WO2010104007A1

WO2010104007A1 - Deionization module and electric device for producing deionized water

Info

Publication number: WO2010104007A1
Application number: PCT/JP2010/053653
Authority: WO
Inventors: 井上　洋; 山中　弘次
Original assignee: オルガノ株式会社
Priority date: 2009-03-10
Filing date: 2010-03-05
Publication date: 2010-09-16
Also published as: TW201038490A

Abstract

A deionization module obtained by filling an organic porous ion exchanger into the inner space formed between a cation-exchange membrane attached to one side of a frame so as to seal the side and an anion-exchange membrane attached to the other side so as to seal the side, the porous ion exchanger being a continuous macroporous structure which, in a water-wet state, has openings (mesopores) with an average diameter of 30-300 µm and which has an overall pore volume of 0.5-5 ml/g and a water-wet-state ion-exchange capacity of 0.4-5 mg-eq/ml. In an SEM image of a cut section of the continuous macroporous structure (dry state), the area of skeletal parts appearing in the section is 25-50% of the image region. An EDI equipped with the module is provided. In this EDI, since the ion exchanger has high strength, the pressure loss caused when water passes can be reduced and the quality of treated water is improved.

Description

Deionization module and electric deionized water production apparatus

The present invention relates to an electrical deionization liquid production used in various industries such as semiconductor manufacturing industry, pharmaceutical industry, food industry, power plant, laboratory, etc. using deionized water, or in the production of sugar liquid, juice, wine, etc. The present invention relates to a deionization module preferably used in the apparatus and an electric deionized water production apparatus including the deionization module.

An electric deionized water production apparatus that has been put into practical use is basically a mixed ion exchange resin of an anion exchange resin and a cation exchange resin as an ion exchanger in a gap formed by a cation exchange membrane and an anion exchange membrane. The desalting chamber is filled with water to pass the water to be treated through the ion exchange resin, and a direct current is applied in a direction perpendicular to the flow of the water to be treated through the both ion exchange membranes. Deionized water is produced while electrically removing ions in the water to be treated in the concentrated water flowing outside the exchange membrane. Since impurity ions in the water to be treated are electrically removed by such an operation, deionized water can be continuously obtained without regenerating the filled ion exchange resin with a chemical solution at all.

In the electric deionized water production apparatus, regeneration with a chemical solution is not necessary, so the operating cost is determined by the amount of power consumption. Except for the rectification loss when converting alternating current to direct current, the power consumption in the electrical deionized water production apparatus is expressed as direct current x voltage between both electrodes. Here, the direct current is determined by the amount of ions contained in the water to be treated, the kind of ions, and the required quality of the treated water. That is, in the electric deionized water production apparatus, it is necessary to continuously discharge ions captured by the ion exchange resin in the desalting chamber to the concentrated water side by electrophoretic migration, which is necessary for the migration of ions. The above current is indispensable for the electric deionized water production apparatus to exhibit its performance normally. Therefore, in a normal case, in the electric deionized water production apparatus, a constant current operation is performed in which a constant current value exceeding the minimum current value required under the operation conditions is maintained. On the other hand, the voltage is determined by the electric resistance between the two electrodes, and greatly depends on the performance of the ion exchange membrane or ion exchange resin used in the electric deionized water production apparatus. That is, the electric resistance is the sum of the electric resistance by the electrode chamber, the concentrating chamber, and the desalting chamber disposed between both electrodes. If the interelectrode distance and the operating temperature are constant, Concentration and type of ions contained, type of ion exchange membrane, type of ion exchange resin and type of counter ion of the ion exchange group, furthermore, ion exchange resin filling method (single bed or mixed bed), and all these electric resistances The contact resistance at the interface of the component influences. Among the electrical resistance components, the concentration and type of ions contained in the electrode water and the concentrated water are determined by the quality of the treated water and the required quality of the treated water, but the other elements are electric deionization. It depends on the performance of the ion exchanger used in the water production apparatus and its method of use.

However, in the conventional electric deionized water production apparatus, as the ion exchange resin filled in the demineralization module, general-purpose products that have been widely used are used as they are, and the operation of the electric deionized water production apparatus is not performed. In order to reduce the cost, the electric resistance value is not considered to be minimized. That is, in a conventional electric deionized water production apparatus, generally, a copolymer of styrene and divinylbenzene (DVB) is used as an ion exchange resin, and a sulfonic acid group (R—SO ₃ ⁻ H ⁺ is used as a cation exchange group. ), and as the anion-exchange group is filled with those of the quaternary ammonium base ^{_{_{(R-N + R 1 R}}} 2 R 3) spherical diameter of about 0.2 ~ 0.5 mm was obtained by introducing the Yes. In this case, the current transfer in the ion exchange resin particles, that is, the transfer of electrons and ions, is performed with low resistance via the ion exchange groups present uniformly and densely in the polymer gel, whereas the ion exchange resin At the particle interface, when ions and electrons move, in the case of ions, the migration distance of the ions in water is long, and in the case of electrons, the electron transfer path via hydrogen bonds between water molecules is long and spherical. For this reason, since the contact area between the particles is small, the flow of ions concentrates on the contact portion, which is an obstacle to current transmission, that is, electric resistance, and is a main factor of electric resistance derived from the ion exchange resin.

In addition, since the conventional electric deionized water production apparatus fills the deionization module with a general-purpose ion exchange resin, it requires considerable time and labor for production. In particular, the assembly of the deionization module that forms the desalination chamber must be uniformly filled with a wet ion exchange resin while laminating and bonding a plurality of sandwich-like edges using an adhesive. Requires considerable skill and is difficult to automate. Even when no adhesive is used, it is difficult to handle a wet ion exchange resin.

As a solution to these problems, for example, Japanese Patent Application Laid-Open No. 2002-306976 has an open cell structure having macropores connected to each other and mesopores having an average diameter of 1 to 1000 μm in the walls of the macropores. A porous ion exchanger having a volume of 1 to 50 ml / g, an ion exchange group uniformly distributed, and an ion exchange capacity of 0.5 mg equivalent / g or more of a dry porous body is placed on one side of the frame. A deionization module used in an electric deionized water production apparatus is formed by filling an internal space formed by a sealed cation exchange membrane and an anion exchange membrane sealed on the other side. It is disclosed. Since the electric deionized water production apparatus using this deionization module has high demineralization efficiency, it can be a power-saving type capable of reducing power consumption by reducing the voltage during operation.

JP 2002-306976 A (Claims) JP 2009-62512 A JP 2009-67982 A

However, the organic porous ion exchanger described in JP-A No. 2002-306976 has a common monolithic opening (mesopore) of 1 to 1,000 μm, but has a total pore volume of 5 ml / g or less. For monoliths with a small pore volume, the amount of water droplets in the water-in-oil emulsion needs to be reduced, so that the common opening becomes small, and those having an average diameter of 20 μm or more cannot be manufactured. For this reason, there existed a problem that the pressure loss at the time of water flow was large. In addition, there is a problem that the ion exchange capacity per volume is small, the quality of the treated water is not sufficient, and the power consumption is low.

Therefore, an object of the present invention is to provide a deionization module that is easy to assemble and has a simple structure. Another object of the present invention is to provide an electric deionized water production apparatus that has high ion exchanger strength, can reduce pressure loss during water flow, and improves the quality of treated water. It is in.

Under such circumstances, the present inventors have conducted intensive studies, and as a result, obtained a monolithic organic porous material (intermediate) having a relatively large pore volume obtained by the method described in JP-A-2002-306976. In the presence, if the vinyl monomer and the crosslinking agent are allowed to stand and polymerize in a specific organic solvent, a thick monolith having a larger skeleton than the skeleton of the intermediate organic porous body can be obtained. When an ion exchange group is introduced into a thick monolith, the swelling is large due to the thick bone, so that the opening can be further increased, and the monolith ion exchanger in which the ion exchange group is introduced into the thick monolith is electrically deionized water produced. When used as an ion exchanger for the device, it has high strength, can reduce pressure loss during water flow, improves the quality of treated water, and consumes less power. Out, it has led to the completion of the present invention (A1).

Further, as a result of intensive studies, the present inventors have found that in the presence of a monolithic organic porous material (intermediate) having a large pore volume obtained by the method described in JP-A-2002-306976, fragrance Group vinyl monomer and cross-linking agent are allowed to stand in a specific organic solvent to form a three-dimensionally continuous aromatic vinyl polymer skeleton and three-dimensionally continuous pores between the skeleton phases. A monolith with a co-continuous structure intertwined with each other, this monolith with a co-continuous structure has a high continuity of pores, is not biased in size, and has a low pressure loss during fluid permeation, Since the skeleton of this co-continuous structure is thick, if an ion exchange group is introduced, a monolithic organic porous ion exchanger having a large ion exchange capacity per volume can be obtained, and the monolithic organic porous ion exchanger Expression When used as an ion exchanger for an on-water production apparatus, as with the first monolithic ion exchanger, it has high strength and can reduce pressure loss during water flow, improve the quality of treated water, and consume power. As a result, the present invention (A1) was completed.

Further, as a result of intensive studies, the present inventors have found that in the presence of a monolithic organic porous material (intermediate) having a relatively large pore volume obtained by the method described in JP-A-2002-306976. In addition, if the vinyl monomer and the crosslinking agent are allowed to stand in an organic solvent under specific conditions, a large number of particles having a diameter of 2 to 20 μm are fixed on the surface of the skeleton constituting the organic porous body, or protrusions are formed. A monolith having a formed composite structure is obtained, and a composite monolith ion exchanger in which an ion exchange group is introduced into this composite monolith has high strength and can be used as an ion exchanger in an electric deionized water production apparatus. It has been found that pressure loss during water can be reduced, the quality of treated water is improved, and power consumption is low, and the present invention (A2) has been completed.

That is, the present invention (A1) is a continuous macropore structure in which bubble-shaped macropores overlap each other, and the overlapping portion is an opening having an average diameter of 30 to 300 μm in a wet state with a total pore volume of 0.5 to 5 ml. / G, ion exchange capacity per volume in a wet state of water of 0.4 to 5 mg equivalent / ml, ion exchange groups are uniformly distributed in the porous ion exchanger, and the continuous macropore structure In the SEM image of the cut surface of the (dry body), the organic porous ion exchanger (hereinafter referred to as “first monolith ion exchanger”) whose skeleton area appearing in the cross section is 25 to 50% in the image region. ) In an internal space formed by a cation exchange membrane sealed on one side of the frame and an anion exchange membrane sealed on the other side, Used in manufacturing equipment There is provided a deionization module, wherein Rukoto.

Further, the present invention (A1) is a tertiary having a thickness of 1 to 60 μm made of an aromatic vinyl polymer containing 0.3 to 5.0 mol% of a crosslinked structural unit among all the structural units into which ion exchange groups are introduced. A co-continuous structure composed of an originally continuous skeleton and three-dimensionally continuous pores having a diameter of 10 to 100 μm between the skeletons, with a total pore volume of 0.5 to 5 ml / g An organic porous ion exchanger (hereinafter referred to as an ion exchange capacity of 0.3 to 5 mg equivalent / ml per volume in a wet state of water) in which the ion exchange groups are uniformly distributed in the porous ion exchanger. , Also referred to as “second monolithic ion exchanger”) is filled in the internal space formed by the cation exchange membrane sealed on one side of the frame and the anion exchange membrane sealed on the other side. Which is used in an electric deionized water production apparatus. There is provided a deionization module, wherein the door.

In addition, the present invention (A1) includes an intermediate ion exchange membrane disposed between the cation exchange membrane sealed on one side of the frame and the anion exchange membrane sealed on the other side. A first internal space formed by the membrane is filled with the first monolith ion exchanger or the second monolith ion exchanger, and further, the intermediate ion exchange membrane and the anion exchange membrane sealed on the other side; The second internal space formed by filling the first monolith ion exchanger or the second monolith ion exchanger is used for an electric deionized water production apparatus. A deionization module is provided.

In the present invention (A2), the internal space formed by the cation exchange membrane sealed on one side of the frame and the anion exchange membrane sealed on the other side is filled with the ion exchanger. , A deionization module used in an electrical deionized water production apparatus, wherein the ion exchanger comprises an organic porous body composed of a continuous skeleton phase and a continuous pore phase, and a skeleton surface of the organic porous body. A composite structure of a large number of particles having a diameter of 4 to 40 μm to be fixed or a large number of protrusions having a size of 4 to 40 μm formed on the skeleton surface of the organic porous body, Monolithic organic porous ion exchanger having an average diameter of 10 to 150 μm, a total pore volume of 0.5 to 5 ml / g, and an ion exchange capacity of 0.2 mg equivalent / ml or more per volume in a water-wet state ( Hereinafter, it is also referred to as “third monolith ion exchanger”. The deionization module characterized by the above is provided.

Further, the present invention (A2) includes a cation exchange membrane sealed on one side of the frame and an intermediate ion exchange disposed between the cation exchange membrane and the anion exchange membrane sealed on the other side. A first ion exchanger is filled in a first internal space formed by a membrane, and a second ion exchanger is formed in a second internal space formed by the intermediate ion exchange membrane and an anion exchange membrane sealed on the other side. A deionization module used in an electrical deionized water production apparatus, wherein one or both of the first ion exchanger and the second ion exchanger are third monolithic ions. The present invention provides a deionization module characterized by being an exchanger.

The present invention also provides an electric deionized water production apparatus provided with the deionization module.

The “first monolith ion exchanger”, the “second monolith ion exchanger”, and the “third monolith ion exchanger” are novel types different from conventional monoliths having an open cell structure and bicontinuous structures. It is a structure. According to this deionization module, the porous ion exchanger filled in the space between the ion exchange membranes can be formed into, for example, a flat plate shape or a cylindrical shape, and a polymer material that can be easily cut can be used. An easy and simple structure can be obtained. Moreover, the electric deionized water production apparatus of the present invention has high ion exchanger strength, can reduce pressure loss during water flow, and can improve the quality of treated water.

It is a SEM image of the monolith in the 1st monolith ion exchanger. It is an EPMA image which showed the distribution state of the sulfur atom in the surface of the monolith of FIG. 2 is an EPMA image showing a distribution state of sulfur atoms in the cross-section (thickness) direction of the monolith of FIG. FIG. 6 is a diagram showing the correlation between the differential pressure coefficient and the ion exchange capacity per volume in Reference Examples 1 to 13 and Reference Examples 20 to 23. It is a manual transfer of the skeleton part that appears as a cross section of the SEM image of FIG. It is the figure which showed typically the co-continuous structure of the 2nd monolith ion exchanger. It is a SEM image of the monolith intermediate in a bicontinuous structure. It is a SEM image of the monolith cation exchanger which has a bicontinuous structure. It is the EPMA image which showed the distribution state of the sulfur atom in the surface of the monolith cation exchanger which has a bicontinuous structure. It is the EPMA image which showed the distribution state of the sulfur atom in the cross section (thickness) direction of the monolith cation exchanger which has a bicontinuous structure. It is a SEM image of the other monolith cation exchanger which has a bicontinuous structure. 3 is a SEM photograph of a conventional organic porous body (Japanese Patent Laid-Open No. 2002-306976). It is a schematic diagram explaining the deionization module of this invention. It is a schematic diagram explaining the other deionization module of this invention. It is a schematic diagram explaining the electric deionized water manufacturing apparatus of this invention. It is a schematic diagram explaining the other electric deionized water manufacturing apparatus of this invention. It is a schematic diagram explaining the other electric deionized water manufacturing apparatus of this invention. It is a schematic diagram explaining the other electric deionized water manufacturing apparatus of this invention. 18 is a SEM image of a monolith obtained in Reference Example 27 at a magnification of 100. 18 is a SEM image of a monolith obtained in Reference Example 27 at a magnification of 300. 10 is a SEM image of the monolith obtained in Reference Example 27 at a magnification of 3000. 7 is an EPMA image showing the distribution state of sulfur atoms on the surface of the monolith cation exchanger obtained in Reference Example 27. FIG. It is the EPMA image which showed the distribution state of the sulfur atom in the cross section (thickness) direction of the monolith cation exchanger obtained in Reference Example 27. 10 is a SEM image of a monolith obtained in Reference Example 28 at a magnification of 100. It is a SEM image of magnification of 600 of the monolith obtained in Reference Example 28. It is a SEM image of the monolith obtained in Reference Example 28 at a magnification of 3000. It is a SEM image of magnification 600 of the monolith obtained in Reference Example 29 10 is a SEM image of the monolith obtained in Reference Example 29 at a magnification of 3000. 4 is a SEM image of the monolith obtained in Reference Example 30 at a magnification of 3000. 10 is a SEM image of a monolith obtained in Reference Example 31 at a magnification of 100. FIG. 4 is a SEM image of the monolith obtained in Reference Example 31 at a magnification of 3000. 10 is an SEM image of a monolith obtained in Reference Example 32 at a magnification of 100. FIG. 10 is a SEM image of a monolith obtained in Reference Example 32 at a magnification of 600. 10 is a SEM image of the monolith obtained in Reference Example 32 at a magnification of 3000. . It is typical sectional drawing of a protrusion.

Hereinafter, the present invention will be described by dividing it into the invention (A1) and the invention (A2).
[Invention (A1)]
In the deionization module according to the embodiment of the present invention (A1), at least one of the internal space of the frame and the two internal spaces of the frame having the intermediate film is filled with the first monolith ion exchanger Or a second monolith ion exchanger. In the present specification according to the invention (A1), “monolithic organic porous body” is simply “monolith”, “monolithic organic porous ion exchanger” is simply “monolith ion exchanger”, “monolithic The “organic porous intermediate” is also simply referred to as “monolith intermediate”.

<Description of the first monolith ion exchanger>
The first monolith ion exchanger is obtained by introducing an ion exchange group into a monolith. Bubble-shaped macropores are overlapped with each other, and the overlapped portion is in a wet state in water with an average diameter of 30 to 300 μm, preferably 30. It is a continuous macropore structure having openings (mesopores) of ˜200 μm, particularly 35 to 150 μm. The average diameter of the opening of the monolith ion exchanger is larger than the average diameter of the opening of the monolith because the entire monolith swells when an ion exchange group is introduced into the monolith. If the average diameter of the openings is less than 30 μm, the pressure loss at the time of water flow is increased, which is not preferable. If the average diameter of the openings is too large, contact between the fluid and the monolith ion exchanger becomes insufficient. As a result, the ion exchange characteristics deteriorate, which is not preferable. In the present invention (A1), the average diameter of the opening of the dried monolith intermediate, the average diameter of the dried monolith, and the average diameter of the dried monolith ion exchanger are measured by the mercury intrusion method. Is the value to be Further, the average diameter of the openings of the monolith ion exchanger in the wet state is a value calculated by multiplying the average diameter of the openings of the monolith ion exchanger in the dry state by the swelling rate. Specifically, the water-wet monolith ion exchanger has a diameter of x1 (mm), the water-wet monolith ion exchanger is dried, and the resulting dried monolith ion exchanger has a diameter of y1 ( mm), and the average diameter of the opening of the monolith ion exchanger in the dry state measured by the mercury intrusion method was z1 (μm), the average diameter of the opening of the monolith ion exchanger in the water wet state ( μm) is calculated by the following formula: “average diameter of openings of monolith ion exchanger in water wet state (μm) = z1 × (x1 / y1)”. In addition, the average diameter of the opening of the dried monolith before introduction of the ion exchange group, and the swelling ratio of the monolith ion exchanger in the water wet state relative to the dried monolith when the ion exchange group is introduced into the dried monolith. In this case, the average diameter in the water-wet state of the pores of the monolith ion exchanger can also be calculated by multiplying the average diameter of the opening of the monolith in the dry state by the swelling rate.

In the first monolithic ion 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. If the area of the skeleton part appearing in the cross section is less than 25% in the image region, it becomes a thin skeleton, which is not preferable because the ion exchange capacity per volume decreases, and if it exceeds 50%, the skeleton becomes too thick. Since the uniformity of ion exchange characteristics is lost, it is not preferable. Note that the monolith described in JP-A-2002-346392 has a limit to the blending ratio in order to ensure a common opening even if the blending ratio of the oil phase part to water is actually increased and the skeleton portion is thickened. Yes, 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 skeleton appearing in the cross section of the cut surface appears clearly. For example, the magnification is 100 to 600, and the photographic area is about 150 mm × 100 mm. 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. The skeleton part of the cut surface in the SEM image will be described with reference to FIGS. FIG. 5 is a transcribed skeleton that appears as a cross section of the SEM photograph of FIG. In FIGS. 1 and 5, what is generally indeterminate and shown in cross section is the “skeleton portion (reference numeral 12)” in the present invention, the circular hole shown in FIG. 1 is an opening (mesopore), and A relatively large curvature or curved surface is a macropore (reference numeral 13 in FIG. 5). The skeleton area shown in the cross section of FIG. 5 is 28% in the rectangular photographic region 11. Thus, the skeleton can be clearly determined.

In the SEM photograph, 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 skeletal part by performing known computer processing or the like, calculation by automatic calculation by a computer or manual calculation 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 first monolith ion exchanger has a total pore volume of 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 at the time of fluid permeation increases, which is not preferable. Further, the amount of permeated fluid per unit cross-sectional area becomes smaller, and the treatment ability is reduced. Therefore, it is not preferable. On the other hand, if the total pore volume exceeds 5 ml / g, the ion exchange capacity per volume decreases, which is not preferable. Since the monolith of the present invention has an average diameter and total pore volume of openings in the above ranges and is a thick skeleton, when it is used as an ion exchanger of an electric deionized water production apparatus, the strength is high. The water flow can be increased, the quality of treated water is improved, and the power consumption is reduced. In the present invention, the total pore volume of the monolith (monolith intermediate, monolith, monolith ion exchanger) is a value measured by a mercury intrusion method. In addition, the total pore volume of the monolith (monolith intermediate, monolith, monolith ion 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 ion exchanger is the pressure loss at the time of letting water flow through the column filled with 1 m of the porous body at a water flow rate (LV) of 1 m / h (hereinafter referred to as “pressure loss”). , “Differential pressure coefficient”) is preferably in the range of 0.001 to 0.1 MPa / m · LV, particularly 0.001 to 0.05 MPa / m · LV. If the permeation rate and the total pore volume are in this range, when this is used as an ion exchanger in an electrical deionized water production apparatus, pressure loss during water flow is suppressed and the quality of treated water is improved. Furthermore, it is preferable because it has sufficient mechanical strength.

The first monolith ion exchanger has an ion exchange capacity of 0.4 to 5.0 mg equivalent / ml per volume when wet in water. 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 to increase the exchange capacity per volume. In addition, since the opening diameter is reduced, the pressure loss increases. On the other hand, since the monolith ion exchanger of the present invention (A1) can further increase the opening diameter and thicken the skeleton of the continuous macropore structure (thicken the skeleton wall), The desalination performance can be greatly increased while keeping the pressure loss low. If the ion exchange capacity per volume is less than 0.4 mg equivalent / ml, the electrical resistance increases and the quality of the treated water decreases, which is not preferable. The ion exchange capacity per weight of the monolith ion exchanger of the present invention (A1) is not particularly limited. However, since the ion exchange groups are uniformly introduced to the surface of the porous body and the inside of the skeleton, 3 to 5 mg Equivalent / g. The ion exchange capacity of a porous body in which ion exchange groups are introduced only on the surface cannot be determined unconditionally depending on the type of the porous body or ion exchange groups, but is at most 500 μg equivalent / g.

In the first monolith ion exchanger, the material constituting the skeleton of the continuous macropore structure is an organic polymer material having a crosslinked structure. The crosslink density of the polymer material is not particularly limited, but includes 0.3 to 50 mol%, preferably 0.3 to 5 mol% of cross-linked structural units with respect to all the structural units constituting the polymer material. It is preferable. If the cross-linking structural unit is less than 0.3 mol%, it is not preferable because the mechanical strength is insufficient. On the other hand, if it exceeds 50 mol%, embrittlement of the porous body proceeds and flexibility is lost. In particular, in the case of an ion exchanger, the amount of ion exchange groups introduced is decreased, which is not preferable. 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 high due to the ease of forming a continuous macropore structure, the ease of introducing ion-exchange groups and the high mechanical strength, and the high stability to acids and alkalis. A styrene-divinylbenzene copolymer and a vinylbenzyl chloride-divinylbenzene copolymer are particularly preferable materials.

Examples of the ion exchange group of the first monolith ion exchanger include cation exchange groups such as a sulfonic acid group, a carboxylic acid group, an iminodiacetic acid group, a phosphoric acid group, and a phosphoric acid ester group; a quaternary ammonium group and a tertiary amino group And anion exchange groups such as secondary amino group, primary amino group, polyethyleneimine group, tertiary sulfonium group, and phosphonium group.

In the first monolith ion exchanger, the introduced ion exchange groups are uniformly distributed not only on the surface of the porous body but also within the skeleton of the porous body. Here, “ion exchange groups are uniformly distributed” means that the distribution of ion exchange groups is uniformly distributed on the surface and inside the skeleton in the order of at least μm. The distribution of ion exchange groups can be confirmed relatively easily by using EPMA or the like. In addition, if the ion 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 shrinkage can be achieved. The durability against is improved.

(Method for producing first monolithic ion exchanger)
The first monolith ion exchanger is prepared by preparing 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 polymerizing the water-in-oil emulsion. Step I for obtaining a monolithic organic porous intermediate having a continuous macropore structure with a total pore volume of 5 to 16 ml / g, a vinyl monomer, a crosslinking agent having at least two vinyl groups in one molecule, a vinyl monomer, Step II for preparing a mixture comprising an organic solvent and a polymerization initiator that dissolves the cross-linking agent but does not dissolve the polymer formed by polymerization of the vinyl monomer. The mixture obtained in Step II is allowed to stand still and in Step I. Polymerization is performed in the presence of the obtained monolithic organic porous intermediate to obtain a thick organic porous body having a skeleton thicker than the skeleton of the organic porous intermediate. It is obtained by performing the IV step of introducing an ion exchange group into the thick organic porous material obtained in the step III.
In the first method for producing a monolithic ion 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 alone 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 50 mol% in the total oil-soluble monomer, preferably 0.3 to 5 mol% is preferable in that the mechanical strength necessary for introducing a large amount of ion-exchange groups in a later step can be obtained.

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 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 alone 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, azobiscyclohexanenitrile, azobiscyclohexanecarbonitrile, benzoyl peroxide, potassium persulfate, ammonium persulfate, Examples thereof include hydrogen oxide-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. The mixing apparatus for forming the emulsion is not particularly limited, and a normal mixer, homogenizer, high-pressure homogenizer, or the like can be used, and an appropriate apparatus may be selected to obtain a 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 is formed using the structure of the monolith intermediate as a template. The monolith intermediate is an organic polymer material having a crosslinked structure. The crosslinking density of the polymer material is not particularly limited, but it contains 0.3 to 50 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, it is preferable to contain 2 mol% or more of crosslinked structural units in order to maintain a continuous macropore structure. On the other hand, if it exceeds 50 mol%, the porous body becomes brittle and the flexibility is lost.

The type of 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 water passage becomes large, 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 monomer to water may be about 1: 5 to 1:20.

In addition, in the monolith intermediate, the average diameter of the opening (mesopore) that is the overlapping portion of the macropore and the macropore is 20 to 200 μm in a dry state. When the average diameter of the openings is less than 20 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes small, and the pressure loss at the time of passing water becomes large, 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 ion exchanger becomes insufficient, resulting in a decrease in desalting efficiency. This 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 alone or in combination of two or more. The vinyl monomer suitably used in the present invention (A1) is an aromatic vinyl monomer such as styrene or vinyl benzyl chloride.

The amount of these vinyl monomers added is 3 to 40 times, preferably 4 to 30 times, by weight with respect to the monolith intermediate coexisting during 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 adsorption capacity per volume and the volume after introduction of ion-exchange groups. Since the ion exchange capacity per unit becomes small, it is not preferable. On the other hand, when the addition amount of vinyl monomer exceeds 40 times, the opening diameter becomes small, and the pressure loss at the time of passing water becomes large.

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 0.3 to 50 mol%, particularly 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 50 mol%, the brittleness of the monolith proceeds and the flexibility is lost, and the introduction amount of ion exchange groups is reduced. It is preferable to use it so as to be approximately equal to the crosslinking density of the monolith intermediate coexisting during the polymerization of the vinyl monomer / crosslinking agent. If the amounts used of both are too large, the crosslink density distribution is biased in the produced monolith, and cracks are likely to occur during the ion 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 vinyl monomer concentration 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 (A1) 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-cyano (Valeric 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 the 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 cross-linking agent are adsorbed or distributed from the liquid phase to the skeleton of the porous body, and polymerization proceeds in the porous body to obtain a thick skeleton monolith. It is thought that. 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 a mixture (solution). The blending ratio of the mixture obtained in Step II and the monolith intermediate is such that, as described above, the amount of vinyl monomer added is 3 to 40 times, preferably 4 to 30 times, by weight with respect 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 can be 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 The polymerization may be carried out by heating at 30 to 100 ° C. for 1 to 48 hours in a sealed container under an inert atmosphere. 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 ion exchange group is preferable in that the porous structure of the resulting monolith ion exchanger can be strictly controlled.

The method for introducing an ion exchange group into the monolith is not particularly limited, and a known method such as polymer reaction or graft polymerization can be used. For example, as a method of introducing a sulfonic acid group, if the monolith is a styrene-divinylbenzene copolymer, etc., a method of sulfonation using chlorosulfuric acid, concentrated sulfuric acid or fuming sulfuric acid; A method in which a mobile group is introduced into the skeleton surface and inside the skeleton, and graft polymerization of sodium styrenesulfonate or acrylamido-2-methylpropanesulfonic acid is performed; after glycidyl methacrylate is similarly grafted, a sulfonic acid group is introduced by functional group conversion. And the like. As a method for 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. Examples of the method for introducing betaine include a method in which a tertiary amine is introduced into a monolith by the above method and then introduced by reacting with monoiodoacetic acid. Among these methods, the method of introducing a sulfonic acid group includes a method of introducing a sulfonic acid group into a styrene-divinylbenzene copolymer using chlorosulfuric acid, and a method of introducing a quaternary ammonium group includes styrene. -Introducing a chloromethyl group into the divinylbenzene copolymer with chloromethyl methyl ether, etc., then reacting with a tertiary amine, or producing a monolith by copolymerization of chloromethylstyrene and divinylbenzene and reacting with a tertiary amine The method is preferable in that the ion exchange group can be introduced uniformly and quantitatively. The ion exchange groups to be introduced include cation exchange groups such as carboxylic acid groups, iminodiacetic acid groups, sulfonic acid groups, phosphoric acid groups, and phosphoric ester groups; quaternary ammonium groups, tertiary amino groups, and secondary amino groups. Groups, primary amino groups, polyethyleneimine groups, tertiary sulfonium groups, phosphonium groups and the like.

The first monolith ion exchanger swells greatly, for example, 1.4 to 1.9 times that of the thick monolith because the ion 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 No. 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 first monolith ion exchanger has a high mechanical strength because it has a thick bone skeleton despite the remarkably large opening diameter.

<Description of Second Monolith Ion Exchanger>
The second monolith ion exchanger is a tertiary having a thickness of 1 to 60 μm made of an aromatic vinyl polymer containing 0.3 to 5.0 mol% of a cross-linking structural unit among all the structural units into which ion exchange groups are introduced. A co-continuous structure composed of an originally continuous skeleton and three-dimensionally continuous pores having a diameter of 10 to 100 μm between the skeletons, with a total pore volume of 0.5 to 5 ml / g In other words, the ion exchange capacity per volume in a wet state of water is 0.3 to 5 mg equivalent / ml, and the ion exchange groups are uniformly distributed in the porous ion exchanger.

The second monolith ion exchanger has a three-dimensionally continuous skeleton having an average thickness of 1 to 60 μm, preferably 3 to 58 μm in a water-wet state in which ion-exchange groups are 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 20 to 80 μm in a wet state. That is, as shown in the schematic diagram of FIG. 6, the co-continuous structure is a structure 10 in which a continuous skeleton phase 61 and a continuous vacancy phase 62 are intertwined and each of them is three-dimensionally continuous. The continuous vacancies 62 have higher continuity of vacancies than the conventional open-cell monolith and particle agglomeration monolith, and the size of the vacancies is not biased. Therefore, an 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 second monolith ion exchanger are larger than the monolith skeleton thickness and pore diameter because the entire monolith swells when an ion exchange group is introduced into the monolith. It becomes. These continuous pores have higher continuity of pores and are not biased in size compared to conventional open-cell monolithic organic porous ion exchangers and particle-aggregated monolithic organic porous ion exchangers. Therefore, extremely uniform ion adsorption behavior can be achieved. If the diameter of the three-dimensionally continuous pores is less than 10 μm, the pressure loss when passing through the fluid increases, which is not preferable. If it exceeds 100 μm, the contact between the water to be treated and the organic porous ion exchanger As a result, the ion exchange characteristics are not uniform, that is, the length of the ion exchange zone becomes long, and a small amount of adsorbed ions are likely to leak, which is not preferable. In addition, if the thickness of the skeleton is less than 1 μm, it is not preferable because the ion exchange capacity per volume decreases and the mechanical strength decreases, which is not preferable. On the other hand, if the skeleton thickness is too large, Since the uniformity of the exchange characteristics is lost and the ion exchange zone length becomes long, it is not preferable.

The average diameter of the pores of the above-mentioned continuous structure in the water wet state is a value calculated by multiplying the average diameter of the pores of the monolith ion exchanger in the dry state measured by a known mercury intrusion method and the swelling ratio. It is. Specifically, the water-wet monolith ion exchanger has a diameter of x2 (mm), and the water-wet monolith ion exchanger is dried, and the resulting dried monolith ion exchanger has a diameter of y2 ( mm), and the average diameter of the pores when the dried monolith ion exchanger was measured by the mercury intrusion method was z2 (μm), the pores of the monolith ion exchanger in the water-wet state The average diameter (μm) is calculated by the following formula: “average diameter (μm) of water holes in the monolith ion exchanger pores = z2 × (x2 / y2)”. In addition, the average diameter of the pores of the dried monolith before introduction of the ion exchange groups, and the swelling ratio of the water-dried monolith ion exchanger with respect to the dried monolith when the ion exchange groups are introduced into the dried monolith. If it is known, the average diameter of the monolith ion exchanger pores in the water-wet state can be calculated by multiplying the average diameter of the pores of the dry monolith by the swelling rate. Further, the average thickness of the skeleton of the continuous structure in the water-wet state is obtained by performing SEM observation of the dried monolith ion exchanger at least three times, and measuring the thickness of the skeleton in the obtained image. It is a value calculated by multiplying the average value by the swelling rate. Specifically, the water-wet monolith ion exchanger has a diameter of x3 (mm), the water-wet monolith ion exchanger is dried, and the resulting dried monolith ion exchanger has a diameter of y3 ( SEM observation of this dried monolith ion exchanger at least three times, the thickness of the skeleton in the obtained image was measured, and the average value was z3 (μm). The average thickness (μm) of the skeleton of the continuous structure of the ion exchanger in the water wet state is expressed by the following formula: “average thickness of the skeleton of the continuous structure of the monolith ion exchanger (μm) = z3 × (X3 / y3) ". In addition, the average thickness of the skeleton of the dried monolith before the introduction of the ion exchange group, and the swelling ratio of the monolith ion exchanger in the water wet state relative to the dried monolith when the ion exchange group is introduced into the dried monolith. When it is understood, the average thickness of the skeleton of the monolith ion exchanger can be calculated by multiplying the average thickness of the skeleton of the monolith in the dry state by the swelling ratio. 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.

If the thickness of the three-dimensional continuous rod-like skeleton is less than 10 μm, the second monolithic ion exchanger is not preferable because the ion exchange capacity per volume is reduced. This is not preferable because the uniformity of the film is lost. The definition and measurement method of the wall of the monolith ion exchanger are the same as those of the monolith.

The second monolith ion exchanger has a total pore volume of 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 fluid permeation increases, 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 ion exchange capacity per volume 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 fluid is extremely uniform and the contact area is large, so the ion exchange zone length is shortened and the adsorbed ions It is difficult to cause a slight leak. Further, since the fluid can be permeated under a low pressure loss, excellent performance as an ion exchanger can be exhibited. The total pore volume of the monolith (monolith intermediate, monolith, monolith ion exchanger) is the same in the dry state and in the water wet state.

The pressure loss when water was permeated through the second monolith ion exchanger was the pressure loss when water was passed through a column filled with 1 m of a porous material at a water flow rate (LV) of 1 m / h (hereinafter referred to as “pressure loss”). , Referred to as “differential pressure coefficient”), it is in the range of 0.001 to 0.5 MPa / m · LV, particularly 0.001 to 0.1 MPa / m · LV. If the permeation rate and the total pore volume are in this range, when this is used as an ion exchanger in an electrical deionized water production apparatus, pressure loss during water flow is suppressed and the quality of treated water is improved. Furthermore, it is preferable because it has sufficient mechanical strength.

In the second monolith ion exchanger, the material constituting the skeleton of the co-continuous structure includes 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 used because of its ease of forming a co-continuous structure, ease of introduction of ion-exchange groups, high mechanical strength, and high stability against acids and alkalis. And vinylbenzyl chloride-divinylbenzene copolymer is preferred.

The second monolith ion exchanger has an ion exchange capacity of 0.3 to 5 mg equivalent / ml per volume under water wet condition. 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 to increase the exchange capacity per volume. In addition, since the opening diameter is reduced, the pressure loss increases. On the other hand, since the monolith ion exchanger of the present invention has high continuity and uniformity of three-dimensionally continuous pores, the pressure loss does not increase so much even if the total pore volume is reduced. Therefore, the ion exchange capacity per volume can be dramatically increased while keeping the pressure loss low, and the electrical resistance is reduced and the quality of the treated water is improved. The ion exchange capacity per weight in the dry state of the second monolith ion exchanger is not particularly limited. However, since the ion exchange groups are uniformly introduced to the skeleton surface and inside the skeleton of the porous body, 3 to 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.

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

(Method for producing second monolith ion exchanger)
The second monolith ion 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 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 0.3 to 5 mol% of the cross-linking agent, aromatic vinyl monomer and cross-linking agent dissolved in the total oil-soluble monomer, but from the organic solvent and polymerization initiator that does not dissolve the polymer formed by polymerization of the aromatic vinyl monomer Step II for preparing the mixture, the mixture obtained in Step II is allowed to stand, and polymerization is performed in the presence of the monolithic organic porous intermediate obtained in Step I. III to obtain a continuous structure, obtained by performing the IV step of introducing ion exchange groups to resulting co-continuous structure in the step III.

The I step for obtaining the monolith intermediate in the second monolith ion exchanger may be performed according to the method described in JP-A-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 alone 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 3 mol% is preferable in that a mechanical strength necessary for introducing a large amount of ion-exchange groups in a later step can be obtained.

The surfactant is the same as the surfactant used in step I of the first monolith ion 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 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, in the step I of the first monolith ion exchanger This is the same as the mixing method, and the description thereof is omitted.

In the second method for producing a monolith ion exchanger, the monolith intermediate obtained in the step I is an organic polymer material having a crosslinked structure, preferably an aromatic vinyl polymer. The crosslinking density of the polymer material is not particularly limited, but it contains 0.3 to 5 mol%, preferably 0.3 to 3 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. 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 first monolith ion exchanger, and the description thereof is omitted.

The total pore volume of the monolith intermediate is more than 16 ml / g and not more than 30 ml / g, preferably 6 to 25 ml / g. In other words, this monolith intermediate is basically a continuous macropore structure, but the opening (mesopore) that is the overlap between macropores and macropores is remarkably large. It has a structure that is 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 template. 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 ion exchange capacity per volume is lowered. In order for the total pore volume of the monolith intermediate to be in a specific range of the second monolith ion exchanger, the ratio of monomer to water may be approximately 1:20 to 1:40.

In addition, in the monolith intermediate, the average diameter of openings (mesopores), which are the overlapping portions of macropores and macropores, is 5 to 100 μm in a dry state. If the average diameter of the openings is less than 5 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes small, and the pressure loss during water passage becomes large, 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 fluid to be treated and the monolith ion exchanger becomes insufficient, resulting in a decrease in ion exchange characteristics. This 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 second method for producing a monolithic ion 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. This is a step of preparing 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 second method for producing a monolithic ion exchanger, the aromatic vinyl monomer used in step II includes a lipophilic aromatic vinyl monomer that contains a polymerizable vinyl group in the molecule and has 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 alone 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 aromatic vinyl monomer added is less than 5 times that of the porous body, the rod-like skeleton cannot be thickened, the ion exchange capacity per volume after the introduction of ion exchange groups is reduced, and the electrical resistance is increased. It also leads to a decline in the quality of treated water.

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, the brittleness of the monolith proceeds and the flexibility is lost. This is not preferable because a problem arises in that the amount of introduction of is reduced. 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 is biased in the produced monolith, and cracks are likely to occur during the ion 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 first monolith ion exchanger, and the description thereof is omitted.

In the second method for producing a monolith ion 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 changing the continuous macropore structure of the body to a co-continuous structure to obtain a monolith with a bone skeleton. 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 specific continuous macropore structure is present in the polymerization system as in the second 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 first monolith ion exchanger, and the description thereof is omitted.

In step III, the monolith intermediate is placed in a reaction vessel impregnated with a 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, by 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 a monolith having a co-continuous structure is a three-dimensional continuous skeleton with an average thickness of 0.8 to 40 μm in a dry state, and a three-dimensional continuous sky with a diameter of 8 to 80 μm between the skeletons. This is a structure in which holes are arranged. The average diameter of the three-dimensionally continuous pores can be obtained as a maximum value of the pore distribution curve by measuring the pore distribution curve by the mercury intrusion method. The thickness of the skeleton of the 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.

Polymerization conditions are the same as the description of the polymerization conditions in the III step of the first monolith ion exchanger, and the description thereof is omitted.

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

The second monolith ion exchanger swells to a large extent 1.4 to 1.9 times that of the monolith, for example, because the ion 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 second monolith ion 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. In addition, since the skeleton is thick, it is possible to increase the ion exchange capacity per volume in a wet state of water, and it is possible to pass water to be treated for a long time at a low pressure and a large flow rate. It can be suitably used by filling.

[Invention (A2)]
In the deionization module according to the embodiment of the present invention (A2), at least one of the internal space of the frame body and the two internal spaces of the frame body having the intermediate film is filled in the third monolith ion exchanger. It is. In this specification, “monolithic organic porous body” is simply “composite monolith”, “monolithic organic porous ion exchanger” is simply “composite monolithic ion exchanger”, and “monolithic organic porous intermediate”. "Body" is also simply called "monolith intermediate".

<Description of composite monolith ion exchanger>
A composite monolith ion exchanger is obtained by introducing an ion exchange group into a composite monolith, and is fixed to an organic porous body composed of a continuous skeleton phase and a continuous pore phase, and to the skeleton surface of the organic porous body. Or an organic porous body composed of a continuous skeleton phase and a continuous pore phase and a size formed on the skeleton surface of the organic porous body. A composite structure with a large number of protrusions having a thickness of 4 to 40 μm, and having an average pore diameter of 10 to 150 μm and a total pore volume of 0.5 to 5 ml / g in a water-wet state, The ion exchange capacity per volume is 0.2 mg equivalent / ml or more, and the ion exchange groups are uniformly distributed in the composite structure. In addition, in this specification which concerns on this invention (A2), a "particle body" and a "projection body" may be collectively called "particle body etc.".

The continuous skeleton phase and the continuous pore phase (dried body) of the organic porous body can be observed by an SEM image. Examples of the basic structure of the organic porous material include a continuous macropore structure and a co-continuous structure. The skeletal phase of the organic porous material appears as a columnar continuum, a concave wall continuum, or a composite thereof, and has a shape that is clearly different from a particle shape or a protrusion shape.

As a preferred structure of the organic porous body, bubble-like macropores overlap each other, and the overlapped portion is a continuous macropore structure in which an opening having an average diameter of 30 to 150 μm is formed in a water wet state, and an average thickness is 1 in a water wet state. Examples thereof include a co-continuous structure comprising a three-dimensionally continuous skeleton of ˜60 μm and three-dimensionally continuous pores having an average diameter of 10 to 100 μm in a wet state between the skeletons.

The average diameter of the opening of the composite monolith ion exchanger having a continuous macropore structure is such that the introduction of the ion exchange group into the composite monolith causes the composite monolith ion exchanger to swell. It becomes larger than the average diameter. If the average diameter of the openings is less than 30 μm, the pressure loss during water flow is increased, which is not preferable. If the average diameter of the openings is too large, the contact between the fluid and the composite monolith ion exchanger becomes insufficient. As a result, the ion exchange characteristics deteriorate, which is not preferable.

In a composite monolith ion exchanger having a co-continuous structure, if the diameter of the three-dimensionally continuous pores is less than 10 μm, it is not preferable because the pressure loss during fluid permeation increases. This is not preferable because the uniformity of salt characteristics is lost.

In the composite monolithic ion exchanger having a co-continuous structure, if the average diameter of the three-dimensionally continuous skeleton is less than 1 μm, it is not preferable because the ion exchange capacity per volume is reduced. This is not preferable because the uniformity of salt characteristics is lost.

In the present invention (A2), the average diameter of the openings of the monolith intermediate in the dry state, the average diameter of the pores or openings of the composite monolith in the dry state, and the average of holes or openings of the composite monolith ion exchanger in the dry state The diameter is a value measured by a mercury intrusion method. In the composite monolith ion exchanger of the present invention (A2), the average diameter of the pores or openings of the composite monolith ion exchanger in a wet state is the average diameter of the pores or openings of the dry composite monolith ion exchanger. Is a value calculated by multiplying the swelling ratio, and the specific calculation method is the same as the calculation method of the invention (A1).

The preferred value of the average diameter of the pores in the wet state of the composite monolith ion exchanger is 10 to 120 μm. When the organic porous body constituting the composite monolith ion exchanger is a continuous macropore structure, the preferred pore size of the composite monolith ion exchanger is 30 to 120 μm, and the organic porous body constituting the composite monolith ion exchanger is co-continuous. In the case of a structure, a preferable value of the pore size of the composite monolith ion exchanger is 10 to 90 μm.

In the composite monolith ion exchanger according to the present invention (A2), the diameter of the particles and the size of the protrusions in a wet state of water are 4 to 40 μm, preferably 4 to 30 μm, particularly preferably 4 to 20 μm. In the present invention (A2), both the particles and the protrusions are observed as protrusions on the surface of the skeleton, and the particles observed are referred to as particles, and the protrusions that cannot be said to be granular A thing is called a protrusion. FIG. 35 shows a schematic cross-sectional view of the protrusion. As shown in (A) to (E) of FIG. 35, the protrusions protruding from the skeleton surface 61 are the protrusions 62. The protrusions 62 are like the protrusions 62a shown in (A). The shape close to a granular shape, a hemispherical shape like a projection 62b shown in (B), and a swell of the skeleton surface like a projection 62c shown in (C). In addition, the protrusion 61 has a shape that is longer in the direction perpendicular to the skeleton surface 61 than in the plane direction of the skeleton surface 61, like the protrusion 62d shown in FIG. There is a thing of the shape which protruded in the several direction like the protrusion 62e shown to (E). Further, the size of the protrusions is determined by the SEM image when observed by SEM, and indicates the length of the portion where the width of each protrusion is the largest in the SEM image.

In the composite monolith ion exchanger according to the present invention (A2), the proportion of 4 to 40 μm particles in a wet state in water is 70% or more, preferably 80% or more. The ratio of 4 to 40 μm particles in the wet state in all particles refers to the number ratio of 4 to 40 μm particles in the wet state in the total number of particles. Further, the surface of the skeletal phase is covered by 40% or more, preferably 50% or more by the whole particles. The coverage ratio of the surface of the skeleton layer with particles or the like refers to the area ratio on the SEM image when the surface is observed by SEM, that is, the area ratio when the surface is viewed in plan. If the size of the particle covering the wall surface or the skeleton deviates from the above range, the effect of improving the contact efficiency between the fluid and the skeleton surface of the composite monolith ion exchanger and the inside of the skeleton is not preferable. Note that the total particle body and the like are all the particle bodies formed on the surface of the skeleton layer, including all the particle bodies and protrusions in a size range other than 4 to 40 μm particle bodies in a wet state. And a protrusion.

The diameter or size of the particles attached to the surface of the skeleton of the composite monolith ion exchanger in the water-wet state is the diameter or size of the particles obtained by observing the SEM image of the composite monolith ion exchanger in the dry state. Further, the value calculated by multiplying the swelling rate when the dry state is changed to the wet state, or the diameter or size of the particulates obtained by observing the SEM image of the composite monolith in the dry state before introducing the ion exchange group And a value calculated by multiplying the swelling ratio before and after introduction of the ion exchange group. Specifically, the diameter of the composite monolith ion exchanger in the water wet state is x4 (mm), the diameter of the composite monolith ion exchanger in the dry state obtained by drying the composite monolith ion exchanger in the water wet state. Is y4 (mm), and the diameter or size of the particles in the SEM image of the dried composite monolith ion exchanger observed by SEM is z4 (μm). The diameter or size (μm) of the particles of the monolith ion exchanger is expressed by the following formula: “diameter or size (μm) of the particles of the composite monolith ion exchanger in a water-wet state” = z4 × (x4 / y4) Is calculated. Then, the diameter or size of all particles observed in the SEM image of the composite monolith ion exchanger in the dry state is measured, and based on the value, all particles in one field of view SEM image, etc. The diameter or size of the water in a wet state is calculated. The SEM observation of the dried composite monolith ion exchanger is performed at least three times, and the diameter or size of the whole particle in the SEM image in the water-wet state is calculated in all fields of view. It is confirmed whether or not the particles in the range of 4 to 40 μm are observed, and when confirmed in the entire field of view, the diameter or size is 4 to 40 μm in a wet state on the skeleton surface of the composite monolith ion exchanger. It is determined that the particle body at is formed. In addition, the diameter or size of all particles in the SEM image in the water wet state is calculated for each field of view according to the above, and particles of 4 to 40 μm in the water wet state occupying the whole particles for each field of view. When the proportion of the particles, etc. is 4% to 40 μm in the wet state in all the particles in the entire visual field is 70% or more, the skeleton surface of the composite monolith ion exchanger is obtained. It is determined that the proportion of 4 to 40 μm particles in the wet state is 70% or more in all particles formed in the above. Further, according to the above, the coverage ratio of the surface of the skeletal layer with all particles in the SEM image was determined for each field of view, and the coverage ratio of the surface of the skeleton layer with all particles in all fields was 40% or more. In this case, it is determined that the ratio of the surface of the skeleton layer of the composite monolith ion exchanger covered with all the particulates is 40% or more. In addition, the diameter or size of the particles of the composite monolith in the dry state before the introduction of the ion exchange group and the composite monolith ion exchange in the wet state with respect to the dry composite monolith when the ion exchange group is introduced into the monolith in the dry state If the swelling rate of the body is known, the diameter or size of the particles of the composite monolith in the dry state is multiplied by the swelling rate to obtain the diameter or size of the particles of the composite monolith ion exchanger in the water wet state. In the same manner as described above, the diameter or size of the particles of the composite monolith ion exchanger in the water wet state, the ratio of the particles of 4 to 40 μm in the water wet state in the total particles, etc. In addition, the coverage ratio of the surface of the skeleton layer with particle bodies can be obtained.

If the coverage of the skeletal phase surface with particles and the like is less than 40%, the effect of improving the contact efficiency between the fluid and the inside of the skeleton of the composite monolith ion exchanger and the skeleton surface is reduced, and the desalting behavior is uniform. Since it will be damaged, it is not preferable. Examples of the method for measuring the coverage with the particulates include an image analysis method using a monolith (dry body) SEM image.

Also, the total pore volume of the composite monolith ion exchanger is the same as the total pore volume of the composite monolith. That is, even when the ion exchange group is introduced into the composite monolith to swell and increase the opening diameter, the total pore volume hardly changes because the skeletal phase is thick. If the total pore volume is less than 0.5 ml / g, the pressure loss at the time of fluid permeation increases, 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 ion exchange capacity per volume decreases, which is not preferable. Note that the total pore volume of the composite monolith (monolith intermediate, composite monolith, composite monolith ion exchanger) is the same both in the dry state and in the water wet state.

The composite monolith ion exchanger of the present invention (A2) has an ion exchange capacity of 0.2 mg equivalent / ml or more, preferably 0.3 to 1.8 mg equivalent / ml per volume when wet in water. Have. If the ion exchange capacity per volume is less than 0.2 mg equivalent / ml, the desalting efficiency is lowered, which is not preferable. The ion exchange capacity per weight in the dry state of the composite monolith ion exchanger of the present invention is not particularly limited. However, since the ion exchange groups are uniformly introduced to the skeleton surface and inside the skeleton of the composite monolith, 3 to 5 mg equivalent / g. The ion exchange capacity of the organic porous material in which the ion exchange group is introduced only on the surface of the skeleton cannot be determined depending on the kind of the organic porous material or the ion exchange group, but is 500 μg equivalent / g at most.

The ion exchange group introduced into the composite monolith of the present invention (A2) is the same as the ion exchange group of the invention (A1).

In the composite monolith ion exchanger of the present invention (A2), the introduced ion exchange groups, the definition of uniform distribution, the confirmation of the distribution status of ion exchange groups, and the technical significance of being uniformly distributed to the inside of the skeletal phase are This is the same as the invention (A1).

Also, the composite monolith ion exchanger of the present invention (A2) has high mechanical strength because the basic structure of the skeleton is a continuous pore structure.

The composite monolith ion exchanger of the present invention (A2) stirs a mixture of an oil-soluble monomer containing no ion exchange group, a first crosslinking agent having at least two or more vinyl groups in one molecule, a surfactant and water. Preparing a water-in-oil emulsion, and then polymerizing the water-in-oil emulsion to obtain a monolithic organic porous intermediate having a continuous macropore structure with a total pore volume of 5 to 30 ml / g, Vinyl monomer, second cross-linking agent having at least two or more vinyl groups in one molecule, organic solvent and polymerization initiator that dissolves vinyl monomer and second cross-linking agent but does not dissolve polymer formed by polymerization of vinyl monomer Step II for preparing a mixture comprising the following: polymerization in the presence of the mixture obtained in Step II and standing in the presence of the monolithic organic porous intermediate obtained in Step I The following steps (1) to (5) are carried out when the monolithic organic porous material is produced by performing the step III and the IV step of introducing an ion exchange group into the monolithic organic porous material obtained in the step III.
(1) The polymerization temperature in step III is at least 5 ° C. lower than the 10-hour half-life temperature of the polymerization initiator;
(2) The mol% of the second cross-linking agent used in step II is at least twice the mol% of the first cross-linking agent used in step I;
(3) The vinyl monomer used in Step II is a vinyl monomer having a structure different from that of the oil-soluble monomer used in Step I;
(4) The organic solvent used in step II is a polyether having a molecular weight of 200 or more;
(5) The concentration of the vinyl monomer used in Step II is 30% by weight or less in the mixture of Step II; obtained by performing Step II or Step III under conditions that satisfy at least one of the conditions .

(Method for producing monolith intermediate)
In the method for producing a monolith of the present invention (A2), the step I comprises an oil-soluble monomer containing no ion exchange group, a first crosslinking agent having at least two vinyl groups in one molecule, a surfactant and water. A step of preparing a water-in-oil emulsion by stirring the mixture and then polymerizing the water-in-oil emulsion to obtain a monolith intermediate having a continuous macropore structure with a total pore volume of 5 to 30 ml / g. The step I for obtaining the monolith intermediate may be performed according to the method described in JP-A-2002-306976.

Examples of the oil-soluble monomer that does not contain an ion exchange group include an oleophilic monomer that does not contain an ion exchange group such as a carboxylic acid group, a sulfonic acid group, and a quaternary ammonium group and has low solubility in water. 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 alone or in combination of two or more.

Examples of the first crosslinking agent having at least two or more vinyl groups in one molecule include divinylbenzene, divinylnaphthalene, divinylbiphenyl, and ethylene glycol dimethacrylate. These crosslinking agents can be used singly or in combination of two or more. A preferred first cross-linking agent is an aromatic polyvinyl compound such as divinylbenzene, divinylnaphthalene, and divinylbiphenyl because of its high mechanical strength. The amount of the first crosslinking agent used is 0.3 to 10 mol%, particularly 0.3 to 5 mol%, and more preferably 0.3 to 3 mol%, based on the total amount of the vinyl monomer and the first crosslinking agent. Is preferred. If the amount of the first 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 monolith becomes more brittle and the flexibility is lost, and the amount of ion exchange groups introduced decreases, which is not preferable.

dimethyl

2,2′-azobisisobutyrate, 4,4′-azobis ( 4-Cyanovaleric acid), 1,1'-azobis (cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, hydrogen peroxide-ferrous chloride, sodium persulfate- Examples include acidic sodium sulfite.

There is no particular limitation on the mixing method when mixing the oil-soluble monomer containing no ion exchange group, the first cross-linking agent, the surfactant, water and the polymerization initiator to form a water-in-oil emulsion, A method of mixing components all at once, an oil-soluble monomer, a first crosslinking agent, a surfactant, an oil-soluble component that is an oil-soluble polymerization initiator, and a water-soluble component that is water or a water-soluble polymerization initiator For example, a method in which each component is mixed after being uniformly dissolved separately can be used. The mixing apparatus for forming the emulsion is not particularly limited, and a normal mixer, homogenizer, high-pressure homogenizer, or the like can be used, and an appropriate apparatus may be selected to obtain a 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, particles or the like are formed on the surface of the skeleton phase of the continuous macropore structure using the structure of the monolith intermediate as a template, or particles or the like are formed on the surface of the skeleton phase of the co-continuous structure. Or The monolith intermediate is an organic polymer material having a crosslinked structure. The crosslinking density of the polymer material is not particularly limited, but it 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. On the other hand, if it exceeds 10 mol%, the porous body becomes brittle and the flexibility is lost, which is not preferable.

The total pore volume of the monolith intermediate is 5 to 30 ml / g, preferably 6 to 28 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 tends to be non-uniform, and in some cases, the structure collapses, which is not preferable. In order to make the total pore volume of the monolith intermediate within the above numerical range, the ratio of monomer to water (weight) may be set to approximately 1: 5 to 1:35.

If the ratio of this monomer to water is approximately 1: 5 to 1:20, a monolith intermediate having a total macropore structure of 5 to 16 ml / g and a continuous macropore structure can be obtained and obtained through the step III. The resulting composite monolithic organic porous body has a continuous macropore structure. Further, when the blending ratio is approximately 1:20 to 1:35, a monolith intermediate having a total pore volume exceeding 16 ml / g and having a continuous macropore structure of 30 ml / g or less can be obtained. The organic porous body of the composite monolith obtained through the above is obtained as a bicontinuous structure.

Also, in the monolith intermediate, the average diameter of the opening (mesopore) that is the overlapping portion of the macropore and the macropore is 20 to 100 μm in a dry state. When the average diameter of the openings is less than 20 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes small, and the pressure loss at the time of passing water becomes large, 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 ion exchanger becomes insufficient. As a result, the removal efficiency of ion components Is unfavorable because it decreases. Monolith intermediates preferably have a uniform structure with uniform macropore size and aperture diameter, but are not limited to this, and the uniform structure is dotted with nonuniform macropores larger than the size of the uniform macropore. You may do.

(Production method of composite monolith)
Step II is an organic solvent in which a vinyl monomer, a second cross-linking agent having at least two vinyl groups in one molecule, a vinyl monomer or a second cross-linking agent dissolves, but a polymer formed by polymerization of the vinyl monomer does not dissolve. And a step of preparing a mixture comprising a polymerization initiator. 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 that contains a polymerizable vinyl group in the molecule and has high solubility in an organic solvent. 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 alone or in combination of two or more. The vinyl monomer suitably used in the present invention is an aromatic vinyl monomer such as styrene or vinyl benzyl chloride.

The amount of these vinyl monomers added is 3 to 40 times, preferably 4 to 30 times, by weight with respect to the monolith intermediate coexisting during polymerization. If the amount of vinyl monomer added is less than 3 times that of the porous body, it is preferable because the particles cannot be formed in the skeleton of the produced monolith, and the ion exchange capacity per volume after introduction of the ion exchange groups is reduced. Absent. On the other hand, if the amount of vinyl monomer added exceeds 40 times, the opening diameter becomes small and the pressure loss during fluid permeation increases, which is not preferable.

As the second cross-linking agent used in step II, one having at least two polymerizable vinyl groups in the molecule and having high solubility in an organic solvent is preferably used. Specific examples of the second crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol diacrylate, and the like. These 2nd crosslinking agents can be used individually by 1 type or in combination of 2 or more types. A preferred second crosslinking agent is an aromatic polyvinyl compound such as divinylbenzene, divinylnaphthalene, and divinylbiphenyl because of its high mechanical strength and stability to hydrolysis. The amount of the second crosslinking agent used is preferably 0.3 to 20 mol%, particularly 0.3 to 10 mol%, based on the total amount of the vinyl monomer and the second 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 20 mol%, the monolith becomes more brittle and the flexibility is lost, and the amount of ion exchange groups introduced decreases, which is not preferable.

The organic solvent used in step II is an organic solvent that dissolves the vinyl monomer and the second cross-linking 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. It is. 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, propylene glycol, tetramethylene glycol; chain (poly) ethers such as diethyl ether, butyl cellosolve, polyethylene glycol, polypropylene glycol, polytetramethylene glycol Chain saturated hydrocarbons such as hexane, heptane, octane, isooctane, decane, dodecane, etc .; Ethyl acetate, isopropyl acetate, cellosolve acetate, ethyl propionate, etc. Ethers, and the like. 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 5 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 5% by weight, the polymerization rate is lowered, which is not preferable. 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, tetramethylthiuram disulfide and the like. The amount of 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 second crosslinking agent. .

Step III is a step in which the mixture obtained in Step II is allowed to stand still and in the presence of the monolith intermediate obtained in Step I, to obtain a composite monolith. The monolith intermediate used in Step III plays an extremely important role in creating a monolith having a novel structure of the present invention (A2). As disclosed in JP-A-7-501140, etc., when a vinyl monomer and a second crosslinking agent are allowed to stand in a specific organic solvent in the absence of a monolith intermediate, a particle aggregation type monolithic organic material is obtained. A porous 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 specific skeleton described above is lost. A monolith having a structure is obtained.

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 monolith after polymerization does not receive any pressure from the inner wall of the vessel and enters the reaction vessel without any gap, so that 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 a mixture (solution). The blending ratio of the mixture obtained in Step II and the monolith intermediate is such that, as described above, the amount of vinyl monomer added is 3 to 40 times, preferably 4 to 30 times, by weight with respect to the monolith intermediate. It is suitable to mix. Thereby, it is possible to obtain a monolith having a specific 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 can be 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, or the like is used as an initiator, an inert atmosphere What is necessary is just to heat-polymerize at 20-100 degreeC for 1 to 48 hours in the lower sealed container. By heat polymerization, the vinyl monomer adsorbed and distributed on the skeleton of the monolith intermediate and the crosslinking agent are polymerized in the skeleton to form the specific skeleton structure. After completion of the polymerization, the content is taken out and extracted with a solvent such as acetone for the purpose of removing unreacted vinyl monomer and organic solvent to obtain a monolith having a specific skeleton structure.

When the above-described composite monolith is produced, if the step II or step III is performed under the conditions satisfying at least one of the following conditions (1) to (5), the characteristic structure of the present invention (A2) is obtained. A composite monolith in which particles and the like are formed on the skeleton surface can be produced.

(1) The polymerization temperature in step III is a temperature that is at least 5 ° C. lower than the 10-hour half-life temperature of the polymerization initiator.
(2) The mol% of the second cross-linking agent used in step II is at least twice the mol% of the first cross-linking agent used in step I.
(3) The vinyl monomer used in step II is a vinyl monomer having a structure different from that of the oil-soluble monomer used in step I.
(4) The organic solvent used in step II is a polyether having a molecular weight of 200 or more.
(5) The concentration of the vinyl monomer used in Step II is 30% by weight or less in the mixture of Step II.

(Description of (1) above)
The 10-hour half temperature is a characteristic value of the polymerization initiator, and if the polymerization initiator to be used is determined, the 10-hour half temperature can be known. Moreover, if there exists desired 10-hour half temperature, the polymerization initiator applicable to it can be selected. In step III, the polymerization rate is lowered by lowering the polymerization temperature, and particles and the like can be formed on the surface of the skeleton phase. The reason for this is that the monomer concentration drop inside the skeleton phase of the monolith intermediate becomes gradual, and the monomer distribution rate from the liquid phase part to the monolith intermediate decreases, so the surplus monomer is on the surface of the skeleton layer of the monolith intermediate. It is thought that it was concentrated in the vicinity and polymerized in situ.

The preferred polymerization temperature is a temperature that is at least 10 ° C. lower than the 10-hour half-life temperature of the polymerization initiator used. The lower limit of the polymerization temperature is not particularly limited, but the polymerization rate decreases as the temperature decreases, and the polymerization time becomes unacceptably long. Therefore, the polymerization temperature is 5 to 20 ° C. with respect to the half-temperature of 10 hours. It is preferable to set to a low range.

(Description of (2))
When the mol% of the second cross-linking agent used in Step II is set to be twice or more of the mol% of the first cross-linking agent used in Step I, the composite monolith of the present invention is obtained. The reason for this is that the compatibility between the monolith intermediate and the polymer produced by impregnation polymerization is reduced and phase separation proceeds, so the polymer produced by impregnation polymerization is excluded in the vicinity of the surface of the skeleton phase of the monolith intermediate, It is considered that irregularities such as particles are formed on the surface. In addition, mol% of a crosslinking agent is a crosslinking density mol%, Comprising: The crosslinking agent amount (mol%) with respect to the total amount of a vinyl monomer and a crosslinking agent is said.

The upper limit of the second crosslinker mol% used in step II is not particularly limited, but if the second crosslinker mol% is extremely large, cracks occur in the monolith after polymerization, and the brittleness of the monolith proceeds and flexibility is increased. This is not preferable because it causes a problem that the amount of ion exchange groups to be lost is reduced. The preferred multiple of the second crosslinker mol% is 2 to 10 times. On the other hand, even when the mol% of the first cross-linking agent used in step I is set to be twice or more the mol% of the second cross-linking agent used in step II, the formation of particles on the surface of the skeleton phase does not occur. The composite monolith of the present invention cannot be obtained.

(Explanation of (3))
When the vinyl monomer used in Step II is a vinyl monomer having a structure different from that of the oil-soluble monomer used in Step I, the composite monolith of the present invention (A2) is obtained. For example, if the structures of vinyl monomers are slightly different, such as styrene and vinyl benzyl chloride, a composite monolith having particles or the like formed on the surface of the skeleton phase is generated. In general, two types of homopolymers obtained from two types of monomers that are slightly different in structure are not compatible with each other. Therefore, a monomer having a structure different from that of the monomer used for forming the monolith intermediate used in Step I, that is, a monomer other than the monomer used for forming the monolith intermediate used in Step I is used in Step II to polymerize in Step III. The monomer used in Step II is uniformly distributed and impregnated into the monolith intermediate, but when the polymerization proceeds and the polymer is produced, the produced polymer is not compatible with the monolith intermediate. Separation proceeds, and the produced polymer is considered to be excluded in the vicinity of the surface of the skeleton phase of the monolith intermediate, and irregularities such as particles are formed on the surface of the skeleton phase.

(Explanation of (4))
When the organic solvent used in step II is a polyether having a molecular weight of 200 or more, the composite monolith of the present invention is obtained. Polyethers have a relatively high affinity with monolith intermediates, especially low molecular weight cyclic polyethers are good solvents for polystyrene, and low molecular weight chain polyethers are not good solvents but have considerable affinity. . However, as the molecular weight of the polyether increases, the affinity with the monolith intermediate dramatically decreases and shows little affinity with the monolith intermediate. When such a solvent having poor affinity is used as the organic solvent, diffusion of the monomer into the skeleton of the monolith intermediate is inhibited, and as a result, the monomer is polymerized only near the surface of the skeleton of the monolith intermediate. It is considered that particles and the like are formed on the phase surface and irregularities are formed on the skeleton surface.

The upper limit of the molecular weight of the polyether is not particularly limited as long as it is 200 or more. However, when the molecular weight is too high, the viscosity of the mixture prepared in the step II becomes high, and it is difficult to impregnate the monolith intermediate. Therefore, it is not preferable. The preferred polyether has a molecular weight of 200 to 100,000, particularly preferably 200 to 10,000. The terminal structure of the polyether may be an unmodified hydroxyl group, etherified with an alkyl group such as a methyl group or an ethyl group, or esterified with acetic acid, oleic acid, lauric acid, stearic acid, or the like. It may be made.

(Explanation of (5))
When the concentration of the vinyl monomer used in Step II is 30% by weight or less in the mixture in Step II, the composite monolith of the present invention (A2) is obtained. By reducing the monomer concentration in the step II, the polymerization rate is reduced, and for the same reason as the above (1), particles and the like can be formed on the surface of the skeleton phase, and irregularities can be formed on the surface of the skeleton phase. . The lower limit of the monomer concentration is not particularly limited, but the monomer concentration may be set to 10 to 30% by weight because the polymerization rate decreases and the polymerization time becomes unacceptably long as the monomer concentration decreases. preferable.

The composite monolith obtained in the step III includes an organic porous body composed of a continuous skeleton phase and a continuous pore phase, a large number of particles fixed to the skeleton surface of the organic porous body, or a skeleton surface of the organic porous body. It is a composite structure with a number of protrusions formed on it. The continuous skeleton phase and the continuous pore phase of the organic porous body can be observed by SEM images. The basic structure of the organic porous body is a continuous macropore structure or a co-continuous structure.

The continuous macropore structure in the composite monolith is such that bubble-shaped macropores overlap each other, and the overlapping portion becomes an opening having an average diameter of 20 to 100 μm in a dry state. The bicontinuous structure in the composite monolith has an average thickness. Consists of a three-dimensionally continuous skeleton of 0.8 to 40 μm in a dry state and three-dimensionally continuous pores having an average diameter of 8 to 80 μm by drying between the skeletons.

Step IV is a step of introducing an ion exchange group into the composite monolith obtained in Step III. According to this introduction method, the porous structure of the obtained composite monolith ion exchanger can be strictly controlled.

The method for introducing an ion exchange group into the composite monolith is the same as the method of the invention (A1).

[Common Description of Invention (A1) and Invention (A2)]
As a deionization module used in the electric deionized water production apparatus of the present invention, for example, as shown in FIG. 13, a plate-shaped porous ion exchanger 100 is placed on one side of a frame 103. A deionization module 10A formed by filling the internal space 104 formed by the sealed cation exchange membrane 101 and the anion exchange membrane 102 sealed on the other side, or as shown in FIG. A porous ion exchanger 100a formed into a cation exchange membrane 101 sealed on one side of a frame 103a and an intermediate ion exchange membrane 105 sealed between the frame 103a and the frame 103b. The porous ion exchanger 100b, which is filled in the first internal space 104a and formed into a plate shape, is sealed on the other side of the intermediate ion exchange membrane 105 and the frame body 103b. Deionized module 10B and the like formed by filling the second internal space 104b formed between. The

porous ion exchangers

100, 100a, and 100b are the first monolith ion exchanger, the second monolith ion exchanger, or the third monolith ion exchanger according to the present invention. In the deionization module 10B, the porous ion exchanger formed into a plate shape is filled in either the first internal space 104a or the second internal space 104b, and a granular ion exchange resin is filled in the other interior. It may be filled. That is, the mode of filling the deionization module of the porous ion exchanger of the present invention is not particularly limited as long as the purpose of producing deionized water is achieved, but the ion in the conventional deionization module is not limited. A packing mode in which the exchanger is replaced with the porous ion exchanger of the present invention can be adopted. In addition, the deionization module of the present invention can be prepared by pasting together an ion exchange membrane and a porous ion exchanger using an adhesive or the like without using a frame. Assembling work of the apparatus can be simplified.

The electric deionized water production apparatus of the present invention includes the deionization module described above, and is an apparatus for producing deionized water by electrically removing impurity ions trapped by the porous ion exchanger. If there is, it will not restrict | limit in particular, A flat type, a cylindrical type, and a spiral type electric deionized water manufacturing apparatus are mentioned. The flat plate type electric deionized water production apparatus includes, for example, a desalination chamber in which a porous ion exchanger is filled between a cation exchange membrane and an anion exchange membrane, and the cation exchange membrane and the anion exchange membrane. A device comprising a concentrating chamber provided on both sides of a desalting chamber, an anode and a cathode disposed on both sides thereof, a cation exchange membrane, and an intermediate disposed between the cation exchange membrane and the anion exchange membrane The first small desalting chamber formed by the ion exchange membrane and the second small desalting chamber formed by the intermediate ion exchange membrane and the anion exchange membrane are each filled with a porous ion exchanger. An apparatus comprising a salt chamber, a concentration chamber provided on both sides of the desalting chamber via the cation exchange membrane and the anion exchange membrane, an anode and a cathode arranged on both sides thereof can be used.

Hereinafter, an electric deionized water production apparatus according to an embodiment of the present invention will be described with reference to FIG. In FIG. 15, reference numeral 1 denotes a desalting chamber, and 2 denotes a concentrating chamber, and these desalting chambers 1 are manufactured as module products as described above. The number of deionization modules is appropriately determined according to usage conditions such as processing capability. In FIG. 15, two deionization modules are displayed for the purpose of simplifying the drawing. The deionization module 10A used in the apparatus of FIG. 15 is manufactured by making a porous cation exchanger 100d introduced with a cation exchange group and a porous anion exchanger 100e introduced with an anion exchange group into small blocks. The porous cation exchanger 100d, the porous anion exchanger 100e, the porous cation exchanger 100d, and the porous anion exchanger 100e are stacked from the treated water inflow side, and the anion exchange membrane 102 and the cation exchange membrane are stacked. 101 is configured to be sandwiched between 101. The porous cation exchanger 100d and the porous anion exchanger 100e are the first monolith ion exchanger, the second monolith ion exchanger, or the third monolith ion exchanger according to the present invention. A plurality of deionization modules 10A are arranged side by side. Between each of the

deionization modules

10A and 10A, a spacer (not shown) made of a watertight member such as a rubber packing formed in a frame shape is interposed. The anode 110 and the cathode 109 are arranged on both sides of the alternate arrangement of the desalting chamber 1 and the concentration chamber 2, and

partition films

113 and 114 are provided in the vicinity of the anode 110 and the cathode 109, respectively. A space between the partition film 114 and the cathode 109 is defined as a cathode chamber 112. In FIG. 15, the porous ion exchanger and the anion exchange membrane 102 and the cation exchange membrane 101 located on both sides of the porous ion exchanger are separated from each other. However, in actuality, the porous ion exchanger and the anion exchange membrane are actually separated. 102 and the cation exchange membrane 101 are in close contact with each other. 16 to 18 described later, the monolithic porous ion exchanger forming the desalting chamber and the ion exchange membrane are in close contact with each other.

The electric deionized water production apparatus in FIG. 15 is operated as follows. First, water to be treated flows into the desalting chamber 1, concentrated water flows into the concentration chamber 2, and electrode water flows into the anode chamber 111 and the cathode chamber 112, respectively. As the concentrated water, the same water as the treated water supplied to the desalting chamber 1 is usually used. On the other hand, a voltage is applied between the anode 110 and the cathode 109, and a direct current is passed in a direction perpendicular to the flow direction of the water to be treated and the concentrated water. The treated water that has flowed into the desalting chamber 1 is introduced into the open cell structure when it flows through the open cell structure or the co-continuous structure composed of macropores and mesopores (openings) of the porous ion exchanger. Ions are trapped by the ion exchange groups, and the ions pass through the

ion exchange membranes

101 and 102 and are excluded into the concentration chamber 2.

16 to 18 show an electric deionized water production apparatus according to another embodiment. 16 to 18, the same components are denoted by the same reference numerals, description thereof is omitted, and different points are mainly described. 16 is different from FIG. 15 in that the deionization module stacking form is changed. The deionization module 10A used in the apparatus of FIG. 16 includes a porous cation exchanger 100d and a porous anion exchanger. 100e is a configuration in which the side surfaces of the porous ion exchanger are brought into contact with each other, and both sides opposite to the corresponding contact surface are sandwiched between the anion exchange membrane 102 and the cation exchange membrane 101.

17 differs from FIG. 15 in that two deionization modules are connected in series, and the outflow water of one deionization module is treated water of the other deionization module. That is, the deionization module 10A used in the apparatus of FIG. 17 includes a cation exchange group introduced porous cation exchanger 100d and an anion exchange group introduced porous anion exchanger 100e, respectively, with anion exchange membrane 102 and cation exchange. filled so as to sandwich the membrane 101, in which the respectively decationized module 10A ₁ and the de-anion module 10A _2, the effluent leaving the anion module 10A ₂ water to be treated of decationized module 10A _1.

Any of the deionization modules used in the apparatus of FIGS. 15 to 17 can use the deionization module 10A shown in FIG.

On the other hand, the deionization module 10B shown in FIG. 14 can be used as the deionization module used in the apparatus of FIG. That is, the apparatus of FIG. 18 is divided into two small cation exchange membranes 101, anion exchange membrane 102 on the other side, and two intermediate ion exchange membranes 105 positioned between the cation exchange membrane 101 and the anion exchange membrane 102. A small desalting chamber 1b on the cation exchange membrane 101 side of the desalting chambers 1a and 1b is filled with a laminate 100f of a porous anion exchanger and a porous cation exchanger, and the small desalting chamber 1a on the anion exchange membrane 102 side is filled. The desalination chamber 1 is configured by filling the porous anion exchanger 100e, and the concentration chambers 2 are provided on both sides of the desalination chamber via the cation exchange membrane 101 and the anion exchange membrane 102. The chamber 2 is arranged between the anode 110 and the cathode 109. In this example, the intermediate ion exchange membrane 105 uses an anion exchange membrane.

The electric deionized water production apparatus in FIG. 18 is operated as follows. First, the water to be treated flows into the small desalination chamber 1a, then the effluent from the small desalination chamber 1a flows into another adjacent small desalination chamber 1b, and the concentrated water flows into the concentration chamber 2. In addition, electrode water flows into the anode chamber 111 and the cathode chamber 112, respectively. As the concentrated water, the same water as the treated water supplied to the small desalting chamber 1a is usually used. On the other hand, a voltage is applied between the anode 110 and the cathode 109, and a direct current is passed in a direction perpendicular to the flow direction of the water to be treated and the concentrated water. The water to be treated that flowed into the small desalting chamber 1a was introduced into the open cell structure when it circulated in the open cell structure or the co-continuous structure composed of macropores and mesopores of the porous anion exchanger 100e. Ions are trapped and removed from the ion exchange groups. Furthermore, when the effluent of the small desalting chamber 1a flows through the open cell structure or the co-continuous structure composed of macropores and mesopores of the laminate 100f of the porous anion exchanger and porous cation exchanger, the open cell structure Ions are trapped and removed by the ion exchange groups introduced into the inside. The concentrated water rises in each concentration chamber, receives impurity ions moving through the cation exchange membrane 101 and the anion exchange membrane 102, and is discharged out of the system as concentrated water in which the impurity ions are concentrated.

(Example)
EXAMPLES Next, the present invention will be described more specifically with reference to examples. However, this is merely an example and does not limit the present invention. Hereinafter, Reference Examples 1 to 26, Examples 1 to 4 and Comparative Examples 1 and 2 relate to the invention (A1), and Reference Examples 27 to 40, Examples 5 and 6 and Comparative Examples 3 and 4 are inventions ( This relates to A2).

<Production of first monolithic ion exchanger (Reference Example 1)>
(Step I; production of monolith intermediate)
19.2 g of styrene, 1.0 g of divinylbenzene, 1.0 g of sorbitan monooleate (hereinafter abbreviated as SMO) and 0.26 g of 2,2′-azobis (isobutyronitrile) were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / SMO / 2,2′-azobis (isobutyronitrile) mixture is added to 180 g of pure water 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 openings (mesopores) where the macropores and macropores of the monolith intermediate were measured by mercury porosimetry 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 (step III).

FIG. 1 shows the result of observing the internal structure of a monolith (dry body) containing 1.3 mol% of a cross-linking component composed of a styrene / divinylbenzene copolymer obtained by SEM, as described above. The SEM image in FIG. 1 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. 1, the monolith has a continuous macropore structure, and the skeleton constituting the continuous macropore structure is much thicker than that of the comparative example of FIG. The thickness of the part 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. The results are summarized in Tables 1 and 2. In Table 1, the preparation column shows, in order from the left, the vinyl monomer used in Step II, the crosslinking agent, the monolith intermediate obtained in Step I, and the organic solvent used in Step II.

(Production of monolith cation 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. The weight of the monolith was 27 g. To this, 1500 ml of dichloromethane was added and heated at 35 ° C. for 1 hour, then cooled to 10 ° C. or lower, 145 g of chlorosulfuric acid was gradually added, and the temperature was raised and reacted at 35 ° C. for 24 hours. Thereafter, methanol was added to quench the remaining chlorosulfuric acid, which was then washed with methanol to remove dichloromethane and further washed with pure water to obtain a monolith cation exchanger having a continuous macropore structure.

The swelling rate before and after the reaction of the obtained cation exchanger was 1.7 times, and the ion exchange capacity per volume was 0.67 mg equivalent / ml in a water wet state. The average diameter of the openings of the organic porous ion exchanger in the water wet state was estimated from the value of the organic porous body and the swelling ratio of the cation exchanger in the water wet state, and was 54 μm, and was obtained by the same method as for the monolith. The average thickness of the walls constituting the skeleton was 50 μm, the skeleton area was 28% in the photographic region of the SEM photograph, and the total pore volume was 2.2 ml. Moreover, the ion exchange zone length regarding the sodium ion of this monolith cation exchanger was 22 mm in LV = 20 m / h. The differential pressure coefficient, which is an index of pressure loss when water is permeated, was 0.016 MPa / m · LV. The results are summarized in Table 2.

Next, in order to confirm the distribution state of the sulfonic acid group in the monolith cation exchanger, the distribution state of sulfur atoms was observed by EPMA. The results are shown in FIGS. FIG. 2 shows a distribution state of sulfur atoms on the surface of the cation exchanger, and FIG. 3 shows a distribution state of sulfur atoms in the cross-section (thickness) direction of the cation exchanger. 2 and 3, it can be seen that the sulfonic acid groups are uniformly introduced into the surface of the cation exchanger and inside the skeleton (cross-sectional direction).

<Production of first monolithic ion exchanger (Reference Examples 2 to 11)>
(Manufacture of monoliths)
Table 1 shows the amount of styrene used, the type and amount of crosslinking agent, the type and amount of organic solvent, the porous structure of the monolith intermediate that coexists during styrene and divinylbenzene impregnation polymerization, the crosslinking density and the amount used. A monolith was produced in the same manner as in Reference Example 1 except for the change. The results are shown in Tables 1 and 2. From the SEM images (not shown) of Reference Examples 2 to 11 and Table 2, the average diameter of the openings of the monoliths of Reference Examples 2 to 11 is as large as 22 to 70 μm, and the average thickness of the walls constituting the skeleton is also 25 to It was as thick as 50 μm, and the skeletal area was 26-44% in the SEM image area, which was a thick monolith.

(Production of monolith cation exchanger)
The monolith produced by the above method was reacted with chlorosulfuric acid in the same manner as in Reference Example 1 to produce a monolith cation exchanger having a continuous macropore structure. The results are shown in Table 2. The average diameter of the openings of the monolith cation exchangers of Reference Examples 2 to 11 is 46 to 138 μm, the average thickness of the wall portion constituting the skeleton is as large as 45 to 110 μm, and the skeleton area is 26 to 44% in the SEM image region. The exchange capacity per volume also showed a large value. The ion exchange zone length was shorter than the conventional one, and the differential pressure coefficient was also low. The monolith cation exchanger of Reference Example 8 was also evaluated for mechanical properties.

(Mechanical property evaluation of monolith cation exchanger)
The monolith cation exchanger obtained in Reference Example 8 was cut into a strip of 4 mm × 5 mm × 10 mm in a wet state, and used as a test piece for a tensile strength test. The test piece was attached to a tensile tester, the head speed was set to 0.5 mm / min, and the test was performed at 25 ° C. in water. As a result, the tensile strength and the tensile modulus were 45 kPa and 50 kPa, respectively, which were much larger than those of the conventional monolith cation exchanger. Further, the tensile elongation at break was 25%, which was a value larger than that of the conventional monolith cation exchanger.

<Production of first monolithic ion exchanger (Reference Examples 12 and 13)>
(Manufacture of monoliths)
A monolith having the same composition and structure as Reference Example 4 was produced in the same manner as Reference Example 1 except that the amount of styrene used, the amount of crosslinking agent used, and the amount of organic solvent used were changed to the amounts shown in Table 1. . Reference Example 13 was carried out in the same manner as Reference Example 12 except that a reaction vessel having an inner diameter of 110 mm was used instead of the reaction vessel having an inner diameter of 75 mm. The results are shown in Tables 1 and 2.

(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.

Ion exchange capacity per volume of the anion exchangers of Reference Example 12 and Reference Example 13, average diameter of openings of organic porous ion exchangers in a wet state of water, and walls constituting the skeleton obtained by the same method as that of monolith Table 2 summarizes the average thickness, skeleton area (ratio in the photographic region of the SEM photograph), total pore volume, ion exchange zone length, differential pressure coefficient, and the like.

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

<Production of Second Monolith Ion Exchanger (Reference Example 14)>
(Step I; production of monolith intermediate)
5.4 g of styrene, 0.17 g of divinylbenzene, 1.4 g of sorbitan monooleate (hereinafter abbreviated as SMO) and 0.26 g of 2,2′-azobis (isobutyronitrile) were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / SMO / 2,2′-azobis (isobutyronitrile) mixture was added to 180 g of pure water, and a vacuum stirring defoaming mixer (manufactured by EM Co.) as a planetary stirring device. Was stirred under reduced pressure in a temperature range of 5 to 20 ° C. to obtain a water-in-oil emulsion. This emulsion was quickly transferred to a reaction vessel and allowed to polymerize at 60 ° C. for 24 hours in a static state after sealing. After completion of the polymerization, the content was taken out, extracted with methanol, and then dried under reduced pressure to produce a monolith intermediate having a continuous macropore structure. When the internal structure of the monolith intermediate (dry body) obtained in this way was observed with an SEM image (FIG. 7), the wall portion separating two adjacent macropores was very thin and rod-shaped, but the open cell structure The average diameter of the openings (mesopores) where the macropores overlap with each other as measured by the mercury intrusion method was 70 μm, and the total pore volume was 21.0 ml / g.

(Manufacture of monocontinuous monolith)
Subsequently, 76.0 g of styrene, 4.0 g of divinylbenzene, 120 g of 1-decanol, and 0.8 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and dissolved uniformly (step II). Next, the monolith intermediate was cut into a disk shape having a diameter of 70 mm and a thickness of about 40 mm to fractionate 4.1 g. The separated monolith intermediate is placed in a reaction vessel having an inner diameter of 75 mm, immersed in the styrene / divinylbenzene / 1-decanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture, and removed in a vacuum chamber. After bubbling, the reaction vessel was sealed and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the monolithic contents having a thickness of about 60 mm were taken out, subjected to Soxhlet extraction with acetone, and then dried under reduced pressure at 85 ° C. overnight (step III).

When the internal structure of the monolith (dry body) containing 3.2 mol% of the crosslinking component composed of the styrene / divinylbenzene copolymer obtained in this way was observed by SEM, the monolith had a skeleton and pores, respectively. It was a three-dimensional continuous structure with both phases intertwined. Moreover, the thickness of the skeleton measured from the SEM image was 10 μm. Further, the size of the three-dimensionally continuous pores of the monolith measured by mercury porosimetry was 17 μm, and the total pore volume was 2.9 ml / g. The results are summarized in Tables 3 and 4. In Table 4, the thickness of the skeleton was represented by the diameter of the skeleton.

(Production of co-continuous monolithic cation exchanger)
The monolith produced by the above method was cut into a disk shape having a diameter of 75 mm and a thickness of about 15 mm. The weight of the monolith was 18 g. To this was added 1500 ml of dichloromethane, heated at 35 ° C. for 1 hour, cooled to 10 ° C. or lower, gradually added 99 g of chlorosulfuric acid, heated up and reacted at 35 ° C. for 24 hours. Thereafter, methanol was added to quench the remaining chlorosulfuric acid, which was then washed with methanol to remove dichloromethane and further washed with pure water to obtain a monolith cation exchanger having a co-continuous structure.

A part of the obtained cation exchanger was cut out and dried, and then its internal structure was observed by SEM. As a result, it was confirmed that the monolith cation body maintained a co-continuous structure. The SEM image is shown in FIG. Moreover, the swelling ratio before and after the reaction of the cation exchanger was 1.4 times, and the ion exchange capacity per volume was 0.74 mg equivalent / ml in a water-wet state. The size of the continuous pores of the monolith in the water wet state was estimated from the value of the monolith and the swelling ratio of the cation exchanger in the water wet state to be 24 μm, the skeleton diameter was 14 μm, and the total pore volume was 2. It was 9 ml / g.

Further, the differential pressure coefficient, which is an index of pressure loss when water is permeated, was 0.052 MPa / m · LV. Furthermore, when the ion exchange zone length for sodium ions of the monolith cation exchanger was measured, the ion exchange zone length at LV = 20 m / h was 16 mm. Amberlite IR120B (a commercially available strong acid cation exchange resin) It was not only overwhelmingly shorter than the value (320 mm) manufactured by Rohm and Haas, but also shorter than the value of the monolithic porous cation exchanger having a conventional open cell structure. The results are summarized in Table 4.

Next, in order to confirm the distribution state of the sulfonic acid group in the monolith cation exchanger, the distribution state of sulfur atoms was observed by EPMA. The results are shown in FIGS. 9 and 10, the left and right photographs correspond to each other. FIG. 9 shows a distribution state of sulfur atoms on the surface of the cation exchanger, and FIG. 10 shows a distribution state of sulfur atoms in the cross-section (thickness) direction of the cation exchanger. In the photograph on the left side of FIG. 9, a part extending in a horizontal direction is a skeleton part, and in the photograph on the left side of FIG. 9 and 10, it can be seen that the sulfonic acid groups are uniformly introduced into the surface of the cation exchanger and inside the skeleton (cross-sectional direction).

<Production of Second Monolith Ion Exchanger (Reference Examples 15 to 17)>
(Manufacture of monolith with co-continuous structure)
Except for changing the amount of styrene used, the amount of crosslinking agent used, the amount of organic solvent used, the porous structure of the monolith intermediate coexisting during styrene and divinylbenzene impregnation polymerization, the crosslinking density and the amount used as shown in Table 3. A monolith having a co-continuous structure was produced in the same manner as in Reference Example 14. Reference Example 17 was carried out in the same manner as Reference Example 14 except that a reaction vessel having an inner diameter of 110 mm was used instead of the reaction vessel having an inner diameter of 75 mm. The results are shown in Tables 3 and 4.

(Manufacture of monolith with co-continuous structure)
The amount of styrene used, the amount of crosslinking agent used, the type and amount of organic solvent used, the porous structure of the monolith intermediate coexisting during styrene and divinylbenzene impregnation polymerization, the crosslinking density and the amount used were changed to the amounts shown in Table 4. Except for the above, a monolith having a co-continuous structure was produced in the same manner as in Reference Example 14. The results are shown in Tables 3 and 4.

(Production of monolith cation exchanger having a co-continuous structure)
The monolith produced by the above method was reacted with chlorosulfuric acid in the same manner as in Reference Example 14 to produce a monolith cation exchanger having a co-continuous structure. The results are shown in Table 4. Further, the internal structure of the obtained monolithic cation exchanger having a co-continuous structure is as follows. The monolithic cation exchangers obtained in Reference Examples 15 to 17 from the SEM images (not shown) and Table 4 have conventional ion exchanger lengths. It was shorter and the differential pressure coefficient also showed a low value. Also, the exchange capacity per unit volume was larger than the conventional one. The monolith cation exchanger of Reference Example 15 was also evaluated for mechanical properties.

(Mechanical property evaluation of monolith cation exchanger)
The monolith cation exchanger obtained in Reference Example 15 was cut into a strip of 4 mm × 5 mm × 10 mm in a wet state of water and used as a test piece for a tensile strength test. The test piece was attached to a tensile tester, the head speed was set to 0.5 mm / min, and the test was performed at 25 ° C. in water. As a result, the tensile strength and the tensile modulus were 23 kPa and 15 kPa, respectively, which were significantly larger than the conventional monolith cation exchanger. Further, the tensile elongation at break was 50%, which was a value larger than that of the conventional monolith cation exchanger.

<Production of Second Monolith Ion Exchanger (Reference Examples 18 and 19)>
(Manufacture of monolith with co-continuous structure)
Except that the amount of styrene used, the amount of crosslinking agent used, the amount of organic solvent used, the porous structure of the monolith intermediate coexisting during styrene and divinylbenzene impregnation polymerization, the crosslinking density and the amount used were changed to the amounts shown in Table 4. A monolith having a co-continuous structure was produced in the same manner as in Reference Example 14. Reference Example 19 was carried out in the same manner as Reference Example 18 except that a reaction vessel having an inner diameter of 110 mm was used instead of the reaction vessel having an inner diameter of 75 mm. The results are shown in Tables 3 and 4.

(Production of monolith anion exchanger having a co-open cell structure)
The monolith produced by the above method was cut into a disk shape having a diameter of 70 mm and a thickness of about 15 mm. To this, 1400 ml of dimethoxymethane and 20 ml of tin tetrachloride were added, and 560 ml of chlorosulfuric acid was added dropwise under ice cooling. After completion of the dropping, the temperature was raised and the reaction was carried out at 35 ° C. for 5 hours to introduce a chloromethyl group. After completion of the reaction, the mother liquor was extracted with a siphon, washed with a mixed solvent of THF / water = 2/1, and further washed with THF. To this chloromethylated monolithic organic porous material, 1000 ml of THF and 600 ml of a 30% trimethylamine aqueous solution were added and reacted at 60 ° C. for 6 hours. After completion of the reaction, the product was washed with a methanol / water mixed solvent, then washed with pure water and isolated.

The ion exchange capacity per volume of the anion exchangers of Reference Example 18 and Reference Example 19, the average diameter of the continuous pores of the organic porous ion exchanger in a water-wet state, and the thickness of the skeleton obtained by the same method as that of the monolith Table 4 summarizes the total pore volume, ion exchange zone length, differential pressure coefficient, and the like. Moreover, the internal structure of the obtained monolith anion exchanger having a co-continuous structure was observed by an SEM image (not shown).

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 chlorine atoms was observed by EPMA. As a result, it was confirmed that the chlorine atoms were uniformly distributed not only on the surface of the anion exchanger but also inside, and the quaternary ammonium groups were uniformly introduced into the anion exchanger.

Reference Example 20
(Manufacture of monolithic organic porous material having a continuous macropore structure (known product))
A monolithic organic porous material having a continuous macropore structure was produced according to the production method described in JP-A-2002-306976. That is, 19.2 g of styrene, 1.0 g of divinylbenzene, 1.0 g of SMO and 0.26 g of 2,2′-azobis (isobutyronitrile) were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / SMO / 2,2′-azobis (isobutyronitrile) mixture is added to 180 g of pure water, and a vacuum stirring defoaming mixer (manufactured by EM Corp.) which is a planetary stirring device. Was 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 monolithic organic porous body having a continuous macropore structure.

The SEM representing the internal structure of the organic porous material containing 3.3 mol% of the cross-linking component made of the styrene / divinylbenzene copolymer thus obtained was the same as that shown in FIG. As is clear from FIG. 12, the organic porous body has a continuous macropore structure, but the thickness of the wall portion constituting the skeleton of the continuous macropore structure is thinner than that of the example, and from the SEM image The measured wall thickness average thickness was 5 μm, and the skeleton area was 10% in the SEM image area. Moreover, the average diameter of the opening of the organic porous material measured by mercury porosimetry was 29 μm, and the total pore volume was 8.6 ml / g. The results are summarized in Table 5. In Tables 1, 2 and 5, the mesopore diameter means the average diameter of the openings. In Tables 1 to 5, the values of the thickness, the skeleton diameter, and the pores are averages.

(Production of monolithic organic porous cation exchanger having a continuous macropore structure (known product))
The organic porous body 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. The weight of the organic porous material was 6 g. To this was added 1000 ml of dichloromethane, and the mixture was heated at 35 ° C. for 1 hour, then cooled to 10 ° C. or less, 30 g of chlorosulfuric acid was gradually added, and the temperature was raised and reacted at 35 ° C. for 24 hours. Thereafter, methanol was added to quench the remaining chlorosulfuric acid, which was washed with methanol to remove dichloromethane and further washed with pure water to obtain a monolithic porous cation exchanger having a continuous macropore structure. The swelling ratio before and after the reaction of the obtained cation exchanger was 1.6 times, and the ion exchange capacity per volume was 0.22 mg equivalent / ml in a wet state of water, which was a small value compared to Reference Examples 1 to 16. Indicated. The average diameter of the mesopores of the organic porous ion exchanger in the water wet state was 46 μm as estimated from the value of the organic porous body and the swelling ratio of the cation exchanger in the water wet state. The average thickness was 8 μm, the skeleton part area was 10% in the SEM image area, and the total pore volume was 8.6 ml / g. The differential pressure coefficient, which is an index of pressure loss when water is permeated, was 0.013 MPa / m · LV. The results are summarized in Table 5. The monolith cation exchanger obtained in Reference Example 20 was also evaluated for mechanical properties.

(Mechanical property evaluation of conventional monolith cation exchanger)
The monolith cation exchanger obtained in Reference Example 20 was subjected to a tensile test by the same method as the evaluation method of Reference Example 8. As a result, the tensile strength and the tensile modulus were 28 kPa and 12 kPa, respectively, which were lower than the monolith cation exchanger of Reference Example 8. The tensile elongation at break was 17%, which was smaller than that of the monolith cation exchanger of the present invention.

Reference Examples 21-23
(Manufacture of monolithic organic porous body having continuous macropore structure)
A monolithic organic porous material having a continuous macropore structure according to the conventional technique in the same manner as in Reference Example 20, except that the amount of styrene used, the amount of divinylbenzene, and the amount of SMO used are changed to the amounts shown in Table 5. The body was manufactured. The results are shown in Table 5. Further, the internal structure of the monolith of Reference Example 23 was observed with an SEM (not shown). In addition, Reference Example 23 is a condition for minimizing the total pore volume, and an opening cannot be formed by adding less water to the oil phase part. In all of the monoliths of Reference Examples 21 to 23, the opening diameter is small as 9 to 18 μm, the average thickness of the wall portion constituting the skeleton is as thin as 15 μm, and the skeleton area is as small as 22% at the maximum in the SEM image region. It was.

(Production of monolithic organic porous cation exchanger having a continuous macropore structure)
The organic porous material produced by the above method was reacted with chlorosulfuric acid in the same manner as in Reference Example 20 to produce a monolithic porous cation exchanger having a continuous macropore structure. The results are shown in Table 5. If the opening diameter is increased, the thickness of the wall portion is reduced or the skeleton is reduced. On the other hand, when the wall portion was made thicker or the skeleton was made thicker, the diameter of the opening tended to decrease. As a result, when the differential pressure coefficient was kept low, the ion exchange capacity per volume decreased, and when the ion exchange capacity was increased, the differential pressure coefficient increased.

The relationship between the differential pressure coefficient and the ion exchange capacity per volume for the monolith ion exchangers produced in Reference Examples 1 to 11 and Reference Examples 20 to 23 is shown in FIG. As is apparent from FIG. 4, it is understood that the known reference examples 20 to 23 have a poor balance between the differential pressure coefficient and the ion exchange capacity with respect to the reference examples 1 to 11. On the other hand, it can be seen that Reference Examples 1 to 11 have a large ion exchange capacity per volume and a low differential pressure coefficient. *

Reference Example 24
(Production of porous cation exchanger (known))
27.7 g of styrene, 6.9 g of divinylbenzene, 0.14 g of azobisisobutyronitrile and 3.8 g of sorbitan monooleate were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / azobisisobutyronitrile / sorbitan monooleate mixture is added to 450 ml of pure water, stirred at 20,000 rpm for 2 minutes using a homogenizer, and a water-in-oil emulsion. Got. After emulsification, the water-in-oil emulsion was transferred to a stainless steel autoclave, sufficiently substituted with nitrogen, sealed, and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the content was taken out, extracted with Soxhlet for 18 hours with isopropanol, unreacted monomer and sorbitan monooleate were removed, and dried under reduced pressure at 40 ° C. overnight. 5 g of a porous material containing 14 mol% of a crosslinking component composed of a styrene / divinylbenzene copolymer obtained in this manner was collected, 500 g of tetrachloroethane was added, and the mixture was heated at 60 ° C. for 30 minutes, and then to room temperature. After cooling, 25 g of chlorosulfuric acid was gradually added and reacted at room temperature for 24 hours. Thereafter, acetic acid was added, the reaction product was poured into a large amount of water, washed with water and dried to obtain a porous cation exchanger. The ion exchange capacity of this porous material is 4.0 mg equivalent / g in terms of dry porous material, and sulfonic acid groups are uniformly introduced into the porous material by mapping of sulfur atoms using EPMA. It was confirmed. Further, as a result of SEM observation (not shown), the internal structure of the porous body has an open cell structure, and most of the macropores having an average diameter of 30 μm are overlapped, and the mesopores formed by the overlap of the macropores and the macropores. The average diameter was 5 μm and the total pore volume was 10.1 ml / g. The porous body was cut out to a thickness of 10 mm, and the water permeation rate was measured. As a result, it was 14,000 l / min · m ² · MPa.

Reference Example 25
(Production of porous anion exchanger (known))
A water-in-oil emulsion similar to that of Reference Example 24 except that 18.0 g of p-chloromethylstyrene was used instead of 27.7 g of styrene, and 17.3 g of divinylbenzene and 0.26 g of azobisisobutyronitrile were used. Polymerization was performed to produce a porous body containing 50 mol% of a cross-linking component composed of a p-chloromethylstyrene / divinylbenzene copolymer. After separating 5 g of this porous material, adding 500 g of dioxane and heating at 80 ° C. for 30 minutes, the mixture was cooled to room temperature, 65 g of a trimethylamine (30%) aqueous solution was gradually added, and reacted at 50 ° C. for 3 hours. It was left overnight at room temperature. After completion of the reaction, the porous body was taken out, washed with acetone, washed with water, and dried to obtain a porous anion exchanger. The ion exchange capacity of this porous material was 2.5 mg equivalent / g in terms of dry porous material, and it was confirmed by SIMS that trimethylammonium groups were uniformly introduced into the porous material. Moreover, as a result of SEM observation, the internal structure of this porous body has an open cell structure, most of the macropores having an average diameter of 30 μm overlap, and the average diameter of the mesopores formed by the overlap of the macropores and the macropores. The value was 4 μm and the total pore volume was 9.9 ml / g. The porous body was cut out to a thickness of 10 mm, and the water permeation rate was measured. As a result, it was 12,000 l / min · m ² · MPa.

Reference Example 26
Monolith production was attempted in the same manner as in Reference Example 1, except that the type of organic solvent used in Step II was changed to dioxane, which is a good solvent for polystyrene. However, the isolated product was transparent, suggesting collapse / disappearance of the porous structure. SEM observation was performed for confirmation, but only a dense structure was observed, and the continuous macropore structure disappeared.

(Production of deionization module A)
The porous cation exchanger and the porous anion exchanger obtained in Reference Example 8 and Reference Example 13 were cut into a size of 125 mm in length, 100 mm in width, and 8 mm in width to form four small blocks. That is, the porous cation exchanger 100d and the porous anion exchanger 100e are manufactured in small blocks, respectively, and the porous cation exchanger 100d, the porous anion exchanger 100e, and the porous cation exchange are formed from the inflow side of the water to be treated. 15d and porous anion exchanger 100e are stacked so as to be sandwiched between anion exchange membrane 102 and cation exchange membrane 101 to obtain a deionization module as used in the apparatus of FIG. It was.

(Preparation of deionization module B)
Instead of the porous cation exchanger of Reference Example 8, the porous anion exchanger of Reference Example 19 was used instead of the porous cation exchanger of Reference Example 17 and the porous anion exchanger of Reference Example 13. A deionization module B was produced by the same method as in Example 1.

(Production and operation of electric deionized water production apparatus A)
An electric deionized water production apparatus A was produced using the obtained deionization module A as a demineralization chamber. The electric deionized water production apparatus was an apparatus composed of one desalting chamber, one anode chamber, and one cathode chamber. A concentrating chamber was formed by inserting spacers between the desalting chamber and the anode chamber and between the desalting chamber and the cathode chamber, respectively. The electric deionized water production apparatus was operated by supplying water having a conductivity of 3.6 μS / cm obtained by treating city water with a reverse osmosis membrane as treated water at 16 L / h. Treated water having a specific resistance of 10.0 MΩcm was obtained at an operating current of 0.16 A of the electrical deionized water production apparatus. The operating voltage at this time was 14V. Moreover, the water flow differential pressure to the desalting chamber at this time was 36 kPa.

(Production and operation of electric deionized water production apparatus B)
An electric deionized water production apparatus B was produced and operated in the same manner as in Example 3 except that the deionization module B was used instead of the deionization module A. As a result, treated water having a specific resistance of 11.0 MΩcm was obtained at an operating current of 0.16 A of the electrical deionized water production apparatus. The operating voltage at this time was 13V. Moreover, the water flow differential pressure to the desalting chamber at this time was 30 kPa.

Comparative Example 1
(Production of deionization module C)
The porous cation exchanger of Reference Example 24 was used instead of the porous cation exchanger of Reference Example 8, and the porous anion exchanger of Reference Example 25 was replaced with the porous anion exchanger of Reference Example 13. A deionization module C was produced in the same manner as in Example 1 except that it was used.
Comparative Example 2

(Production and operation of electric deionized water production apparatus C)
An electric deionized water production apparatus C was manufactured and operated in the same manner as in Comparative Example 1 except that the deionization module C was used instead of the deionization module A. As a result, treated water having a specific resistance of 5.0 MΩcm was obtained at an operating current of 0.16 A of the electrical deionized water production apparatus. The operating voltage at this time was 20V. Moreover, the water flow differential pressure to the desalting chamber at this time was 510 kPa.

The monolith ion exchanger used in Examples 3 and 4 has a small differential pressure coefficient compared with the monolith ion exchanger used in Comparative Example 2, and also reduces the operating voltage of the electric deionized water production apparatus and consumes it. It was confirmed that power can be saved and good treated water can be obtained.
Table 1, Table 2, Table 3, Table 4, and Table 5 are shown sequentially in the following order.

<Production of Third Monolith Ion Exchanger (Reference Example 27)>
(Step I; production of monolith intermediate)
9.28 g of styrene, 0.19 g of divinylbenzene, 0.50 g of sorbitan monooleate (hereinafter abbreviated as SMO) and 0.26 g of 2,2′-azobis (isobutyronitrile) were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / SMO / 2,2′-azobis (isobutyronitrile) mixture is added to 180 g of pure water, and a vacuum stirring defoaming mixer (manufactured by EM Corp.) which is a planetary stirring device. Was 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 openings (mesopores) where the macropores and macropores of the monolith intermediate were measured by mercury porosimetry was 40 μm, and the total pore volume was 15.8 ml / g.

(Manufacture of composite monolith)
Next, 36.0 g of styrene, 4.0 g of divinylbenzene, 60 g of 1-decanol, and 0.4 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and dissolved uniformly (step II). The 10-hour half-life temperature of 2,2′-azobis (2,4-dimethylvaleronitrile) used as the polymerization initiator was 51 ° C. The amount of divinylbenzene used is 6.6 mol% with respect to the total amount of styrene and divinylbenzene used in Step II, while the crosslink density of the monolith intermediate is 1.3 mol%, and the crosslink density ratio is 5.1 times. Met. 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 3.2 g was collected. The separated monolith intermediate is put in a reaction vessel having an inner diameter of 73 mm, and the styrene / divinylbenzene / 1-
After immersing in a decanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture and degassing in a vacuum chamber, the reaction vessel was sealed and polymerized 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 (step III).

The results of observing the internal structure of the composite monolith (dried body) made of the styrene / divinylbenzene copolymer thus obtained by SEM are shown in FIG. 19 to FIG. The SEM images in FIG. 19 to FIG. 21 have different magnifications, and are images at arbitrary positions on the cut surface obtained by cutting the monolith at arbitrary positions. As is apparent from FIGS. 19 to 21, the composite monolith has a continuous macropore structure, and the surface of the skeleton phase constituting the continuous macropore structure is coated with particles having an average particle diameter of 4 μm, so that all particles The particle coverage of the skeleton surface by the body and the like was 80%. In addition, the ratio of the particles having a particle diameter of 3 to 5 μm to the entire particles was 90%.

Further, the average diameter of the opening of the composite monolith measured by mercury porosimetry was 16 μm, and the total pore volume was 2.3 ml / g. The results are summarized in Tables 6 and 7. In Table 6, the preparation column shows the vinyl monomer used in Step II, the crosslinking agent, the organic solvent, and the monolith intermediate obtained in Step I in order from the left. Further, the particle bodies and the like are shown as particles.

(Production of complex monolith cation exchanger)
The composite 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. The weight of the monolith was 19.6 g. To this, 1500 ml of dichloromethane was added and heated at 35 ° C. for 1 hour, then cooled to 10 ° C. or less, 98.9 g of chlorosulfuric acid was gradually added, and the temperature was raised and reacted at 35 ° C. for 24 hours. Thereafter, methanol was added to quench the remaining chlorosulfuric acid, which was then washed with methanol to remove dichloromethane and further washed with pure water to obtain a composite monolith cation exchanger.

The swelling rate before and after the reaction of the obtained cation exchanger was 1.3 times, and the ion exchange capacity per volume was 1.11 mg equivalent / ml in a wet state. The average diameter of the openings of the organic porous ion exchanger in the water wet state was 21 μm as estimated from the value of the organic porous body and the swelling ratio of the cation exchanger in the water wet state. The average particle size of the particles was 5 μm. The particle coverage of the skeletal surface with all particles was 80%, and the total pore volume was 2.3 ml / g. Further, the ratio of the particle bodies having a particle diameter of 4 to 7 μm to the entire particle bodies was 90%. The differential pressure coefficient, which is an index of pressure loss when water is permeated, is 0.057 MPa / m · LV, which is a lower pressure loss than that required for practical use. It was. Further, the length of the ion exchange zone was 9 mm, showing a remarkably short value. The results are summarized in Table 7.

Next, in order to confirm the distribution state of the sulfonic acid group in the composite monolith cation exchanger, the distribution state of sulfur atoms was observed by EPMA. The results are shown in FIGS. 22 and 23, the left and right photographs correspond to each other. FIG. 22 shows a distribution state of sulfur atoms on the surface of the cation exchanger, and FIG. 23 shows a distribution state of sulfur atoms in the cross-section (thickness) direction of the cation exchanger. 22 and 23, it can be seen that the sulfonic acid groups are uniformly introduced into the surface of the cation exchanger and inside the skeleton (cross-sectional direction).

<Production of third monolith ion exchanger (Reference Examples 28 to 31)>
(Manufacture of composite monolith)
Table 6 shows the amount of vinyl monomer used, the amount of crosslinking agent used, the type and amount of organic solvent used, the porous structure of the monolith intermediate coexisting during polymerization in step III, the crosslinking density and amount used, and the polymerization temperature. A monolith was produced in the same manner as in Reference Example 27, except for the change. The results are shown in Tables 6 and 7. Further, the results of observation of the internal structure of the composite monolith (dried body) by SEM are shown in FIGS. 24 to 26 are of Reference Example 28, FIGS. 27 and 28 are of Reference Example 29, FIG. 29 is of Reference Example 30, and FIGS. 30 and 31 are of Reference Example 31. For Reference Example 28, the crosslinking density ratio (2.5 times), for Reference Example 29, the type of organic solvent (PEG; molecular weight 400), for Reference Example 30, the vinyl monomer concentration (28.0%), Reference Example About 31, it manufactured on the conditions which satisfy | fill the manufacturing conditions of this invention about polymerization temperature (40 degreeC; 11 degreeC lower than the 10-hour half-life temperature of a polymerization initiator). What adhered to the skeleton surface of the composite monoliths of Reference Examples 29 to 31 from FIGS. 24 to 31 were projections rather than particles. The “particle average diameter” of the protrusion is the average diameter of the protrusions (maximum diameter). From FIG. 24 to FIG. 31 and Table 7, the average diameter of the particles adhering to the surface of the monolith skeleton in Reference Examples 28 to 32 is 3 to 8 μm, and the particle coverage of the skeleton surface by all particles is 50 to 95%. there were. In addition, the ratio of the particles of Reference Example 28 having a particle size of 3 to 6 μm to the entire particles is 80%, and the ratio of the protrusions of Reference Example 29 having a particle size of 3 to 10 μm to the total particles is 80%. In Reference Example 30, the proportion of particles having a particle diameter of 3 to 5 μm accounted for 90% of the total particles, and in Reference Example 31, the proportion of particles having a particle diameter of 3 to 7 μm accounted for 90%. .

(Production of complex monolith cation exchanger)
The composite monolith produced by the above method was reacted with chlorosulfuric acid in the same manner as in Reference Example 27 to produce a composite monolith cation exchanger. The results are shown in Table 7. The average diameter of the continuous pores of the composite monolith cation exchanger in Reference Examples 28 to 31 is 21 to 52 μm, the average diameter of the particles attached to the skeleton surface is 5 to 13 μm, and the skeleton surface due to all the particles etc. The particle coverage was as high as 50 to 95%, the differential pressure coefficient was as small as 0.010 to 0.057 MPa / m · LV, and the ion exchange zone length was as extremely small as 8 to 12 mm. Further, the proportion of the particles having a particle size of 5 to 10 μm in the total particles was 90%.

<Production of third monolith ion exchanger (Reference Example 32)>
(Manufacture of composite monolith)
Table 6 shows the types and amounts of vinyl monomers used, the amounts of crosslinking agents used, the types and amounts of organic solvents used, the porous structure of monolith intermediates that coexist during polymerization in step III, the crosslinking density, and the amounts used. A monolith was produced in the same manner as in Reference Example 27, except for the change. The results are shown in Tables 6 and 7. In addition, the results of observation of the internal structure of the composite monolith (dried body) by SEM are shown in FIGS. What adhered to the skeleton surface of the composite monolith of Reference Example 32 was a protrusion. In the monolith of Reference Example 32, the average diameter of the maximum diameter of the protrusions formed on the surface was 10 μm, and the particle coverage of the skeleton surface by all the particulates and the like was 100%. Further, the ratio of the particle bodies having a particle size of 6 to 12 μm to the entire particle bodies was 80%.

(Production of complex monolith anion exchanger)
The composite 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. The weight of the composite monolith was 17.9 g. To this was added 1500 ml of tetrahydrofuran, heated at 40 ° C. for 1 hour, cooled to 10 ° C. or lower, gradually added 114.5 g of a 30% trimethylamine aqueous solution, heated to react at 40 ° C. for 24 hours. After completion of the reaction, the resultant was washed with methanol to remove tetrahydrofuran, and further washed with pure water to obtain a monolith anion exchanger.

The swelling rate before and after the reaction of the obtained composite anion exchanger was 2.0 times, and the ion exchange capacity per volume was 0.32 mg equivalent / ml in a water-wet state. The average diameter of the continuous pores of the organic porous ion exchanger in the water wet state was 58 μm as estimated from the value of the monolith and the swelling ratio of the monolith anion exchanger in the water wet state. The average diameter of the body was 20 μm, the particle coverage of the skeletal surface with all particles was 100%, and the total pore volume was 2.1 ml / g. The ion exchange zone length was as short as 16 mm. The differential pressure coefficient, which is an index of pressure loss when water is permeated, is 0.041 MPa / m · LV, which is a lower pressure loss than that required for practical use. It was. In addition, the proportion of the particles having a particle size of 12 to 24 μm in the entire particles was 80%. The results are summarized in Table 7.

<Production of third monolith ion exchanger (Reference Example 33)>
(Manufacture of monolith intermediates)
In the same manner as in Reference Example 27, a monolith intermediate was obtained.

(Manufacture of composite monolith)
38.0 g of styrene, 2.0 g of divinylbenzene, 60 g of 1-decanol, and 0.4 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and dissolved uniformly (step II). The 10-hour half-life temperature of 2,2′-azobis (2,4-dimethylvaleronitrile) used as the polymerization initiator was 51 ° C. The amount of divinylbenzene used is 3.3 mol% with respect to the total amount of styrene and divinylbenzene used in Step II, with a crosslink density ratio of 2.5 times the crosslink density of the monolith intermediate of 1.3 mol%. Met. Next, the monolith intermediate was cut into a disk shape having a diameter of 70 mm and a thickness of about 30 mm to obtain 3.3 g. The separated monolith intermediate is put in a reaction vessel having an inner diameter of 73 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 (step III).

The internal structure of the monolith (dry body) containing 3.3 mol% of the crosslinking component composed of the styrene / divinylbenzene copolymer thus obtained was observed by SEM. The monolith has a continuous macropore structure, and the surface of the skeleton phase constituting the continuous macropore structure is coated with particles having an average particle diameter of 5 μm, and the particle coverage of the skeleton surface by all particles is 50%. Met. Further, the ratio of the particle bodies having a particle diameter of 3 to 7 μm to the entire particle bodies was 90%. Moreover, the average diameter of the opening of the monolith measured by mercury porosimetry was 35 μm, and the total pore volume was 3.8 ml / g.

(Production of complex monolith anion exchanger)
The monolith produced by the above method was cut into a disk shape having a diameter of 70 mm and a thickness of about 15 mm. To this, 1400 ml of dimethoxymethane and 20 ml of tin tetrachloride were added, and 560 ml of chlorosulfuric acid was added dropwise under ice cooling. After completion of the dropping, the temperature was raised and the reaction was carried out at 35 ° C. for 5 hours to introduce a chloromethyl group. After completion of the reaction, the mother liquor was extracted with a siphon, washed with a mixed solvent of THF / water = 2/1, and further washed with THF. To this chloromethylated monolith, 1000 ml of THF and 600 ml of a 30% trimethylamine aqueous solution were added and reacted at 60 ° C. for 6 hours. After completion of the reaction, the product was washed with a methanol / water mixed solvent, then washed with pure water and isolated.

The swelling ratio of the obtained monolith anion exchanger before and after the reaction was 1.5 times, and the anion exchange capacity per volume was 0.72 mg equivalent / ml in a wet state with water. The average diameter of the openings of the monolith anion exchanger in the water wet state was estimated to be 53 μm from the value of the monolith and the swelling ratio of the monolith anion exchanger in the water wet state, and the average particle diameter of the coated particles determined by the same method The diameter was 8 μm. The particle coverage of the skeleton surface by all particles on the skeleton surface was 50%, and the total pore volume was 3.8 ml / g. Further, the ratio of the particle bodies having a particle diameter of 4 to 8 μm to the entire particle bodies was 90%.

The differential pressure coefficient, which is an index of pressure loss when water is permeated, is 0.017 MPa / m · LV, which is a low pressure loss that does not cause any practical problems. Furthermore, when the ion exchange zone length regarding the fluoride ion of the monolith anion exchanger was measured, the ion exchange zone length at LV = 20 m / h was 14 mm, and amberlite which is a commercially available strong basic anion exchange resin. It was overwhelmingly shorter than the value (165 mm) of IRA402BL (made by Rohm and Haas).

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

Reference Example 34
(Manufacture of monoliths)
Except that the amount of vinyl monomer used, the amount of cross-linking agent used, the type and amount of organic solvent used, and the amount of monolith intermediate used during polymerization in Step III were changed to the amounts shown in Table 6, Reference Example 27 and A monolith was produced in a similar manner. The results are shown in Tables 6 and 7. From the SEM photograph (not shown), the formation of particles and protrusions was not observed at all on the skeleton surface. From Table 6 and Table 7, when the monolith is produced under conditions deviating from the specific production conditions of the present invention, that is, conditions deviating from the requirements (1) to (5) above, particle formation on the surface of the monolith skeleton is caused. It turns out that it is not recognized.

(Production of monolith cation exchanger)
The monolith produced by the above method was reacted with chlorosulfuric acid in the same manner as in Reference Example 27 to produce a monolith cation exchanger. The results are shown in Table 7. The obtained monolith cation exchanger had an ion exchange zone length of 26 mm, which was a large value as compared with Reference Examples 27 to 33.

Reference examples 35-37
(Manufacture of monoliths)
The amount of vinyl monomer used, the amount of crosslinking agent used, the type and amount of organic solvent used, the porous structure of the monolith intermediate that coexists during polymerization in step III, the crosslinking density, and the amount used were changed to the amounts shown in Table 6. Produced a monolith in the same manner as in Reference Example 27. The results are shown in Tables 6 and 7. For Reference Example 35, the crosslinking density ratio (0.2 times), for Reference Example 36, the type of organic solvent (2- (2-methoxyethoxy) ethanol; molecular weight 120), and for Reference Example 37, the polymerization temperature (50 And 1 ° C. lower than the 10-hour half-life temperature of the polymerization initiator). The results are shown in Table 7. For the monoliths of Reference Examples 35 and 37, there was no particle formation on the skeleton surface. In Reference Example 36, the isolated product was transparent, and the porous structure was collapsed and disappeared.

(Production of monolith cation exchanger)
Except for Reference Example 36, the organic porous material produced by the above method was reacted with chlorosulfuric acid in the same manner as in Reference Example 34 to produce a monolith cation exchanger. The results are shown in Table 7. The obtained monolith cation exchanger had an ion exchange zone length of 23 to 26 mm, which was a larger value than those of Reference Examples 27 to 33.

Reference Example 38
(Manufacture of monoliths)
Reference Example 34, except that the amount of vinyl monomer used, the amount of crosslinking agent used, the amount of organic solvent used, the porous structure of monolith intermediate coexisting during polymerization in step III and the amount used were changed to the amounts shown in Table 6. A monolith was produced in the same manner as described above. The results are shown in Tables 6 and 7, and it can be seen that when a monolith is produced outside the specific production conditions of the present invention, particle formation on the monolith skeleton surface is not observed.

(Production of monolith anion exchanger)
The monolith produced by the above method was cut into a disk shape having a diameter of 70 mm and a thickness of about 15 mm. To this, 1400 ml of dimethoxymethane and 20 ml of tin tetrachloride were added, and 560 ml of chlorosulfuric acid was added dropwise under ice cooling. After completion of the dropping, the temperature was raised and the reaction was carried out at 35 ° C. for 5 hours to introduce a chloromethyl group. After completion of the reaction, the mother liquor was extracted with a siphon, washed with a mixed solvent of THF / water = 2/1, and further washed with THF. To this chloromethylated monolith, 1000 ml of THF and 600 ml of a 30% trimethylamine aqueous solution were added and reacted at 60 ° C. for 6 hours. After completion of the reaction, the product was washed with a methanol / water mixed solvent, then washed with pure water and isolated. The results are shown in Table 7. The obtained monolith anion exchanger had an ion exchange zone length of 47 mm, which was a large value as compared with Reference Examples 27 to 33. In Tables 6 and 7, the mesopore diameter and pore value are average values.

Reference Example 39
(Production of monolith cation exchanger (known))
27.7 g of styrene, 6.9 g of divinylbenzene, 0.14 g of azobisisobutyronitrile (ABIBN) and 3.8 g of sorbitan monooleate were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / azobisisobutyronitrile / sorbitan monooleate mixture is added to 450 ml of pure water, and stirred for 2 minutes at 20,000 rpm with a homogenizer, and a water-in-oil emulsion. Got. After emulsification, the water-in-oil emulsion was transferred to a stainless steel autoclave, sufficiently substituted with nitrogen, sealed, and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the content was taken out, extracted with Soxhlet for 18 hours with isopropanol, unreacted monomer and sorbitan monooleate were removed, and dried under reduced pressure at 40 ° C. overnight. After separating 11.5 g of an organic porous material containing 14 mol% of a crosslinking component composed of the styrene / divinylbenzene copolymer thus obtained, 800 ml of dichloroethane was added, and the mixture was heated at 60 ° C. for 30 minutes. After cooling to room temperature, 59.1 g of chlorosulfuric acid was gradually added and reacted at room temperature for 24 hours. Thereafter, acetic acid was added, the reaction product was poured into a large amount of water, washed with water and dried to obtain a porous cation exchanger. The porous body has an ion exchange capacity of 4.4 mg equivalent / g in terms of dry porous body and 0.32 mg equivalent / ml in terms of wet volume. By mapping sulfur atoms using EPMA, sulfonic acid groups It was confirmed that was uniformly introduced into the porous body. Further, as a result of SEM observation, the internal structure of this organic porous body has an open-cell structure without the formation of particles or the like as in the present invention, and most of the macropores having an average diameter of 30 μm overlap with each other. The pore diameter of the mesopore formed by the macropore overlap was 5 μm, the total pore volume was 10.1 ml / g, and the BET specific surface area was 10 m ² / g.

Reference Example 40
(Production of porous anion exchanger (known))
Instead of 27.7 g of styrene, 18.0 g of p-chloromethylstyrene is used, 17.3 g of divinylbenzene is used instead of 6.9 g of divinylbenzene, and azobisisobutyronitrile is used instead of 0.14 g. A water-in-oil emulsion was polymerized in the same manner as in Reference Example 39 except that 0.26 g of bisisobutyronitrile was used, and contained 50 mol% of a cross-linking component consisting of a p-chloromethylstyrene / divinylbenzene copolymer. A porous body was produced. After separating 5 g of this porous material, adding 500 g of dioxane and heating at 80 ° C. for 30 minutes, the mixture was cooled to room temperature, 65 g of a trimethylamine (30%) aqueous solution was gradually added, and reacted at 50 ° C. for 3 hours. It was left overnight at room temperature. After completion of the reaction, the porous body was taken out, washed with acetone, washed with water, and dried to obtain a porous anion exchanger. The ion exchange capacity of this porous material was 2.5 mg equivalent / g in terms of dry porous material, and it was confirmed by SIMS that trimethylammonium groups were uniformly introduced into the porous material. Moreover, as a result of SEM observation, the internal structure of this porous body has an open cell structure, most of the macropores having an average diameter of 30 μm overlap, and the average diameter of the mesopores formed by the overlap of the macropores and the macropores. The value was 4 μm and the total pore volume was 9.9 ml / g. The porous body was cut out to a thickness of 10 mm, and the water permeation rate was measured. As a result, it was 12,000 l / min · m 2 · MPa.

(Production of deionization module A)
The porous cation exchanger and the porous anion exchanger obtained in Reference Example 28 and Reference Example 29 were cut into a size of 125 mm in length, 100 mm in width, and 8 mm in width to form four small blocks. That is, the porous cation exchanger 100d and the porous anion exchanger 100e are manufactured in small blocks, respectively, and the porous cation exchanger 100d, the porous anion exchanger 100e, and the porous cation exchange are formed from the inflow side of the water to be treated. The deionization module A as used in the apparatus of FIG. 15 is formed by laminating the body 100d and the porous anion exchanger 100e so as to be sandwiched between the anion exchange membrane 102 and the cation exchange membrane 101. Obtained.

(Production and operation of electric deionized water production apparatus A)
An electric deionized water production apparatus A was produced using the obtained deionization module A as a demineralization chamber. The electric deionized water production apparatus was an apparatus composed of one desalting chamber, one anode chamber, and one cathode chamber. A concentrating chamber was formed by inserting spacers between the desalting chamber and the anode chamber and between the desalting chamber and the cathode chamber, respectively. The electric deionized water production apparatus was operated by supplying water having a conductivity of 3.6 μS / cm obtained by treating city water with a reverse osmosis membrane as treated water at 16 L / h. Treated water having a specific resistance of 13.0 MΩcm was obtained at an operating current of 0.16 A of the electrical deionized water production apparatus. The operating voltage at this time was 12V. Moreover, the water flow differential pressure to the desalting chamber at this time was 64 kPa.

Comparative Example 3
(Preparation of deionization module B)
Instead of the porous cation exchanger of Reference Example 28, the porous cation exchanger of Reference Example 39 was used. Instead of the porous anion exchanger of Reference Example 33, the porous anion exchanger of Reference Example 40 was used. A deionization module B was produced in the same manner as in Example 5 except that it was used.
Comparative Example 4

(Production and operation of electric deionized water production apparatus B)
An electric deionized water production apparatus B was produced and operated in the same manner as in Example 6 except that the deionization module B was used instead of the deionization module A. As a result, treated water having a specific resistance of 5.0 MΩcm was obtained at an operating current of 0.16 A of the electrical deionized water production apparatus. The operating voltage at this time was 20V. Moreover, the water flow differential pressure to the desalting chamber at this time was 510 kPa.

Compared with the monolith ion exchanger used in Comparative Example 4, the composite monolith ion exchanger used in Example 6 has a low water flow differential pressure and reduces the operating voltage of the electric deionized water production apparatus. It was confirmed that power can be saved and good treated water can be obtained.
Tables 6 and 7 are sequentially shown below in order.

The deionization module of the present invention can be assembled because the porous ion exchanger filled in the space between the ion exchange membranes can be formed into, for example, a flat plate shape or a cylindrical shape and can be easily cut. An easy and simple structure can be obtained. Moreover, the electric deionized water production apparatus of the present invention has high ion exchanger strength, can reduce pressure loss during water flow, and can improve the quality of treated water.

1 desalting chamber 2 concentration chamber 61 skeletal phase 62 Soraanasho _{_{10A, 10A 1, 10A 2,}} 10B deionized

module

100, 100a, 100b porous ion exchanger 100d porous cation exchanger 100e porous anion exchanger 100f porous Laminated body of porous cation exchanger and porous anion exchanger 101 Cation exchange membrane 102

Anion exchange membrane

103, 103a,

103b Frame body

104, 104a, 104b Space portion 105 Intermediate ion exchange membrane 109 Cathode 110 Anode

Claims

Bubble-shaped macropores overlap each other, and the overlapping portion is a continuous macropore structure having an average diameter of 30 to 300 μm when wet, and has a total pore volume of 0.5 to 5 ml / g. SEM of the cut surface of the continuous macropore structure (dried body) with an ion exchange capacity of 0.4 to 5 mg equivalent / ml per unit area, ion exchange groups uniformly distributed in the porous ion exchanger In the image, an organic porous ion exchanger having a skeleton area of 25 to 50% in the image area in the image area is sealed with a cation exchange membrane sealed on one side of the frame and the other side. A deionization module characterized by being filled in an internal space formed by an anion exchange membrane and used in an electric deionized water production apparatus.
A three-dimensionally continuous skeleton having a thickness of 1 to 60 μm composed of an aromatic vinyl polymer containing 0.3 to 5.0 mol% of a cross-linking structural unit among all the structural units having an ion exchange group introduced therein; A co-continuous structure consisting of three-dimensionally continuous pores with a diameter of 10 to 100 μm between the skeletons, with a total pore volume of 0.5 to 5 ml / g, per volume in a water-wet state An organic porous ion exchanger having an ion exchange capacity of 0.3 to 5 mg equivalent / ml and having ion exchange groups uniformly distributed in the porous ion exchanger is sealed on one side of the frame The inner space formed by the formed cation exchange membrane and the anion exchange membrane sealed on the other side is used for an electric deionized water production apparatus. Ion module.
An electrical deionized water production apparatus comprising an ion exchanger filled in an internal space formed by a cation exchange membrane sealed on one side of a frame and an anion exchange membrane sealed on the other side. A deionization module to be used, in which the ion exchanger includes an organic porous body composed of a continuous skeleton phase and a continuous pore phase, and a large number of 4 to 40 μm in diameter fixed to the skeleton surface of the organic porous body. A composite structure with a large number of protrusions having a size of 4 to 40 μm formed on the skeleton surface of the particle body or the organic porous body, and having an average pore diameter of 10 to 150 μm in a wet state, Deionization module characterized by being a monolithic organic porous ion exchanger having a pore volume of 0.5 to 5 ml / g and an ion exchange capacity of 0.2 mg equivalent / ml or more per volume in a water-wet state .
Bubble-shaped macropores overlap each other, and the overlapping portion is a continuous macropore structure having an average diameter of 30 to 300 μm when wet, and has a total pore volume of 0.5 to 5 ml / g. SEM of the cut surface of the continuous macropore structure (dried body) with an ion exchange capacity of 0.4 to 5 mg equivalent / ml per unit area, ion exchange groups uniformly distributed in the porous ion exchanger In the image, a cation exchange membrane in which an organic porous ion exchanger having a skeletal area of 25 to 50% in a cross section in an image region is sealed on one side of the frame, the cation exchange membrane and the other The first internal space formed by the intermediate ion exchange membrane disposed between the anion exchange membranes sealed on the other side and further filled with the intermediate ion exchange membrane and the other side Formed with exchange membrane Second it is comprised by filling the interior space, deionized module, characterized in that for use in electrodeionization water producing apparatus that.
A three-dimensionally continuous skeleton having a thickness of 1 to 60 μm composed of an aromatic vinyl polymer containing 0.3 to 5.0 mol% of a cross-linking structural unit among all the structural units having an ion exchange group introduced therein; A co-continuous structure consisting of three-dimensionally continuous pores with a diameter of 10 to 100 μm between the skeletons, with a total pore volume of 0.5 to 5 ml / g, per volume in a water-wet state An organic porous ion exchanger having an ion exchange capacity of 0.3 to 5 mg equivalent / ml and having ion exchange groups uniformly distributed in the porous ion exchanger is sealed on one side of the frame A first internal space formed by the formed cation exchange membrane and an intermediate ion exchange membrane disposed between the cation exchange membrane and the anion exchange membrane sealed on the other side; Formed by an ion exchange membrane and an anion exchange membrane sealed on the other side Second it is comprised by filling the interior space, deionized module, characterized in that for use in electrodeionization water producing apparatus that.
A first internal space formed by a cation exchange membrane sealed on one side of the frame, and an intermediate ion exchange membrane disposed between the cation exchange membrane and the anion exchange membrane sealed on the other side The first ion exchanger is filled, and the second ion exchanger is filled in the second internal space formed by the intermediate ion exchange membrane and the anion exchange membrane sealed on the other side. A deionization module used in an ionized water production apparatus, wherein one or both of the first ion exchanger and the second ion exchanger are composed of a continuous skeleton phase and a continuous pore phase. And a large number of particles having a diameter of 4 to 40 μm fixed to the skeleton surface of the organic porous body or a large number of protrusions having a size of 4 to 40 μm formed on the skeleton surface of the organic porous body A structure having an average pore diameter of 10 to 15 in a wet state with water It is a monolithic organic porous ion exchanger having 0 μm, a total pore volume of 0.5 to 5 ml / g, and an ion exchange capacity of 0.2 mg equivalent / ml or more per volume under water wet condition. Deionizing module.
7. The organic porous body is a continuous macropore structure in which bubble-shaped macropores overlap each other, and the overlapping portion forms an opening having an average diameter of 30 to 150 μm in a wet state of water. Deionization module.
The organic porous body is a three-dimensionally continuous skeleton having an average thickness of 1 to 60 μm in a water-wet state, and a three-dimensionally continuous skeleton having an average diameter of 10 to 100 μm in a water-wet state between the skeletons. The deionization module according to claim 3 or 6, wherein the deionization module is a co-continuous structure composed of pores.
The intermediate ion exchange membrane is an anion exchange membrane, the porous ion exchanger filled in the first internal space is a laminate of a porous anion exchanger and a porous cation exchanger, and the second internal space has The deionization module according to any one of claims 4 to 6, wherein the porous ion exchanger to be filled is a porous anion exchanger.
An electric deionized water production apparatus comprising the deionization module according to any one of claims 1 to 9.