TWI476048B - Platinum metal-supported catalyst, hydrogen peroxide decomposition method, dissolved oxygen removal method, and electronic part washing method - Google Patents

Description

Method for producing treated water of platinum group metal, catalytic water for decomposing hydrogen peroxide, method for producing water for removing dissolved oxygen, and method for cleaning electronic parts

The invention relates to a platinum group metal supporting catalyst, which is used for precision processing washing water for power station water and semiconductor manufacturing, etc., for removing oxidizing property such as hydrogen peroxide or dissolved oxygen in ultrapure water. substance.

It is known that dissolved oxygen in water used in power plants causes corrosion of components such as pipes and heat exchangers, especially in primary systems and secondary systems of atomic power plants.

Further, in the semiconductor manufacturing industry, ultra-pure water with high impurity removal is used to wash the silicon wafer. Ultrapure water is usually removed from the pretreatment step by one of the suspended matter and organic matter contained in the raw water (river water, ground water, industrial water, etc.), and the treated water is once pure water system and secondary pure water. The system (subsystem) is manufactured in sequence and supplied to the point of use for wafer cleaning. Such ultrapure water has a purity which is difficult to quantify impurities, and is not completely free of impurities.

For example, the dissolved oxygen contained in the ultrapure water forms a natural oxide film on the surface of the tantalum wafer. If the natural oxide film is formed on the surface of the wafer, the growth of the epitaxial Si film at a low temperature is hindered, or the film pressure of the gate oxide film and the fine control of the film quality are hindered, or the contact resistance of the contact hole is increased. . Therefore, it is necessary to suppress the formation of a natural oxide film on the wafer surface as much as possible.

Therefore, in an ultrapure water manufacturing apparatus, particularly in a primary pure water system, a deaerator is used to reduce dissolved oxygen. With the deaerator, the dissolved oxygen concentration in the treated water (primary pure water) at the inlet of the secondary pure water system is usually lowered to 100 μg/L or less. Furthermore, there are cases where the management is 10 μg/L or less.

In the production of the above ultrapure water, the decomposition of the organic matter is usually carried out by an ultraviolet ray oxidizing device provided in a secondary pure water system. Hydrogen peroxide is generated in the process of ultraviolet oxidation treatment, and thus hydrogen peroxide is usually left in the treated water of the ultraviolet oxidation device. The hydrogen peroxide is partially decomposed in the finishing step of the secondary pure water system to generate oxygen, and the dissolved oxygen concentration in the treated water is increased.

Therefore, there has been proposed a method of adsorbing and removing hydrogen peroxide contained in treated water of an ultraviolet ray oxidizing device using a synthetic carbon-based particulate adsorbent (Japanese Patent Laid-Open Publication No. Hei 9-29233). According to this method, since the hydrogen peroxide remaining in the treated water of the ultraviolet ray oxidizing device is removed by itself, the formation of the natural oxide film on the surface of the wafer can be suppressed. 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 is required.

Further, a method of decomposing hydrogen peroxide contained in the treated water of the ultraviolet ray oxidizing device by a catalyst for supporting the platinum group metal nanocolloid particles on the carrier has been proposed (Japanese Patent Laid-Open Publication No. 2007-185587).

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. Hei 9-29233 (Application No.)

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2007-185587 (Application No.)

However, the catalyst described in Japanese Laid-Open Patent Publication No. 2007-185587 can be used only in a relatively low area where the space velocity (SV) is 100 to 2000 h ^-1 , and if the SV exceeds 2000 h ^{- 1} , there is a disadvantage that the decomposition and removal of hydrogen peroxide becomes insufficient.

Therefore, an object of the present invention is to provide a high-performance catalyst capable of removing hydrogen peroxide or removing dissolved oxygen even when a large SV water having an SV of more than 2000 h ^-1 is used, and further, even if the catalyst is used The high-thinning filling layer can also be subjected to decomposition of hydrogen peroxide or removal of dissolved oxygen.

The present inventors have conducted intensive studies on the above-mentioned facts, and as a result, it has been found that a monolithic body having a relatively large pore volume obtained by the method described in Japanese Laid-Open Patent Publication No. 2002-306976 is obtained. In the presence of an organic porous material (intermediate), by allowing the vinyl monomer and the crosslinking agent to be statically polymerized in a specific organic solvent, a skeleton having a large opening diameter and an organic porous body having a larger intermediate can be obtained. When a monolithic organic porous body having a coarse skeleton of a skeleton is introduced into an ion exchange group in a monolithic organic porous body having a coarse skeleton, the swelling is large due to the coarse skeleton, so that the opening can be made larger. The monolithic organic porous anion exchanger (hereinafter also referred to as "first monolithic anion exchanger") having an anion exchange group introduced into the monolithic organic porous body of the coarse skeleton is carried on the top A platinum group metal-supporting catalyst (hereinafter also referred to as "the first platinum group metal-supporting catalyst") of a platinum group metal nanoparticle having an average particle diameter of 1 to 100 nm, even if the SV exceeds 2000 h ^-1 Larger SV water can also be decomposed or removed by hydrogen peroxide or dissolved in oxygen. Further, even if the filling layer of the catalyst is made thinner, the decomposition of hydrogen peroxide or the removal of dissolved oxygen can be performed, thereby completing the process. this invention.

Further, as a result of intensive studies, the present inventors have found that a monolithic organic porous body having a large pore volume obtained by the method described in JP-A-2002-306976 (middle) In the presence of a compound, by allowing the aromatic vinyl monomer and the crosslinking agent to be statically polymerized in a specific organic solvent, a three-dimensional continuous aromatic vinyl polymer skeleton and a three-dimensional continuous phase between the skeletons can be obtained. A hydrophobic monolith consisting of a hollow hole and a two-phase winding structure, the continuous structure of the monolithic system has high continuity and no deviation in size, and the pressure loss during fluid penetration is low. Further, since the skeleton of the co-continuous structure is coarse, when a ion exchange group is introduced, a monolithic organic porous ion exchanger having a large ion exchange capacity per unit volume can be obtained. The monolithic organic porous anion exchanger (hereinafter also referred to as "second monolithic anion exchanger") having an anion exchange group introduced into the monolith of the co-continuous structure has an average particle diameter of 1 The platinum group metal-supporting catalyst (hereinafter also referred to as "the second platinum group metal-supporting catalyst") of the platinum group metal nanoparticles of ~100 nm is the same as the first platinum group metal-supporting catalyst, even The larger SV water with an SV of more than 2000 h ^-1 can also be used for the decomposition of hydrogen peroxide or the removal of dissolved oxygen. Further, even if the filling layer of the catalyst is made thinner, the hydrogen peroxide can be decomposed or removed. The removal of dissolved oxygen completes the present invention.

That is, the present invention (1) provides a platinum group metal-supporting catalyst which is obtained by carrying a platinum group metal nanoparticle having an average particle diameter of 1 to 100 nm on an organic porous anion exchanger, and is characterized in that: The organic porous anion exchange system has a bubble-like macroscopic pores which are overlapped with each other and an overlapping portion thereof is formed in a continuous giant pore structure having an opening diameter of 30 to 300 μm in a water-wet state, and the total pore volume is 0.5 to 5 Ml/g, the anion exchange capacity per unit volume of the wet state of water is 0.4 to 1.0 mg equivalent/ml, the anion exchange is uniformly distributed based on the organic porous anion exchanger, and the continuous giant pore structure (dry body) In the scanning electron microscope (SEM) image of the cut surface, the area of the skeleton portion shown in the cross section is 25 to 50% in the image region; and the amount of the platinum group metal is 0.004 to 20 in the dry state. weight%.

Further, the present invention (2) provides a platinum group metal-supporting catalyst which is a nanoparticle of a platinum group metal having an average particle diameter of 1 to 100 nm supported on an organic porous anion exchanger, and is characterized in that: The organic porous anion exchange system is formed of an aromatic vinyl polymer having a crosslinked structural unit of 0.3 to 5.0 mol% in a total constituent unit to which an anion exchange group is introduced, and has a water wet state of 1 a three-dimensional continuous skeleton of ~60 μm, and a co-continuous structure composed of three-dimensional continuous pores having a diameter of 10 to 100 μm between the skeletons, and a total pore volume of 0.5 to 5 ml/ g, the anion exchange capacity per unit volume in the wet state of water is 0.3 to 1.0 mg equivalent/ml, the anion exchange is uniformly distributed based on the organic porous anion exchanger; and the carrying amount of the platinum group metal is in a dry state 0.004 to 20% by weight.

Further, the present invention (3) provides a process for producing treated water which decomposes hydrogen peroxide, which is characterized in that the treated water containing hydrogen peroxide is brought into contact with the platinum group of any one of the inventions (1) or (2). The metal carries a catalyst to decompose and decompose the hydrogen peroxide in the treated water containing hydrogen peroxide.

Further, the present invention (4) provides a method for cleaning an electronic component, which is characterized in that the treated water obtained by the method for producing treated water for decomposing hydrogen peroxide according to the invention (3) is used to wash electronic parts or electrons. Manufacturing equipment for parts.

Further, the present invention (5) provides a method for producing treated water for removing dissolved oxygen, which is characterized in that in the presence of the platinum group metal-supporting catalyst according to any one of the inventions (1) or (2), Hydrogen reacts with dissolved oxygen in the treated water containing oxygen to form water, thereby removing dissolved oxygen from the treated water containing oxygen.

Further, the invention (6) provides a method for cleaning an electronic component, which is characterized in that the treated water obtained by the method for producing the treated water for removing dissolved oxygen of the invention (5) is used to wash the electronic component or the electronic component. Manufacturing equipment.

According to the platinum group metal-supporting catalyst of the present invention, even if the SV of the SV exceeds 2000 h ^-1 , the decomposition of hydrogen peroxide or the removal of dissolved oxygen can be performed, and even if the catalyst is filled. High thinning can also be carried out by decomposition of hydrogen peroxide or removal of dissolved oxygen.

The organic porous anion exchanger used as a carrier of the platinum group metal-supporting catalyst of the present invention is a "first monolith anion exchanger" or a "second monolith anion exchanger". In the present specification, the "monolithic organic porous body" is also simply referred to as "monolithic body", and the "monolithic organic porous anion exchanger" is also simply referred to as "monolithic anion exchanger". The "monolithic organic porous intermediate" is also simply referred to as "monolithic intermediate". Further, the platinum group metal-supporting catalyst carrying the platinum group metal on the first monolith anion exchanger is also referred to as "the first platinum group metal carrier catalyst", and the second monolith anion exchange is performed. The platinum group metal-supporting catalyst holding a platinum group metal is also referred to as a "second platinum group metal-carrying catalyst".

<Description of the first monolithic anion exchanger>

The first monolithic anion exchange system is obtained by introducing an anion exchange group into a monolith, and the bubble-like macroscopic pores overlap each other and the overlapping portion thereof is formed in a water-wet state with an average diameter of 30 to 300 μm, preferably A continuous giant pore structure of an opening (gap hole) of 30 to 200 μm, particularly preferably 40 to 100 μm. Since the monolith is swollen as a whole when the anion exchange group is introduced into the monolith, the average diameter of the openings of the monolith anion exchanger is larger than the average diameter of the openings of the monolith. If the average diameter of the opening of the water-wet state is less than 30 μm, the pressure loss at the time of water passing becomes large, which is not preferable; if the average diameter of the opening of the water-wet state is too large, the treated water and the monolithic anion exchanger and the The contact of the platinum group metal nanoparticles to be supported is insufficient, and as a result, the hydrogen peroxide decomposition property or the dissolved oxygen removal property is deteriorated, which is not preferable. Further, in the present invention, the average diameter of the opening of the monolith intermediate body in a dry state, the average diameter of the opening of the monolith in a dry state, and the average diameter of the opening of the monolith anion exchanger in a dry state are utilized by mercury. The value measured by the infiltration method. Further, the average diameter of the opening of the monolithic anion exchanger in the water-wet state is a value calculated by multiplying the average diameter of the opening of the monolithic anion exchanger in the dry state by the swelling ratio. Specifically, the monolith anion exchanger having a diameter of x1 (mm) in a water-wet state and a monolith anion exchanger obtained by drying the monolith anion exchanger in a water-wet state is dried. The average diameter of the opening of the monolithic anion exchanger in the dry state is z1 (μm) when the diameter is y1 (mm), and the average diameter of the opening of the monolithic anion exchanger in the water-wet state is y1 (mm) (μm) is calculated by the following formula "average diameter (μm) of the opening of the monolithic anion exchanger in the water-wet state = z1 × (x1/y1)". Further, the average diameter of the opening of the monolith in the dry state before the introduction of the anion exchange group, and the monolith anion exchanger in the water-wet state are when the anion exchange group is introduced into the monolith in the dry state. The swelling ratio of the monolith in the dry state is known, and the average diameter of the opening of the monolith anion exchanger in the water-wet state can be calculated by multiplying the average diameter of the opening of the monolith in the dry state by the swelling ratio.

In the first monolith anion exchanger, in the SEM image of the cut surface of the continuous giant pore structure, the area of the skeleton shown by the cross section is 25 to 50%, preferably 25, in the image region. ~45%. If the area of the skeleton shown in the cross section is less than 25% in the image area, it becomes a fine skeleton, and the mechanical strength is lowered, especially when the monolith anion exchanger is greatly deformed when water is passed at a high flow rate, which is not preferable. . Further, the contact efficiency between the water to be treated and the monolith anion exchanger and the platinum group metal nanoparticles supported thereon is lowered, and the catalytic effect is lowered, which is not preferable; if it exceeds 50%, the skeleton becomes too thick. The pressure loss during the passage of water increases, so it is not good. In the monolith described in Japanese Laid-Open Patent Publication No. 2002-306976, even if the ratio of the oil phase portion to the water is actually increased, the skeleton portion is thickened, and the blending ratio is also limited to ensure a common opening. The maximum area of the skeleton shown in the section cannot exceed 25% in the image area.

The conditions for obtaining the SEM image may be such that the skeleton portion shown by the cross section of the cut surface is fresh, for example, the magnification is 100 to 600, and the photographing area is about 150 mm × 100 mm. The SEM observation is preferably carried out in an image in which three or more, preferably five or more, different portions of the cut portion or the photographed portion are obtained by taking an arbitrary portion of the cut surface of the subject monolith. The cut monolith is in a dry state when supplied to an electron microscope. The skeleton portion of the cut surface in the SEM image will be described with reference to Figs. 1 and 4 . Moreover, FIG. 4 is a skeleton portion which is transferred and shown as a cross section of the SEM photograph of FIG. In Fig. 1 and Fig. 4, the shape of the skeleton is substantially indefinite and the cross-section of the skeleton (component symbol 12) shown in the section of the present invention is shown in Fig. 1. The circular hole shown in Fig. 1 is an opening (gap Hole), again, a relatively large curvature or curved surface is a giant pore (component symbol 13 in Figure 4). The area of the skeleton shown in the cross section of Fig. 4 is 28% in the rectangular image area 11. In this way, the skeleton can be clearly judged.

In the SEM image, the method of measuring the area of the skeleton portion indicated by the cross section of the cut surface is not particularly limited, and an automatic calculation using a computer or the like is performed after the skeleton portion is determined by a known computer processing or the like. Or the method of calculating by hand. As a manual calculation, a method of converting an indefinite shape into a square, a triangle, a circle, a trapezoid, or the like, and laminating them to obtain an area is exemplified.

Further, the total pore volume of the first monolith anion exchanger is from 0.5 to 5 ml/g, preferably from 0.8 to 4 ml/g. When the total pore volume is less than 0.5 ml/g, the pressure loss at the time of water passage becomes large, which is unsatisfactory. Further, the amount of the penetrating fluid per unit sectional area becomes small, and the treatment ability is lowered, which is not preferable. On the other hand, when the total pore volume exceeds 5 ml/g, the mechanical strength is lowered, and in particular, when the water is discharged at a high flow rate, the monolith anion exchanger is largely deformed, which is not preferable. Further, the contact efficiency between the water to be treated and the monolith anion exchanger and the platinum group metal nanoparticles supported thereon is lowered, so that the catalytic effect is also lowered, which is not preferable. Further, in the present invention, the total pore volume of the monolith (monolith intermediate, monolith, monolith anion exchanger) is measured by a mercury permeation method. Further, the total pore volume of the monolith (monolith intermediate, monolith, and monolith anion exchanger) was the same in both the dry state and the water wet state.

Further, the pressure loss when the water passes through the first monolith anion exchanger is such that when the water is passed through the column packed with the anion exchanger 1 m at a water velocity (LV) of 1 m/h. The pressure loss (hereinafter referred to as "differential pressure coefficient") is preferably in the range of 0.001 to 0.1 MPa/m‧LV, and particularly preferably 0.005 to 0.05 MPa/m‧LV.

The anion exchange capacity per unit volume of the water-wet state of the first monolith anion exchanger is 0.4 to 1.0 mg equivalent/ml. A conventional monolithic organic porous anion exchanger having a continuous giant pore structure different from the present invention as described in Japanese Laid-Open Patent Publication No. 2002-306976 has the following disadvantages: When the opening pressure is increased by the low pressure loss, the total pore volume is also increased, so the anion exchange capacity per unit volume is decreased; if the total pore volume is decreased to increase the exchange capacity per unit volume, the opening diameter is changed. Small, so the pressure loss increases. On the other hand, since the first monolith anion exchanger can further enlarge the opening diameter and thicken the skeleton of the continuous giant pore structure (the wall portion of the skeleton is thickened), the pressure loss can be suppressed to At a lower state, the anion exchange capacity per unit volume is dramatically expanded. If the anion exchange capacity per unit volume is less than 0.4 mg equivalent/ml, the amount of nanoparticle supported per unit volume of the platinum group metal is lowered, which is not preferable. On the other hand, if the anion exchange capacity per unit 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 unit weight of the first monolith anion exchanger is not particularly limited, but the anion exchange group is uniformly introduced into the surface of the porous body and the inside of the skeleton to be 3.5 to 4.5 mg equivalent/g. . Further, the ion exchange capacity of the porous body introduced into the surface only by the ion exchange group differs depending on the type of the porous body or the ion exchange group, and cannot be determined in any way, but is at most 500 μg equivalent/g.

In the first monolith anion exchanger, the material constituting the skeleton of the continuous giant pore structure is an organic polymer material having a crosslinked structure. The crosslinking density of the polymer material is not particularly limited, and is preferably from 0.3 to 10 mol%, more preferably from 0.3 to 5 mol%, based on the total constituent unit of the polymer material. When the crosslinked structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, if it exceeds 10 mol%, introduction of an anion exchange group becomes difficult, which is not preferable. The kind of the polymer material is not particularly limited, and examples thereof include polystyrene, poly(α-methylstyrene), polyvinyltoluene, polyvinylbenzyl chloride, polyvinylbiphenyl, and polyethylene. Aromatic vinyl polymer such as naphthalene; polyolefin such as polyethylene or polypropylene; poly(halogenated polyolefin) such as polyvinyl chloride or polytetrafluoroethylene; nitrile polymer such as polyacrylonitrile; polymethyl methacrylate A crosslinked polymer such as a (meth)acrylic polymer such as polyglycidyl methacrylate or polyethyl acrylate. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, or a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or may be A combination of two or more polymers. Among these organic polymer materials, the ease of formation of a continuous giant pore structure, the ease of introduction of an anion exchange group, the height of mechanical strength, and the height of stability to an acid or a base are preferably aromatic. As the crosslinked polymer of the group vinyl polymer, a styrene-divinylbenzene copolymer or a vinylbenzyl chloride-divinylbenzene copolymer is particularly exemplified as a preferred material.

Examples of the anion exchange group of the first monolithic anion exchanger include a trimethylammonium group, a triethylammonium group, a tributylammonium group, a dimethylhydroxyethylammonium group, and a dimethylhydroxypropyl group. a quaternary ammonium group such as an ammonium group or a methyl dihydroxyethyl ammonium group; or a third fluorenyl group or a fluorenyl group.

In the first monolithic anion exchanger, the introduced anion exchange group is not only uniformly distributed on the surface of the porous body but also uniformly distributed inside the skeleton of the porous body. As used herein, "an even distribution of anion exchange groups" means that the distribution of anion exchange groups is uniformly distributed on the surface and inside the skeleton at least in the order of μm. The distribution of the anion exchange group is relatively simple to confirm by ion-exchange of the counter anion into a chloride ion, a bromide ion or the like using EPMA. Further, if the anion exchange group is not only uniformly distributed on the surface of the monolith and uniformly distributed inside the skeleton of the porous body, the physical properties and chemical properties of the surface and the inside can be made uniform, so that the durability against swelling and shrinkage is improved.

(Method for producing first monolithic anion exchanger)

The first monolithic anion exchange system is obtained by the following steps: In the first step, a water-drop type emulsion in an oil is prepared by stirring a mixture of an oil-soluble monomer, a surfactant, and water without an ion exchange group. Then, the water droplet type emulsion in the oil is polymerized to obtain a monolithic organic porous intermediate (monolith intermediate) having a continuous pore size of 5 to 16 ml/g; Preparation of an organic solvent containing a vinyl monomer, a crosslinking agent having at least two vinyl groups in one molecule, a vinyl monomer or a crosslinking agent dissolved, but a polymer formed by polymerization of a vinyl monomer is insoluble, and polymerization initiation a mixture of the agents; in the step III, the mixture obtained in the step II is allowed to stand under the standing and the polymerization in the presence of the monolithic intermediate obtained in the step I to obtain a skeleton having a relatively monolithic intermediate. a coarse-framed organic porous body having a coarser skeleton; and an IV step of introducing an anion exchange group into the coarse-frame organic porous body obtained in the step III.

In the method for producing the first monolithic anion exchanger, the first step may be carried out in accordance with the method described in JP-A-2002-306976.

In the production of the monolithic intermediate of the first step, the oil-soluble monomer which does not contain an ion-exchange group may, for example, be an ion-exchange group other than a carboxylic acid group, a sulfonic acid group or a quaternary ammonium group, and is soluble in water. Low and lipophilic monomer. Preferred examples of such monomers include styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride, divinylbenzene, ethylene, propylene, isobutylene, butadiene, and ethylene glycol. Dimethacrylate and the like. These monomers may be used alone or in combination of two or more. Wherein at least a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate is selected as one of the oil-soluble monomers, and the content thereof is 0.3 to 10 mol% in all the oil-soluble monomers. Preferably, it is preferably 0.3 to 5 mol%, and the amount of the anion exchange group can be quantitatively introduced in the subsequent step, which is preferable.

The surfactant is not particularly limited as long as it can form an oil-in-water type (W/O) emulsion when the oil-soluble monomer containing no ion-exchange group is mixed with water, and can be used: sorbitan monooleic acid Ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene nonylphenyl ether, polyoxyethylene hard Nonionic surfactants such as aliphatic ethers, polyoxyethylene sorbitan monooleate; anionic surfactants such as potassium oleate, sodium dodecylbenzenesulfonate, dioctyl sodium sulfosuccinate; chlorination a cationic surfactant such as distearyl dimethyl ammonium; an amphoteric surfactant such as lauryl dimethyl betaine. These surfactants may be used alone or in combination of two or more. In addition, the oil-water droplet type emulsion refers to an emulsion in which an oil phase is a continuous phase and water droplets are dispersed therein. The amount of the surfactant added is greatly changed depending on the type of the oil-soluble monomer and the size of the target emulsion particles (gird pores), so that it cannot be generalized with respect to the oil-soluble monomer and the surfactant. The total amount is selected in the range of about 2 to 70%.

Further, in the first step, when a water-drop type emulsion is formed in the oil, a polymerization initiator may be used as needed. As the polymerization initiator, a compound which generates a radical by heat and light irradiation is suitably used. The polymerization initiator may be water-soluble or oil-soluble, and examples thereof include azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanenitrile, azobiscyclohexanecarbonitrile, and benzoic acid peroxide. Barium, potassium persulfate, ammonium persulfate, hydrogen peroxide - ferrous chloride, sodium persulfate - acidic sodium sulfite, tetramethyl thiuram disulfide, and the like.

The method of mixing the oil-soluble monomer, the surfactant, the water, and the polymerization initiator which do not contain an ion-exchange group to form a water-drop type emulsion is not particularly limited, and it is possible to use a combination of components. a one-time mixing method; separately dissolving the oil-soluble component as an oil-soluble monomer, a surfactant, and an oil-soluble polymerization initiator, and water or a water-soluble component as a water-soluble polymerization initiator, and mixing the components Method and so on. The mixing device for forming the emulsion is not particularly limited, and a usual mixer, homogenizer, high-pressure homogenizer, or the like can be used, and a device suitable for obtaining the particle size of the target emulsion can be selected. Further, the mixing conditions are not particularly limited, and the stirring rotation speed or the stirring time at which the particle diameter of the target emulsion can be obtained can be arbitrarily set.

The monolithic intermediate obtained in the first step has a continuous macroporous structure. When it coexists in a polymerization system, the structure of a monolith intermediate body is used as a model, and the porous structure which has the skeleton of a rough skeleton is formed. Further, the monolith intermediate is an organic polymer material having a crosslinked structure. The crosslinking density of the polymer material is not particularly limited, but is preferably a crosslinking structural unit containing 0.3 to 10 mol%, preferably 0.3 to 5 mol%, based on the total constituent unit of the polymer material. If the crosslinked structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable. In particular, in the case where the total pore volume is as large as 10 to 16 ml/g, in order to maintain the continuous macroporous structure, it is preferred to contain 2 mol% or more of a crosslinked structural unit. On the other hand, when it exceeds 10 mol%, introduction of an anion exchange group becomes difficult, and it is unpreferable.

The type of the polymer material as the monolithic intermediate is not particularly limited, and examples thereof are the same as those of the above monolithic polymer material. Thereby, the same polymer is formed on the skeleton of the monolithic intermediate, and the skeleton can be made thick to obtain a monolith having a uniform skeleton structure.

The total pore volume of the monolithic intermediate is 5 to 16 ml/g, preferably 6 to 16 ml/g. When the total pore volume is too small, the total pore volume of the monolith obtained after the polymerization of the vinyl monomer becomes too small, and the pressure loss at the time of fluid penetration becomes large, which is not preferable. On the other hand, if the total pore volume is too large, the structure of the monolith obtained by polymerizing the vinyl monomer deviates from the continuous giant pore structure, which is not preferable. In order to make the total pore volume of the monolith intermediate body into the above numerical range, the ratio of the monomer to water may be approximately 1:5 to 1:20.

Further, the average diameter of the opening (gap hole) in which the macroscopic pores and the giant pores overlap in the monolithic intermediate system is 20 to 200 μm in a dry state. When the average diameter of the opening in the dry state is less than 20 μm, the opening diameter of the monolith obtained after the 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, when it exceeds 200 μm, the opening diameter of the monolith obtained after the polymerization of the vinyl monomer becomes too large, and the contact between the water to be treated and the monolith anion exchanger becomes insufficient, and as a result, Hydrogen peroxide decomposition characteristics or dissolved oxygen removal characteristics are degraded, which is not preferable. The monolithic intermediate is preferably a uniform structure in which the size of the macroscopic pores or the diameter of the openings is uniform, but is not limited thereto, and the size of the uniform macropores may be larger in the uniform structure. Uneven macroscopic pores.

The second step is to prepare an organic solvent comprising a vinyl monomer, a crosslinking agent having at least two vinyl groups in one molecule, a vinyl monomer or a crosslinking agent dissolved, but a polymer formed by polymerization of the vinyl monomer is insoluble. A step of polymerizing a mixture of initiators. Furthermore, there is no order of steps I and II, and step II can be performed after step I, or step I can be performed after step II.

The vinyl monomer to be used in the second step is not particularly limited as long as it is a lipophilic vinyl monomer having a polymerizable vinyl group in the molecule and having high solubility in an organic solvent, and is preferably selected to be produced. The monolithic intermediate coexisting in the above polymerization system is a vinyl monomer of the same or similar polymeric material. Specific examples of the vinyl monomer include aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride, vinylbiphenyl, and vinylnaphthalene; Alpha-olefin such as ethylene, propylene, 1-butene or isobutylene; diene monomer such as butadiene, isoprene or chloroprene; vinyl chloride, vinyl bromide, vinylidene chloride, tetrafluoroethylene, etc. Halogenated olefin; nitrile monomer such as acrylonitrile or methacrylonitrile; vinyl ester such as vinyl acetate or vinyl propionate; methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl Methyl acrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, methacrylic acid epoxy A (meth)acrylic monomer such as propyl ester. These monomers may be used alone or in combination of two or more. The vinyl monomer suitably used in the present invention is an aromatic vinyl monomer such as styrene or vinylbenzyl chloride.

The amount of the vinyl monomer to be added is 3 to 50 times, preferably 4 to 40 times by weight based on the weight of the monolithic intermediate which is present during the polymerization. When the amount of the vinyl monomer added is not more than three times that of the porous body, the skeleton of the formed monolith (the thickness of the wall portion of the monolith skeleton) cannot be made thick, and the unit volume after the introduction of the anion exchange group is not obtained. The anion exchange capacity becomes small, which is not preferable. On the other hand, when the amount of the vinyl monomer added exceeds 50 times, the opening diameter 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 which contains at least two polymerizable vinyl groups in the molecule and has high solubility in an organic solvent. Specific examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, and butanediol diacrylate. Wait. These crosslinking agents may be used alone or in combination of two or more. The preferred crosslinking agent is an aromatic polyvinyl compound such as divinylbenzene, divinylnaphthalene or divinylbiphenyl in terms of the height of the mechanical strength and the stability to hydrolysis. The amount of the crosslinking agent used is preferably from 0.3 to 10 mol%, particularly preferably from 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 used is less than 0.3 mol%, the mechanical strength of the monolith is insufficient, which is not preferable. On the other hand, when it exceeds 10 mol%, the introduction amount of an anion exchange group may fall, and it is unpreferable. Further, the crosslinking agent is preferably used in such a manner that the crosslinking density of the monolithic intermediate which coexists with the polymerization of the vinyl monomer/crosslinking agent is substantially equal. If the amount of use of the two is extremely large, a variation in the crosslink density distribution occurs in the resulting monolith, and cracks are likely to occur when the anion exchange group is introduced into the reaction.

The organic solvent used in the step II is an organic solvent in which a vinyl monomer or a crosslinking agent is dissolved but a polymer obtained by polymerizing a vinyl monomer is insoluble, in other words, a poor solvent for a polymer obtained by polymerizing a vinyl monomer. . The organic solvent is largely different depending on the type of the vinyl monomer. Therefore, it is difficult to cite a general example. For example, when the vinyl monomer is styrene, examples of the organic solvent include methanol, ethanol, and propanol. Butanol, hexanol, cyclohexanol, octanol, 2-ethylhexanol, decyl alcohol, dodecanol, ethylene glycol, propylene glycol, tetramethylene glycol, glycerol and other alcohols; diethyl ether , ethylene glycol dimethyl ether, 赛路苏, methyl 赛路苏, butyl 赛路苏, polyethylene glycol, polypropylene glycol, polytetramethylene glycol and other chain (poly) ethers; hexane Chain-saturated hydrocarbons such as heptane, octane, isooctane, decane, and dodecane; esters such as ethyl acetate, isopropyl acetate, celecoxib acetate, and ethyl propionate. Again, even as two Alkane, THF or toluene is a good solvent for polystyrene. It can also be used as an organic solvent when it is used together with the above-mentioned poor solvent and its use amount is small. The amount of the organic solvent used is preferably such that the concentration of the above vinyl monomer is 30 to 80% by weight. If the amount of the organic solvent used is out of the above range and the vinyl monomer concentration is less than 30% by weight, the polymerization rate is lowered, or the monolithic structure after polymerization deviates from the range of the present invention, which is not preferable. On the other hand, if the vinyl monomer concentration exceeds 80% by weight, there is a possibility that the polymerization is out of control, 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 oil-soluble. Specific examples of the polymerization initiator used in the present invention include 2,2'-azobis(isobutyronitrile) and 2,2'-azobis(2,4-dimethylvaleronitrile). ), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'- Dimethyl azobisisobutyrate, 4,4'-azobis(4-cyanovaleric acid), 1,1-azobis(cyclohexyl-1-carbonitrile), benzammonium peroxide, Peroxidized laurel, potassium persulfate, ammonium persulfate, tetramethyl thiuram disulfide, and the like. The amount of the polymerization initiator to be used varies greatly depending on the type of the monomer, the polymerization temperature, and the like, but 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.

In the third step, the mixture obtained in the step II is subjected to polymerization under the condition of standing and the monolith intermediate obtained in the step I, to obtain a skeleton having a coarser than the monolith intermediate. The step of a single block of the skeleton of the skeleton. The monolithic intermediate used in the third step not only creates a monolith having a novel structure of the present invention, but also plays a very important role. As disclosed in Japanese Patent Laid-Open No. Hei 7-501140, if a vinyl monomer and a crosslinking agent are allowed to stand in a specific organic solvent in the absence of a monolithic intermediate, a monolith of particle agglomerated type is obtained. Bulk organic porous body. On the other hand, when the monolith intermediate body having a continuous macroscopic pore structure is present in the polymerization system as described in the present invention, the structure of the monolithic body after polymerization changes rapidly, and the particle agglomerate structure disappears, and the above coarse skeleton is obtained. Monolithic body. The reason for this is not ascertained, and it is considered that, in the case where the monolith intermediate is not present, the crosslinked polymer produced by the polymerization is precipitated in the form of particles, thereby forming a particle agglomerated structure. When a porous body (intermediate) is present in the polymerization system, the vinyl monomer and the crosslinking agent are adsorbed or distributed from the liquid phase to the skeleton portion of the porous body (intermediate), and are carried out in the porous body (intermediate). Polymerization to obtain a monolithic body of a coarse skeleton. Further, the opening diameter is narrowed as the polymerization progresses, but since the total pore volume of the monolith intermediate body is large, an opening diameter of an appropriate size is obtained even if the skeleton becomes a thick skeleton.

The internal volume of the reaction vessel is not particularly limited as long as the monolith intermediate is present in the reaction vessel, and may be formed in a plan view and placed around the monolith when the monolith intermediate is placed in the reaction vessel. Any one of the gaps and the monolith intermediates are placed in the reaction vessel without a gap. Among them, the monolithic body of the thick skeleton after the polymerization is not pressed into the reaction container without being pressed by the inner wall of the container, and the monolith is not deformed, and the raw material is not wasted and efficiently. Furthermore, even if the internal volume of the reaction vessel is large, there is a gap around the monolithic body after polymerization, and the vinyl monomer or the crosslinking agent is adsorbed and distributed to the monolith intermediate, and the reaction is carried out. The particle agglomerate structure is not formed in the gap portion in the container.

In the third step, in the reaction vessel, the monolithic intermediate system is placed in a state of being impregnated with the mixture (solution). The preparation of the mixture obtained in the step II and the monolith intermediate is, as described above, preferably, the amount of the vinyl monomer added is 3 to 50 times by weight relative to the monolith intermediate. It is 4 to 40 times. Thereby, a monolith having a moderate opening diameter and having a thick skeleton can be obtained. In the reaction vessel, the vinyl monomer and the crosslinking agent in the mixture are adsorbed and distributed to the skeleton of the standing monolith intermediate, and polymerization is carried out 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. For example, 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), benzammonium peroxide, lauric acid peroxide, persulfuric acid When potassium or the like is used as the initiator, it may be heated and polymerized at 30 to 100 ° C for 1 to 48 hours in a sealed container under an inert gas atmosphere. By heating polymerization, a vinyl monomer adsorbed and distributed to the skeleton of the monolith intermediate is polymerized in the skeleton to thicken the skeleton. After the completion of the polymerization, the contents are taken out, and the unreacted vinyl monomer and the organic solvent are removed for extraction, and a monolith of a crude skeleton is obtained by extraction with a solvent such as acetone.

Then, the method of producing a monolith and introducing an anion exchange group by the above method is preferable in that the porous structure of the obtained monolith anion exchanger can be closely controlled.

The method of introducing the anion exchange group into the monolith is not particularly limited, and a known method such as polymer reaction or graft polymerization can be used. For example, as a method of introducing a quaternary ammonium group, when a monolith is a styrene-divinylbenzene copolymer or the like, a chloromethyl group is introduced by chloromethyl methyl ether or the like, and then it is combined with a third stage. A method for reacting an amine; a method for producing a monolith by copolymerization of chloromethylstyrene and divinylbenzene to react with a tertiary amine; uniformly conducting a radical starting group in a monolith Or a chain transfer group introduced into the surface of the skeleton and the inside of the skeleton to graft or polymerize N,N,N-trimethylammoniumethyl acrylate or N,N,N-trimethylammoniumpropyl acrylamide; After the graft polymerization of glycidyl methacrylate is carried out, a method of introducing a quaternary ammonium group by a functional group conversion or the like is carried out. In these methods, as a method of introducing a quaternary ammonium group, the ion exchange group can be introduced uniformly and quantitatively, and it is preferred to use chloromethyl group in the styrene-divinylbenzene copolymer. A method in which an ether or the like is introduced into a chloromethyl group to cause reaction with a tertiary amine; or a method in which a monolith is produced by copolymerization of chloromethylstyrene and divinylbenzene to react with a tertiary amine. Further, examples of the ion exchange group to be introduced include a trimethylammonium group, a triethylammonium group, a tributylammonium group, a dimethylhydroxyethylammonium group, a dimethylhydroxypropylammonium group, and a A quaternary ammonium group such as a bishydroxyethylammonium group, or a third fluorenyl group or a fluorenyl group.

Since the first monolith anion exchange system introduces an anion exchange group into a monolith of a coarse skeleton, it is greatly swollen to, for example, 1.4 to 1.9 times the coarse skeleton monolith. That is, the degree of swelling is much larger than that of the conventional monolith introduced into the ion exchange group described in JP-A-2002-306976. Therefore, even if the opening diameter of the coarse skeleton monolith is small, the opening diameter of the monolithic ion exchanger becomes substantially larger at the above magnification. Further, even if the opening diameter is increased due to swelling, the total pore volume does not change. Therefore, although the first monolith ion exchanger has a very large opening diameter, it has a high mechanical strength due to a thick skeleton.

<Description of the second monolithic anion exchanger>

The second monolith anion exchange system is formed of an aromatic vinyl polymer containing 0.3 to 5.0 mol% of a crosslinked structural unit in a total constituent unit to which an anion exchange group is introduced, and has an average thickness in a water-wet state. a three-dimensional continuous skeleton of 1 to 60 μm and a co-continuous structure composed of three-dimensional continuous pores having an average diameter of 10 to 100 μm in a water-wet state, and a total pore volume of 0.5 to ～ 5 ml/g, the ion exchange capacity per unit volume in the wet state of water is 0.3 to 1.0 mg equivalent/ml, and anion exchange is uniformly distributed based on the porous ion exchanger.

The second monolith anion exchange system has a three-dimensional continuous skeleton in which the average thickness of the anion exchange group is 1 to 60 μm, preferably 3 to 58 μm, and the average diameter between the skeletons is The water-wet state is a co-continuous structure composed of three-dimensional continuous pores of 10 to 100 μm, preferably 15 to 90 μm, and more preferably 20 to 80 μm. That is, the co-continuous structure is shown in the schematic view of Fig. 6, and is a structure 10 in which a continuous skeleton phase 1 is wound with a continuous pore phase 2, and each of which is three-dimensionally continuous. The continuous pores 2 have higher continuity of pores and no deviation in size compared with the conventional continuous bubble type monolith or particle agglomerated monolith, so that extremely uniform ion adsorption behavior can be achieved. Moreover, the mechanical strength is high due to the coarse skeleton.

Since the monolith is swollen as a whole when the anion exchange group is introduced into the monolith, the thickness of the skeleton of the second monolith anion exchanger and the diameter of the pores are larger than the thickness of the skeleton of the monolith and the diameter of the pores. . The continuous pores have higher continuity of pores and no deviation in size compared with the conventional continuous bubble type monolithic organic porous anion exchanger or particle agglomerated monolithic organic porous anion exchanger. Therefore, an extremely uniform anion adsorption behavior can be achieved. If the average diameter of the three-dimensional continuous pores is less than 10 μm in the wet state of water, the pressure loss during the passage of water becomes large, which is not preferable; if it exceeds 100 μm, the contact of the treated water with the organic porous anion exchanger The result is insufficient, and as a result, the decomposition of hydrogen peroxide or the removal of dissolved oxygen in the treated water becomes insufficient, which is not preferable. Further, if the average thickness of the skeleton is less than 1 μm in the water-wet state, the mechanical strength is lowered in addition to the disadvantage that the anion exchange capacity per unit volume is lowered, especially when the water flows at a high flow rate, the monolith anion exchanger is largely large. Deformation, so it is not good. Further, the contact efficiency between the water to be treated 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 μm, 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 pores in the water-wet state of the continuous structure is a value calculated by multiplying the average diameter of the pores of the monolithic anion exchanger in a dry state measured by the mercury permeation method by the swelling ratio. Specifically, a monolithic anion exchanger having a diameter of x2 (mm) in a water-wet state and a monolith anion exchanger obtained by drying the monolithic anion exchanger in a wet state is provided. When the diameter of the monolith anion exchanger in the dry state is z2 (μm) by the mercury permeation method, the pores of the monolithic anion exchanger are wetted by water. The average diameter (μm) is calculated by the following formula "average diameter (μm) of the pores of the monolith anion exchanger in the water-wet state = z2 × (x2 / y2)". Further, the average diameter of the pores in the dry state before the introduction of the anion exchange group, and the monolith anion exchanger in the water-wet state are introduced to the anion exchange group in the monolith of the dry state. In the case where the swelling rate of the monolith in the dry state is known, the average diameter of the pores of the monolith in the dry state may be multiplied by the swelling ratio to calculate the pores of the monolith anion exchanger in the water-wet state. The average diameter. Further, the average thickness of the water-wet state of the skeleton of the continuous structure is SEM observation of a monolithic anion exchanger at least three times in a dry state, and the thickness of the skeleton in the obtained image is measured and averaged. The value is multiplied by the value of the swelling rate. Specifically, a monolithic anion exchanger having a diameter of x3 (mm) in a water-wet state and a monolith anion exchanger in which the water is wet is dried to obtain a dry state. SEM observation of a monolithic anion exchanger having a diameter of y3 (mm) and at least three times of this dry state, and measuring the thickness of the skeleton in the obtained image, and setting the average value to Z3 (μm) The average thickness (μm) of the skeleton of the continuous structure of the monolithic anion exchanger in the water-wet state is the average thickness (μm) of the skeleton of the continuous structure of the monolithic anion exchanger in the water-wet state. ) = z3 × (x3 / y3)" is calculated. Further, the average bulk of the skeleton of the monolith in the dry state before the introduction of the anion exchange group, and the monolith anion exchanger in the water-wet state are introduced with the anion exchange group in the monolith of the dry state. In the case where the swelling rate of the monolith in the dry state is known, the average of the skeleton of the monolith in the dry state is multiplied by the swelling ratio to calculate the average of the skeleton of the monolith anion exchanger in the water-wet state. roughness. Further, the skeleton has a rod shape and a circular cross-sectional shape, and may also include a cross-sectional profile such as a circular cross-sectional shape. The thickness at this time is the average of the short diameter and the long diameter.

Further, the total pore volume of the second monolith anion exchanger is 0.5 to 5 ml/g. When the total pore volume is less than 0.5 ml/g, the pressure loss at the time of water passage becomes large, which is unsatisfactory. Further, the amount of permeated water per unit sectional area becomes small, and the amount of treated water decreases, which is not preferable. On the other hand, when the total pore volume exceeds 5 ml/g, the anion exchange capacity per unit volume decreases, and the amount of platinum group metal nanoparticles is also lowered, and the catalytic effect is lowered, which is not preferable. Further, the mechanical strength is lowered, and in particular, when the water is passed through at a high flow rate, the monolith anion exchanger is largely deformed, which is not preferable. Further, since the contact efficiency between the water to be treated and the monolith anion exchanger is lowered, the hydrogen peroxide decomposition effect or the dissolved oxygen removal effect is also lowered, which is not preferable. When the size of the three-dimensional continuous pores and the total pore volume are within the above range, the contact with the water to be treated is extremely uniform, the contact area is also large, and water passing under low pressure loss can be performed. Further, the total pore volume of the monolith (monolith intermediate, monolith, monolith anion exchanger) was the same in both the dry state and the water wet state.

Further, the pressure loss when the water penetrates the second monolith anion exchanger is such that the pressure in the column filled with the porous body 1 m is water at a water velocity (LV) of 1 m/h. The loss (hereinafter referred to as "differential pressure coefficient") means a range of 0.001 to 0.5 MPa/m ‧ LV, particularly 0.005 to 0.1 MPa/m ‧ LV.

In the second monolith anion exchanger, the material constituting the skeleton of the co-continuous structure is an aromatic group containing 0.3 to 5 mol%, preferably 0.5 to 3.0 mol% of the crosslinked structural unit in the total constituent unit. A vinyl polymer that is hydrophobic. If the crosslinked structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, if it exceeds 5 mol%, the structure of the porous body tends to deviate from the co-continuous structure. The type of the aromatic vinyl polymer is not particularly limited, and examples thereof include polystyrene, poly(α-methylstyrene), polyvinyltoluene, polyvinylbenzyl chloride, and polyvinylbiphenyl. Polyvinyl naphthalene and the like. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, or a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or may be A combination of two or more polymers. Among these organic polymer materials, styrene-second is preferable in terms of easiness of formation of a continuous structure, easiness of introduction of anion exchange groups, height of mechanical strength, and height of stability to an acid or a base. Vinyl benzene copolymer or vinylbenzyl chloride-divinylbenzene copolymer.

The second monolith anion exchanger has an ion exchange capacity of from 0.3 to 1.0 mg equivalent/ml per unit volume of the anion exchange capacity in a water-wet state. A conventional monolithic organic porous ion exchanger having a continuous macroscopic pore structure different from the present invention as described in Japanese Laid-Open Patent Publication No. 2002-306976 has the following disadvantages: When the opening diameter is increased by the low pressure loss, the total pore volume becomes larger, so the ion exchange capacity per unit volume decreases; if the total pore volume is decreased to increase the exchange capacity per unit volume, the opening diameter becomes smaller. Therefore, the pressure loss increases. On the other hand, in the second monolith anion exchanger of the present invention, since the continuity or uniformity of the three-dimensional continuous pores is high, the pressure loss does not increase even if the total pore volume is decreased. Therefore, the anion exchange capacity per unit volume can be dramatically expanded in a state where the pressure loss is suppressed to be low. If the anion exchange capacity per unit volume is less than 0.3 mg equivalent/ml, the amount of nanoparticle supported per unit volume of the platinum group metal is lowered, which is not preferable. On the other hand, if the anion exchange capacity per unit 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 unit weight of the dry state of the second monolith anion exchanger is not particularly limited, and the ion exchange group is uniformly introduced into the skeleton surface of the porous body and the inside of the skeleton, and is 3.5 to 4.5 mg. Equivalent / g. Further, the ion exchange capacity in which the ion exchange group is introduced only into the porous body on the surface of the skeleton differs depending on the type of the porous body or the ion exchange group, and cannot be determined in a single manner, but is at most 500 μg equivalent/g.

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

(Method for producing second monolithic anion exchanger)

The second monolithic anion exchange system is obtained by the following steps: In the first step, a water-drop type emulsion in an oil is prepared by stirring a mixture of an oil-soluble monomer, a surfactant, and water without an ion exchange group. Then, the water-drop type emulsion in the oil is polymerized to obtain a monolithic organic porous intermediate having a continuous pore volume of more than 16 ml/g and 30 ml/g or less; II step, preparation comprising aroma a vinyl group monomer having at least 2 or more vinyl groups in one molecule of 0.3 to 5 mol% of a crosslinker, an aromatic vinyl monomer or a crosslinker dissolved in all oil-soluble monomers but aromatic a mixture of an organic solvent insoluble in a polymer obtained by polymerizing a vinyl monomer and a polymerization initiator; a step of III, a monolith obtained in the step I, which is obtained in the step I, and obtained in the step I The polymerization is carried out in the presence of an organic porous intermediate to obtain a co-continuous structure; in the IV step, an anion exchange group is introduced into the co-continuous structure obtained in the III step.

The I step of obtaining the monolithic intermediate in the second monolith anion exchanger may be carried out in accordance with the method described in JP-A-2002-306976.

In other words, in the first step, the oil-soluble monomer which does not contain an ion-exchange group is, for example, an ion-exchange group which does not contain a carboxylic acid group, a sulfonic acid group or a quaternary ammonium group, and has low solubility in water and is lipophilic. monomer. Specific examples of the monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride, vinylbiphenyl, and vinylnaphthalene; and ethylene; Alpha-olefins such as propylene, 1-butene and isobutylene; diene monomers such as butadiene, isoprene and chloroprene; halogenated olefins such as vinyl chloride, vinyl bromide, vinylidene chloride and tetrafluoroethylene Nitrile monomers such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate and vinyl propionate; methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, and methacrylic acid Ester, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, glycidyl methacrylate A (meth)acrylic monomer. Among these monomers, an aromatic vinyl monomer is suitable, and examples thereof include styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride, and divinylbenzene. These monomers may be used alone or in combination of two or more. Wherein at least a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate is selected as one of the oil-soluble monomeric esters and the content thereof is 0.3 to 5 mol% in the total oil-soluble monomer. Preferably, 0.3 to 3 mol% is advantageous for the formation of a co-continuous structure, which is preferred.

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

Further, in the first step, a polymerization initiator may be used as needed in the formation of the water droplet type emulsion in the oil. As the polymerization initiator, a compound which generates a radical by heat and light irradiation is suitably used. The polymerization initiator may be water-soluble or oil-soluble, and examples thereof include 2,2'-azobis(isobutyronitrile) and 2,2'-azobis(2,4-dimethylvaleronitrile). ), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'- Dimethyl azobisisobutyrate, 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexyl-1-carbonitrile), benzammonium peroxide , oxidized laurel, potassium persulfate, ammonium persulfate, tetramethyl thiuram disulfide, hydrogen peroxide - ferrous chloride, sodium persulfate - acidic sodium sulfite, and the like.

a method for mixing a water-soluble monomer, an intervening agent, water, and a polymerization initiator which do not contain an ion exchange group to form a water-drop type emulsion, and the first monolith anion exchanger ester I step Since the mixing method is the same, the description thereof is omitted.

In the method for producing the second monolith anion exchanger, the monolith intermediate obtained in the first step is an organic polymer material having a crosslinked structure, and is preferably an aromatic vinyl polymer. The crosslinking density of the polymer material is not particularly limited, and is preferably a crosslinking structural unit containing 0.3 to 5 mol%, preferably 0.3 to 3 mol%, based on the total constituent unit of the polymer material. If the crosslinked structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, if it exceeds 5 mol%, the structure of the monolith tends to deviate from the co-continuous structure, which is not preferable. Particularly, in the case where the total pore volume is as small as 16 to 20 ml/g in the present invention, in order to form a co-continuous structure, the crosslinking structural unit is preferably less than 3 mol%.

The type of the polymer material of the monolithic intermediate is the same as the type of the polymer material of the monolithic intermediate of the first monolith anion exchanger, and therefore the description thereof will be omitted.

The total pore volume of the monolithic intermediate is more than 16 ml/g and less than 30 ml/g, more preferably more than 16 ml/g and less than 25 ml/g. That is, the monolith intermediate body is basically a continuous giant pore structure, but since the overlap between the macroscopic pores and the giant pores, that is, the opening (gap pore) is very large, the skeleton constituting the monolithic structure has The wall from the two-dimensional wall is infinitely close to the structure of the one-dimensional rod-shaped skeleton. When it coexists in a polymerization system, a porous body of a co-continuous structure is formed by using the structure of a monolith intermediate body as a model. If the total pore volume is too small, the structure of the monolith obtained after the polymerization of the vinyl monomer is changed from a co-continuous structure to a continuous giant pore structure, which is not preferable; on the other hand, if the total pore volume is too large Then, the mechanical strength of the monolith obtained after the polymerization of the vinyl monomer is lowered, and the anion exchange capacity per unit volume is lowered, which is not preferable. In order to make the total pore volume of the monolith intermediate body a specific range of the second monolith anion exchanger, the ratio of the monomer to water may be approximately 1:20 to 1:40.

Further, the average diameter of the opening (gap hole) in which the macroscopic pores and the giant pores overlap in the monolithic intermediate system is 5 to 100 μm in a dry state. When the average diameter of the opening is less than 5 μm in the dry state, the opening diameter of the monolith obtained after the polymerization of the vinyl monomer becomes small, and the pressure loss at the time of fluid penetration becomes large, which is not preferable. On the other hand, when it exceeds 100 μm, the opening diameter of the monolith obtained after the polymerization of the vinyl monomer becomes too large, and the contact between the water to be treated and the monolith anion exchanger becomes insufficient, and as a result, Hydrogen peroxide decomposition characteristics or dissolved oxygen removal characteristics are degraded, which is not preferable. The monolithic intermediate is preferably a uniform structure in which the size of the macroscopic pores or the diameter of the openings is uniform, but is not limited thereto, and the size of the uniform macropores may be larger in the uniform structure. Uneven macroscopic pores.

In the method for producing the second monolithic anion exchanger, the second step is to prepare an aromatic vinyl monomer, and at least two or more vinyl groups in one molecule are 0.3 to 5 mol% of all the oil-soluble monomers. The step of dissolving the cross-linking agent, the aromatic vinyl monomer or the cross-linking agent, but dissolving the mixture of the organic solvent and the polymerization initiator which are formed by polymerizing the aromatic vinyl monomer. Furthermore, there is no order of steps I and II, and step II can be performed after step I, or step I can be performed after step II.

In the method for producing the second monolith anion exchanger, the aromatic vinyl monomer used in the second step is a lipophilic aromatic having a polymerizable vinyl group in the molecule and having high solubility in an organic solvent. The vinyl monomer is not particularly limited, and it is preferred to select a vinyl monomer which is a polymer material of the same or similar type as the monolith intermediate which is present in the above polymerization system. Specific examples of the vinyl monomer include styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride, vinylbiphenyl, and vinylnaphthalene. These monomers may be used alone or in combination of two or more. The aromatic vinyl monomer suitably used in the present invention is styrene, vinylbenzyl chloride or the like.

The amount of the aromatic vinyl monomer to be added is 5 to 50 times, preferably 5 to 40 times by weight based on the weight of the monolithic intermediate which is present during the polymerization. When the amount of the aromatic vinyl monomer added is less than 5 times the amount of the monolithic intermediate, the rod-shaped skeleton cannot be made thick, and the anion exchange capacity per unit volume after the introduction of the anion exchange group becomes small, which is not preferable. On the other hand, when the amount of the aromatic vinyl monomer added exceeds 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 second step is preferably one which contains at least two polymerizable vinyl groups in the molecule and has high solubility in an organic solvent. Specific examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol diacrylate, trimethylolpropane triacrylate, butanediol diacrylate, and the like. . These crosslinking agents may be used alone or in combination of two or more. The preferred crosslinking agent is an aromatic polyvinyl compound such as divinylbenzene, divinylnaphthalene or divinylbiphenyl in terms of the height of the mechanical strength and the stability to hydrolysis. The amount of the crosslinking agent 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 (all oil-soluble monomers). When the amount of the crosslinking agent used is less than 0.3 mol%, the mechanical strength of the monolith is insufficient, which is not preferable. On the other hand, if the amount is too large, the quantitative introduction of the anion exchange group becomes difficult, so that it is not preferable. . Further, the amount of the crosslinking agent used is preferably such that the crosslinking density of the monolithic intermediate which coexists with the polymerization of the vinyl monomer/crosslinking agent is substantially equal. If the amount of use of the two is extremely large, a variation in the crosslink density distribution occurs in the resulting monolith, and cracks are likely to occur when the anion exchange group is introduced into the reaction.

The organic solvent used in the step II is an organic solvent in which an aromatic vinyl monomer or a crosslinking agent is dissolved but a polymer obtained by polymerizing an aromatic vinyl monomer is insoluble, in other words, a polymerization of an aromatic vinyl monomer A poor solvent for the polymer. Since the organic solvent differs greatly depending on the type of the aromatic vinyl monomer, it is difficult to cite a general example. For example, when the aromatic vinyl monomer is styrene, examples of the organic solvent include methanol and ethanol. , alcohols such as propanol, butanol, hexanol, cyclohexanol, octanol, 2-ethylhexanol, decyl alcohol, dodecanol, propylene glycol, tetramethylene glycol; diethyl ether, butyl Chain-like (poly)ethers such as Lucu, polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; chain saturation such as hexane, heptane, octane, isooctane, decane, and dodecane Hydrocarbons; esters of ethyl acetate, isopropyl acetate, celecoxib acetate, ethyl propionate, and the like. Again, even as two Alkane, THF or toluene is a good solvent for polystyrene. It can also be used as an organic solvent when it is used together with the above-mentioned poor solvent and its use amount is small. The amount of the organic solvent 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 is out of the above range and the aromatic vinyl monomer concentration is less than 30% by weight, the polymerization rate is lowered, and the monolith structure after polymerization deviates from the range of the present invention, which is not preferable. On the other hand, when the aromatic vinyl monomer concentration exceeds 80% by weight, the polymerization is uncontrolled, which is not preferable.

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

In the method for producing the second monolith anion exchanger, the step III is carried out by subjecting the mixture obtained in the step II to stand-up and allowing the polymerization in the presence of the monolith intermediate obtained in the first step. The step of changing the continuous macroscopic pore structure of the monolithic intermediate to a co-continuous structure to obtain a monocontinuum of a co-continuous structure. The monolithic intermediate used in the third step not only creates a monolith having a novel structure of the present invention, but also plays a very important role. If the vinyl monomer and the crosslinking agent are allowed to stand in a specific organic solvent in the absence of the monolithic intermediate, as disclosed in Japanese Patent Laid-Open No. Hei 7-501140, a particle agglomerated monolith is obtained. Bulk organic porous body. On the other hand, when the monolithic intermediate having a specific continuous macroscopic pore structure is present in the polymerization system as in the second monolith of the present invention, the structure of the monolith after polymerization is rapidly changed, and the particles are agglomerated. The structure disappears, and the monolithic body of the above-described co-continuous structure is obtained. The reason for this is not ascertained, and it is considered that, in the case where the monolith intermediate is not present, the crosslinked polymer produced by the polymerization is precipitated in the form of particles, thereby forming a particle agglomerated structure. When a porous body (intermediate) having a large total pore solvent is present in the polymerization system, the vinyl single system is adsorbed or distributed from the liquid phase to the skeleton portion of the porous body, and polymerization is carried out in the porous body to form a single sheet. The skeleton of the block structure changes from a two-dimensional wall surface to a one-dimensional rod-shaped skeleton to form a monolithic organic porous body having a co-continuous structure.

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

In the step III, in the reaction vessel, the monolith intermediate is placed in a state of being impregnated with the mixture (solution). The blending of the mixture obtained in the step II with the monolithic intermediate is, as described above, preferably 5 to 50 times by weight based on the amount of the aromatic vinyl monomer added to the monolith intermediate. It is preferably 5 to 40 times. Thereby, a monolithic body having a three-dimensional continuous shape of a moderately sized pore and a three-dimensional continuous continuous skeleton structure can be obtained. In the reaction vessel, the aromatic vinyl monomer and the crosslinking agent in the mixture are adsorbed and distributed to the skeleton of the standing monolith intermediate, and polymerization is carried out in the skeleton of the monolith intermediate.

The basic structure of the monolith having a co-continuous structure is a three-dimensional continuous skeleton having an average thickness of 0.8 to 40 μm in a dry state, and a three-dimensionality in which the average diameter between the skeletons is 8 to 80 μm in a dry state. The construction of continuous holes. The average diameter of the dry state of the three-dimensional continuous pores can be determined by a mercury permeation method to determine a pore distribution curve as a maximum value of the pore distribution curve. The thickness of the skeleton of the monolith in the dry state may be calculated by performing at least three SEM observations and measuring the average thickness of the skeleton in the obtained image. Further, the monolith having a co-continuous structure has a total pore volume of 0.5 to 5 ml/g.

The polymerization conditions are the same as those of the polymerization conditions of the first step of the first monolith anion exchanger, and the description thereof will be omitted.

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

Since the second monolith anion exchange system introduces an anion exchange group into a monolith of a co-continuous structure, it is greatly swollen to, for example, 1.4 to 1.9 times the monolith. Further, even if the pore diameter is swollen and becomes large, the total pore volume does not change. Therefore, the second monolith anion exchanger has a high mechanical strength although it has a very large size due to the three-dimensional continuous pores. Further, since the skeleton is thick, the anion exchange capacity per unit volume in the water-wet state can be increased, and further, the water to be treated can be passed through the water at a low pressure and a large flow rate for a long period of time.

<The first platinum group metal supported catalyst and the second platinum group metal supported catalyst>

The first platinum group metal-supporting catalyst of the present invention is a platinum group metal-supporting catalyst carrying a platinum group metal-containing nanoparticle in the first monolith anion exchanger. Further, the second platinum group metal-supporting catalyst of the present invention is a platinum group metal-supporting catalyst in which a platinum group metal nanoparticle is carried on a second monolith anion exchanger.

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

The platinum group metal nanoparticles of the present invention have an average particle diameter of from 1 to 100 nm, preferably from 1 to 50 nm, more preferably from 1 to 20 nm. When the average particle diameter is less than 1 nm, the possibility that the nanoparticles are detached from the carrier becomes high, which is not preferable. On the other hand, if the average particle diameter exceeds 100 nm, the surface area per unit mass of the metal is small, and it is impossible to It is not good to get the catalyst effect efficiently. Further, in the case where the average particle diameter of the nanoparticles is within the above range, the surface particles are strongly colored by the surface plasma resonance, so that it can be visually confirmed.

The amount of platinum group metal nanoparticles supported in the first platinum group metal supporting catalyst in a dry state ((platinum group metal nanoparticles/first platinum group metal carrier in a dry state) × 100) is 0.004 to 20% by weight, preferably 0.005 to 15% by weight. Further, the amount of platinum group metal nanoparticles supported on the second platinum group metal supporting catalyst in a dry state ((platinum group metal nanoparticles/second platinum group metal carrier in a dry state) × 100 ) is 0.004 to 20% by weight, preferably 0.005 to 15% by weight. When the amount of the platinum group metal nanoparticles is less than 0.004% by weight, the hydrogen peroxide decomposition effect or the dissolved oxygen removal effect is insufficient, which is not preferable. On the other hand, when the amount of the platinum group metal nanoparticles is more than 20% by weight, it is confirmed that the metal is eluted into the water, which is not preferable.

The method for producing the first platinum group metal-supporting catalyst and the second platinum group metal-carrying catalyst is not particularly limited, and the first mono-block anion exchanger or the second mono-block anion can be obtained by a known method. The exchange body carries the platinum group metal nanoparticles to obtain the first platinum group metal carrier catalyst or the second platinum group metal carrier catalyst. For example, the first monolith anion exchanger or the second monolith anion exchanger in a dry state may be immersed in an aqueous hydrochloric acid solution of palladium chloride, and the palladium chloride anion may be adsorbed to the single by ion exchange. a method of supporting a palladium metal nanoparticle on a first monolith anion exchanger or a second monolith anion exchanger in contact with a reducing agent in contact with a reducing agent; or a first monolith The anion exchanger or the second monolith anion exchanger is filled in a column, and a hydrochloric acid aqueous solution of palladium chloride is introduced, and the palladium chloride anion is adsorbed to the first monolith anion exchanger or the second by ion exchange. A method of carrying a palladium metal nanoparticle on a monolithic anion exchanger or a second monolith anion exchanger, followed by a reducing agent in a monolithic anion exchanger. The reducing agent to be used is not particularly limited, and examples thereof include alcohols such as methanol, ethanol, and isopropanol; or carboxylic acids such as formic acid, oxalic acid, citric acid, and ascorbic acid; ketones such as acetone and methyl ethyl ketone; and formaldehyde. Or an aldehyde such as acetaldehyde; sodium borohydride;

In the first platinum group metal-supporting catalyst, the ionic shape of the first monolith anion exchanger as a carrier of the platinum group metal nanoparticles is usually in the form of a chloride after supporting the platinum group metal nanoparticles. Salt shape. In the present invention, such a salt form can be used as a catalyst for decomposing hydrogen peroxide or removing dissolved oxygen. Further, the first platinum group metal-supporting catalyst is not limited thereto, and the ion shape of the first monolith anion exchanger may be regenerated into an OH shape. Further, among these, the ionic shape of the first monolithic anion exchanger is preferably OH-shaped, so that a high catalytic effect can be obtained. In the same manner, in the second platinum group metal-supporting catalyst, the ionic shape of the second monolith anion exchanger as a carrier of the platinum group metal nanoparticles is usually after the platinum group metal nanoparticles are supported. Such as the shape of a salt of chloride. In the present invention, such a salt form can be used as a catalyst for decomposing hydrogen peroxide or removing dissolved oxygen. Further, the second platinum group metal-supporting catalyst is not limited thereto, and the ion shape of the second monolith anion exchanger may be regenerated into an OH shape. Further, among these, the ionic shape of the second monolith anion exchanger is preferably an OH form, and a higher catalyst effect is obtained. The method of regenerating the monolith anion exchanger after carrying the platinum group metal nanoparticles to have an OH shape is not particularly limited, and a known method such as passing an aqueous sodium hydroxide solution or the like may be used.

<Method for Producing Process Water for Decomposing Hydrogen Peroxide of the Present Invention>

In the method for producing treated water for decomposing hydrogen peroxide according to the present invention, the water to be treated containing hydrogen peroxide is contacted with the first platinum group metal supporting catalyst or the second platinum group metal supporting catalyst, and the hydrogen peroxide is contained. A method for producing treated water decomposing hydrogen peroxide which is decomposed by hydrogen peroxide in the treated water. In the following, the first platinum group metal-supporting catalyst and the second platinum group metal-supporting catalyst are collectively referred to as the platinum group metal-supporting 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, it can be exemplified in the manufacture of electronic components such as semiconductor manufacturing and the production of ultrapure water for cleaning electronic parts. The water produced by the various steps therein, specifically, the water after the ultraviolet oxidation treatment step for decomposing the organic matter in the water. In addition, the water to be treated containing hydrogen peroxide may be, for example, a treatment liquid or treated water obtained by adding hydrogen peroxide to a wastewater system to be oxidized, reduced, sterilized, or washed, or using the treatment liquid or treated water. Waste liquid or drainage after treatment. For example, in order to recover and reuse the cleaned water containing hydrogen peroxide discharged from the semiconductor manufacturing step and the organic waste water discharged from the semiconductor manufacturing step as ultrapure water, the hydrogen peroxide is present. a treatment water obtained by oxidizing and decomposing an organic substance by oxidative decomposition; a treatment water obtained by decomposing an organic substance using Fenton's reagent; and sterilizing or washing a reverse osmosis membrane, an ultrafiltration membrane, etc. with hydrogen peroxide The latter drainage water and treated water containing hexavalent chromium are treated by reduction treatment with hydrogen peroxide.

The concentration of hydrogen peroxide in the treated water containing hydrogen peroxide is not particularly limited and is usually from 0.01 to 100 mg/L. In the subsystem manufactured by ultrapure water, the hydrogen peroxide concentration is usually 10 to 50 μg/L. When the hydrogen peroxide concentration exceeds 100 mg/L, the deterioration of the monolith anion exchanger as a precursor easily proceeds.

The method for bringing the water to be treated containing hydrogen peroxide into contact with the platinum group metal-supporting catalyst of the present invention is not particularly limited, and examples thereof include a method of filling a platinum group metal of the present invention in a catalyst packed column. The treated liquid containing hydrogen peroxide is supplied to the catalyst packed column, and the treated water containing hydrogen peroxide is supplied to the platinum group metal supporting catalyst of the present invention.

In the case of the above method, the platinum group metal-supporting catalyst of the present invention can be supplied with treated water containing hydrogen peroxide at SV = 2000 to 20000 h ^-1 , preferably SV = 5000 to 10000 h ^-1 . When the platinum group metal-supporting catalyst of the present invention is used, even if a large SV having a SV of more than 2000 h ^{-1 is introduced} into the water to be treated, decomposition and removal of hydrogen peroxide can be performed. Further, even if the SV is 10000 h ^-1 , if the platinum group metal of the present invention carries a catalyst, decomposition of hydrogen peroxide can be performed, and the platinum group metal-supporting catalyst of the present invention exhibits a significant overshoot of the particulate anion. The exchange resin carries excellent performance in the processing limits of conventional catalysts holding platinum group metal nanoparticles. The water to be treated containing hydrogen peroxide is not particularly limited to the flow rate of the platinum group metal-carrying catalyst of the present invention, and is preferably SV = 2,000 to 20,000 h ^-1 , and more preferably SV = 5,000 to 10,000 h ^-1 . Furthermore, since the platinum group metal-supporting catalyst of the present invention has a significantly high decomposition ability due to hydrogen peroxide, it is not necessary to set the water passing speed to an area less than SV=2000 h ^-1 , but the water passing speed can also be set to area under SV = 2000 h ^-1, so that even in the case of water-passing speed was set to SV = h ^-1 under the area 2000, carrying a platinum group metal catalyst of the present invention also exhibits excellent decomposition of hydrogen peroxide ability. On the other hand, when the SV exceeds 20,000 h ^-1 , the water-passing differential pressure tends to be excessive.

Further, since the platinum group metal-supporting catalyst of the present invention has a remarkably high decomposing ability of hydrogen peroxide, decomposition and removal of hydrogen peroxide can be performed even if the filling layer of the catalyst is made thinner.

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

The method (I) for cleaning an electronic component according to the present invention is a process for washing an electronic component of a manufacturing tool for cleaning an electronic component or an electronic component by using the process water obtained by the method for producing the treated water of decomposing hydrogen peroxide of the present invention. method.

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

As shown in Fig. 13, a first embodiment of the method (I) for cleaning an electronic component according to the present invention includes a first step 21 for bringing the object to be washed into contact with ozone-containing water (hereinafter also referred to as ozone-containing). Water), washing the washed matter; in the second step 22, the washed object is brought into contact with water containing hydrogen (hereinafter also referred to as hydrogen-containing water), and washed and washed while being vibrated at 500 kHz or more. The third step 23 is for bringing the washed object into contact with water containing hydrofluoric acid and hydrogen peroxide to wash the washed matter; and in the fourth step 24, contacting the washed object with water containing hydrogen, The object to be washed is washed while applying vibration of 500 kHz or more.

The washing water supplied to the first step 21 is ozone-containing water prepared by dissolving ozone in the ultrapure water 32. Further, the ultrapure water contains hydrogen peroxide because it is subjected to ultraviolet oxidation treatment or the like in the production step. Therefore, in the first aspect of the method for cleaning the electronic component (I) of the present invention, the ultrapure water 32 is treated as the water to be treated, and the decomposition of the present invention is performed before the ozone 33 is dissolved in the ultrapure water 32. In the hydrogen peroxide removal step 25 of the method for producing treated water of hydrogen peroxide, the ozone 33 is dissolved in the obtained treated water and supplied as the washing water in the first step 21.

Further, the washing water supplied to the second step 22 is a hydrogen-containing water prepared by dissolving hydrogen in the ultrapure water 32. Therefore, in the first embodiment of the method (I) for cleaning an electronic component according to the present invention, the ultrapure water 32 is treated as the water to be treated, and the decomposition of the present invention is performed before the hydrogen 34 is dissolved in the ultrapure water 32. In the hydrogen peroxide removal step 26 of the method for producing treated water of hydrogen peroxide, the hydrogen 34 is dissolved in the obtained treated water and supplied as the washing water in the second step 22. In the first aspect of the method for cleaning the electronic component (I) of the present invention, in the fourth step 24, the ultrapure water is treated as the water to be treated before the hydrogen 36 is dissolved in the ultrapure water 32. In the hydrogen peroxide removal step 28 of the method for producing hydrogen peroxide-treated water of the present invention, hydrogen 36 is dissolved in the obtained treated water and supplied as the washing water in the fourth step 24. Further, the period in which the hydrogen 34 or 36 is dissolved may be the previous stage of the hydrogen peroxide removal step 26 or 28.

Further, in the first aspect of the method for cleaning the electronic component (I) of the present invention, the method for producing the treated water for decomposing hydrogen peroxide according to the present invention may be carried out by using the ultrapure water 32 as the water to be treated. In the hydrogen peroxide removal step 27, hydrofluoric acid and hydrogen peroxide 35 are dissolved in the obtained treated water, and the obtained water containing hydrofluoric acid and hydrogen peroxide is supplied as the washing water in the third step 23.

Then, the electronic component 20a before washing is used as the object to be washed, and the first step 21 to the fourth step 24 are sequentially performed to obtain the cleaned electronic component 30a.

As shown in Fig. 14, a second embodiment of the method (I) for cleaning an electronic component according to the present invention includes a first step 41 for bringing the object to be washed into contact with a solution containing sulfuric acid and hydrogen peroxide, and washing the solution. The second step 42 is to rinse with ultrapure water; the third step is 43 to bring the washed matter into contact with hydrofluoric acid-containing water (dilute hydrofluoric acid) to wash the washed matter; 44, rinse with ultrapure water; in step 5, the washed matter is contacted with water containing ammonia and hydrogen peroxide, and the washed matter is washed; in step 6, 46, rinse with ultrapure water; step 7 For washing the object to be washed with heated ultrapure water, washing the object to be washed; in step 8, step 48, washing with ultrapure water; and step 9 in order to bring the object to be washed into contact with hydrochloric acid and Washing the washed water with water of hydrogen peroxide; step 10, washing with ultrapure water; step 11 of step 51, contacting the washed object with water containing hydrofluoric acid (dilute hydrofluoric acid), washing The net is washed; and in step 12, rinse with ultrapure water.

The washing waters 63, 65, 69, and 71 supplied to the third, fifth, ninth, and eleventh steps in Fig. 14 are such that the chemicals necessary for each step are dissolved in water in ultrapure water. Therefore, in the second embodiment of the method (I) for cleaning the electronic component of the present invention, the steps are the same as in the first embodiment of the cleaning method (I) of the electronic component of the present invention shown in FIG. The hydrogen peroxide removal step of the method for producing the treated water for decomposing hydrogen peroxide of the present invention by using ultrapure water as the water to be treated is dissolved in the ultrapure water, and the necessary reagents for each step are prepared. It is dissolved in the obtained treated water, and is supplied as washing water (washing liquid) of each step.

Further, the washing waters 62, 64, 66, 67, 68, 70, and 72 supplied to the second, fourth, sixth, seventh, eighth, tenth, and twelfth steps in Fig. 14 are ultrapure water. Therefore, in the second aspect of the method (I) for cleaning the electronic component of the present invention, hydrogen peroxide is produced by using the ultrapure water as the water to be treated and the method for producing the treated water for decomposing hydrogen peroxide of the present invention. In the removal step, the obtained treated water is supplied as washing water in each step.

Then, the electronic component 20b before washing is used as the object to be washed, and the first step 41 to the twelfth step 52 are sequentially performed to obtain the cleaned electronic component 30b.

Further, as described above, in the present invention, the manufacturing apparatus for washing the electronic parts or the electronic parts by the treated water obtained by the method for producing the treated water for decomposing hydrogen peroxide of the present invention is not limited to the use of the original The invention relates to a method for manufacturing a treated water for decomposing hydrogen peroxide, which is a manufacturing device for washing an electronic component or an electronic component, and refers to an ultrapure water used for cleaning a manufacturing device for manufacturing an electronic component or an electronic component. The method for producing the treated water for decomposing hydrogen peroxide of the present invention at any one or two or more steps, and the ultrapure water obtained by performing all the steps of the ultrapure water manufacturing step, and washing the electronic parts or electronic parts Manufacturing equipment.

<Method for Producing Treated Water for Removing Dissolved Oxygen of the Present Invention>

The method for producing treated water for removing dissolved oxygen according to the present invention is a method for reacting dissolved oxygen with hydrogen in a treated water containing oxygen in the presence of a first platinum group metal supported catalyst or a second platinum group metal supported catalyst. A method for producing water, thereby removing dissolved oxygen from the treated water containing oxygen to remove dissolved oxygen.

The water to be treated containing oxygen is not particularly limited as long as it contains oxygen, and examples thereof include the production of electronic components such as semiconductor manufacturing and the raw water used in the production of ultrapure water for cleaning electronic parts and the like. Specific examples of the water and the like in the production step include circulating water of an ultrapure water production subsystem, such as outlet water of an ultraviolet oxidation apparatus. In addition, as water to be treated containing dissolved oxygen, water used in a power station, boiler water or cooling water used in various factories, and the like can be cited.

The dissolved oxygen concentration in the water to be treated containing oxygen is not particularly limited and is usually from 0.01 to 10 mg/L.

The amount of hydrogen to be reacted with the dissolved oxygen is not particularly limited, and is 1 to 10 equivalents, preferably 1.1 to 5 equivalents, of the oxygen concentration.

The method of reacting dissolved oxygen with hydrogen in the water to be treated containing oxygen in the presence of the platinum group metal-supporting catalyst of the present invention is not particularly limited, and examples thereof include the following methods: filling in a catalyst packed column The platinum group metal supporting catalyst of the present invention supplies a liquid containing oxygen to the catalyst charging tower, and simultaneously injects hydrogen into the supply pipe of the liquid to be treated, thereby carrying the catalyst to the platinum group metal of the present invention. The treated water containing dissolved hydrogen and dissolved oxygen is introduced.

In the case of the above method, the platinum group metal-supporting catalyst of the present invention may be supplied with treated water containing oxygen at SV = 2000 to 20000 h ^-1 , preferably SV = 5000 to 10000 h ^-1 . When the platinum group metal-supporting catalyst of the present invention is used, the dissolved oxygen can be removed even if a large SV is introduced into the water to be treated as the SV exceeds 2000 h ^-1 . Further, even if the SV is 10000 h ^-1 , if the platinum group metal-supporting catalyst of the present invention is used, the dissolved oxygen can be removed, and the platinum group metal-supporting catalyst of the present invention exhibits a large excess of the particulate anion. The exchange resin carries excellent performance in the processing limits of conventional catalysts holding platinum group metal nanoparticles. The flow rate of the water to be treated containing oxygen to the platinum group metal-supporting catalyst of the present invention is not particularly limited, and is preferably SV = 2000 to 20000 h ^-1 , and more preferably SV = 5000 to 10000 h ^-1 . Furthermore, since the platinum group metal-supporting catalyst of the present invention has a significantly high dissolved oxygen removal ability, even a conventional carrier catalyst which carries a platinum group metal nanoparticle on a particulate anion exchange resin is carried out. The limit water flow rate is passed into the treated water, and the dissolved oxygen in the treated water can also be decomposed.

Further, since the platinum group metal-carrying catalyst of the present invention has a remarkably high oxygen removal ability, the dissolved oxygen can be removed even if the filler layer of the catalyst is made thinner.

The dissolved oxygen concentration in the treated water obtained by the method for producing the treated water for removing dissolved oxygen of the present invention is preferably 10 μg/L or less.

The method for cleaning an electronic component according to the present invention (II) is a method for cleaning an electronic component by using the process water obtained by the method for producing a treated water for removing dissolved oxygen of the present invention, and for manufacturing an electronic component or an electronic component. .

The oxygen in the air dissolves into the water to become dissolved oxygen. The dissolved oxygen is managed as an impurity in ultrapure water. As described above, the dissolved oxygen concentration in the treated water (primary pure water) at the inlet of the secondary pure water system of the ultrapure water production apparatus is usually reduced to 100. Below μg/L. Furthermore, there are cases where it is managed to be 10 μg/L or less. Furthermore, the dissolved oxygen concentration in ultrapure water is also managed to 10 μg/L or less, and is managed to 1 μg/L or less. On the other hand, in the manufacturing process of ultrapure water, oxygen is generated when hydrogen peroxide is decomposed by ultraviolet oxidation treatment or the like. Therefore, in the embodiment of the method (II) for cleaning the electronic component of the present invention, the treated water obtained by the dissolved oxygen removing step of the method for producing the treated water for removing dissolved oxygen of the present invention is supplied to the electronic component. Washing water (washing liquid) for each step of the washing method or ultrapure water for preparation thereof.

The first embodiment of the method (II) for cleaning an electronic component of the present invention replaces the hydrogen peroxide removing steps 25, 26, 27, and 28 in FIG. 13 with the ultrapure water 32 as treated water to carry out the present invention. The dissolved oxygen removal step of the method for producing dissolved oxygen treatment water. Then, the electronic component 20a before washing is used as the object to be washed, and the first step 21 to the fourth step 24 are sequentially performed to obtain the cleaned electronic component 30a.

The second aspect of the method for cleaning an electronic component of the present invention (II) is a step of removing a dissolved oxygen by performing the method for producing treated water for removing dissolved oxygen according to the present invention by using ultrapure water as water to be treated, and performing each step. The necessary chemicals are dissolved in the treated water obtained, thereby preparing the washing water (washing liquid) 63, 65, 69 and 71 supplied to the steps 3, 5, 9 and 11 in Fig. 14, and further, The dissolved oxygen removal step of the method for producing treated water for removing dissolved oxygen of the present invention is carried out by using ultrapure water as the treated water, thereby obtaining the supply to the second, fourth, sixth, seventh, eighth, and tenth portions in FIG. 12 steps of washing water 62, 64, 66, 67, 68, 70 and 72. Then, the electronic component 20b before washing is used as the object to be washed, and the first step 41 to the twelfth step 52 are sequentially performed to obtain the cleaned electronic component 30b.

In the present invention, the manufacturing apparatus for washing the electronic parts or the electronic parts by the treated water obtained by the method for producing the treated water for removing dissolved oxygen of the present invention is not limited to the use of the present invention. A process for washing an electronic component or an electronic component after the process for removing the dissolved oxygen treatment water, and a step of using ultrapure water used for cleaning the manufacturing device for manufacturing an electronic component or an electronic component. The method for producing the treated water for removing dissolved oxygen of the present invention, the ultrapure water obtained by performing all the steps of the ultrapure water production step, and the manufacturing apparatus for cleaning the electronic component or the electronic component.

The present invention is specifically described by the following examples, which are merely illustrative and not restrictive.

[Examples]

<Manufacture of the first monolithic anion exchanger (Reference Example 1)>

(I step: manufacture of monolithic intermediates)

Mixing 19.9 g of styrene, 0.4 g of divinylbenzene, 1.0 g of sorbitan monooleate (hereinafter abbreviated as SMO) and 0.26 g of 2,2'-azobis(isobutyronitrile) to make it uniform Dissolved. Then, the styrene/divinylbenzene/SMO/2,2'-azobis(isobutyronitrile) mixture was added to 180 g of pure water containing 1.8 ml of THF, using a vacuum as a planetary stirring device. A stirred defoaming mixer (manufactured by EME Co., Ltd.) was stirred under reduced pressure at a temperature of 5 to 20 ° C to obtain a water-drop type emulsion in oil. The emulsion was quickly transferred to a reaction vessel, sealed, and polymerized at 60 ° C for 24 hours under standing. After completion of the polymerization, the content was taken out, extracted with isopropyl alcohol, and dried under reduced pressure to produce a monolith intermediate having a continuous macroporous structure. The opening (gap hole) of the portion in which the macroscopic pores and the macroscopic pores of the monolith intermediate body were measured by the mercury permeation method had an average diameter of 56 μm and a total pore volume of 7.5 ml/g.

(Manufacture of single block)

Then, 49.0 g of styrene, 1.0 g of divinylbenzene, 50 g of 1-nonanol, and 0.5 g of 2,2'-azobis(2,4-dimethylvaleronitrile) were mixed to uniformly dissolve ( Step II). Then, the above monolith intermediate body was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 20 mm, and 7.6 g was taken. The fractionated monolith intermediate was placed in a reaction vessel having an inner diameter of 90 mm and immersed in the above styrene/divinylbenzene/1-nonanol/2,2'-azobis (2, After defoaming in a decompression chamber in a 4-dimethylvaleronitrile mixture, the reaction vessel was sealed and polymerized at 60 ° C for 24 hours under standing. After the completion of the polymerization, a monolithic body having a thickness of about 30 mm was taken out, subjected to Soxhlet extraction with acetone, and dried under reduced pressure at 85 ° C overnight (Step III).

The internal structure of the monolith (dry body) containing 1.3 mol% of the cross-linking component composed of the styrene/divinylbenzene copolymer obtained in the above manner was observed by SEM, and the results are shown in Fig. 1. in. The SEM image of Fig. 1 is an image obtained by cutting a single block at an arbitrary position and obtaining an arbitrary position of the cut surface. As shown in Fig. 1, the monolith has a continuous giant pore structure, and the skeleton constituting the continuous giant pore structure is much thicker than the SEM image of the known product of Reference Example 3 (Fig. 11), and constitutes a skeleton. The thickness of the wall portion is thicker.

Then, the thickness of the wall portion and the area of the skeleton portion indicated by the cross section were measured based on two SEM images obtained by cutting the obtained monolithic body at a position different from the above position by excluding the subject. The thickness of the wall portion is an average of 8 points obtained from one SEM photograph, and the skeleton portion area is obtained by image analysis. Furthermore, the wall portion is defined above. Further, the skeleton portion area is represented by an average of three SEM images. As a result, the average thickness of the wall portion was 30 μm, and the area of the skeleton portion shown by the cross section was 28% in the SEM image. Further, the opening of the monolith was measured by the mercury infiltration method to have an average diameter of 31 μm and a total pore volume of 2.2 ml/g.

(Manufacture of monolithic anion exchanger)

The monolith produced by the above method was cut into a disk 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 thereto under ice cooling. After completion of the dropwise addition, the mixture was heated, and allowed to react at 35 ° C for 5 hours to introduce a chloromethyl group. After completion of the reaction, the mother liquid was extracted with a siphon, washed with a mixed solvent of THF/water = 2/1, and further washed with THF. To the chloromethylated monolith, 1000 ml of THF and 600 ml of a 30% aqueous solution of trimethylamine were added, and the mixture was reacted at 60 ° C for 6 hours. After completion of the reaction, the product was washed with a methanol/water mixed solvent, followed by washing with pure water to separate.

The swelling ratio of the obtained monolithic anion exchanger before and after the reaction was 1.7 times, and the anion exchange capacity per unit volume was 0.60 mg equivalent/ml in the water wet state. The average diameter of the opening of the monolithic anion exchanger in the water-wet state was estimated from the value of the monolith and the swelling ratio of the monolith anion exchanger in the water-wet state, and the result was 54 μm in the same manner as the monolith. The average thickness of the wall portion constituting the skeleton was 50 μm, the area of the skeleton portion was 28% in the imaging region of the SEM photograph, and the total pore volume was 2.2 ml/g. Further, the differential pressure coefficient as an index of the pressure loss at the time of water penetration is 0.017 MPa/m‧LV, which is a lower pressure loss than the practically required pressure loss. Further, the length of the ion exchange band associated with the fluoride ion of the monolithic anion exchanger was measured, and as a result, the length of the ion exchange zone of LV = 20 m/h was 25 mm, and a commercially available Amberlite as a strongly basic anion exchange resin. The value of IRA402BL (manufactured by Rohm and Hass) (165 mm) is absolutely shorter.

Then, 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 form, and then the distribution state of the chloride ions was observed by EPMA. The distribution state of the chloride ions on the surface of the monolithic anion exchanger is shown in Fig. 2, and the distribution state of the chloride ions in the skeleton cross section is shown in Fig. 3. It is confirmed that the chloride ions are not uniformly distributed in the monolith. The surface of the skeleton of the anion exchanger is uniformly distributed inside the skeleton, and the quaternary ammonium group is uniformly introduced into the monolith anion exchanger. Further, in Fig. 3, the chloride ion concentration in the lower portion of the skeleton is apparently higher than the chloride ion concentration in the upper portion of the skeleton, but the lower portion of the skeleton is less than the upper portion of the skeleton due to insufficient planarity of the cross section at the time of cutting. Upon cutting, the distribution of chloride ions is substantially uniform.

<Manufacture of second monolithic anion exchanger (Reference Example 2)>

(I step: manufacture of monolithic intermediates)

Mixing 5.29 g of styrene, 0.28 g of divinylbenzene, 1.39 g of sorbitan monooleate (hereinafter abbreviated as SMO) and 0.26 g of 2,2'-azobis(isobutyronitrile) to make it uniform Dissolved. Then, the styrene/divinylbenzene/SMO/2,2'-azobis(isobutyronitrile) mixture was added to 180 g of pure water using a vacuum stirring defoaming mixer as a planetary stirring device. (manufactured by EME Co., Ltd.), the mixture was stirred under reduced pressure at a temperature of 5 to 20 ° C to obtain a water-drop type emulsion in oil. The emulsion was quickly transferred to a reaction vessel, sealed, and polymerized at 60 ° C for 24 hours under standing. After completion of the polymerization, the content was taken out, extracted with methanol, and dried under reduced pressure to produce a monolith intermediate having a continuous macroporous structure. The internal structure of the monolith intermediate body (dried body) obtained in the above manner was observed by the SEM image (Fig. 12), and as a result, the wall portion adjacent to the two giant pores was extremely thin and rod-shaped, but had a continuous bubble structure. The opening (gap hole) of the portion where the macroscopic pores and the macroscopic pores overlap by the mercury permeation method has an average diameter of 70 μm and a total pore volume of 17.8 ml/g.

(Manufacture of single block)

Then, 39.2 g of styrene, 0.8 g of divinylbenzene, 60 g of 1-nonanol, and 0.8 g of 2,2'-azobis(2,4-dimethylvaleronitrile) were mixed to uniformly dissolve ( Step II). Then, the monolith intermediate was cut into a disk shape having a diameter of 70 nm and a thickness of about 30 mm, and 2.4 g was taken. The fractionated monolith intermediate was placed in a reaction vessel having an inner diameter of 75 mm and immersed in the above styrene/divinylbenzene/1-nonanol/2,2'-azobis (2, After defoaming in a decompression chamber in a 4-dimethylvaleronitrile mixture, the reaction vessel was sealed and polymerized at 60 ° C for 24 hours under standing. After the completion of the polymerization, a monolithic body having a thickness of about 60 mm was taken out, subjected to Soxhlet extraction with acetone, and dried under reduced pressure at 85 ° C overnight (Step III).

The internal structure of the monolith (dry body) containing 1.3 mol% of the cross-linking component composed of the styrene/divinylbenzene copolymer obtained in the above manner was observed by SEM, and the results are shown in Fig. 7. . As shown in Fig. 7, the monolithic system skeleton and the voids are respectively three-dimensionally continuous and two-phase wound in a continuous structure. Further, the thickness of the skeleton measured from the SEM image was 8 μm. Further, the three-dimensional continuous pores of the monolith were measured by the mercury infiltration method to have an average diameter of 18 μm and a total pore volume of 2.0 ml/g.

(Manufacture of monolithic anion exchanger)

The monolith produced by the above method was cut into a disk 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 thereto under ice cooling. After completion of the dropwise addition, the mixture was heated, and allowed to react at 35 ° C for 5 hours to introduce a chloromethyl group. After completion of the reaction, the mother liquid was extracted with a siphon, washed with a mixed solvent of THF/water = 2/1, and further washed with THF. To the chloromethylated monolith, 1000 ml of THF and 600 ml of a 30% aqueous solution of trimethylamine were added, and the mixture was reacted at 60 ° C for 6 hours. After completion of the reaction, the product was washed with a methanol/water mixed solvent, followed by washing with pure water to separate.

The swelling ratio of the obtained monolithic anion exchanger before and after the reaction was 1.6 times, and the anion exchange capacity per unit volume was 0.44 mg equivalent/ml in the water wet state. The average diameter of the continuous pores of the monolithic ion exchanger in the water-wet state was estimated from the value of the monolith and the swelling ratio of the monolith anion exchanger in the water-wet state. The result was 29 μm, and the average thickness of the skeleton was 13 μm with a total pore volume of 2.0 ml/g.

Moreover, the differential pressure coefficient which is an index of the pressure loss at the time of water penetration is 0.040 MPa/m‧LV, and it is a practically unobstructed low pressure loss. Further, the length of the ion exchange band associated with the fluoride ion of the monolithic anion exchanger was measured, and as a result, the length of the ion exchange band of LV = 20 m/h was 22 mm, and a commercially available Amberlite as a strongly basic anion exchange resin. The value of IRA402BL (manufactured by Rohm and Hass) (165 mm) is absolutely shorter.

Then, 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 prepare a chloride pattern, and then the distribution state of the chloride ions was observed by EPMA. The distribution state of the chloride ions on the surface of the monolithic anion exchanger is shown in Fig. 8. The distribution state of the chloride ions in the skeleton cross section is shown in Fig. 9, and it is confirmed that the chloride ions are not uniformly distributed in the monolith. The surface of the skeleton of the anion exchanger is uniformly distributed inside the skeleton, and the quaternary ammonium group is uniformly introduced into the monolith anion exchanger. Further, in Fig. 9, the chloride ion concentration in the peripheral portion of the skeleton is apparently higher than the chloride ion concentration in the center portion of the skeleton, but the peripheral portion of the skeleton is more internal due to the insufficient planarity of the cross section at the time of cutting. The state is cut off and the distribution of chloride ions is substantially uniform.

<Reference Example 3>

(Manufacture of monolithic organic porous body (known product) having a continuous giant pore structure)

According to the production method described in Japanese Laid-Open Patent Publication No. 2002-306976, a monolithic organic porous body having a continuous giant pore structure is produced. 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. Then, the styrene/divinylbenzene/SMO/2,2'-azobis(isobutyronitrile) mixture was added to 180 g of pure water using a vacuum stirring defoaming mixer as a planetary stirring device. (manufactured by EME Co., Ltd.), the mixture was stirred under reduced pressure at a temperature of 5 to 20 ° C to obtain a water-drop type emulsion in oil. The emulsion was quickly transferred to a reaction vessel, sealed, and polymerized at 60 ° C for 24 hours under standing. After completion of the polymerization, the content was taken out, extracted with isopropyl alcohol, and dried under reduced pressure to produce a monolithic organic porous body having a continuous macroporous structure.

The internal structure of the monolith containing 3.3 mol% of the cross-linking component composed of the styrene/divinylbenzene copolymer obtained in the above manner was observed by SEM, and the results are shown in Fig. 11 . As shown in Fig. 11, the monolith has a continuous giant pore structure, but the thickness of the wall portion constituting the skeleton of the continuous giant pore structure is thinner than that of Reference Example 1 (Fig. 1). The average thickness of the wall portion measured by the SEM image of the monolith was 5 μm, and the skeleton portion area was 10% in the SEM image region. Further, the opening of the monolith was measured by the mercury infiltration method to have an average diameter of 29 μm and a total pore volume of 8.6 ml/g.

[Example 1]

(Preparation of the first platinum group metal-supporting catalyst)

The monolithic anion exchanger (first monolith anion exchanger) of Reference Example 1 was ion-exchanged into a Cl shape, and then cut into a column shape in a wet state of water, and dried under reduced pressure. The weight of the monolithic anion exchanger after drying was 1.2 g. The monolithic anion exchanger in a dry state was immersed in dilute hydrochloric acid in which 270 mg of palladium chloride was dissolved for 24 hours, and ion-exchanged into a palladium chloride acid type. After the completion of the immersion, the monolith anion exchanger was washed several times with pure water, and immersed in a hydrazine aqueous solution for 24 hours to carry out a reduction treatment. The palladium chloride-based monolith anion exchanger is brown. On the other hand, the monolith anion exchange system after the reduction treatment is colored black, suggesting the formation of palladium nanoparticles. The first palladium nanoparticle-carrying catalyst a obtained in the above manner was washed several times with pure water and dried.

The amount of the palladium nanoparticle supported on the first palladium nanoparticle-carrying catalyst a in a dry state was 10.9% by weight. In order to measure the average particle diameter of the palladium nanoparticles held, a transmission electron microscope (TEM) observation was performed. The obtained TEM image is shown in Fig. 5. The average particle size of the palladium nanoparticles is 5 nm. The palladium nanoparticle-carrying catalyst a in a dry state is filled in a column having an inner diameter of 10 mm, and an aqueous sodium hydroxide solution is passed to make a monolithic anion exchanger as a carrier into an OH shape for hydrogen peroxide. Evaluation of decomposition characteristics. The filling layer height of the first palladium nanoparticle-carrying catalyst a was 11 mm. At this time, the loading amount of the resin volume of the palladium nanoparticle with respect to the water-wet state was 9.7 g-Pd/L-R (the weight of palladium carried per 1 L of the palladium nanoparticle-supporting catalyst).

(evaluation of catalyst)

The first palladium nanoparticle-loaded catalyst a filled in a column having an inner diameter of 10 mm was supplied with hydrogen peroxide 15 to 30 μg at a flow rate of SV=5000 h ^-1 for 27 hours. /L ultra pure water, sample water was taken at the outlet of the column, and the hydrogen peroxide concentration was measured. As a result, the concentration of hydrogen peroxide in the sample water taken at the outlet of the column was less than 1 μg/L, and the hydrogen peroxide was decomposed and removed. Then, the same processing was performed by setting SV to 10000 h ^-1 . Although the SV is very fast at 10000 h ^-1 and the filling layer of the catalyst is as thin as 11 mm, the hydrogen peroxide concentration in the sample water taken at the outlet of the column is less than 1 μg/L, and the hydrogen peroxide is decomposed. Remove.

[Embodiment 2]

(Preparation of the second platinum group metal-supporting catalyst)

The monolith anion exchanger (the second monolith anion exchanger) of Reference Example 1 was used instead of the monolithic anion exchanger (the first monolith anion exchanger) of Reference Example 1 as a catalyst carrier, and The monolithic anion exchanger of the reference example 2 was used in the same manner as in Example 1 except that the weight of the monolith anion exchanger to be cut was 1.4 g instead of 1.2 g (the second monolith anion exchange) The palladium nanoparticle is loaded on the body to obtain the second palladium nanoparticle-carrying catalyst a.

The amount of the palladium nanoparticle supported on the second palladium nanoparticle-carrying catalyst a in the obtained dry state was 9.8% by weight. In order to measure the average particle diameter of the palladium nanoparticles held, a transmission electron microscope (TEM) observation was performed. The obtained TEM image is shown in Fig. 10. The average particle size of the palladium nanoparticles is 3 nm. The second palladium nanoparticle-carrying catalyst in a dry state is filled in a column having an inner diameter of 10 mm, and a sodium hydroxide aqueous solution is introduced to make a monolithic anion exchanger as a carrier into an OH shape for peroxidation. Evaluation of hydrogen decomposition characteristics. The fill level of the catalyst is 13 mm. At this time, the loading amount of the palladium nanoparticle with respect to the resin in a wet state of water was 8.7 g-Pd/L-R.

(evaluation of catalyst)

The second palladium nanoparticle-carrying catalyst a was evaluated in the same manner as in Example 1 except that the second palladium nanoparticle-carrying catalyst a was used instead of the first palladium nanoparticle-carrying catalyst as a catalyst. Hydrogen peroxide decomposition effect. As a result, even if any of the ultrapure waters are to be introduced at SV=5000 h ^-1 and 10000 h ^-1 , the hydrogen peroxide concentration in the sample water taken at the outlet of the column is less than 1 μg/L. Hydrogen peroxide is removed by decomposition.

[Example 3]

The same method as in Example 1 except that the weight of the first monolith anion exchanger excised was 1.7 g instead of 1.2 g, and 2.5 mg of palladium chloride was dissolved instead of dissolving 270 mg of palladium chloride. Palladium nanoparticle was carried on the monolithic anion exchanger (first monolith anion exchanger) of Reference Example 1, and the first palladium nanoparticle-carrying catalyst b was obtained.

The amount of the palladium nanoparticle supported on the first palladium nanoparticle-carrying catalyst b in the obtained dry state was 0.05% by weight. The first palladium nanoparticle-carrying catalyst b in a dry state is filled in a column having an inner diameter of 10 mm, and a sodium hydroxide aqueous solution is introduced to form a monolithic anion exchanger as a carrier into an OH shape. Evaluation of the decomposition characteristics of hydrogen peroxide. The fill level of the catalyst is 19 mm. At this time, the loading amount of the palladium nanoparticle relative to the resin volume in the wet state of water was 0.07 g-Pd/L-R.

(evaluation of catalyst)

The first palladium nanoparticle-carrying catalyst b was evaluated in the same manner as in Example 1 except that the first palladium nanoparticle-carrying catalyst b was used instead of the first palladium nanoparticle-carrying catalyst a as a catalyst. The hydrogen peroxide decomposition effect. In the case of water passing SV=5000 h ^-1 , the concentration of hydrogen peroxide in the sample water taken at the outlet of the column is less than 1 μg/L, and the hydrogen peroxide is decomposed and removed. The SV is then set to 10000 h ^-1 for the same processing. The concentration of hydrogen peroxide in the sample water taken at the outlet of the column was 1.7 μg/L, and although the loading amount of the palladium nanoparticles was 0.07 g-Pd/LR, the decomposition effect of hydrogen peroxide was high.

[Comparative Example 1]

Palladium nanoparticle-supported particles are supported by a known method by carrying a palladium nanoparticle on a gel-like particulate strong alkali anion exchange resin (type I) having a water retention capacity of 60 to 70% on a OH basis. Ion exchange resin catalyst. The Cl-shaped particulate anion exchange resin was immersed in a hydrochloric acid aqueous solution of palladium chloride, washed with water, and then subjected to reduction treatment with a hydrazine aqueous solution. The aqueous solution of sodium hydroxide was passed through to make the particulate anion exchange resin into an OH form for evaluation of hydrogen peroxide decomposition characteristics. At this time, the palladium nanoparticle-supporting amount was 0.4% by weight in a dry state and 970 mg-Pd/L-R in a water-wet state. The OH-form particle-shaped ion exchange resin containing palladium was filled in a column of an inner diameter of 25 mm in 40 mL (layer height: 80 mm), and an experiment of reducing hydrogen peroxide was carried out in the same manner as in Example 1.

(evaluation of catalyst)

In addition to using the above-mentioned palladium nanoparticle-carrying granular ion-exchange resin catalyst instead of the first palladium nanoparticle-carrying catalyst a as a catalyst, and introducing ultrapure water at SV=1500 h ^-1 and 2500 h ^-1 The hydrogen peroxide decomposition effect of the palladium nanoparticle-supporting particulate ion exchange resin catalyst was evaluated in the same manner as in Example 1 except for the same method as in Example 1. As a result, the concentration of hydrogen peroxide in the sample water taken at the outlet of the column was less than 1 μg/L and 1.6 μg/L, respectively. Hydrogen peroxide was less than 1 μg/L at SV=1500 h ^-1 , but if SV was increased to 2500 h ^-1 , hydrogen peroxide leaked into the treated water. Thus, the prior art in the particulate anion exchange resin carries the catalyst of the palladium nanoparticle, even if the SV is slower than the embodiment, and the thicker catalyst filler layer is high, the condition for easily removing hydrogen peroxide is Hydrogen peroxide also leaks when SV = 2500 h ^-1 .

[Comparative Example 2]

Peroxidation at SV = 10000 h ^-1 was evaluated in the same manner as in Example 1 except that the palladium nanoparticle was not supported and only the monolith anion exchanger (the first monolith anion exchanger) of Reference Example 1 was used. Hydrogen decomposition effect. As a result, it was confirmed that the decomposition effect of hydrogen peroxide was not obtained.

<Manufacture of monolith of the first monolithic anion exchanger (Reference Examples 4 to 13)>

(Manufacture of single block)

In addition to the amount of styrene used, the type and amount of the crosslinking agent, the type and amount of the organic solvent, the porous structure of the monolithic intermediate which coexists in the styling polymerization of styrene and divinylbenzene, and the crosslinking density and A monolith was produced in the same manner as in Reference Example 1 except that the amount of use was changed to the amount shown in Table 1. The results are shown in Tables 1 and 2. Further, according to the SEM images (not shown) of Reference Examples 4 to 13 and Table 2, the average diameter of the openings of the monoliths of Reference Examples 4 to 13 was as large as 22 to 70 μm, and the average of the wall portions constituting the skeleton. The thickness is also as thick as 25 to 50 μm, and the area of the skeleton is 26 to 44% in the SEM image area, which is a monolithic body of a thick skeleton. Further, in Table 1, the "addition" column sequentially indicates the vinyl monomer used in the step II, the crosslinking agent, the monolith intermediate obtained in the step I, and the step II used in the step from the left. Organic solvents. Further, the diameter of the clearance hole, the thickness of the wall surface, the diameter (thickness) of the skeleton, and the diameter of the pores shown in the following table are average values.

<Manufacture of the first monolithic anion exchanger (Reference Example 14)>

(Manufacture of single block)

A monolith was produced in the same manner as in Reference Example 1 except that the amount of styrene used, the amount of the crosslinking agent used, and the amount of the organic solvent used were changed to those shown in Table 1. The results are shown in Tables 1 and 2. In the monolithic system of Reference Example 14, the average diameter of the opening of the overlapping portion of the macroscopic pores and the macroscopic pores was as large as 38 μm, and the wall portion of the skeleton was also 25 μm, and the wall portion was thick and organic porous. Platinum.

(Manufacture of monolithic anion exchanger)

The monolith produced by the above method was cut into a disk 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 thereto under ice cooling. After completion of the dropwise addition, the mixture was heated, and allowed to react at 35 ° C for 5 hours to introduce a chloromethyl group. After completion of the reaction, the mother liquid was extracted with a siphon, washed with a mixed solvent of THF/water = 2/1, and further washed with THF. To the chloromethylated monolith, 1000 ml of THF and 600 ml of a 30% aqueous solution of trimethylamine were added, and the mixture was reacted at 60 ° C for 6 hours.

After completion of the reaction, the product was washed with a methanol/water mixed solvent, followed by washing with pure water to separate.

The swelling ratio of the obtained monolithic anion exchanger before and after the reaction was 1.6 times, and the anion exchange capacity per unit volume was 0.56 mg equivalent/ml in the water wet state. The average diameter of the opening of the monolithic anion exchanger in the water-wet state was estimated from the value of the monolith and the swelling ratio of the monolith anion exchanger in the water-wet state, and the result was 61 μm in the same manner as the monolith. The obtained wall portion constituting the skeleton had an average thickness of 40 μm, the skeleton portion area was 26% in the imaging region of the SEM photograph, and the total pore volume was 2.9 ml/g. Further, the differential pressure coefficient as an index of the pressure loss at the time of water penetration is 0.020 MPa/m‧LV, which is lower than the pressure loss required in practical use, and is lower than the pressure loss.

Then, 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 prepare a chloride pattern, and then the distribution state of the chloride ions was observed by EPMA. As a result, it was confirmed that chloride ions were not uniformly distributed on the skeleton surface of the monolith anion exchanger, but also uniformly distributed inside the skeleton, and the quaternary ammonium group was uniformly introduced into the monolith anion exchanger.

<Manufacture of second monolithic anion exchanger (Reference Example 15)>

(I step: manufacture of monolithic intermediates)

Mixing 5.4 g of styrene, 0.17 g of divinylbenzene, 1.4 g of sorbitan monooleate (hereinafter abbreviated as SMO) and 0.26 g of 2,2'-azobis(isobutyronitrile) to make it uniform Dissolved. The styrene/divinylbenzene/SMO/2,2'-azobis(isobutyronitrile) mixture was then added to 180 g of pure water using a vacuum stirred defoaming mixer as a planetary stirring device ( The EME company is stirred at a temperature of 5 to 20 ° C under reduced pressure to obtain a water-drop type emulsion in oil. The emulsion was quickly transferred to a reaction vessel, sealed, and polymerized at 60 ° C for 24 hours under standing. After completion of the polymerization, the content was taken out, extracted with methanol, and dried under reduced pressure to produce a monolith intermediate having a continuous macroporous structure. The internal structure of the monolith intermediate body (dried body) obtained in the above manner was observed by an SEM image (not shown), and as a result, the wall portion adjacent to the two giant pores was extremely thin and rod-shaped, but had continuous bubbles. The average diameter of the opening (gap hole) of the portion where the macroscopic pore and the giant pore are overlapped by the mercury permeation method is 70 μm, and the total pore volume is 21.0 ml/g.

(Manufacture of a continuous continuous monolith)

Then, 76.0 g of styrene, 4.0 g of divinylbenzene, 120 g of 1-nonanol, and 0.8 g of 2,2'-azobis(2,4-dimethylvaleronitrile) were mixed to uniformly dissolve ( Step II). The monolith intermediate was then cut into a disc having a diameter of 70 mm and a thickness of about 40 mm, and 4.1 g was taken. The fractionated monolith intermediate was placed in a reaction vessel having an inner diameter of 75 mm and immersed in the above styrene/divinylbenzene/1-nonanol/2,2'-azobis (2, After defoaming in a decompression chamber in a 4-dimethylvaleronitrile mixture, the reaction vessel was sealed and polymerized at 60 ° C for 24 hours under standing. After the completion of the polymerization, a monolithic body having a thickness of about 60 mm was taken out, subjected to Soxhlet extraction with acetone, and dried under reduced pressure at 85 ° C overnight (Step III).

The internal structure of a monolith (dry body) containing 3.2 mol% of a cross-linking component composed of a styrene/divinylbenzene copolymer obtained in the above manner was observed by SEM, and as a result, the monolithic system skeleton was observed. And the co-continuous structure in which the holes are three-dimensionally continuous and two-phase is wound. Further, the average thickness of the skeleton measured from the SEM image was 10 μm. Further, the three-dimensional continuous pores of the monolith were measured by the mercury infiltration method to have an average diameter of 17 μm and a total pore volume of 2.9 ml/g. The results are summarized in Tables 3 and 4. In Table 4, the thickness of the skeleton is expressed by the average diameter of the skeleton.

(Manufacture of monolithic anion exchanger with co-continuous bubble structure)

The monolith produced by the above method was cut into a disk 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 thereto under ice cooling. After completion of the dropwise addition, the mixture was heated, and allowed to react at 35 ° C for 5 hours to introduce a chloromethyl group. After completion of the reaction, the mother liquid was extracted with a siphon, washed with a mixed solvent of THF/water = 2/1, and further washed with THF. To the chloromethylated monolith, 1000 ml of THF and 600 ml of a 30% aqueous solution of trimethylamine were added, and the mixture was reacted at 60 ° C for 6 hours. After completion of the reaction, the product was washed with a methanol/water mixed solvent, followed by washing with pure water to separate.

The swelling ratio of the obtained monolithic anion exchanger before and after the reaction was 1.5 times, and the anion exchange capacity per unit volume was 0.54 mg equivalent/ml in the water wet state. The average diameter of the continuous pores of the monolithic ion exchanger in the water-wet state was estimated from the value of the monolith and the swelling ratio of the monolith anion exchanger in the water-wet state. The result was 26 μm, and the average thickness of the skeleton was 15 μm, total pore volume 2.9 ml/g.

Moreover, the differential pressure coefficient which is an index of the pressure loss at the time of water penetration is 0.045 MPa/m‧LV, and it is a practically unobstructed low pressure loss. Further, the length of the ion exchange band associated with the fluoride ion of the monolithic anion exchanger was measured, and as a result, the length of the ion exchange band of LV = 20 m/h was 20 mm, and a commercially available Amberlite as a strongly basic anion exchange resin. The value of IRA402BL (manufactured by Rohm and Hass) (165 mm) is relatively short compared to the value of the monolithic porous anion exchanger having the continuous cell structure. The results are summarized in Table 5. Further, the internal structure of the obtained monolithic anion exchanger having a co-continuous structure was observed by an SEM image (not shown).

Then, 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 form, and then the distribution state of the chloride ions was observed by EPMA. As a result, it was confirmed that chloride ions were not uniformly distributed on the surface of the monolith anion exchanger, but also uniformly distributed inside, and the quaternary ammonium group was uniformly introduced into the monolith anion exchanger.

<Manufacture of second monolithic anion exchanger (Reference Examples 16 and 17)>

(Manufacture of monolithic bodies with a co-continuous structure)

In addition to the amount of styrene used, the amount of the crosslinking agent used, the amount of the organic solvent used, the porous structure of the monolithic intermediate which coexists in the styrene and divinylbenzene impregnation polymerization, the crosslinking density and the amount of use are changed to A monolith having a co-continuous structure was produced in the same manner as in Reference Example 15 except for the amount shown in Table 3. The internal structure (not shown) of the monolith (dry body) was observed by SEM, and as a result, the monolithic system skeleton and the pores were three-dimensionally continuous and a two-phase continuous continuous structure. The results are shown in Tables 3 and 4.

In addition, a known method can be suitably applied to the monoliths obtained in the above Reference Examples 4 to 13 and Reference Examples 16 to 17, and for example, the anion exchange group can be introduced by the method shown in Reference Example 1 or Reference Example 2. Further, the monolithic anion exchanger into which the anion exchange group was introduced into the monolith obtained in Reference Examples 4 to 13 and Reference Examples 16 to 17 and the monolith obtained in Reference Example 14 and Reference Example 15 were used. The bulk anion exchanger is suitably subjected to a known method, for example, by using the method shown in Example 1 or Example 2, the platinum group metal nanoparticles can be carried.

[Example 4]

Palladium nanoparticles were supported on the monolithic anion exchanger (1st monolithic anion exchanger) of Reference Example 1 in the same manner as in Example 1 except that 190 mg of palladium chloride was dissolved instead of dissolving 270 mg of palladium chloride. The particles obtained the first palladium nanoparticle-carrying catalyst c.

The amount of the palladium nanoparticle supported on the first palladium nanoparticle-carrying catalyst c in a dry state was 7.4% by weight. The first palladium nanoparticle-carrying catalyst c in a dry state was filled in a column having an inner diameter of 10 mm for evaluation of dissolved oxygen removal characteristics. The fill level of the catalyst is 20 mm. At this time, the loading amount of the palladium nanoparticle relative to the resin volume in the wet state of water was 10.5 g-Pd/L-R.

(evaluation of catalyst)

The first palladium nanoparticle-carrying catalyst c filled in a column having an inner diameter of 10 mm was adjusted to have a dissolved oxygen concentration of 32 μg/L and a dissolved hydrogen concentration of 11 μg/at SV=7500 h ^-1 . The ultrapure water of L is measured until the dissolved oxygen concentration in the treated water at the outlet of the column is stabilized. As a result, the dissolved oxygen concentration at the outlet of the column was reduced to 3.8 μg/L.

[Comparative Example 3]

The water-holding ability is 60 to 70% on a OH basis and is a gel-like particulate strong alkali anion exchange resin (Cl), and palladium is supported by 910 mg-Pd/LR in a hydrated state. Cl-shaped catalyst resin. Catalyst evaluation was carried out in the same manner as in Example 4 except that the Cl-type catalyst resin was passed through a water column having a height of 360 mm and a flow rate of SV 430 in a column having an inner diameter of 10 mm. As a result, the dissolved oxygen concentration at the outlet of the column at the time point when the treated water was stable was 4.1 μg/L. The evaluation results of Example 4 and Comparative Example 3 are summarized in Table 5.

In Example 4, although the flow rate was very high as SV 7500, and the flow rate per unit mass of the supported palladium metal catalyst was higher than that of Comparative Example 3, the same degree as that of Comparative Example 3 was obtained. Buried water at the oxygen concentration. Therefore, when the platinum group metal-supporting catalyst of the present invention is used, even if the flow rate is high and the resin layer is high, the dissolved oxygen can be effectively removed, thereby reducing the amount of catalyst used and miniaturizing the device and simultaneously achieving Reduction of the dissolution.

1. . . Skeleton phase

2. . . Empty hole phase

10. . . Monolithic body

11. . . Image area

12. . . Skeleton part shown in the section

13. . . Giant pore

20a, 20b. . . Electronic parts before washing

30a, 30b. . . Washed electronic parts

21, 41. . . Step 1

22, 42. . . Step 2

23, 43. . . Step 3

24, 44. . . Step 4

25, 26, 27, 28. . . Hydrogen peroxide removal step

32. . . Ultra-pure water

33. . . ozone

34, 36. . . hydrogen

35. . . Hydrofluoric acid and hydrogen peroxide

45. . . Step 5

46. . . Step 6

47. . . Step 7

48. . . Step 8

49. . . Step 9

50. . . Step 10

51. . . Step 11

52. . . Step 12

62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72. . . Washing water

Figure 1 is an SEM image of a first monolith.

Fig. 2 is an EPMA image showing the distribution state of chloride ions on the surface of the first monolith anion exchanger.

Fig. 3 is an EPMA image showing the distribution state of chloride ions in the cross-sectional (thickness) direction of the first monolith anion exchanger.

Fig. 4 is a view showing a skeleton portion which is manually transferred and has a cross section as an SEM image of Fig. 1.

Fig. 5 is a TEM image showing a state of dispersion of palladium nanoparticles of a first platinum group metal-supporting catalyst.

Fig. 6 is a view schematically showing a co-continuous structure of a second monolith anion exchanger.

Figure 7 is an SEM image of the second monolith.

Fig. 8 is an EPMA image showing the distribution state of chloride ions on the surface of the second monolith anion exchanger.

Fig. 9 is an EPMA image showing the distribution state of chloride ions in the cross-sectional (thickness) direction of the second monolith anion exchanger.

Fig. 10 is a TEM image showing a state of dispersion of palladium nanoparticles of a second platinum group metal-supporting catalyst.

Fig. 11 is an SEM image of a monolith (a known product) of Reference Example 3.

Figure 12 is an SEM image of the second monolith intermediate.

Fig. 13 is a schematic flow chart showing a first embodiment of the method (I) for cleaning an electronic component according to the present invention.

Fig. 14 is a schematic flow chart showing a second embodiment of the cleaning method (I) of the electronic component of the present invention.

Claims (10)

A platinum group metal supporting catalyst which is obtained by loading an organic porous anion exchanger with a platinum group metal nanoparticle having an average particle diameter of 1 to 100 nm, wherein the organic porous anion exchange system has a bubble shape The giant pores are superposed on each other, and the overlapping portions thereof are formed in a continuous giant pore structure having an opening diameter of 30 to 300 μm in a water-wet state, and the total pore volume is 0.5 to 5 ml/g, and the unit volume of the water-wet state. The anion exchange capacity is 0.4 to 1.0 mg equivalent/ml, and the anion exchange is uniformly distributed in the organic porous anion exchanger, and in the SEM image of the cut surface of the continuous giant pore structure (dry body) The cross-sectional area of the skeleton portion shown in the SEM image is 25 to 50% in the image region; the amount of the platinum group metal supported is 0.004 to 20% by weight in the dry state. A platinum group metal supporting catalyst which is obtained by loading an organic porous anion exchanger with a platinum group metal nanoparticle having an average particle diameter of 1 to 100 nm, wherein the organic porous anion exchange system is A three-dimensional continuous skeleton formed of an aromatic vinyl polymer having 0.3 to 5.0 mol% of a crosslinked structural unit in all constituent units having an anion exchange group and having an average thickness of 1 to 60 μm in a water-wet state And a co-continuous structure composed of three-dimensional continuous pores having an average diameter between 10 and 100 μm in a water-wet state, a total pore volume of 0.5 to 5 ml/g, and an anion per unit volume in a water-wet state. The exchange capacity is 0.3 to 1.0 mg equivalent/ml, and the anion exchange is uniformly distributed based on the organic porous anion exchanger; the amount of the platinum group metal supported is 0.004 to 20% by weight in a dry state. A method for producing treated water for decomposing hydrogen peroxide, characterized in that a treated water containing hydrogen peroxide is brought into contact with a platinum group metal supporting catalyst according to claim 1 or 2, and the hydrogen peroxide is contained. The hydrogen peroxide in the treated water is decomposed and removed. The method for producing treated water for decomposing hydrogen peroxide according to the third aspect of the invention, wherein the organic porous anion exchanger is in the form of an OH. The method for producing treated water for decomposing hydrogen peroxide according to the third aspect of the invention, wherein the treated water containing hydrogen peroxide is contacted with the platinum group metal supporting catalyst at SV=2000 to 20000 h ^-1 . A method for cleaning an electronic component, which is characterized in that the processing water obtained by the method for producing water for decomposing hydrogen peroxide according to the third application of the patent application is used, and the manufacturing tool for the electronic component or the electronic component is washed. A method for producing treated water for removing dissolved oxygen, characterized in that: in the presence of a platinum group metal-supporting catalyst of claim 1 or 2, hydrogen is reacted with dissolved oxygen in the treated water containing oxygen. Water is generated to remove dissolved oxygen from the treated water containing oxygen. The method for producing treated water for removing dissolved oxygen according to the seventh aspect of the invention, wherein the organic porous anion exchanger has an OH shape. The method for producing treated water for removing dissolved oxygen according to the seventh aspect of the invention, wherein the treated water containing oxygen is contacted with the platinum group metal supporting catalyst at SV=2000 to 20000 h ^-1 . A method for cleaning an electronic component, characterized in that the processing water obtained by the method for producing a treated water for removing dissolved oxygen in the seventh application of the patent application is used, and the manufacturing device for the electronic component or the electronic component is washed.