JP2010214320A - Supported catalyst of platinum group metal, method of producing treated water removed of hydrogen peroxide by decomposing the same, method of producing treated water removed of dissolved oxygen, and method of washing electronic parts - Google Patents

Abstract

SOLUTION: Even if water is passed with a large SV such that SV exceeds 2000h ⁻¹ , hydrogen peroxide can be decomposed or dissolved oxygen can be removed even if the packed bed height of the catalyst is reduced. To provide a high performance catalyst.
A platinum group metal-supported catalyst in which platinum group metal nanoparticles having an average particle diameter of 1 to 100 nm are supported on an organic porous anion exchanger, and the organic porous anion exchanger is connected to each other. Having an open cell structure having a common opening (mesopore) having an average diameter of 1 to 1000 μm in a dry state in the wall of the macropore and the macropore, the total pore volume being 1 to 50 ml / g, and an anion exchange group Is uniformly distributed, the anion exchange capacity is 0.5 to 5.0 mg equivalent / g dry porous body, and the supported amount of the platinum group metal is 0.004 to 20% by weight in a dry state. A platinum group metal-supported catalyst,
[Selection] Figure 2

Description

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

  It is known that dissolved oxygen in the water used at power plants will cause corrosion of components such as pipes and heat exchangers. In particular, dissolved oxygen is used as much as possible in the primary and secondary systems of nuclear power plants. There is a need to reduce.

  In the semiconductor manufacturing industry, silicon wafers are cleaned using ultrapure water from which impurities are highly removed. Ultrapure water generally removes part of suspended matter and organic matter contained in raw water (river water, groundwater, industrial water, etc.) in the pretreatment process, and then treats the treated water with the primary pure water system and secondary pure water. Manufactured by sequential processing in an aqueous system (subsystem) and supplied to a use point for wafer cleaning. Such ultrapure water has such a purity that it is difficult to quantify the impurities, but it does not have no impurities at all.

  For example, dissolved oxygen contained in ultrapure water forms a natural oxide film on the surface of a silicon wafer. When a natural oxide film is formed on the wafer surface, it prevents growth of epitaxial Si thin films at low temperatures, hinders precise control of gate oxide film pressure and film quality, and causes increase in contact resistance of contact holes. It becomes. Therefore, it is necessary to suppress the formation of the natural oxide film on the wafer surface as much as possible.

  Therefore, in the ultrapure water production apparatus, particularly in the primary pure water system, dissolved oxygen is reduced by using a deaeration device. With this deaeration device, the dissolved oxygen concentration in the water to be treated (primary pure water) at the entrance of the secondary pure water system is usually reduced to 100 μg / L or less. Furthermore, it may be controlled to 10 μg / L or less.

  In the above-described production of ultrapure water, organic substances are generally decomposed by an ultraviolet oxidizer installed in a secondary pure water system. Since hydrogen peroxide is by-produced in the process of ultraviolet oxidation, it is common that hydrogen peroxide remains in the treated water of the ultraviolet oxidation apparatus. This hydrogen peroxide is partially decomposed in the polisher process of the secondary pure water system to generate oxygen, and increase the dissolved oxygen concentration in the treated water.

  Therefore, a method has been proposed in which hydrogen peroxide contained in the treated water of the ultraviolet oxidation apparatus is adsorbed and removed using a synthetic carbon-based granular adsorbent (Japanese Patent Laid-Open No. 9-29233). According to this method, it is possible to suppress the formation of a natural oxide film on the wafer surface because hydrogen peroxide itself remaining in the treated water of the ultraviolet oxidation apparatus is removed. However, this method requires a large adsorption tower filled with a large amount of a synthetic carbon-based particulate adsorbent in order to achieve a predetermined hydrogen peroxide removal rate.

  In addition, a method has been proposed in which hydrogen peroxide contained in treated water of an ultraviolet oxidation apparatus is decomposed with a catalyst in which platinum group metal nanocolloid particles are supported on a carrier (Japanese Patent Laid-Open No. 2007-185587).

JP-A-9-29233 (Claims) JP 2007-185587 A (Claims)

However, the catalysts described in JP-A-2007-185587, can only be used at relatively low region passing water space velocity (SV) is a 100～2000H ^-1, the SV exceeds 2000h ^-1, peroxide There was a disadvantage that the decomposition and removal of hydrogen was insufficient.

Therefore, the object of the present invention is to allow the decomposition and removal of hydrogen peroxide or the removal of dissolved oxygen even when water is passed through a large SV with an SV exceeding 2000 h ⁻¹ , and the catalyst packed bed height is reduced. It is an object to provide a high-performance catalyst that can decompose hydrogen peroxide or remove dissolved oxygen.

Under such circumstances, as a result of intensive studies, the present inventors have conducted monolithic organic porous anion exchange in which an anion exchange group is introduced into the monolithic organic porous material obtained by the method described in JP-A-2002-306976. The platinum group metal-supported catalyst in which the platinum group metal nanoparticles having an average particle diameter of 1 to 100 nm are supported on the body (hereinafter also referred to as “monolith anion exchanger”) has a large SV such that the SV exceeds 2000 h ^−1. It is possible to decompose and remove hydrogen peroxide or dissolved oxygen even if water is passed through, and to decompose and remove hydrogen peroxide or dissolved oxygen even if the packed bed height of the catalyst is reduced. As a result, the present invention has been completed.

That is, the present invention (1) is a platinum group metal supported catalyst in which platinum group metal nanoparticles having an average particle diameter of 1 to 100 nm are supported on an organic porous anion exchanger,
The organic porous anion exchanger has an open cell structure having a common pore (mesopore) having an average diameter of 1 to 1000 μm in a dry state in a macropore and a macropore wall connected to each other, and the total pore volume is 1 to 50 ml / g, anion exchange groups are uniformly distributed, anion exchange capacity is 0.5 to 5.0 mg equivalent / g dry porous body,
The supported amount of the platinum group metal is 0.004 to 20% by weight in a dry state;
The platinum group metal supported catalyst characterized by these is provided.

  In addition, the present invention (2) is a method in which the platinum group metal-supported catalyst of the present invention (1) is brought into contact with water to be treated containing hydrogen peroxide, and hydrogen peroxide in the water to be treated containing the hydrogen peroxide. The present invention provides a method for producing hydrogen peroxide-decomposed water characterized in that it is decomposed and removed.

  Further, the present invention (3) is an electronic device characterized in that an electronic component or an electronic component manufacturing instrument is washed with treated water obtained by performing the method for producing hydrogen peroxide decomposition treated water of the present invention (2). A method for cleaning parts is provided.

  Moreover, this invention (4) reacts hydrogen and dissolved oxygen in the to-be-processed water containing oxygen in presence of the platinum group metal carrying | support catalyst of this invention (1), and produces | generates this, Disclosed is a method for producing treated water for removing dissolved oxygen, wherein dissolved oxygen is removed from water to be treated containing oxygen.

  Further, the present invention (5) is an electronic component characterized by washing an electronic component or an electronic component manufacturing instrument with treated water obtained by performing the method for producing dissolved oxygen removal treated water of the present invention (4). The cleaning method is provided.

According to the platinum group metal-supported catalyst of the present invention, hydrogen peroxide can be decomposed or dissolved oxygen can be removed even when the SV is passed through a large SV exceeding 2000 h ^−1. Even if the layer height is reduced, hydrogen peroxide can be decomposed or dissolved oxygen can be removed.

4 is a SEM image of the monolith of Reference Example 1. 2 is a TEM image showing a dispersion state of palladium nanoparticles in the palladium nanoparticle-supported catalyst of Example 1. FIG. It is a typical flowchart of the 1st form example of the washing | cleaning method (I) of the electronic component of this invention. It is a typical flowchart of the 2nd form example of the washing | cleaning method (I) of the electronic component of this invention.

  In the platinum group metal-supported catalyst of the present invention, the platinum group metal nanoparticle support is a monolithic organic porous anion exchanger. In the present specification, “monolithic organic porous material” is also simply referred to as “monolith”, and “monolithic organic porous anion exchanger” is also simply referred to as “monolith anion exchanger”.

<Description of monolith anion exchanger>
In the platinum group metal-supported catalyst of the present invention, the monolith anion exchanger serving as a support for the platinum group metal is obtained by introducing an anion exchange group into the monolith. In the monolith anion exchanger according to the present invention, bubble-shaped macropores overlap each other, and the overlapping portion is in a dry state and has an average diameter of 1 to 1000 μm, preferably 10 to 200 μm, particularly preferably 20 to 100 μm. Is a continuous macropore structure, most of which has an open pore structure. In the open pore structure, when water is flowed, the inside of bubbles formed by the macropores and the mesopores becomes a flow path. The number of overlapping macropores is 1 to 12 for one macropore, and 3 to 10 for many. The average diameter of the mesopores of the monolith anion exchanger is larger than the average diameter of the monolith mesopores because the whole monolith swells when an anion exchange group is introduced into the monolith. If the average diameter in the dry state of the mesopores is less than 1 μm, the pressure loss during water passage becomes extremely large, which is not preferable. If the average diameter in the dry state of the mesopores exceeds 1000 μm, the water to be treated and the monolith The contact with the anion exchanger becomes insufficient, and the hydrogen peroxide decomposition characteristic or the dissolved oxygen removal characteristic is deteriorated. Since the structure of the monolith anion exchanger has an open cell structure as described above, the macropore group and the mesopore group can be uniformly formed, and the particle-aggregated porous material as described in JP-A-8-252579 Compared to the body, the pore volume and specific surface area can be significantly increased. In the present invention, the average diameter of the opening of the dried monolith and the average diameter of the opening of the dried monolith anion exchanger are values measured by a mercury intrusion method. Further, the average diameter of the openings of the monolith anion exchanger in the wet state is a value calculated by multiplying the average diameter of the openings of the monolith anion exchanger in the dry state by the swelling rate. Specifically, the diameter of the monolith anion exchanger in the water wet state is x1 (mm), the monolith anion exchanger in the water wet state is dried, and the diameter of the resulting monolith anion exchanger in the dry state is y1 ( mm), and the average diameter of the opening of the monolith anion exchanger in the dry state measured by the mercury intrusion method is z1 (μm), the average diameter of the opening of the monolith anion exchanger in the water wet state ( μm) is calculated by the following formula “average diameter (μm) = z1 × (x1 / y1) of the opening of the monolith anion exchanger in a wet state of water”. In addition, the average diameter of the opening of the dry monolith before the introduction of the anion exchange group and the swelling ratio of the monolith anion exchanger in the water wet state relative to the dry monolith when the anion exchange group is introduced into the dry monolith are known. In this case, the average diameter of the opening of the monolith anion exchanger in the wet state can be calculated by multiplying the average diameter of the opening of the monolith in the dry state by the swelling ratio.

  The total pore volume of the monolith anion exchanger according to the present invention is 1 to 50 ml / g, preferably 2 to 30 ml / g. If the total pore volume is less than 1 ml / g, it is not preferable because the pressure loss at the time of passing water increases, and further, the amount of permeated water per unit cross-sectional area decreases, and the treatment capacity decreases. Absent. On the other hand, if the total pore volume exceeds 50 ml / g, the mechanical strength is lowered, and the monolith anion exchanger is greatly deformed particularly when water is passed at a high flow rate. Furthermore, since the contact efficiency between the water to be treated, the monolith anion exchanger and the platinum group metal nanoparticles supported thereon is lowered, the catalytic effect is also lowered, which is not preferable. In the conventional particulate porous ion exchange resin, the total pore volume is 0.1 to 0.9 ml / g at the most. Those having a specific surface area can be used. In the present invention, the total pore volume of a monolith (monolith, monolith anion exchanger) is a value measured by a mercury intrusion method. Further, the total pore volume of the monolith (monolith, monolith anion exchanger) is the same both in the dry state and in the water wet state.

  In addition, the pressure loss at the time of making water permeate | transmit the monolith anion exchanger which concerns on this invention is the pressure loss (henceforth, the following) when water is passed through the column which filled this with 1 m of water velocity (LV) 1m / h. In the case of “differential pressure coefficient”), 0.005 to 0.5 MPa / m · LV is preferable, and 0.005 to 0.05 MPa / m · LV is particularly preferable.

  The anion exchange capacity per weight in the dry state of the monolith anion exchanger according to the present invention is 0.5 to 5.0 mg equivalent / g. When the anion exchange capacity per weight in a dry state is less than 0.5 mg equivalent / g, the amount of platinum group metal nanoparticles supported decreases, and the hydrogen peroxide decomposition characteristics or dissolved oxygen removal characteristics decrease. Therefore, it is not preferable. On the other hand, when the anion exchange capacity per weight in the dry state exceeds 5.0 mg equivalent / g, the volume change of the swelling and shrinkage of the monolith anion exchanger due to the change of the ionic form becomes remarkably large. This is not preferable because cracks and crushing occur in the exchanger. In addition, although the anion exchange capacity per volume in the water wet state of the monolith anion exchanger according to the present invention is not particularly limited, it is usually 0.05 to 0.5 mg equivalent / ml. Note that the ion exchange capacity of the porous body in which the ion exchange group is introduced only on the surface cannot be determined unconditionally depending on the kind of the porous body or the ion exchange group, but is at most 500 μg equivalent / g.

  In the monolith anion exchanger according to the present invention, the material constituting the skeleton of the continuous macropore structure is an organic polymer material having a crosslinked structure. Although the crosslinking density of the polymer material is not particularly limited, it contains 0.3 to 10 mol%, preferably 0.3 to 5 mol% of crosslinked structural units with respect to all structural units constituting the polymer material. It is preferable. If the cross-linking 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%, it may be difficult to introduce an anion exchange group. The type of the polymer material is not particularly limited, and examples thereof include aromatic vinyl polymers such as polystyrene, poly (α-methylstyrene), polyvinyl toluene, polyvinyl benzyl chloride, polyvinyl biphenyl, and polyvinyl naphthalene; polyolefins such as polyethylene and polypropylene; Poly (halogenated polyolefin) such as vinyl chloride and polytetrafluoroethylene; Nitrile-based polymer such as polyacrylonitrile; Cross-linking weight of (meth) acrylic polymer such as polymethyl methacrylate, polyglycidyl methacrylate, and polyethyl acrylate Coalescence is mentioned. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or a blend of two or more types of polymers. It may be what was done. Among these organic polymer materials, the cross-linking weight of the aromatic vinyl polymer is easy due to the ease of forming a continuous macropore structure, the ease of introducing an anion exchange group and the high mechanical strength, and the high stability to acids or alkalis. A styrene-divinylbenzene copolymer and a vinylbenzyl chloride-divinylbenzene copolymer are particularly preferable materials.

  Examples of the anion exchange group of the monolith anion exchanger according to the present invention include a quaternary ammonium group such as a trimethylammonium group, a triethylammonium group, a tributylammonium group, a dimethylhydroxyethylammonium group, a dimethylhydroxypropylammonium group, and a methyldihydroxyethylammonium group. And a tertiary sulfonium group, a phosphonium group, and the like.

  In the monolith anion exchanger according to the present invention, the introduced anion exchange groups are uniformly distributed not only on the surface of the porous body but also inside the skeleton of the porous body. Here, “anion exchange groups are uniformly distributed” means that the distribution of anion exchange groups is uniformly distributed on the surface and inside the skeleton in the order of at least μm. The distribution state of the anion exchange group can be confirmed relatively easily by using EPMA after ion exchange of the counter anion with chloride ion, bromide ion or the like. In addition, if the anion exchange groups are uniformly distributed not only on the surface of the monolith but also within the skeleton of the porous body, the physical and chemical properties of the surface and the interior can be made uniform, so that the swelling and shrinking The durability against is improved.

(Method for producing monolith anion exchanger)
The method for producing a monolith anion exchanger according to the present invention is not particularly limited, and a method for forming a component containing an anion exchange group into a monolith anion exchanger in one step, forming a monolith with a component not containing an anion exchange group, Then, the method of introduce | transducing an anion exchange group etc. are mentioned. Among these methods, the method of forming a monolith with a component that does not contain an anion exchange group and then introducing the anion exchange group makes it easy to control the porous structure of the monolith anion exchanger, and quantitatively determines the anion exchange group. Since introduction is also possible, it is preferable. An example of a production method according to the method described in JP-A-2002-306976 is shown below. That is, the monolith anion exchanger is obtained by mixing an oil-soluble monomer not containing an anion exchange group, a surfactant, water and a polymerization initiator as necessary to obtain a water-in-oil emulsion and polymerizing the emulsion. A porous body is formed, and then an anion exchange group is introduced.

  The oil-soluble monomer that does not contain an anion exchange group refers to a lipophilic monomer that does not contain an anion exchange group such as a quaternary ammonium group and has low solubility in water. Specific examples of these monomers include styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, divinyl benzene, ethylene, propylene, isobutene, butadiene, isoprene, chloroprene, vinyl chloride, vinyl bromide, vinylidene chloride, tetrafluoroethylene. , Acrylonitrile, methacrylonitrile, vinyl acetate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, trimethylolpropane triacrylate, butanediol diacrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate , Butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, glycidyl methacrylate, ethylene glycol dimethyl ester Acrylate, and the like. These monomers can be used singly or in combination of two or more. However, in the present invention, a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate is selected as at least one component of the oil-soluble monomer, and its content is preferably 0.3 to 10 mol% in the total oil-soluble monomer. Is preferably 0.3 to 5 mol% in that an anion exchange group can be quantitatively introduced in a later step and a sufficient mechanical strength can be secured practically.

  The surfactant is not particularly limited as long as it can form a water-in-oil (W / O) emulsion when an oil-soluble monomer containing no anion exchange group and water are mixed, and sorbitan monooleate, Nonionic surfactants such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene nonylphenyl ether, polyoxyethylene stearyl ether, polyoxyethylene sorbitan monooleate; potassium oleate Anionic surfactants such as sodium dodecylbenzene sulfonate and dioctyl sodium sulfosuccinate; cationic surfactants such as distearyl dimethyl ammonium chloride; amphoteric surfactants such as lauryl dimethyl betaine can be used. That. These surfactants can be used singly or in combination of two or more. The water-in-oil 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 may vary depending on the type of oil-soluble monomer and the size of the target emulsion particles (macropores), but it cannot be generally stated, but the total amount of oil-soluble monomer and surfactant Can be selected within a range of about 2 to 70%. Although not necessarily essential, in order to control the bubble shape and size of the porous material, alcohols such as methanol and stearyl alcohol; carboxylic acids such as stearic acid; hydrocarbons such as octane, dodecane and toluene; tetrahydrofuran, dioxane It is also possible to coexist cyclic ethers such as

  Moreover, the compound which generate | occur | produces a radical by a heat | fever and light irradiation is used suitably for the polymerization initiator used as needed in the case of porous body formation. The polymerization initiator may be water-soluble or oil-soluble. For example, azobisisobutyronitrile, azobisdimethylvaleronitrile, azobiscyclohexanenitrile, azobiscyclohexanecarbonitrile, benzoyl peroxide, persulfate Examples include potassium, ammonium persulfate, hydrogen peroxide-ferrous chloride, sodium persulfate-sodium acid sulfite, and tetramethylthiuram disulfide. However, in some cases, there is a system in which the polymerization proceeds only by heating or light irradiation without adding a polymerization initiator, and in such a system, the addition of the polymerization initiator is unnecessary.

  The mixing method for mixing the oil-soluble monomer not containing an anion exchange group, a surfactant, water and a polymerization initiator to form a water-in-oil emulsion is not particularly limited. Method of mixing at once, oil-soluble monomer, surfactant and oil-soluble polymerization initiator oil-soluble component and water or water-soluble polymerization initiator water-soluble component separately and uniformly dissolved, A method of mixing the components can be used. There is no particular limitation on the mixing apparatus for forming the emulsion, and ordinary mixers, homogenizers, high-pressure homogenizers, and objects to be treated are placed in a mixing container, and the mixing container is tilted and revolved around the revolution axis. While rotating, a so-called planetary stirring device that stirs and mixes the object to be processed can be used, and an appropriate device may be selected to obtain the desired emulsion particle size. Moreover, there is no restriction | limiting in particular about mixing conditions, The stirring rotation speed and stirring time which can obtain the target emulsion particle size can be set arbitrarily. Among these mixing apparatuses, the planetary stirring apparatus is preferably used because it can uniformly generate water droplets in the W / O emulsion and can arbitrarily set the average diameter within a wide range.

  Various conditions can be selected as the polymerization conditions for polymerizing the water-in-oil emulsion thus obtained depending on the type of monomer and the initiator system. For example, when azobisisobutyronitrile, benzoyl peroxide, potassium persulfate, or the like is used as a polymerization initiator, it can be heated and polymerized at 30 to 100 ° C. for 1 to 48 hours in a sealed container under an inert atmosphere. When hydrogen peroxide-ferrous chloride, sodium persulfate-sodium acid sulfite, etc. are used as initiators, polymerization can be carried out at 0-30 ° C. for 1-48 hours in a sealed container under an inert atmosphere. That's fine. After completion of the polymerization, the contents are taken out and subjected to Soxhlet extraction with a solvent such as isopropanol to remove the unreacted monomer and the remaining surfactant to obtain a monolith.

  There is no restriction | limiting in particular as a method of introduce | transducing an anion exchange group into the monolith obtained in this way, Well-known methods, such as a polymer reaction and graft polymerization, can be used. For example, as a method of introducing a quaternary ammonium group, if the monolith is a styrene-divinylbenzene copolymer or the like, a chloromethyl group is introduced with chloromethyl methyl ether or the like and then reacted with a tertiary amine for introduction; Monolith is produced by copolymerization of chloromethylstyrene and divinylbenzene and introduced by reacting with a tertiary amine; radical initiation group or chain transfer group is introduced into monolith, and N, N, N-trimethylammonium ethyl acrylate or N , N, N-trimethylammonium propylacrylamide; a method of grafting glycidyl methacrylate in the same manner and then introducing a quaternary ammonium group by functional group conversion. Among these methods, the method of introducing a quaternary ammonium group includes a method of introducing a chloromethyl group into a styrene-divinylbenzene copolymer with chloromethyl methyl ether and then reacting with a tertiary amine, or chloromethylstyrene. A method of producing a monolith by copolymerization with divinylbenzene and reacting with a tertiary amine is preferable in that the ion exchange groups can be introduced uniformly and quantitatively. Examples of anion exchange groups to be introduced include quaternary ammonium groups such as trimethylammonium group, triethylammonium group, tributylammonium group, dimethylhydroxyethylammonium group, dimethylhydroxypropylammonium group, methyldihydroxyethylammonium group, and tertiary sulfonium. Group, phosphonium group and the like.

<Platinum group metal supported catalyst>
The platinum group metal-supported catalyst of the present invention is a platinum group metal-supported catalyst in which platinum group metal nanoparticles are supported on the monolith anion exchanger according to the present invention.

  The platinum group metal according to the present invention is ruthenium, rhodium, palladium, osmium, iridium, or platinum. These platinum group metals may be used alone or in combination of two or more metals, and more than one metal may be used as an alloy. Among these, platinum, palladium, and platinum / palladium alloys have high catalytic activity and are preferably used.

  The average particle diameter of the platinum group metal nanoparticles according to the present invention is 1 to 100 nm, preferably 1 to 50 nm, and more preferably 1 to 20 nm. If the average particle size is less than 1 nm, the possibility that the nanoparticles are detached from the carrier increases, which is not preferable. On the other hand, if the average particle size exceeds 100 nm, the surface area per unit mass of the metal is reduced and the catalytic effect is reduced. Is not preferred because it cannot be obtained efficiently. When the average particle diameter of the nanoparticles is within the above range, the nanoparticles are strongly colored by surface plasmon resonance and can be confirmed by visual observation.

  The supported amount of platinum group metal nanoparticles in the platinum group metal supported catalyst of the present invention in a dry state ((platinum group metal nanoparticles / platinum group metal supported catalyst of the present invention in a dry state) × 100) is 0.004 to 20% by weight, preferably 0.005 to 15% by weight. If the supported amount of platinum group metal nanoparticles is less than 0.004% by weight, the effect of decomposing hydrogen peroxide or the effect of removing dissolved oxygen becomes insufficient. On the other hand, when the amount of platinum group metal nanoparticles is more than 20% by weight, metal elution into water is observed, which is not preferable.

  The production method of the platinum group metal-supported catalyst of the present invention is not particularly limited, and the platinum group metal of the present invention is supported on the monolith anion exchanger according to the present invention by supporting platinum group metal nanoparticles by a known method. A metal supported catalyst can be obtained. For example, the monolith anion exchanger according to the present invention in a dry state is immersed in an aqueous hydrochloric acid solution of palladium chloride, the chloropalladate anion is adsorbed on the monolith anion exchanger by ion exchange, and then contacted with a reducing agent to form a palladium metal nanoparticle. A method of supporting particles on the monolith anion exchanger according to the present invention, or a column filled with the monolith anion exchanger according to the present invention, and passing through an aqueous hydrochloric acid solution of palladium chloride to ionize the palladium chloride anion. And the like, and a method in which palladium metal nanoparticles are supported on the monolith anion exchanger according to the present invention by adsorbing to the monolith anion exchanger according to the present invention and then passing through a reducing agent. There are no particular restrictions on the reducing agent used, alcohols such as methanol, ethanol and isopropanol, carboxylic acids such as formic acid, oxalic acid, citric acid and ascorbic acid, ketones such as acetone and methyl ethyl ketone, aldehydes such as formaldehyde and acetaldehyde, Examples thereof include sodium borohydride and hydrazine.

  In the platinum group metal-supported catalyst of the present invention, the ionic form of the monolith anion exchanger according to the present invention, which is a support for the platinum group metal nanoparticles, is usually like the chloride form after the platinum group metal nanoparticles are supported. It becomes a salt form. In the present invention, such a salt form may be used as a catalyst for decomposing hydrogen peroxide or removing dissolved oxygen. Further, the platinum group metal-supported catalyst of the present invention is not limited to this, and the ionic form of the monolith anion exchanger according to the present invention may be regenerated to OH form. Of these, the ionic form of the monolith anion exchanger according to the present invention is preferably an OH form because a high catalytic effect is obtained. The method for regenerating the monolith anion exchanger after supporting the platinum group metal nanoparticles to the OH form is not particularly limited, and a known method such as passing a sodium hydroxide aqueous solution may be used.

<Method for Producing Hydrogen Peroxide Decomposition Treatment Water>
In the method for producing hydrogen peroxide decomposition treated water of the present invention, the platinum group metal-supported catalyst of the present invention is brought into contact with water to be treated containing hydrogen peroxide, so that the water in the water to be treated containing hydrogen peroxide is treated. This is a method for producing hydrogen peroxide decomposition treated water that decomposes and removes hydrogen oxide.

  The water to be treated containing hydrogen peroxide is not particularly limited as long as it contains hydrogen peroxide. For example, ultrapure water used for manufacturing electronic components such as semiconductor manufacturing and for cleaning electronic device manufacturing equipment. In the production of water, water generated by various processes therein can be mentioned, and specifically, water after performing an ultraviolet oxidation process for decomposing organic substances in the water. In addition, as the water to be treated containing hydrogen peroxide, in addition to the treatment liquid or treatment water obtained by adding hydrogen peroxide to the waste water system, and performing oxidation, reduction, sterilization and washing, these treatment liquids or The waste liquid or waste water after processing using treated water is mentioned. For example, in order to collect and reuse cleaning wastewater containing hydrogen peroxide discharged from the semiconductor manufacturing process and cleaning wastewater containing organic matter discharged from the semiconductor manufacturing process as ultrapure water, ultraviolet rays are used in the presence of hydrogen peroxide. Treated water obtained by oxidative decomposition of organic matter by irradiation, treated water obtained by decomposing organic matter using Fenton reagent, reverse osmosis membrane, waste water after sterilizing or washing ultrafiltration membrane with hydrogen peroxide, Examples thereof include treated water obtained by reducing wastewater containing hexavalent chromium with hydrogen peroxide.

  The concentration of hydrogen peroxide in the water to be treated containing hydrogen peroxide is not particularly limited, but is usually 0.01 to 100 mg / L. In the ultrapure water production subsystem, the hydrogen peroxide concentration is typically 10-50 μg / L. When the hydrogen peroxide concentration exceeds 100 mg / L, deterioration of the base monolith anion exchanger tends to proceed.

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

In the case of the above method, water to be treated containing hydrogen peroxide can be passed through the platinum group metal supported catalyst of the present invention at SV = 2000-20000h ⁻¹ , preferably SV = 5000-10000h ^−1. . When the platinum group metal-supported catalyst of the present invention is used, hydrogen peroxide can be decomposed and removed even when the water to be treated is passed with a large SV such that the SV exceeds 2000 h- ¹ . Furthermore, even if SV is 10000h- ¹ , if the platinum group metal-supported catalyst of the present invention is used, hydrogen peroxide can be decomposed, and the platinum group metal-supported catalyst of the present invention can be used as a particulate anion exchange resin. It shows outstanding performance that far exceeds the processing limit of conventional supported catalysts supporting platinum group metal nanoparticles. The flow rate of the water to be treated containing hydrogen peroxide to the platinum group metal supported catalyst of the present invention is not particularly limited, but is preferably SV = 2000 to 20000 h ⁻¹ , particularly preferably SV = 5000 to 10000 h ^−1. It is. In addition, since the platinum group metal supported catalyst of the present invention has a remarkably high hydrogen peroxide decomposition ability, it is not necessary to dare to set the water flow rate to an area below SV = 2000 h ^−1, but the water flow rate is set to SV = 2000 h ^−. It may be less than ^one region, even if the water flow rate was region below SV = 2000h ^-1, platinum group metal supported catalyst of the present invention exhibits excellent hydrogen peroxide decomposition ability. On the other hand, when SV exceeds 20000 h ⁻¹ , the water flow differential pressure tends to be too large.

  Furthermore, since the platinum group metal-supported catalyst of the present invention has a remarkably high hydrogen peroxide decomposition ability, hydrogen peroxide can be decomposed and removed even if the packed bed height of the catalyst is reduced.

  It is preferable that the hydrogen peroxide concentration in the treated water obtained by the method for producing hydrogen peroxide-decomposed treated water of the present invention is 1 μg / L or less.

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

  An example of the electronic component cleaning method (I) of the present invention will be described with reference to FIGS. FIG. 3 is a schematic flow diagram of the first embodiment of the electronic component cleaning method (I) of the present invention, and FIG. 4 is the second embodiment of the electronic component cleaning method (I) of the present invention. It is a typical flowchart of an example.

  As shown in FIG. 3, in the first embodiment of the electronic component cleaning method (I) of the present invention, an object to be cleaned is brought into contact with water containing ozone (hereinafter also referred to as ozone-containing water). The object to be cleaned is brought into contact with the first step 21 for cleaning the object to be cleaned and water containing hydrogen (hereinafter also referred to as hydrogen-containing water), and vibrations of 500 kHz or more are applied. A second process 22 for cleaning the object, a third process 23 for cleaning the object to be cleaned by bringing the object to be cleaned into contact with water containing hydrofluoric acid and hydrogen peroxide, and a process for cleaning the hydrogen-containing water. And a fourth step 24 for cleaning the object to be cleaned while bringing the object into contact with each other and applying a vibration of 500 kHz or more.

  The cleaning water supplied to the first step 21 is ozone-containing water prepared by dissolving ozone in the ultrapure water 32. And the ultrapure water contains hydrogen peroxide because it has been subjected to an ultraviolet oxidation process or the like in its manufacturing process. Therefore, in the first embodiment of the electronic component cleaning method (I) of the present invention, before the ozone 33 is dissolved in the ultrapure water 32, the ultrapure water 32 is used as water to be treated. A hydrogen peroxide removal step 25 that performs a method for producing decomposition treated water is performed, ozone 33 is dissolved in the obtained treated water, and supplied as cleaning water in the first step 21.

  The cleaning water supplied to the second step 22 is hydrogen-containing water prepared by dissolving hydrogen in the ultrapure water 32. Therefore, in the first embodiment of the electronic component cleaning method (I) of the present invention, before the hydrogen 34 is dissolved in the ultrapure water 32, the ultrapure water 32 is used as water to be treated. A hydrogen peroxide removing step 26 that performs a method for producing decomposition treated water is performed, and hydrogen 34 is dissolved in the obtained treated water and supplied as cleaning water in the second step 22. In the first embodiment of the electronic component cleaning method (I) of the present invention, in the fourth step 24 as well, before the hydrogen 36 is dissolved in the ultrapure water 32, the ultrapure water 32 is used as the water to be treated. The hydrogen peroxide removal step 28 in which the method for producing hydrogen peroxide decomposition treatment water according to the invention is carried out, hydrogen 36 is dissolved in the obtained treated water, and supplied as cleaning water in the fourth step 24. It should be noted that the hydrogen 34 or 36 may be dissolved before the hydrogen peroxide removing step 26 or 28.

  Further, in the first embodiment of the electronic component cleaning method (I) of the present invention, the hydrogen peroxide removing step of performing the method for producing hydrogen peroxide decomposition treated water of the present invention using ultrapure water 32 as water to be treated. 27, the hydrofluoric acid and hydrogen peroxide 35 are dissolved in the obtained treated water, and the water containing the obtained hydrofluoric acid and hydrogen peroxide is supplied as cleaning water in the third step 23. You can also

  And the electronic component 20a before washing | cleaning is made into a to-be-cleaned object, the 1st process 21-the 4th process 24 are performed in order, and the electronic component 30a after washing | cleaning is obtained.

  As shown in FIG. 4, in the second embodiment of the electronic component cleaning method (I) of the present invention, the cleaning object is cleaned by bringing the cleaning object into contact with a liquid containing sulfuric acid and hydrogen peroxide. The first step 41 for cleaning, the second step 42 for rinsing with ultrapure water, and the object to be cleaned in contact with water containing hydrofluoric acid (dilute hydrofluoric acid) for cleaning the object to be cleaned A third step 43, a fourth step 44 for rinsing with ultrapure water, a fifth step 45 for cleaning the object to be cleaned by contacting the object to be cleaned with water containing ammonia and hydrogen peroxide, A sixth step 46 for rinsing with ultrapure water, a seventh step 47 for bringing the object to be cleaned into contact with the heated ultrapure water and cleaning the object to be cleaned, and an eighth step 48 for rinsing with ultrapure water And a ninth step 49 for cleaning the cleaning object by bringing the cleaning object into contact with water containing hydrochloric acid and hydrogen peroxide. A tenth step 50 for rinsing with ultrapure water, an eleventh step 51 for cleaning the object to be cleaned by bringing the object to be cleaned into contact with water containing hydrofluoric acid (dilute hydrofluoric acid), And a twelfth step 52 of rinsing with pure water.

  The washing waters 63, 65, 69 and 71 supplied to the third, fifth, ninth and eleventh steps in FIG. 4 are water in which chemicals necessary for each step are dissolved in ultrapure water. Therefore, in the second embodiment of the electronic component cleaning method (I) of the present invention, as in the first embodiment of the electronic component cleaning method (I) of the present invention shown in FIG. Before dissolving the necessary chemicals in each step, a hydrogen peroxide removal step is performed in which the method for producing hydrogen peroxide decomposition treatment water of the present invention is performed using ultrapure water as water to be treated. The chemicals required in the process are dissolved and supplied as cleaning water (cleaning liquid) for each process.

  Further, the cleaning water 62, 64, 66, 67, 68, 70 and 72 supplied to the second, fourth, sixth, seventh, eighth, tenth and twelfth steps in FIG. 4 are ultrapure water. Therefore, in the second embodiment of the electronic component cleaning method (I) of the present invention, a hydrogen peroxide removal step is performed in which the method for producing hydrogen peroxide decomposition treated water of the present invention is performed using ultrapure water as the treated water. The treated water obtained is supplied as cleaning water for each step.

  And the electronic component 20b before washing | cleaning is made into a to-be-washed | cleaned object, the 1st process 41-the 12th process 52 are performed in order, and the electronic component 30b after washing | cleaning is obtained.

  As described above, in the present invention, washing an electronic component or an electronic component manufacturing instrument with treated water obtained by performing the method for producing hydrogen peroxide-decomposed treated water of the present invention means that the peroxidation of the present invention is used. Ultrapure water used for cleaning electronic components or electronic component manufacturing equipment as well as cleaning electronic components or electronic component manufacturing equipment with treated water immediately after the hydrogen decomposition treatment water manufacturing method is performed. In any one or two or more of the steps of producing the hydrogen peroxide decomposition treatment water production method of the present invention, ultrapure water obtained by performing all steps of the ultrapure water production step, It means that an electronic component or an electronic component manufacturing apparatus is cleaned.

<Method for Producing Dissolved Oxygen Removal Water of the Present Invention>
The method for producing treated water for removing dissolved oxygen according to the present invention comprises reacting dissolved oxygen and hydrogen in water to be treated containing oxygen in the presence of the platinum group metal-supported catalyst of the present invention to produce water. A method for producing water for removing dissolved oxygen, which removes dissolved oxygen from water to be treated containing oxygen.

  The water to be treated containing oxygen is not particularly limited as long as it contains oxygen. For example, the manufacture of electronic parts such as semiconductor manufacturing and the manufacture of ultrapure water for cleaning electronic parts manufacturing equipment, etc. The raw water used in the production process or various kinds of water in the production process thereof, specifically, circulating water of the ultrapure water production subsystem, for example, the outlet water of the ultraviolet oxidizer. Other examples of water to be treated containing dissolved oxygen include water used at power plants, boiler water and cooling water used at various factories.

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

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

  The method for reacting dissolved oxygen and hydrogen in the water to be treated containing oxygen in the presence of the platinum group metal supported catalyst of the present invention is not particularly limited. For example, the platinum group metal of the present invention is added to a catalyst packed tower. The supported catalyst is packed, and the treatment liquid containing oxygen is supplied to the catalyst packed tower, and hydrogen gas is injected into the supply pipe of the treatment liquid to dissolve in the platinum group metal supported catalyst of the present invention. Examples include a method of passing hydrogen and water to be treated containing dissolved oxygen.

In the case of said method, the to-be-processed water containing oxygen can be made to flow into the platinum group metal carrying | support catalyst of this invention by SV = 2000-20000h < ^-1 >, Preferably SV = 5000-10000h- ¹ . When the platinum group metal-supported catalyst of the present invention is used, dissolved oxygen can be removed even when the water to be treated is passed through with a large SV such that SV exceeds 2000 h- ¹ . Furthermore, even if SV is 10000h- ¹ , if the platinum group metal-supported catalyst of the present invention is used, dissolved oxygen can be removed. The platinum group metal-supported catalyst of the present invention can be used as a particulate anion exchange resin. Excellent performance, far exceeding the processing limit of conventional supported catalysts supporting group metal nanoparticles. The flow rate of the water to be treated containing oxygen to the platinum group metal supported catalyst of the present invention is not particularly limited, but is preferably SV = 2000 to 20000 h ⁻¹ , particularly preferably SV = 5000 to 10000 h ⁻¹ . . In addition, since the platinum group metal supported catalyst of the present invention has a remarkably high dissolved oxygen removal capability, the water flow rate greatly exceeds the processing limit of the conventional supported catalyst in which platinum group metal nanoparticles are supported on the particulate anion exchange resin. Even if the water to be treated is passed, dissolved oxygen in the water to be treated can be removed.

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

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

  The electronic component cleaning method (II) of the present invention is an electronic component cleaning method of cleaning an electronic component or an electronic component manufacturing instrument with treated water obtained by performing the dissolved oxygen removal treated water manufacturing method of the present invention. is there.

  Oxygen in the air dissolves in water as dissolved oxygen. Dissolved oxygen is managed as impurities in ultrapure water. As described above, the dissolved oxygen concentration in the treated water (primary pure water) at the secondary pure water system entrance of the ultrapure water production apparatus is usually 100 μg / It is reduced to L or less. Furthermore, it may be controlled to 10 μg / L or less. And the dissolved oxygen concentration in ultrapure water may be controlled to 10 μg / L or less, and further to 1 μg / L or less. On the other hand, in the production process of ultrapure water, oxygen is generated when hydrogen peroxide generated by ultraviolet oxidation or the like is decomposed. Therefore, in the embodiment of the electronic component cleaning method (II) of the present invention, the dissolved oxygen removal step is performed in which the dissolved oxygen removal treatment water production method of the present invention is performed, and the resulting treated water is washed with the electronic components. The cleaning water (cleaning liquid) supplied to each step of the method or ultrapure water for its preparation is used.

  The first embodiment of the electronic component cleaning method (II) according to the present invention uses the hydrogen peroxide removing steps 25, 26, 27 and 28 in FIG. It replaces the dissolved oxygen removal process which performs the manufacturing method of the removal water of oxygen removal. And the electronic component 20a before washing | cleaning is made into a to-be-cleaned object, the 1st process 21-the 4th process 24 are performed in order, and the electronic component 30a after washing | cleaning is obtained.

  In the second embodiment of the electronic component cleaning method (II) of the present invention, cleaning water (cleaning liquid) 63, 65, 69 and 71 supplied to the third, fifth, ninth and eleventh steps in FIG. Prepared by performing a dissolved oxygen removal step in which the method for producing treated water for removing dissolved oxygen of the present invention is performed using ultrapure water as treated water, and dissolving the necessary chemicals in each step in the obtained treated water, and The cleaning water 62, 64, 66, 67, 68, 70 and 72 supplied to the second, fourth, sixth, seventh, eighth, tenth and twelfth steps in FIG. It is obtained by performing the dissolved oxygen removal process which performs the manufacturing method of the removal water of the dissolved oxygen removal process of the invention. Then, using the electronic component 20b before cleaning as an object to be cleaned, the first step 41 to the twelfth step 52 are sequentially performed to obtain the electronic component 30b after cleaning.

  As described above, in the present invention, washing an electronic component or an electronic component manufacturing instrument with treated water obtained by performing the method for producing dissolved oxygen removal treated water of the present invention means that the dissolved oxygen of the present invention is used. Produces ultra-pure water used for cleaning electronic components or electronic component manufacturing equipment, as well as cleaning electronic components or electronic component manufacturing equipment with treated water immediately after the removal treatment water manufacturing method is performed. In any one or two or more of the steps to be performed, the method for producing dissolved oxygen removal treated water of the present invention is performed, and the ultrapure water obtained by performing all steps of the ultrapure water production step This means that the electronic component manufacturing equipment is cleaned.

(Example)
Next, the present invention will be specifically described by way of examples, but this is merely an example and does not limit the present invention.

<Production of monolith anion exchanger (reference example)>
(Manufacture of monoliths)
19.2 g of styrene, 1.0 g of divinylbenzene, 1.0 g of sorbitan monooleate (hereinafter abbreviated as SMO) and 0.26 g of 2,2′-azobis (isobutyronitrile) were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / SMO / 2,2′-azobis (isobutyronitrile) mixture is added to 180 g of pure water, and a vacuum stirring defoaming mixer (manufactured by EM Corp.) which is a planetary stirring device. Was used under reduced pressure in a temperature range of 5 to 20 ° C. to obtain a water-in-oil emulsion. The emulsion was immediately transferred to a reaction vessel, and after sealing, it was allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the content was taken out, extracted with isopropanol, and then dried under reduced pressure to obtain a monolith. The monolith was a styrene / divinylbenzene copolymer containing 3.3 mol% of a crosslinking component, and was confirmed to have a continuous macropore structure by SEM observation. The SEM image is shown in FIG. The average diameter of the opening (mesopore) where the macropores of the monolith overlapped with the macropores determined by the mercury intrusion method was 29 μm, and the total pore volume was 8.6 ml / g.

(Production of monolith 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. To this, 1400 ml of dimethoxymethane and 20 ml of tin tetrachloride were added, and 560 ml of chlorosulfuric acid was added dropwise under ice cooling. After completion of the dropwise addition, the temperature was raised and reacted at 35 ° C. for 5 hours to introduce a chloromethyl group. After completion of the reaction, the mother liquor was extracted with a siphon, washed with a mixed solvent of THF / water = 2/1, and further washed with THF. To this chloromethylated monolith, 1000 ml of THF and 600 ml of a 30% trimethylamine aqueous solution were added and reacted at 60 ° C. for 6 hours. After completion of the reaction, the product was washed with a methanol / water mixed solvent, then washed with pure water and isolated.

  The swelling ratio of the obtained monolith anion exchanger before and after the reaction was 1.5 times, and the anion exchange capacity per weight in the dry state was 4.3 mg equivalent / g. The average diameter of the opening of the monolith 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 to be 44 μm, and the total pore volume was 8.6 ml / g. Met. The differential pressure coefficient, which is an index of pressure loss when water is permeated, is 0.014 MPa / m · LV, which is a lower pressure loss than that required for practical use. It was. Furthermore, when the ion exchange zone length regarding the fluoride ion of the monolith anion exchanger was measured, the ion exchange zone length at LV = 20 m / h was 84 mm, which is a commercially available strong basic anion exchange resin, amberlite. Compared to the value (165 mm) of IRA402BL (Rohm and Haas), it was about half, indicating a short value.

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

Example (Preparation of platinum group metal supported catalyst)
The monolith anion exchanger of Reference Example 1 was ion-exchanged into Cl form, cut into a cylindrical shape in a wet state, and dried under reduced pressure. The weight of the monolith anion exchanger after drying was 1.2 g. This dried monolith anion exchanger was immersed in dilute hydrochloric acid in which 140 mg of palladium chloride was dissolved for 24 hours, and ion-exchanged into the palladium chloride acid form. After completion of the immersion, the monolith anion exchanger was washed several times with pure water, and immersed in an aqueous hydrazine solution for 24 hours for reduction treatment. The chloropalladium acid form monolith anion exchanger was brown, whereas the monolith anion exchanger after the reduction treatment was colored black, suggesting the formation of palladium nanoparticles. The palladium nanoparticle-supported catalyst thus obtained was washed several times with pure water and dried.

  The amount of palladium supported on the palladium nanoparticle-supported catalyst in a dry state was 5.5% by weight. In order to measure the average particle diameter of the supported palladium nanoparticles, observation with a transmission electron microscope (TEM) was performed. The obtained TEM image is shown in FIG. The average particle diameter of the palladium nanoparticles was 3 nm. The dried palladium nanoparticle-supported catalyst was cut out and packed into a column with an inner diameter of 10 mm, and an aqueous sodium hydroxide solution was passed through to convert the monolith anion exchanger as a carrier into OH form, which was used for evaluation of hydrogen peroxide decomposition characteristics. . The packed bed height of the palladium nanoparticle-supported catalyst was 13 mm. At this time, the supported amount of palladium nanoparticles with respect to the water-wet resin volume was 2.0 g-Pd / LR (weight of palladium supported per 1 L of palladium nanoparticle-supported catalyst).

(Evaluation of catalyst)
Ultrapure water containing hydrogen peroxide 15-30 μg / L was passed through the above palladium nanoparticle-supported catalyst packed in a column with an inner diameter of 10 mm for 27 hours at SV = 5000 h ^{−1 for} 27 hours. Sample water was collected and the hydrogen peroxide concentration was measured. As a result, the hydrogen peroxide concentration in the sample water collected at the column outlet was less than 1 μg / L, and the hydrogen peroxide was decomposed and removed. Next, the SV was set to 10,000 h ⁻¹ and the same processing was performed. The hydrogen peroxide concentration in the sample water sampled at the column outlet is very fast as SV is 10,000 h ⁻¹ and the catalyst packed bed height is as thin as 13 mm, and is less than 1 μg / L. It was disassembled and removed.

Comparative Example 1
Moisture retention capacity was 60 to 70% on the basis of OH form, and palladium nanoparticles were suspended by a known method on a particulate strong base anion exchange resin (type I) in a gel form. The Cl-type particulate anion exchange resin was immersed in an aqueous hydrochloric acid solution of palladium chloride, washed with water, and then reduced with an aqueous hydrazine solution. An aqueous sodium hydroxide solution was passed through to convert the particulate anion exchange resin into OH form, which was used for evaluation of hydrogen peroxide decomposition characteristics. At this time, the supported amount of palladium nanoparticles was 970 mg-Pd / LR in a wet state with water. An OH-type particulate ion exchange resin carrying palladium was packed in a column with an inner diameter of 25 mm in 40 mL (layer height 80 mm), and an experiment for reducing hydrogen peroxide was conducted in the same manner as in Example 1.

(Evaluation of catalyst)
As the catalyst, the palladium nanoparticle-supported granular ion exchange resin catalyst was used instead of the palladium nanoparticle-supported catalyst obtained in Example 1, and ultrapure water was passed through at SV = 1500 h ⁻¹ and 2500 h ^−1. Except for this, the hydrogen peroxide decomposition effect of the catalyst was evaluated in the same manner as in Example 1. As a result, the hydrogen peroxide concentrations in the sample water collected at the column outlet were less than 1 μg / L and 1.6 μg / L, respectively. At SV = 1500 h ⁻¹ , hydrogen peroxide was less than 1 μg / L, but when SV was increased to 2500 h ⁻¹ , hydrogen peroxide leaked into the treated water. In this way, in the catalyst in which palladium nanoparticles are supported on the particulate anion exchange resin that is the prior art, even if the conditions for easily removing hydrogen peroxide such as SV slower than the example and the high catalyst packed bed height are set, At SV = 2500 h ⁻¹ , hydrogen peroxide leaked.

Comparative Example 2
Using only the monolith anion exchanger of the reference example without supporting palladium nanoparticles, the hydrogen peroxide decomposition effect at SV = 10000 h ⁻¹ was evaluated in the same manner as in the example. As a result, no decomposition of hydrogen peroxide was observed.

Claims (9)

A platinum group metal-supported catalyst in which platinum group metal nanoparticles having an average particle diameter of 1 to 100 nm are supported on an organic porous anion exchanger,
The organic porous anion exchanger has an open cell structure having a common pore (mesopore) having an average diameter of 1 to 1000 μm in a dry state in a macropore and a macropore wall connected to each other, and the total pore volume is 1 to 50 ml / g, anion exchange groups are uniformly distributed, anion exchange capacity is 0.5 to 5.0 mg equivalent / g dry porous body,
The supported amount of the platinum group metal is 0.004 to 20% by weight in a dry state;
A platinum group metal supported catalyst.   A platinum group metal-supported catalyst according to claim 1 is brought into contact with water to be treated containing hydrogen peroxide to decompose and remove hydrogen peroxide in the water to be treated containing hydrogen peroxide. A method for producing hydrogen oxide decomposition treated water.   3. The method for producing hydrogen peroxide decomposition treated water according to claim 2, wherein the organic porous anion exchanger is in the OH form. The treated water containing the hydrogen peroxide is brought into contact with the platinum group metal-supported catalyst at SV = 2000 to 20000 h ^-1 . A method for producing cracked water.   An electronic component cleaning method, comprising: cleaning an electronic component or an electronic component manufacturing instrument with treated water obtained by performing the method for producing hydrogen peroxide decomposition treated water according to any one of claims 2 to 4. .   In the presence of the platinum group metal-supported catalyst according to claim 1, by reacting hydrogen with dissolved oxygen in the water to be treated containing oxygen to generate water, dissolved oxygen is produced from the water to be treated containing the oxygen. A method for producing water for removing dissolved oxygen, characterized by removing water.   The method for producing treated water for removing dissolved oxygen according to claim 6, wherein the organic porous anion exchanger is in OH form. The treated water containing oxygen is brought into contact with the platinum group metal-supported catalyst at SV = 2000 to 20000 h ⁻¹ , The dissolved oxygen removal treated water according to claim 6 or 7. Manufacturing method.   An electronic component cleaning method, comprising: cleaning an electronic component or an electronic component manufacturing instrument with treated water obtained by performing the dissolved oxygen removal treated water manufacturing method according to any one of claims 6 to 8.