JP2010240641A - Method of manufacturing hydrogen peroxide decomposition treated water, apparatus for manufacturing hydrogen peroxide decomposition treated water, treating tank, method of manufacturing ultrapure water, apparatus for manufacturing ultrapure water, method of manufacturing hydrogen dissolved water, apparatus for manufacturing hydrogen dissolved water, method of manufacturing ozone dissolved water, apparatus for manufacturing ozone dissolved water, and method of cleaning electronic components - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing hydrogen peroxide decomposition treated water by efficiently decomposing and removing hydrogen peroxide without requiring a large-size catalyst tower even when causing water to pass through the tower with such a large water passage velocity (SV) exceeding 2,000 h<SP>-1</SP>or thinning a packed bed height of catalyst. <P>SOLUTION: In the method of manufacturing hydrogen peroxide decomposition treated water, hydrogen peroxide-containing water is brought into contact with a platinum group metal carrier catalyst prepared by carrying platinum group metal to a monolith organic porous anion exchanger. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing hydrogen peroxide-decomposed treated water, an apparatus for producing hydrogen peroxide-decomposed treated water, a treatment tank, a method for producing ultrapure water, an apparatus for producing ultrapure water, a method for producing hydrogen-dissolved water, and hydrogen dissolving. The present invention relates to a water production device, a method for producing ozone-dissolved water, a device for producing ozone-dissolved water, and a method for cleaning electronic components.

  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.

  In the above-described method for producing ultrapure water, generally, organic substances are decomposed by an ultraviolet oxidation apparatus installed in a subsystem. 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.

  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 (see Patent Document 1 (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 oxidizer is removed. In order to achieve the removal rate of hydrogen oxide, a large adsorption tower filled with a large amount of a synthetic carbon-based granular adsorbent was required.

  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 (Patent Document 2 (Japanese Patent Laid-Open No. 2007-185587). )reference).

  On the other hand, in the semiconductor manufacturing process, hydrogen-dissolved water and ozone-dissolved water are known as cleaning water for the object to be processed such as a substrate. The hydrogen-dissolved water and ozone-dissolved water are obtained by using ultrapure water as raw water. This is formed by dissolving hydrogen gas or ozone gas, and it is desired that the hydrogen-dissolved water and ozone-dissolved water also have a reduced hydrogen peroxide content. By reducing the hydrogen peroxide content, hydrogen-dissolved water has an effect of suppressing oxidation on the surface of the object to be treated, and ozone-dissolved water has a degree of decrease in ozone concentration during pipe transfer due to suppression of ozone self-decomposition reaction. There is a reduction effect.

JP-A-9-29233 JP 2007-185587 A

However, the method described in Patent Document 1 requires a large adsorption tower packed with a large amount of a synthetic carbon-based granular adsorbent in order to achieve a predetermined hydrogen peroxide removal rate. Further, in the method described in Patent Document 2, the water passage space velocity (SV) is not available a catalyst only in a relatively low region and 100～2000H ^-1, the SV exceeds 2000h ^-1, hydrogen peroxide Decomposition and removal become insufficient.

Under such circumstances, the present invention is able to decompose and remove hydrogen peroxide with high efficiency even when water is passed with a large SV exceeding SVh- ¹ or the packed bed height of the catalyst is reduced. It is a first object of the present invention to provide a method and a production apparatus for producing hydrogen oxide decomposition treated water. In addition, the present invention decomposes hydrogen peroxide with high efficiency even when water is passed through a large SV that exceeds 2000 h ⁻¹ during the decomposition treatment of hydrogen peroxide or the packed bed height of the decomposition catalyst is reduced. It is a second object of the present invention to provide a method and an apparatus for producing ultrapure water by removing. Furthermore, the present invention decomposes hydrogen peroxide with high efficiency even when water is passed through a large SV that exceeds 2000 h ⁻¹ during the decomposition treatment of hydrogen peroxide or the packed bed height of the decomposition catalyst is reduced. A third object is to provide a method and a production apparatus for producing hydrogen-dissolved water while removing it. In addition, according to the present invention, hydrogen peroxide can be made highly efficient even when water is passed through a large SV that exceeds 2000 h ⁻¹ during the decomposition treatment of hydrogen peroxide or the packed bed height of the decomposition catalyst is reduced. A fourth object is to provide a method and a production apparatus for producing ozone-dissolved water while decomposing and removing it. In addition, the fifth aspect of the present invention is to provide a treatment tank that can downsize and easily maintain and manage the ultrapure water production apparatus, the hydrogen dissolved water production apparatus, the ozone dissolved water production apparatus, and the like. It is the purpose. The present invention provides at least one type of cleaning water selected from cleaning water containing the hydrogen peroxide decomposition treated water, cleaning water containing ultrapure water, cleaning water containing hydrogen-dissolved water, and cleaning water containing ozone-dissolved water. It is a sixth object to provide a cleaning method for the used electronic component.

  As a result of intensive studies to achieve the above object, the present inventors have obtained a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger, hydrogen peroxide-containing water, The present inventors have found that the above technical problem can be solved by bringing them into contact with each other, and have completed the present invention based on this finding.

That is, the present invention
(1) A method for producing hydrogen peroxide decomposition treated water, comprising contacting a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger and hydrogen peroxide-containing water. ,
(2) The method for producing hydrogen peroxide decomposition treated water according to (1), wherein the amount of the platinum group metal supported is 10 to 30000 mg per liter of the platinum group metal supported catalyst,
(3) The method for producing hydrogen peroxide-decomposed water according to (1) or (2), wherein the monolithic organic porous anion exchanger is in the OH form,
(4) The hydrogen peroxide decomposition treatment according to any one of the above (1) to (3), wherein the hydrogen peroxide-containing water is brought into contact with the platinum group metal supported catalyst at a space velocity of 2000 h ^{−1 to} 20000 h ^−1. Water production method,
(5) A peroxide comprising a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger, and having a contact treatment section between the catalyst and hydrogen peroxide-containing water. Production equipment for hydrocracked water,
(6) A platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger and a non-regenerative ion exchange resin or a monolithic organic porous ion exchanger with respect to water to be treated. A processing tank (hereinafter, appropriately referred to as the processing tank 1 of the present invention), which is arranged in the same container so as to come into contact in this order,
(7) A platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger, a non-regenerative ion exchange resin or monolithic organic porous ion exchanger, and a separation membrane. A treatment tank (hereinafter, appropriately referred to as the treatment tank 2 of the present invention), which is arranged in the same container so as to come into contact with the treated water in this order;
(8) A platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger and a separation membrane are arranged in the same container so as to come into contact with water to be treated in this order. A processing tank (hereinafter, appropriately referred to as the processing tank 3 of the present invention),
(9) UV treatment for water to be treated, hydrogen peroxide decomposition treatment in which a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger, and non-regenerative ions A method for producing ultrapure water, characterized in that an ion exchange treatment to be brought into contact with an exchange resin and a filtration treatment with a separation membrane are performed in this order;
(10) The ultraviolet oxidation apparatus, the apparatus for producing hydrogen peroxide decomposition treated water described in (5) above, the non-regenerative ion exchange apparatus including the non-regenerative ion exchange resin, and the membrane separation apparatus in this order. A device for producing ultrapure water (hereinafter referred to as the ultrapure water production device 1 of the present invention as appropriate),
(11) An apparatus for producing ultrapure water (hereinafter referred to as “appropriate”), wherein the ultraviolet oxidation apparatus, the treatment tank described in (6) above, and the membrane separation apparatus are installed so as to pass water in this order. , Called ultrapure water production apparatus 2 of the present invention),
(12) A device for producing ultrapure water (hereinafter referred to as “appropriately”), wherein the ultraviolet oxidizer and the treatment tank described in (7) or (8) are installed so as to pass water in this order. Called ultrapure water production apparatus 3 of the present invention),
(13) contacting a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger and hydrogen peroxide-containing water; and the platinum group metal-supported catalyst and hydrogen peroxide-containing water. A method for producing hydrogen-dissolved water, comprising a step of dissolving hydrogen in water to be treated as a pre-process or a post-process of the step of contacting
(14) The hydrogen peroxide decomposition treated water production apparatus according to (5) above and a hydrogen dissolution treatment apparatus for water to be treated are provided upstream or downstream of the hydrogen peroxide decomposition treated water production apparatus. A hydrogen-dissolved water production apparatus (hereinafter referred to as the hydrogen-dissolved water production apparatus 1 of the present invention as appropriate),
(15) The treatment tank according to the above (6) and the membrane separation apparatus are installed so as to pass water in this order, and a hydrogen dissolution treatment apparatus for water to be treated on the upstream side or the downstream side of the treatment tank. An apparatus for producing hydrogen-dissolved water (hereinafter referred to as the apparatus for producing hydrogen-dissolved water 2 of the present invention as appropriate),
(16) Hydrogen-dissolved water comprising the treatment tank according to (7) or (8) above and a hydrogen-dissolution treatment apparatus for water to be treated upstream or downstream of the treatment tank Manufacturing apparatus (hereinafter referred to as the hydrogen dissolved water manufacturing apparatus 3 of the present invention as appropriate),
(17) A step of contacting a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger and hydrogen peroxide-containing water, and the platinum group metal-supported catalyst and hydrogen peroxide-containing water. And a step of dissolving ozone in the treated water obtained by contacting with ozone, a method for producing ozone-dissolved water,
(18) Ozone characterized by comprising the apparatus for producing hydrogen peroxide decomposition treated water as described in (5) above and an ozone dissolution treatment apparatus downstream of the apparatus for producing hydrogen peroxide decomposition treated water Dissolved water production apparatus (hereinafter referred to as ozone dissolved water production apparatus 1 of the present invention as appropriate),
(19) The apparatus for producing ozone-dissolved water according to (18) above, further comprising a membrane separation device on the downstream side of the apparatus for producing hydrogen peroxide-decomposed treated water and upstream of the ozone-dissolving treatment apparatus. ,
(20) An ion exchange tank further comprising a non-regenerative ion exchange resin or a monolithic organic porous ion exchanger on the downstream side of the hydrogen peroxide decomposition treated water production apparatus and upstream of the ozone dissolution treatment apparatus And the apparatus for producing ozone-dissolved water according to (18) above, wherein the membrane separator is provided in this order,
(21) The treatment tank described in (6) above and the membrane separation apparatus are installed so as to pass water in this order, and an ozone dissolution treatment apparatus is provided on the downstream side of the membrane separation apparatus. A device for producing ozone-dissolved water (hereinafter referred to as the device for producing ozone-dissolved water 2 of the present invention as appropriate)
(22) An apparatus for producing ozone-dissolved water comprising the treatment tank according to (7) above and an ozone dissolution treatment apparatus on the downstream side of the treatment tank (hereinafter appropriately referred to as ozone according to the present invention). Dissolved water production device 3),
(23) An apparatus for producing ozone-dissolved water comprising the treatment tank according to (8) above and an ozone dissolution treatment apparatus downstream of the treatment tank (hereinafter referred to as ozone of the present invention as appropriate). Dissolved water manufacturing device 4),
(24) Washing water containing hydrogen peroxide decomposition treated water obtained by the method according to any one of (1) to (4) above or the apparatus according to (5) above, the method according to (9) above or Washing water containing ultrapure water obtained by the apparatus according to any one of (10) to (12) above, the method according to (13) above, or the apparatus according to any of (14) to (16) above Any one selected from wash water containing hydrogen-dissolved water obtained by the above, or wash water containing ozone-dissolved water obtained by the method described in (17) above or the apparatus described in any of (18) to (23) above. A method for cleaning electronic parts, characterized by cleaning the surface with one or more types of cleaning water,
Is to provide.

According to the present invention, by using a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger, by decomposing hydrogen peroxide in water to be treated, SV is reduced to 2000 h ⁻¹ . To provide a method and a production apparatus for producing hydrogen peroxide decomposition treated water by decomposing and removing hydrogen peroxide with high efficiency even if water is passed through an SV exceeding the above or the packed bed height of the catalyst is reduced. it can. In addition, according to the present invention, hydrogen peroxide is highly efficient even when water is passed through a large SV that exceeds 2000 h ⁻¹ during the decomposition treatment of hydrogen peroxide or the packed bed height of the decomposition catalyst is reduced. It is possible to provide a method and apparatus for producing ultrapure water, a method and apparatus for producing hydrogen-dissolved water, a method and apparatus for producing ozone-dissolved water. Furthermore, according to the present invention, it is possible to provide a treatment tank capable of downsizing and easily maintaining and managing the ultrapure water production apparatus, the hydrogen dissolved water production apparatus, the ozone dissolved water production apparatus, and the like. And according to this invention, the washing | cleaning method of the electronic component using the washing water containing the said hydrogen peroxide decomposition | disassembly water, ultrapure water, hydrogen solution water, or ozone solution water can be provided.

It is a figure which shows the example of a mode of a processing tank. It is a figure which shows the example of an aspect of the manufacturing apparatus of ultrapure water. It is the figure ((a) figure) which shows the example of an aspect of a hydrogen dissolution processing apparatus, and the figure ((b) figure) which shows the example of an aspect of an ozone dissolution processing apparatus. It is a figure which shows the example of an aspect of the manufacturing apparatus of ozone dissolution water. It is a typical flowchart of the 1st form example of the washing | cleaning method of the electronic component of this invention. It is a typical flowchart of the 2nd example of the washing | cleaning method of the electronic component of this invention. It is a SEM image of the monolith produced in the Example of this invention. It is a TEM image which shows the dispersion state of the palladium nanoparticle in the palladium nanoparticle carrying | support catalyst produced in the Example of this invention. It is a SEM image of the monolith produced in the Example of this invention. It is the EPMA image which showed the distribution state of the chloride ion in the surface of the monolith anion exchanger produced in the Example of this invention. It is the EPMA image which showed the distribution state of the chloride ion in the cross section (thickness) direction of the monolith anion exchanger produced in the Example of this invention. It is a TEM image which showed the dispersion state of the palladium nanoparticle in the palladium nanoparticle carrying | support catalyst produced in the Example of this invention. It is the figure which transcribe | transferred manually the skeleton part which appears as a cross section of the SEM image (a) and the SEM image of the monolith produced in the Example of this invention. It is the EPMA image which showed the distribution state of the chloride ion in the surface of the monolith anion exchanger produced in the Example of this invention. It is the EPMA image which showed the distribution state of the chloride ion in the cross section (thickness) direction of the monolith anion exchanger produced in the Example of this invention. It is a TEM image which showed the dispersion state of the palladium nanoparticle in the supported catalyst produced in the Example of this invention. It is a SEM image of the monolith produced in the Example of this invention. It is the EPMA image which showed the distribution state of the chloride ion in the surface of the monolith anion exchanger produced in the Example of this invention. It is the EPMA image which showed the distribution state of the chloride ion in the cross section (thickness) direction of the monolith anion exchanger produced in the Example of this invention. It is a TEM image which showed the dispersion state of the palladium nanoparticle in the supported catalyst produced in the Example of this invention. It is a SEM image of the monolith intermediate body produced in the Example of this invention. It is the figure which showed typically the co-continuous structure of the 4th monolith anion exchanger. It is a figure which shows the form of the processing tank used by the Example and comparative example of this invention.

  The present invention relates to a method for producing hydrogen peroxide-decomposed treated water, an apparatus for producing hydrogen peroxide-decomposed treated water, a treatment tank, a method for producing ultrapure water, an apparatus for producing ultrapure water, a method for producing hydrogen-dissolved water, and hydrogen dissolving. A water production apparatus, a method for producing ozone-dissolved water, a production apparatus for ozone-dissolved water, and a method for cleaning electronic components. These inventions comprise a platinum group metal supported on a monolithic organic porous anion exchanger. The point which uses a platinum group metal carrying | support catalyst is made common. For this reason, after explaining points other than the platinum group metal supported catalyst in each invention, the platinum group metal supported catalyst will be described in detail.

<Method for producing hydrogen peroxide decomposition treated water>
First, the manufacturing method of the hydrogen peroxide decomposition treatment water of this invention is demonstrated.

  The method for producing hydrogen peroxide decomposition treated water of the present invention comprises contacting a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger and hydrogen peroxide-containing water. It is what.

  The hydrogen peroxide-containing water is not particularly limited as long as it contains hydrogen peroxide. For example, various kinds of water in the manufacturing process of ultrapure water for cleaning semiconductor electronic component surfaces and semiconductor electronic component manufacturing equipment can be used. Water produced in this step can be mentioned, and specifically, water after undergoing an ultraviolet oxidation treatment step for oxidizing and decomposing organic substances in the water. In addition, as the hydrogen peroxide-containing water, other treatment liquid or treatment water obtained by adding hydrogen peroxide to the waste water for use, oxidation, reduction, sterilization, and washing, or these treatment liquid or treatment water is used. The waste liquid or waste water after processing 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 hydrogen peroxide concentration in the hydrogen peroxide-containing water is not particularly limited, but is usually 0.01 to 100 mg / L (10 ppb to 100 ppm). When the hydrogen peroxide concentration exceeds 100 mg / L (100 ppm), the deterioration of the organic porous anion exchanger as the base material is likely to proceed. In addition, the density | concentration of the hydrogen peroxide contained in the to-be-processed water of the subsystem which comprises the manufacturing apparatus of ultrapure water which is a kind of hydrogen peroxide containing water is 10-50 microgram / L (10-50ppb) normally. It is.

  The method for bringing the water to be treated containing hydrogen peroxide into contact with the platinum group metal supported catalyst is not particularly limited. For example, the catalyst packed tower packed with the platinum group metal supported catalyst in layers contains hydrogen peroxide. The method of supplying the to-be-processed water to supply and water-flowing is mentioned.

The flow rate of the hydrogen peroxide-containing water with respect to the platinum group metal-supported catalyst is not particularly limited, but is preferably SV2000-20000h- ¹ , more preferably SV5000-10000h- ¹ . Incidentally, platinum group metal supported catalyst of the present invention has a remarkably high hydrogen peroxide decomposition ability, dares need not be a water flow rate of less than SV2000h ^-1, may be a water flow rate of less than SV2000h ^-1, Even when the water flow rate is less than SV2000h- ¹ , excellent hydrogen peroxide decomposability is exhibited. On the other hand, when SV exceeds 20000 h ⁻¹ , the water flow differential pressure tends to be too large.

In the method for producing hydrogen peroxide-decomposed treated water of the present invention, by using a platinum group metal-supported catalyst, even if the treated water is passed through with a large SV such that SV exceeds 2000h- ¹ , hydrogen peroxide As compared with the case where a conventional supported catalyst in which platinum group metal nanoparticles are supported on the particulate anion exchange resin is used, an excellent effect can be obtained.

  The layer height of the platinum group metal supported catalyst layer through which hydrogen peroxide-containing water is passed is suitably 5 to 100 mm, more preferably 10 to 50 mm, and 10 to 25 mm. It is even more appropriate to be. If the layer height of the platinum group metal supported catalyst is less than 5 mm, the mechanical strength of the catalyst layer may be insufficient and hydrogen peroxide may leak. On the other hand, when the layer height of the platinum group metal supported catalyst exceeds 100 mm, the water flow differential pressure increases.

  In the method for producing hydrogen peroxide decomposition treated water of the present invention, the temperature at which the platinum group metal-supported catalyst and the hydrogen peroxide-containing water are brought into contact is preferably 5 to 60 ° C, more preferably 10 to 50 ° C, and 20 to 30. More preferably.

  In the method for producing hydrogen peroxide decomposition treated water of the present invention, since a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger is used, normal particulate anion exchange is performed. Compared with the case where resin is used, contact efficiency with to-be-processed water can be raised significantly. In the method for producing hydrogen peroxide decomposition treated water of the present invention, since the platinum group metal supported catalyst is used, the ability to decompose hydrogen peroxide can be remarkably increased, and the packed bed height of the catalyst can be reduced. However, hydrogen peroxide in the water to be treated can be sufficiently decomposed and removed.

  As described above, in the subsystem of the ultrapure water production apparatus, the concentration of a trace amount of hydrogen peroxide generated by the ultraviolet oxidation treatment is in the range of 10 to 50 μg / L (10 to 50 ppb), and 15 to 30 μg / L. Although often in the range of (15-30 ppb), in the method for producing hydrogen peroxide decomposition treated water of the present invention, the hydrogen peroxide in the obtained hydrogen peroxide decomposition treated water is 10 μg / L (10 ppb) or less, Preferably, it can be reduced to 1 μg / L (1 ppb) or less.

  The degree to which hydrogen peroxide is reduced can be adjusted by adjusting the layer height of the platinum group metal-supported catalyst layer, the SV during water passage, or the amount of white metal metal supported on the catalyst.

<Production equipment for hydrogen peroxide decomposition treated water>
Next, the apparatus for producing hydrogen peroxide decomposition treated water of the present invention will be described.

  The apparatus for producing hydrogen peroxide decomposition treated water of the present invention includes a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger, and the contact of the catalyst with hydrogen peroxide-containing water. It has a processing part.

  In the apparatus for producing hydrogen peroxide decomposition treated water of the present invention, the hydrogen peroxide-containing water, the contact conditions such as SV when water is passed, and the obtained hydrogen peroxide decomposition treated water are the hydrogen peroxide decomposition of the present invention. This is the same as described in the explanation of the method for producing treated water.

  The form of the contact treatment portion between the platinum group metal supported catalyst and the hydrogen peroxide-containing water is not particularly limited. For example, a form of a platinum group metal catalyst layer in which a catalyst packed tower is packed with a platinum group metal supported catalyst is given. be able to.

  The layer height of the platinum group metal supported catalyst in the catalyst packed tower is suitably 5 to 100 mm, more suitably 10 to 50 mm, and even more suitably 10 to 25 mm. . If the layer height of the platinum group metal supported catalyst is less than 5 mm, the mechanical strength of the catalyst layer may be insufficient and hydrogen peroxide may leak. On the other hand, when the layer height of the platinum group metal supported catalyst exceeds 100 mm, the water flow differential pressure increases.

  In the apparatus for producing hydrogen peroxide-decomposed treated water of the present invention, since a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger is used, normal particulate anion exchange is performed. Compared with the case where resin is used, contact efficiency with to-be-processed water can be raised significantly. And since the said platinum group metal carrying | support catalyst has a remarkably high hydrogen peroxide decomposition | disassembly capability, even if it makes the packed bed height of a catalyst thin, hydrogen peroxide in to-be-processed water can fully be decomposed | disassembled and removed.

  In the catalyst packed tower, the platinum group metal-supported catalyst layer may be a single stage or a multistage of two or more stages, and the catalyst packed tower may be composed of one tower. It may consist of the above multiple towers. When the catalyst layers are multi-staged or when the catalyst packed tower is multi-columned, the total height of the catalyst layers may be in the above range.

<Treatment tank>
Next, the treatment tank of the present invention will be described.

  The treatment tank 1 of the present invention comprises a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger, and a non-regenerative ion exchange resin or a monolithic organic porous ion exchanger. It arrange | positions in the same container so that to-be-processed water may contact in this order, It is characterized by the above-mentioned.

  In the treatment tank 1 of the present invention, the container containing the platinum group metal supported catalyst and the non-regenerative ion exchange resin or the monolithic organic porous ion exchanger may have an inlet and an outlet for water flow. There is no particular limitation, and examples thereof include a cylindrical thing such as a column and a cartridge.

  Further, the arrangement form of the platinum group metal supported catalyst and the non-regenerative ion exchange resin or the monolithic organic porous ion exchanger in the container is arranged so as to come into contact with the water to be treated in this order. If it becomes, it will not restrict | limit in particular, For example, the form shown to Fig.1 (a)-FIG.1 (c) can be mentioned.

  FIG. 1 (a) shows a platinum group metal-supported catalyst α at the bottom of a container in a substantially cylindrical container having a water inlet and outlet for passing water to be treated introduced from below in the figure. The container is filled with non-regenerative ion exchange resin or monolithic organic porous ion exchanger β, and the platinum group metal-supported catalyst α and non-regenerative ion exchange resin or monolith are filled in the container. The arrangement | positioning form which carries out the lamination | stacking filling with the gaseous organic porous ion exchanger (beta) is shown.

  FIG. 1B shows a cartridge-like substantially cylindrical container having a water inlet for introducing the water to be treated into the interior from the outer side surface of the container and a water outlet for draining the water to be treated introduced into the interior from above. In addition, a layer made of a platinum group metal supported catalyst α is formed on the inner periphery of the container, and a layer made of a non-regenerative ion exchange resin or a monolithic organic porous ion exchanger β is formed in the core at the inner center of the container. The arrangement form formed is shown.

  FIG. 1 (c) has an upper inlet and a lower outlet for passing water to be treated introduced from the top of the figure in the downward direction, and water flowing downward on the inlet side for passing water. In a cartridge-like cylindrical container provided with an adjustment chamber for controlling the amount and direction of water flow into the container by a pipe, the adjustment chamber is filled with a platinum group metal-supported catalyst α, and the entire outside of the adjustment chamber is not covered. A regenerative ion exchange resin or monolithic organic porous ion exchanger β is filled, and a platinum group metal-supported catalyst α and a non-regenerative ion exchange resin or monolithic organic porous ion exchanger β are placed in a container. The arrangement | positioning form to fill is shown.

  In the embodiment shown in FIG. 1 (a), the layer height of the platinum group metal supported catalyst in the container is suitably 5 to 100 mm, more preferably 10 to 50 mm, and 10 to 25 mm. It is even more appropriate to be. If the layer height of the platinum group metal supported catalyst is less than 5 mm, the mechanical strength of the catalyst layer may be insufficient and hydrogen peroxide may leak. On the other hand, when the layer height of the platinum group metal supported catalyst exceeds 100 mm, the water flow differential pressure increases.

  In the embodiment shown in FIG. 1A, when the container contains a non-regenerative ion exchange resin, the layer height is preferably 30 to 1000 mm, more preferably 50 to 1000 mm. In the embodiment shown in FIG. 1A, when the monolithic organic porous ion exchanger is contained in the container, the layer height is preferably 5 to 100 mm, more preferably 10 to 50 mm, and further preferably 10 to 25 mm. .

  In the treatment tank 1 of the present invention, the non-regenerative ion exchange resin is preferably a non-regenerative mixed bed ion exchange resin. For example, a mixture of a strongly acidic cation exchange resin and a strongly basic anion exchange resin, Examples include a single bed layer of a basic anion exchange resin provided on the inlet side, and a mixed bed layer of a strongly acidic cation exchange resin and a strongly basic anion exchange resin provided on the outlet side to form a multilayer. .

  In the treatment tank 1 of the present invention, the monolithic organic porous ion exchanger preferably includes a monolithic organic porous anion exchanger, and is composed of only a monolithic organic porous anion exchanger or a monolithic organic anion exchanger. The thing containing a porous anion exchanger and a monolithic organic porous cation exchanger can be mentioned. A plate-like monolithic organic porous anion exchanger and a plate-like monolithic organic porous cation exchanger are joined as a monolithic organic porous anion exchanger and a monolithic organic porous cation exchanger. Can be mentioned.

  Examples of the monolithic organic porous anion exchanger include those similar to those used as a support for a platinum group metal-supported catalyst described later.

  Examples of the monolithic organic porous cation exchanger include those obtained by introducing a cation exchange group into the monolith used as the base material in the first to fourth monolith anion exchangers described later. it can. Examples of the cation exchange group introduced into the monolith include a carboxylic acid group, an iminodiacetic acid group, a sulfonic acid group, a phosphoric acid group, and a phosphoric acid ester group.

  There is no restriction | limiting in particular as a method of introduce | transducing a cation exchange group with respect to monolith, Well-known methods, such as a polymer reaction and graft polymerization, can be used. For example, as a method of introducing a sulfonic acid group, if the monolith is a styrene-divinylbenzene copolymer or the like, a method of sulfonation using chlorosulfuric acid, concentrated sulfuric acid or fuming sulfuric acid, Examples include a method of introducing a mobile group and graft polymerization of sodium styrenesulfonate or acrylamide-2-methylpropanesulfonic acid, and a method of introducing a sulfonic acid group by functional group conversion after graft polymerization of glycidyl methacrylate in the same manner. .

  The treatment tank 1 of the present invention comprises a platinum group metal supported catalyst and a non-regenerative ion exchange resin or a monolithic organic porous ion exchanger housed in the same container. In the manufacturing apparatus and the ozone dissolved water manufacturing apparatus, the apparatus configuration can be simplified and the installation area can be reduced. Especially when the treatment tank is made into a cartridge shape, even if the treatment tank reaches the end of its life, the cartridge-like treatment tank normally stored in the housing can be easily replaced without disconnecting the piping. Maintenance work can be reduced. Even if platinum group metal or the like is eluted from the platinum group metal supported catalyst, it can be adsorbed and removed by a non-regenerative ion exchange resin or a monolithic organic porous ion exchanger.

  The method for producing the treatment tank 1 of the present invention is not particularly limited. For example, a platinum group metal-supported catalyst and a non-regenerative type can be obtained by a known method on a container such as a cartridge having a desired internal space shape. Examples thereof include a method of filling an ion exchange resin or a monolithic organic porous ion exchanger.

  The treatment tank 2 of the present invention comprises a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger, a non-regenerative ion exchange resin or a monolithic organic porous ion exchanger, The membrane is arranged in the same container so as to come into contact with the water to be treated in this order.

  The treatment tank 2 of the present invention is the same as the treatment tank 1 of the present invention except that a separation membrane is included in the container, and a platinum group metal-supported catalyst, a non-regenerative ion exchange resin, or a monolithic organic porous material. It is preferable that the specific examples of the solid ion exchanger and the layer height at the time of filling are the same.

  Moreover, in the treatment tank 2 of the present invention, the arrangement form of the platinum group metal-supported catalyst, the non-regenerative ion exchange resin or monolithic organic porous ion exchanger, and the separation membrane in the vessel is treated water. If it arrange | positions so that it may contact with this order with respect to this, it will not restrict | limit in particular, For example, the form shown to FIG.1 (d) and FIG.1 (e) can be mentioned.

  FIG. 1 (d) shows a platinum group metal-supported catalyst α at the lower part of a cartridge-like substantially cylindrical container having an inlet and an outlet for passing water to be treated introduced upward from the bottom of the figure. Is filled with a non-regenerative ion exchange resin or a monolithic organic porous ion exchanger β, and further filled with a separation membrane γ, whereby a platinum group metal supported catalyst α is filled in the container. And a non-regenerative ion exchange resin or monolithic organic porous ion exchanger β and a separation membrane γ are stacked and filled.

  FIG. 1 (e) shows a cylindrical container having an internal structure that is divided into an outer peripheral portion and a central portion, and the outer peripheral portion is divided into two layers, upper and lower, and water to be treated is introduced into the lower portion of the outer peripheral portion. A container having a conduit for passing water to be treated introduced into the upper part of the outer peripheral part of one end and then passing from the upper part of the central part of the container toward the lower part. Is packed with a platinum group metal-supported catalyst α and a non-regenerative ion exchange resin or monolithic organic porous ion exchanger β in the upper and lower directions in the flow direction of the water to be treated, and separated in the center of the container. An arrangement in which a container is filled with a platinum group metal-supported catalyst α, a non-regenerative ion exchange resin or monolithic organic porous ion exchanger β, and a separation membrane γ by filling the membrane γ It is.

  In the treatment tank 2 of the present invention, examples of the separation membrane include a microfiltration membrane and an ultrafiltration membrane. The microfiltration membrane is preferably an organic membrane having pores with a pore diameter of about 0.05 to 1 μm, and the ultrafiltration membrane is a polysulfone membrane having pores with a fractional molecular weight of about 3,000 to 10,000, acetic acid It is preferable to use a cellulose membrane or the like. Examples of the overall shape (module shape) of the microfiltration membrane and the ultrafiltration membrane include a hollow fiber shape, a spiral shape, a tubular shape, and a flat membrane shape.

  The treatment tank 2 of the present invention is provided with a separation membrane at the rear stage of the treatment tank 1 of the present invention, so that in addition to the effects obtained in the treatment tank 1, a platinum group metal supported catalyst, a non-regenerative ion exchange resin or Even when platinum group metals and fine particles are eluted from the monolithic organic porous ion exchanger, the effect of being able to be separated and separated more easily is exhibited.

  The method for producing the treatment tank 2 of the present invention is not particularly limited. For example, a platinum group metal supported catalyst and a non-regenerative type can be obtained by a known method on a container such as a cartridge having a desired internal space shape. Examples thereof include an ion exchange resin or a monolithic organic porous ion exchanger and a method of filling a separation membrane.

  In the treatment tank 3 of the present invention, a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger and a separation membrane are in contact with water to be treated in this order. It is arranged in the same container.

  The treatment tank 3 of the present invention is the same as the treatment tank 2 of the present invention except that it does not contain a non-regenerative ion exchange resin or a monolithic organic porous ion exchanger, a platinum group metal supported catalyst, It is preferable that the specific examples of the separation membrane and the layer height at the time of filling are the same.

  Further, in the treatment tank 3 of the present invention, the arrangement form of the platinum group metal supported catalyst and the separation membrane in the container may be arranged so as to come into contact with the water to be treated in this order. There is no particular limitation, and for example, the form shown in FIG.

  FIG. 1 (f) shows a platinum group metal-supported catalyst α at the lower part of a cartridge-like substantially cylindrical container having an inlet and an outlet for passing water to be treated introduced upward from the bottom of the figure. And a separation membrane γ is filled in the upper portion of the container, whereby a platinum group metal supported catalyst α and a separation membrane γ are stacked and filled in a container.

  The treatment tank 3 of the present invention can obtain the same effect as the treatment tank 1 of the present invention by providing a platinum group metal-supported catalyst and a separation membrane in the same container. Even when a group metal or fine particles are eluted, it can be separated by filtration more easily.

  The method for producing the treatment tank 3 of the present invention is not particularly limited. For example, a platinum group metal-supported catalyst and a separation membrane are formed on a container such as a cartridge having a desired internal space shape by a known method. A filling method can be mentioned.

  The treatment tank 1, the treatment tank 2 and the treatment tank 3 of the present invention can be suitably used as a treatment tank for performing a decomposition treatment of hydrogen peroxide.

<Method for producing ultrapure water>
Next, the manufacturing method of the ultrapure water of this invention is demonstrated.

  The method for producing ultrapure water according to the present invention comprises hydrogen peroxide that is subjected to ultraviolet oxidation treatment to a water to be treated and a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger. A decomposition treatment, an ion exchange treatment to be brought into contact with a non-regenerative ion exchange resin, and a filtration treatment with a separation membrane are performed in this order.

  The method for producing ultrapure water of the present invention can be carried out, for example, by the ultrapure water production apparatus 1 shown in FIG. 2 (a) or 2 (b).

  That is, in the apparatus for producing ultrapure water shown in FIGS. 2 (a) and 2 (b), first, the raw water is passed through the pretreatment system 2 to remove suspended substances and colloidal substances in the raw water. Then, the obtained pretreated water is supplied to the primary pure water system 3 through a filtered water tank (not shown), for example, a desalting apparatus for removing impurity ions in water, inorganic ions in water, organic substances, Reverse osmosis membrane device that removes fine particles, vacuum deaeration device that removes dissolved gas such as dissolved oxygen in water, regenerative mixed bed type dewatering that produces high purity pure water by removing remaining ions Water is sequentially passed through the salt device to remove ionic components, organic components, dissolved oxygen, and the like to obtain primary pure water.

  As shown in FIGS. 2 (a) and 2 (b), the obtained primary pure water is stored in a pure water storage tank constituting the subsystem 4, and thereafter, an ultraviolet oxidation apparatus, hydrogen peroxide decomposition treated water production In apparatus, non-regenerative ion exchange device, and membrane separation device, in order, ultraviolet oxidation treatment, hydrogen peroxide decomposition treatment in contact with platinum group metal supported catalyst, ion exchange treatment in contact with non-regenerative ion exchange resin, and separation membrane Filtration is performed, and ultrapure water 5 is obtained. The obtained ultrapure water residue is circulated through the circulation line 6 to the pure water storage tank.

  In the method for producing ultrapure water of the present invention, the ultraviolet oxidation apparatus for performing the ultraviolet oxidation treatment is not particularly limited as long as it can decompose organic substances in the water to be treated, but the water to be treated is irradiated with a wavelength of at least about 185 nm. Those equipped with possible ultraviolet lamps are preferred. The ultraviolet oxidation apparatus is more preferably an apparatus that can irradiate ultraviolet rays having a wavelength of around 254 nm, which has a lower ability to decompose organic substances, in addition to ultraviolet rays having a wavelength of around 185 nm. There is an ultraviolet irradiation apparatus that irradiates a wavelength near 254 nm but hardly irradiates a wavelength near 185 nm. This ultraviolet irradiation apparatus is mainly used for sterilization purposes and is generally called an ultraviolet sterilization apparatus. It is used in distinction. In the present invention, it is preferable to use an ultraviolet oxidizer that can strongly irradiate ultraviolet rays having a wavelength of around 185 nm and a wavelength of around 254 nm because organic substances can be decomposed satisfactorily. The ultraviolet lamp used in the ultraviolet oxidation apparatus is not particularly limited, but a low-pressure mercury lamp is preferable. In addition, examples of the ultraviolet oxidation apparatus include a distribution type and an immersion type, and among these, the distribution type is preferable from the viewpoint of processing efficiency.

  In the method for producing ultrapure water of the present invention, the hydrogen peroxide decomposing apparatus that performs the hydrogen peroxide decomposing treatment is preferably the apparatus for producing hydrogen peroxide decomposing water of the present invention. The production apparatus for hydrogen peroxide-decomposed water of the present invention, the water flow conditions for the apparatus, and the like are as described above.

  In the method for producing ultrapure water of the present invention, as the non-regenerative ion exchange apparatus (cartridge polisher) used for the ion exchange treatment to be brought into contact with the non-regenerative ion exchange resin, a non-regenerative mixed bed ion exchange resin is preferable. For example, an ion exchange device (mixed-bed single-column ion exchange device) using a mixed bed of a strongly acidic cation exchange resin and a strongly basic anion exchange resin or a single bed layer of a strongly basic anion exchange resin on the inlet side , A multi-layer type ion exchange device (multi-layer single tower type) provided with a mixed bed layer of strong acidic cation exchange resin and strong basic anion exchange resin on the outlet side; There may be mentioned an ion exchange apparatus (two-column type) in which a resin tower with a bed is provided on the front stage side, and a resin tower with a mixed bed of a strongly acidic cation exchange resin and a strongly basic anion exchange resin is provided on the rear stage side.

  Among these ion exchange devices, when a mixed-bed single-column ion exchange device is used, since there is no change in the pH of water at any position in the mixed bed layer, efficient ion exchange is performed. Can do.

  In the method for producing ultrapure water of the present invention, examples of the membrane separation apparatus that performs filtration treatment with a separation membrane include membrane treatment apparatuses such as a microfiltration membrane apparatus and an ultrafiltration membrane apparatus. As the microfiltration membrane, it is preferable to use an organic membrane having pores having a pore diameter of about 0.05 to 1 μm. As the ultrafiltration membrane, a polysulfone membrane having a fractional molecular weight of about 3,000 to 10,000, a cellulose acetate membrane, or the like can be used. As a module shape in the microfiltration membrane device and the ultrafiltration membrane device, a hollow fiber shape, a spiral shape, a tubular shape, a flat membrane shape, or the like can be used.

  In the method for producing ultrapure water of the present invention, deaeration treatment may be performed, and the deaeration treatment is preferably performed as a pre-process or a post-process of the non-regenerative ion exchange apparatus. The deaeration treatment is preferably performed by a deaeration device. As shown in FIGS. 2 (a) and 2 (b), the deaeration device is preferably a membrane deaeration device, and this membrane deaeration device is placed in one chamber partitioned by a gas separation membrane. This is a device that removes the gas contained in the water to be treated by moving it into the other chamber through the gas separation membrane by flowing the treated water and depressurizing the other chamber. As the gas separation membrane, a membrane in which a hydrophobic polymer membrane such as tetrafluoroethylene or silicone rubber is formed into an appropriate shape such as a hollow fiber membrane is usually used. A degassing device such as a vacuum degassing tower or a heating degassing device may be used as the degassing device. However, when these devices are used, the size of the device is increased, so a membrane degassing device is used. It is preferable.

In the method for manufacturing ultra-pure water of the present invention, water flow rate, during at least the hydrogen peroxide decomposition treatment ^is preferably SV2000h ^-1 ~20000h ^-1, more to be SV5000h ^-1 ~10000h -1 preferable. The method for producing ultrapure water of the present invention is to decompose hydrogen peroxide in water to be treated using a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger. From the above, even if water to be treated is passed through with a large SV such that SV exceeds 2000h ⁻¹ , hydrogen peroxide can be decomposed and removed, and even if SV is about 10,000 h ⁻¹ , the platinum group By using a metal-supported catalyst, hydrogen peroxide can be decomposed. Incidentally, platinum group metal supported catalyst used in the present invention has high markedly hydrogen peroxide decomposition ability, dares need not be a water flow rate of less than SV2000h ^-1, may be a water flow rate of less than SV2000h ^-1 Even when the water flow rate is less than SV2000h- ¹ , excellent hydrogen peroxide decomposability is exhibited. On the other hand, when SV exceeds 20000 h ⁻¹ , the water flow differential pressure tends to be too large.

In the method for producing ultrapure water of the present invention, treatment conditions such as a water flow rate when performing treatment other than hydrogen peroxide decomposition treatment on the water to be treated may be conventionally known conditions, for example, The water flow rate when the ion exchange treatment to be brought into contact with the non-regenerative ion exchange resin is performed by a non-regenerative mixed bed ion exchange apparatus is preferably about SV30 to 100 h- ¹ .

  Thus, in the method for producing ultrapure water of the present invention, a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger is used as a hydrogen peroxide decomposition treatment catalyst. For this reason, the contact efficiency with the water to be treated can be remarkably increased in the decomposition treatment of hydrogen peroxide as compared with the case where a normal particulate anion exchange resin is used. In the method for producing ultrapure water according to the present invention, since the platinum group metal-supported catalyst is used as the hydrogen peroxide decomposition treatment catalyst, the hydrogen peroxide decomposition ability can be remarkably increased, and the catalyst packed bed Even if the height is reduced, ultrapure water can be produced while sufficiently decomposing and removing hydrogen peroxide in the water to be treated.

<Ultrapure water production equipment>
Next, the apparatus for producing ultrapure water of the present invention will be described.

  The ultrapure water production apparatus 1 of the present invention includes an ultraviolet oxidation apparatus, a hydrogen peroxide decomposition treated water production apparatus of the present invention, a non-regenerative ion exchange apparatus including a non-regenerative ion exchange resin, and a membrane separation apparatus. Are installed so as to pass water in this order.

  The preferred embodiments of the ultrapure water production apparatus 1 of the present invention and the processing conditions such as the water flow rate are the same as those described in the description of the method for producing ultrapure water of the present invention.

  The ultrapure water production apparatus 1 of the present invention can be suitably used when carrying out the invention of the ultrapure water production method of the present invention.

  In the ultrapure water production apparatus 1 of the present invention, the hydrogen peroxide decomposition treated water production apparatus of the present invention is used. In this apparatus, platinum is used as a monolithic organic porous anion exchanger as a hydrogen peroxide decomposition treatment catalyst. Since the platinum group metal supported catalyst on which the group metal is supported is used, the contact efficiency with the water to be treated can be improved in the decomposition treatment of hydrogen peroxide compared with the case of using a normal particulate anion exchange resin. It can be significantly improved. In the ultrapure water production apparatus 1 of the present invention, since the platinum group metal-supported catalyst is used as the hydrogen peroxide decomposition treatment catalyst, the hydrogen peroxide decomposition ability can be remarkably increased, and the catalyst filling Even if the bed height is reduced, ultrapure water can be produced while sufficiently decomposing and removing hydrogen peroxide in the water to be treated.

  The ultrapure water production apparatus 2 of the present invention is characterized in that the ultraviolet oxidation apparatus, the treatment tank 1 of the present invention, and the membrane separation apparatus are installed so as to pass water in this order, The apparatus for producing ultrapure water 3 of the present invention is characterized in that the ultraviolet oxidation apparatus and the treatment tank 2 of the present invention or the treatment tank 3 of the present invention are installed so as to pass water in this order. is there.

  The ultrapure water production apparatus 2 of the present invention is the same as the ultrapure water production apparatus 1 of the present invention except that the hydrogen peroxide decomposition treated water production apparatus and the non-regenerative ion exchange apparatus are replaced with the treatment tank 1 of the present invention. The ultrapure water production apparatus 3 of the present invention is different from the ultrapure water production apparatus 1 of the present invention in that the hydrogen peroxide decomposition treated water production apparatus, non-regenerative ion exchange apparatus, and membrane The difference is that the treatment tank 2 of the present invention or the treatment tank 3 of the present invention is provided in place of the separation device, but the use conditions such as the apparatus configuration and water flow rate other than the above are the ultrapure water of the present invention. This is the same as the manufacturing apparatus 1.

  The ultrapure water production apparatus 2 of the present invention and the ultrapure water production apparatus 3 of the present invention, in addition to the effects obtained by the ultrapure water production apparatus 1 of the present invention, include a platinum group metal supported catalyst, a non-regenerative type Since the treatment tank 1, treatment tank 2 or treatment tank 3 of the present invention in which the ion exchange resin or the monolithic organic porous ion exchanger or the separation membrane is housed in the same container is used, ultrapure water is used. The apparatus configuration of the manufacturing apparatus can be simplified, the installation area can be reduced, and particularly when the processing tank is in the form of a cartridge, the processing tank can be easily replaced. In addition, even if platinum group metal or fine particles are eluted from the platinum group metal supported catalyst or the like, it is possible to perform filtration and separation more easily.

<Method for producing hydrogen-dissolved water>
Next, the method for producing hydrogen-dissolved water of the present invention will be described.

  The method for producing hydrogen-dissolved water of the present invention comprises a step of contacting a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger and hydrogen peroxide-containing water, and the platinum group metal. As a pre-process or a post-process of the step of bringing the supported catalyst and hydrogen peroxide-containing water into contact with each other, a hydrogen dissolution step for water to be treated is included.

  In the step of bringing the platinum group metal-supported catalyst into contact with the hydrogen peroxide-containing water in the method for producing hydrogen-dissolved water of the present invention, the hydrogen peroxide-containing water, the contact method between the platinum group metal and the hydrogen peroxide-containing water, The contact conditions such as SV during water flow and the hydrogen peroxide decomposition treated water obtained are the same as those described in the description of the method for producing hydrogen peroxide decomposition treated water of the present invention.

  In the method for producing hydrogen-dissolved water of the present invention, the hydrogen-dissolving step is performed as a pre-step or a post-step of the step of bringing the platinum group metal supported catalyst into contact with the hydrogen peroxide-containing water. The hydrogen dissolving step is performed by a desired hydrogen dissolving device after passing through a manufacturing step of ultra pure water using an ultra pure water manufacturing device as shown in FIG. 2 (a) or FIG. 2 (b). However, the hydrogen dissolution step may be performed on primary pure water or water of lower quality, or may be performed on ultrapure water added with chemicals.

  As a hydrogen dissolution treatment apparatus used when performing the hydrogen dissolution step, for example, as shown in FIG. 3A, a gas permeable film (not shown) is provided in the treatment line 8 of the water to be treated, and hydrogen is passed through the gas permeable film. A hydrogen dissolution treatment apparatus 7 having a structure in which hydrogen is supplied from the supply source 10 through the pipe 11 and dissolved is suitably used. As the hydrogen dissolution treatment apparatus 7 having such a structure, the gas permeable membrane is preferably made of a hollow fiber membrane, and a device in which a large number of the hollow fiber membranes are arranged in parallel is particularly preferred. In addition, as a hydrogen dissolution treatment apparatus, an apparatus for bubbling and dissolving hydrogen gas in the water to be treated, an apparatus for dissolving the hydrogen gas by dissolving the ejector in the water to be treated, and an upstream side of a pump for supplying the water to be treated An apparatus for supplying hydrogen gas and dissolving it by stirring in the pump can be given, and hydrogen may be dissolved by these apparatuses.

  Examples of the hydrogen supply source 10 include a water electrolysis device and a hydrogen gas cylinder. When a water electrolyzer is used, ultrapure water is supplied to the electrolyzer, electrolyzed in the electrolyzer, and high-purity hydrogen gas generated in the cathode chamber of the electrolyzer is introduced into the hydrogen dissolution treatment apparatus through the pipe 11. It is preferable.

In the method for producing hydrogen-dissolved water of the present invention, hydrogen peroxide that oxidizes the surface of the object to be treated is decomposed by a platinum group metal-supported catalyst, and the oxidation-reduction potential of the treated water is set to the reduction potential side and used as a cleaning liquid Sometimes, hydrogen-dissolved water that can further suppress the oxidation of the surface of the object to be processed can be obtained. Further, when the hydrogen dissolution step is performed as a pre-step of the step of bringing the platinum group metal-supported catalyst into contact with the hydrogen peroxide-containing water, decomposition of dissolved oxygen and hydrogen peroxide in the water to be treated (2H ₂ O ₂ → (Dissolved) oxygen (O ₂ ) generated by (2H ₂ O + O ₂ ) can be removed.

In the method for producing hydrogen-dissolved water of the present invention, a deaeration device as described in the explanation of the ultrapure water production device of the present invention is provided upstream of the hydrogen-dissolving treatment device used when performing the hydrogen-dissolving step. By disposing, degassing treatment may be performed. By removing the dissolved oxygen in advance by degassing, the amount of dissolved oxygen in the water to be treated is reduced, and the amount of hydrogen consumed in the reaction (O ₂ + 2H ₂ → 2H ₂ O) with the white metal metal supported catalyst is small. Therefore, in producing hydrogen-dissolved water, the amount of hydrogen to be added (the amount of hydrogen added to remove dissolved oxygen and adjust the oxidation-reduction potential described later) can be reduced.

  On the other hand, since it is possible to perform degassing with a platinum group metal supported catalyst without performing degassing on the upstream side of the hydrogen dissolving means, it is not necessary to perform degassing on the upstream side. In this case, the apparatus configuration can be simplified because there is no degassing treatment.

  Hydrogen-dissolved water obtained by dissolving hydrogen gas in the hydrogen dissolution treatment apparatus 7 usually has a negative redox potential. That is, the oxidation-reduction potential of hydrogen-dissolved water is usually on the reduction potential side, and can be set to a potential of −100 mV to −600 mV with respect to the standard hydrogen electrode, for example. For this reason, the hydrogen-dissolved water obtained by the method of the present invention can be used as a cleaning liquid when it is not desired to oxidize the surface of the object to be treated or when a film such as Cu is easily oxidized on the surface of the object to be treated. It can be used as a cleaning liquid for removal.

  The dissolved hydrogen concentration in the hydrogen-dissolved water obtained by the method of the present invention is preferably 0.05 ppm or more at 25 ° C. and 1 atm, and more preferably 0.8 to 1.6 ppm. If the dissolved hydrogen concentration is less than 0.05 ppm, the redox potential of the hydrogen-dissolved water cannot be set to a sufficient reduction potential side. As a result, when the hydrogen-dissolved water is used as a cleaning liquid, The effect of suppressing oxidation is insufficient, and the particle removal efficiency on the surface of the object to be processed is lowered.

  The method for producing hydrogen-dissolved water of the present invention comprises a step of bringing a platinum group metal-supported catalyst into contact with hydrogen peroxide-containing water, and a platinum group formed by supporting a platinum group metal on a monolithic organic porous anion exchanger. Since hydrogen peroxide is decomposed by the metal-supported catalyst, the contact efficiency with the water to be treated is greatly improved when hydrogen peroxide is decomposed compared to the case of using a normal particulate anion exchange resin. be able to. In the method for producing hydrogen-dissolved water of the present invention, the platinum group metal-supported catalyst is used as the hydrogen peroxide decomposition treatment catalyst. Even if the height is reduced, hydrogen-dissolved water can be produced while sufficiently decomposing and removing hydrogen peroxide in the water to be treated.

<Production equipment for hydrogen-dissolved water>
Next, the apparatus for producing hydrogen-dissolved water of the present invention will be described.

  The apparatus 1 for producing hydrogen-dissolved water according to the present invention includes a device for producing hydrogen peroxide-decomposed treated water according to the present invention and a hydrogen-dissolving treatment for water to be treated upstream or downstream of the apparatus for producing hydrogen peroxide-decomposed treated water. And an apparatus.

  In the hydrogen-dissolved water production apparatus 1 of the present invention, the preferred embodiment of the hydrogen peroxide decomposition-treated water production apparatus of the present invention, the production conditions of the hydrogen peroxide decomposition-treated water, etc. are the same as described above, The aspect of the hydrogen dissolution treatment apparatus, the type of water to be treated, the hydrogen dissolution water obtained by this apparatus, and the like are the same as those described in the description of the method for producing hydrogen dissolution water of the present invention.

  In the hydrogen-dissolved water producing apparatus 1 of the present invention, the hydrogen-dissolving treatment apparatus is provided on the upstream side or the downstream side of the apparatus for producing hydrogen peroxide decomposition treated water.

  In the hydrogen-dissolved water producing apparatus 1 of the present invention, the hydrogen-dissolving apparatus is provided immediately after the subsystem 4 of the ultra-pure water producing apparatus as shown in FIG. 2 (a) or 2 (b). A mode in which hydrogen is added to pure water is preferable, but a mode in which hydrogen is added to primary pure water by providing it immediately before the subsystem 4 (immediately after the primary pure water system 3) or just before the primary pure water system (before An embodiment may be provided immediately after the treatment system 2 to add hydrogen to the pretreatment water, or an embodiment may be provided immediately before the pretreatment system to add hydrogen to the raw water. Moreover, the aspect which provides hydrogen to the ultrapure water which added the chemical | medical agent by providing the hydrogen dissolution processing apparatus immediately after the chemical addition apparatus not shown provided in the back | latter stage of the subsystem 4 may be sufficient.

  The apparatus 1 for producing hydrogen-dissolved water of the present invention can be suitably used when carrying out the invention of the method for producing hydrogen-dissolved water of the present invention.

  An apparatus for producing hydrogen-dissolved water 1 of the present invention has the apparatus for producing hydrogen peroxide-decomposed water of the present invention, in which a platinum group metal is supported on a monolithic organic porous anion exchanger. Since the hydrogen peroxide is decomposed by the group-metal-supported catalyst, the contact efficiency with the water to be treated is markedly higher when hydrogen peroxide is decomposed than when a normal particulate anion exchange resin is used. Can be increased. In the apparatus for producing hydrogen-dissolved water of the present invention, since the platinum group metal-supported catalyst is used as the hydrogen peroxide decomposition treatment catalyst, the hydrogen peroxide decomposition ability can be remarkably increased, and the catalyst packed bed Even if the height is reduced, hydrogen-dissolved water can be produced while sufficiently decomposing and removing hydrogen peroxide in the water to be treated.

  The apparatus 2 for producing hydrogen-dissolved water of the present invention is installed so that the treatment tank 1 of the present invention and the membrane separation device are passed in this order, and is treated on the upstream side or the downstream side of the treatment tank 1. A hydrogen dissolution treatment apparatus for water is provided.

  In the hydrogen-dissolved water production apparatus 2 of the present invention, the details of the treatment tank 1 of the present invention, the production conditions of the hydrogen-dissolved water, the membrane separation apparatus, etc. are the same as described above, The aspect of the treatment apparatus, the type of water to be treated, the hydrogen-dissolved water obtained by this apparatus, and the like are the same as those described in the description of the method for producing hydrogen-dissolved water of the present invention.

  In the hydrogen-dissolved water production apparatus 2 of the present invention, the position where the treatment tank 1 is installed is the same as the installation position of the hydrogen peroxide decomposition treated water production apparatus described above, on the upstream side or downstream side of the treatment tank 1. The installation position of the hydrogen dissolution treatment apparatus provided is also the same as the installation position described above.

  The apparatus 3 for producing hydrogen-dissolved water of the present invention can be suitably used when carrying out the invention of the method for producing hydrogen-dissolved water of the present invention.

  The apparatus 3 for producing hydrogen-dissolved water according to the present invention includes the treatment tank 2 or the treatment tank 3 according to the present invention, and a hydrogen dissolution treatment apparatus for water to be treated on the upstream side or the downstream side of the treatment tank 2 or the treatment tank 3. It is characterized by.

  In the hydrogen-dissolved water production apparatus 3 of the present invention, the treatment tank 2 or the treatment tank 3 of the present invention and the production conditions of the hydrogen-dissolved water are the same as those described above. The kind of treated water, the hydrogen-dissolved water obtained by this apparatus, and the like are the same as those described in the description of the method for producing hydrogen-dissolved water of the present invention.

  In the hydrogen-dissolved water production apparatus 3 of the present invention, the position where the treatment tank 2 or the treatment tank 3 is installed is the position where the hydrogen-dissolved water production apparatus 1 is installed in the hydrogen-dissolved water production apparatus 1 of the present invention. Similarly, the installation position of the hydrogen dissolution treatment apparatus provided on the upstream side or the downstream side of the processing tank 2 or the processing tank 3 is the same as the above-described installation position.

  The apparatus 3 for producing hydrogen-dissolved water of the present invention can be suitably used when carrying out the invention of the method for producing hydrogen-dissolved water of the present invention.

  The hydrogen-dissolved water production apparatus 2 and the hydrogen-dissolved water production apparatus 3 of the present invention include a platinum group metal-supported catalyst and a non-regenerative ion exchange resin in addition to the effects obtained by the hydrogen-dissolved water production apparatus 1 of the present invention. Alternatively, since the monolithic organic porous ion exchanger or the treatment tank 1, the treatment tank 2 or the treatment tank 3 of the present invention in which the separation membrane is housed in the same container is used, The apparatus configuration can be simplified, the installation area can be reduced, and the processing tank can be easily replaced, particularly when the processing tank is in the form of a cartridge. Moreover, even if platinum group metals and fine particles are eluted from the platinum group metal supported catalyst, etc., they can be easily separated by filtration and removed by adsorption.

<Method for producing ozone-dissolved water>
Next, the method for producing ozone-dissolved water of the present invention will be described.

  The method for producing ozone-dissolved water of the present invention comprises a step of contacting a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger and hydrogen peroxide-containing water, and the platinum group metal. And a step of dissolving ozone in the treated water obtained by bringing the supported catalyst and the hydrogen peroxide-containing water into contact with each other.

  In the step of contacting the platinum group metal-supported catalyst and the hydrogen peroxide-containing water in the method for producing ozone-dissolved water of the present invention, the hydrogen peroxide-containing water, the method for contacting the platinum group metal and the hydrogen peroxide-containing water, The treatment conditions such as SV during water flow and the hydrogen peroxide decomposition treated water obtained are the same as those described in the description of the method for producing hydrogen peroxide decomposition treated water of the present invention.

  The step of dissolving ozone is performed as a subsequent step of the step of bringing the platinum group metal supported catalyst into contact with the hydrogen peroxide-containing water. The process of dissolving ozone is performed by a desired ozone dissolver after passing through the process of producing ultrapure water using the ultrapure water production apparatus 1 as shown in FIG. 2 (a) or 2 (b). However, the ozone dissolution step may be performed on primary pure water or water of lower quality, or may be performed on ultrapure water added with chemicals.

  As an ozone dissolution treatment apparatus that performs the ozone dissolution process, for example, as shown in FIG. 3B, a gas permeable film (not shown) is provided in the treatment line 13 of the water to be treated, and the ozone supply source 15 passes through the gas permeable film. An ozone dissolution treatment apparatus 12 having a structure for supplying and dissolving ozone is preferably used. As the ozone dissolution treatment apparatus 12 having such a structure, a fluororesin hydrophobic porous film in which the gas permeable film can withstand the strong oxidizing power of ozone is suitable. In addition, as an ozone dissolution treatment device, a device for bubbling and dissolving ozone gas in the water to be treated, a device for dissolving ozone gas by disassembling the ejector in the water to be treated, and an ozone gas upstream of a pump for supplying the water to be treated. An apparatus for supplying and dissolving by stirring in the pump can be mentioned, and ozone may be dissolved by these apparatuses.

  Examples of the ozone supply source 15 include an ozone generator by silent discharge, electrolysis, or the like, and the generated ozone gas is introduced into the ozone dissolution treatment apparatus through a pipe 16, for example.

  The dissolved ozone concentration in the ozone-dissolved water obtained by the method of the present invention is preferably 0.05 mg / L (0.05 ppm) or more, and preferably 1 mg / L (1 ppm) to 150 mg / L (150 ppm). More preferred. If the dissolved ozone concentration is less than 0.05 ppm, the redox potential of the ozone-dissolved water cannot be brought to a sufficient oxidation potential side. As a result, when ozone-dissolved water is used as the cleaning liquid, the desired cleaning effect is obtained. It becomes impossible to demonstrate.

  The ozone-dissolved water obtained by the method of the present invention is treated water obtained by contacting a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger and hydrogen peroxide-containing water. Therefore, the concentration of hydrogen peroxide in the ozone-dissolved water is low, and the degree of decrease in ozone concentration during pipe transfer can be reduced. Therefore, the half-life of the dissolved ozone concentration in the ozone-dissolved water obtained by the method of the present invention can be set to 4 minutes or more, for example.

  In the method for producing ozone-dissolved water of the present invention, the pH of the treated water for dissolving ozone is preferably acidic, and more preferably about pH 2-6. Under acidic conditions, the ozone life in the resulting ozone-dissolved water can be extended, so that more stable ozone-dissolved water can be obtained. Examples of the method for acidifying the pH of ultrapure water include a method of dissolving carbon dioxide in treated water during the production of ultrapure water. In the above method, carbon dioxide is not persistent and is low in cost. This is preferable.

  The method for producing ozone-dissolved water of the present invention comprises a step of contacting a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger and hydrogen peroxide-containing water. Since the hydrogen peroxide is decomposed by the group metal supported catalyst, the contact efficiency with the water to be treated is markedly higher when hydrogen peroxide is decomposed than when a normal particulate anion exchange resin is used. Can be increased. In the method for producing ozone-dissolved water according to the present invention, since the platinum group metal-supported catalyst is used as a hydrogen peroxide decomposition treatment catalyst, the hydrogen peroxide decomposition ability can be remarkably increased, and the catalyst packed bed Even if the height is reduced, ozone-dissolved water can be produced while sufficiently decomposing and removing hydrogen peroxide in the water to be treated.

<Ozone-dissolved water production equipment>
Next, the ozone dissolved water manufacturing apparatus of the present invention will be described.

  An apparatus for producing ozone-dissolved water 1 according to the present invention includes an apparatus for producing hydrogen peroxide-decomposed treated water according to the present invention and an ozone-dissolving treatment apparatus for water to be treated on the downstream side of the apparatus for producing hydrogen peroxide-decomposed treated water. It is characterized by being provided.

  In the ozone-dissolved water production apparatus 1 of the present invention, the preferred embodiment of the hydrogen peroxide decomposition treated water production apparatus of the present invention, the production conditions of the hydrogen peroxide decomposition treated water, etc. are the same as described above, The aspect of the ozone dissolution treatment apparatus, the type of water to be treated, the ozone dissolution water to be obtained, and the like are the same as those described in the description of the method for producing ozone dissolution water of the present invention.

  In the ozone-dissolved water producing apparatus 1 of the present invention, the ozone-dissolving treatment apparatus is provided on the downstream side of the apparatus for producing hydrogen peroxide decomposition treated water.

  In the ozone-dissolved water producing apparatus of the present invention, an ozone-dissolving treatment apparatus is provided immediately after the subsystem 4 of the apparatus for producing ultrapure water as shown in FIG. 2 (a) or 2 (b). An embodiment in which ozone is added to water is preferable. Moreover, the aspect which adds ozone to the ultrapure water which provided the ozone melt | dissolution processing apparatus immediately after the chemical addition apparatus not shown provided in the back | latter stage of the subsystem 4 and added the chemical | drug | medicine may be sufficient.

  The apparatus for producing ozone-dissolved water 1 of the present invention can be suitably used when carrying out the invention of the method for producing ozone-dissolved water of the present invention.

  The ozone-dissolved water producing apparatus 1 of the present invention is a downstream side of the hydrogen peroxide-decomposed treated water producing apparatus, further comprising a membrane separation device on the upstream side of the ozone-dissolving treatment apparatus. Alternatively, the ion exchange may further include a non-regenerative ion exchange resin or a monolithic organic porous ion exchanger on the downstream side of the hydrogen peroxide decomposition treatment water production apparatus and on the upstream side of the ozone dissolution treatment apparatus. A tank and a membrane separation device may be provided in this order.

  Examples of the membrane separation device include the same ones as described above. Further, the non-regenerative ion exchange resin or monolithic organic porous ion exchanger contained in the ion exchange tank may be the same as described above.

  Since the ozone-dissolved water production apparatus 1 of the present invention has a membrane separation apparatus, platinum group metals and fine particles are obtained from a platinum group metal supported catalyst, a non-regenerative ion exchange resin, or a monolithic organic porous ion exchanger. Even in the case of elution, it can be easily separated by filtration.

  An apparatus for producing ozone-dissolved water 1 according to the present invention includes the apparatus for producing hydrogen peroxide decomposition treated water according to the present invention, wherein a platinum group metal is supported on a monolithic organic porous anion exchanger. Since the hydrogen peroxide is decomposed by the group metal supported catalyst, the contact efficiency with the water to be treated is markedly higher when hydrogen peroxide is decomposed than when a normal particulate anion exchange resin is used. Can be increased. In the ozone dissolved water production apparatus 1 of the present invention, since the platinum group metal-supported catalyst is used as the hydrogen peroxide decomposition treatment catalyst, the hydrogen peroxide decomposition ability can be remarkably increased, Even if the layer height is reduced, ozone-dissolved water can be produced while sufficiently decomposing and removing hydrogen peroxide in the water to be treated.

  An apparatus for producing ozone-dissolved water 2 according to the present invention installs the treatment tank 1 of the present invention and a membrane separator so as to pass water in this order, and an ozone-dissolve treatment apparatus downstream of the membrane separator. It is characterized by providing.

  An apparatus for producing ozone-dissolved water 2 according to the present invention is a treatment tank 1 in place of the apparatus for producing hydrogen peroxide-decomposed treated water according to the present invention, wherein a platinum group metal is supported on a monolithic organic porous anion exchanger. Except that the platinum group metal-supported catalyst and the non-regenerative ion exchange resin or monolithic organic porous ion exchanger are disposed in the same container as essential components. This is the same as the ozone dissolved water production apparatus 1. Moreover, the detail of the processing tank 1 is as having mentioned above.

  The apparatus for producing ozone-dissolved water 3 of the present invention is characterized in that the treatment tank 2 of the present invention and an ozone dissolution treatment apparatus are provided on the downstream side of the treatment tank.

  The apparatus for producing ozone-dissolved water 3 according to the present invention is a treatment tank 2 in which a platinum group metal is supported on a monolithic organic porous anion exchanger, instead of the apparatus for producing hydrogen peroxide-decomposed treated water according to the present invention. Except that a platinum group metal supported catalyst, a non-regenerative ion exchange resin or monolithic organic porous ion exchanger, and a separation membrane arranged in the same container are essential constituent uses, This is the same as the ozone dissolved water production apparatus 1 of the present invention. Moreover, the detail of the processing tank 2 is as having mentioned above.

  The specific aspect of the manufacturing apparatus 3 of the ozone dissolved water of this invention is shown in FIG.

  In the left figure of FIG. 4, the to-be-processed water supplied from the outside is supplied to a processing tank (the enlarged view of a processing tank is shown on the right of FIG. 4). As shown in FIG. 4, the treatment tank comprises a platinum group metal supported catalyst α, a non-regenerative ion exchange resin or monolithic organic porous ion exchanger β, and a separation membrane γ with respect to the water to be treated. It arrange | positions in the same container so that it may contact in order. The water that has passed through the treatment tank is mixed with ozone supplied from the ozone supply source 15 in the ozone dissolution treatment device 12 to produce ozone-dissolved water.

  The apparatus for producing ozone-dissolved water 4 of the present invention is characterized in that the treatment tank 3 of the present invention and an ozone dissolution treatment apparatus are provided on the downstream side of the treatment tank.

  The ozone-dissolved water production apparatus 4 of the present invention is a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger, instead of the hydrogen peroxide decomposition-treated water production apparatus of the present invention. And the separation membrane and the treatment tank 3 arranged in the same container so as to come into contact with the water to be treated in this order, except that the essential component is the production of the ozone-dissolved water of the present invention. It is the same as the device 1. Examples of the separation membrane used in the ozone dissolved water production apparatus 4 of the present invention include the same ones as described above.

  A platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger and a separation membrane are arranged in the same container so as to come into contact with the water to be treated in this order. The details of the treatment tank 3 are as described above. For example, in the treatment tank shown in FIG. 1 (d) or FIG. 1 (e), the platinum group metal-supported catalyst α and the non-regenerative ion exchange resin or Examples of the monolithic organic porous ion exchanger β may include those in which the laminated portion is entirely composed of a platinum group metal-supported catalyst α and those shown in FIG.

  The ozone-dissolved water manufacturing apparatus 2 of the present invention, the ozone-dissolved water manufacturing apparatus 3 of the present invention, and the ozone-dissolved water manufacturing apparatus 4 of the present invention are a treatment tank in which a platinum group metal supported catalyst or the like is accommodated in the same container. In addition to the effects obtained with the ozone dissolved water manufacturing apparatus 1 of the present invention, the apparatus configuration of the ozone dissolved water manufacturing apparatus can be simplified, the installation area can be reduced, In the case where the treatment tank is in the form of a cartridge, the effect of reducing the labor for replacement can be achieved. The ozone-dissolved water production apparatus 3 of the present invention and the ozone-dissolved water production apparatus 4 of the present invention use the treatment tank 2 or the treatment tank 3 of the present invention in which a separation membrane is housed in the container. Therefore, in addition to the above effects, even if platinum group metals and fine particles elute from platinum group metal supported catalysts, non-regenerative ion exchange resins or monolithic organic porous ion exchangers, they can be filtered easily. The effect that it can be separated is exhibited.

<Cleaning method for electronic parts>
Next, the electronic component cleaning method of the present invention will be described.

  The electronic component cleaning method of the present invention includes a cleaning water containing a hydrogen peroxide decomposing water obtained by the method for producing hydrogen peroxide decomposing water of the present invention or the hydrogen peroxide decomposing water of the present invention, Obtained by the method for producing ultrapure water of the invention or the cleaning water containing ultrapure water obtained by the apparatus for producing ultrapure water of the present invention, the method for producing hydrogen-dissolved water of the present invention, or the apparatus for producing hydrogen-dissolved water of the present invention The cleaning water containing hydrogen-dissolved water or the ozone-dissolved water manufacturing method of the present invention or the ozone-dissolved water-containing cleaning water obtained by the ozone-dissolved water manufacturing apparatus of the present invention, The surface is washed.

  Details of the method for producing hydrogen peroxide-decomposed treated water of the present invention or the method for obtaining hydrogen peroxide-decomposed treated water by the apparatus for producing hydrogen peroxide-decomposed treated water of the present invention, the method for producing ultrapure water of the present invention or the present invention Details of the method for obtaining ultrapure water by the apparatus for producing ultrapure water of the present invention, details of the method for producing hydrogen dissolved water of the present invention or the method for obtaining hydrogen dissolved water by the apparatus for producing hydrogen dissolved water of the present invention, ozone of the present invention About the detail of the method of obtaining ozone dissolved water with the manufacturing method of dissolved water or the manufacturing apparatus of ozone dissolved water of this invention, it is the same as that of the content mentioned above.

   An example of the electronic component cleaning method of the present invention will be described with reference to FIGS. FIG. 5 is a schematic flow diagram of the first embodiment of the electronic component cleaning method of the present invention, and FIG. 6 is a schematic flow of the second embodiment of the electronic component cleaning method of the present invention. FIG.

  As shown in FIG. 5, the first embodiment of the electronic component cleaning method of the present invention includes a first step 21 for cleaning an object to be cleaned by contacting the object to be cleaned with ozone-dissolved water, and hydrogen. A second step 22 in which the object to be cleaned is brought into contact with dissolved water and the object to be cleaned is washed while applying vibration of 500 kHz or more, and the object to be cleaned is brought into contact with water containing hydrofluoric acid and hydrogen peroxide. The third step 23 for cleaning the object to be cleaned and the fourth step 24 for cleaning the object to be cleaned while bringing the object to be cleaned into contact with hydrogen-dissolved water and applying vibrations of 500 kHz or higher.

  The cleaning water supplied to the first step 21 is ozone-dissolved 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 of the present invention, before the ozone 33 is dissolved in the ultrapure water 32, the hydrogen peroxide decomposition treated water of the present invention is treated with the ultrapure water 32 as the water to be treated. A hydrogen peroxide removing step 25 for applying the manufacturing method is performed, and ozone 33 is dissolved in the obtained treated water and supplied as the cleaning water in the first step 21.

  The cleaning water supplied to the second step 22 is hydrogen-dissolved water prepared by dissolving hydrogen in the ultrapure water 32. Therefore, in the first embodiment of the electronic component cleaning method of the present invention, before the hydrogen 34 is dissolved in the ultrapure water 32, the hydrogen peroxide decomposition treated water of the present invention is treated with the ultrapure water 32 as the water to be treated. A hydrogen peroxide removal step 26 for applying the manufacturing method 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 of the present invention, in the fourth step 24, before the hydrogen 36 is dissolved in the ultrapure water 32, the ultrapure water 32 is used as the water to be treated. A hydrogen peroxide removal step 28 for applying a method for producing hydrogen oxide decomposition treated water is performed, 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.

  In the first embodiment of the electronic component cleaning method of the present invention, the hydrogen peroxide removal step 27 is performed in which the method for producing hydrogen peroxide decomposition treated water of the present invention is performed using ultrapure water 32 as the water to be treated. 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 can be supplied as cleaning water in the third step 23. .

  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. 6, the second embodiment of the electronic component cleaning method of the present invention is a first embodiment for cleaning an object to be cleaned by bringing the object to be cleaned into contact with a liquid containing sulfuric acid and hydrogen peroxide. A first step 41, a second step 42 for rinsing with ultrapure water, and a third step for cleaning the object to be cleaned by bringing the object to be cleaned into contact with water containing hydrofluoric acid (dilute hydrofluoric acid) 43, a fourth process 44 for rinsing with ultrapure water, a fifth process 45 for cleaning the object to be cleaned by bringing the object to be cleaned into contact with water containing ammonia and hydrogen peroxide, and ultrapure water A sixth process 46 for rinsing with water, a seventh process 47 for cleaning the object to be cleaned by bringing the object to be cleaned into contact with heated ultrapure water, an eighth process 48 for rinsing with ultrapure water, and hydrochloric acid. And a ninth step 49 for cleaning the cleaning object by bringing the cleaning object into contact with water containing 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 water 63, 65, 69, and 71 supplied to the third step 43, the fifth step 45, the ninth step 49, and the eleventh step 51 in FIG. 6 dissolves the chemicals required in each step in ultrapure water. Water. Therefore, in the second embodiment of the electronic component cleaning method of the present invention as shown in FIG. 6, as in the first embodiment of the electronic component cleaning method of the present invention as shown in FIG. Before dissolving the chemicals required in each process in ultrapure water, perform the hydrogen peroxide removal process in which the method for producing hydrogen peroxide decomposition treated water of the present invention is performed using ultrapure water as the water to be treated, and the resulting treatment It is preferable that chemicals required in each step are dissolved in water and supplied as cleaning water (cleaning liquid) in each step.

  In addition, the cleaning water 62, 64 supplied to the second step 42, the fourth step 44, the sixth step 46, the seventh step 47, the eighth step 48, the tenth step 50, and the twelfth step 52 in FIG. 66, 67, 68, 70 and 72 are ultrapure water. Therefore, in the second embodiment of the electronic component cleaning method of the present invention, the hydrogen peroxide removing step is performed by applying the method for producing hydrogen peroxide decomposition treated water of the present invention using ultrapure water as water to be treated. It is preferable to supply the treated water as washing water for each step.

  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.

  In each of the above-described embodiments, when the ultrapure water manufacturing method of the present invention is applied to obtain cleaning water (treated water) containing ultrapure water, it is preferable to use the ultrapure water manufacturing apparatus of the present invention.

When using ultrapure water to which a chemical is added as the washing water,
Examples thereof include hydrofluoric acid, hydrochloric acid, carbonic acid, ammonia, TMAH (tetramethylammonium hydroxide), and choline.

<Platinum group metal supported catalyst>
Next, the method for producing hydrogen peroxide decomposition treated water of the present invention, the apparatus for producing hydrogen peroxide decomposition treated water, the method for producing ultrapure water, the apparatus for producing ultrapure water, the method for producing hydrogen dissolved water, the hydrogen dissolved water Commonly used in manufacturing apparatus, ozone-dissolved water manufacturing apparatus, ozone-dissolved water manufacturing apparatus, and electronic component cleaning method, a platinum group metal supported on a monolithic organic porous anion exchanger The catalyst will be described.

  Examples of the platinum group metal supported catalyst include those in which platinum group metal nanoparticles are supported on a monolithic organic porous anion exchanger.

  Hereinafter, a preferred embodiment of the platinum group metal supported catalyst will be described. In the present application documents, “monolithic organic porous material” is simply referred to as “monolith”, and “monolithic organic porous anion exchanger” is simply referred to as “ The “monolith anion exchanger” and the “monolithic organic porous intermediate” are simply referred to as “monolith intermediate”.

<Monolith anion exchanger>
In a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolith anion exchanger, the monolith anion exchanger serving as a carrier is obtained by introducing an anion exchange group into the monolith.

  Examples of the monolith anion exchanger include a first monolith anion exchanger to a fourth anion exchanger described in detail below.

(First monolith anion exchanger)
In the first monolith anion exchanger, bubble-like macropores overlap each other, and the overlapping portion is in a dry state with a common opening (mesopore) having an average diameter of 1 to 1000 μm, preferably 10 to 200 μm, more preferably 20 to 100 μm. 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 mesopore average diameter of the first monolith anion exchanger is larger than the average diameter of the monolith mesopore 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 will be extremely large, which is not preferable. If the average diameter in the dry state of the mesopores exceeds 1000 μm, This is not preferable because contact with the monolith anion exchanger 1 is insufficient, and the hydrogen peroxide decomposition characteristics are deteriorated. When the structure of the first monolith anion exchanger is an open cell structure as described above, the macropore group and the mesopore group can be uniformly formed, and the particle aggregation as described in JP-A-8-252579 is also possible. The pore volume and specific surface area can be remarkably increased compared to the type porous body. In the first monolith anion exchanger, the average diameter of the opening of the monolith in the dry state and the average diameter of the opening of the monolith anion exchanger in the dry state are values measured by a mercury intrusion method. The average diameter of the opening of the first monolith anion exchanger water humid conditions, the average diameter of the opening of the first monolith anion exchanger in the dry state is a value calculated by multiplying the swelling ratio. Specifically, the water humid state first diameter of the monolith anion exchanger is X _{1 (mm),} the water humid state monolith anion exchanger is dried, first in the dry state obtained in When the diameter of the monolith anion exchanger is Y ₁ (mm), and the average diameter of the opening when the dried first monolith anion exchanger is measured by the mercury intrusion method is Z ₁ (μm), The average diameter (μm) of the opening of the first monolith anion exchanger in the water wet state is expressed by the following formula: “average diameter of the opening of the first monolith anion exchanger in the water wet state (μm) = Z ₁ × (X ₁ / Y ₁ ) ”. The average diameter of the opening of the monolith a dry state prior introduction anion exchange group, and the first monolith anion exchanger water humid state for monolith dry state when introduced monolith anion exchange groups of the dry If swelling ratio can be known, can the average diameter of the opening in the monolith in a dry state, by multiplying the swelling ratio, also possible to calculate the average diameter of the opening of the first monolith anion exchanger water humid conditions.

  The total pore volume of the first monolith anion exchanger is 1-50 ml / g, preferably 2-30 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 first 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 and the first monolith anion exchanger and the platinum group metal nanoparticles supported thereon decreases, the catalytic effect also decreases, 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. The total pore volume of the 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 1st monolith anion exchanger is the pressure loss at the time of water-flowing at the water velocity (LV) of 1 m / h to the column packed with this 1m (henceforth, " The pressure differential coefficient is preferably 0.005 to 0.5 MPa / m · LV, and particularly preferably 0.005 to 0.05 MPa / m · LV.

  The anion exchange capacity per weight of the first monolith anion exchanger in the dry state 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 is lowered, and the hydrogen peroxide decomposition property is lowered, which 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 first monolith anion exchanger due to the change of the ion form becomes remarkably large. Since the first monolith anion exchanger is cracked or crushed, it is not preferable. In addition, the anion exchange capacity per volume of the first monolith anion exchanger in a water-wet state is not particularly limited, but 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 first monolith anion exchanger, 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. There is no restriction | limiting in particular in the kind of said polymer material, For example, Polyvinyl, Polypropylene, Polypropylene, Polypropylene, Polypropylene, Polypropylene, Polypropylene, Polypropylene, Polypropylene, Polypropylene, Polypropylene, Polypropylene, 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 first monolith anion exchanger 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. , Tertiary sulfonium group, phosphonium group and the like.

  In the first monolith anion exchanger, 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 first monolith anion exchanger)
The production method of the first monolith anion exchanger is not particularly limited, and is a method in which a component containing an anion exchange group is converted into a monolith anion exchanger in one step, a monolith is formed by a component not containing an anion exchange group, and then And a method of introducing an anion exchange group. 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 resulting monolith anion exchanger. Since quantitative 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, in this method, an oil-soluble monomer that does not contain an anion exchange group, a surfactant, water and, if necessary, a polymerization initiator are mixed to obtain a water-in-oil emulsion, which is polymerized to be porous. After forming the body, 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, a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate is selected as at least one component of the oil-soluble monomer, and the content thereof is 0.3 to 10 mol%, preferably 0.3 in the total oil-soluble monomer. It is preferable to set it to ˜5 mol% in that an anion exchange group can be quantitatively introduced in a later step and a practically sufficient mechanical strength can be secured.

  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.

(Second monolith anion exchanger)
The second monolith anion exchanger is obtained by introducing an anion exchange group into the particle aggregation type monolith. The basic structure of the second monolith anion exchanger is a skeletal portion in which organic polymer particles having an average particle diameter of 1 to 50 μm, preferably 1 to 30 μm in a water-wet state, having a crosslinked structural unit are aggregated to be three-dimensionally continuous. And a particle aggregation type structure having three-dimensionally continuous pores having an average diameter of 20 to 100 μm, preferably 20 to 90 μm in a water-wet state between the skeletons. A hole becomes a flow path of liquid or gas. If the average particle diameter of the organic polymer particles is less than 1 μm in the water-wet state, the average diameter of the continuous pores between the skeletons will be less than 20 μm in the water-wet state, which is not preferable. The contact between the treated water and the monolith anion exchanger becomes insufficient, and as a result, the hydrogen peroxide decomposition effect is lowered, which is not preferable. Further, if the average diameter of the three-dimensionally continuous pores existing between the skeletons is less than 20 μm in the water-wet state, it is not preferable because the pressure loss when the treated water is permeated increases. If the thickness exceeds 100 μm, the contact between the water to be treated and the second monolith anion exchanger becomes insufficient, and the hydrogen peroxide decomposition effect decreases, which is not preferable.

In the present invention, the average particle size of the organic polymer particles in a wet state with water is easily measured by using SEM. Specifically, first, an SEM photograph of an arbitrarily extracted portion of the cross section of the second monolith anion exchanger in the dry state is taken, and the diameters of the organic polymer particles of all the particles in the SEM photograph are measured and dried. The average particle size of the organic polymer particles in the second monolith anion exchanger in the state is measured. Next, the average particle size of the organic polymer particles in the second monolith anion exchanger in the wet state is calculated by multiplying the average particle size of the obtained organic polymer particles in the dry state by the swelling rate. For example, the diameter of the second monolith anion exchanger in the water wet state is X _2a (mm), the second monolith anion exchanger in the water wet state is dried, and the resulting second monolith anion in the dry state is obtained. When the diameter of the exchanger is Y _2a (mm), an SEM photograph of the cross section of the dried second monolith anion exchanger is taken, and the diameter of the organic polymer particles of all particles in the SEM photograph is measured. Assuming that the average particle size is Z _2a (μm), the average particle size (μm) of the organic polymer particles in the second monolith anion exchanger in the water wet state is expressed by the following formula “second monolith in the water wet state”. The average particle diameter of organic polymer particles in the anion exchanger (μm) = Z _2a × (X _2a / Y _2a ) ”is calculated. Further, the average particle diameter of the organic polymer particles in the dry monolith before the introduction of the anion exchange group, and the second monolith anion in the water wet state relative to the dry monolith when the anion exchange group is introduced into the monolith in the dry state If the swelling ratio of the exchanger is known, the average particle diameter of the organic polymer particles in the second monolith anion exchanger in the water wet state is obtained by multiplying the average particle diameter of the organic polymer particles in the dry monolith by the swelling ratio. The diameter can also be calculated.

The average diameter of the three-dimensional continuous pores existing between the skeletons of the dried monolith and the average diameter of the three-dimensional continuous pores existing between the skeletons of the second monolith anion exchanger in the dry state are It is obtained by the mercury intrusion method and indicates the maximum value of the pore distribution curve obtained by the mercury intrusion method. In addition, the average diameter of the three-dimensionally continuous pores existing between the skeletons of the second monolith anion exchanger in the water wet state is the three-dimensional dimension existing between the skeletons of the second monolith anion exchanger in the dry state. This is a value calculated by multiplying the average diameter of continuous pores by the swelling rate. Specifically, the diameter of the second monolith anion exchanger in the water wet state is X _2b (mm), the second monolith anion exchanger in the water wet state is dried, and the second in the dry state obtained is obtained. The diameter of the monolith anion exchanger is Y _2b (mm), and the second monolith anion exchanger in the dry state is measured by the mercury intrusion method, and the three-dimensional continuous pores existing between the skeletons are measured. Assuming that the average diameter is Z _2b (μm), the average diameter (μm) of three-dimensionally continuous pores existing between the skeletons of the second monolith anion exchanger in the water wet state is expressed by the following formula: “water The average diameter (μm) of three-dimensionally continuous pores existing between the skeletons of the monolith anion exchanger in a wet state is calculated by “Z _2b × (X _2b / Y _2b )”. In addition, the average diameter of three-dimensional continuous pores existing between the skeletons of the dried monolith before introduction of the anion exchange group, and the dry monolith when the anion exchange group is introduced into the dried monolith When the swelling ratio of the second monolith anion exchanger in the water wet state is known, the average diameter of three-dimensionally continuous pores existing between the skeletons of the monolith in the dry state is multiplied by the swelling ratio to It is also possible to calculate the average diameter of three-dimensionally continuous pores existing between the skeletons of the second monolith anion exchanger in the state.

  The total pore volume of the second monolith anion exchanger is 1-5 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 5 ml / g, the ion exchange capacity per volume of the second monolith anion exchanger decreases, and the amount of platinum group metal supported per volume decreases. The total pore volume of the monolith (monolith, monolith anion exchanger) is determined 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.

  The pressure loss when water is permeated through the second monolith anion exchanger is the pressure loss (hereinafter referred to as “differential pressure”) when water is passed through a column packed with 1 m at a water flow velocity (LV) of 1 m / h. It is preferably 0.005 to 0.1 MPa / m · LV, and particularly preferably 0.005 to 0.05 MPa / m · LV. If the differential pressure coefficient and the total pore volume are in the above ranges, when this is used as a catalyst, the contact area with the water to be treated is large, and the water to be treated can be smoothly circulated. Can be demonstrated.

  In the second monolith anion exchanger, the material of the skeleton part in which the organic polymer particles are aggregated and three-dimensionally continuous is an organic polymer material having a crosslinked structural unit. That is, the organic polymer material has a constitutional unit composed of a vinyl monomer and a cross-linking agent structural unit having two or more vinyl groups in the molecule, and the polymer material comprises all the constitutions constituting the polymer material. 1 to 5 mol%, preferably 1 to 4 mol% of a crosslinked structural unit is contained with respect to the unit. When the cross-linking structural unit is less than 1 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, when it exceeds 5 mol%, the pore diameter that exists three-dimensionally continuously between the skeletons is reduced. Therefore, the pressure loss increases, which is not preferable.

  The type of the polymer material is not particularly limited, and examples thereof include styrene-based polymers such as polystyrene, poly (α-methylstyrene), and polyvinylbenzyl chloride; polyolefins such as polyethylene and polypropylene; polymers such as polyvinyl chloride and polytetrafluoroethylene. (Halogenated polyolefin); nitrile polymers such as polyacrylonitrile; (meth) acrylic polymers such as polymethyl methacrylate, polyglycidyl methacrylate, and polyethyl acrylate; styrene-divinylbenzene copolymer, vinylbenzyl chloride-divinyl A benzene copolymer etc. are mentioned. The polymer may be a polymer obtained by copolymerizing a single monomer and a crosslinking agent, or may be a polymer obtained by polymerizing a plurality of monomers and a crosslinking agent, and two or more kinds of polymers are blended. It may be a thing. Among these organic polymer materials, styrene-divinylbenzene copolymer is used because of its easy formation of particle aggregate structure, ease of ion exchange group introduction and high mechanical strength, and high stability against acid or alkali. Preferred materials include a polymer and a vinylbenzyl chloride-divinylbenzene copolymer.

  The anion exchange capacity of the second monolith anion exchanger is 0.3 to 1.0 mg equivalent / ml per volume in a water wet state. In the monolithic organic porous anion exchanger having an open cell structure as described in JP-A No. 2002-306976, the anion exchange capacity per volume is lowered when trying to achieve a practically required low pressure loss. However, when the exchange capacity per volume is increased, the pressure loss increases. However, the second monolith anion exchanger has an anion exchange capacity per volume while keeping the pressure loss low. Can be significantly increased. When the ion exchange capacity per volume is less than 0.3 mg equivalent / ml, the amount of platinum group metal nanoparticles supported per volume decreases, which is not preferable. On the other hand, when the anion exchange capacity per volume exceeds 1.0 mg equivalent / ml, the volume change of the swelling and shrinkage of the second monolith anion exchanger due to the change of the ionic form becomes remarkably large. Since the monolith anion exchanger is cracked or crushed, it is not preferable. The anion exchange capacity per dry weight of the second monolith anion exchanger is not particularly limited. However, since the anion exchange groups are uniformly introduced to the surface of the porous body and the inside of the skeleton, 3 to 5 mg equivalent / The value of g is shown. The ion exchange capacity of the porous body in which the ion exchange group is introduced only on the surface is 500 μg equivalent / g at most, although it cannot be generally determined depending on the kind of the porous body or the ion exchange group. Examples of the anion exchange group of the second monolith anion exchanger include the same ones as mentioned in the description of the first monolith anion exchanger.

  In addition, the distribution of anion exchange groups, the meaning of “anion exchange groups are uniformly distributed”, the method for confirming the distribution of anion exchange groups, and the anion exchange groups are porous as well as the surface of the monolith. The effect of uniform distribution even inside the body skeleton is the same as that of the first monolith anion exchanger.

(Method for producing second monolith anion exchanger)
A monolith anion exchanger is produced by mixing a vinyl monomer, a specific amount of a crosslinking agent, an organic solvent and a polymerization initiator and polymerizing the mixture in a stationary state (particle-aggregated monolithic organic porous material). The material) may be a method of introducing an anion exchange group.

  The vinyl monomer is not particularly limited as long as it is a lipophilic monomer that contains a polymerizable vinyl group in the molecule and has high solubility in an organic solvent. Specific examples of these vinyl monomers include styrene monomers such as styrene, α-methylstyrene, vinyl toluene, and vinyl benzyl chloride; α-olefins such as ethylene, propylene, 1-butene, and isobutene; butadiene, isoprene, chloroprene, and the like. Diene monomers; 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 and Acrylic Ethyl acetate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate And (meth) acrylic monomers such as benzyl methacrylate and glycidyl methacrylate. These monomers are used singly or in combination of two or more. The vinyl monomer suitably used in the present invention is a styrene monomer such as styrene or vinyl benzyl chloride.

  The cross-linking agent preferably 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, butanediol diacrylate, and the like. These crosslinking agents are used singly or in combination of two or more. Preferred cross-linking agents are aromatic polyvinyl compounds such as divinylbenzene, divinylnaphthalene and divinylbiphenyl because of their high mechanical strength and stability to hydrolysis. The amount of crosslinking agent used ({crosslinking agent / (vinyl monomer + crosslinking agent)} × 100) relative to the total amount of vinyl monomer and crosslinking agent is 1 to 5 mol%, preferably 1 to 4 mol%. The use amount of the crosslinking agent has a great influence on the porous structure of the resulting monolith, and if the use amount of the crosslinking agent exceeds 5 mol%, the size of the continuous pores formed between the skeletons is preferably reduced. Absent. On the other hand, when the amount of the crosslinking agent used is less than 1 mol%, the mechanical strength of the porous body is insufficient, and it is not preferable because it deforms greatly during water passage or causes the porous body to break. The organic solvent is an organic solvent that dissolves the vinyl monomer and the crosslinking agent but does not dissolve the polymer formed by polymerization of the vinyl monomer, in other words, a poor solvent for the polymer formed by polymerization of the vinyl monomer. Since the organic solvent varies greatly depending on the type of vinyl monomer, it is difficult to list general specific examples. For example, when the vinyl monomer is styrene, the organic solvent includes methanol, ethanol, propanol, butanol, Hexanol, cyclohexanol, octanol, 2-ethylhexanol, decanol, dodecanol, alcohols such as ethylene glycol, tetramethylene glycol, glycerin; chain ethers such as diethyl ether, ethylene glycol dimethyl ether; hexane, octane, decane, dodecane, etc. And the like. Among these, alcohols are preferable because the particle aggregation structure is easily formed by stationary polymerization and the three-dimensional continuous pores are increased. Moreover, even if it is a good solvent of polystyrene like benzene and toluene, it is used with the said poor solvent, and when the usage-amount is small, it is used as an organic solvent.

  As the polymerization initiator, a compound that generates radicals by heat and light irradiation is preferable. The polymerization initiator is preferably oil-soluble. Specific examples of the polymerization initiator include 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylbutyronitrile). Nitrile), 2,2'-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2'-azobisisobutyrate, 4,4'-azobis (4-cyanovaleric acid), 1,1 ' -Azobis (cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, tetramethylthiuram disulfide and the like. The amount of polymerization initiator used varies greatly depending on the type of monomer, polymerization temperature, etc., but the amount of polymerization initiator used relative to the total amount of vinyl monomer and crosslinking agent ({polymerization initiator / (vinyl monomer + crosslinking agent)} × 100) is about 0.01 to 5 mol%.

  Various conditions can be selected as polymerization conditions depending on the type of monomer and the type of initiator. For example, when 2,2'-azobis (isobutyronitrile), 2,2'-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, etc. are used as initiators In a sealed container under an inert atmosphere, heat polymerization may be performed at 30 to 100 ° C. for 1 to 48 hours. After completion of the polymerization, the content is taken out and extracted with a solvent such as acetone to obtain a monolith for the purpose of removing unreacted vinyl monomer and organic solvent.

  In the production of monolith, if the polymerization of the vinyl monomer dissolved in the organic solvent proceeds under a fast condition, the organic polymer particles having an average particle diameter of 1 μm settle and aggregate to form a three-dimensional continuous skeleton portion. it can. The conditions under which the polymerization of the vinyl monomer proceeds rapidly vary depending on the vinyl monomer, the crosslinking agent, the polymerization initiator, the polymerization temperature, etc., but cannot be determined unconditionally, but increase the crosslinking agent, increase the monomer concentration, increase the temperature, etc. is there. Taking such polymerization conditions into consideration, the polymerization conditions for aggregating organic polymer particles having an average particle diameter of 1 to 50 μm may be appropriately determined. In addition, in order to form three-dimensionally continuous pores having an average diameter of 20 to 100 μm between the skeletons, as described above, the amount of crosslinking agent used should be a specific amount with respect to the total amount of vinyl monomer and crosslinking agent. That's fine. Moreover, in order to set the total pore volume of the monolith to 1 to 5 ml / g, depending on the vinyl monomer, the crosslinking agent, the polymerization initiator, the polymerization temperature, etc. If the amount of organic solvent used relative to the total amount used ({organic solvent / (organic solvent + monomer + crosslinking agent)} × 100) is polymerized under conditions such as 30 to 80% by weight, preferably 40 to 70% by weight Good. The method for introducing an anion exchange group into the monolith thus obtained is not particularly limited, and examples thereof include the same method as described in the description of the method for producing the first monolith anion exchanger. Specific examples of the anion exchange group are as described above.

(Third monolith anion exchanger)
The third monolith anion exchanger is obtained by introducing an anion exchange group into the monolith. The macroscopic pores overlap each other, and the overlapping portion has an average diameter of 30 to 300 μm, preferably 30 when wet. A continuous macropore structure having an opening (mesopore) of ˜200 μm, particularly preferably 40˜100 μm. The average diameter of the opening of the third monolith anion exchanger is larger than the average diameter of the opening of the monolith because the whole monolith swells when an anion exchange group is introduced into the monolith. It is not preferable that the average diameter of the openings in the water-wet state is less than 30 μm, because the pressure loss during water passage increases, and it is not preferable. 3 is not preferable because contact with the monolith anion exchanger 3 and the supported platinum group metal nanoparticles becomes insufficient, resulting in deterioration of hydrogen peroxide decomposition characteristics. The average diameter of the opening of the monolith intermediate in the dry state, the average diameter of the opening of the monolith in the dry state, and the average diameter of the opening of the monolith anion exchanger in the dry state mean values measured by the mercury intrusion method. In addition, the average diameter of the openings of the third monolith anion exchanger in the wet state is a value calculated by multiplying the average diameter of the openings of the third monolith anion exchanger in the dry state by the swelling rate. Specifically, the diameter of the third monolith anion exchanger in the water wet state is X ₃ (mm), the third monolith anion exchanger in the water wet state is dried, and the third in the dry state obtained is obtained. The diameter of the monolith anion exchanger is Y ₃ (mm), and the average diameter of the opening when the dried third monolith anion exchanger is measured by the mercury intrusion method is Z ₃ (μm). The average diameter (μm) of the opening of the third monolith anion exchanger in the water wet state is expressed by the following formula: “average diameter of the opening of the monolith anion exchanger in the water wet state (μm) = Z ₃ × (X ₃ / Y ₃ ) ”. Further, the average diameter of the opening of the dried monolith before the introduction of the anion exchange group, and the swelling of the third monolith anion exchanger in the wet state with respect to the dried monolith when the anion exchange group is introduced into the dried monolith When the ratio is known, the average diameter of the opening of the monolith in the dry state can be multiplied by the swelling ratio to calculate the average diameter of the opening of the third monolith anion exchanger in the water wet state.

  In the third monolith anion exchanger, in the SEM image of the cut surface of the continuous macropore structure, the skeleton part area appearing in the cross section is 25 to 50%, preferably 25 to 45% in the image region. When the area of the skeletal part appearing in the cross section is less than 25% in the image region, the skeleton becomes a thin skeleton, the mechanical strength is lowered, and the monolith anion exchanger is greatly deformed particularly when water is passed at a high flow rate. Therefore, it is not preferable. Furthermore, the contact efficiency between the water to be treated and the third 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 thick. This is not preferable because the pressure loss during water passage increases.

  In addition, the monolith described in JP-A-2002-306976 is actually limited to the blending ratio in order to ensure a common opening even if the blending ratio of the oil phase part with respect to water is increased and the skeleton portion is thickened. The maximum value of the skeleton part area appearing in the cross section cannot exceed 25% in the image region.

  The conditions for obtaining the SEM image may be any conditions as long as the skeletal portion appearing in the cross section of the cut surface appears clearly. For example, the magnification is 100 to 600 times, and the photographic area is about 150 mm × 100 mm. The SEM observation is preferably performed on three or more images, preferably five or more images, taken at arbitrary locations on an arbitrary cut surface of the monolith excluding subjectivity and at different locations. The monolith to be cut is in a dry state for use in an electron microscope. FIG. 13A shows a skeleton portion of a cut surface in an SEM image, and FIG. 13A is described with reference to FIG. FIG. 13B is a transcribed skeleton that appears as a cross section of the SEM photograph of FIG. In FIG. 13A and FIG. 13B, what is substantially indeterminate in shape and shown in cross section is the “skeleton part (reference numeral 82)” in the present invention, and circular holes appearing in FIG. 13A. Is an opening (mesopore), and a relatively large curvature or curved surface is a macropore (reference numeral 83 in FIG. 13B). The area of the skeleton part that appears in the cross section of FIG. 13B is 28% in the rectangular image region 81. Thus, the skeleton can be clearly determined.

  In the SEM image, the method for measuring the area of the skeletal part appearing in the cross section of the cut surface is not particularly limited, and after specifying the skeleton part by performing known computer processing, etc., calculation by automatic calculation or manual calculation by a computer or the like A method is mentioned. The manual calculation includes a method in which an indefinite shape is replaced with an aggregate such as a quadrangle, a triangle, a circle, or a trapezoid, and the areas are obtained by stacking them.

  The total pore volume of the third monolith anion exchanger is 0.5 to 5 ml / g, preferably 0.8 to 4 ml / g. If the total pore volume is less than 0.5 ml / g, the pressure loss during water flow will increase, which is not preferable. Further, the amount of permeated fluid per unit cross-sectional area decreases, and the processing capacity decreases. Therefore, it is not preferable. On the other hand, if the total pore volume exceeds 5 ml / g, the mechanical strength decreases, and the third 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 third monolith anion exchanger and the platinum group metal nanoparticles supported thereon is lowered, the catalytic effect is also lowered, which is not preferable. The total pore volume of the monolith (monolith intermediate, monolith, monolith anion exchanger) means a value measured by mercury porosimetry. In addition, the total pore volume of the monolith (monolith intermediate, monolith, monolith anion exchanger) is the same both in the dry state and in the water wet state.

  The pressure loss when water is permeated through the third monolith anion exchanger is the pressure loss when water is passed through a column packed with 1 m at a water flow velocity (LV) of 1 m / h (hereinafter referred to as “ In this case, it is preferably in the range of 0.001 to 0.1 MPa / m · LV, particularly 0.005 to 0.05 MPa / m · LV.

  The third monolith anion exchanger has an anion exchange capacity per volume of 0.4 to 1.0 mg equivalent / ml in a water-wet state. In the conventional monolithic organic porous anion exchanger having a continuous macropore structure different from the present invention as described in JP-A-2002-306976, in order to achieve a low pressure loss that is practically required, When the opening diameter is increased, the total pore volume also increases accordingly, so the anion exchange capacity per volume decreases, and the total pore volume is decreased to increase the exchange capacity per volume. In addition, since the opening diameter is reduced, the pressure loss increases. On the other hand, the third monolith anion exchanger can further increase the opening diameter and thicken the skeleton of the continuous macropore structure (thicken the skeleton wall), so that the pressure loss can be kept low. The anion exchange capacity per volume can be dramatically increased. If the anion exchange capacity per volume is less than 0.4 mg equivalent / ml, the amount of platinum group metal nanoparticles supported per volume will be unfavorable. On the other hand, if the anion exchange capacity per volume exceeds 1.0 mg equivalent / ml, the pressure loss at the time of passing water increases, which is not preferable. The anion exchange capacity per weight of the third monolith anion exchanger is not particularly limited. However, since the anion exchange group is uniformly introduced to the surface of the porous body and the inside of the skeleton, the anion exchange capacity is 3.5-4. 5 mg equivalent / g. 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 third monolith anion exchanger, 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 third monolith anion exchanger include the same as those mentioned in the description of the first monolith anion exchanger.

  In addition, the distribution of anion exchange groups, the meaning of “anion exchange groups are uniformly distributed”, the method for confirming the distribution of anion exchange groups, and the anion exchange groups are porous as well as the surface of the monolith. The effect of uniform distribution even inside the body skeleton is the same as that of the first monolith anion exchanger.

(Method for producing third monolith anion exchanger)
The third monolith anion exchanger prepares a water-in-oil emulsion by stirring a mixture of oil-soluble monomer, surfactant and water that does not contain ion-exchange groups, and then polymerizes the water-in-oil emulsion. Step I for obtaining a monolithic organic porous intermediate (monolith intermediate) having a continuous macropore structure with a total pore volume of 5 to 16 ml / g, a vinyl monomer, a cross-link having at least two vinyl groups in one molecule Agent, the vinyl monomer and the crosslinking agent dissolve, but the polymer produced by polymerization of the vinyl monomer does not dissolve the organic solvent and the polymerization initiator II step II, the mixture obtained in step II is left standing, And polymerizing in the presence of the monolith intermediate obtained in the step I to obtain a thick organic porous body having a skeleton thicker than the skeleton of the monolith intermediate II Step IV the step of introducing an anion exchange group boned organic porous body obtained in the step III, obtained by performing.

  In the third method for producing a monolith anion exchanger, the step I may be performed according to the method described in JP-A-2002-306976.

  In the production of the monolith intermediate of step I, the oil-soluble monomer that does not contain an ion exchange group includes, for example, an ion exchange group such as a carboxylic acid group, a sulfonic acid group, and a quaternary ammonium group, and is soluble in water. Low and lipophilic monomers may be mentioned. Preferable examples of these monomers include styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, divinyl benzene, ethylene, propylene, isobutene, butadiene, ethylene glycol dimethacrylate, and the like. These monomers can be used singly or in combination of two or more. However, a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate is selected as at least one component of the oil-soluble monomer, and the content thereof is 0.3 to 10 mol% in the total oil-soluble monomer, preferably 0.3 to 5 mol% is preferable because the amount of anion exchange groups can be quantitatively introduced in the subsequent step.

  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 ion 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 dodecylbenzenesulfonate and dioctyl sodium sulfosuccinate; cationic surfactants such as distearyldimethylammonium chloride; amphoteric surfactants such as lauryldimethylbetaine can be used . 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%.

  In Step I, a polymerization initiator may be used as necessary when forming a water-in-oil emulsion. As the polymerization initiator, a compound that generates radicals by heat and light irradiation is preferably used. 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.

  The mixing method for mixing the oil-soluble monomer not containing an ion 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 a normal mixer, homogenizer, high-pressure homogenizer, or the like can be used, and an appropriate apparatus 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.

  The monolith intermediate obtained in Step I has a continuous macropore structure. When this coexists in the polymerization system, a porous structure having a thick skeleton with the structure of the monolith intermediate as a mold is formed. The monolith intermediate 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 the structural units constituting the polymer material. Is preferred. When the cross-linking structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable. In particular, when the total pore volume is as large as 10 to 16 ml / g, in order to maintain a continuous macropore structure, it is preferable to contain 2 mol% or more of cross-linked structural units. On the other hand, if it exceeds 10 mol%, it may be difficult to introduce an anion exchange group, which is not preferable.

  The type of the polymer material of the monolith intermediate is not particularly limited, and examples thereof include the same materials as the monolith polymer material described above. Thereby, the same polymer can be formed in the skeleton of the monolith intermediate, and the skeleton can be thickened to obtain a monolith having a uniform skeleton structure.

  The total pore volume of the monolith intermediate is 5 to 16 ml / g, preferably 6 to 16 ml / g. If the total pore volume is too small, the total pore volume of the monolith obtained after polymerizing the vinyl monomer becomes too small, and the pressure loss during fluid permeation increases, which is not preferable. On the other hand, if the total pore volume is too large, the structure of the monolith obtained after polymerizing the vinyl monomer deviates from the continuous macropore structure, which is not preferable. In order to make the total pore volume of the monolith intermediate within the above numerical range, the ratio of the monomer and water may be about 1: 5 to 1:20.

  Moreover, the average diameter of the opening (mesopore) which is an overlap part of a macropore and a macropore is 20-200 micrometers in a monolith intermediate body in a dry state. If the average diameter of the openings in the dry state is less than 20 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer is reduced, and the pressure loss during water passage is increased, which is not preferable. On the other hand, if it exceeds 200 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes too large, and the contact between the water to be treated and the monolith anion exchanger becomes insufficient. Is unfavorable because it decreases. Monolith intermediates preferably have a uniform structure with uniform macropore size and aperture diameter, but are not limited to this, and the uniform structure is dotted with nonuniform macropores larger than the size of the uniform macropore. You may do.

  Step II consists of a vinyl monomer, a crosslinking agent having at least two vinyl groups in one molecule, an organic solvent and a polymerization initiator that dissolves the vinyl monomer and the crosslinking agent but does not dissolve the polymer formed by polymerization of the vinyl monomer. A step of preparing a mixture of In addition, there is no order of I process and II process, II process may be performed after I process, and I process may be performed after II process.

  The vinyl monomer used in step II is not particularly limited as long as it is a lipophilic vinyl monomer containing a polymerizable vinyl group in the molecule and having high solubility in an organic solvent, but is allowed to coexist in the polymerization system. It is preferred to select a vinyl monomer that produces the same or similar polymer material as the monolith intermediate. Specific examples of these vinyl monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, vinyl biphenyl and vinyl naphthalene; α-olefins such as ethylene, propylene, 1-butene and isobutene; 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 such as vinyl acetate and vinyl propionate Esters: methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-methacrylic acid 2- Hexyl, cyclohexyl methacrylate, benzyl methacrylate, and (meth) acrylic monomer of glycidyl methacrylate. These monomers can be used singly 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 vinyl benzyl chloride.

  The added amount of these vinyl monomers is 3 to 50 times, preferably 4 to 40 times, by weight with respect to the monolith intermediate coexisting at the time of polymerization. If the amount of vinyl monomer added is less than 3 times that of the porous material, the resulting monolith skeleton (the thickness of the monolith skeleton wall) cannot be increased, and the anion exchange capacity per volume after the introduction of anion exchange groups is reduced. Since it becomes small, it is not preferable. On the other hand, if the amount of vinyl monomer added exceeds 50 times, the opening diameter becomes small, and the pressure loss during water passage becomes large, which is not preferable.

  As the crosslinking agent used in step II, a crosslinking agent containing at least two polymerizable vinyl groups in the molecule and having high solubility in an organic solvent is preferably used. Specific examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol diacrylate, and the like. These crosslinking agents can be used singly or in combination of two or more. Preferred cross-linking agents are aromatic polyvinyl compounds such as divinylbenzene, divinylnaphthalene and divinylbiphenyl because of their high mechanical strength and 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. 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 it exceeds 10 mol%, the amount of introduced anion exchange groups may decrease, which is not preferable. In addition, it is preferable to use the said crosslinking agent usage-amount so that it may become substantially equal to the crosslinking density of the monolith intermediate body coexisted at the time of vinyl monomer / crosslinking agent polymerization. If the amounts used of both are too large, the crosslink density distribution will be biased in the produced monolith, and cracks are likely to occur during the anion exchange group introduction reaction.

  The organic solvent used in Step II is an organic solvent that dissolves the vinyl monomer and the crosslinking agent but does not dissolve the polymer formed by polymerization of the vinyl monomer. In other words, it is a poor solvent for the polymer formed by polymerization of the vinyl monomer. . Since the organic solvent varies greatly depending on the type of vinyl monomer, it is difficult to list general specific examples. For example, when the vinyl monomer is styrene, the organic solvent includes methanol, ethanol, propanol, butanol, Alcohols such as hexanol, cyclohexanol, octanol, 2-ethylhexanol, decanol, dodecanol, ethylene glycol, propylene glycol, tetramethylene glycol, glycerin; diethyl ether, ethylene glycol dimethyl ether, cellosolve, methyl cellosolve, butyl cellosolve, polyethylene glycol, polypropylene Chain (poly) ethers such as glycol and polytetramethylene glycol; hexane, heptane, octane, isooctane, decane, dode Chain saturated hydrocarbons such as down, ethyl acetate, isopropyl acetate, cellosolve acetate, esters such as ethyl propionate. Moreover, even if it is a good solvent of polystyrene like a dioxane, THF, and toluene, when it is used with the said poor solvent and the usage-amount is small, it can be used as an organic solvent. These organic solvents are preferably used so that the concentration of the vinyl monomer is 30 to 80% by weight. If the amount of the organic solvent used deviates from the above range and the vinyl monomer concentration is less than 30% by weight, the polymerization rate is lowered, or the monolith structure after polymerization deviates from the range of the present invention. On the other hand, if the vinyl monomer concentration exceeds 80% by weight, the polymerization may run away, which is not preferable.

  As the polymerization initiator, a compound that generates radicals by heat and light irradiation is preferably used. The polymerization initiator is preferably oil-soluble. Specific examples of the polymerization initiator used in the present invention include 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis ( 2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate, 4,4′-azobis (4-cyanovaleric acid) 1,1′-azobis (cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, tetramethylthiuram disulfide and the like. The amount of the polymerization initiator used varies greatly depending on the type of monomer, polymerization temperature, etc., but can be used in a range of about 0.01 to 5% with respect to the total amount of vinyl monomer and crosslinking agent.

  In step III, the mixture obtained in step II is allowed to stand and polymerize in the presence of the monolith intermediate obtained in step I to obtain a thick monolith having a skeleton thicker than the skeleton of the monolith intermediate. It is a process to obtain. The monolith intermediate used in the step III plays a very important role in creating the monolith having the novel structure of the present invention. As disclosed in JP-A-7-501140 and the like, when a vinyl monomer and a crosslinking agent are allowed to stand in a specific organic solvent in the absence of a monolith intermediate, a particle aggregation type monolithic organic porous material is obtained. The body is obtained. On the other hand, when a monolith intermediate having a continuous macropore structure is present in the polymerization system as in the present invention, the structure of the monolith after polymerization changes dramatically, the particle aggregation structure disappears, and the above-mentioned thick monolith is lost. Is obtained. The reason for this has not been elucidated in detail, but in the absence of a monolith intermediate, the cross-linked polymer produced by polymerization precipitates and precipitates in the form of particles, while a particle aggregate structure is formed. When a porous body (intermediate) is present in the system, the vinyl monomer and the crosslinking agent are adsorbed or distributed from the liquid phase to the skeleton of the porous body (intermediate), and polymerization proceeds in the porous body (intermediate). Thus, it is considered that a monolith having a thick bone skeleton can be obtained. Although the opening diameter is narrowed by the progress of the polymerization, since the total pore volume of the monolith intermediate is large, an appropriate opening diameter can be obtained even if the skeleton becomes thick.

  The internal volume of the reaction vessel is not particularly limited as long as it is large enough to allow the monolith intermediate to exist in the reaction vessel. When the monolith intermediate is placed in the reaction vessel, there is a gap around the monolith in plan view. Or a monolith intermediate in the reaction vessel with no gap. Of these, the thick monolith after polymerization is not pressed from the inner wall of the container and enters the reaction container without any gap, and the monolith is not distorted, and the reaction raw materials are not wasted and efficient. Even when the internal volume of the reaction vessel is large and there are gaps around the monolith after polymerization, the vinyl monomer and the crosslinking agent are adsorbed and distributed on the monolith intermediate, so the gaps in the reaction vessel A particle aggregate structure is not generated in the portion.

  In step III, the monolith intermediate is placed in a reaction vessel impregnated with the mixture (solution). As described above, the blending ratio of the mixture obtained in Step II and the monolith intermediate is 3 to 50 times by weight, preferably 4 to 40 times by weight, relative to the monolith intermediate. It is suitable to mix. Thereby, it is possible to obtain a monolith having a thick skeleton while having an appropriate opening diameter. In the reaction vessel, the vinyl monomer and the crosslinking agent in the mixture are adsorbed and distributed on the skeleton of the monolith intermediate that has been allowed to stand, and polymerization proceeds in the skeleton of the monolith intermediate.

  Various polymerization conditions are selected depending on the type of monomer and the type of initiator. For example, when 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, etc. are used as initiators In a sealed container under an inert atmosphere, heat polymerization may be performed at 30 to 100 ° C. for 1 to 48 hours. By heat polymerization, the vinyl monomer adsorbed and distributed on the skeleton of the monolith intermediate and the cross-linking agent are polymerized in the skeleton to thicken the skeleton. After completion of the polymerization, the contents are taken out and extracted with a solvent such as acetone for the purpose of removing unreacted vinyl monomer and organic solvent to obtain a thick monolith.

  Next, after producing a monolith by the above method, a method of introducing an anion exchange group is preferred in that the porous structure of the resulting monolith anion exchanger can be strictly controlled.

  There is no restriction | limiting in particular as a method of introduce | transducing an anion exchange group into the said monolith, 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 method of introducing a chloromethyl group with chloromethyl methyl ether or the like and then reacting with a tertiary amine; A method in which chloromethylstyrene and divinylbenzene are produced by copolymerization and reacted with a tertiary amine; N, N, N-trimethylammonium is introduced into the monolith by introducing radical initiation groups and chain transfer groups uniformly into the skeleton surface and inside the skeleton. Examples include a method of graft polymerization of ethyl acrylate and N, N, N-trimethylammoniumpropylacrylamide; a method of grafting glycidyl methacrylate in the same manner and then introducing a quaternary ammonium group by functional group conversion. Among these methods, as a method for introducing a quaternary ammonium group, a method in which a chloromethyl group is introduced into a styrene-divinylbenzene copolymer with chloromethyl methyl ether and then reacted with a tertiary amine, or chloromethyl styrene. 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 ion 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.

  The third monolith anion exchanger swells greatly, for example, 1.4 to 1.9 times that of the thick monolith because an anion exchange group is introduced into the thick monolith. That is, the degree of swelling is much greater than that obtained by introducing an ion exchange group into a conventional monolith described in JP-A-2002-306976. For this reason, even if the opening diameter of the thick monolith is small, the opening diameter of the monolith ion exchanger generally increases at the above magnification. In addition, the total pore volume does not change even when the opening diameter increases due to swelling. Therefore, the third monolith ion exchanger has a high mechanical strength because it has a thick bone skeleton despite the remarkably large opening diameter.

(Fourth monolith anion exchanger)
The fourth monolith anion exchanger has an average thickness of an aromatic vinyl polymer containing 0.3 to 5.0 mol% of a cross-linking structural unit in all the structural units into which an anion exchange group has been introduced. A co-continuous structure comprising a three-dimensionally continuous skeleton of 1 to 60 μm and three-dimensionally continuous pores having an average diameter of 10 to 100 μm in a wet state between the skeletons. The volume is 0.5 to 5 ml / g, the ion exchange capacity per volume under water wet condition is 0.3 to 1.0 mg equivalent / ml, and the anion exchange group is uniform in the porous ion exchanger. Is distributed.

  The fourth monolith anion exchanger has a three-dimensional continuous skeleton having an average thickness of 1 to 60 μm, preferably 3 to 58 μm, in an wet state in which an anion exchange group is introduced, and an average diameter between the skeletons. A co-continuous structure composed of three-dimensionally continuous pores of 10 to 100 μm, preferably 15 to 90 μm, particularly preferably 20 to 80 μm in a wet state. That is, as shown in the schematic diagram of FIG. 22, the co-continuous structure is a structure 90 in which a continuous skeleton phase 91 and a continuous vacancy phase 92 are intertwined and each of them is three-dimensionally continuous. The continuous vacancies 92 have higher continuity of vacancies and are not biased in size compared to conventional open cell monoliths and particle agglomeration monoliths, so that extremely uniform ion adsorption behavior can be achieved. Moreover, since the skeleton is thick, the mechanical strength is high.

  The skeleton thickness and pore diameter of the fourth monolith anion exchanger are larger than the monolith skeleton thickness and pore diameter because the entire monolith swells when an anion exchange group is introduced into the monolith. It becomes. These continuous pores have higher continuity of the pores than the conventional open-cell type monolithic organic porous anion exchanger and particle aggregation type monolithic organic porous anion exchanger, and the size thereof is not biased. Therefore, an extremely uniform anion adsorption behavior can be achieved. If the average diameter of the three-dimensionally continuous pores is less than 10 μm in the water-wet state, it is not preferable because the pressure loss at the time of water flow increases, and if it exceeds 100 μm, the water to be treated and the organic porous anion The contact with the exchanger becomes insufficient, and as a result, the decomposition of hydrogen peroxide in the water to be treated becomes insufficient. In addition, when the average thickness of the skeleton is less than 1 μm in a wet state of water, the anion exchange capacity per volume decreases, and the mechanical strength decreases. This is not preferable because the monolith anion exchanger 4 is greatly deformed. Furthermore, the contact efficiency between the water to be treated and the fourth monolith anion exchanger decreases, and the catalytic effect decreases, which is not preferable. On the other hand, if the thickness of the skeleton exceeds 60 μm, the skeleton becomes too thick and pressure loss during water passage increases, which is not preferable.

The average diameter of the pores of the continuous structure in the water-wet state is a value calculated by multiplying the average diameter of the pores of the monolith anion exchanger in the dry state measured by the mercury intrusion method and the swelling ratio. Specifically, the diameter of the fourth monolith anion exchanger water wet state is X _{4a (mm),} drying the fourth monolith anion exchanger of the water-wet state, in the dry state obtained 4 The diameter of the monolith anion exchanger was Y _4a (mm), and the average diameter of the pores was Z _4a (μm) when the dried fourth monolith anion exchanger was measured by the mercury intrusion method. Then, the average diameter (μm) of the pores of the fourth monolith anion exchanger in the water wet state is expressed by the following formula: “average diameter of the pores (μm) of the fourth monolith anion exchanger in the water wet state” = Z _4a × (X _4a / Y _4a ) ”. Further, the average diameter of the pores of the dried monolith before the introduction of the anion exchange group, and the fourth monolith anion exchanger in the water wet state with respect to the dried monolith when the anion exchange group is introduced into the dried monolith. When the swelling ratio is known, the average diameter of the pores of the fourth monolith anion exchanger in the wet state can be calculated by multiplying the average diameter of the pores of the monolith in the dry state by the swelling ratio. The average thickness of the skeleton of the continuous structure in the water-wet state is determined by performing SEM observation of the fourth monolith anion exchanger in the dry state at least three times and measuring the thickness of the skeleton in the obtained image. The average value is calculated by multiplying the swelling ratio. Specifically, the diameter of the fourth monolith anion exchanger in the water wet state is X _4b (mm), and the fourth monolith anion exchanger in the water wet state is dried, and the resulting fourth in the dry state is obtained. The diameter of the monolith anion exchanger is Y _4b (mm), and SEM observation of the dried fourth monolith anion exchanger is performed at least three times, and the thickness of the skeleton in the obtained image is measured. When the average value is Z _4b (μm), the average thickness (μm) of the skeleton of the continuous structure of the fourth monolith anion exchanger in the water wet state is expressed by the following formula: The average thickness (μm) of the skeleton of the continuous structure of the monolith anion exchanger = Z _4b × (X _4b / Y _4b ) ”. Further, the average thickness of the skeleton of the dried monolith before the introduction of the anion exchange group, and the fourth monolith anion exchanger in the water wet state relative to the dried monolith when the anion exchange group is introduced into the dried monolith. When the swelling ratio is known, the average thickness of the skeleton of the monolith in the dry state can be multiplied by the swelling ratio to calculate the average thickness of the skeleton of the fourth monolith anion exchanger in the water wet state. The skeleton has a rod-like shape and a circular cross-sectional shape, but may have a cross-section with a different diameter such as an elliptical cross-sectional shape. The thickness in this case is the average of the minor axis and the major axis.

  The total pore volume of the fourth monolith anion exchanger is 0.5 to 5 ml / g. If the total pore volume is less than 0.5 ml / g, the pressure loss at the time of water flow is increased, which is not preferable. Further, the amount of permeated water per unit cross-sectional area is decreased, and the amount of treated water is decreased. Therefore, it is not preferable. On the other hand, if the total pore volume exceeds 5 ml / g, the anion exchange capacity per volume decreases, the amount of platinum group metal nanoparticles supported decreases, and the catalytic effect decreases. In addition, the mechanical strength is lowered, and the fourth monolith anion exchanger is greatly deformed particularly when water is passed at a high flow rate, which is not preferable. Furthermore, the contact efficiency between the water to be treated and the fourth monolith anion exchanger is lowered, and the hydrogen peroxide decomposition effect is also lowered. If the three-dimensional continuous pore size and total pore volume are within the above ranges, the contact with the water to be treated is extremely uniform, the contact area is large, and water can flow through under low pressure loss. Become. Note that the total pore volume of the monolith (monolith intermediate, monolith, monolith anion exchanger) is the same in both the dry state and the water wet state.

  The pressure loss when water is permeated through the fourth monolith anion exchanger is the pressure loss when water is passed through a column filled with 1 m of a porous body at a water flow rate (LV) of 1 m / h (hereinafter referred to as “pressure loss”). , “Differential pressure coefficient”), the range is 0.001 to 0.5 MPa / m · LV, particularly 0.005 to 0.1 MPa / m · LV.

  In the fourth monolith anion exchanger, the material constituting the skeleton of the co-continuous structure is 0.3 to 5 mol%, preferably 0.5 to 3.0 mol% of the crosslinked structural unit in all the structural units. It is an aromatic vinyl polymer containing and is hydrophobic. 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 5 mol%, the structure of the porous body tends to deviate from the bicontinuous structure. There is no restriction | limiting in particular in the kind of this aromatic vinyl polymer, For example, a polystyrene, poly ((alpha) -methylstyrene), polyvinyl toluene, polyvinyl benzyl chloride, polyvinyl biphenyl, polyvinyl naphthalene etc. are 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, a styrene-divinylbenzene copolymer is obtained because of the ease of forming a co-continuous structure, the ease of introducing an anion exchange group, the high mechanical strength, and the high stability to acids or alkalis. And vinylbenzyl chloride-divinylbenzene copolymer is preferred.

  The fourth monolith anion exchanger has an ion exchange capacity of 0.3 to 1.0 mg equivalent / ml per anion volume in a water wet state. In the conventional monolithic organic porous ion exchanger having a continuous macropore structure different from the present invention as described in JP-A-2002-306976, in order to achieve a low pressure loss that is practically required, When the opening diameter is increased, the total pore volume is increased accordingly, so that the ion exchange capacity per volume is decreased, and the total pore volume is decreased in order to increase the exchange capacity per volume. In addition, since the opening diameter is reduced, the pressure loss increases. On the other hand, the fourth monolith anion exchanger of the present invention has high continuity and uniformity of three-dimensionally continuous pores, so that the pressure loss does not increase so much even if the total pore volume is reduced. Therefore, the anion exchange capacity per volume can be dramatically increased while keeping the pressure loss low. If the anion exchange capacity per volume is less than 0.3 mg equivalent / ml, the amount of platinum group metal nanoparticles supported per volume will be unfavorable. On the other hand, if the anion exchange capacity per volume exceeds 1.0 mg equivalent / ml, the pressure loss at the time of passing water increases, which is not preferable. In addition, the anion exchange capacity per weight in the dry state of the fourth monolith anion exchanger is not particularly limited, but the ion exchange groups are uniformly introduced to the skeleton surface and the skeleton inside the porous body. 5-4.5 mg equivalent / g. The ion exchange capacity of a porous body in which ion exchange groups are introduced only on the surface of the skeleton cannot be determined unconditionally depending on the kind of the porous body or ion exchange groups, but is at most 500 μg equivalent / g.

  Examples of the anion exchange group of the fourth monolith anion exchanger include the same as those mentioned in the description of the first monolith anion exchanger.

  In addition, the distribution of anion exchange groups, the meaning of “anion exchange groups are uniformly distributed”, the method for confirming the distribution of anion exchange groups, and the anion exchange groups are porous as well as the surface of the monolith. The effect of uniform distribution even inside the body skeleton is the same as that of the first monolith anion exchanger.

(Method for producing fourth monolith anion exchanger)
The fourth monolith anion exchanger prepares a water-in-oil emulsion by stirring a mixture of oil-soluble monomer, surfactant and water that does not contain ion-exchange groups, and then polymerizes the water-in-oil emulsion. Step I to obtain a monolithic organic porous intermediate having a continuous macropore structure having a total pore volume of more than 16 ml / g and 30 ml / g or less, an aromatic vinyl monomer, and at least two or more vinyl groups in one molecule From an organic solvent and a polymerization initiator in which 0.3 to 5 mol% of the cross-linking agent, aromatic vinyl monomer and cross-linking agent dissolve but the polymer formed by polymerization of the aromatic vinyl monomer does not dissolve in the total oil-soluble monomer having Polymerization is carried out in the presence of the monolithic organic porous intermediate obtained in Step I, while allowing the mixture obtained in Step II and Step II to stand. Obtained by performing a co-continuous structure III to obtain a, IV introducing an anion exchange group to the resulting co-continuous structure in the step III.

  What is necessary is just to perform the I process of obtaining the monolith intermediate body in a 4th monolith anion exchanger based on the method of Unexamined-Japanese-Patent No. 2002-306976.

  That is, in the step I, as the oil-soluble monomer not containing an ion exchange group, for example, it does not contain an ion exchange group such as a carboxylic acid group, a sulfonic acid group, and a quaternary ammonium group, has low solubility in water, and is lipophilic. These monomers are mentioned. Specific examples of these monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, vinyl biphenyl and vinyl naphthalene; α-olefins such as ethylene, propylene, 1-butene and isobutene; butadiene Diene monomers 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, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethyl methacrylate Sill, cyclohexyl methacrylate, benzyl methacrylate, and (meth) acrylic monomer of glycidyl methacrylate. Among these monomers, preferred are aromatic vinyl monomers such as styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, divinyl benzene and the like. These monomers can be used singly or in combination of two or more. However, 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 0.3 to 5 mol%, preferably 0.3 to the total oil-soluble monomer. 3 mol% is preferable because it is advantageous for forming a co-continuous structure.

  The surfactant is the same as the surfactant used in Step I of the third monolith anion exchanger, and the description thereof is omitted.

  In Step I, a polymerization initiator may be used as necessary when forming a water-in-oil emulsion. As the polymerization initiator, a compound that generates radicals by heat and light irradiation is preferably used. The polymerization initiator may be water-soluble or oil-soluble. For example, 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), 2 , 2′-azobis (2-methylbutyronitrile), 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), dimethyl 2,2′-azobisisobutyrate, 4,4′-azobis ( 4-cyanovaleric acid), 1,1'-azobis (cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, tetramethylthiuram disulfide, hydrogen peroxide-ferrous chloride Sodium persulfate-sodium acid sodium sulfite and the like.

  As a mixing method when an oil-soluble monomer not containing an ion exchange group, a surfactant, water, and a polymerization initiator are mixed to form a water-in-oil emulsion, the first monolith anion exchanger in Step I is used. This is the same as the mixing method, and the description thereof is omitted.

  In the fourth method for producing a monolith anion exchanger, the monolith intermediate obtained in the step I is an organic polymer material having a crosslinked structure, preferably an aromatic vinyl polymer. Although the crosslinking density of the polymer material is not particularly limited, it contains 0.3 to 5 mol%, preferably 0.3 to 3 mol% of crosslinked structural units with respect to all structural units constituting the polymer material. Is preferred. When 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 5 mol%, the structure of the monolith tends to deviate from the co-continuous structure, which is not preferable. In particular, when 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 cross-linking structural unit is preferably less than 3 mol%.

  The type of the polymer material of the monolith intermediate is the same as the type of the polymer material of the monolith intermediate of the third monolith anion exchanger, and the description thereof is omitted.

  The total pore volume of the monolith intermediate is greater than 16 ml / g and not greater than 30 ml / g, preferably greater than 16 ml / g and not greater than 25 ml / g. In other words, this monolith intermediate basically has a continuous macropore structure, but the opening (mesopore) that is the overlapping part of the macropore and the macropore is remarkably large, so that the skeleton constituting the monolith structure is primary from the two-dimensional wall surface. It has a structure as close as possible to the original rod-like skeleton. When this coexists in the polymerization system, a porous body having a co-continuous structure is formed using the structure of the monolith intermediate as a mold. If the total pore volume is too small, the structure of the monolith obtained after polymerizing the vinyl monomer is not preferable because it changes from a co-continuous structure to a continuous macropore structure. On the other hand, if the total pore volume is too large, This is not preferable because the mechanical strength of the monolith obtained after polymerizing the vinyl monomer is lowered and the anion exchange capacity per volume is lowered. In order to make the total pore volume of the monolith intermediate within a specific range of the fourth monolith anion exchanger, the ratio of monomer to water may be about 1:20 to 1:40.

  Moreover, the average diameter of the opening (mesopore) which is an overlap part of a macropore and a macropore is a monolith intermediate body is 5-100 micrometers in a dry state. When the average diameter of the openings is less than 5 μm in the dry state, the opening diameter of the monolith obtained after polymerizing the vinyl monomer is reduced, and the pressure loss during fluid permeation is increased, which is not preferable. On the other hand, if it exceeds 100 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes too large, and the contact between the water to be treated and the monolith anion exchanger becomes insufficient. Is unfavorable because it decreases. Monolith intermediates preferably have a uniform structure with uniform macropore size and aperture diameter, but are not limited to this, and the uniform structure is dotted with nonuniform macropores larger than the size of the uniform macropore. You may do.

  In the fourth method for producing a monolith anion exchanger, the step II includes 0.3 to 5 mol% of a crosslinking agent in the aromatic vinyl monomer and the total oil-soluble monomer having at least two or more vinyl groups in one molecule. In this step, a mixture comprising an organic solvent and a polymerization initiator that dissolves the aromatic vinyl monomer and the crosslinking agent but does not dissolve the polymer formed by polymerization of the aromatic vinyl monomer. In addition, there is no order of I process and II process, II process may be performed after I process, and I process may be performed after II process.

  In the fourth method for producing a monolith anion exchanger, the aromatic vinyl monomer used in the step II includes a lipophilic aromatic vinyl monomer having a polymerizable vinyl group in the molecule and having high solubility in an organic solvent. If it is, there is no particular limitation, but it is preferable to select a vinyl monomer that produces the same or similar polymer material as the monolith intermediate coexisting in the polymerization system. Specific examples of these vinyl monomers include styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, vinyl biphenyl, vinyl naphthalene and the like. These monomers can be used singly or in combination of two or more. Aromatic vinyl monomers preferably used in the present invention are styrene, vinyl benzyl chloride and the like.

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

  As the crosslinking agent used in step II, a crosslinking agent containing at least two polymerizable vinyl groups in the molecule and having high solubility in an organic solvent is preferably used. Specific examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol diacrylate, and the like. These crosslinking agents can be used singly or in combination of two or more. Preferred cross-linking agents are aromatic polyvinyl compounds such as divinylbenzene, divinylnaphthalene and divinylbiphenyl because of their high mechanical strength and 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 vinyl monomer and crosslinking agent (total oil-soluble monomer). When the amount of the crosslinking agent used is less than 0.3 mol%, it is not preferable because the mechanical strength of the monolith is insufficient. On the other hand, when the amount is too large, it may be difficult to quantitatively introduce the anion exchange group. . In addition, it is preferable to use the said crosslinking agent usage-amount so that it may become substantially equal to the crosslinking density of the monolith intermediate body coexisted at the time of vinyl monomer / crosslinking agent polymerization. If the amounts used of both are too large, the crosslink density distribution will be biased in the produced monolith, and cracks are likely to occur during the anion exchange group introduction reaction.

  The organic solvent used in step II is an organic solvent that dissolves the aromatic vinyl monomer and the crosslinking agent but does not dissolve the polymer formed by polymerization of the aromatic vinyl monomer, in other words, is formed by polymerization of the aromatic vinyl monomer. It is a poor solvent for polymers. Since the organic solvent varies greatly depending on the type of the aromatic vinyl monomer, it is difficult to list general specific examples. For example, when the aromatic vinyl monomer is styrene, the organic solvent includes methanol, ethanol, Alcohols such as propanol, butanol, hexanol, cyclohexanol, octanol, 2-ethylhexanol, decanol, dodecanol, propylene glycol, tetramethylene glycol; chain structures such as diethyl ether, butyl cellosolve, polyethylene glycol, polypropylene glycol, polytetramethylene glycol (Poly) ethers; chain saturated hydrocarbons such as hexane, heptane, octane, isooctane, decane, dodecane; ethyl acetate, isopropyl acetate, cellosolve acetate, propionic acid Examples include esters such as ethyl. Moreover, even if it is a good solvent of polystyrene like a dioxane, THF, and toluene, when it is used with the said poor solvent and the usage-amount is small, it can be used as an organic solvent. These organic solvents are preferably used so that the concentration of the aromatic vinyl monomer is 30 to 80% by weight. If the amount of the organic solvent used deviates from the above range and the aromatic vinyl monomer concentration becomes less than 30% by weight, the polymerization rate is lowered, or the monolith structure after polymerization deviates from the scope of the present invention, which is not preferable. On the other hand, if the concentration of the aromatic vinyl monomer exceeds 80% by weight, the polymerization may run away, which is not preferable.

  The polymerization initiator is the same as the polymerization initiator used in Step II of the third monolith anion exchanger, and the description thereof is omitted.

  In the fourth method for producing a monolith anion exchanger, in the step III, the mixture obtained in the step II is allowed to stand, and polymerization is performed in the presence of the monolith intermediate obtained in the step I. This is a process of obtaining a monolith having a co-continuous structure by changing the continuous macropore structure of the body into a co-continuous structure. The monolith intermediate used in the step III plays a very important role in creating a monolith having a novel structure. As disclosed in JP-A-7-501140 and the like, when a vinyl monomer and a crosslinking agent are allowed to stand in a specific organic solvent in the absence of a monolith intermediate, a particle aggregation type monolithic organic porous material is obtained. The body is obtained. On the other hand, when a monolith intermediate having a specific continuous macropore structure is present in the polymerization system as in the fourth monolith of the present invention, the structure of the monolith after the polymerization changes dramatically and the particle aggregation structure disappears. Thus, a monolith having the above-described bicontinuous structure can be obtained. The reason for this has not been elucidated in detail, but in the absence of a monolith intermediate, the cross-linked polymer produced by polymerization precipitates and precipitates in the form of particles, while a particle aggregate structure is formed. When a porous body (intermediate) having a large total pore volume is present in the system, the vinyl monomer and the crosslinking agent are adsorbed or distributed from the liquid phase to the skeleton of the porous body, and polymerization proceeds in the porous body. It is considered that the skeleton constituting the monolith structure is changed from a two-dimensional wall surface to a one-dimensional rod-like 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 description of the internal volume of the reaction vessel of the third monolith anion exchanger, and the description thereof is omitted.

  In step III, the monolith intermediate is placed in a reaction vessel impregnated with the mixture (solution). As described above, the blending ratio of the mixture obtained in Step II and the monolith intermediate is 5 to 50 times, preferably 5 to 40 times the weight of the aromatic vinyl monomer added to the monolith intermediate. It is preferable to blend them as described above. Thereby, it is possible to obtain a monolith having a co-continuous structure in which pores of an appropriate size are three-dimensionally continuous and a thick skeleton is three-dimensionally continuous. In the reaction vessel, the aromatic vinyl monomer and the cross-linking agent in the mixture are adsorbed and distributed on the skeleton of the monolith intermediate that is allowed to stand, and polymerization proceeds in the skeleton of the monolith intermediate.

  The basic structure of the monolith having a co-continuous structure is a three-dimensional structure in which the average thickness is 0.8 to 40 μm in a dry state and an average diameter between the skeletons is 8 to 80 μm in a dry state. In this structure, continuous holes are arranged. The average diameter of the three-dimensionally continuous pores in the dry state can be obtained as a maximum value of the pore distribution curve by measuring the pore distribution curve by a mercury intrusion method. The thickness of the skeleton of the dried monolith may be calculated by performing SEM observation at least three times and measuring the average thickness of the skeleton in the obtained image. A 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 the description of the polymerization conditions in the third step of the third monolith anion exchanger, and the description thereof is omitted.

  In the IV step, the method for introducing an anion exchange group into the monolith having a co-continuous structure is the same as the method for introducing an anion exchange group into the monolith in the third monolith anion exchanger, and the description thereof is omitted.

  The fourth monolith anion exchanger swells greatly to 1.4 to 1.9 times that of the monolith, for example, because an anion exchange group is introduced into the monolith having a co-continuous structure. Further, the total pore volume does not change even if the pore diameter becomes larger due to swelling. Therefore, the fourth monolith anion exchanger has a high mechanical strength because it has a thick bone skeleton even though the size of three-dimensionally continuous pores is remarkably large. Further, since the skeleton is thick, the anion exchange capacity per volume in a water-wet state can be increased, and furthermore, the water to be treated can be passed for a long time at a low pressure and a large flow rate.

(Platinum group metal supported catalyst)
The platinum group metal supported catalyst is a platinum group metal supported catalyst in which a platinum group metal is supported on a monolith anion exchanger, and platinum group metal nanoparticles are supported on the monolith anion exchanger. preferable.

  As the monolith anion exchanger, the above-described first to fourth monolith anion exchangers are preferable.

  The platinum group metal is ruthenium, rhodium, palladium, osmium, iridium, or platinum. These platinum group metals may be used individually by 1 type, may be used in combination of 2 or more types of metals, and may also use 2 or more types of metals 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 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 in the dry state ((platinum group metal nanoparticles / dried platinum group metal supported catalyst) × 100) is preferably 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 is insufficient, which is not preferable. 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 method for producing the platinum group metal-supported catalyst is not particularly limited, and can be obtained by supporting platinum group metal nanoparticles on a monolith anion exchanger by a known method. For example, a dried monolith anion exchanger is immersed in an aqueous solution of palladium chloride in hydrochloric acid, the chloropalladate anion is adsorbed on the monolith anion exchanger by ion exchange, and then contacted with a reducing agent to bring the palladium metal nanoparticles into the monolith anion. The column is packed with a monolith anion exchanger or a monolith anion exchanger, and an aqueous hydrochloric acid solution of palladium chloride is passed through the column to adsorb the chloropalladate anion to the monolith anion exchanger by ion exchange, and then a reducing agent is passed through. And a method in which palladium metal nanoparticles are supported on a monolith anion exchanger. 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, the ionic form of the monolith anion exchanger, which is the carrier of the platinum group metal nanoparticles, usually becomes a salt form such as a chloride form after the platinum group metal nanoparticles are supported. The platinum group metal-supported catalyst may be one obtained by regenerating the ionic form of the monolith anion exchanger into the OH form. Of these, the ionic form of the monolith anion exchanger is preferably the 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.

  EXAMPLES Next, although an Example is given and this invention is demonstrated more concretely, this is only an illustration and does not restrict | limit this invention.

Example 1
<Production of palladium nanoparticle-supported catalyst 1>
(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 electron microscope (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 monolithic organic porous material, 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 to obtain a monolith anion exchanger 1.

  The swelling ratio of the obtained monolith anion exchanger 1 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 openings of the monolith anion exchanger 1 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 was 44 μm, and the total pore volume was 8.6 ml / g. 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 a linear velocity LV of 20 m / h was 84 mm, and amberlite which is a commercially available strong basic anion exchange resin. 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 1, 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. .

(Preparation of platinum group metal supported catalyst)
The monolith anion exchanger 1 was ion-exchanged into Cl form, cut into a columnar 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 for 24 hours in dilute hydrochloric acid in which 140 mg of palladium chloride was dissolved, and ion-exchanged to the palladium 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 palladium acid form monolith anion exchanger was white, whereas the monolith anion exchanger after the reduction treatment was colored black, suggesting the formation of palladium nanoparticles. The palladium nanoparticle-supported catalyst 1 thus obtained was washed several times with pure water and dried.

  The amount of palladium supported on the dried palladium nanoparticle supported catalyst 1 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.

<Manufacture of hydrogen peroxide decomposition treated water>
The palladium nanoparticle-supported catalyst 1 in a dry state is cut out and packed into a column having an inner diameter of 10 mm, and an aqueous sodium hydroxide solution is passed through to form a monolith anion exchanger as a carrier in the OH form to evaluate hydrogen peroxide decomposition characteristics. Using. At this time, the packed bed height of the palladium nanoparticle-supported catalyst 1 was 13 mm. Moreover, the palladium nanoparticle carrying amount with respect to 1 L of palladium nanoparticle carrying | support catalyst of a water wet state was 2.0g.

Ultrapure water containing 15 to 30 μg / L (15 to 30 ppb) of hydrogen peroxide was passed through the packing of the palladium nanoparticle-supported catalyst 1 at SV = 5000 h ^{−1 for} 27 hours in a downward flow, Sample water was collected at the column outlet 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. Hydrogen peroxide concentration of the sample water and water sampling in the column outlet, SV is very fast and 10000h ^-1, even though packed bed height of the supported catalyst 13mm and thin, less than 1 [mu] g / L, hydrogen peroxide Was decomposed and removed.

Comparative Example 1
Moisture retention capacity is 60 to 70% on the basis of OH form, and palladium nanoparticle is supported on a particulate strong base anion exchange resin (type I) in a gel form by a known method, and the palladium nanoparticle supported granular ion An exchange resin catalyst was obtained. 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 60 mg with respect to 1 L of the palladium nanoparticle-supported catalyst in a wet state.

  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.

<Manufacture of hydrogen peroxide decomposition treated water>
Palladium nanoparticles supported by the same method as in Example 1 except that the above-described palladium nanoparticle-supported granular ion exchange resin catalyst was used as a catalyst and ultrapure water was passed at SV = 1000 h ^−1. The hydrogen peroxide decomposition effect of the granular ion exchange resin catalyst was evaluated. As a result, the hydrogen peroxide concentration in the sample water collected at the column outlet was 1.5 μg / L, and 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 which is the prior art, even if the conditions for easily decomposing hydrogen peroxide such as SV slower than the example and the high catalyst packed bed height are set, There was a leak of hydrogen peroxide.

Comparative Example 2
Moisture retention capacity is 60 to 70% on the basis of OH form, and palladium nanoparticle is supported by a known method on particulate strong base anion exchange resin (type I) in gel form, and palladium ion supported particulate ion exchange A resin catalyst was obtained. 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 with respect to 1 L of the palladium nanoparticle-supported catalyst in a wet state. 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.

<Manufacture of hydrogen peroxide decomposition treated water>
As a catalyst, the same method as in Example 1 except that the palladium nanoparticle-supported granular ion exchange resin catalyst was used and that ultrapure water was passed through at SV = 1500 h ⁻¹ and 2500 h ^−1. The hydrogen peroxide decomposition effect of the palladium nanoparticle-supported granular ion exchange resin catalyst was evaluated. 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 which is the prior art, even if the conditions for easily decomposing 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 3
The hydrogen peroxide decomposition effect at SV = 10000 h ⁻¹ was evaluated in the same manner as in Example 1 using only the monolith anion exchanger 1 without supporting palladium nanoparticles. As a result, the decomposition effect of hydrogen peroxide was not recognized.

Example 2
<Production of palladium nanoparticle-supported catalyst 2>
(Production of particle agglomerated monolithic organic porous material)
38.8 g of vinylbenzyl chloride, 1.2 g of divinylbenzene, 60 g of 1-butanol and 0.4 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and dissolved uniformly. Divinylbenzene was 2.8 mol% with respect to the total amount of vinylbenzyl chloride and divinylbenzene. Next, the vinylbenzyl chloride / divinylbenzene / 1-decanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture was placed in a polyethylene cylinder, purged with nitrogen three times, sealed, and allowed to stand. The polymerization was carried out at 60 ° C. for 24 hours. After completion of the polymerization, the monolithic contents having a thickness of about 30 mm were taken out, subjected to Soxhlet extraction with acetone for 10 hours to remove unreacted monomers and 1-butanol, and then dried under reduced pressure at 85 ° C. overnight. The diameter of the obtained cylindrical monolithic porous body (monolith) was 76 mm.

  FIG. 9 shows the result of observing the internal structure of the monolith containing 2.8 mol% of the crosslinking component composed of the vinylbenzyl chloride / divinylbenzene copolymer obtained by SEM. As is apparent from FIG. 9, it can be seen that the monolith is formed by agglomerating crosslinked polyvinylbenzyl chloride particles having a diameter of about 15 μm to form a three-dimensionally continuous skeleton portion. The maximum value (diameter) of the pore distribution curve of the monolith measured by mercury porosimetry was 60 μm. The total pore volume of the monolith was 1.4 ml / g.

(Production of monolith anion exchanger)
The monolith produced by the above method was cut into a disk shape having a thickness of about 15 mm. To this was added 1500 ml of tetrahydrofuran, heated at 40 ° C. for 1 hour, then cooled to 10 ° C. or less, 140 g of a 30% trimethylamine aqueous solution was gradually added, and the temperature was raised and reacted at 40 ° C. for 24 hours. After completion of the reaction, the product was taken out and washed with methanol and pure water in this order to obtain a monolith anion exchanger 2. The resulting monolith anion exchanger 2 had a diameter of 111 mm and an anion exchange capacity per volume of 0.65 mg equivalent / ml in a wet state. When the pore diameter of the monolith anion exchanger 2 in a wet state with water was estimated from the change in diameter (swelling ratio) before and after introduction of the anion exchange group, it was 88 μm. The total pore volume was 1.4 ml / g. In addition, the differential pressure coefficient, which is an index of pressure loss when water is permeated, is 0.010 MPa / m · LV, which is a low pressure loss lower than that required for practical use. It was.

  Next, in order to confirm the distribution state of the quaternary ammonium group in the monolith anion exchanger 2, the distribution state of chloride ions was observed by EPMA. The results are shown in FIGS. FIG. 10 shows a distribution state of chloride ions on the surface of the monolith anion exchanger 2. FIG. 10 shows that quaternary ammonium groups are uniformly introduced on the surface of the monolith anion exchanger 2. FIG. 11 shows a distribution state of chloride ions in the cross-section (thickness) direction of the monolith anion exchanger 2, but it can be seen that quaternary ammonium groups are uniformly introduced also in the cross-section direction. From this, it can be seen that in the obtained monolith anion exchanger 2, quaternary ammonium groups are uniformly introduced into the surface of the porous body and inside the skeleton. Furthermore, when the ion exchange zone length regarding the fluoride ion of the monolith anion exchanger 2 was measured, the ion exchange zone length at a linear velocity of 20 m / h was 17 mm, which is a commercially available strong basic anion exchange resin. Compared with the value (165 mm) of Light IRA402BL (made by Rohm and Haas), the value was overwhelmingly short.

(Preparation of platinum group metal supported catalyst)
The monolith anion exchanger 2 was ion-exchanged into Cl form, then cut into a cylindrical shape in a wet state of water, 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 270 mg of palladium chloride was dissolved, and ion exchanged to the palladium acid form. After completion of the immersion, the ion-exchanged monolith anion exchanger was washed several times with pure water and immersed in a hydrazine aqueous solution for 24 hours for reduction treatment. The palladium acid form monolith anion exchanger was white, whereas the monolith anion exchanger after the reduction treatment was colored black, suggesting the formation of palladium nanoparticles. The palladium nanoparticle-supported catalyst 2 thus obtained was washed several times with pure water and dried.

  The amount of palladium supported on the dried palladium nanoparticle-supported catalyst 2 was 10.2% 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 5 nm.

<Manufacture of hydrogen peroxide decomposition treated water>
The dried palladium nanoparticle-supported catalyst 2 was packed in a column having an inner diameter of 10 mm, and a sodium hydroxide aqueous 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 2 was 12 mm. At this time, the supported amount of the palladium nanoparticles was 9.1 g with respect to 1 L of the palladium nanoparticle-supported catalyst in a water wet state.

Ultrapure water containing 15-30 μg / L of hydrogen peroxide was passed through the palladium nanoparticle-supported catalyst 2 at SV5000h ^{-1 for} 27 hours, and sample water was collected at the column outlet to collect 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. Hydrogen peroxide concentration of the sample water and water sampling in the column outlet, SV is very fast and 10000h ^-1, even though packed bed height of palladium nanoparticles supported catalyst 12mm and thin, less than 1 [mu] g / L, Hydrogen peroxide was decomposed and removed.

Comparative Example 4
The hydrogen peroxide decomposition effect at SV = 10000 h ⁻¹ was evaluated in the same manner as in Example 2 using only the monolith anion exchanger 2 without supporting palladium nanoparticles. As a result, the decomposition effect of hydrogen peroxide was not recognized.

Example 3
<Production of palladium nanoparticle-supported catalyst 3>
(Manufacture of monolith intermediates)
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) were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / SMO / 2,2′-azobis (isobutyronitrile) mixture is added to 180 g of pure water containing 1.8 ml of THF, and a vacuum stirring defoaming mixer which is a planetary stirring device. (EM Co., Ltd.) was used and stirred 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 produce a monolith intermediate having a continuous macropore structure. The average diameter of the opening (mesopore) where the macropores and macropores of the monolith intermediate overlap was 56 μm, and the total pore volume was 7.5 ml / g.

(Manufacture of monoliths)
Subsequently, 49.0 g of styrene, 1.0 g of divinylbenzene, 50 g of 1-decanol, 0.5 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and dissolved uniformly (step II). Next, the monolith intermediate 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 collected. The separated monolith intermediate is put in a reaction vessel having an inner diameter of 90 mm, immersed in the styrene / divinylbenzene / 1-decanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture, and removed in a vacuum chamber. After bubbling, the reaction vessel was sealed and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the monolith-like contents having a thickness of about 30 mm were taken out, subjected to Soxhlet extraction with acetone, and dried under reduced pressure at 85 ° C. overnight.

  FIG. 13 (a) shows the result of observing the internal structure of the monolith (dry body) containing 1.3 mol% of the crosslinking component composed of the styrene / divinylbenzene copolymer obtained by SEM as described above. The SEM image in FIG. 13A is an image at an arbitrary position on a cut surface obtained by cutting a monolith at an arbitrary position. As is clear from FIG. 13 (a), the monolith has a continuous macropore structure, and the skeleton constituting the continuous macropore structure is much thicker than known products, and the wall portion constituting the skeleton The thickness of was thick.

  Next, the thickness of the wall part and the area of the skeleton part appearing in the cross section were measured from two SEM images obtained by cutting the obtained monolith at a position different from the above position, excluding subjectivity, and three convenient points. The wall thickness was an average of 8 points obtained from one SEM photograph, and the skeleton area was determined by image analysis. The wall portion has the above definition. Moreover, the skeleton part area was shown by the 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 represented by the cross section was 28% in the SEM image. Moreover, the average diameter of the opening of the monolith measured by mercury porosimetry was 31 μm, and the total pore volume was 2.2 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 monolithic organic porous material, 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 to obtain a monolith anion exchanger 3.

  The swelling ratio of the obtained monolith anion exchanger 3 before and after the reaction was 1.7 times, and the ion exchange capacity per volume was 0.60 mg equivalent / ml in a wet state with water. The average diameter of the opening of the organic porous ion exchanger in the water-wet state was estimated to be 54 μm from the value of the organic porous body and the swelling ratio of the anion exchanger in the water-wet state. The average thickness of the wall part constituting the skeleton was 50 μm, the skeleton part area was 28% in the photographic region of the SEM photograph, and the total pore volume was 2.2 ml / g. The differential pressure coefficient, which is an index of pressure loss when water is permeated, is 0.017 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 a linear velocity of 20 m / h was 25 mm. Amberlite which is a commercially available strongly basic anion exchange resin Compared with the value (165 mm) of IRA402BL (Rohm and Haas), it was overwhelmingly short.

  Next, in order to confirm the distribution state of the quaternary ammonium groups in the monolith anion exchanger 3, the anion exchanger was treated with a hydrochloric acid aqueous solution to form a chloride form, and then the distribution state of chloride ions was observed by EPMA. . FIG. 14 shows the distribution state of chloride ions on the surface of the monolith anion exchanger, and FIG. 15 shows the distribution state of chloride ions on the skeleton cross section. It was also distributed uniformly inside, and it was confirmed that the quaternary ammonium group was uniformly introduced into the monolith anion exchanger 3. In FIG. 15, the chloride ion concentration in the lower part of the skeleton is apparently higher than that in the upper part of the skeleton, but this is not sufficient in cross-sectional flatness at the time of cutting, and the lower part of the skeleton is raised from the upper part of the skeleton. This is because the distribution of chloride ions is substantially uniform.

(Preparation of platinum group metal supported catalyst)
The monolith anion exchanger 3 was ion-exchanged into Cl form, then cut into a cylindrical shape in a wet state of water, 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 270 mg of palladium chloride was dissolved, and ion exchanged to the palladium 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 palladium acid form monolith anion exchanger was white, whereas the monolith anion exchanger after the reduction treatment was colored black, suggesting the formation of palladium nanoparticles. The palladium nanoparticle-supported catalyst 3 thus obtained was washed several times with pure water and dried.

  The amount of palladium nanoparticles supported on the dried palladium nanoparticle-supported catalyst 3 was 10.3% 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 5 nm. A palladium nanoparticle-supported catalyst in a dry state was packed in a column having 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 3 was 11 mm. At this time, the supported amount of palladium nanoparticles was 14.7 g with respect to 1 L of the palladium nanoparticle-supported catalyst in a wet state.

<Manufacture of hydrogen peroxide decomposition treated water>
Ultrapure water containing 15 to 30 μg / L of hydrogen peroxide was passed through the palladium nanoparticle-supported catalyst 3 packed in a column with an inner diameter of 10 mm for 27 hours at SV = 5000 h ⁻¹ at the column outlet. 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 10000 h ⁻¹ and the packed bed height of the catalyst is as thin as 11 mm, which is less than 1 μg / L. It was disassembled and removed.

Example 4
<Production of palladium nanoparticle-supported catalyst 4>
The dried palladium nanoparticle-supported catalyst was prepared in the same manner as in Example 3 except that the weight of the dried monolith anion exchanger was 1.7 g and the monolith anion exchanger was immersed in dilute hydrochloric acid in which 2.5 mg of palladium chloride was dissolved for 24 hours. 4 was produced. The amount of palladium nanoparticles supported on the dried palladium nanoparticle-supported catalyst 4 was 0.05% by weight.

  The palladium nanoparticle-supported catalyst 4 in a dry state was packed in a column having an inner diameter of 10 mm, and a sodium hydroxide aqueous 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 4 was 19 mm. At this time, the supported amount of palladium nanoparticles was 0.07 g with respect to 1 L of the palladium nanoparticle-supported catalyst in a wet state.

<Manufacture of hydrogen peroxide decomposition treated water>
Ultrapure water containing 15 to 30 μg / L of hydrogen peroxide was passed through the palladium nanoparticle-supported catalyst packed in a column with an inner diameter of 10 mm at SV = 5000 h ⁻¹ for 27 hours, and sample water was discharged at the column outlet. 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 1.7 μg / L, and the amount of palladium nanoparticles supported on 1 L of the palladium nanoparticle-supported catalyst is very low at 0.07 g. The result with high hydrogen oxide decomposition effect was obtained.

Comparative Example 5
The hydrogen peroxide decomposition effect at SV = 10000 h ⁻¹ was evaluated in the same manner as in Example 3 using only the monolith anion exchanger 3 without supporting palladium nanoparticles. As a result, the decomposition effect of hydrogen peroxide was not recognized.

Example 5
<Production of palladium nanoparticle-supported catalyst 5>
(Manufacture of monolith intermediates)
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) were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / SMO / 2,2′-azobis (isobutyronitrile) mixture was added to 180 g of pure water, and a vacuum stirring defoaming mixer (manufactured by EM Co.) as 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. This emulsion was quickly transferred to a reaction vessel and allowed to polymerize at 60 ° C. for 24 hours in a static state after sealing. After completion of the polymerization, the content was taken out, extracted with methanol, and then dried under reduced pressure to produce a monolith intermediate having a continuous macropore structure. When the internal structure of the monolith intermediate (dry body) thus obtained was observed with an SEM image (FIG. 21), the wall portion separating two adjacent macropores was extremely thin and rod-shaped, but the open cell structure The average diameter of the openings (mesopores) where the macropores overlap with each other as measured by the mercury intrusion method was 70 μm, and the total pore volume was 17.8 ml / g.

(Manufacture of monoliths)
Subsequently, 39.2 g of styrene, 0.8 g of divinylbenzene, 60 g of 1-decanol, and 0.8 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and dissolved uniformly. Next, the monolith intermediate was cut into a disk shape having a diameter of 70 mm and a thickness of about 30 mm to obtain 2.4 g. The separated monolith intermediate is placed in a reaction vessel having an inner diameter of 75 mm, immersed in the styrene / divinylbenzene / 1-decanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture, and removed in a vacuum chamber. After bubbling, the reaction vessel was sealed and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the monolith-like contents having a thickness of about 60 mm were taken out, subjected to Soxhlet extraction with acetone, and dried under reduced pressure at 85 ° C. overnight.

  FIG. 17 shows the result of observing the internal structure of the monolith (dry body) containing 1.3 mol% of the crosslinking component composed of the styrene / divinylbenzene copolymer obtained by SEM as described above. As is clear from FIG. 17, the monolith has a co-continuous structure in which the skeleton and the vacancies are three-dimensionally continuous, and both phases are intertwined. Moreover, the thickness of the skeleton measured from the SEM image was 8 μm. Further, the size of the three-dimensionally continuous pores of the monolith measured by mercury porosimetry was 18 μm, and the total pore volume was 2.0 ml / g.

(Production of monolith 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. 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 dropping, the temperature was raised and the reaction was carried out 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 monolithic organic porous material, 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 to obtain a monolith anion exchanger 5.

  The swelling ratio of the obtained monolith anion exchanger 5 before and after the reaction was 1.6 times, and the ion exchange capacity per volume was 0.44 mg equivalent / ml in a water wet state. The diameter of the continuous pores of the monolith ion exchanger 5 in the water wet state was estimated from the value of the monolith and the swelling ratio of the anion exchanger in the water wet state to be 29 μm, the thickness of the skeleton was 13 μm, and the total pores The volume was 2.0 ml / g.

  Further, the differential pressure coefficient, which is an index of pressure loss when water is permeated, is 0.040 MPa / m · LV, which is a low pressure loss that does not cause any practical problems. Furthermore, when the ion exchange zone length regarding the fluoride ion of the monolith anion exchanger 4 was measured, the ion exchange zone length at LV = 20 m / h was 22 mm, which is a commercially available strong basic anion exchange resin. It was overwhelmingly shorter than the value (165 mm) of Light IRA402BL (Rohm and Haas).

  Next, in order to confirm the distribution state of the quaternary ammonium groups in the monolith anion exchanger 5, 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. . The distribution state of chloride ions on the surface of the monolith anion exchanger 5 is shown in FIG. 18, and the distribution state of chloride ions in the skeleton cross section is shown in FIG. 19, but the chloride ions are not limited to the skeleton surface of the anion exchanger. It was uniformly distributed inside, and it was confirmed that quaternary ammonium groups were uniformly introduced into the monolith anion exchanger. In FIG. 19, the chloride ion concentration in the peripheral part of the skeleton is apparently higher than that in the central part of the skeleton. It is because it cut | disconnected in the raised state, and the distribution of a chloride ion is substantially uniform.

(Preparation of platinum group metal supported catalyst)
Monolith anion exchange was carried out in the same manner as in Example 3 except that monolith anion exchanger 5 was used as the catalyst carrier and that the weight of dried monolith anion exchanger 5 was 1.4 g. The palladium nanoparticle was supported on the body 5 to obtain a palladium nanoparticle-supported catalyst 5.

  The supported amount of palladium nanoparticles supported on the dried palladium nanoparticle-supported catalyst 5 was 9.8% 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. A column with a diameter of 10 mm is packed with a second palladium nanoparticle-supported catalyst in a dry state, and an aqueous sodium hydroxide solution is passed through to convert the monolith anion exchanger as a carrier into OH form, which is used for evaluation of hydrogen peroxide decomposition characteristics. It was. The packed bed height of the catalyst was 13 mm. At this time, the supported amount of palladium nanoparticles was 8.7 g based on 1 L of the palladium nanoparticle-supported catalyst in a wet state.

<Manufacture of hydrogen peroxide decomposition treated water>
The hydrogen peroxide decomposition effect of the palladium nanoparticle-supported catalyst was evaluated in the same manner as in Example 3 except that the palladium nanoparticle-supported catalyst 5 was used as a catalyst. As a result, in either case that passed through the ultra-pure water at SV = 5000h ^-1 and 10000h ^-1, the hydrogen peroxide concentration of the sample water and water sampling in the column outlet is less than 1 [mu] g / L, hydrogen peroxide It was disassembled and removed.

Comparative Example 6
The hydrogen peroxide decomposition effect at SV = 10000 h ⁻¹ was evaluated in the same manner as in Example 4 using only the monolith anion exchanger 4 without supporting palladium nanoparticles. As a result, the decomposition effect of hydrogen peroxide was not recognized.

According to the present invention, by using a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger, by decomposing hydrogen peroxide in water to be treated, SV is reduced to 2000 h ⁻¹ . To provide a method and a production apparatus for producing hydrogen peroxide decomposition treated water by decomposing and removing hydrogen peroxide with high efficiency even if water is passed through an SV exceeding the above or the packed bed height of the catalyst is reduced. it can. Further, according to the present invention, SV is or passed through in large SV exceeding 2000h ^-1, even by reducing the packed bed height of the catalyst, and decomposing and removing hydrogen peroxide with high efficiency, ultra-pure A method and apparatus for producing water, a method and apparatus for producing hydrogen-dissolved water, a method and apparatus for producing ozone-dissolved water can be provided. Furthermore, according to the present invention, it is possible to provide a treatment tank capable of downsizing and easily maintaining and managing the ultrapure water production apparatus, the hydrogen dissolved water production apparatus, the ozone dissolved water production apparatus, and the like. According to the present invention, cleaning of electronic components using the cleaning water containing the hydrogen peroxide decomposition treated water, the cleaning water containing ultrapure water, the cleaning water containing hydrogen-dissolved water, or the cleaning water containing ozone-dissolved water is performed. A method can be provided.

DESCRIPTION OF SYMBOLS 1 Ultrapure water production device 2 Pretreatment system 3 Primary pure water system 4 Subsystem 5 Ultrapure water 6 Circulation line 7 Hydrogen dissolution treatment device 8 Treatment line 10 Hydrogen supply source 11 Piping 12 Ozone dissolution treatment device 13 Treatment line 15 Ozone Supply source 16 Piping

Claims (24)

  A method for producing hydrogen peroxide decomposition treated water, comprising contacting a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger and hydrogen peroxide-containing water.   The method for producing hydrogen peroxide decomposition treated water according to claim 1, wherein the amount of the platinum group metal supported is 10 to 30000 mg per liter of the platinum group metal supported catalyst.   The method for producing hydrogen peroxide-decomposed water according to claim 1 or 2, wherein the monolithic organic porous anion exchanger is in an OH form. The method for producing hydrogen peroxide decomposition treated water according to any one of claims 1 to 3, wherein the hydrogen peroxide-containing water is brought into contact with the platinum group metal-supported catalyst at a space velocity of 2000 h ^{-1 to} 20000 h ^-1. .   A hydrogen peroxide decomposition treatment comprising a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger, and having a contact treatment section between the catalyst and hydrogen peroxide-containing water Water production equipment.   A platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger and a non-regenerative ion exchange resin or a monolithic organic porous ion exchanger in this order with respect to the water to be treated. It is arrange | positioned in the same container so that it may contact, and the processing tank characterized by the above-mentioned.   A platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger, a non-regenerative ion exchange resin or monolithic organic porous ion exchanger, and a separation membrane are added to the water to be treated. It arrange | positions in the same container so that it may contact with this order with respect to this, The processing tank characterized by the above-mentioned.   A platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger and a separation membrane are arranged in the same container so as to come into contact with the water to be treated in this order. A treatment tank characterized by that.   UV oxidation treatment of water to be treated, hydrogen peroxide decomposition treatment in which a platinum group metal supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger, and a non-regenerative ion exchange resin A method for producing ultrapure water, characterized in that an ion exchange treatment to be contacted and a filtration treatment with a separation membrane are performed in this order.   The ultraviolet oxidation apparatus, the hydrogen peroxide decomposition treated water production apparatus according to claim 5, the non-regenerative ion exchange apparatus including the non-regenerative ion exchange resin, and the membrane separation apparatus are passed in this order. A device for producing ultrapure water, characterized in that it is installed as described above.   An apparatus for producing ultrapure water, wherein the ultraviolet oxidation apparatus, the treatment tank according to claim 6 and the membrane separation apparatus are installed so as to pass water in this order.   An apparatus for producing ultrapure water, wherein an ultraviolet oxidation apparatus and the treatment tank according to claim 7 or 8 are installed so as to pass water in this order.   Contacting a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger and hydrogen peroxide-containing water; and contacting the platinum group metal-supported catalyst and hydrogen peroxide-containing water. A method for producing hydrogen-dissolved water, comprising a hydrogen-dissolving step for water to be treated as a pre-process or a post-process of the step to be performed.   6. The apparatus for producing hydrogen peroxide decomposition treated water according to claim 5, and a hydrogen dissolution treatment apparatus for water to be treated on the upstream side or downstream side of the apparatus for producing hydrogen peroxide decomposition treated water. An apparatus for producing hydrogen-dissolved water.   The treatment tank according to claim 6 and the membrane separation apparatus are installed so as to pass water in this order, and a hydrogen dissolution treatment apparatus for water to be treated is provided upstream or downstream of the treatment tank. An apparatus for producing hydrogen-dissolved water.   An apparatus for producing hydrogen-dissolved water, comprising: the treatment tank according to claim 7 or 8; and a hydrogen dissolution treatment apparatus for water to be treated on an upstream side or a downstream side of the treatment tank.   Contacting a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger and hydrogen peroxide-containing water; and contacting the platinum group metal-supported catalyst and hydrogen peroxide-containing water. And a step of dissolving ozone in the treated water obtained by the method.   An apparatus for producing ozone-dissolved water, comprising the apparatus for producing hydrogen peroxide-decomposed treated water according to claim 5 and an ozone-dissolving treatment apparatus on the downstream side of the apparatus for producing hydrogen peroxide-decomposed treated water. apparatus.   The apparatus for producing ozone-dissolved water according to claim 18, further comprising a membrane separation device on the downstream side of the apparatus for producing hydrogen peroxide-decomposed water and upstream of the ozone-dissolving treatment apparatus.   An ion exchange tank further comprising a non-regenerative ion exchange resin or a monolithic organic porous ion exchanger on the downstream side of the apparatus for producing hydrogen peroxide decomposition treated water and upstream of the ozone dissolution treatment apparatus, and a membrane The apparatus for producing ozone-dissolved water according to claim 18, wherein the separator is provided in this order.   The treatment tank according to claim 6 and a membrane separation device are installed so as to pass water in this order, and an ozone dissolution treatment device is provided on the downstream side of the membrane separation device. Dissolved water production equipment.   An apparatus for producing ozone-dissolved water, comprising: the treatment tank according to claim 7; and an ozone dissolution treatment apparatus on a downstream side of the treatment tank.   An apparatus for producing ozone-dissolved water, comprising: the treatment tank according to claim 8; and an ozone dissolution treatment apparatus on a downstream side of the treatment tank.   Washing water containing hydrogen peroxide decomposition treated water obtained by the method according to any one of claims 1 to 4 or the apparatus according to claim 5, the method according to claim 9, or the claims 10 to 10. Washing water containing ultrapure water obtained by the apparatus according to any one of claims 12 to 13, Washing containing hydrogen-dissolved water obtained by the method according to claim 13 or the apparatus according to any one of claims 14 to 16. Washing the surface with water or at least one kind of washing water selected from washing water containing ozone-dissolved water obtained by the method according to claim 17 or the apparatus according to any one of claims 18 to 23. A method for cleaning electronic components.