KR101668132B1 - Catalyst with supported platinum-group metal, process for producing water in which hydrogen peroxide has been decomposed, process for producing water from which dissolved oxygen has been removed, and method of cleaning electronic part - Google Patents

Abstract

The macropores in the form of bubbles overlap each other and the overlapping portions become openings with an average diameter of 30 to 300 탆 in the water wet state. The continuous macropore structure has a total pore volume of 0.5 to 5 ml / g, The anion exchanger is uniformly distributed in the organic porous anion exchanger, and in the SEM image of the cut surface of the continuous macropore structure (dried body), the anion exchange capacity of 0.4 to 1.0 mg equivalent / The platinum group metal nanoparticles having an average particle diameter of 1 to 100 nm in an amount of 0.004 to 20% by weight supported on the organic porous anion exchanger having a skeleton area in the cross section of 25 to 50% Metal supported catalyst. According to the present invention, it is possible to provide a high-performance catalyst that allows the SV to pass through a large SV exceeding 2000 h ^-1 and enables the decomposition of hydrogen peroxide or the removal of dissolved oxygen even if the height of the packed bed of the catalyst is made thinner.

Description

Technical Field [0001] The present invention relates to a process for producing dissolved oxygen, a process for producing dissolved oxygen, a process for producing dissolved oxygen, and a method for cleaning electronic components, PROCESS FOR PRODUCING WATER FROM WHICH DISSOLVED OXYGEN HAS BEEN REMOVED, AND METHOD OF CLEANING ELECTRONIC PART}

TECHNICAL FIELD The present invention relates to a platinum group metal supported catalyst for removing oxidizing substances such as hydrogen peroxide and dissolved oxygen in ultrapure water, which is used in water for precision processing, such as water for power generation and semiconductor manufacturing.

It is known that dissolved oxygen in the water used in power plants causes corrosion of members such as piping and heat exchangers. Particularly, in primary and secondary systems of nuclear power plants, it is necessary to reduce dissolved oxygen as much as possible.

Further, in the semiconductor manufacturing industry, cleaning and the like of silicon wafers are carried out by using ultra pure water in which impurities are highly removed. Ultrapure water is generally obtained by removing a part of suspended substances or organic substances contained in raw water (river water, ground water, industrial water, etc.) from the pretreatment process, and then treating the treated water with a primary pure water system and a secondary pure water system (subsystem) , And is supplied to a use site where wafer cleaning is performed. Such ultrapure water has a purity such that it is difficult to quantify impurities, but it does not have any impurities at all.

For example, dissolved oxygen contained in ultrapure water forms a natural oxide film on the surface of a silicon wafer. If the native oxide film is formed on the surface of the wafer, it may interfere with the growth of the epitaxial silicon thin film at a low temperature, obstruct the precise control of the film pressure and the film quality of the gate oxide film, or increase the contact resistance of the contact hole. Therefore, formation of a natural oxide film on the surface of the wafer needs to be suppressed as much as possible.

Therefore, in the ultrapure water producing apparatus, in particular, in the primary pure water system, the dissolved oxygen is reduced by using the degassing apparatus. With this deaerator, the dissolved oxygen concentration in the for-treatment water (primary pure water) at the inlet of the secondary pure water system system is reduced to 100 μg / L or lower. In some cases, the concentration is controlled to 10 μg / L or less.

In the above-mentioned production of ultrapure water, organic matter is generally decomposed by an ultraviolet oxidation apparatus installed in a secondary pure water system. Since hydrogen peroxide is by-produced in the course of the ultraviolet oxidation treatment, it is general that hydrogen peroxide remains in the treated water of the ultraviolet oxidation apparatus. This hydrogen peroxide is partially decomposed in the polisher process of the secondary pure water system to generate oxygen, thereby increasing the concentration of dissolved oxygen in the treated water.

Thus, a method of adsorbing and removing hydrogen peroxide contained in the treated water of the ultraviolet oxidation apparatus using a synthetic carbon-based particulate adsorbent has been proposed (Japanese Patent Application Laid-Open No. 9-29233). According to this method, it is possible to suppress the formation of a natural oxide film on the wafer surface by removing the hydrogen peroxide remaining in the treated water of the ultraviolet oxidation apparatus. However, in this method, in order to achieve a predetermined hydrogen peroxide removal rate, a large adsorption column filled with a large amount of synthetic carbon-based particulate adsorbent was required.

A method of decomposing hydrogen peroxide contained in treated water of an ultraviolet oxidation apparatus by a catalyst in which platinum group metal nano-colloid particles are carried on a carrier has been proposed (Japanese Patent Application Laid-Open No. 2007-185587).

Patent Document 1: JP-A-9-29233 (Claims) Patent Document 2: Japanese Patent Application Laid-Open No. 2007-185587 (Claims)

However, the catalyst disclosed in Japanese Patent Application Laid-Open No. 2007-185587 can only be used in a region where the space velocity (SV) is in a relatively low range of 100 to 2000 h ^-1 , and when the SV exceeds 2000 h ^-1 , It has a disadvantage that it becomes insufficient.

Therefore, it is an object of the present invention to provide a method of decomposing hydrogen peroxide or eliminating dissolved oxygen even when the SV is passed through a large SV exceeding 2000 h ^-1 , Which is capable of removing the catalyst from the catalyst.

In such a situation, the inventors of the present invention have conducted intensive studies and have found that, in the presence of a monolithic organic porous material (intermediate) having a comparatively large pore volume obtained by the method described in JP 2002-306976 A, a vinyl monomer and a crosslinking agent . When the polymerization is carried out in a specific organic solvent, a thick monolithic organic porous material having a large opening diameter and a larger skeleton than the skeleton of the organic porous material of the intermediate can be obtained. When an ion exchanger is introduced into the large monolith organic porous material , It is found that the swelling is large due to the large thickness, and therefore the opening can be made larger. A nanoparticle of a platinum group metal having an average particle diameter of 1 to 100 nm is added to a monolithic organic porous anion exchanger (hereinafter also referred to as " first monolith anion exchanger ") in which an anion exchanger is introduced into this thick monolithic organic porous material (Hereinafter, also referred to as " the first platinum group metal supported catalyst ") can carry out the decomposition of hydrogen peroxide or the removal of dissolved oxygen even if the SV passes a large SV exceeding 2000 h ^-1 , The inventors have found that hydrogen peroxide can be decomposed or dissolved or dissolved oxygen can be removed even if the height of the packed bed of the catalyst is made thinner, and the present invention has been accomplished.

As a result of intensive studies, the inventors of the present invention have found that, in the presence of a monolithic organic porous material (intermediate) having a large pore volume and obtained by the method described in JP 2002-306976 A, an aromatic vinyl monomer and a cross- When the polymerization is carried out in a solvent, a hydrophobic monolith comprising a three-dimensionally continuous aromatic vinyl polymer skeleton and a three-dimensionally continuous pore between the skeletal phase and having a bidentate structure is obtained The monolith of this performance structure has a high degree of continuity in the air, has no deflection in its size, has a low pressure loss at the time of permeation of the fluid, and the ion exchanger is introduced because the skeleton of this structure in the air- A monolithic organic porous ion exchanger having a large ion exchange capacity per volume can be obtained. A nanoparticle of a platinum group metal having an average particle diameter of 1 to 100 nm is supported on a monolithic organic porous anion exchanger (hereinafter also referred to as " second monolith anion exchanger ") having an anion exchanger introduced into the monolith of this performance structure A platinum group metal supported catalyst (hereinafter, also referred to as a " second platinum group metal supported catalyst ") can decompose or remove hydrogen peroxide even when passing through a large SV exceeding 2000 h ^-1 , such as a first platinum group metal supported catalyst, And that the decomposition of hydrogen peroxide can be removed or the dissolved oxygen can be removed even if the height of the packed bed of the catalyst is made thinner, thereby completing the present invention.

That is, the present invention (1) is a platinum group metal supported catalyst in which nanoparticles of a platinum group metal having an average particle diameter of 1 to 100 nm are supported on an organic porous anion exchanger,

The organic porous anion exchanger is a continuous macro-pore structure in which bubble-like macropores overlap each other, and the overlapping portions become openings with an average diameter of 30 to 300 μm in a wetted state, and a total pore volume of 0.5 And an anion exchange capacity of 0.4 to 1.0 mg equivalent / ml per volume in a wetted state, the anion exchanger is uniformly distributed in the organic porous anion exchanger, and the continuous macropore structure (dried body) , The skeleton area appearing on the cross section is 25 to 50% of the image area,

And a supported amount of the platinum group metal is 0.004 to 20% by weight in a dry state.

The present invention (2) is a platinum group metal supported catalyst in which nanoparticles of a platinum group metal having an average particle diameter of 1 to 100 nm are supported on an organic porous anion exchanger,

The organic porous anion exchanger preferably comprises an aromatic vinyl polymer containing 0.3 to 5.0 mol% of crosslinking structural units among all the constituent units into which an anion-exchange group is introduced, and has a thickness of 1 to 60 μm in a water- A structure having a skeleton and three-dimensionally continuous pores having a diameter of 10 to 100 占 퐉 in a water-wet state between the skeletons, the porous structure having a bulk density of 0.5 to 5 ml / g, The anion exchange capacity per volume is 0.3 to 1.0 mg equivalent / ml, the anion exchanger is uniformly distributed in the organic porous anion exchanger,

And a supported amount of the platinum group metal is 0.004 to 20% by weight in a dry state.

In the present invention (3), the water to be treated containing hydrogen peroxide is brought into contact with the platinum group metal supported catalyst of the present invention (1) or (2) to decompose and remove hydrogen peroxide in the water to be treated containing the hydrogen peroxide And a method for producing hydrogen peroxide decompositionally treated water.

The present invention (4) is a process for cleaning an electronic component or an electronic component, which comprises cleaning the electronic component or the electronic component manufacturing apparatus with treated water obtained by performing the method for producing decompositionally treated water of the peroxide- Method.

The present invention (5) is a process for producing water by reacting dissolved oxygen in the water-for-treatment water containing hydrogen and oxygen in the presence of the platinum group metal supported catalyst of the present invention (1) or (2) And the dissolved oxygen is removed from the for-treatment water containing the dissolved oxygen.

The present invention (6) is a cleaning method for electronic parts or electronic parts, characterized by cleaning the manufacturing equipment of electronic parts or electronic parts with the treated water obtained by carrying out the manufacturing method of dissolved oxygen depleted water of the present invention (5) Method.

According to the platinum group metal supported catalyst of the present invention, hydrogen peroxide can be removed or dissolved oxygen can be removed even when the SV passes through a large SV exceeding 2000 h ^-1 , and even if the height of the packed bed of the catalyst is made thin, Dissolved oxygen can be removed.

1 is a SEM image of the first monolith.
2 is an EPMA image showing the state of distribution of chloride ions on the surface of the first monolithic anion exchanger.
3 is an EPMA image showing the distribution state of chloride ions in the cross-sectional (thickness) direction of the first monolithic anion exchanger.
4 is a skeleton portion appearing as a cross section of the SEM image of Fig. 1, which is manually transferred.
5 is a TEM image showing the dispersion state of palladium nanoparticles in the first platinum group metal supported catalyst.
FIG. 6 is a diagram schematically showing the structure of the second monolithic anion exchanger during performance.
7 is a SEM image of the second monolith.
8 is an EPMA image showing the state of distribution of chloride ions on the surface of the second monolithic anion exchanger.
9 is an EPMA image showing the state of distribution of chloride ions in the cross-sectional (thickness) direction of the second monolithic anion exchanger.
10 is a TEM image showing the dispersion state of palladium nanoparticles in the second platinum group metal supported catalyst.
11 is an SEM image of a monolith (known product) of Reference Example 3. Fig.
12 is a SEM image of the second monolith intermediate.
Fig. 13 is a schematic flow chart of the first embodiment of the cleaning method (I) of the electronic component of the present invention.
Fig. 14 is a schematic flow chart of a second embodiment of the cleaning method (I) of the electronic component of the present invention.

The organic porous anion exchanger used as a carrier of the platinum group metal supported catalyst of the present invention is a "first monolith anion exchanger" or a "second monolith anion exchanger". In the present specification, "monolithic organic porous material" is referred to simply as "monolith", "monolithic organic porous anion exchanger" as "monolithic anion exchanger" and "monolithic organic porous intermediate" " The platinum group metal supported catalyst in which the platinum group metal supported on the first monolithic anion exchanger is referred to as a "first platinum group metal supported catalyst" and the platinum group metal supported catalyst in which the platinum group metal is supported on the second monolithic anion exchanger is referred to as " Metal-supported catalyst ".

<Description of the First Monolith Anion Exchanger>

The first monolithic anion exchanger is obtained by introducing an anion exchanger into the monolith, and bubble-like macropores are superimposed on each other, and the overlapping portions are formed in the water wet state with an average diameter of 30 to 300 mu m, preferably 30 to 200 mu m, And particularly preferably 40 to 100 μm (mesopore). The average diameter of the openings of the monolithic anion exchanger becomes larger than the average diameter of the openings of the monolith because the entire monolith swells when the anion exchanger is introduced into the monolith. If the average diameter of the openings in the water wet state is less than 30 占 퐉, the pressure loss at the time of water passage becomes large. If the average diameter of the openings in the water wet state is too large, the water to be treated and the monolith anion exchanger The contact of the supported platinum group metal nanoparticles becomes insufficient, and as a result, the hydrogen peroxide decomposition property or the dissolved oxygen removal property is lowered. Further, in the present invention, the average diameter of the openings of the monolith intermediate in a dried state, the average diameter of the openings of the monolith in the dried state, and the average diameters of the openings of the monolith anion exchanger in the dry state are values measured by the mercury porosimetry . The average diameter of the openings of the monolithic anion exchanger in the water wet state is a value calculated by multiplying the average diameter of the openings of the monolith anion exchanger in the dry state by the swelling rate. Specifically, the monolith anion exchanger having a water-wetted state has a diameter of × 1 (mm), the monolith anion exchanger having a water-wet state is dried, and the diameter of the obtained monolith anion exchanger in a dry state is set to y1 (M) of the openings of the monolithic anion exchanger in a water-wet state, when the average diameter of the openings measured by the mercury porosimetry is z1 (mu m) The average diameter (占 퐉) of the opening of the monolithic anion exchanger in the wetted state of water = z1 x (x1 / y1) &quot; The average diameter of the openings of the monolith in the dry state before introduction of the anion exchanger and the swelling rate of the monolith anion exchanger in the water wet state relative to the dry state monolith when the anion exchanger is introduced into the monolith in the dry state are known The average diameter of the openings of the monolith anion exchanger in the water wet state may be calculated by multiplying the average diameter of the openings of the monolith in the dry state by the swelling rate.

In the first monolithic anion exchanger, the skeleton area appearing in the cross section in the SEM image of the cut surface of the continuous macropore structure is 25 to 50%, preferably 25 to 45% in the image area. When the skeleton area appearing on the cross section is less than 25% of the image area, it becomes a fine skeleton and the mechanical strength is lowered, and the monolith anion exchanger largely deforms when passing through the intrinsic body, which is not preferable. Further, the contact efficiency between the water to be treated and the monolithic anion exchanger and the platinum group metal nanoparticles carried thereon is lowered and the catalytic effect is lowered, which is undesirable. When it exceeds 50%, the skeleton becomes too thick, It is not preferable because the pressure loss is increased. In addition, the monolith described in Japanese Patent Application Laid-Open No. 2002-306976 has a limitation in the compounding ratio in order to secure a common opening even if the mixing ratio of the oil phase portion to water is increased and the skeleton portion is made thick, The maximum value of the skeleton area appearing on the cross section can not exceed 25% of the image area.

The conditions for obtaining the SEM image are such that the skeleton portion appearing on the cross section of the cut surface clearly appears. For example, the magnification is 100 to 600 and the photographic region is about 150 mm x 100 mm. The SEM observation is preferably performed on three or more, preferably five or more, images which are taken at arbitrary positions on arbitrary cut surfaces of the monolith excluding the main pipe and different from each other in the photographed portions. The monolith to be cut is in a dry state because it is provided to an electron microscope. The skeleton of the cut surface in the SEM image will be described with reference to Figs. 1 and 4. Fig. Fig. 4 shows a skeleton portion transferred as a cross section of the SEM photograph of Fig. 1 and 4, a substantially irregular shape and a cross-sectional view are a skeleton (symbol 12) in the cross section of the present invention, and the circular hole shown in Fig. 1 is an opening (mesopore) And a macro-pore (13 in Fig. 4) having a large curvature or a curved surface. The skeleton area shown in the cross section of Fig. 4 is 28% in the rectangular image area 11. Fig. Thus, the skeleton can be clearly judged.

In the SEM image, the method of measuring the area of the skeleton portion appearing on the cross section of the cut surface is not particularly limited. After the skeleton portion is subjected to known computer processing and the like, a calculation method by a computer or the like . As a manual calculation, there is a method of replacing an indefinite article with an aggregate such as a quadrangle, a triangle, a circle or a trapezoid, and laminating them to obtain an area.

The total pore volume of the first monolithic anion exchanger is 0.5 to 5 ml / g, preferably 0.8 to 4 ml / g. If the volume ratio of the premix is less than 0.5 ml / g, the pressure loss at the time of water passage becomes large, which is undesirable because the amount of permeate fluid per unit cross-sectional area becomes small and the treatment capacity is lowered. On the other hand, when the volume of the premixed water exceeds 5 ml / g, the mechanical strength decreases and the monolith anion exchanger is significantly deformed when passing through the intrinsic fluid, which is not preferable. In addition, since the contact efficiency between the water to be treated and the monolith anion exchanger and the platinum group metal nano-particles carried thereon is lowered, the catalytic effect is lowered, which is not preferable. Further, in the present invention, the total internal volume of the monolith (monolith intermediate, monolith, and monolith anion exchanger) is a value measured by a mercury pressing method. In addition, the lean space capacity of the monolith (monolith intermediate, monolith, and monolith anion exchanger) is the same even in the dry state and the water wet state.

The pressure loss when permeating water through the first monolithic anion exchanger is expressed by a pressure loss (hereinafter, referred to as &quot; differential pressure coefficient &quot;) when water is passed through the column filled with 1 m at a water flow rate (LV) of 1 m / ), It is preferably in the range of 0.001 to 0.1 MPa / m · LV, particularly 0.005 to 0.05 MPa / m · LV.

The first monolithic anion exchanger has an anion exchange capacity per volume of 0.4 to 1.0 mg equivalent / ml in a water wet state. In the conventional monolithic organic porous anion exchanger having a continuous macropore structure different from that of the present invention as described in Japanese Patent Application Laid-Open No. 2002-306976, in order to achieve a practically required low pressure loss, The larger the volume of the chamber, the larger the anion exchange capacity per volume, and the smaller the volume of the chamber, in order to increase the exchange capacity per volume, . On the other hand, since the first monolithic anion exchanger can make the skeleton of the continuous macropore structure thicker (thicker the wall portion of the skeleton) in addition to enlarging the aperture diameter, the anion exchange per volume The capacity can be dramatically increased. If the anion exchange capacity per volume is less than 0.4 mg equivalent / ml, the amount of supported nanoparticles of platinum group metal per volume decreases, which is not preferable. On the other hand, if the anion exchange capacity per volume exceeds 1.0 mg equivalent / ml, the pressure loss at the time of water passage increases, which is not preferable. The anion exchange capacity per weight of the first monolith anion exchanger is not particularly limited, but is 3.5 to 4.5 mg equivalent / g since the anion exchanger is uniformly introduced into the surface of the porous body and the inside of the skeleton. The ion exchange capacity of the porous body into which the ion exchanger is introduced only on the surface can not be determined collectively depending on the type of the porous body or ion exchanger, but is only 500 당 equivalent / g.

In the first monolithic anion exchanger, the material constituting the framework of the continuous macropore structure is an organic polymer material having a crosslinked structure. The crosslinking density of the polymer material is not particularly limited, but it is preferable that the crosslinking structural unit includes 0.3 to 10 mol%, preferably 0.3 to 5 mol%, of the crosslinking structural unit with respect to all the constituent units constituting the polymer material. When the amount of the crosslinking structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, when the amount exceeds 10 mol%, introduction of an anion-exchange group becomes difficult. There are no particular restrictions on the kind of the polymer material, and examples thereof include aromatic vinyl polymers such as polystyrene, poly (? -Methylstyrene), polyvinyltoluene, polyvinylbenzyl chloride, polyvinylbiphenyl, and polyvinylnaphthalene; (Halogenated polyolefin) such as polyvinyl chloride and polytetrafluoroethylene; nitrile-based polymers such as polyacrylonitrile; methyl polymethacrylate, glycidyl polymethacrylate, ethyl polyacrylate and the like (Meth) acryl-based polymer, and the like. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or a polymer obtained by blending two or more kinds of polymers. Among these organic polymer materials, crosslinked aggregates of aromatic vinyl polymers are preferable from the standpoint of easiness of formation of a continuous macropore structure, ease of introduction of anion exchanger, high mechanical strength, and high stability to an acid or an alkali, Benzene copolymer or a vinylbenzyl chloride-divinylbenzene copolymer can be mentioned as a preferable material.

Examples of the anion exchanger of the first monolithic anion exchanger include quaternary ammonium groups such as trimethylammonium group, triethylammonium group, tributylammonium group, dimethylhydroxyethylammonium group, dimethylhydroxypropylammonium group and methyldihydroxyethylammonium group, A phosphorus group, a phosphorus group, and a phosphonium group.

In the first monolithic anion exchanger, the introduced anion exchanger is uniformly distributed not only on the surface of the porous body but also inside the skeleton of the porous body. Here, "anion exchanger is uniformly distributed" means that the distribution of the anion exchanger is uniformly distributed on the surface and the inside of the skeleton on the order of 탆. The distribution of the anion exchanger can be relatively simply confirmed by ion-exchanging the counter anion with a chloride ion, a bromide ion or the like and then using EPMA. Further, when the anion exchanger is uniformly distributed not only on the surface of the monolith but also inside the skeleton of the porous body, the physical and chemical properties of the surface and the interior can be made uniform, thereby improving the durability against swelling and shrinkage .

(Production method of the first monolithic anion exchanger)

The first monolithic anion exchanger is prepared by preparing a water-in-water emulsion by stirring a mixture of an oil-soluble monomer containing no ion-exchanger, a surfactant and water, and then polymerizing a water-in-water emulsion to form a water- / g, a vinyl monomer, a crosslinking agent having at least two or more vinyl groups in one molecule, a vinyl monomer or a crosslinking agent are dissolved, but the vinyl monomer is polymerized to form a monolithic organic porous intermediate (monolith intermediate) The polymer to be produced is subjected to polymerization in the presence of the monolith intermediate obtained in the step I and the mixture obtained in the step (II) and the step (II) to prepare a mixture comprising an organic solvent and a polymerization initiator which are insoluble, A step III for obtaining a coarse organic porous body having a thick skeleton, By performing a coarse Ⅳ step of introducing an anion exchanger in an organic porous body obtained it can be obtained.

In the method for producing the first monolithic anion exchanger, the step I may be carried out in accordance with the method described in Japanese Patent Application Laid-Open No. 2002-306976.

In the preparation of the monolith intermediate of Process I, the usable monomer which does not contain an ion-exchange group includes, for example, an ion exchange resin which does not contain an ion exchanger such as a carboxylic acid group, a sulfonic acid group or a quaternary ammonium group, And an oleophilic monomer. Suitable examples of these monomers include styrene,? -Methylstyrene, vinyltoluene, vinylbenzyl chloride, divinylbenzene, ethylene, propylene, isobutene, butadiene, and ethylene glycol dimethacrylate. These monomers may be used singly or in combination of two or more. However, a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate is selected as a component of at least an oil-soluble monomer and the content thereof is 0.3 to 10 mol%, preferably 0.3 to 5 mol% Is preferable because the amount of anion exchanger can be quantitatively introduced in a later step.

The surfactant is not particularly limited as long as it can form a water-in-oil type (W / O) emulsion when water-miscible with an oil-soluble monomer containing no ion exchanger, and includes sorbitan monooleate, sorbitan monolaurate Nonionic surfactants such as sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene nonylphenyl ether, polyoxyethylene stearyl ether, and polyoxyethylene sorbitan monooleate; , Sodium dodecylbenzenesulfonate, and sodium dioctylsulfate sulfate; cationic surfactants such as distearyldimethylammonium chloride; and amphoteric surfactants such as lauryldimethylbetaine. These surfactants may be used alone or in combination of two or more. The water-in-water type emulsion refers to an emulsion in which the oil phase is a continuous phase and the water phase is dispersed therein. The amount of the surfactant to be added can not be determined collectively because the amount varies depending on the type of the useful monomer and the size of the desired emulsion particle (macropore). However, the total amount of the surfactant is about 2 To 70%.

In the step I, a polymerization initiator may be used as needed in forming the water-in-water emulsion. As the polymerization initiator, a compound which generates radicals by heat and light irradiation is suitably used. The polymerization initiator may be water-soluble or oil-soluble. Examples thereof include azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanenitrile, azobiscyclohexanecarbonitrile, benzoyl peroxide, potassium persulfate, ammonium persulfate , Hydrogen peroxide-ferrous chloride, sodium persulfate-acidic sodium sulfite, tetramethylthiourea disulfide, and the like.

A mixing method for mixing an oil-soluble monomer not containing an ion exchanger, a surfactant, water and a polymerization initiator, and forming a water-in-oil type emulsion is not particularly limited, and a method of collectively mixing the components one at a time , An oil-soluble monomer, a surfactant, and an oil-soluble component as an oil-soluble polymerization initiator, and water or a water-soluble component as a water-soluble polymerization initiator are dissolved uniformly and then mixed with each other. The mixing apparatus for forming the emulsion is not particularly limited, and a conventional mixer, homogenizer, high-pressure homogenizer, or the like can be used, and an apparatus suitable for obtaining the desired emulsion particle size can be selected. The mixing conditions are not particularly limited, and the number of revolutions of stirring and the stirring time at which the intended emulsion particle diameter can be obtained can be arbitrarily set.

The monolith intermediate obtained in step I has a continuous macropore structure. When this is coexisted in the polymerization system, a porous structure having a thick skeleton is formed with the structure of the monolith intermediate as a mold. The monolith intermediate is an organic polymer material having a crosslinked structure. The crosslinking density of the polymer material is not particularly limited, but it is preferable that the crosslinking structural unit includes 0.3 to 10 mol%, preferably 0.3 to 5 mol%, of the crosslinking structural unit with respect to all the constituent units constituting the polymer material. When the amount of the crosslinking structural unit is less than 0.3 mol%, the mechanical strength is insufficient. Particularly, in the case where the total pore volume is as large as 10 to 16 ml / g, it is preferable that the pore structure unit contains 2 mole% or more of the crosslinked structural unit in order to maintain the continuous macropore structure. On the other hand, if it exceeds 10 mol%, introduction of an anion exchanger becomes difficult, which is not preferable.

The type of the polymer material of the monolith intermediate is not particularly limited, and the polymer material of the monolith described above may be used. As a result, the same polymer as the skeleton of the monolith intermediate can be formed, and the skeleton can be thickened to obtain a monolith having a uniform skeleton structure.

The char space volume of the monolith intermediate is 5 to 16 ml / g, suitably 6 to 16 ml / g. If the volume of the premix is too small, the volume of the premixed monolith obtained after polymerization of the vinyl monomer is too small and the pressure loss during permeation of the fluid becomes large, which is not preferable. On the other hand, if the bulk density of the polymer is too large, the structure of the monolith obtained after polymerization of the vinyl monomer deviates from the continuous macropore structure, which is not preferable. In order to set the volume ratio of the monolith intermediate to the above range, the ratio of monomer to water may be approximately 1: 5 to 1:20.

In the monolith intermediate, the average diameter of the openings (mesopores) which are the overlapping portions of the macropores and the macropores is 20 to 200 탆 in the dry state. If the average diameter of the openings in the dry state is less than 20 占 퐉, the diameter of the monolith obtained after polymerization of the vinyl monomer becomes small and the pressure loss at the time of water passage becomes large, which is not preferable. On the other hand, if it exceeds 200 탆, the diameter of the monolith obtained after polymerization of the vinyl monomer becomes too large, the contact between the water to be treated and the monolith anion exchanger becomes insufficient, and as a result, the hydrogen peroxide decomposition property or the dissolved oxygen removal property It is not desirable because it does. The monolith intermediate is preferably a homogeneous structure in which the size of the macro pores and the diameter of the openings are uniform. However, the present invention is not limited to this, and it is also possible that uneven macropores larger than the uniform macro pores are present in the uniform structure.

Step II is a step of preparing a mixture comprising a vinyl monomer, a crosslinking agent having at least two or more vinyl groups in one molecule, an organic solvent which dissolves a vinyl monomer or a crosslinking agent but does not dissolve a polymer produced by polymerization of a vinyl monomer, and a polymerization initiator to be. In addition, there is no sequence of the I step and the II step, and the II step may be performed after the I step, or the I step may be performed after the II step.

The vinyl monomer used in the step (II) is not particularly limited as long as it is a lipophilic vinyl monomer containing a vinyl group polymerizable in the molecule and having high solubility in an organic solvent, but may be of the same kind or similar type as the monolith intermediate coexisting in the polymerization system It is preferable to select a vinyl monomer that produces a polymer material. Specific examples of these vinyl monomers include aromatic vinyl monomers such as styrene,? -Methylstyrene, vinyltoluene, vinylbenzyl chloride, vinylbiphenyl and vinylnaphthalene;? -Olefins such as ethylene, propylene, 1-butene and isobutene; , Isoprene, and chloroprene; halogenated olefins such as vinyl chloride, vinyl bromide, vinylidene chloride and tetrafluoroethylene; nitrile monomers such as acrylonitrile and methacrylonitrile; vinyl acetate and vinyl propionate; Vinyl esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, (Meth) acrylic monomers such as hexyl, benzyl methacrylate, and glycidyl methacrylate. These monomers may be used singly or in combination of two or more. The vinyl monomers suitably used in the present invention are aromatic vinyl monomers such as styrene and vinyl benzyl chloride.

The amount of these vinyl monomers to be added is 3 to 50 times by weight, preferably 4 to 40 times by weight, with respect to the monolith intermediate to be coexisted at the time of polymerization. If the amount of the vinyl monomer added is less than 3 times the amount of the porous material, the skeleton of the produced monolith (thickness of the wall portion of the monolith structure) can not be made thick and the anion exchange capacity per volume after introduction of the anion exchanger becomes small. On the other hand, if the addition amount of the vinyl monomer is more than 50 times, the opening diameter becomes small and the pressure loss at the time of passing water becomes large, which is not preferable.

The crosslinking agent used in the step (II) is preferably one having at least two polymerizable vinyl groups in the molecule and having a high solubility in an organic solvent. Specific examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, and butanediol diacrylate. These crosslinking agents may be used singly or in combination of two or more. A preferred crosslinking agent is an aromatic polyvinyl compound such as divinylbenzene, divinylnaphthalene, divinylbiphenyl and the like because of its high mechanical strength and stability against hydrolysis. The amount of the crosslinking agent is preferably 0.3 to 10 mol%, more preferably 0.3 to 5 mol% based on the total amount of the vinyl monomer and the crosslinking agent. If the amount of the crosslinking agent is less than 0.3 mol%, the mechanical strength of the monolith is insufficient. On the other hand, if it exceeds 10 mol%, the amount of the anion-exchange group introduced may decrease, which is not preferable. It is preferable that the amount of the cross-linking agent used is approximately the same as the cross-linking density of the monolith intermediate which coexists in polymerization of the vinyl monomer / cross-linker. If the amount of use is too large, deflection of the crosslinked density distribution occurs in the produced monolith, and cracks tend to occur at the time of anion exchange group introduction reaction.

The organic solvent used in the step (II) is an organic solvent which dissolves the vinyl monomer or the crosslinking agent but does not dissolve the polymer produced by polymerization of the vinyl monomer, in other words, a poor solvent for the polymer produced by polymerization of the vinyl monomer, to be. Since the organic solvent varies greatly depending on the type of the vinyl monomer, it is difficult to list general examples. For example, when the vinyl monomer is styrene, examples of the organic solvent include methanol, ethanol, propanol, butanol, Alcohols such as cyclohexanol, cyclohexanol, octanol, 2-ethylhexanol, decanol, dodecanol, ethylene glycol, propylene glycol, tetramethylene glycol and glycerin; ethers such as diethyl ether, ethylene glycol dimethyl ether, Chain saturated hydrocarbons such as hexane, heptane, octane, isooctane, decane and dodecane, and the like; esters such as ethyl acetate, acetic acid Isopropyl acetate, cellosolve acetate and ethyl propionate. Also, a good solvent for polystyrene such as dioxane, THF and toluene is used together with the poor solvent, and when the amount is small, it can be used as an organic solvent. The amount of these organic solvents to be used is preferably such that the concentration of the vinyl monomer is 30 to 80% by weight. When the amount of the organic solvent used deviates from the above range and the vinyl monomer concentration is less than 30% by weight, the polymerization rate is lowered or the monolith structure after polymerization is deviated from the scope of the present invention. On the other hand, when the vinyl monomer concentration exceeds 80% by weight, polymerization may be runaway, which is not preferable.

As the polymerization initiator, a compound which generates a radical by heat and light irradiation is suitably used. The polymerization initiator is preferably useful. Specific examples of the polymerization initiator used in the present invention include 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 4,4'-azobis (4-cyanovaleric acid), 1,1'-azobis (cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, tetramethylthioram disulfide . The amount of the polymerization initiator to be used varies greatly depending on the type of the monomer, the polymerization temperature, etc. However, it can be used in the range of about 0.01 to 5% based on the total amount of the vinyl monomer and the crosslinking agent.

Step III is a step of obtaining a coarse monolith having a skeleton larger than the skeleton of the monolith intermediate by placing the mixture obtained in the step II and allowing polymerization in the presence of the monolith intermediate obtained in the step I. The monolith intermediate used in step III plays a very important role in creating a monolith having the novel structure of the present invention. As disclosed in Japanese Patent Application Laid-Open No. 7-501140 and the like, when the vinyl monomer and the cross-linking agent are subjected to stationary polymerization in the presence of the monolith intermediate in a specific organic solvent, a particle-aggregated monolithic organic porous body can be obtained. On the other hand, when a monolith intermediate of a continuous macropore structure is present in the polymerization system as in the present invention, the structure of the monolith after polymerization dramatically changes and the particle aggregation structure disappears, and the above-described thick monolith is obtained. The reason for this is not clarified in detail, but when the monolith intermediate is not present, the aggregation structure of the particles is formed by precipitation and precipitation of the aggregation of the aggregates formed by the polymerization in the form of particles, It is considered that the vinyl monomer and the crosslinking agent are adsorbed or distributed from the liquid phase to the skeleton of the porous body (intermediate body), and the polymerization proceeds in the porous body (intermediate body) to obtain a monolith of a thick skeleton. In addition, although the aperture diameter can be narrowed by the progress of the polymerization, since the monolith intermediate is large in size, for example, even if the skeleton is thick, an aperture of a suitable size can be obtained.

The content of the reaction vessel is not particularly limited as far as the content of the monolith intermediate exists in the reaction vessel, and when the monolith intermediate is placed in the reaction vessel, a gap is formed around the monolith when viewed from the plane. It can be any one of entering without gap. Among them, the large monolith after the polymerization is not pressurized from the inner wall of the container and enters the reaction vessel without gaps, does not cause distortion in the monolith, has no waste of reaction materials, and is efficient. In addition, even when the content of the reaction vessel is large and there is a gap around the monolith after polymerization, since the vinyl monomer and the crosslinking agent are adsorbed and distributed on the monolith intermediate, a particle cohesive structure is not generated in the gap portion in the reaction vessel .

In step III, in the reaction vessel, the monolith intermediate is impregnated with the mixture (solution). The mixture ratio of the mixture obtained in the step II and the monolith intermediate is preferably such that the addition amount of the vinyl monomer to the monolith intermediate is 3 to 50 times, preferably 4 to 40 times by weight, as described above. This makes it possible to obtain a monolith having an appropriate diameter and a thick skeleton. In the reaction vessel, the vinyl monomer and the cross-linking agent in the mixture are adsorbed and distributed on the skeleton of the stationary monolith intermediate, and the polymerization proceeds in the skeleton of the monolith intermediate.

The polymerization conditions are selected depending on the kind of the monomer and the kind of the initiator. Examples of the initiator include 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate , It may be heated and polymerized at 30 to 100 ° C for 1 to 48 hours in a sealed container under an inert atmosphere. By heating polymerization, the vinyl monomers and the crosslinking agent adsorbed and distributed on the skeleton of the monolith intermediate are polymerized in the skeleton thereof, and the skeleton thereof is made thick. After completion of the polymerization, the contents are taken out and extracted with a solvent such as acetone for the purpose of removing unreacted vinyl monomers and an organic solvent to obtain a thick monolith.

Next, a method of introducing an anion exchanger after preparing the monolith by the above method is preferable in that the porous structure of the obtained monolith anion exchanger can be strictly controlled.

The method for introducing the anion exchanger into the monolith is not particularly limited and known methods such as polymer reaction and graft polymerization can be used. For example, as a method for introducing a quaternary ammonium group, a method of introducing a chloromethyl group into a monolith using a styrene-divinylbenzene copolymer or the like with chloromethyl methyl ether and then reacting with a tertiary amine; And divinylbenzene, and reacting with a tertiary amine; introducing a radical initiator or chain moiety into the monolith uniformly on the skeletal surface and in the skeleton; and reacting N, N, N-trimethylammonium ethyl acrylate Or N, N, N-trimethylammonium propyl acrylamide; graft polymerization of glycidyl methacrylate and then introducing a quaternary ammonium group by functional group conversion. Among these methods, as a method of introducing a quaternary ammonium group, a method of introducing a chloromethyl group into a styrene-divinylbenzene copolymer with chloromethyl methyl ether and then reacting with a tertiary amine, a method of introducing chloromethylstyrene and divinylbenzene A method of preparing a monolith by copolymerization and reacting with a tertiary amine is preferable in that the ion-exchange can be introduced uniformly and quantitatively. Examples of the ion exchanger to be introduced include quaternary ammonium groups such as trimethylammonium group, triethylammonium group, tributylammonium group, dimethylhydroxyethylammonium group, dimethylhydroxypropylammonium group and methyldihydroxyethylammonium group, and tertiary ammonium groups such as tertiary sulfonium group, And a phosphorus group.

The first monolithic anion exchanger swells largely as, for example, 1.4 to 1.9 times of the coarse monolith because an anion exchanger is introduced into the coarse monolith. That is, the degree of swelling is much larger than that in the conventional monolith described in Japanese Patent Application Laid-Open No. 2002-306976, in which an ion exchanger is introduced. Therefore, even if the diameter of the coarse monolith is small, the aperture diameter of the monolith ion exchanger becomes large at the above magnification. Also, even if the diameter of an opening increases due to swelling, the volume of the lease does not change. Therefore, the first monolith ion exchanger has a large skeleton, though its aperture diameter is remarkably large, and thus has a high mechanical strength.

&Lt; Description of Second Monolith Anion Exchanger >

The second monolithic anion exchanger is an aromatic vinyl polymer comprising an aromatic vinyl polymer containing 0.3 to 5.0 mol% of crosslinking structural units among all the constituent units into which an anion-exchange group is introduced, and has an average thickness of 1 to 60 μm Wherein the hollow structure has a continuous skeleton and three-dimensionally continuous pores having an average diameter of 10 to 100 占 퐉 in an aqueous wet state between the skeletons, the porous structure having a bulk density of 0.5 to 5 ml / g, The ion exchange capacity per volume is 0.3 to 1.0 mg equivalent / ml, and the anion exchanger is uniformly distributed in the porous ion exchanger.

The second monolithic anion exchanger preferably has a three-dimensionally continuous skeleton having an average thickness of 1 to 60 탆, preferably 3 to 58 탆, in which the anion exchanger is introduced in a wetted water state, and a water- Is in the range of 10 to 100 占 퐉, preferably 15 to 90 占 퐉, particularly preferably 20 to 80 占 퐉. That is, as shown in the schematic diagram of FIG. 6, the structure in the performance mode is a structure 10 in which a continuous skeleton image 1 and a continuous hollow image 2 are entangled and each is three-dimensionally continuous. Since the continuous openings 2 are higher in continuity of the open space than the open-celled open-cell type monolith or particle-coalesced monoliths of the prior art, there is no deviation in the size, so that a very uniform adsorption behavior of the ions can be achieved. In addition, since the skeleton is thick, the mechanical strength is high.

The thickness of the skeleton of the second monolithic anion exchanger and the diameter of the pore become larger than the thickness of the monolith of the monolith and the diameter of the pore because the entire monolith swells when an anion exchanger is introduced into the monolith. This continuous air has a higher continuity of the public than the conventional open-celled monolithic organic porous anion exchanger and the particle-aggregated monolithic organic porous anion exchanger, and since there is no deviation in the size thereof, a very uniform adsorption behavior Can be achieved. If the average diameter of the three-dimensionally continuous pores is less than 10 mu m in the wetted water state, the pressure loss at the time of water passage becomes large, and if the average diameter exceeds 100 mu m, contact between the water to be treated and the organic porous anion exchanger is insufficient And as a result, decomposition of hydrogen peroxide in the water to be treated or removal of dissolved oxygen becomes insufficient. In addition, when the average thickness of the skeleton is less than 1 탆 in the water wet state, the mechanical strength is lowered, besides the drawback that the anion exchange capacity per volume is lowered, and the monolith anion exchanger is greatly deformed I do not. Further, the contact efficiency between the for-treatment water and the monolith anion exchanger is lowered, and the catalytic effect is lowered, which is not preferable. On the other hand, if the thickness of the skeleton exceeds 60 탆, the skeleton becomes too thick and the pressure loss at the time of water passage increases, which is not preferable.

The average diameter of the continuous structure in the water wet state of the continuous structure is a value calculated by multiplying the average diameter of the vacancies of the monolithic anion exchanger in a dried state measured by the mercury infusion method by the swelling rate. More specifically, the monolith anion exchanger having a diameter of x2 (mm) and having a water wet state is dried to obtain a monolith anion exchanger having a diameter of y2 (mm) (Μm) of the monolith anion exchanger measured in the dry state by the mercury intrusion method is z2 (탆), the average diameter (탆) of the monolith anion exchanger in the water- Is calculated by the following equation: average diameter (占 퐉) of the pores of the monolith anion exchanger in a water wet state = z2 占 (x2 / y2). The swelling rate of the monolith anion exchanger in the water wet state relative to the monolith in the dry state before introduction of the anion exchanger and the dry state monolith when the anion exchanger is introduced into the monolith in the dry state is known , The average pore size of the monolith anion exchanger in the water wet state may be calculated by multiplying the average pore diameter of the monolith in the dry state by the swelling rate. The average thickness of the skeleton of the continuous structure in the water wet state was measured by observing the SEM of the monolithic anion exchanger in the dry state at least three times and measuring the thickness of the skeleton in the obtained image and calculating the swelling rate And is a value calculated by multiplying. More specifically, the monolith anion exchanger having a diameter of x3 (mm) in a water wet state is dried and the monolith anion exchanger in a wet state is dried to obtain a monolith anion exchanger having a diameter of y3 (mm) , And the monolith anion exchanger in this dry state was subjected to SEM observation at least three times, and the thickness of the skeleton in the obtained image was measured. When the average value was z3 (mu m) The average thickness (mu m) of the skeleton is calculated by the following equation (3): &quot; average thickness (mu m) of skeleton of continuous structure of monolith anion exchanger in water wet state = z3 x (x3 / y3) &quot;. The average thickness of the monoliths in the dry state before introduction of the anion exchanger and the swelling rate of the monolith anion exchanger in the water wet state with respect to the monolith in the dry state when the anion exchanger is introduced into the monolith in the dry state are known The average thickness of the skeleton of the monolith in the dry state can be multiplied by the swelling rate to calculate the average thickness of the skeleton of the monolith anion exchanger in the water wet state. The skeleton may have a rod-like shape and a circular cross-sectional shape, but may have a different-diameter cross-section such as an elliptical cross-sectional shape. In this case, the thickness is the average of the short diameter and the long diameter.

In addition, the second monolithic anion exchanger has a lean mass capacity of 0.5 to 5 ml / g. If the volume ratio of the premix is less than 0.5 ml / g, the pressure loss at the time of passing becomes large, which is undesirable because the permeation rate per unit surface area becomes small and the amount of water to be treated decreases. On the other hand, when the volume ratio of the carbon black exceeds 5 ml / g, the anion exchange capacity per volume decreases, the amount of platinum group metal nanoparticles to be loaded decreases, and the catalytic effect decreases, which is not preferable. Further, the mechanical strength is lowered, and the monolithic anion exchanger is largely deformed when passing through the intrinsic core, which is not preferable. Further, since the contact efficiency between the water to be treated and the monolith anion exchanger is lowered, the effect of decomposing hydrogen peroxide or the effect of removing dissolved oxygen is also undesirable. When the three-dimensionally continuous pore size and the pore volume are within the above ranges, the contact with the for-treatment water is very uniform, the contact area is large, and the water passing under low pressure loss becomes possible. In addition, the charcoal capacity of the monolith (monolith intermediate, monolith, and monolith anion exchanger) is the same even in the dry state and the water wet state.

The pressure loss when permeating water to the second monolithic anion exchanger was measured by measuring the pressure loss (hereinafter, referred to as &quot; differential pressure meter &quot;) when passing through a column packed with 1 m of porous body at a water flow rate (LV) of 1 m / ) Is in the range of 0.001 to 0.5 MPa / m · LV, particularly 0.005 to 0.1 MPa / m · LV.

In the second monolithic anion exchanger, the material constituting the skeleton of the performance structure is preferably an aromatic vinyl polymer containing 0.3 to 5 mol%, preferably 0.5 to 3.0 mol%, of the total structural units, And is hydrophobic. When the amount of the crosslinking structural unit is less than 0.3 mol%, the mechanical strength is insufficient, and when it is more than 5 mol%, the structure of the porous material tends to deviate from the structure of the air-fuel ratio. The type of the aromatic vinyl polymer is not particularly limited, and examples thereof include polystyrene, poly (? -Methylstyrene), polyvinyltoluene, polyvinylbenzyl chloride, polyvinylbiphenyl, polyvinylnaphthalene and the like. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or a polymer obtained by blending two or more kinds of polymers. Among these organic polymer materials, a styrene-divinylbenzene copolymer, a vinylbenzyl chloride-divinylbenzene copolymer, a styrene-divinylbenzene copolymer and a styrene-divinylbenzene copolymer are preferably used because of easiness of formation of a structure in the air- .

The second monolithic anion exchanger has an ion exchange capacity of 0.3 to 1.0 mg equivalent / ml in terms of anion exchange capacity per volume in wetted water. In the conventional monolithic organic porous ion exchanger having a continuous macropore structure different from that of the present invention as described in Japanese Patent Application Laid-Open No. 2002-306976, in order to achieve a practically required low pressure loss, The volume of the premixed air is increased accordingly. Therefore, if the volume of the premixed air is decreased to increase the exchange capacity per volume, the ion exchange capacity per volume decreases. As the opening diameter decreases, the pressure loss increases Had the same drawbacks as the. On the other hand, since the second monolithic anion exchanger of the present invention has high continuity and uniformity of three-dimensionally continuous pores, the pressure loss does not increase much even if the pore volume is reduced. Therefore, the anion exchange capacity per volume can be dramatically increased while the pressure loss is kept low. If the anion exchange capacity per volume is less than 0.3 mg equivalent / ml, the amount of the platinum group metal nanoparticles supported per volume decreases, which is not preferable. On the other hand, if the anion exchange capacity per volume exceeds 1.0 mg equivalent / ml, the pressure loss at the time of water passage increases, which is not preferable. In addition, the anion exchange capacity per weight in the dry state of the second monolith anion exchanger is not particularly limited. However, since the ion exchanger is uniformly introduced into the skeleton surface and skeleton of the porous body, 3.5 to 4.5 mg equivalent / g. The ion exchange capacity of the porous body introduced only into the skeleton surface of the ion exchanger can not be determined collectively depending on the type of the porous body or ion exchanger, but is only 500 당 equivalent / g.

The anion exchanger in the second monolith anion exchanger is the same as the anion exchanger in the first monolith anion exchanger, and a description thereof will be omitted. In the second monolithic anion exchanger, the introduced anion exchanger is uniformly distributed not only on the surface of the porous body, but also inside the skeleton of the porous body. The definition of the uniform distribution is the same as the definition of the uniform distribution of the first monolithic anion exchanger.

(Production method of the second monolithic anion exchanger)

The second monolithic anion exchanger is prepared by preparing a water-in-water emulsion by stirring a mixture of an oil-soluble monomer containing no ion-exchanger, a surfactant and water, and then polymerizing a water-in-water emulsion to form a water- In the step (I) of obtaining a monolithic organic porous intermediate having a continuous macropore structure of not more than 30 ml / g, an aromatic vinyl monomer, and 0.3 to 5 mol% of an organopolysiloxane monomer having at least two vinyl groups in a molecule The mixture obtained in the step (II) and the step (II) for preparing a mixture of an organic solvent and a polymerization initiator which dissolve the crosslinking agent, the aromatic vinyl monomer or the crosslinking agent but does not dissolve the polymer produced by polymerization of the aromatic vinyl monomer, Polymerization is carried out in the presence of the obtained monolithic organic porous intermediate to obtain a coin structure Ⅲ process, can be obtained by carrying out the Ⅳ step of introducing an anion exchanger to perform in the structure obtained in the step Ⅲ.

The step I for obtaining the monolith intermediate in the second monolithic anion exchanger may be carried out in accordance with the method described in Japanese Patent Application Laid-Open No. 2002-306976.

That is, in the step I, the usable monomer which does not contain an ion-exchange group includes, for example, an ion-exchange resin which does not contain an ion exchanger such as a carboxylic acid group, a sulfonic acid group or a quaternary ammonium group and has a low solubility in water, Monomers. Specific examples of these monomers include aromatic vinyl monomers such as styrene,? -Methylstyrene, vinyltoluene, vinylbenzyl chloride, vinylbiphenyl and vinylnaphthalene;? -Olefins such as ethylene, propylene, 1-butene, and isobutene; Halogenated olefins such as vinyl chloride, vinyl bromide, vinylidene chloride and tetrafluoroethylene; nitrile-based monomers such as acrylonitrile and methacrylonitrile; vinyl monomers such as vinyl acetate and vinyl propionate; Esters such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate (Meth) acrylic monomers such as benzyl methacrylate, and glycidyl methacrylate. Among these monomers, suitable examples include aromatic vinyl monomers such as styrene,? -Methylstyrene, vinyltoluene, vinylbenzyl chloride, and divinylbenzene. These monomers may be used singly or in combination of two or more. However, a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate is selected as a component of at least an oil-soluble monomer and the content thereof is 0.3 to 5 mol%, preferably 0.3 to 3 mol% Is preferable because it is advantageous in forming a structure in a performance.

The surfactant is the same as the surfactant used in the I step of the first monolith anion exchanger, and a description thereof will be omitted.

In the step I, a polymerization initiator may be used as needed in forming the water-in-water emulsion. As the polymerization initiator, a compound which generates radicals by heat and light irradiation is suitably used. The polymerization initiator may be water-soluble or oil-soluble. Examples thereof include 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile) Azobis (2-methylbutyronitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, Azobis (4-cyanovaleric acid), 1,1'-azobis (cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, tetramethylthiazol disulfide, Hydrogen peroxide-ferrous chloride, sodium persulfate-sodium acid sulfite, and the like.

The mixing method in mixing an oil-soluble monomer, a surfactant, water and a polymerization initiator not containing an ion exchanger and a water-in-oil type emulsion is the same as the mixing method in the first step of the first monolithic anion exchanger, The description thereof will be omitted.

In the method for producing the second monolithic anion exchanger, the monolith intermediate obtained in the step I is an organic polymer material having a crosslinked structure, preferably an aromatic vinyl polymer. The crosslinking density of the polymer material is not particularly limited, but it is preferable that the crosslinking structural unit contains 0.3 to 5 mol%, preferably 0.3 to 3 mol%, of the crosslinking structural unit with respect to all the constituent units constituting the polymer material. When the amount of the crosslinking structural unit is less than 0.3 mol%, the mechanical strength is insufficient. On the other hand, if it exceeds 5 mol%, the structure of the monolith tends to deviate from the structure of the air-permeability, which is not preferable. Particularly, in the case of the small pitch of the present invention at a pitch of 16 to 20 ml / g, it is preferable that the cross-linking structural unit is less than 3 mol% in order to form a coin structure.

The kind of the polymer material of the monolith intermediate is the same as that of the polymer material of the monolith intermediate of the first monolith anion exchanger, and a description thereof is omitted.

The bulk density of the monolith intermediate is greater than 16 ml / g but not greater than 30 ml / g, suitably greater than 16 ml / g and not greater than 25 ml / g. That is, this monolith intermediate is basically a continuous macropore structure. However, since the opening (mesopore) which is the overlapping portion of the macropores and the macropores is remarkably large, the skeleton constituting the monolith structure is separated from the two- It has an infinitely close structure to the shape skeleton. When this is coexisted in the polymerization system, a porous body having a structure of the air-permeable structure is formed with the structure of the monolith intermediate as a mold. If the volume of the premix is too small, the structure of the monolith obtained after the polymerization of the vinyl monomer is changed from the structure of the coenzyme to the continuous macropore structure, which is not preferable. On the other hand, The mechanical strength of the obtained monolith is lowered or the anion exchange capacity per volume is lowered. In order to set the volume of the monolith intermediate to a specific range of the second monolithic anion exchanger, the ratio of monomer to water may be generally from 1:20 to 1:40.

In the monolith intermediate, the average diameter of the openings (mesopores) which are the overlapping portions of the macropores and the macropores is 5 to 100 mu m in the dry state. If the average diameter of the openings is less than 5 占 퐉 in the dry state, the openings of the monoliths obtained after polymerization of the vinyl monomer become small, and the pressure loss during permeation of the fluid becomes large. On the other hand, if it exceeds 100 탆, the diameter of the monolith obtained after polymerization of the vinyl monomer becomes too large, the contact between the water to be treated and the monolith anion exchanger becomes insufficient, and as a result, the hydrogen peroxide decomposition characteristic or the dissolved oxygen removal characteristic It is not desirable because it does. The monolith intermediate is preferably a uniform structure in which the size of the macro pores and the diameter of the openings are uniform. However, the present invention is not limited to this, and macropores having a uniformity larger than the uniform macro pores may be dotted.

In the process for producing the second monolithic anion exchanger, the step (II) is preferably a step of dissolving the aromatic vinyl monomer, 0.3 to 5 mol% of the crosslinking agent, the aromatic vinyl monomer or the crosslinking agent in the total amount of the monofunctional monomer having at least two vinyl groups in one molecule However, the polymer produced by polymerization of an aromatic vinyl monomer is a step of preparing a mixture comprising an organic solvent which does not dissolve and a polymerization initiator. In addition, there is no sequence of the I step and the II step, and the II step may be performed after the I step, or the I step may be performed after the II step.

In the method for producing the second monolithic anion exchanger, the aromatic vinyl monomer used in the step II is not particularly limited as far as it is a lipophilic aromatic vinyl monomer containing a vinyl group polymerizable in the molecule and having high solubility in an organic solvent , It is preferable to select a vinyl monomer which produces the same or similar polymer material as the monolith intermediate which coexists in the polymerization system. Specific examples of these vinyl monomers include styrene,? -Methylstyrene, vinyltoluene, vinylbenzyl chloride, vinylbiphenyl, and vinylnaphthalene. These monomers may be used singly or in combination of two or more. The aromatic vinyl monomers suitably used in the present invention are styrene, vinylbenzyl chloride, and the like.

The amount of these aromatic vinyl monomers to be added is 5 to 50 times, preferably 5 to 40 times, by weight with respect to the monolith intermediate to be coexisted at the time of polymerization. If the addition amount of the aromatic vinyl monomer is less than 5 times as large as that of the monolith intermediate, the rod-shaped skeleton can not be made thick and the anion exchange capacity per volume after introduction of the anion-exchange group becomes small. On the other hand, when the amount of the aromatic vinyl monomer added is more than 50 times, the diameter of the continuous pores becomes small and the pressure loss at the time of water passage becomes large, which is not preferable.

The crosslinking agent used in the step (II) is preferably one having at least two polymerizable vinyl groups in the molecule and having a high solubility in an organic solvent. Specific examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, and butanediol diacrylate. These crosslinking agents may be used singly or in combination of two or more. A preferred crosslinking agent is an aromatic polyvinyl compound such as divinylbenzene, divinylnaphthalene, divinylbiphenyl and the like because of its high mechanical strength and stability against hydrolysis. The amount of the crosslinking agent to be used is 0.3 to 5 mol%, particularly 0.3 to 3 mol%, based on the total amount of the vinyl monomer and the crosslinking agent (prepolymerizable monomer). If the amount of the cross-linking agent is less than 0.3 mol%, the mechanical strength of the monolith is insufficient, which is undesirable. On the other hand, if the amount is too large, quantitative introduction of the anion-exchange group may become difficult. It is preferable that the amount of the crosslinking agent used is approximately equal to the crosslinking density of the monolith intermediate which coexists in the polymerization of the vinyl monomer / crosslinking agent. If the amount of use is too large, deflection of the crosslinked density distribution occurs in the produced monolith, and cracks tend to occur at the time of anion exchange group introduction reaction.

The organic solvent used in the step II is a poor solvent for an organic solvent which dissolves an aromatic vinyl monomer or a crosslinking agent but does not dissolve a polymer produced by polymerization of an aromatic vinyl monomer, in other words, a polymer produced by polymerization of an aromatic vinyl monomer . Since the organic solvent differs greatly depending on the kind of the aromatic vinyl monomer, it is difficult to list general examples. For example, when the aromatic vinyl monomer is styrene, examples of the organic solvent include methanol, ethanol, propanol, Alcohols such as cyclohexanol, cyclohexanol, octanol, 2-ethylhexanol, decanol, dodecanol, propylene glycol, tetramethylene glycol and the like; ethers such as diethyl ether, butyl cellosolve, polyethylene glycol, polypropylene glycol, Chain saturated hydrocarbons such as hexane, heptane, octane, isooctane, decane and dodecane; esters such as ethyl acetate, isopropyl acetate, cellosolve acetate and ethyl propionate; . Further, both of the use of polystyrene such as dioxane, THF and toluene can be used together with the above-mentioned poor solvent, and when the amount of use is small, it can be used as an organic solvent. The amount of these organic solvents to be used is preferably such that the concentration of the aromatic vinyl monomer is 30 to 80% by weight. When the amount of the organic solvent used deviates from the above range and the concentration of the aromatic vinyl monomer is less than 30% by weight, the polymerization rate is lowered or the monolith structure after polymerization deviates from the scope of the present invention. On the other hand, if the concentration of the aromatic vinyl monomer exceeds 80% by weight, the polymerization may be runaway, which is not preferable.

The polymerization initiator is the same as the polymerization initiator used in the II step of the first monolithic anion exchanger, and a description thereof will be omitted.

In the method for producing the second monolithic anion exchanger, the step (III) is a step of carrying out polymerization in the presence of the monolith intermediate obtained in the step (I) and standing the mixture obtained in the step (II) And a monolith of the performance structure is obtained. The monolith intermediate used in step III plays a very important role in creating a monolith having the novel structure of the present invention. As disclosed in Japanese Patent Application Laid-Open No. 7-501140 and the like, when the vinyl monomer and the cross-linking agent are subjected to stationary polymerization in the presence of the monolith intermediate in a specific organic solvent, a particle-aggregated monolithic organic porous body can be obtained. On the other hand, when a monolith intermediate of a specific continuous macropore structure is present in the polymerization system like the second monolith of the present invention, the structure of the monolith after polymerization changes dramatically and the particle aggregation structure disappears, Structure monolith can be obtained. The reason for this is not clarified in detail, but when the monolith intermediate is not present, the aggregation structure is formed by precipitation and precipitation of the crosslinked aggregate formed by the polymerization in the form of particles, In the presence of the porous material (intermediate), the vinyl monomer and the cross-linking agent are adsorbed or distributed from the liquid phase to the skeleton of the porous material, the polymerization proceeds in the porous material, and the skeleton constituting the monolith structure becomes a one- It is supposed that the monolithic organic porous material having the structure at the air-fuel ratio is formed.

The content of the reaction vessel is the same as that of the reaction vessel of the first monolith anion exchanger, and a description thereof will be omitted.

In step III, in the reaction vessel, the monolith intermediate is impregnated with the mixture (solution). The mixture ratio of the mixture obtained in the step II and the monolith intermediate is preferably such that the addition amount of the aromatic vinyl monomer to the monolith intermediate is 5 to 50 times, preferably 5 to 40 times by weight, as described above. This makes it possible to obtain a monolith with a concave structure in which the pores having a proper size are three-dimensionally continuous and the coarse framework is three-dimensionally continuous. In the reaction vessel, the aromatic vinyl monomer and the cross-linking agent in the mixture are adsorbed and distributed on the skeleton of the stationary monolith intermediate, and the polymerization proceeds in the skeleton of the monolith intermediate.

The basic structure of a monolith having a structure in a performance mode is a three-dimensionally continuous skeleton having an average thickness of 0.8 to 40 탆 in a dry state and a three-dimensionally continuous skeleton having an average diameter of 8 to 80 탆 in a dry state . The average diameter of the dried three-dimensionally continuous pores can be obtained as the maximum value of the pore distribution curve by measuring the pore distribution curve by the mercury porosimetry. The thickness of the skeleton of the monolith in a dry state can be measured by performing SEM observation at least three times and measuring the average thickness of the skeleton in the obtained image. In addition, the monolith having the performance structure has a lean space capacity of 0.5 to 5 ml / g.

The polymerization conditions are the same as the description of the polymerization conditions in the step (III) of the first monolithic anion exchanger, and a description thereof will be omitted.

In the step IV, the method of introducing the anion-exchange group into the monolith having the structure of the performance structure is the same as the method of introducing the anion-exchange group into the monolith in the first monolithion anion exchanger, and a description thereof will be omitted.

In the second monolithic anion exchanger, since an anion-exchange group is introduced into the monolith of the structure of the performance-type structure, the second monolithic anion exchanger swells to, for example, 1.4 to 1.9 times as large as that of the monolith. Also, even if the public diameter increases due to the swelling, the volume of the public space does not change. Therefore, the second monolithic anion exchanger has a high mechanical strength because it has a large skeleton although the size of the three-dimensionally continuous pores is remarkably large. In addition, since the skeleton is thick, the anion exchange capacity per volume in the wetted state can be increased, and the for-treatment water can be pumped for a long time at a low pressure and a large flow rate.

<First Platinum Group Metal Supporting Catalyst and Second Platinum Group Metal Supporting Catalyst>

The first platinum group metal supported catalyst of the present invention is a platinum group metal supported catalyst in which nanoparticles of a platinum group metal are supported on a first monolithic anion exchanger. The second platinum group metal supported catalyst of the present invention is a platinum group metal supported catalyst having nanoparticles of a platinum group metal carried on a second monolithic anion exchanger.

The platinum group metals according to the present invention are ruthenium, rhodium, palladium, osmium, iridium, and platinum. These platinum group metals may be used singly or in combination of two or more kinds of metals, or two or more kinds of metals may be used as alloys. Among these, platinum, palladium, platinum / palladium alloy have high catalytic activity and are suitably used.

The average particle diameter of the platinum group metal nanoparticles according to the present invention is 1 to 100 nm, preferably 1 to 50 nm, and more preferably 1 to 20 nm. On the other hand, if the average particle diameter exceeds 100 nm, the surface area per unit mass of the metal becomes small and the catalytic effect is efficiently obtained It is not preferable. When the average particle diameter of the nanoparticles is within the above range, the nanoparticles are strongly colored due to the surface plasmon resonance, and thus can be visually confirmed.

The amount of platinum group metal nanoparticles ((platinum group metal nanoparticles / first platinum group metal supported catalyst in a dry state) x 100) in the dry first platinum group metal supported catalyst is 0.004 to 20 wt%, preferably 0.005 to 15 wt% Weight%. The amount of the platinum group metal nanoparticles ((platinum group metal nanoparticles / second platinum group metal supported catalyst in a dry state) x 100) in the dried second platinum group metal supported catalyst is 0.004 to 20 wt%, preferably 0.005 To 15% by weight. If the loading amount of the platinum group metal nano-particles is less than 0.004% by weight, the hydrogen peroxide decomposition effect or the dissolved oxygen removal effect becomes insufficient. On the other hand, when the loading amount of the platinum group metal nano-particles exceeds 20% by weight, the elution of the metal into water is confirmed, which is not preferable.

The first platinum group metal supported catalyst and the second platinum group metal supported catalyst are not particularly limited, and the first monolith anion exchanger or the second monolith anion exchanger may be supported with nanoparticles of a platinum group metal by a known method The first platinum group metal supported catalyst or the second platinum group metal supported catalyst can be obtained. For example, the first monolith anion exchanger or the second monolith anion exchanger in a dry state is immersed in an aqueous hydrochloric acid solution of palladium chloride, the palladium chloride anion is adsorbed to the monolith anion exchanger by ion exchange, The palladium metal nanoparticles are contacted with a reducing agent to carry the palladium metal nanoparticles on the first monolith anion exchanger or the second monolith anion exchanger, or a method in which the first monolith anion exchanger or the second monolith anion exchanger is packed in a column, Hydrochloric acid aqueous solution is passed through the first monolithic anion exchanger or the second monolithic anion exchanger by ion exchange to adsorb the palladium metal anion chloride to the first monolith anion exchanger or the second monolith anion exchanger, And a method of supporting on a second monolithic anion exchanger. There are no particular restrictions on the reducing agent used. Examples of the reducing agent include alcohols such as methanol, ethanol and isopropanol, carboxylic acids such as formic acid, oxalic acid, citric acid and ascorbic acid, ketones such as acetone and methyl ethyl ketone, aldehydes such as formaldehyde and acetaldehyde , Sodium borohydride, and hydrazine.

In the first platinum group metal supported catalyst, the ionic form of the first monolithic anion exchanger, which is a carrier of the platinum group metal nano-particles, usually has a salt form such as a chloride form after carrying the platinum group metal nano-particles. In the present invention, such a salt type may be used as a catalyst for decomposing hydrogen peroxide or for removing dissolved oxygen. The first platinum group metal supported catalyst is not limited to this, and the ionic form of the first monolithic anion exchanger may be regenerated with an OH type. Of these, it is preferable that the ion type of the first monolith anion exchanger is an OH type because a high catalytic effect can be obtained. Similarly, in the second platinum group metal supported catalyst, the ionic form of the second monolithic anion exchanger, which is a carrier of the platinum group metal nano-particles, usually has a salt-like form after carrying the platinum group metal nano-particles. In the present invention, such a salt type may be used as a catalyst for decomposing hydrogen peroxide or for removing dissolved oxygen. The second platinum group metal supported catalyst is not limited to this, and the ionic form of the second monolithic anion exchanger may be regenerated in an OH form. Of these, it is preferable that the ion type of the second monolith anion exchanger is an OH type because a high catalytic effect can be obtained. The method of regenerating the monolith anion exchanger into an OH form after supporting the platinum group metal nanoparticles is not particularly limited, and a known method such as passing through an aqueous solution of sodium hydroxide may be used.

&Lt; Process for producing decompositionally treated water of hydrogen peroxide of the present invention &

The method for producing hydrogen peroxide decomposition-treated water according to the present invention comprises the steps of bringing a for-treatment water containing hydrogen peroxide into contact with a first platinum group metal supported catalyst or a second platinum group metal supported catalyst to decompose hydrogen peroxide in the for- Decomposing treatment water of hydrogen peroxide. Hereinafter, the first platinum group metal supported catalyst and the second platinum group metal supported catalyst are collectively referred to as the platinum group metal supported catalyst of the present invention.

The water to be treated containing hydrogen peroxide is not particularly limited as long as it contains hydrogen peroxide. For example, in the production of electronic parts such as semiconductor manufacturing and the production of ultrapure water for cleaning electronic parts manufacturing equipment, Water generated by various processes can be mentioned. Specifically, water after the ultraviolet oxidation treatment process for decomposing organic matter in water can be mentioned. As the water to be treated containing hydrogen peroxide, hydrogen peroxide is added to the wastewater system, and the treatment is carried out by using a treatment solution or treatment water in which hydrogen peroxide is added, oxidized, reduced, sterilized, Waste water or drainage. For example, cleaning wastewater containing hydrogen peroxide discharged from a semiconductor manufacturing process and rinsing wastewater containing organic matter discharged from a semiconductor manufacturing process are recovered and reused as ultrapure water, and ultraviolet rays are irradiated in the presence of hydrogen peroxide, Treated water obtained by decomposing organic matter using Fenton's reagent, waste water obtained by sterilizing or washing the treated water, reverse osmosis membrane, ultrafiltration membrane, etc. with hydrogen peroxide, treated water obtained by reducing waste water containing hexavalent chromium with hydrogen peroxide And the like.

The concentration of hydrogen peroxide in the water to be treated containing hydrogen peroxide is not particularly limited, but is usually 0.01 to 100 mg / L. In a subsystem for ultrapure water production, the concentration of hydrogen peroxide is usually 10 to 50 占 퐂 / L. If the concentration of hydrogen peroxide exceeds 100 mg / L, deterioration of the mother monolith anion exchanger tends to proceed.

The method of bringing the water to be treated containing hydrogen peroxide into contact with the platinum group metal supported catalyst of the present invention is not particularly limited and, for example, a method of charging the platinum group metal supported catalyst of the present invention into a catalyst- For example, a method of supplying a to-be-treated liquid containing hydrogen peroxide by passing the to-be-treated water containing hydrogen peroxide through the platinum group metal supported catalyst of the present invention.

In the case of the above method, the to-be-treated water containing hydrogen peroxide can be passed through the platinum group metal supported catalyst of the present invention at an SV = 2000 to 20000 h ^-1 , preferably an SV = 5000 to 10000 h ^-1 . By using the platinum group metal supported catalyst of the present invention, hydrogen peroxide can be decomposed and removed even if the SV undergoes a large SV exceeding 2000 h ^-1 to pass the for-treatment water. Even if the SV is 10000 h &lt; ^{-1 &} gt ;, the use of the platinum group metal supported catalyst of the present invention enables decomposition of hydrogen peroxide, and the platinum group metal supported catalyst of the present invention can be produced by a conventional method in which platinum group metal nanoparticles are supported on a particulate anion exchange resin Which is much higher than the treatment limit of the supported catalyst of the present invention. The flow rate of the hydrogen peroxide-containing water to be treated with the platinum group metal supported catalyst of the present invention is not particularly limited, but SV = 2000 to 20000 h ^-1 , particularly preferably SV = 5000 to 10000 h ^-1 . In addition, the platinum group metal supported catalyst of the present invention, due to high hydrogen peroxide decomposition ability considerably, it is not necessary to dare to the water flow rate to an area of less than SV = ^2000h-1, the water flow rate to an area of less than SV = 2000h ^-1 The platinum group metal supported catalyst of the present invention exhibits excellent hydrogen peroxide decomposing ability even when the feed rate is set in the range of SV = 2000h ^{-1 or} less. On the other hand, when the SV exceeds 20000 h ^-1 , the water pressure difference tends to become too large.

In addition, since the platinum group metal supported catalyst of the present invention has a remarkably high ability to decompose hydrogen peroxide, hydrogen peroxide can be decomposed and removed even when the height of the packed bed of the catalyst is reduced.

The concentration of hydrogen peroxide in the treated water obtained by carrying out the method for producing hydrogen peroxide decomposition-treated water of the present invention is preferably 1 μg / L or less.

The cleaning method (I) of the electronic component of the present invention is a cleaning method of an electronic component for cleaning an electronic component or a manufacturing apparatus of an electronic component with treated water obtained by performing the method for producing hydrogen peroxide decompositionally treated water of the present invention.

Examples of the cleaning method (I) of the electronic component of the present invention will be described with reference to Figs. 13 and 14. Fig. Fig. 13 is a schematic flow chart of a first embodiment of the cleaning method (I) of the electronic component of the present invention, and Fig. 14 is a schematic flow chart of the second embodiment of the cleaning method (I) of the electronic component of the present invention.

As shown in Fig. 13, the first embodiment of the cleaning method (I) of the electronic component of the present invention is characterized in that the object to be cleaned is brought into contact with water containing ozone (hereinafter also referred to as ozone- A first step (21) for cleaning the washed material, and a step (21) for cleaning the object to be cleaned by contacting the object to be cleaned with water containing hydrogen (hereinafter also referred to as hydrogen-containing water) A third step (23) for contacting the object to be cleaned with water containing hydrofluoric acid and hydrogen peroxide to clean the object to be cleaned; and a third step (23) for bringing the object to be cleaned into contact with the hydrogen- And a fourth step (24) of cleaning the object to be cleaned while causing the above vibration to occur.

The washing water supplied to the first step (21) is ozone-containing water prepared by dissolving ozone in the ultrapure water (32). The ultrapure water contains hydrogen peroxide because it is subjected to ultraviolet oxidation treatment in its production process. Therefore, in the first embodiment of the cleaning method (I) of the electronic component of the present invention, before the ozone 33 is dissolved in the ultrapure water 32, the ultrapure water 32 is treated as the water to be treated to decompose the hydrogen peroxide The hydrogen peroxide removal step 25 for performing the production method of the treated water is carried out and the ozone 33 is dissolved in the obtained treated water and supplied as the washing water for the first step 21.

The washing water supplied to the second step (22) is a hydrogen-containing water prepared by dissolving hydrogen in the ultra-pure water (32). Therefore, in the first embodiment of the cleaning method (I) of the electronic component of the present invention, before the hydrogen (34) is dissolved in the ultrapure water (32), the ultrapure water (32) The hydrogen peroxide removal step 26 for performing the production method of the treated water is performed and the hydrogen 34 is dissolved in the obtained treated water and supplied as the washing water for the second step 22. In the first embodiment of the cleaning method (I) of the electronic component of the present invention, similarly to the fourth step (24), before the hydrogen (36) is dissolved in the ultrapure water (32), the ultrapure water The hydrogen peroxide removal step 28 for performing the method of producing decompositionally treated hydrogen peroxide of the present invention is carried out and the hydrogen 36 is dissolved in the obtained treated water and supplied as the washing water for the fourth step 24. The time for dissolving the hydrogen (34 or 36) may be the front end of the hydrogen peroxide removal step (26 or 28).

In the first embodiment of the cleaning method (I) of the electronic component of the present invention, the hydrogen peroxide removal step (27) for performing the production method of the decompositionally treated water of the present invention using the ultrapure water (32) And hydrofluoric acid and hydrogen peroxide 35 are dissolved in the obtained treated water, and water containing the obtained hydrofluoric acid and hydrogen peroxide can be supplied as the washing water in the third step (23).

Then, the electronic components 20a before cleaning are subjected to the first to fourth steps (21) to (24) in this order to obtain the cleaned electronic component 30a.

As shown in Fig. 14, the second embodiment of the cleaning method (I) of the electronic component of the present invention is a cleaning method for cleaning an object to be cleaned by contacting the object to be cleaned with a liquid containing sulfuric acid and hydrogen peroxide (43) for cleaning the object to be cleaned by contacting the object to be cleaned with water (hydrofluoric acid) containing hydrofluoric acid, and a second step (42) of rinsing with ultrapure water, A fourth step (44) of rinsing with ultrapure water, a fifth step (45) of contacting the object to be cleaned with water containing ammonia and hydrogen peroxide to clean the object to be cleaned, and a sixth step of rinsing with ultrapure water A seventh step (47) for cleaning the object to be cleaned, an eighth step (48) for rinsing with ultrapure water, and a step for purifying the object to be cleaned in water containing hydrochloric acid and hydrogen peroxide A ninth step (49) for cleaning the object to be cleaned by contacting the object to be cleaned, a tenth step (50) for rinsing with ultrapure water, An eleventh step (51) for cleaning the object to be cleaned, and a twelfth step (52) for rinsing with ultrapure water by bringing the object to be cleaned into contact with water (dilute hydrofluoric acid) containing hydrofluoric acid.

The cleaning water 63, 65, 69, and 71 supplied to the third, fifth, ninth, and eleventh steps in Fig. 14 are water in which the agent necessary for each step is dissolved in ultrapure water. Therefore, in the second embodiment of the cleaning method (I) of the electronic component of the present invention, as in the first embodiment of the cleaning method (I) of the electronic component of the present invention shown in FIG. 13, The hydrogen peroxide removal step of performing the production method of the hydrogen peroxide decomposition treated water of the present invention using ultrapure water as the for-treatment water is performed, the necessary agent for each step is dissolved in the obtained treated water, and the washing water Cleaning liquid).

The cleaning water 62, 64, 66, 67, 68, 70 and 72 supplied to the second, fourth, sixth, seventh, eighth, tenth and twelfth processes in Fig. Thus, in the second embodiment of the cleaning method (I) of the electronic component of the present invention, the hydrogen peroxide removal step for performing the method for producing the decompositionally treated water of the present invention using the ultrapure water as the for-treatment water is performed, , And supplied as cleaning water for each process.

Then, the electronic components 20b before cleaning are subjected to the first to eighth processes (41) to (52) in this order to obtain the cleaned electronic component 30b.

As described above, in the present invention, the cleaning of the electronic parts or the manufacturing equipment of the electronic parts with the treated water obtained by the method of producing hydrogen peroxide decomposition-treated water of the present invention means that the hydrogen peroxide decomposition- The process for producing ultrapure water used for cleaning an electronic component or an electronic component manufacturing apparatus as well as for cleaning an electronic component or an electronic component manufacturing apparatus with the treated water immediately after the production method of Means cleaning the manufacturing equipment of electronic parts or electronic parts with ultrapure water obtained by carrying out the manufacturing method of the hydrogen peroxide decompositionally treated water of the present invention and performing all the steps of the production process of the ultrapure water.

&Lt; Method of producing dissolved oxygen depleted water of the present invention >

The method for producing dissolved oxygen depleted water of the present invention is a method for producing water by reacting dissolved oxygen and hydrogen in the for-treatment water containing oxygen in the presence of a first platinum group metal supported catalyst or a second platinum group metal supported catalyst , And a method for producing dissolved oxygen depleted water for removing dissolved oxygen from the for-treatment water containing oxygen.

The oxygen-containing water to be treated is not particularly limited as long as it contains oxygen. For example, raw water used in the production of ultrapure water for cleaning electronic parts, Or various kinds of water in the manufacturing process. Specific examples thereof include the circulating water of the ultrapure water production subsystem, for example, the number of outlets of the ultraviolet oxidation apparatus, and the like. Further, examples of the water to be treated containing dissolved oxygen include water used in power plants, boilers used in various factories, cooling water, and the like.

The concentration of dissolved oxygen in the oxygen-containing water to be treated is not particularly limited, but is usually 0.01 to 10 mg / L.

The amount of hydrogen to be reacted with dissolved oxygen is not particularly limited, but is an amount from 1 to 10 times the oxygen concentration, preferably from 1.1 to 5 times the oxygen concentration.

The method of reacting dissolved oxygen and hydrogen in the for-treatment water containing oxygen in the presence of the platinum group metal supported catalyst of the present invention is not particularly limited and, for example, a method of reacting the platinum group metal supported catalyst And a hydrogen gas is injected into the supply pipe of the liquid to be treated to supply a solution containing dissolved hydrogen and dissolved oxygen to the platinum group metal supported catalyst of the present invention And a method of passing through the water to be treated.

In the case of the above-described way, it is that the platinum group metal in the supported catalyst of the present invention, the for-treatment water containing oxygen, SV = 2000 ~ 20000h ^-1, preferably can be a water flow SV = 5000 ~ 10000h ^-1. With the use of the platinum group metal supported catalyst of the present invention, dissolved oxygen can be removed even if the SV undergoes a large SV exceeding 2000 h ^-1 to pass the for-treatment water. Even if the SV is 10000 h &lt; ^{-1 &} gt ;, the use of the platinum group metal supported catalyst of the present invention enables the removal of dissolved oxygen, and the platinum group metal supported catalyst of the present invention is a catalyst in which platinum group metal nanoparticles are supported on the particulate anion exchange resin Exhibits excellent performance exceeding the processing limit of the conventional supported catalyst. The flow rate of the oxygen-containing water to be treated to the platinum group metal supported catalyst of the present invention is not particularly limited, but SV = 2000 to 20000 h ^-1 , particularly preferably SV = 5000 to 10000 h ^-1 . In addition, since the platinum group metal supported catalyst of the present invention has a remarkably high dissolved oxygen removing ability, it is possible to provide a platinum group metal supported on the surface of the platinum group metal supported nano- The dissolved oxygen in the for-treatment water can be decomposed.

Further, since the platinum group metal supported catalyst of the present invention has a remarkably high dissolved oxygen removing capability, it is possible to remove dissolved oxygen even if the height of the packed bed of the catalyst is reduced.

It is preferable that the dissolved oxygen concentration in the treated water obtained by the method of producing dissolved oxygen depleted water of the present invention is 10 占 퐂 / L or less.

The cleaning method (II) of an electronic component of the present invention is a cleaning method of an electronic component for cleaning an electronic component or a manufacturing apparatus for an electronic component with treated water obtained by performing the method for producing dissolved oxygen depleted water of the present invention.

Oxygen in the air dissolves in the water as dissolved oxygen. As described above, the dissolved oxygen concentration in the for-treatment water (primary pure water) at the inlet of the secondary pure water system of the ultrapure water producing apparatus is generally 100 μg / L or less . In some cases, the concentration is controlled to 10 μg / L or less. The concentration of dissolved oxygen in the ultrapure water may be controlled to 10 μg / L or less and 1 μg / L or less. On the other hand, in the production process of ultrapure water, oxygen is generated when hydrogen peroxide generated by ultraviolet oxidation treatment or the like is decomposed. Therefore, in the form of the cleaning method (II) of the electronic component of the present invention, the dissolved oxygen removing step of performing the method of producing dissolved oxygen depleted water of the present invention is performed, (Cleaning liquid) supplied to each process or ultrapure water for preparation thereof.

The first embodiment of the cleaning method (II) of the electronic component of the present invention is characterized in that the hydrogen peroxide removal steps 25, 26, 27 and 28 in FIG. 13 are performed by using the ultrapure water 32 as the water to be treated, The dissolved oxygen removing step is performed instead of the dissolved oxygen removing step. Then, the electronic components 20a before cleaning are subjected to the first to fourth steps (21) to (24) in this order to obtain the cleaned electronic component 30a.

The second embodiment of the cleaning method (II) of the electronic component of the present invention is characterized in that the cleaning water (cleaning liquid) 63, 65, 69 and 71 supplied to the third, fifth, Treated water is subjected to a dissolved oxygen removing step of performing the method for producing dissolved oxygen depleted water of the present invention and the necessary medicines in each step are dissolved in the obtained treated water, The cleaning water 62, 64, 66, 67, 68, 70 and 72 supplied to the process steps 4, 6, 7, 8, 10 and 12 is treated with ultrapure water as the water to be treated And a dissolved oxygen removing step for carrying out the production method of the present invention. Then, the electronic components 20b before cleaning are subjected to the first to eighth processes (41) to (52) in this order to obtain the cleaned electronic component 30b.

As described above, in the present invention, cleaning the electronic parts or the manufacturing equipment of electronic parts with the treated water obtained by performing the method of producing dissolved oxygen depleted water of the present invention means that the dissolved oxygen removal It is preferable that any one of the processes for cleaning the electronic parts or the manufacturing equipment of the electronic parts as well as the process for producing the ultra pure water used for cleaning the electronic parts or the manufacturing equipments of the electronic parts, Means that the manufacturing method of the dissolved oxygen depleted water of the present invention is carried out at two or more places and the manufacturing process of the electronic component or the electronic component is cleaned with the ultrapure water obtained by performing all the steps of the manufacturing process of the ultrapure water.

EXAMPLES Next, the present invention will be described specifically by way of examples, but these are only illustrative and do not limit the present invention.

Example

&Lt; Preparation of first monolithic anion exchanger (Reference Example 1) >

(Step I: Preparation of Monolith Intermediate)

19.9 g of styrene, 0.4 g of divinylbenzene, 1.0 g of sorbitan monooleate (hereinafter referred to as SMO) and 0.26 g of 2,2'-azobis (isobutyronitrile) were mixed and uniformly dissolved. Next, the mixture of styrene / divinylbenzene / SMO / 2, 2'-azobis (isobutyronitrile) was added to 180 g of purified water containing 1.8 ml of THF, and the mixture was stirred in a vacuum stirring defoaming mixer Under the reduced pressure in a temperature range of 5 to 20 占 폚 to obtain a water-in-oil type emulsion. The emulsion was quickly transferred to a reaction vessel, and after sealing, polymerization was carried out at 60 DEG C for 24 hours under standing. After completion of the polymerization, the contents were taken out, extracted with isopropanol, and dried under reduced pressure to prepare a monolith intermediate having a continuous macropore structure. The average diameter of the opening (mesopore) at the overlapping portion of the macropores and macropores of the monolith intermediate measured by mercury porosimetry was 56 탆, and the bulk density was 7.5 ml / g.

(Preparation of Monolith)

Next, 49.0 g of styrene, 1.0 g of divinylbenzene, 50 g of 1-decanol and 0.5 g of 2,2'-azobis (2,4-dimethylvaleronitrile) were mixed and uniformly dissolved (Step II) . Next, the monolith intermediate was cut into a disc shape having an outer diameter of 70 mm and a thickness of about 20 mm, and 7.6 g of the product was collected. The separated monolith intermediate was placed in a reaction vessel having an inner diameter of 90 mm and immersed in the mixture of styrene / divinylbenzene / 1-decanol / 2,2'-azobis (2,4-dimethylvaleronitrile) , The reaction vessel was sealed and polymerized at 60 deg. C for 24 hours. After completion of the polymerization, the monolithic contents having a thickness of about 30 mm were taken out, Soxhlet extracted with acetone, and dried under reduced pressure at 85 캜 overnight (Step III).

The internal structure of the monolith (dried body) containing the crosslinking component of the styrene / divinylbenzene copolymer thus obtained in an amount of 1.3 mol% was observed by SEM, and the result is shown in Fig. The SEM image of Fig. 1 is an image at an arbitrary position on the cut surface obtained by cutting the monolith at an arbitrary position. As apparent from Fig. 1, the monolith has a continuous macropore structure, and the skeleton constituting the continuous macropore structure is much thicker than the SEM image (Fig. 11) of the known product of Reference Example 3, The thickness of the wall portion constituting the wall was large.

Next, the thickness of the wall portion and the skeleton area appearing on the cross section were measured from two points of SEM images obtained by cutting the obtained monolith at a position different from the above position excluding the main pipe, in total three points. The thickness of the wall portion was an average of 8 points obtained from one SEM photograph, and the skeleton area was obtained by image analysis. Further, the wall portion has the above definition. Also, the skeleton area was expressed as an average of three SEM images. As a result, the average thickness of the wall portion was 30 μm, and the skeleton area appearing on the cross section was 28% of the SEM images. The average diameter of the openings of the monoliths measured by the mercury porosimetry was 31 mu m and the bulk density was 2.2 mL / g.

(Preparation of Monolith Anion Exchanger)

The monolith prepared by the above method was cut into a disc shape having an outer diameter of 70 mm and a thickness of about 15 mm. 1400 ml of dimethoxymethane and 20 ml of tin tetrachloride were added thereto, and 560 ml of chlorosulfuric acid was added dropwise under ice-cooling. After completion of the dropwise addition, the mixture was heated to react at 35 DEG C for 5 hours to introduce a chloromethyl group. After completion of the reaction, the mother liquor was taken out with a siphon, washed with a mixed solvent of THF / water = 2/1, and then washed again with THF. 1000 ml of THF and 600 ml of a 30% aqueous solution of trimethylamine were added to the chloromethylated monolith and reacted at 60 ° C for 6 hours. After completion of the reaction, the product was washed with a mixed solvent of methanol and water, and then washed with pure water and isolated.

The swelling rate of the obtained monolith anion exchanger before and after the reaction was 1.7 times, and the anion exchange capacity per volume was 0.60 mg equivalent / ml in the wetted state. The average diameter of the openings of the monolith anion exchanger in the water wet state was estimated to be 54 占 퐉 from the value of the monolith and the swelling rate of the monolith anion exchanger in the water wet state. The average thickness of the part was 50 μm, the skeleton area was 28% of the SEM photo area, and the volume of the space was 2.2 ml / g. The differential pressure coefficient, which is an index of the pressure loss when water was permeated, was 0.017 MPa / m · LV, which was lower than the pressure loss required in practice. The ion exchange length of the monolith anion exchanger with respect to the fluoride ion was measured. As a result, the ion exchange length at LV = 20 m / h was 25 mm, and the commercially available strong basic anion exchange resin Amberlite IRA402BL (Manufactured by Rohm &amp; Haas Co., Ltd.) (165 mm).

Next, in order to confirm the distribution state of the quaternary ammonium group in the monolith anion exchanger, the monolith anion exchanger was treated with an aqueous hydrochloric acid solution to form a chloride type, and the distribution state of the chloride ion was observed by EPMA. The distribution state of chloride ion on the surface of the monolith anion exchanger is shown in Fig. 2, and the distribution state of chloride ion on the skeleton cross section is shown in Fig. 3. The chloride ion shows not only the skeleton surface of the monolith anion exchanger, It was confirmed that the quaternary ammonium group was uniformly introduced into the monolith anion exchanger. 3, the chloride ion concentration at the lower portion of the skeleton is apparently higher than that at the upper portion of the skeleton. This is due to the fact that the planarity of the section is not sufficient at the time of cutting, and the lower portion of the skeleton is cut off, The distribution of chloride ions is substantially uniform.

&Lt; Preparation of second monolithic anion exchanger (Reference Example 2) >

(Step I: Preparation of Monolith Intermediate)

5.29 g of styrene, 0.28 g of divinylbenzene, 1.39 g of sorbitan monooleate (hereinafter referred to as SMO) and 0.26 g of 2,2'-azobis (isobutyronitrile) were mixed and uniformly dissolved. Next, 180 g of pure water was added to the styrene / divinylbenzene / SMO / 2,2'-azobis (isobutyronitrile) mixture, and the mixture was stirred using a vacuum stirring defoaming mixer The mixture was stirred under reduced pressure at a temperature range of 5 to 20 占 폚 to obtain a water-in-oil type emulsion. The emulsion was quickly transferred to a reaction vessel, and after polymerization, polymerized at 60 DEG C for 24 hours under standing. After completion of the polymerization, the contents were taken out, extracted with methanol, and dried under reduced pressure to prepare a monolith intermediate having a continuous macropore structure. The internal structure of the monolith intermediate product (dried body) thus obtained was observed by an SEM image (Fig. 12). As a result, the wall portion dividing the adjacent two macropores was very thin and rod- The average diameter of the openings (mesopores) at the overlapping portions of the macropores and macropores measured by the compression method was 70 μm and the bulk density was 17.8 ml / g.

(Preparation of Monolith)

Subsequently, 39.2 g of styrene, 0.8 g of divinylbenzene, 60 g of 1-decanol and 0.8 g of 2,2'-azobis (2,4-dimethylvaleronitrile) were mixed and uniformly dissolved (Step II) . Next, the monolith intermediate was cut into a disc shape having a diameter of 70 mm and a thickness of about 30 mm, and 2.4 g of the monolith intermediate was collected. The separated monolith intermediate was placed in a reaction vessel having an inner diameter of 75 mm and immersed in the mixture of styrene / divinylbenzene / 1-decanol / 2,2'-azobis (2,4-dimethylvaleronitrile) , The reaction vessel was sealed and polymerized at 60 deg. C for 24 hours. After completion of the polymerization, the monolithic contents having a thickness of about 60 mm were taken out, Soxhlet extracted with acetone, and dried under reduced pressure at 85 캜 overnight (Step III).

7 shows the result of observation of the internal structure of the monolith (dried body) containing the crosslinking component of the styrene / divinylbenzene copolymer thus obtained in an amount of 1.3 mol% by SEM. As apparent from Fig. 7, the monolith was a concert structure in which the skeleton and the pore were three-dimensionally continuous and entangled. The thickness of the skeleton measured from the SEM image was 8 m. In addition, the average diameter of the three-dimensionally continuous pores of the monolith measured by the mercury porosimetry was 18 탆, and the pore volume was 2.0 ml / g.

(Preparation of Monolith Anion Exchanger)

The monolith prepared by the above method was cut into a disc shape having a diameter of 70 mm and a thickness of about 15 mm. 1400 ml of dimethoxymethane and 20 ml of tin tetrachloride were added thereto, and 560 ml of chlorosulfuric acid was added dropwise under ice-cooling. After completion of the dropwise addition, the mixture was heated to react at 35 DEG C for 5 hours to introduce a chloromethyl group. After completion of the reaction, the mother liquor was taken out with a siphon, washed with a mixed solvent of THF / water = 2/1, and then washed again with THF. 1000 ml of THF and 600 ml of a 30% aqueous solution of trimethylamine were added to the chloromethylated monolith and reacted at 60 ° C for 6 hours. After completion of the reaction, the product was washed with a mixed solvent of methanol and water, and then washed with pure water and isolated.

The swelling rate of the obtained monolith anion exchanger before and after the reaction was 1.6 times, and the anion exchange capacity per volume was 0.44 mg equivalent / ml in the water wet state. The average diameter of the continuous pores of the monolith ion exchanger in the water wet state was 29 탆 as estimated from the value of the monolith and the swelling rate of the monolith anion exchanger in the water wet state. The average thickness of the skeleton was 13 탆, The volume was 2.0 ml / g.

The differential pressure coefficient, which is an index of pressure loss when water was permeated, was 0.040 MPa / m · LV, and it was a low pressure loss with no problem in practical use. The length of the ion exchange barrel with respect to the fluoride ion of the monolith anion exchanger was measured. As a result, the length of the ion exchange bar at the LV = 20 m / h was 22 mm, and the commercially available strong basic anion exchange resin Amberlite IRA402BL (Manufactured by Rohm &amp; Haas Co., Ltd.) (165 mm).

Next, in order to confirm the distribution state of the quaternary ammonium group in the monolith anion exchanger, the monolith anion exchanger was treated with an aqueous hydrochloric acid solution to form a chloride type, and the distribution state of the chloride ion was observed by EPMA. The distribution of the chloride ion on the surface of the monolith anion exchanger is shown in Fig. 8, and the distribution of chloride ion on the skeleton cross section is shown in Fig. 9. The chloride ion shows not only the skeleton surface of the monolith anion exchanger, It was confirmed that the quaternary ammonium group was uniformly introduced into the monolith anion exchanger. In FIG. 9, the chloride ion concentration at the periphery of the framework is apparently higher than that at the center of the framework. This is because the planarity of the section is not sufficient at the time of cutting and the periphery of the framework rises above the inside. The distribution of the ions is substantially uniform.

Reference Example 3

(Production of a monolithic organic porous material (known product) having a continuous macropore structure)

A monolithic organic porous material having a continuous macropore structure was produced in accordance with the production method described in JP-A-2002-306976. Namely, 19.2 g of styrene, 1.0 g of divinylbenzene, 1.0 g of SMO and 0.26 g of 2,2'-azobis (isobutyronitrile) were mixed and uniformly dissolved. Next, 180 g of pure water was added to the mixture of styrene / divinylbenzene / SMO / 2, 2'-azobis (isobutyronitrile), and the mixture was stirred using a vacuum stirring defoaming mixer The mixture was stirred under reduced pressure at a temperature range of 5 to 20 占 폚 to obtain a water-in-oil type emulsion. The emulsion was quickly transferred to a reaction vessel, and after sealing, polymerization was carried out at 60 DEG C for 24 hours under standing. After completion of the polymerization, the contents were taken out, extracted with isopropanol, and dried under reduced pressure to prepare a monolithic organic porous material having a continuous macropore structure.

Fig. 11 shows the result of observation of the internal structure of the monolith containing 3.3 mol% of the crosslinking component composed of the styrene / divinylbenzene copolymer obtained by the SEM. 11, the monolith has a continuous macro-pore structure, but the thickness of the wall constituting the framework of the continuous macro-pore structure is thinner than that of Reference Example 1 (Fig. 1). The average thickness of the wall portion measured from the SEM image of the monolith was 5 mu m, and the skeleton area was 10% of the SEM image area. The average diameter of the openings of the monoliths measured by the mercury porosimetry method was 29 탆, and the bulk density of the monoliths was 8.6 ml / g.

Example 1

(Preparation of first platinum group metal supported catalyst)

The monolithic anion exchanger (first monolith anion exchanger) of Reference Example 1 was ion-exchanged with Cl type, and then cut into a cylindrical shape in a water wet state and dried under reduced pressure. The weight of the monolith anion exchanger after drying was 1.2 g. The dry monolithic anion exchanger was immersed in dilute hydrochloric acid in which 270 mg of palladium chloride had been dissolved for 24 hours and ion-exchanged in the form of palladium chloride. After completion of the immersion, the monolith anion exchanger was washed several times with pure water and immersed in an aqueous hydrazine solution for 24 hours to perform reduction treatment. The palladium chloride type monolith anion exchanger was brown, whereas the monolith anion exchanger after the reduction treatment was colored black, suggesting the formation of palladium nanoparticles. The first palladium nano-particle-supporting catalyst (a) thus obtained was washed with pure water several times and dried.

The loading amount of the palladium nanoparticles carried on the dried first palladium nano-particle-supporting catalyst (a) was 10.9% by weight. In order to measure the average particle diameter of the supported palladium nanoparticles, a transmission electron microscope (TEM) observation was performed. The obtained TEM image is shown in Fig. The average particle diameter of the palladium nanoparticles was 5 nm. The dried palladium nano-particle-supported catalyst (a) was packed in a column having an inner diameter of 10 mm, and an aqueous solution of sodium hydroxide was passed therethrough to prepare a monolith anion exchanger as a carrier, which was used for evaluation of hydrogen peroxide decomposition characteristics. The packed bed height of the first palladium nano-particle-supported catalyst (a) was 11 mm. At this time, the loading amount of the palladium nanoparticles relative to the resin volume in the wetted water state was 9.7 g-Pd / L-R (weight of palladium supported per 1 L of the palladium nano-particle supporting catalyst).

(Evaluation of catalyst)

A first palladium nanoparticles supported catalyst (a) charged in a column having an inner diameter of 10㎜, hydrogen peroxide 15 ~ 30㎍ / ultrapure water containing L SV = water flow from 5000h ^-1 in 27 hours down-flow and, at the column outlet The sample water was collected and the concentration of hydrogen peroxide was measured. As a result, the concentration of hydrogen peroxide in the sample water collected at the column outlet was less than 1 μg / L, and the hydrogen peroxide was decomposed and removed. Next, the SV was changed to 10000 h ^-1 and the same process was performed. The concentration of hydrogen peroxide in the sample water collected at the column outlet was less than 1 μg / L, and the hydrogen peroxide was decomposed and removed, even though the SV was as high as 10000 h ^-1 and the packed bed height of the catalyst was as thin as 11 mm.

Example 2

(Preparation of second platinum group metal supported catalyst)

As the catalyst carrier, the monolith anion exchanger (second monolith anion exchanger) of Reference Example 2 was used in place of the monolith anion exchanger (first monolith anion exchanger) of Reference Example 1, and the monolith anion exchanger Palladium nanoparticles were loaded on the monolith anion exchanger (second monolith anion exchanger) of Reference Example 2 in the same manner as in Example 1, except that the weight of the palladium nanoparticles was changed to 1.4 g instead of 1.2 g 2 palladium nanoparticle-supported catalyst (a) was obtained.

The amount of the supported palladium nanoparticles carried on the obtained second palladium nano-particle-supporting catalyst (a) was 9.8% by weight. In order to measure the average particle diameter of the supported palladium nanoparticles, a transmission electron microscope (TEM) observation was performed. The obtained TEM image is shown in Fig. The average particle diameter of the palladium nanoparticles was 3 nm. Dried palladium nano-particle-supported catalyst was packed in a column having an inner diameter of 10 mm, and an aqueous solution of sodium hydroxide was passed through to prepare a monolithic anion exchanger as a carrier, which was used for evaluation of hydrogen peroxide decomposition characteristics. The packed bed height of the catalyst was 13 mm. At this time, the loading amount of the palladium nanoparticles relative to the resin volume in the water wet state was 8.7 g-Pd / L-R.

(Evaluation of catalyst)

The hydrogen peroxide decomposition effect of the second palladium nano-particle-supported catalyst (a) was evaluated in the same manner as in Example 1, except that the second palladium nano-particle-supported catalyst (a) was used as the catalyst instead of the first palladium nano- . As a result, the hydrogen peroxide concentration in the sample water collected at the column outlet was less than 1 占 퐂 / L, and the hydrogen peroxide was decomposed and removed in any case of passing ultrapure water at SV = 5000h- ¹ and 10000h- ¹ .

Example 3

The dried first monolith anion exchanger was dried in the same manner as in Example 1, except that the weight of the first monolith anion exchanger was changed to 1.7 g instead of 1.2 g and that 2.5 mg of palladium chloride was dissolved instead of 270 mg of palladium chloride Palladium nanoparticles were supported on the monolith anion exchanger (first monolith anion exchanger) of Reference Example 1 to obtain a first palladium nano-particle-supporting catalyst (b).

The amount of the supported palladium nanoparticles carried on the dried first palladium nano-particle-supporting catalyst (b) was 0.05% by weight. The dried palladium nano-particle-supporting catalyst (b) in a dry state was packed in a column having an inner diameter of 10 mm, and an aqueous solution of sodium hydroxide was passed therethrough to prepare a monolithic anion exchanger as a carrier and used for evaluation of hydrogen peroxide decomposition characteristics. The packed bed height of the catalyst was 19 mm. At this time, the loading amount of the palladium nanoparticles relative to the resin volume in the water wet state was 0.07 g-Pd / L-R.

(Evaluation of catalyst)

(B) was prepared in the same manner as in Example 1 except that the first palladium nano-particle-supported catalyst (b) was used as the catalyst instead of the first palladium nano-particle-supported catalyst (a) The hydrogen peroxide decomposition effect was evaluated. When passing through SV = 5000h ^-1 , the concentration of hydrogen peroxide in the sample water collected at the column outlet was less than 1 μg / L, and hydrogen peroxide was decomposed and removed. Next, the SV was changed to 10000 h ^-1 and the same process was performed. The concentration of hydrogen peroxide in the sample water collected at the column outlet was 1.7 μg / L. Despite the very low loading of palladium nanoparticles of 0.07 g-Pd / LR, the hydrogen peroxide decomposition effect was high.

Comparative Example 1

The palladium nanoparticles carrying the palladium nanoparticles are supported on a strongly basic anion exchange resin (type I) having a water-retaining ability of 60 to 70% in the OH type standard, . Cl-type particulate anion exchange resin was immersed in a hydrochloric acid aqueous solution of palladium chloride, and after washing, reduction treatment was performed with an aqueous hydrazine solution. Sodium hydroxide aqueous solution was passed through to make an anion exchange resin in the form of particles as an OH type and used for evaluation of hydrogen peroxide decomposition characteristics. At this time, the loading amount of palladium nanoparticles was 0.4 wt% in the dry state and 970 mg-Pd / L-R in the water wet state. An OH type particulate ion exchange resin having palladium supported thereon was filled in a column having an inner diameter of 25 mm in an amount of 40 ml (layer height 80 mm), and experiments for reducing hydrogen peroxide were carried out in the same manner as in Example 1.

(Evaluation of catalyst)

As a catalyst, the one with the palladium nanoparticles supported particulate ion-exchange resin catalyst in place of the first palladium nanoparticles supported catalyst (a), and, except that the water passing the pure water to SV = 1500h and 2500h ^{-1 -1} , The effect of decomposing hydrogen peroxide on the palladium nano-particle-supported particle-shaped ion exchange resin catalyst was evaluated in the same manner as in Example 1. [ As a result, the concentration of hydrogen peroxide in the sample water collected at the column outlet was less than 1 μg / L and 1.6 μg / L, respectively. According to SV = 1500h ^-1 hydrogen peroxide, but this 1㎍ / less than L, to raise the SV 2500h ^-1, hydrogen peroxide has the leakage during the treatment. In this way, in the supported palladium nanoparticles in the prior art particulate anion exchange resin catalyst, than in the embodiment, setting the easiest condition to eliminate the hydrogen peroxide, such as the late SV, a thick catalyst packed bed height, SV = 2500h ^-1 hydrogen peroxide "He said.

Comparative Example 2

The hydrogen peroxide decomposition effect at SV = 10000 h ^-1 was evaluated in the same manner as in Example 1 by using only the monolith anion exchanger (first monolith anion exchanger) of Reference Example 1 without supporting the palladium nanoparticles. As a result, the decomposition effect of hydrogen peroxide was not recognized.

&Lt; Preparation of monoliths related to the first monolithic anion exchanger (Reference Examples 4 to 13) >

(Preparation of Monolith)

Except that the amount of styrene used, the type and amount of crosslinking agent used, the type and amount of organic solvent used, the porous structure of the monolith intermediate coexisting in styrene and divinylbenzene impregnation polymerization, the crosslinking density, and the amount used were changed to those shown in Table 1, A monolith was produced in the same manner as in Reference Example 1. The results are shown in Tables 1 and 2. From the SEM images (not shown) of Reference Examples 4 to 13 and Table 2, it can be seen that the average diameters of the openings of the monoliths of Reference Examples 4 to 13 were as large as 22 to 70 占 퐉, 50 ㎛, and the skeleton area was 26 ~ 44% of the SEM image area, which was thick monolith. In Table 1, the injection column shows the vinyl monomers, crosslinking agents, monolith intermediate obtained in Process I, and organic solvent used in Process II, which were used in the II process in this order from left to right. The diameters of the mesopores, the thickness of the wall, the diameter (thickness) of the skeleton, and the diameter of the pores shown in the following table are average values.

&Lt; Preparation of first monolithic anion exchanger (Reference Example 14) >

(Preparation of Monolith)

Monoliths were prepared in the same manner as in Reference Example 1, except that the amount of styrene, the amount of cross-linking agent, and the amount of organic solvent used were changed to those shown in Table 1. The results are shown in Tables 1 and 2. In the monolith of Reference Example 14, the average diameter of the openings in the overlapping portions of the macrophores and the macro-pores was 38 占 퐉, and the average thickness of the wall portions constituting the framework was 25 占 퐉.

(Preparation of Monolith Anion Exchanger)

The monolith prepared by the above method was cut into a disc shape having an outer diameter of 70 mm and a thickness of about 15 mm. 1400 ml of dimethoxymethane and 20 ml of tin tetrachloride were added thereto, and 560 ml of chlorosulfuric acid was added dropwise under ice-cooling. After completion of the dropwise addition, the mixture was heated to react at 35 DEG C for 5 hours to introduce a chloromethyl group. After completion of the reaction, the mother liquor was taken out with a siphon, washed with a mixed solvent of THF / water = 2/1, and then washed again with THF. 1000 ml of THF and 600 ml of a 30% aqueous solution of trimethylamine were added to the chloromethylated monolith and reacted at 60 ° C for 6 hours. After completion of the reaction, the product was washed with a mixed solvent of methanol and water, and then washed with pure water and isolated.

The swelling rate of the obtained monolith anion exchanger before and after the reaction was 1.6 times, and the anion exchange capacity per volume was 0.56 mg equivalent / ml in the water wet state. The average diameter of the openings of the monolith anion exchanger in the water wet state was estimated to be 61 탆 from the value of the monolith and the swelling rate of the monolith anion exchanger in the water wet state. The average thickness of the part was 40 μm, the skeleton area was 26% of the photographic area of the SEM photograph, and 2.9 ml / g of the charcoal volume. The differential pressure coefficient, which is an index of pressure loss when water was permeated, was 0.020 MPa / m · LV, which was lower than the pressure loss required in practice.

Next, in order to confirm the distribution state of the quaternary ammonium group in the monolith anion exchanger, the monolith anion exchanger was treated with an aqueous hydrochloric acid solution to form a chloride type, and the distribution state of the chloride ion was observed by EPMA. As a result, it was confirmed that the chloride ion was uniformly distributed not only on the skeleton surface of the monolith anion exchanger but also inside the skeleton, and the quaternary ammonium group was uniformly introduced into the monolith anion exchanger.

&Lt; Preparation of second monolithic anion exchanger (Reference Example 15) >

(Step I: Preparation of Monolith Intermediate)

5.4 g of styrene, 0.17 g of divinylbenzene, 1.4 g of sorbitan monooleate (hereinafter referred to as SMO) and 0.26 g of 2,2'-azobis (isobutyronitrile) were mixed and uniformly dissolved. Next, 180 g of pure water was added to the styrene / divinylbenzene / SMO / 2,2'-azobis (isobutyronitrile) mixture, and the mixture was stirred using a vacuum stirring defoaming mixer The mixture was stirred under reduced pressure at a temperature range of 5 to 20 占 폚 to obtain a water-in-oil type emulsion. The emulsion was quickly transferred to a reaction vessel, and after polymerization, polymerized at 60 DEG C for 24 hours under standing. After completion of the polymerization, the contents were taken out, extracted with methanol, and dried under reduced pressure to prepare a monolith intermediate having a continuous macropore structure. The internal structure of the monolith intermediate product (dried body) thus obtained was observed by an SEM image (not shown). As a result, the wall portion dividing the adjacent two macropores was very thin and had a bar shape but had an open cell structure, The average diameter of the openings (mesopores) at the overlapping portions of the macropores and the macropores measured by the compression method was 70 탆 and the total vacancy volume was 21.0 ml / g.

(Production of structure monolith in performance)

Next, 76.0 g of styrene, 4.0 g of divinylbenzene, 120 g of 1-decanol and 0.8 g of 2,2'-azobis (2,4-dimethylvaleronitrile) were mixed and uniformly dissolved (Step II) . Next, the monolith intermediate was cut into a disc shape having a diameter of 70 mm and a thickness of about 40 mm, and 4.1 g of the monolith intermediate was collected. The separated monolith intermediate was placed in a reaction vessel having an inner diameter of 75 mm and immersed in the mixture of styrene / divinylbenzene / 1-decanol / 2,2'-azobis (2,4-dimethylvaleronitrile) , The reaction vessel was sealed and polymerized at 60 deg. C for 24 hours. After completion of the polymerization, the monolithic contents having a thickness of about 60 mm were taken out, Soxhlet extracted with acetone, and dried under reduced pressure at 85 캜 overnight (Step III).

The internal structure of the monolith (dried body) containing 3.2 mol% of the crosslinking component composed of the styrene / divinylbenzene copolymer thus obtained was observed by SEM. As a result, the skeleton and the voids of the monolith were three-dimensionally continuous It was a structure in which performances were intertwined. The average thickness of the skeleton measured from the SEM image was 10 占 퐉. In addition, the average diameter of the voids in which the monoliths were three-dimensionally continuous as measured by the mercury porosimetry was 17 占 퐉, and the bulk density was 2.9 ml / g. The results are summarized in Tables 3 and 4. In Table 4, the thickness of the skeleton is represented by the average diameter of the skeleton.

(Preparation of monolith anion exchanger having air bubble structure in performance)

The monolith prepared by the above method was cut into a disc shape having a diameter of 70 mm and a thickness of about 15 mm. 1400 ml of dimethoxymethane and 20 ml of tin tetrachloride were added thereto, and 560 ml of chlorosulfuric acid was added dropwise under ice-cooling. After completion of the dropwise addition, the mixture was heated to react at 35 DEG C for 5 hours to introduce a chloromethyl group. After completion of the reaction, the mother liquor was taken out with a siphon, washed with a mixed solvent of THF / water = 2/1, and then washed again with THF. 1000 ml of THF and 600 ml of a 30% aqueous solution of trimethylamine were added to the chloromethylated monolith and reacted at 60 ° C for 6 hours. After completion of the reaction, the product was washed with a mixed solvent of methanol and water, and then washed with pure water and isolated.

The swelling rate of the obtained monolith anion exchanger before and after the reaction was 1.5 times, and the anion exchange capacity per volume was 0.54 mg equivalent / ml in a wetted state. The average diameter of the continuous pores of the monolith ion exchanger in the water wet state was 26 탆 as estimated from the value of the monolith and the swelling rate of the monolith anion exchanger in the water wet state. The average thickness of the skeleton was 15 탆, The volume was 2.9 ml / g.

The differential pressure coefficient, which is an index of the pressure loss when water was permeated, was 0.045 MPa / m · LV, and it was a low pressure loss without any problem in practical use. The length of the ion exchange barrel with respect to the fluoride ion of the monolith anion exchanger was measured. As a result, the length of the ion exchange barrel at the LV = 20 m / h was 20 mm, and the commercially available strong basic anion exchange resin Amberlite IRA402BL (165 mm) manufactured by Rohm &amp; Haas Co., Ltd., as well as the value of the monolithic porous anion exchanger having the conventional open cell structure was short. The results are summarized in Table 5. The internal structure of the obtained monolith anion exchanger having the through-air structure was observed with an SEM image (not shown).

Next, in order to confirm the distribution state of the quaternary ammonium group in the monolith anion exchanger, the monolith anion exchanger was treated with an aqueous hydrochloric acid solution to form a chloride type, and the distribution state of the chloride ion was observed by EPMA. As a result, it was confirmed that the chloride ion was uniformly distributed not only on the surface of the monolith anion exchanger but also inside the monolith anion exchanger, and that the quaternary ammonium group was uniformly introduced into the monolith anion exchanger.

&Lt; Preparation of second monolithic anion exchanger (Reference Examples 16 and 17) >

(Production of monolith having structure in performance)

The use amount of styrene, the amount of the crosslinking agent, the amount of the organic solvent used, the porous structure of the monolith intermediate coexisting in the styrene and divinylbenzene impregnation polymerization, the crosslinking density and the amount used were changed to the amounts shown in Table 3, In the same manner, a monolith having a performance structure was manufactured. The internal structure of the monolith (dried body) was observed by an SEM (not shown). The monolith had a structure in which the skeleton and the pore were three-dimensionally continuous each other and entangled with each other. The results are shown in Tables 3 and 4.

Table 1, Table 2, Table 3, and Table 4 are shown successively in the following order.

An anion exchanger can be introduced into the monoliths obtained in Reference Examples 4 to 13 and Reference Examples 16 to 17 by the method shown in Reference Example 1 or Reference Example 2 by appropriately applying a known method . The monolith anion exchanger into which the anion exchanger was introduced into the monolith obtained in Reference Examples 4 to 13 and Reference Examples 16 to 17 and the monolith anion exchanger obtained in the reference example 14 and the reference example 15 were appropriately applied, For example, the platinum group metal nanoparticles can be supported by the method shown in Example 1 or 2. [

Example 4

Palladium nanoparticles were supported on the monolith anion exchanger (first monolith anion exchanger) of Reference Example 1 in the same manner as in Example 1, except that 270 mg of palladium chloride was dissolved instead of 190 mg of palladium chloride, To obtain the first palladium nano-particle-supporting catalyst (c).

The loading amount of palladium nanoparticles carried on the first palladium nano-particle-supporting catalyst (c) in the dried state was 7.4% by weight. The first palladium nano-particle-supporting catalyst (c) in a dry state was filled in a column having an inner diameter of 10 mm and used for evaluation of dissolved oxygen removal characteristics. The packed bed height of the catalyst was 20 mm. At this time, the loading amount of the palladium nanoparticles relative to the resin volume in the water wet state was 10.5 g-Pd / L-R.

(Evaluation of catalyst)

Internal diameter at a first palladium nanoparticles supported catalyst (c) charging to the column of 10㎜, and water through a deionized water adjusted to a concentration of dissolved oxygen 32㎍ / L also dissolved hydrogen concentration 11㎍ / L to SV = 7500h ^-1, Measurement was carried out until the dissolved oxygen concentration in the treated water at the column outlet was stabilized. As a result, the dissolved oxygen concentration at the column outlet was reduced to 3.8 μg / L.

(Comparative Example 3)

A Cl type catalyst resin was prepared in which 910 mg-Pd / LR of palladium was supported on a strongly basic anion exchange resin (Cl type) having a water-holding capacity of 60 to 70% in the OH type standard and in a gel-like particle shape . The catalyst was evaluated in the same manner as in Example 4, except that this Cl-type catalyst resin was passed through a column having an inner diameter of 10 mm at a packed bed height of 360 mm at a flow rate of SV430. As a result, the dissolved oxygen concentration at the column outlet at the time when the treated water was stabilized was 4.1 占 퐂 / L. The evaluation results in Example 4 and Comparative Example 3 are summarized in Table 5.

Table 5 is shown below.

Example 4 is very inherently succinct by SV7500, and even though the feed flow rate per mass of the supported palladium metal catalyst is larger than that of Comparative Example 3 in Example 4, the dissolved oxygen of the same degree as in Comparative Example 3 Concentration treated water could be obtained. Therefore, by using the platinum group metal supported catalyst of the present invention, it is possible to effectively remove the dissolved oxygen even at the height of the reservoir layer with a high velocity, so that the amount of catalyst used can be reduced, the size of the apparatus can be reduced, and the amount of leached product can be reduced.

1: skeleton image 2: public image
10: Monolith 11: Image area
12: skeleton in section 13: macrophore

Claims (18)

As a platinum group metal supported catalyst in which nanoparticles of a platinum group metal having an average particle diameter of 1 to 100 nm are supported on an organic porous anion exchanger,
The organic porous anion exchanger is a continuous macropore structure in which bubble-like macropores overlap each other and the overlapping portions become openings with an average diameter of 30 to 300 탆 in a water-wet state, and the total pore volume is 0.5 to 5 ml / g, the anion exchange capacity per volume in a wetted state is 0.4 to 1.0 mg equivalent / ml, the anion exchanger is uniformly distributed in the organic porous anion exchanger, and the cut surface of the continuous macropore structure (dried body) In the SEM image, the skeleton area appearing on the cross section is 25 to 50% of the image area,
Wherein the supported amount of the platinum group metal is 0.004 to 20 wt% in a dry state. As a platinum group metal supported catalyst in which nanoparticles of a platinum group metal having an average particle diameter of 1 to 100 nm are supported on an organic porous anion exchanger,
The organic porous anion exchanger preferably comprises an aromatic vinyl polymer containing 0.3 to 5.0 mol% of crosslinking structural units among all the constituent units into which an anion-exchange group is introduced, and has an average thickness of 1 to 60 μm A continuous concave structure comprising a continuous bar-shaped skeleton and three-dimensionally continuous voids having an average diameter of 10 to 100 μm between the skeletons in a wetted state, And an anion exchange capacity per volume in a wetted state is 0.3 to 1.0 mg equivalent / ml, an anion exchanger is uniformly distributed in the organic porous anion exchanger,
Wherein the supported amount of the platinum group metal is 0.004 to 20 wt% in a dry state. A process for producing hydrogen peroxide decomposition-treated water characterized by comprising bringing the for-treatment water containing hydrogen peroxide into contact with the platinum group metal supported catalyst according to claim 1 or 2 to decompose and remove the hydrogen peroxide in the for-treatment water containing hydrogen peroxide . The method according to claim 3, wherein the organic porous anion exchanger is of the OH type. The method according to claim 3, wherein the to-be-treated water containing hydrogen peroxide is brought into contact with the platinum group metal supported catalyst at an SV = 2000 to 20000 h ^-1 . The method according to claim 4, wherein the to-be-treated water containing hydrogen peroxide is brought into contact with the platinum group metal supported catalyst at an SV = 2000 to 20000 h ^-1 . A cleaning method of an electronic part characterized by cleaning an electronic part or a manufacturing apparatus of an electronic part with the treated water obtained by carrying out the method for producing hydrogen peroxide decompositionally treated water according to claim 3. A cleaning method of an electronic part characterized by cleaning an electronic part or a manufacturing device of an electronic part with the treated water obtained by carrying out the method for producing hydrogen peroxide decompositionally treated water according to claim 4. A cleaning method of an electronic part characterized by cleaning an electronic part or a manufacturing apparatus of an electronic part with the treated water obtained by carrying out the method for producing hydrogen peroxide decompositionally treated water according to claim 5. A cleaning method of an electronic part characterized by cleaning an electronic part or a manufacturing device of an electronic part with the treated water obtained by carrying out the method of manufacturing hydrogen peroxide decompositionally treated water according to claim 6. The dissolved oxygen is removed from the for-treatment water containing oxygen by reacting hydrogen and dissolved oxygen in the for-treatment water containing oxygen to produce water in the presence of the platinum group metal supported catalyst according to claim 1 or claim 2 And removing the dissolved oxygen. 12. The method of producing dissolved oxygen depleted water according to claim 11, wherein the organic porous anion exchanger is an OH type. 12. The method of producing dissolved oxygen depleted water according to claim 11, wherein the for-treatment water containing oxygen is brought into contact with the platinum group metal supported catalyst at an SV = 2000 to 20000 h ^-1 . The method for producing dissolved oxygen depleted water according to claim 12, wherein the for-treatment water containing oxygen is brought into contact with the platinum group metal supported catalyst at an SV = 2000 to 20000 h ^-1 . A cleaning method of an electronic part, characterized by cleaning the manufacturing equipment of an electronic part or an electronic part with the treated water obtained by performing the method of manufacturing dissolved oxygen depleted water according to claim 11. A cleaning method of an electronic part characterized by cleaning an electronic part or a manufacturing device of an electronic part with the treated water obtained by performing the method of manufacturing dissolved oxygen depleted water according to claim 12. A cleaning method of an electronic part characterized by cleaning an electronic part or a manufacturing device of an electronic part with the treated water obtained by performing the method of manufacturing dissolved oxygen depleted water according to claim 13. A cleaning method of an electronic part, characterized by cleaning the manufacturing equipment of an electronic part or an electronic part with the treated water obtained by performing the method of manufacturing dissolved oxygen depleted water according to claim 14.

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