like.

Suitable specific examples of the aromatic hydrocarbon group include, for example, aryl groups such as phenyl and naphthyl, and alkylaryl groups such as methylphenyl, dimethylphenyl, trimethylphenyl, ethylphenyl and butylphenyl. Suitable specific examples of the aromatic-aliphatic hydrocarbon include, for example, benzyl, phenylethyl, phenylpropyl, phenylbutyl, methylphenylethyl and the like. In addition, these hydrocarbon groups include a halogen atom, an acyl group, a hydroxyl group, a carboxyl group, an amide group,
It may be substituted by a functional group such as an amino group or a nitro group. Examples of the halogenated hydrocarbon group include those in which the same hydrocarbon groups as those described above for Y are substituted with a halogen atom, and preferred ones are also the same. The halogen atom may be any of fluorine, chlorine, bromine and iodine. As the acyl group, those similar to the acyl group described in the aforementioned X can be mentioned, and preferred ones are also the same. In the hydroxyl group, carboxyl group, amide group, and amino group, part or all of the hydrogen atoms constituting each group may be substituted with a hydrocarbon group. As the hydrocarbon group, those similar to the hydrocarbon groups described in X are mentioned, and preferred ones are also the same.

The alkyl portion of the alkoxysulfonyloxy group is the same as the above-mentioned Y hydrocarbon group. Also,
In the general formula (1), Y is a sulfonic acid salt such as a metal salt of a sulfonic acid group, an ammonium salt, a lower alkyl ammonium salt, a lower alkanol ammonium salt, and a pyridinium salt. Specific examples of the metal in the metal salt of the sulfonic acid group include alkali metals such as sodium and potassium, and alkaline earth metals such as calcium and magnesium. Specific examples of lower alkylammonium in the lower alkylammonium salt of a sulfonic acid group include methylammonium, ethylammonium, n-propylammonium, iso-propylammonium, n-butylammonium, iso-butylammonium, sec.
-Butyl ammonium, tert-butyl ammonium, dimethyl ammonium, diethyl ammonium, di-n-propyl ammonium, di-iso-propyl ammonium, di-n-butyl ammonium, di-iso
-Butylammonium, di-sec-butylammonium, di-tert-butylammonium, trimethylammonium, triethylammonium and the like.

Specific examples of the lower alkanol ammonium in the lower alkanol ammonium salt of a sulfonic acid group include ethanol ammonium, diethanol ammonium, triethanol ammonium and the like. Specific examples of the pyridinium salt of a sulfonic acid group include pyridinium and N-methylpyridinium. In the general formula (1), Y is 4 to 4 in one molecule.
Although there are eight, each of those Y may be the same or different. N in the general formula (1) is
It is an integer of 4 to 8. M in the general formula (1) is a transition metal or a Group IIB metal. Specific examples of the transition metal include manganese (Mn), iron (Fe), and cobalt (C
o), nickel (Ni), copper (Cu) and the like.
Group IB metals include zinc (Zn) and the like. Of these, Fe (III), Fe (II), Ni, Cr,
Ti, Pd and the like are preferable. P and q in the general formula (1) represent composition ratios and are integers of 1 or more. The ratio of p to q varies depending on the type of metal, the type of cyclic phenol sulfide, the type of solvent used, and the like, but is usually about 1: 1.

The method for producing the cyclic phenol sulfide metal complex of the general formula (1) is not particularly limited. For example, a solution in which a cyclic phenol sulfide is dissolved and a solution in which metal ions are dissolved are stirred, shaken, and heated. It can be produced by contacting with a method such as reflux. The solvent to be used only needs to dissolve each substance.When the oil-soluble cyclic phenol sulfide is used as a raw material, benzene, an aromatic solvent such as toluene, chloroform, a halogenated solvent such as dichloromethane, hexane,
Examples include aliphatic solvents such as heptane. When a water-soluble cyclic phenol sulfide is used, water, a ketone solvent such as acetone and methyl ethyl ketone, and an alcohol solvent such as methanol and ethanol can be used.

As the metal ion source, organic metal salts and inorganic metal salts such as metal halides, metal sulfates, metal nitrates, metal salts of toluenesulfonic acid, and metal salts of picric acid can be used. And an organic complex such as a carbonyl complex such as an acetylacetone complex. When the raw material is a metal salt, the metal ion is preferably made into an aqueous solution and brought into contact with the above solution. However, a water-soluble solvent such as a ketone or an alcohol may be used together. In the case of an organic complex, an aprotic organic solvent is preferable.Specifically, for example, aromatic solvents such as benzene and toluene, halogen-based solvents such as chloroform and dichloromethane, and aliphatic solvents such as hexane and heptane are used. No. The concentration of the metal in the solvent is not particularly limited, but is preferably 1 × 10 ⁻⁶ M or more, particularly preferably 1 × 10 ⁻⁵ M or more. The time for contacting the cyclic phenol sulfide with the metal ion solution is usually 1 to 48 hours.

The obtained cyclic phenol sulfide metal complex
Can be isolated by ordinary methods such as distilling off the solvent.
However, purification operations such as recrystallization may be performed as necessary.
In addition, the use of the cyclic phenol sulfide metal complex
Is mixed or supported on a solid carrier
The carrier can be silica gel, ion
Ion exchangers such as exchange resins, cellulose and chitosan are preferred.
Good. As the loading method, cyclic phenol sulfide gold
The solid-liquid contact between the metal complex solution and the carrier
Mixing a carrier with a metal sulfide metal complex solution and stirring
The method is simple. Cyclic phenol sulfide metal complexes on supports
The amount of body supported depends on the carrier and preparation conditions, but usually
1 to 500 μmol can be supported per 1 g of carrier
You. The decomposition of hydrogen peroxide by cyclic phenol sulfide
In a medium containing hydrogen peroxide, the above cyclic phenol sulfide
What is necessary is just to contact a metal complex and hydrogen peroxide. The contact temperature is
It can be carried out if the temperature is 0 ° C or higher, preferably 20 ° C or higher.
Above, more preferably 40 ° C. or higher. Contact time is temperature
15 to 100 at 50 ° C.
Minutes, more preferably 30 to 60 minutes. Of hydrogen peroxide
The higher the concentration, the more efficiently the reaction proceeds,
At very high concentrations, heat generation and explosion due to rapid progress of the reaction
Etc., preferably 1 to 10000 ppm,
More preferably, it is 10 to 1000 ppm. Ring
If the amount of the metal complex used is too small, the reaction is slow,
Because too much is wasteful, the preferred amount is
1 to 100 mmol, more preferably, per 1 mg of hydrogen oxide
Is 2 to 50 mmol. For decomposition reaction of hydrogen peroxide
The pH should be in the range of 7 to 11.
In particular, it is particularly preferable to set the range of 8 to 11. pH
Adjustments can be made by adding buffer.
You. As the buffer, KH₂PO₄-Na₂B₄O ₇system
Buffer solution, Na₂B₄O₇-Na₂Co₃System buffer
No.

[0016]

EXAMPLES The present invention will be described in more detail with reference to the following Examples, which are illustrative only and do not limit the present invention.

[Production Example 1] 5,11,17,23-tetra-tert
-Butyl-25,26,27,28-tetrahydroxy-2,8,14,20-tetrathia [1.9.3.1.
1 ^3, 7 ^{1 9, 13} 1 ^{15, 19]} Okutakosa -1 (2
5), 3, 5, 7 (28), 9, 11, 13 (27),
15, 17, 19 (26), 21, 23-dodecaene (a cyclic phenol sulfide of the formula (1), wherein X is H and Y is t
ert-butyl group, n = 4. ) Synthesis. 4-tert-butylphenol 4 in a glass flask
To 5.2 g, 14.4 g of elemental sulfur, 3.0 g of sodium hydroxide and 7.60 g of tetraethylene glycol dimethyl ether were added, and the mixture was gradually heated to 230 ° C. over 4 hours with stirring under a nitrogen atmosphere, and further 2 hours. Stirred. During this time, water and hydrogen sulfide generated by the reaction were removed. The reaction mixture was cooled to room temperature and ether 500
After adding and dissolving the solution, the solution was hydrolyzed with a 1N aqueous sulfuric acid solution. The separated ether layer was washed with water and dried over magnesium sulfate. The reaction mixture obtained after distilling off ether was further separated by silica gel column chromatography (hexane / chloroform) to obtain a crude product.
This was recrystallized from chloroform / acetone to give colorless and transparent crystals 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetrahydroxy-2,8,14,20. -Tetrathia [1.
9.3.1.1 ^3,7 1 ^9,13 1 ^15,19] Okutakosa -1 (25), 3,5,7 (28), 9,11,1
3 (27), 15, 17, 19 (26), 21, 23
26.5 g of dodecaene was obtained (yield 45%).

[0017]

[Production Example 2] 25,26,27,28-tetrahydroxy-2,8,14,20-tetrathia [1.9.
1.1 ^3,7 1 ^{9, 13} 1 ^{15, 19]} Okutakosa -1
(25), 3, 5, 7 (28), 9, 11, 13 (2
7), 15, 17, 19 (26), 21,23-dodecaen-5,11,17,23-sodium tetrasulfonate (a cyclic phenol sulfide of the formula (1), wherein X is H, Y
Is sodium sulfonate, n = 4. ) Synthesis. 5,11,17,23-tetra-t obtained in Production Example 1
tert-butyl-25,26,27,28-tetrahydroxy-2,8,14,20-tetrathia [1.9.
3.1.1 ^3,7 1 ^9,13 1 ^15,19] Okutakosa -1 (25), 3,5,7 (28), 9,11,13
(27), 15, 17, 19 (26), 21,23-dodecaene (152 mg) was suspended in 95% by mass of concentrated sulfuric acid (15 ml), and the suspension was heated to 80 ° C. and reacted for 4 hours. After allowing the reaction mixture to cool, it was diluted with 100 ml of ion-exchanged water, the insoluble matter was filtered off, and sodium chloride was added for salting out to give 25, 26, 27, 28-tetrahydroxy-2 as a white solid. ,
8,14,20-tetrathia [1.9.9.3.1.1
^3,7 1 ^9,13 1 ^15,19] Okutakosa -1 (2
5), 3, 5, 7 (28), 9, 11, 13 (27),
15, 17, 19 (26), 21, 23-dodecaene
Sodium 5,11,17,23-tetrasulfonate 2
03 mg was obtained (yield 74%).

[0018]

[Production Example 3] Cyclic phenol sulfide iron supported on ion exchanger
(II) Production of Complex Composition Cellulose anion exchanger cellul was added to 20 ml of water.
of A500 (made by Seikagaku Corporation)
The mixture was made turbid, and the cyclic pheno obtained in Production Example 2 was stirred under stirring.
Sulfide aqueous solution (50 μmol / 50 ml) is dropped
After completion of the dropwise addition, stirring was continued for another 60 minutes. Get
The suspension obtained was filtered using a membrane filter to obtain
After the washed solid is washed on the filter, it is taken out.
To P₂O₅In a desiccator with coexisting, dried under reduced pressure,
An ion exchanger-supported cyclic phenol sulfide was obtained. next,
The obtained ion exchanger-supported cyclic phenol sulfide was 10
0 mg and 20 ml of water are mixed, and the suspension with stirring is added to the suspension.
^-2M metal salt (Fe (NH₄)₂(SO ₄)₂6H
₂O) 10 ml of an aqueous solution is added dropwise, and after the addition,
Stirring continued for a minute. Transfer the resulting suspension to a membrane
Filter using a filter and filter the resulting solid on the filter.
Take out after washing with water₂O₅Coexisting
After drying under reduced pressure in a desiccator,
A metal sulfide metal complex composition was obtained. 1 g of ion exchanger
Loading amount of cyclic phenol sulfide metal complex per unit is 10
0 μmol.

[0019]

[Production Example 4] Production Fe _{(NH 4)} of the ion exchanger carrying cyclic phenol sulfide of iron (III) complex composition _{2 (SO 4)} in place of ₂ 6H 2 O, Fe
Except that Cl ₃ 6H ₂ O was used, it was produced in the same manner as in Production Example 3. The loading amount of the cyclic phenol sulfide metal complex per 1 g of the ion exchanger is 100 μmol.

[Production Example 5] Production _{Fe (NH 4) 2 (SO} 4) of the ion exchanger carrying cyclic phenol sulfide cobalt complex composition in place of ₂ 6H 2 O, Co
Except for using Cl ₂ 6H ₂ O, it was produced in the same manner as in Production Example 3. The loading amount of the cyclic phenol sulfide metal complex per 1 g of the ion exchanger is 100 μmol.

[Production Example 6] Production _{Fe (NH 4) 2 (SO} 4) of the ion exchanger carrying cyclic phenol sulfide copper complex composition in place of ₂ 6H 2 O, Cu
Except for using Cl ₂ 2H ₂ O, it was produced in the same manner as in Production Example 3. The loading amount of the cyclic phenol sulfide metal complex per 1 g of the ion exchanger is 100 μmol.

[0020]

[Production Example 7] Production Fe _{(NH 4)} of the ion exchanger carrying the cyclic phenol sulfide of manganese complex composition _{2 (SO 4)} in place of ₂ 6H 2 O, Mn
Production Example 3 except that (CH ₃ COO) ₂ 4H ₂ O was used.
It was manufactured by the same operation as described above. The amount of cyclic phenol sulfide metal complex supported per 1 g of ion exchanger is 100 μmol.
It is.

[Production Example 8] Production _{Fe (NH 4) 2 (SO} 4) of the ion exchanger carrying cyclic phenol sulfide nickel complex composition in place of ₂ 6H 2 O, Ni
Production Example 3 except that (CH ₃ COO) ₂ 4H ₂ O was used.
It was manufactured by the same operation as described above. The amount of cyclic phenol sulfide metal complex supported per 1 g of ion exchanger is 100 μmol.
It is.

[Production Example 9] Production _{Fe (NH 4) 2 (SO} 4) of the ion exchanger carrying cyclic phenol sulfide zinc complex composition in place of ₂ 6H 2 O, Zn
Production Example 3 except that (CH ₃ COO) ₂ 2H ₂ O was used
It was manufactured by the same operation as described above. The amount of cyclic phenol sulfide metal complex supported per 1 g of ion exchanger is 100 μmol.
It is.

[0021]

Example 1 Decomposition of Hydrogen Peroxide by Ion Exchanger-Supported Cyclic Phenolsulfide Iron (III) Complex Composition A buffer solution 3 was added to 2 ml of an aqueous solution containing 70 μg of hydrogen peroxide.
The ion-exchanger-supported cyclic phenol sulfide iron (III) complex composition 20 mg obtained in Production Example 3 was added thereto.
Was added and shaken at 50 ° C. for 30 minutes. After allowing the complex to settle by standing, 2 ml of the supernatant was taken and the amount of hydrogen peroxide remaining therein was quantified. Buffer solution is 0.01M KH ₂
PO ₄ 0.05M of _{Na 2 B 4 O 7 (pH6~9} ),
0.05M of _Na 2 _B 4 _O 7 -0.05M of _Na 2 Co
₃ (pH 10-11) was used. The determination of hydrogen peroxide is
The following method was used. 0.5 ml of 4-aminoantipyrine aqueous solution (2 mg / ml), 0.5 ml of phenol aqueous solution (10 mg / ml), 2 ml of pH7 buffer solution and peroxidase solution (25 uni) were added to 2 ml of the supernatant.
(t / ml) 0.5 ml and shaken at room temperature for 15 minutes. In this solution, the absorbance at 505 nm of the quinoid dye formed by the action of peroxidase from hydrogen peroxide, 4-aminoantipyrine and phenol was measured, and the result of measuring the residual amount of hydrogen peroxide in comparison with the blank was shown in Table 1. Indicated.

[0022]

Example 2 The ion-exchanger-supported cyclic phenol sulfide iron obtained in Preparation Example 4 was replaced with the iron-exchanger-supported cyclic phenol sulfide iron (III) complex composition obtained in Preparation Example 3.
(II) The procedure was performed in the same manner as in Example 1 except that the complex composition was used. Table 1 shows the measurement results of the residual amount of hydrogen peroxide.

Example 3 In place of the ion-exchanger-supported cyclic phenol sulfide iron (III) complex composition obtained in Production Example 3, an ion-exchanger-supported cyclic phenol sulfide cobalt complex composition obtained in Production Example 5 Was carried out in the same manner as in Example 1 except that Table 1 shows the measurement results of the residual amount of hydrogen peroxide.

Example 4 In place of the ion-exchanger-supported cyclic phenol sulfide iron (III) complex composition obtained in Production Example 3, the ion-exchanger-supported cyclic phenol sulfide copper complex composition obtained in Production Example 6 Was carried out in the same manner as in Example 1 except that
Table 1 shows the measurement results of the residual amount of hydrogen peroxide.

[0023]

Example 5 An ion exchanger-supported cyclic phenol sulfide manganese complex composition obtained in Production Example 7 was used instead of the ion exchanger-supported cyclic phenol sulfide iron (III) complex composition obtained in Production Example 3. Was carried out in the same manner as in Example 1 except that Table 1 shows the measurement results of the residual amount of hydrogen peroxide.

Example 6 The ion-exchanger-supported cyclic phenol sulfide nickel complex composition obtained in Production Example 8 was used instead of the ion-exchanger-supported cyclic phenol sulfide iron (III) complex composition obtained in Production Example 3. Was carried out in the same manner as in Example 1 except that Table 1 shows the measurement results of the residual amount of hydrogen peroxide.

Example 7 The ion-exchanger-supported cyclic phenol sulfide zinc complex composition obtained in Production Example 9 was used in place of the ion-exchanger-supported cyclic phenol sulfide iron (III) complex composition obtained in Production Example 3. Was carried out in the same manner as in Example 1 except that Table 1 shows the measurement results of the residual amount of hydrogen peroxide.

[0024]

[Table 1]

[0025]

According to the hydrogen peroxide catalyst or the composition thereof of the present invention, hydrogen peroxide harmful to living organisms can be safely and simply removed.
Can be broken down into safe substances.

Continued on the front page (72) Inventor Haruhiko Takeya 1134-2 Gondogendo, Satte-shi, Saitama Kosumo Research Institute, Inc. 4G069 AA03 AA08 BA23B BA27A BA27B BC29A BC31B BC34A BC35B BC62B BC66B BC67B BC68B BE13A BE21A BE21B BE22B BE33A BE36A BE36B BE37A BE37B CA05 CA10 CA11 CB35 FA08 EA

Claims (3)

[Claims] 1. A compound of the general formula (1) (1) (wherein X is a hydrogen atom, a hydrocarbon group, an acyl group, a carboxyalkyl group or a carbamoylalkyl group;
Is a hydrogen atom, hydrocarbon group, halogenated hydrocarbon group, halogen atom, acyl group, hydroxyl group, carboxyl group, amide group, amino group, nitro group, cyano group, chlorosulfonic acid group, alkoxysulfonyloxy group, sulfonic acid group Or a metal salt, ammonium salt, lower alkyl ammonium salt, lower alkanol ammonium salt or pyridinium salt of a sulfonic acid group, and a plurality of X and Y may be the same or different. n is an integer of 4 to 8, M is a transition metal or a Group IIB metal, and p and q are integers of 1 or more representing a composition ratio). Characteristic hydrogen peroxide decomposition catalyst. 2. A hydrogen peroxide decomposition catalyst composition, comprising mixing or supporting the cyclic phenol sulfide metal complex according to claim 1 on a solid carrier. 3. A method for decomposing hydrogen peroxide, comprising bringing the hydrogen peroxide decomposition catalyst or the hydrogen peroxide decomposition catalyst composition according to claim 1 into contact with hydrogen peroxide.