JP2010240642A - Method of manufacturing dissolved oxygen-removed water, apparatus for manufacturing dissolved oxygen-removed water, dissolved oxygen treatment tank, method of manufacturing ultrapure water, method of manufacturing hydrogen dissolved water, apparatus for manufacturing hydrogen dissolved water, and method of cleaning electronic components - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing dissolved oxygen-removed water by efficiently removing dissolved oxygen in water to be treated 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>and thinning a packed bed height of catalyst. <P>SOLUTION: In the method of manufacturing dissolved oxygen-removed water, hydrogen is dissolved into oxygen-dissolved water, and thereafter, the oxygen-dissolved water into which hydrogen has been dissolved 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 dissolved oxygen removal water, a device for producing dissolved oxygen removal water, a dissolved oxygen treatment tank, a method for producing ultrapure water, a device for producing ultrapure water, a method for producing hydrogen dissolved water, and a method for producing hydrogen dissolved water. The present invention relates to a manufacturing apparatus and a method for cleaning an electronic component.

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

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

  For example, dissolved oxygen contained in ultrapure water forms a natural oxide film on the surface of a silicon wafer. When a natural oxide film is formed on the wafer surface, it prevents growth of epitaxial Si thin films at low temperatures, hinders precise control of gate oxide film pressure and film quality, and causes increase in contact resistance of contact holes. It becomes. Therefore, it is necessary to suppress the formation of a natural oxide film on the wafer surface as much as possible, and various methods for suppressing the amount of dissolved oxygen in ultrapure water have been proposed (for example, Patent Document 1 (Japanese Patent Laid-Open 9-29251)).

  In order to suppress the formation of the natural oxide film, dissolved oxygen is reduced by using a deaerator in the ultrapure water production apparatus, particularly in the primary pure water system. With this deaeration device, the dissolved oxygen concentration in the water to be treated (primary pure water) at the subsystem inlet is usually reduced to 100 μg / L or less. Furthermore, it may be controlled to 10 μg / L or less.

  On the other hand, in a semiconductor manufacturing process, hydrogen-dissolved water is known as cleaning water for an object to be processed such as a substrate. This hydrogen-dissolved water is obtained by dissolving hydrogen gas in ultrapure water as raw water. This hydrogen-dissolved water is also desired to have a natural oxide film formed on the surface of the object to be processed, in which the amount of dissolved oxygen is reduced.

  However, in the semiconductor manufacturing process, a device that supplies cleaning water with a smaller size and higher efficiency has been demanded.

JP-A-9-29251

Under such circumstances, the present invention removes dissolved oxygen with high efficiency even if water is passed with a large SV such that the space velocity (SV) exceeds 2000 h ^-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 dissolved oxygen-removed water. In addition, the present invention eliminates dissolved oxygen with high efficiency even when water is passed through a large SV that exceeds 2000 h ^-1 during the removal of dissolved oxygen, or even if the packed bed height of the catalyst is reduced. A second object is to provide a method and a production apparatus for producing pure water. Furthermore, a third object of the present invention is to provide a dissolved oxygen treatment tank that can downsize the apparatus for producing ultrapure water and the like and can easily maintain and manage it. In addition, the present invention eliminates dissolved oxygen with high efficiency even when water is passed through a large SV such that the SV exceeds 2000 h ^-1 during the dissolved oxygen removal treatment or the packed bed height of the catalyst is reduced. A fourth object is to provide a method and a production apparatus for producing dissolved water. A fifth object of the present invention is to provide a method for cleaning an electronic component using cleaning water containing the dissolved oxygen-removed water, ultrapure water, or hydrogen-dissolved water.

  As a result of intensive studies to achieve the above object, the present inventors have made platinum obtained by dissolving a hydrogen in oxygen-dissolved water and then supporting a platinum group metal on a monolithic organic porous anion exchanger. The present inventors have found that the above technical problem can be solved by producing dissolved oxygen-removed water by bringing it into contact with a Group metal supported catalyst, and have completed the present invention based on this finding.

That is, the present invention
(1) After dissolving hydrogen in oxygen-dissolved water, the dissolved oxygen-removed water is brought into contact with a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger. Production method,
(2) The method for producing dissolved oxygen-removed water according to (1), wherein the supported amount of the platinum group metal is 10 to 30000 mg per liter of the platinum group metal supported catalyst,
(3) The method for producing dissolved oxygen-removed water according to (1) or (2) above, wherein the monolithic organic porous anion exchanger is in the OH form.
(4) The oxygen-dissolved water in which the hydrogen is dissolved is brought into contact with the platinum group metal-supported catalyst at a space velocity of 2000 h ^{−1 to} 20000 h ⁻¹ , according to any one of the above (1) to (3). A method for producing dissolved oxygen removal water,
(5) It includes a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger, and has a reaction part for bringing the catalyst into contact with oxygen-dissolved water in the presence of hydrogen. Dissolved oxygen removal water production equipment,
(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. Dissolved oxygen treatment tank (hereinafter referred to as the dissolved oxygen treatment tank 1 of the present invention as appropriate), which is arranged in the same container so as to 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. Dissolved oxygen treatment tank (hereinafter referred to as the dissolved oxygen treatment tank 2 of the present invention as appropriate), 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 dissolved oxygen treatment tank (hereinafter referred to as the dissolved oxygen treatment tank 3 of the present invention, as appropriate),
(9) Ultraviolet oxidation treatment, hydrogen dissolution treatment, and dissolved oxygen removal treatment in which a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger is brought into contact with oxygen-dissolved water; A method for producing ultrapure water, characterized in that an ion exchange treatment in contact with a non-regenerative ion exchange resin and a filtration treatment with a separation membrane are performed in this order;
(10) An ultraviolet oxidation device, a hydrogen dissolution treatment device, the dissolved oxygen-removed water production device according to (5) above, a non-regenerative ion exchange device containing a non-regenerative ion exchange resin, and a membrane separation device The ultrapure water production apparatus (hereinafter referred to as ultrapure water production apparatus 1 of the present invention as appropriate), characterized in that it is installed to pass water in this order,
(11) Ultra-pure, characterized in that an ultraviolet oxidation device, a hydrogen dissolution treatment device, a dissolved oxygen treatment tank described in (6) above, and a membrane separation device are installed so as to pass water in this order. Water production apparatus (hereinafter referred to as ultrapure water production apparatus 2 of the present invention as appropriate),
(12) A device for producing ultrapure water, characterized in that an ultraviolet oxidation device, a hydrogen dissolution treatment device, and the dissolved oxygen treatment tank described in (7) are installed so as to pass water in this order ( Hereinafter, the ultrapure water production apparatus 3 of the present invention is referred to as appropriate),
(13) A device for producing ultrapure water, characterized in that an ultraviolet oxidation device, a hydrogen dissolution treatment device, and the dissolved oxygen treatment tank described in (8) are installed so as to pass water in this order ( Hereinafter, the ultrapure water production apparatus 4 of the present invention is referred to as appropriate),
(14) A step of dissolving hydrogen in oxygen-dissolved water, and a contact treatment between a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger and the oxygen-dissolved water in which hydrogen is dissolved A process for producing hydrogen-dissolved water, comprising the step of:
(15) The apparatus for producing dissolved oxygen-removed water described in (5) above, and a hydrogen-dissolving treatment apparatus for water to be treated at least upstream of the apparatus for producing dissolved oxygen-removed water, Hydrogen dissolved water production equipment,
(16) Washing water containing dissolved oxygen-removed water obtained by the method according to any one of (1) to (4) above or the device 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 (13) or washing containing hydrogen-dissolved water obtained by the method according to (14) above or the apparatus according to (15) above A method for cleaning an electronic component, wherein the surface is cleaned with at least one cleaning water selected from water,
Is to provide.

According to the present invention, using a monolithic organic porous platinum group metal supported catalyst the anion exchanger platinum group metal is formed by carrying, by removing the dissolved oxygen in the water to be treated, SV exceeds 2000h ^-1 Even if water is passed through such an SV or the packed bed height of the catalyst is made thin, dissolved oxygen can be removed with high efficiency and a method and a production apparatus for producing dissolved oxygen-removed water can be provided. In addition, according to the present invention, even when water is passed through a large SV that exceeds 2000 h ⁻¹ when removing dissolved oxygen, or even if the packed bed height of the dissolved oxygen removal catalyst is reduced, dissolved oxygen can be made highly efficient. It is possible to provide a method and an apparatus for producing ultrapure water by removing and a method and an apparatus for producing hydrogen-dissolved water. Furthermore, according to the present invention, it is possible to provide a dissolved oxygen treatment tank that can downsize the ultrapure water production apparatus and the like and can be easily maintained. In addition, according to the present invention, it is possible to provide a method for cleaning an electronic component using cleaning water containing the dissolved oxygen-removed water, ultrapure water, or hydrogen-dissolved water.

It is a figure which shows the example of an aspect of a hydrogen dissolution processing apparatus. It is a figure which shows the example of an aspect of a dissolved oxygen processing tank. It is a figure which shows the example of an aspect of the manufacturing apparatus of ultrapure 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 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 the apparatus schematic used in the Example and comparative example of this invention. It is a SEM image of a monolith (known product). It is the figure which showed typically the co-continuous structure of the 4th monolith anion exchanger.

  The present invention relates to a method for producing dissolved oxygen removal water, a device for producing dissolved oxygen removal water, a dissolved oxygen treatment tank, a method for producing ultrapure water, a device for producing ultrapure water, a method for producing hydrogen dissolved water, and a method for producing hydrogen dissolved water. The invention consists of a manufacturing apparatus and a method for cleaning an electronic component, but these inventions share the point of using a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger. 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 dissolved oxygen-removed water>
First, the manufacturing method of the dissolved oxygen removal water of this invention is demonstrated.

  In the method for producing dissolved oxygen-removed water of the present invention, hydrogen is dissolved in oxygen-dissolved water, and then contacted with a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger. It is characterized by.

  The oxygen-dissolved water is not particularly limited, and examples thereof include water generated in various steps in the production process of ultrapure water for cleaning semiconductor electronic component surfaces and semiconductor electronic component manufacturing equipment. In addition, water generated in a primary pure water system or a secondary pure water system (subsystem) in the production process of ultrapure water can be mentioned.

  The oxygen concentration in the oxygen-dissolved water is not particularly limited, but is usually 0.01 to 10 mg / L (0.01 to 10 ppm). In addition, the oxygen concentration contained in the to-be-processed water of the subsystem which comprises the manufacturing apparatus of ultrapure water which is 1 type of oxygen dissolved water is about 10-100 microgram / L normally.

  As a hydrogen dissolution treatment apparatus used for dissolving hydrogen in oxygen-dissolved water, for example, as shown in FIG. 1, a gas permeable film (not shown) is provided in a treatment line 8 of 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 suitable. 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.

  The amount of hydrogen supply is preferably equal to or greater than the theoretical amount that generates water by reacting with dissolved oxygen in water, and is usually 1 to 10 times equivalent, and 1.1 to 5 times equivalent. Is more appropriate.

  The method for bringing the hydrogen-dissolved oxygen-dissolved water into contact with the platinum group metal-supported catalyst is not particularly limited. For example, the oxygen-dissolved water is supplied to a catalyst packed tower packed with a platinum group metal-supported catalyst in layers. And a method of passing water.

The flow rate of the oxygen-dissolved 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 dissolved oxygen removal capacity, dare need not be a water flow rate of less than SV2000h ^-1, may be a water flow rate of less than SV2000h ^-1, passing Even when the water speed is less than SV2000h- ¹ , excellent dissolved oxygen removal property 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 dissolved oxygen-removed water of 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, a large SV exceeding 2000 h ⁻¹ is obtained. Even if the water to be treated is passed through the SV, dissolved oxygen can be removed, and an excellent effect can be obtained compared to the case where a conventional supported catalyst in which platinum group metal nanoparticles are supported on a particulate anion exchange resin is used. be able to.

  The layer height of the platinum group metal-supported catalyst layer through which oxygen-dissolved water flows is suitably 5 to 100 mm, more preferably 10 to 50 mm, and 10 to 25 mm. Is more appropriate. 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 the removal of dissolved oxygen may be insufficient. 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 dissolved oxygen-removed water of the present invention, the temperature at which the platinum group metal-supported catalyst and the oxygen-dissolved water in which hydrogen is dissolved is preferably 5 to 60 ° C, more preferably 10 to 50 ° C, and more preferably 20 to 20 ° C. 30 ° C. is more preferable.

  In the method for producing dissolved oxygen-removed water of the present invention, hydrogen is added to the oxygen-dissolved water and brought into contact with the platinum group metal-supported catalyst, whereby oxygen and hydrogen react to produce water, and oxygen in the water to be treated is produced. It can be removed and its concentration reduced.

  In the method for producing dissolved oxygen-removed 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, a normal particulate anion exchange resin is used. Compared with the case where it uses, the contact efficiency with to-be-processed water can be raised significantly. And in the manufacturing method of the dissolved oxygen removal water of this invention, since the said platinum group metal carrying | support catalyst is used, the capability (removal capability of dissolved oxygen) to generate water by reacting dissolved oxygen and hydrogen is produced. The amount of dissolved oxygen in the water to be treated can be sufficiently removed even if the packed bed height of the catalyst is reduced.

  In the method for producing dissolved oxygen-removed water according to the present invention, by reducing the oxygen concentration in the obtained dissolved oxygen-removed water to 10 μg / L (10 ppb) or less, preferably 1 μg / L (1 ppb) or less, It is preferable to suppress the unexpected oxidation of the silicon wafer surface as much as possible, such as formation of a natural oxide film in the silicon wafer cleaning process.

  The degree to which the dissolved oxygen concentration is reduced can be adjusted by adjusting the height of the platinum group metal-supported catalyst layer, the amount of SV or platinum group metal supported when water is passed.

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

  The apparatus for producing dissolved oxygen-removed 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 catalyst and oxygen-dissolved water are contacted in the presence of hydrogen. It has the reaction part to be made.

  In the apparatus for producing dissolved oxygen-removed water according to the present invention, the oxygen-dissolved water, the means and supply amount for supplying hydrogen, the contact conditions such as SV during water flow, and the obtained dissolved oxygen-removed water are The contents are the same as those described in the explanation of the method for producing dissolved oxygen-removed water.

  The form of the reaction portion between the platinum group metal supported catalyst and the oxygen-dissolved water is not particularly limited, and examples thereof include a form of a platinum group metal catalyst layer in which a catalyst packed tower is packed with a platinum group metal supported catalyst. .

  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 the removal of dissolved oxygen may be insufficient. 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 dissolved oxygen removal 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, a normal particulate anion exchange resin is used. Compared with the case where it uses, contact efficiency with to-be-processed water can be improved markedly, and the length of an ion exchange zone can be shortened overwhelmingly. And since the said platinum group metal carrying | support catalyst reacts dissolved oxygen and hydrogen and produces | generates water (dissolved oxygen removal ability) remarkably high, even if it makes the packed bed height of a catalyst thin, Dissolved oxygen can be sufficiently 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.

<Dissolved oxygen treatment tank>
Next, the dissolved oxygen treatment tank of the present invention will be described.

  The dissolved oxygen 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, a non-regenerative ion exchange resin or a monolithic organic porous ion exchanger, However, it is arrange | positioned in the same container so that it may contact with to-be-processed water in this order, It is characterized by the above-mentioned.

  In the dissolved oxygen 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 has an inlet and an outlet for water flow. If it is, it will not restrict | limit in particular, An annular thing, such as a column, a cartridge etc. can be mentioned.

  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.2 (a)-FIG.2 (c) can be mentioned.

  FIG. 2 (a) 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. 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. 2B shows a cartridge-like substantially cylindrical container having a water inlet for introducing the water to be treated into the inside from the outer side surface of the container and a water outlet for draining the water to be treated introduced into the inside from the top. 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. 2 (c) has an inlet and an outlet for passing water to be treated introduced from the top of the figure in the downward direction, and a water pipe extending 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, the adjustment chamber is filled with a platinum group metal-supported catalyst α, and the entire exterior of the adjustment chamber is non-regenerative An 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 filled in a container. An arrangement form is shown.

  In the embodiment shown in FIG. 2 (a), the layer height of the platinum group metal supported catalyst in the container is suitably 5 to 100 mm, more suitably 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. 2A, when the non-regenerative ion exchange resin is included in the container, the layer height is preferably 30 to 1000 mm, and more preferably 50 to 1000 mm. Moreover, in the aspect shown to Fig.2 (a), when a container contains a monolithic organic porous ion exchanger, the layer height is preferably 5 to 100 mm, more preferably 10 to 50 mm, and even more preferably 10 to 25 mm. .

  In the dissolved oxygen 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, Include a single bed layer of strong basic anion exchange resin on the inlet side, a mixed bed layer of strong acid cation exchange resin and strong basic anion exchange resin on the outlet side, etc. Can do.

  In the dissolved oxygen treatment tank 1 of the present invention, as the monolithic organic porous ion exchanger, those containing a monolithic organic porous anion exchanger are preferable. And an organic porous anion exchanger and a monolithic organic porous cation exchanger. 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 dissolved oxygen treatment tank 1 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 a non-regenerative ion exchange resin or a monolithic organic porous ion exchanger. Because it is housed in the same container, the ultrapure water production equipment described below can simplify the equipment configuration, reduce the installation area, and maintain it especially when the treatment tank is made into a cartridge. Can be reduced. In particular, when the treatment tank is made into a cartridge, 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 the platinum group metal 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 dissolved oxygen treatment tank 1 of the present invention is not particularly limited. For example, a platinum group metal-supported catalyst and a non-catalyst can be formed on a container such as a cartridge having a desired internal space shape by a known method. Examples thereof include a method of filling a regenerated ion exchange resin or a monolithic organic porous ion exchanger.

  The dissolved oxygen treatment tank 2 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, a non-regenerative ion exchange resin or a monolithic organic porous ion exchanger, The separation membrane is arranged in the same container so as to come into contact with the water to be treated in this order.

  The dissolved oxygen treatment tank 2 of the present invention is the same as the dissolved oxygen 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, The specific examples of the monolithic organic porous ion exchanger and the layer height at the time of filling are preferably the same.

  Further, in the dissolved oxygen treatment tank 2 of the present invention, the arrangement 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 container is as follows: If it arrange | positions so that it may contact with this order with respect to water, it will not restrict | limit in particular, For example, the form shown to FIG.2 (d) and FIG.2 (e) can be mentioned.

  FIG. 2 (d) shows a platinum group metal-supported catalyst α at the bottom of the container in a cartridge-like schematic 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. 2 (e) shows a cylindrical container having an internal structure that is divided into an outer peripheral part and a central part, and the outer peripheral part is divided into two layers, upper and lower, and water to be treated is introduced into the lower part of the outer peripheral part. 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 dissolved oxygen 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 dissolved oxygen treatment tank 2 of the present invention is further provided with a separation membrane at the rear stage of the dissolved oxygen treatment tank 1 of the present invention, so that the dissolved oxygen treatment tank 1 of the present invention has the effects of the platinum group metal supported catalyst and non- Even when platinum group metals and fine particles are eluted and produced from the regenerative ion exchange resin or the monolithic organic porous ion exchanger, they can be more easily separated by filtration.

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

  In the dissolved oxygen 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. As described above, they are arranged in the same container.

  The dissolved oxygen treatment tank 3 of the present invention is the same as the dissolved oxygen 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, and is a platinum group metal. It is preferable that the specific examples of the supported catalyst, the separation membrane, the bed height at the time of filling, and the like are the same.

  Moreover, in the dissolved oxygen processing tank 3 of this invention, the arrangement | positioning form in a container of a platinum group metal carrying | support catalyst and a separation membrane is arrange | positioned so that it may contact with to-be-processed water in this order. If there is, it will not restrict | limit in particular, For example, the form shown in FIG.1 (f) can be mentioned.

  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 dissolved oxygen treatment tank 3 of the present invention can obtain the same effects as the dissolved oxygen 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 platinum group metals and the like are eluted from the supported catalyst, they can be more easily separated by filtration.

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

  The dissolved oxygen treatment tank 1, the dissolved oxygen treatment tank 2, and the dissolved oxygen treatment tank 3 of the present invention can be suitably used as a treatment tank or the like constituting an ultrapure water production apparatus.

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

  The ultrapure water production method of the present invention comprises an ultraviolet oxidation treatment, a hydrogen dissolution treatment, and a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger with respect to oxygen-dissolved water. The dissolved oxygen removal treatment to be brought into contact, the ion exchange treatment to be brought into contact with the non-regenerative ion exchange resin, and the 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. 3 (a) or 3 (b).

  That is, in the apparatus for producing ultrapure water shown in FIGS. 3A and 3B, first, 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. 3 (a) and 3 (b), the obtained primary pure water is stored in a pure water storage tank constituting the subsystem 4, and thereafter, an ultraviolet oxidation device, a hydrogen dissolution treatment device, and dissolved oxygen. In the apparatus for producing removed water, the non-regenerative ion exchange device, and the membrane separation device, in order, the ultraviolet oxidation treatment, the hydrogen dissolution treatment, the dissolved oxygen removal treatment that makes contact with the platinum group metal supported catalyst, and the non-regeneration ion exchange resin. Ion exchange treatment and filtration treatment with a separation membrane are 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 dissolution treatment apparatus for performing the hydrogen dissolution treatment and the treatment conditions such as the hydrogen supply amount are the same as those described in the explanation of the method for producing dissolved oxygen removal water of the present invention. .

  In the method for producing ultrapure water of the present invention, the dissolved oxygen-removed water producing apparatus for removing dissolved oxygen is preferably the dissolved oxygen-removed water producing apparatus of the present invention. The apparatus for producing dissolved oxygen-removed 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. It is preferable to carry out with a deaeration device. As shown in FIGS. 3 (a) and 3 (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 ultra method for producing pure water of the present invention, water flow rate, during at least the dissolved oxygen removal process ^is preferably SV2000h ^-1 ~20000h ^-1, and more preferably SV5000h ^-1 ~10000h -1 . The ultrapure water production method of the present invention removes dissolved oxygen in the 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. Even if the water to be treated is passed through a large SV such that the SV exceeds 2000 h ⁻¹ , the dissolved oxygen can be removed, and even if the SV is about 10000 h ⁻¹ , the platinum group metal supported catalyst By using, dissolved oxygen can be removed. Incidentally, platinum group metal supported catalyst used in the present invention has high remarkably dissolved oxygen removal capacity, dare 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 dissolved oxygen removal property is exhibited. On the other hand, when SV exceeds 20000 h ⁻¹ , the water flow differential pressure tends to be too large.

Treatment conditions such as a water flow rate when performing treatment other than dissolved oxygen removal treatment on the water to be treated may be conventionally known conditions, for example, an ion exchange treatment in contact with a non-regenerative ion exchange resin. a water flow rate in the case of performing the non-regenerative mixed bed ion exchanger is preferably about SV50~100h ^-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 catalyst for removing dissolved oxygen. In the process of removing dissolved oxygen, the contact efficiency with the water to be treated can be remarkably increased as compared with the case where a normal particulate anion exchange resin is used. In the method for producing ultrapure water of the present invention, since the platinum group metal-supported catalyst is used as the dissolved oxygen removal catalyst, the dissolved oxygen removal ability can be remarkably increased, and the packed bed height of the catalyst can be reduced. Even so, it is possible to produce ultrapure water while sufficiently removing dissolved oxygen 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 dissolution treatment apparatus, a dissolved oxygen removal water production apparatus of the present invention, and a non-regenerative ion exchange apparatus including a non-regenerative ion exchange resin. The membrane separator is 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.

  The ultrapure water production apparatus 1 of the present invention uses the dissolved oxygen removal water production apparatus of the present invention, in which a platinum group metal is supported on a monolithic organic porous anion exchanger as a catalyst for removing dissolved oxygen. Because of the use of the platinum group metal-supported catalyst, the contact efficiency with the water to be treated can be remarkably increased compared to the case of using a normal particulate anion exchange resin during the removal of dissolved oxygen. it can. In the ultrapure water production apparatus 1 of the present invention, since the platinum group metal-supported catalyst is used as a dissolved oxygen removal catalyst, the dissolved oxygen removal capability can be remarkably increased, and the catalyst packed bed Even if the height is reduced, ultrapure water can be produced while sufficiently removing dissolved oxygen in the water to be treated.

  The apparatus for producing ultrapure water 2 of the present invention has an ultraviolet oxidation apparatus, a hydrogen dissolution treatment apparatus, a dissolved oxygen treatment tank 1 of the present invention, and a membrane separation apparatus installed so as to pass water in this order. The ultrapure water production apparatus 3 of the present invention is configured to pass the ultraviolet oxidation apparatus, the hydrogen dissolution treatment apparatus, and the dissolved oxygen treatment tank 2 of the present invention in this order. The ultrapure water production apparatus 4 of the present invention is characterized in that the ultraviolet oxidation apparatus, the hydrogen dissolution treatment apparatus, and the dissolved oxygen treatment tank 3 of the present invention are passed in this order. It is characterized by the installation.

  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 dissolved oxygen removal water production apparatus 1 and the non-regenerative ion exchange apparatus are replaced with the dissolved oxygen treatment tank 1 of the present invention. The ultrapure water production device 3 of the present invention is different from the ultrapure water production device 1 of the present invention in that the dissolved oxygen-removed water production device, non-regenerative ion exchange device, and membrane separation device It replaces with the point which provided the dissolved oxygen treatment tank 2 of this invention, and the manufacturing apparatus 4 of the ultrapure water of this invention differs in the manufacturing apparatus 1 of the ultrapure water of this invention, and manufactures dissolved oxygen removal water. The difference is that the dissolved oxygen treatment tank 3 of the present invention is provided in place of the apparatus, the non-regenerative ion exchange apparatus and the membrane separation apparatus, but the apparatus configuration other than the above and the use conditions such as the water flow rate are the present invention. This is the same as the ultrapure water manufacturing apparatus 1.

  In addition to the effects obtained by the ultrapure water production apparatus 1 of the present invention, the ultrapure water production apparatus 2 of the present invention to the ultrapure water production apparatus 4 of the present invention include a platinum group metal supported catalyst, a non-regenerative type Since the dissolved oxygen treatment tank 1, the dissolved oxygen treatment tank 2 and the dissolved oxygen treatment tank 3 of the present invention, in which the ion exchange resin or the monolithic organic porous ion exchanger is accommodated in the same container, are used. The apparatus configuration of the pure water production apparatus can be simplified, the installation area can be reduced, and particularly when the treatment tank is in a cartridge shape, the treatment tank can be easily replaced. . The ultrapure water production apparatus 3 of the present invention and the ultrapure water production apparatus 4 of the present invention include the dissolved oxygen treatment tank 2 and the dissolved oxygen treatment tank of the present invention in which a separation membrane is further accommodated in the container. 3 is used to further simplify the apparatus configuration and reduce the installation area, and from the platinum group metal supported catalyst, non-regenerative ion exchange resin, or monolithic organic porous ion exchanger. Even if the metal or fine particles are eluted, it can be more easily separated by filtration.

<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 dissolving hydrogen in oxygen-dissolved water, a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger, and the hydrogen is dissolved. And a step of contact treatment with oxygen-dissolved water.

  In the method for producing hydrogen-dissolved water of the present invention, examples of the oxygen-dissolved water include the same as those described in the description of the invention of the method for producing dissolved oxygen-removed water of the present invention.

  Further, in the step of bringing the platinum group metal supported catalyst into contact with the oxygen-dissolved water in which hydrogen is dissolved, the contact method of both, contact conditions such as SV at the time of passing water, etc. These are the same as those described in the description of the method for producing dissolved oxygen-removed 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 of the step of bringing the platinum group metal-supported catalyst into contact with the water to be treated.
The hydrogen dissolution step can be performed by a hydrogen dissolution treatment apparatus or the like, and examples of the hydrogen dissolution treatment apparatus include the same ones as mentioned in the explanation of the method for producing dissolved oxygen-removed water of the present invention.

  In the hydrogen dissolution step, an amount of hydrogen necessary for removing dissolved oxygen is supplied at least in the subsequent step by contact treatment with the white metal-supported catalyst. In order to obtain hydrogen-dissolved water, it is necessary to supply hydrogen for adjusting the oxidation-reduction potential, which will be described later. This hydrogen for adjusting the oxidation-reduction potential is used when supplying the hydrogen for removing the dissolved oxygen. They may be supplied simultaneously, or may be supplied by a hydrogen dissolution treatment apparatus provided separately from a hydrogen dissolution treatment apparatus that supplies hydrogen for removing dissolved oxygen. When a hydrogen dissolution treatment apparatus for adjusting the oxidation-reduction potential is separately provided, it may be provided in a step subsequent to the step of bringing the oxygen-dissolved water into contact with the white metal supported catalyst.

  The hydrogen dissolution step may be performed on primary pure water or water of lower quality, or may be performed on ultrapure water or ultrapure water added with chemicals.

  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 disposed in front of the hydrogen-dissolving treatment device used when performing the hydrogen-dissolving step. By doing so, 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 with the white metal supported catalyst is reduced. , 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. In this case, since the dissolved oxygen concentration in the treated water is low, the amount of platinum group metal-supported catalyst required in the subsequent stage can be reduced, and it is possible to perform the treatment at a high speed using a smaller apparatus. . On the other hand, since it is possible to perform degassing treatment with a platinum group metal-supported catalyst without performing degassing treatment before the hydrogen dissolving means, it is not necessary to degassing at the preceding stage. Since there is no degassing process, the apparatus configuration can be simplified.

  The hydrogen-dissolved water obtained by the method of the present invention 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 processed or when a film such as Cu is easily oxidized on the surface of the object to be processed. it can. It can also be used as a cleaning liquid for removing fine particles.

  The dissolved hydrogen concentration in the hydrogen-dissolved water obtained by the method of the present invention is preferably 0.05 mg / L (0.05 ppm) or more at 25 ° C. and 1 atm, and 0.8 to 1.6 mg / L ( 0.8 to 1.6 ppm) is more preferable. If the dissolved hydrogen concentration is less than 0.05 mg / L, 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 the cleaning liquid, The effect of suppressing the oxidation on the surface is insufficient, and the particle removal efficiency is lowered.

  The method for producing hydrogen-dissolved water of the present invention comprises a step of bringing a platinum group metal-supported catalyst and oxygen-dissolved water into contact with each other, and a platinum group metal supported by a platinum group metal supported on a monolithic organic porous anion exchanger Since the dissolved oxygen is removed by the catalyst, the contact efficiency with the water to be treated can be remarkably increased in the process of removing the dissolved oxygen as compared with the case where a normal particulate anion exchange resin is used. In the method for producing hydrogen-dissolved water of the present invention, since the platinum group metal-supported catalyst is used as the dissolved oxygen removal catalyst, the dissolved oxygen removal ability can be remarkably increased, and the packed bed height of the catalyst can be reduced. Even so, it is possible to produce hydrogen-dissolved water while sufficiently removing dissolved oxygen 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 for producing hydrogen-dissolved water of the present invention comprises the apparatus for producing dissolved oxygen-removed water of the present invention and a hydrogen-dissolving treatment apparatus for treated water at least upstream of the apparatus for producing dissolved oxygen-removed water. It is characterized by this.

  In the hydrogen-dissolved water production apparatus of the present invention, the preferred embodiments of the hydrogen-dissolution treatment apparatus and the dissolved oxygen-removed water production apparatus, the conditions for producing the dissolved oxygen-removed water, and the like are the same as described above, and the treatment target The kind of water and the hydrogen-dissolved water obtained by this apparatus are the same as those described in the description of the method for producing hydrogen-dissolved water of the present invention.

  In the hydrogen dissolution treatment apparatus, an amount of hydrogen necessary for removing dissolved oxygen is supplied by contact treatment with the white metal metal-supported catalyst at least in the apparatus for producing dissolved oxygen removal water on the downstream side. In order to obtain hydrogen-dissolved water, it is necessary to further supply hydrogen for adjusting the redox potential, and this hydrogen for adjusting the redox potential is supplied simultaneously with the supply of the hydrogen for removing the dissolved oxygen. Alternatively, it may be supplied by a hydrogen dissolution treatment apparatus for adjusting oxidation-reduction potential provided separately from a hydrogen dissolution treatment apparatus that supplies hydrogen for removing dissolved oxygen. In the case of providing the oxidation-reduction potential adjusting hydrogen dissolution treatment apparatus, this oxidation-reduction potential adjustment hydrogen dissolution treatment apparatus may be provided in the subsequent stage of the dissolved oxygen-removed water production apparatus. The hydrogen dissolution treatment by the hydrogen dissolution treatment apparatus may be performed on primary pure water or water of lower quality, or may be performed on ultrapure water or ultrapure water added with chemicals.

  In the apparatus for producing hydrogen-dissolved water according to the present invention, a deaeration apparatus as described in the description of the apparatus for producing ultrapure water according to the present invention may be arranged in the preceding stage of the hydrogen-dissolving treatment apparatus. By removing the dissolved oxygen in advance by degassing with a degassing device, the amount of dissolved oxygen in the water to be treated is reduced, and the amount of hydrogen consumed in the reaction with the white metal supported catalyst is reduced. Can be reduced, 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. In this case, since the dissolved oxygen concentration in the treated water is lowered, the amount of platinum group metal-supported catalyst required in the latter stage can be reduced, and a smaller apparatus can be used. On the other hand, since it is possible to perform deaeration treatment with a platinum group metal supported catalyst constituting the apparatus for producing dissolved oxygen removal water, it is not necessary to provide the above deaeration device. The device configuration can be simplified.

  The apparatus 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 for producing hydrogen-dissolved water of the present invention has the apparatus for producing dissolved oxygen-removed water of the present invention, in which a platinum group metal supported by a platinum group metal supported on a monolithic organic porous anion exchanger. Since the dissolved oxygen is removed by the catalyst, the contact efficiency with the water to be treated can be remarkably increased when removing the dissolved oxygen compared to the case of using a normal particulate anion exchange resin. In the apparatus for producing hydrogen-dissolved water of the present invention, since the platinum group metal-supported catalyst is used as a dissolved oxygen removal catalyst, the dissolved oxygen removal capability can be remarkably increased, and the packed bed height of the catalyst can be reduced. Even so, it is possible to produce hydrogen-dissolved water while sufficiently removing dissolved oxygen in the water to be treated.

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

  The method for cleaning an electronic component of the present invention includes a cleaning water containing the dissolved oxygen removing water obtained by the dissolved oxygen removing water manufacturing method of the present invention or the dissolved oxygen removing water manufacturing apparatus of the present invention, and the ultrapure water of the present invention. Includes cleaning water containing ultrapure water obtained by the production method or the ultrapure water production apparatus of the present invention, or hydrogen dissolved water obtained by the method for producing hydrogen dissolved water of the present invention or the hydrogen dissolved water production apparatus of the present invention The surface is washed with at least one kind of washing water selected from washing water.

  The details of the method for producing ultrapure water of the present invention or the method for obtaining ultrapure water by the ultrapure water production apparatus of the present invention are the same as described above.

  Embodiments of the electronic component cleaning method of the present invention will be described with reference to FIGS. FIG. 4 is a schematic flow diagram of the first embodiment of the electronic component cleaning method of the present invention, and FIG. 5 is a schematic flow of the second embodiment of the electronic component cleaning method of the present invention. FIG.

  As shown in FIG. 4, 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 the 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 bringing the object to be cleaned into contact with the hydrogen-dissolved water and cleaning the object to be cleaned while applying vibrations of 500 kHz or higher are included.

  The cleaning water supplied to the first step 21 is ozone-dissolved water prepared by dissolving ozone 33 in ultrapure water 32.

  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 method for producing dissolved oxygen-removed water of the present invention using the ultrapure water 32 as the water to be treated. The dissolved oxygen removing step 26 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, similarly, before the hydrogen 36 is dissolved in the ultrapure water 32, the ultrapure water 32 is used as water to be treated. A dissolved oxygen removing step 28 for applying a method for producing oxygen-removed water is performed, and hydrogen 36 is dissolved in the obtained treated water and supplied as cleaning water in the fourth step 24. Although not shown in FIG. 4, the hydrogen 34 or 36 is also supplied in the previous stage of the dissolved oxygen removal step 26 or 28.

  Further, in the first embodiment of the electronic component cleaning method of the present invention, the dissolved oxygen removing step 27 for applying the manufacturing method for removing dissolved oxygen of the present invention using the ultrapure water 32 as the water to be treated is performed, and the obtained treatment is performed. It is also possible to supply hydrofluoric acid and hydrogen peroxide 35 in water and supply the resulting hydrofluoric acid and hydrogen peroxide-containing water as the 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. 5, 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 contacting the object to be cleaned 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 cleaning 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. 5 dissolves the chemicals necessary for 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. 5, 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 step in the ultrapure water, perform the dissolved oxygen removal step of applying the manufacturing method of the dissolved oxygen removal water of the present invention using the ultrapure water as the water to be treated. It is preferable that chemicals required in the process are dissolved and supplied as cleaning water (cleaning liquid) in each process.

  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 method for cleaning an electronic component of the present invention, the treated water obtained by performing the dissolved oxygen removing step of applying the manufacturing method of the dissolved oxygen removing water of the present invention using ultrapure water as treated water. Is preferably supplied as washing water in 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, a method for producing dissolved oxygen removal water, a device for producing dissolved oxygen removal water, a method for producing ultrapure water, a device for producing ultrapure water, a method for producing hydrogen dissolved water, a device for producing hydrogen dissolved water and A platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger, which is commonly used in a method for cleaning electronic parts, will be described.

  Examples of the platinum group metal supported catalyst include those obtained by supporting platinum group metal nanoparticles 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 of 1 is insufficient, and the dissolved oxygen removing property is 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. Further, the average diameter of the openings of the first monolith anion exchanger in the wet state is a value calculated by multiplying the average diameter of the openings of the first monolith anion exchanger in the dry state by the swelling rate. Specifically, the diameter of the first monolith anion exchanger in the water wet state is X ₁ (mm), the monolith anion exchanger in the water wet state is dried, and the resulting first monolith anion in the dry state is obtained. If the diameter of the exchanger is Y ₁ (mm) and the average diameter of the opening is Z ₁ (μm) when the dry first monolith anion exchanger is measured by mercury porosimetry, The average diameter (μm) of the opening of the first monolith anion exchanger in the 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 ) ”. Further, the average diameter of the opening of the monolith in the dry state before the introduction of the anion exchange group, and the first monolith anion exchanger in the water wet state relative to the dry monolith when the anion exchange group is introduced into the monolith in the dry state. When the swelling 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 first monolith anion exchanger in the water wet state.

  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. If 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 dissolved oxygen removal 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 effect of removing dissolved oxygen 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 effect of removing dissolved oxygen 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 the contact with the monolith anion exchanger 3 and the supported platinum group metal nanoparticles becomes insufficient, and as a result, the dissolved oxygen removing property is deteriorated. 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. 6A shows a skeleton portion of the cut surface in the SEM image, and FIG. 6B is a drawing for explaining FIG. 6A. FIG. 6B is a transcribed skeleton that appears as a cross section of the SEM photograph of FIG. In FIG. 6A and FIG. 6B, what is generally indeterminate and appears in cross section is the “skeleton portion (reference numeral 82)” in the present invention, and is a circular hole appearing in FIG. 6A. Is an opening (mesopore), and a relatively large curvature or curved surface is a macropore (reference numeral 83 in FIG. 6B). The skeleton part area appearing in the cross section of FIG. 6B 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. Since it falls, it is not preferable. 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. 12, 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 a 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 removal of dissolved oxygen in the water to be treated becomes insufficient, which is not preferable. 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 decreases, and the effect of removing dissolved oxygen also decreases, which is not preferable. 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. Since it falls, it is not preferable. 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 removing dissolved oxygen becomes insufficient, such being undesirable. 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>
(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)
Next, 49.0 g of styrene, 1.0 g of divinylbenzene, 50 g of 1-decanol, and 0.5 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and 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. 6A shows the result of observing the internal structure of the monolith (dry body) containing 1.3 mol% of the cross-linking component composed of the styrene / divinylbenzene copolymer obtained by SEM. The SEM image in FIG. 6A 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. 7, the monolith has a continuous macropore structure, and the skeleton constituting the continuous macropore structure is much thicker than the SEM image of a known product (FIG. 11). The wall part which comprises 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.

  The swelling ratio before and after the reaction of the obtained anion exchanger was 1.7 times, and the ion exchange capacity per volume was 0.60 mg equivalent / ml in a water-wet state. 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, 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. FIG. 7 shows the distribution state of chloride ions on the surface of the monolith anion exchanger, and FIG. 8 shows the distribution state of chloride ions in the skeleton cross section. It was confirmed that the quaternary ammonium groups were uniformly introduced into the monolith anion exchanger. In FIG. 8, the chloride ion concentration in the lower part of the skeleton is apparently higher than that in 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 was ion-exchanged into Cl form, cut into a cylindrical shape in a wet state, and dried under reduced pressure. The weight of the monolith anion exchanger after drying was 1.2 g. The dried monolith anion exchanger was immersed in dilute hydrochloric acid in which 190 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 thus obtained was washed several times with pure water and dried.

  The supported amount of palladium nanoparticles supported on the dried palladium nanoparticle-supported catalyst was 7.4% 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 (Cl type) in a dry state was packed in a column having an inner diameter of 10 mm to obtain a dissolved oxygen removing catalyst. The packed bed height of the palladium nanoparticle-supported catalyst was 20 mm. At this time, the supported amount of palladium nanoparticles was 10.5 g with respect to 1 L of the palladium nanoparticle-supported catalyst in a wet state.

<Manufacture of dissolved oxygen removal water>
Dissolved oxygen-removed water was produced using ultrapure water obtained in the ultrapure water subsystem. At this time, the quality of the ultrapure water was such that the resistivity was 18 MΩcm or more, the TOC was less than 1 ppb, the number of fine particles of 0.05 μm or more was less than 1 per mL, and the dissolved oxygen concentration was 30 ppb or less.

  A part of the ultrapure water was branched and an experiment was performed using an apparatus as shown in FIG. Hydrogen gas and / or oxygen gas were respectively dissolved in ultrapure water using gas-dissolved membranes as shown in FIG. 10 to prepare hydrogen-dissolved water and oxygen-dissolved water, respectively. Adjust the concentration of hydrogen dissolved water and / or oxygen dissolved water of a certain concentration using the above device, and operate a valve (not shown) to adjust the mixing ratio of the ultrapure water, hydrogen dissolved water, and oxygen dissolved water. Adjusting the water to be treated to a predetermined dissolved oxygen (DO) concentration and dissolved hydrogen (DH) concentration (concentration measurement at the column inlet using a DO and DH meter not shown), and supporting the palladium nanoparticles Water was passed through a column filled with a catalyst and having an inner diameter of 10 mm. At this time, DO-30A manufactured by TOADKK was used as the DO meter, and DHDI-1 manufactured by the same company was used as the DH meter.

To the palladium nanoparticle-supported catalyst packed in a column processed with a PFA tube having an outer diameter of 12 mm, an inner diameter of 10 mm, and a length of 400 mm, ultrapure water with a dissolved oxygen concentration adjusted to 32 ppb and a dissolved hydrogen concentration adjusted to 11 ppb was added at a flow rate of 200 mL / Minute (SV7500h ^-1 ), water flow rate of 8.5 L / min per gram of supported Pd catalyst, water was flowed in a downward flow until the dissolved oxygen concentration at the column outlet was stabilized under the conditions shown in Table 1. The dissolved oxygen concentration at the column outlet was measured. As a result, the dissolved oxygen concentration in the sample water collected at the column outlet was 3.8 ppb, and the dissolved oxygen was removed. The results are shown in Table 1.

Comparative Example 1
<Production of Palladium Nanoparticle-Supported Granular Ion Exchange Resin Catalyst>
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 immersed in an aqueous hydrazine solution for reduction treatment. Then, it washed with water and used for evaluation as a removal catalyst of dissolved oxygen. At this time, the amount of palladium nanoparticles supported was 910 mg as the amount of palladium nanoparticles supported relative to 1 L of the palladium nanoparticle-supported catalyst in a wet state.

<Manufacture of dissolved oxygen removal water>
The Cl-type particulate ion exchange resin supporting palladium was packed in 28 mL (layer height 36 mm) in a column processed with a PFA tube having an outer diameter of 12 mm, an inner diameter of 10 mm, and a length of 400 mm, as shown in FIG. The above column was installed in parallel with the column used in Example 1, and the flow rate was 200 mL / min (SV430h ⁻¹ ), the water flow rate was 7.9 L / min per 1 g of the supported Pd catalyst, and the conditions shown in Table 1 were satisfied. Then, water was passed in a downward flow until the dissolved oxygen concentration at the column outlet was stabilized, and dissolved oxygen-removed water was produced in the same manner as in Example 1.

  As a result, the dissolved oxygen concentration in the sample water collected at the column outlet at the stable time point was 4.1 ppb. The results are shown in Table 1.

In Example 1, although the water flow rate was high, such as SV7500h- ¹ exceeding the conventional common sense, and the flow rate at the time of water flow was as high as 11.9 L / min per 1 gram of Pd carried, the water flow rate Was SV430h- ¹ , and the dissolved oxygen was removed to a level equivalent to that of Comparative Example 1 having a low flow rate per ¹ g of supported Pd of 7.9 L / min, and dissolved oxygen-removed water could be obtained in a short time. As described above, in the present invention, dissolved oxygen can be removed with high efficiency even if water flow treatment is performed at a high flow rate and a low resin layer height. Can be planned.

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, SV is more than 2000 h ⁻¹ by removing dissolved oxygen in the water to be treated. Even if water is passed through such an SV or the packed bed height of the catalyst is made thin, dissolved oxygen can be removed with high efficiency and a method and a production apparatus for producing dissolved oxygen-removed water can be provided. In addition, according to the present invention, even when water is passed through a large SV that exceeds 2000 h ⁻¹ when removing dissolved oxygen, or even if the packed bed height of the dissolved oxygen removal catalyst is reduced, dissolved oxygen can be made highly efficient. It is possible to provide a method and an apparatus for producing ultrapure water by removing and a method and an apparatus for producing hydrogen-dissolved water. And according to this invention, the washing | cleaning method of the electronic component using the washing water containing the said dissolved oxygen removal water, ultrapure water, or hydrogen dissolution water can be provided.

DESCRIPTION OF SYMBOLS 1 Production apparatus of ultrapure water 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

Claims (16)

  A method for producing dissolved oxygen-removed water, comprising dissolving hydrogen in oxygen-dissolved water and then contacting a platinum group metal-supported catalyst in which a platinum group metal is supported on a monolithic organic porous anion exchanger.   The method for producing dissolved oxygen-removed water according to claim 1, wherein the supported amount of the platinum group metal is 10 to 30000 mg per liter of the platinum group metal supported catalyst.   The method for producing dissolved oxygen-removed water according to claim 1 or 2, wherein the monolithic organic porous anion exchanger is in OH form. The dissolved oxygen-removed water according to any one of claims 1 to 3, wherein oxygen dissolved water in which the hydrogen is dissolved is brought into contact with the platinum group metal-supported catalyst at a space velocity of 2000 h- ^{1 to} 20000 h- ^1. Manufacturing method.   Dissolved oxygen 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 reaction part for bringing the catalyst into contact with oxygen-dissolved water in the presence of hydrogen Removal 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. Dissolved oxygen treatment tank characterized by being arranged in the same container so as to be in contact with each other.   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. A dissolved oxygen treatment tank, which is arranged in the same container so as to come into contact with each other in this order.   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 dissolved oxygen treatment tank characterized by that.   For oxygen-dissolved water, ultraviolet oxidation treatment, hydrogen dissolution treatment, dissolved oxygen removal 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 type A method for producing ultrapure water, characterized in that an ion exchange treatment in contact with an ion exchange resin and a filtration treatment with a separation membrane are performed in this order.   An ultraviolet oxidation device, a hydrogen dissolution treatment device, a device for producing dissolved oxygen-removed water according to claim 5, a non-regenerative ion exchange device including a non-regenerative ion exchange resin, and a membrane separation device in this order. An apparatus for producing ultrapure water, wherein the apparatus is installed so as to pass water.   An apparatus for producing ultrapure water, wherein an ultraviolet oxidation apparatus, a hydrogen dissolution treatment apparatus, the dissolved oxygen treatment tank according to claim 6 and a membrane separation apparatus are installed so as to pass water in this order. .   An apparatus for producing ultrapure water, wherein an ultraviolet oxidation apparatus, a hydrogen dissolution treatment apparatus, and a dissolved oxygen treatment tank according to claim 7 are installed so as to pass water in this order.   An apparatus for producing ultrapure water, wherein an ultraviolet oxidation device, a hydrogen dissolution treatment device, and the dissolved oxygen treatment tank according to claim 8 are installed so as to pass water in this order.   A step of dissolving hydrogen in oxygen-dissolved water, 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 oxygen-dissolved water in which the hydrogen is dissolved, and A method for producing hydrogen-dissolved water, comprising:   6. A hydrogen-dissolved water comprising: the dissolved oxygen-removed water producing apparatus according to claim 5; and a hydrogen-dissolving treatment apparatus for treated water at least upstream of the dissolved oxygen-removed water producing apparatus. Manufacturing equipment.   Washing water containing dissolved oxygen-removed 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 method according to claims 10 to 13. One or more kinds selected from washing water containing ultrapure water obtained by any one of the apparatuses, or washing water containing hydrogen-dissolved water obtained by the method according to claim 14 or the apparatus according to claim 15. A method of cleaning an electronic component, wherein the surface is cleaned with cleaning water.