TWI476052B - Ion adsorption module and water processing method - Google Patents

Description

Ion adsorption module and water treatment method

The present invention relates to an ion adsorption module and a water treatment method in which the length of the ion exchange belt is significantly shorter.

Conventionally, an ion exchange system is represented by a polymer synthetic resin collectively referred to as an ion exchange resin, and is classified according to the shape of the product, and can be classified into a granular or fragmented ion exchange resin, a membrane-like ion exchange membrane, and a fibrous shape. Ion exchange fiber, etc. Further, in addition to the granular ion exchange resin, an organic porous ion exchanger having continuous pores is also known.

For example, Japanese Laid-Open Patent Publication No. 2004-82027 discloses an ion adsorption module including: a container having at least an opening through which water to be treated flows; and a macroporous hole connected to each other and filled in the container; An open cell structure having a clearance hole having an average diameter of 1 to 1000 μm in the wall of the macropore, having a total pore volume of 1 ml/g to 50 ml/g, a uniform distribution of ion exchange groups, and an ion exchange capacity of 0.5 mg equivalent/g dry An organic porous ion exchanger having a three-dimensional network structure of a porous body or more.

According to the ion adsorption module of Japanese Laid-Open Patent Publication No. 2004-82027, the filling of the ion exchanger is extremely easy, and the packed layer does not move even in the upward flow. Further, in the water treatment method using the ion adsorption module, even if the flow rate is increased, the length of the ion exchange belt can be kept short, the volume of the ion exchange device can be reduced, and the adsorbed ions are not slightly leaked. Therefore, the regeneration frequency is reduced, which can improve the processing efficiency. Further, details of a method for producing an organic porous ion exchanger are disclosed in Japanese Laid-Open Patent Publication No. 2002-306976.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-82027 (Application No.)

[Patent Document 2] Japanese Patent Laid-Open Publication No. 2002-306976

[Patent Document 3] Japanese Patent Laid-Open Publication No. 2009-62512

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2009-67982

However, the organic porous ion exchanger used in the ion-adsorbing module described in JP-A-2004-82027 describes that a common opening (gap hole) of a monolith is 1 to 1,000 μm. In the case of a monolith having a small pore volume of 5 ml/g or less, since the amount of water droplets in the water droplet type emulsion is required to be reduced, the common opening is small, and the average diameter of the opening is substantially 20 μm or more. By. Therefore, there is a problem that the water pressure difference becomes large. In addition, when the average opening diameter is about 20 μm, the total pore volume is also increased, so that the ion exchange capacity per unit volume is lowered, and the length of the ion exchange belt is increased, and the exchange frequency of the module is increased. . In addition, it is also desirable to have a monolithic structure that replaces such a continuous bubble structure (continuous macropores).

Accordingly, it is an object of the present invention to provide an ion adsorption module which is extremely easy to fill an ion exchanger. Further, another object of the present invention is to provide a method for reducing the water pressure difference, and even if the flow rate is increased, the length of the ion exchange zone can be kept short, and the ion exchange capacity per unit volume becomes large, and the adsorbed ions are not An ion adsorption module and a water treatment method which increase the processing efficiency by reducing the frequency of the exchange or reducing the regeneration frequency.

In this case, the inventors of the present invention have conducted intensive studies and found that a monolithic organic porous body having a large pore volume obtained by the method described in JP-A-2002-306976 (middle) When the vinyl monomer and the crosslinking agent are allowed to stand still in a specific organic solvent in the presence of a compound, a coarser skeleton having a larger opening diameter and a thicker skeleton than the organic porous skeleton of the intermediate can be obtained. If the ion exchange group is introduced into the rough monolith, the swelling is larger because it belongs to the coarse frame, so that the opening can be made larger, and the ion exchange group is introduced into the monolithic ion exchange in the monolithic block. If the adsorbent is used as the ion adsorption module, the water pressure difference can be reduced, the flow rate is also increased, and the length of the ion exchange zone can be kept short, and the ion exchange capacity per unit volume is large. Since the adsorbed ions do not leak a little, the exchange frequency becomes small or the regeneration frequency is lowered, the processing efficiency can be improved, and the like, and the present invention has been completed.

In addition, the inventors of the present invention have conducted intensive studies and found that the monolithic organic porous body (intermediate) having a large pore volume obtained by the method described in JP-A-2002-306976 has been found. When the aromatic vinyl monomer and the crosslinking agent are subjected to static polymerization in a specific organic solvent, a three-dimensional continuous aromatic vinyl polymer skeleton and a three-dimensional continuous space between the skeletons can be obtained. a hydrophobic monolith having a co-continuous structure in which two phases are entangled; the continuity of the monolithic pores of the co-continuous structure is high and the size thereof is not deviated, and the pressure loss during fluid permeation is low, and further, Since the skeleton of the co-continuous structure is relatively thick, if a ion exchange group is introduced, a monolithic organic porous ion exchanger having a large ion exchange capacity per unit volume can be obtained; if the monolithic organic porous ion exchanger is used, As the adsorbent material of the ion adsorption module, as in the monolithic ion exchanger of the first embodiment, the water pressure difference can be reduced, the flow rate is also increased, and the ion exchange band length can be maintained short, and each single The volume of the ion exchange capacity is large, the adsorbed ions trace does not leak, so the switching frequency is reduced or the frequency of regeneration is reduced, the processing efficiency can be improved, then completed the present invention.

In addition, the inventors of the present invention have conducted intensive studies and found that the monolithic organic porous body (intermediate) having a large pore volume obtained by the method described in JP-A-2002-306976 has been found. Then, if the vinyl monomer and the crosslinking agent are subjected to static polymerization in an organic solvent under specific conditions, a surface having a diameter of 2 to 20 μm adhered to the surface of the skeleton constituting the organic porous body can be obtained. a plurality of particle bodies or a monolith having a composite structure in which protrusions are formed; a composite monolithic ion exchanger in which an ion exchange group is introduced into the composite monolith, and if an adsorption material as an ion adsorption module is used, water can be passed through The pressure difference is reduced, the flow rate is also increased, and the length of the ion exchange zone can be kept short, and the ion exchange capacity per unit volume is large, and the adsorbed ions do not leak a little, so the exchange frequency becomes small or the regeneration frequency decreases. The processing efficiency can be improved, and the present invention can be completed.

That is, the present invention (A1) provides an ion adsorption module comprising a container having at least an opening into which the water to be treated flows, and a monolithic organic porous ion exchanger filled in the container; The monolithic organic porous ion exchange system has bubble-like macropores which overlap each other, and the overlapping portion becomes a continuous macroporous structure having an opening of an average diameter of 30 to 300 μm in a wet state of water, and the total pore volume is 0.5 to 5 ml. /g, the ion exchange capacity per unit volume in the wet state of water is 0.4 to 5 mg equivalent/ml, the ion exchange group is uniformly distributed in the porous ion exchanger, and the continuous macroporous structure (dry body) is cut In the SEM image of the cross section, the area of the cross section of the skeleton portion shown in the SEM image is 25 to 50% in the image region (hereinafter also referred to as "the first monolithic ion exchanger").

Further, the present invention (A1) provides an ion adsorption module comprising a container having at least an opening through which the water to be treated flows, and a monolithic organic porous ion exchanger filled in the container; The monolithic organic porous ion exchange system is composed of an aromatic vinyl polymer having a crosslinked structural unit of 0.3 to 5.0 mol% in a total constituent unit into which an ion exchange group is introduced, and has a thickness of 1 to 1 A three-dimensional continuous skeleton of 60 μm and a co-continuous structure composed of three-dimensional continuous pores having a diameter of 10 to 100 μm between the skeletons, the total pore volume of which is 0.5 to 5 ml/g, and the unit volume per unit of water wet state. The ion exchange capacity is 0.3 to 5 mg equivalent/ml, and the ion exchange group is uniformly distributed in the porous ion exchanger (hereinafter also referred to as "second monolithic ion exchanger").

Further, the present invention (A2) provides an ion adsorption module comprising a container having at least an opening into which the water to be treated flows, and an organic porous ion exchanger filled in the container; characterized in that the organic porous The mass ion exchange system comprises an organic porous body having a continuous skeleton phase and a continuous pore phase, and a plurality of particle bodies having a diameter of 4 to 40 μm adhered to the surface of the skeleton of the organic porous body or formed in the organic porous body. a composite structure of a plurality of protrusions having a size of 4 to 40 μm on the surface of the skeleton, the average diameter of the pores in the wet state of water is 10 to 150 μm, and the total pore volume is 0.5 to 5 ml/g, and each of the water is wet. The ion exchange capacity per unit volume is 0.2 mg equivalent/ml or more (hereinafter also referred to as "third monolith ion exchanger").

According to the invention (A1) and the invention (A2), the porous ion exchanger can be easily produced into, for example, a block shape embedded in a filling container, and can be easily filled. Further, it can be applied to any of the continuous water-passing method generally used in the conventional module and the batch processing method which is carried out in the water in the storage container or the storage tank. Moreover, in the continuous water treatment method, when the content of the ionic impurities is a small amount, the flow pressure difference can be reduced by the simplification device, the flow rate is also increased, and the length of the ion exchange zone can be maintained short, and each unit is maintained. The ion exchange capacity of the volume is large, and the adsorbed ions do not leak a small amount, so the exchange frequency becomes small or the regeneration frequency is lowered, and the treatment efficiency can be improved.

Hereinafter, the present invention will be described by dividing the invention (A1) and the invention (A2).

[Invention (A1)]

In the ion adsorption module according to the embodiment of the invention (A1), the first monolithic ion exchanger or the second monolithic ion exchanger is filled in the container. In the present specification of the invention (A1), the "monolithic organic porous body" may be simply referred to as "monolithic", and the "monolithic organic porous ion exchanger" may be simply referred to as "monolithic ion exchanger". The "monolithic organic porous intermediate" is simply referred to as "monolithic intermediate".

<Description of the first monolithic ion exchanger>

The first monolithic ion exchange system is obtained by introducing an ion exchange group into a monolith, and the bubble-like macropores overlap each other, and the superposed portion has an average diameter of 30 to 300 μm, preferably 30 to 200 μm in a wet state of water. A continuous giant pore structure with an opening (gap hole) of 35 to 150 μm. The average diameter of the openings of the monolithic ion exchangers is such that when the ion exchange groups are introduced into the monoliths, the bulk of the monoliths becomes larger than the average diameter of the openings of the monoliths. If the average diameter of the opening is less than 30 μm, the pressure loss at the time of water passing becomes large, which is not preferable. If the average diameter of the opening is too large, the contact between the fluid and the monolithic ion exchanger is insufficient, and as a result, the ion exchange property is lowered. good. Further, in the present invention, the average diameter of the opening of the monolithic intermediate in the dry state, the average diameter of the opening of the monolith in the dry state, and the average diameter of the opening of the monolithic ion exchanger in the dry state are by mercury intrusion method. The value measured. Further, the average diameter of the opening of the monolithic ion exchanger in the water-wet state is a value calculated by multiplying the average diameter of the opening of the dry monolithic ion exchanger by the swelling ratio. Specifically, the diameter of the monolithic ion exchanger in a water-wet state is set to x1 (mm), and the monolithic ion exchanger in a water-wet state is dried, and the diameter of the monolithic ion exchanger obtained in the dried state is set. For y1 (mm), when the average diameter of the opening when the monolithic ion exchanger in the dry state is measured by the mercury intrusion method is set to z1 (μm), the average of the openings of the monolithic ion exchanger in the water-wet state The diameter (μm) is calculated from the following equation "average diameter (μm) of the opening of the monolithic ion exchanger in the water-wet state = z1 × (x1/y1)". Further, the average diameter of the opening of the monolith in the dry state before the introduction of the ion exchange group, and the dry state of the monolithic ion exchanger in the water-wet state with respect to the ion exchange group introduced into the monolith in the dry state are known. In the case of the swelling ratio of the monolith, the average diameter of the opening of the monolith in the dry state is multiplied by the swelling ratio, and the average diameter of the water wet state of the pores of the monolithic ion exchanger can also be calculated.

In the first monolithic ion exchanger, in the cross-sectional SEM image of the continuous macropore structure, the area of the cross section of the skeleton portion shown in the SEM image is 25 to 50%, preferably 25 to 45 in the image area. %. If the area of the cross section of the skeleton portion shown in the SEM image is less than 25% in the image region, it becomes a fine skeleton, and the ion exchange capacity per unit volume is lowered, which is not preferable. If it exceeds 50%, the skeleton becomes It is coarse and loses the uniformity of ion exchange characteristics, so it is not good. Further, in the monolith described in Japanese Laid-Open Patent Publication No. 2002-346392, the skeleton portion is thickened even if the mixing ratio of the oil phase portion with respect to water is increased, and the mixing ratio is still required to secure the common opening. Boundary, bone shown in the SEM image The maximum area of the section of the frame cannot exceed 25% of the image area.

The condition for obtaining the SEM image may be a condition in which the skeleton portion indicated by the cross section of the cross section is clearly expressed, for example, a magnification of 100 to 600, and a photograph area of about 150 mm × 100 mm. The SEM observation can be performed in an image of three or more, preferably five or more, which are taken at an arbitrary position where the arbitrary cut section of the subjective block is excluded. The cut piece is a dry state for use in an electron microscope. The skeleton portion of the cut section in the SEM image will be described with reference to Figs. 1 and 5 . Moreover, FIG. 5 is a transfer of the skeleton part shown by the cross section of the SEM photograph of FIG. In Fig. 1 and Fig. 5, the shape shown in the cross section is the cross section (symbol 12) of the skeleton portion shown in the SEM image of the present invention, and the circular hole shown in Fig. 1 is an opening ( The clearance hole), in addition, the larger curvature or the curved surface is a giant hole (symbol 13 in Fig. 5). The area of the cross section of the skeleton shown in the SEM image is 28% in the rectangular photo area 11. In this way, the skeleton portion can be clearly determined.

In the SEM photograph, the method of measuring the area of the skeleton portion shown by the cross section of the cross section is not particularly limited. For example, the frame portion is subjected to a known computer processing or the like, and then automatically calculated or manually calculated by a computer or the like. The calculation method. As a manual calculation, a method in which an indefinite shape is replaced with a collection of a quadrangle, a triangle, a circle, or a trapezoid, and the like is laminated to obtain an area.

Further, the first monolith ion exchange system has a total pore volume of 0.5 to 5 ml/g, preferably 0.8 to 4 ml/g. When the total pore volume is less than 0.5 ml/g, the pressure loss at the time of water passing becomes large, which is not preferable. On the other hand, when the total pore volume exceeds 5 ml/g, the ion exchange capacity per unit volume is lowered, which is not preferable. In the monolithic ion exchanger of the present invention (A1), since the average diameter of the opening and the total pore volume are in the above range and are the skeleton of the rough frame, when it is used as an ion-adsorbing material, the contact area with the water to be treated is used. It becomes larger and can exert superior adsorption capacity. Further, in the invention (A1), the total pore volume of a monolith (monolithic intermediate, monolithic, monolithic ion exchanger) is a value measured by a mercury intrusion method. Further, the total pore volume of a monolith (monolithic monolith, monolithic, monolithic ion exchanger) is the same regardless of the dry state or the water wet state.

In addition, the pressure loss when water passes through the first monolithic ion exchanger is based on the pressure loss when the water is filled with water at a line speed (LV) of 1 m/h. The "pressure difference coefficient" is preferably in the range of 0.001 to 0.1 MPa/m ‧ LV, and particularly preferably 0.001 to 0.05 MPa/m LV. When the pressure difference coefficient and the total pore volume are in this range, when it is used as an ion-adsorbing material, the contact area with the water to be treated can be increased, and the water to be treated can be smoothly circulated, and also has sufficient mechanical strength. Therefore, it is better.

The first monolithic ion exchanger has an ion exchange capacity of 0.4 to 5 mg equivalent/ml per unit volume in a water-wet state. In the conventional monolithic organic porous ion exchanger having a continuous macroporous structure different from the present invention as described in JP-A-2002-306976, in order to achieve a practically required low pressure loss When the opening diameter is increased, the total pore volume is also increased, so the ion exchange capacity per unit volume is lowered, and if the total pore volume is reduced in order to increase the exchange capacity per unit volume, the opening diameter becomes small. There are disadvantages of increased pressure loss. On the other hand, in the monolithic ion exchanger of the present invention (A1), the skeleton of the continuous macropore structure can be made thicker (the skeleton wall portion is thickened) while the opening diameter is further increased, so that it can be transmitted through When the pressure loss is suppressed to a low level, the ion adsorption performance is drastically increased. If the ion exchange capacity per unit volume is less than 0.4 mg equivalent/ml, the amount of treated water to be treated before the failure becomes small, and the exchange frequency of the module becomes high, which is not preferable. Further, the ion exchange capacity per unit weight of the monolithic ion exchanger of the invention (A1) is not particularly limited, but is 3 to 5 mg in order to uniformly introduce the ion exchange group into the surface of the porous body and the inside of the skeleton. Equivalent / g. Further, the ion exchange capacity of the porous body in which only the ion exchange group is introduced on the surface cannot be determined depending on the type of the porous body or the ion exchange group, but is approximately 500 μg equivalent/g.

In the first monolithic ion exchanger, the material constituting the skeleton of the continuous macroporous structure is an organic polymer material having a crosslinked structure. The crosslinking density of the polymer material is not particularly limited, and is preferably from 0.3 to 50 mol%, more preferably from 0.3 to 5 mol%, based on the total constituent unit of the polymer material. When the crosslinked structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, if it exceeds 50 mol%, the embrittlement of the porous body proceeds, and the flexibility is lost. Preferably, especially in the case of an ion exchanger, it is not preferable because the amount of introduction of the ion exchange group is reduced. The kind of the polymer material is not particularly limited, and examples thereof include polystyrene, poly(α-methylstyrene), polyvinyltoluene, polyvinylbenzyl chloride, polyvinylbiphenyl, and polyvinyl. An aromatic vinyl polymer such as naphthalene; a polyolefin such as polyethylene or polypropylene; a poly(halogenated polyolefin) such as polyvinyl chloride or polytetrafluoroethylene; a nitrile polymer such as polyacrylonitrile; A crosslinked polymer of a (meth)acrylic polymer such as methyl acrylate, polybutyl methacrylate or polyethyl acrylate. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, or a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, and It may be a blend of two or more polymers. Among these organic polymer materials, the ease of formation of the continuous macropore structure, the ease of introduction of the ion exchange group and the height of the mechanical strength, and the height of the stability of the acid and alkali are preferably aromatic ethylene. As the crosslinked polymer of the base polymer, for example, a styrene-divinylbenzene copolymer or a vinylbenzyl chloride-divinylbenzene copolymer is preferable as a preferred material.

The ion exchange group of the first monolithic ion exchanger may, for example, be a cation exchange group such as a sulfonic acid group, a carboxylic acid group, an iminodiacetate group, a phosphoric acid group or a phosphate group; a quaternary ammonium group and a third stage; An anion exchange group of an amine group, a secondary amine group, a primary amine group, a polyethyleneimine group, a third fluorenyl group, a fluorenyl group or the like. If the ion exchange group is a cation exchanger, it is possible to effectively remove metals which particularly adversely affect the semiconductor device.

In the first monolithic ion exchanger, the introduced ion exchange group is distributed not only on the surface of the porous body but also uniformly inside the skeleton of the porous body. The so-called "uniform distribution of ion exchange groups" means that the distribution of ion exchange groups is uniformly distributed on the surface and inside the skeleton at least μm. The distribution of the ion exchange groups can be confirmed relatively simply by using EPMA or the like. Further, if the ion exchange groups are not only distributed on the surface of the monolith, but also uniformly distributed inside the skeleton of the porous body, the physical properties and chemical properties of the surface and the interior can be made uniform, so that the durability against swelling and shrinkage is improved.

(Method for producing the first monolithic ion exchanger)

The first monolithic ion exchange system is obtained by preparing a water-drop type emulsion in an oil by stirring a mixture of an oil-soluble monomer, a surfactant, and water which does not contain an ion exchange group, and then is made into an oil. The water droplet type emulsion is polymerized to obtain a monolithic organic porous intermediate having a continuous pore volume of 5 to 16 ml/g, and the preparation is carried out by a vinyl monomer having at least 2 in one molecule. Step II of the above-mentioned vinyl crosslinking agent, a mixture of an organic solvent and a polymerization initiator which dissolves a vinyl monomer or a crosslinking agent but does not dissolve a polymer formed by polymerizing a vinyl monomer; The mixture obtained in the step is subjected to polymerization in the presence of the monolithic organic porous intermediate obtained in the first step, thereby obtaining a coarse organic porous material having a skeleton thicker than the skeleton of the organic porous intermediate. Step III of the body; IV step of introducing an ion exchange group into the coarse organic porous body obtained in the step III.

In the method for producing the first monolithic ion exchanger, the first step may be carried out according to the method described in JP-A-2002-306976.

In the production of the monolithic intermediate of the first step, the oil-soluble monomer which does not contain an ion-exchange group may, for example, be an ion-exchange group which does not contain a carboxylic acid group, a sulfonic acid group or a quaternary ammonium group, and is A monomer that is low in solubility and is lipophilic. Preferred examples of such monomers include styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride, divinylbenzene, ethylene, propylene, isoprene, and dibutyl. Alkene, ethylene glycol dimethacrylate, and the like. These monomers may be used alone or in combination of two or more. Among them, from the viewpoint of obtaining necessary mechanical strength when a large number of ion-exchange groups are introduced in the subsequent step, it is preferred to select a cross-linking single such as divinylbenzene or ethylene glycol dimethacrylate. The body is at least one component of the oil-soluble monomer, and the content thereof is 0.3 to 50 mol%, preferably 0.3 to 5 mol%, based on the total oil-soluble monomer.

The surfactant is not particularly limited as long as it can form a water-drop type (W/O) emulsion when the oil-soluble monomer having no ion-exchange group is mixed with water, and sorbitan monooleate can be used. Sorbitan monolaurate, sorbitan monocaprotate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene nonylphenyl ether, polyoxyethylene stearyl ether a nonionic surfactant such as polyoxyethylene sorbitan monooleate; an anionic surfactant such as potassium oleate, sodium dodecylbenzenesulfonate or dioctylsulfonate succinate; a cationic surfactant such as aliphatic dimethyl ammonium chloride; lauryl dimethyl beet Etc. Sexual surfactants. These surfactants can be used alone or in combination of two or more. Moreover, the water-drop type emulsion in oil refers to an emulsion in which an oil phase is a continuous phase in which water droplets are dispersed. The amount of the surfactant added is greatly changed depending on the type of the oil-soluble monomer and the target size of the emulsified particles (macropores), so that it cannot be said to be inferior to the oil-soluble monomer and interface. The total amount of active agents is selected in the range of about 2 to 7%.

Further, in the first step, when a water-drop type emulsion is formed in the oil, a polymerization initiator may be used as needed. The polymerization initiator is preferably a compound which generates a radical by heat and light irradiation. The polymerization initiator may be water-soluble or oil-soluble, and examples thereof include azobisisobutyronitrile, azobiscyclohexanenitrile, azobiscyclohexanecarbonitrile, benzammonium peroxide, potassium persulfate, and ammonium persulfate. Hydrogen peroxide-ferric chloride, sodium persulfate-acidic sodium sulfite, tetramethylammonium sulfonate disulfide, and the like.

The mixing method of mixing the oil-soluble monomer, the surfactant, the water, and the polymerization initiator which do not contain the ion-exchange group to form the water-drop type emulsion in the oil is not particularly limited, and it is possible to use the components in one time. a method in which an oil-soluble monomer, a surfactant, an oil-soluble component belonging to an oil-soluble polymerization initiator, and water-soluble components which are water-soluble polymerization initiators are uniformly dissolved, and the components are mixed. Method, etc. The mixing device for forming the emulsion is not particularly limited, and a suitable apparatus for obtaining the particle size of the target emulsion may be selected using a usual mixer, homogenizer, high-pressure homogenizer or the like. Further, the mixing conditions are not particularly limited, and the number of stirring rotations or the stirring time at which the target emulsion particle diameter can be obtained can be arbitrarily set.

The monolithic intermediate system obtained in the I step has a continuous macropore structure. When it coexists in a polymerization system, a monolithic intermediate structure is used as a mold to form a porous structure having a rough skeleton. Further, the monolithic intermediate system has an organic polymer material having a crosslinked structure. The crosslinking density of the polymer material is not particularly limited, and is preferably a crosslinking structural unit containing 0.3 to 50 mol%, more preferably 0.3 to 5 mol%, based on the total constituent unit constituting the polymer material. If the crosslinked structural unit is less than 0.3 mol%, it is not good because of insufficient mechanical strength. In particular, when the total pore volume is as large as 10 to 16 ml/g, in order to maintain the continuous macroporous structure, it is preferred to contain 2 mol% or more of a crosslinked structural unit. On the other hand, when it exceeds 50 mol%, the embrittlement of the porous body progresses, and the softness is lost, which is not preferable.

The type of the polymer material as the monolithic intermediate is not particularly limited, and may be, for example, the same as the above-mentioned monolithic polymer material. Thereby, the same polymer can be formed on the skeleton of the monolithic intermediate, and a monolith having a skeleton structure in which the skeleton is thickened and uniform can be obtained.

The total pore volume of the monolithic intermediate is 5 to 16 ml/g, preferably 6 to 16 ml/g. When the total pore volume is too small, the total pore volume of the monolith obtained by polymerizing the vinyl monomer becomes too small, and the pressure loss at the time of 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 by polymerizing the vinyl monomer is deviated from the continuous macropore structure, which is not preferable. When the total pore volume of the monolith intermediate is set to the above numerical range, the ratio of the monomer to water can be set to be about 1:5 to 1:20.

Further, in the monolith intermediate body, the average diameter of the opening (gap hole) belonging to the overlapping portion of the macropore and the macropore is 20 to 200 μm in a dry state. If the average diameter of the full opening of 20 m, then polymerizing the vinyl monomer of the resulting monolithic _opening diameter becomes too small, the pressure loss becomes large through the water so poor. On the other hand, when it exceeds 200 μm, the opening diameter of the monolith obtained by polymerizing the vinyl monomer becomes too large, and the contact between the water to be treated and the monolithic ion exchanger is insufficient, and as a result, the removal efficiency of the ion component is lowered. good. The monolithic intermediate is preferably a structure in which the macropore size or the opening diameter is uniform, but is not limited thereto. In the uniform structure, uneven macropores having a larger size than the uniform macropores may be present in a dot shape.

The second step is a polymer prepared by polymerizing a vinyl monomer, a crosslinking agent having at least two or more vinyl groups in one molecule, and dissolving a vinyl monomer or a crosslinking agent without dissolving the vinyl monomer. a step of a mixture of an organic solvent and a polymerization initiator. Further, the steps I and II are not in the order, and the step II can be performed after the step I, or the step I can be performed after the step II.

The vinyl monomer used in the second step is not particularly limited as long as it has a polymerizable vinyl group in the molecule and has high solubility in an organic solvent, and is preferably selected and produced. A vinyl monomer having a monolithic intermediate of the same type or similar polymeric material in the above polymerization system is present. Specific examples of such vinyl monomers include aromatic vinyls such as styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride, vinylbiphenyl, and vinylnaphthalene. Monomer; α-olefin such as ethylene, propylene, 1-butene, isobutylene; diene monomer such as butadiene, isoprene, chloroprene, etc.; vinyl chloride, vinyl bromide, vinylidene chloride a halogenated olefin such as tetrafluoroethylene; a nitrile monomer such as acrylonitrile or methacrylonitrile; a vinyl ester such as vinyl acetate or vinyl propionate; methyl acrylate, ethyl acrylate, butyl acrylate or acrylic acid 2 -ethylhexyl ester, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, methacrylic acid A (meth)acrylic monomer such as benzyl ester or glycidyl methacrylate. These monomers may be used alone or in combination of two or more. The vinyl monomer suitably used in the invention (A1) is an aromatic vinyl monomer such as styrene or vinylbenzyl chloride.

The amount of the vinyl monomer added is 3 to 40 times, preferably 4 to 30 times by weight, based on the monolithic intermediate which is present during the polymerization. If the amount of the vinyl monomer added is less than 3 times that of the porous body, the resulting monolithic skeleton (thickness of the wall portion of the monolithic skeleton) cannot be thickened, and the adsorption capacity per unit volume or the ion exchange group is introduced. The ion exchange capacity per unit volume becomes small, which is not preferable. On the other hand, when the amount of the vinyl monomer added exceeds 40 times, the opening diameter becomes small, and the pressure loss at the time of water passage becomes large, which is not preferable.

The crosslinking agent used in the second step is suitably used in those having at least two polymerizable vinyl groups in the molecule and having high solubility in an organic solvent. Specific examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, and butanediol diacrylic acid. Ester and the like. These crosslinking agents can be used alone or in combination of two or more. The preferred crosslinking agent is an aromatic polyvinyl compound such as divinylbenzene, divinylnaphthalene or divinylbiphenyl, depending on the height of the mechanical strength and the stability to hydrolysis. The amount of the crosslinking agent used is preferably from 0.3 to 50 mol%, particularly preferably from 0.3 to 5 mol%, based on the total amount of the vinyl monomer and the crosslinking agent. If the amount of the crosslinking agent used is less than 0.3 mol%, the mechanical strength of the monolith is insufficient, which is not preferable. On the other hand, when it exceeds 50 mol%, the embrittlement of a monolith is lost and the flexibility is lost, and the problem that the introduction amount of the ion exchange group is reduced is not preferable. Further, the amount of the crosslinking agent to be used is preferably such that it is almost equal to the crosslinking density of the monolithic intermediate which coexists when the vinyl monomer/crosslinking agent is polymerized. If the difference in the amount of use between the two is too large, the deviation of the crosslink density distribution occurs in the generated monolith, and cracks are likely to occur at the time of introduction of the ion exchange group into the reaction.

The organic solvent used in the second step is an organic solvent which dissolves a vinyl monomer or a crosslinking agent but does not dissolve a polymer formed by polymerizing a vinyl monomer, in other words, a polymer formed by polymerizing a vinyl monomer. It is a poor solvent. The organic solvent is largely different depending on the type of the vinyl monomer. Therefore, it is difficult to cite a general specific example. However, when the vinyl monomer is styrene, methanol, ethanol, propanol or butyl as an organic solvent is exemplified. Alcohol, hexanol, cyclohexanol, octanol, 2-ethylhexanol, decyl alcohol, dodecanol, ethylene glycol, propylene glycol, butanediol, glycerol, etc.; diethyl ether, ethylene Chain (poly)ethers such as alcohol dimethyl ether, 赛路苏, methyl 赛路苏, butyl 赛路苏, polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.; hexane, heptane, a chain-like saturated hydrocarbon such as octane, isooctane, decane or dodecane; an ester of ethyl acetate, isopropyl acetate, celecoxib acetate or ethyl propionate. Again, even if it is like two A good solvent for alkane or THF or toluene-like polystyrene can be used as an organic solvent when used together with the above-mentioned poor solvent and used in a small amount. The amount of the organic solvent used is preferably such that the concentration of the vinyl monomer is from 30 to 80% by weight. When the amount of the organic solvent used is out of the above range and the vinyl monomer concentration is less than 30% by weight, the polymerization rate is lowered, or the monolithic structure after polymerization is out of the range of the present invention, which is not preferable. On the other hand, if the concentration of the vinyl monomer exceeds 80% by weight, there is a possibility that the polymerization is out of control, which is not preferable.

As the polymerization initiator, a compound which generates a radical by heat and light irradiation is suitably used. The polymerization initiator is preferably oil-soluble. Specific examples of the polymerization initiator used in the invention (A1) include, for example, 2,2'-azobis(isobutyronitrile) and 2,2'-azobis(2,4-dimethyl group). Valeronitrile), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2 '-Dimethyl azobisisobutyrate, 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexane-1-carbonitrile), peroxidation Benzylmethyl group, lauric acid peroxide, potassium persulfate, ammonium persulfate, tetramethylammonium sulfonate disulfide, and the like. The amount of the polymerization initiator to be used varies greatly depending on the type of the monomer, the polymerization temperature, and the like, and can be used in a range of about 0.01 to 5% based on the total amount of the vinyl monomer and the crosslinking agent.

In the third step, the mixture obtained in the step II is subjected to polymerization under the conditions of standing and obtained by the monolith intermediate obtained in the step I, thereby obtaining a coarse monolith having a skeleton thicker than the skeleton of the monolith intermediate. A step of. The monolithic intermediate used in the third step plays a very important role in creating a monolithic structure having a novel structure in the present invention. When the vinyl monomer and the crosslinking agent are allowed to stand in a specific organic solvent in the absence of a monolithic intermediate, as disclosed in Japanese Patent Laid-Open No. Hei 7-501140, a single particle agglutination type can be obtained. Bulk organic porous body. On the other hand, when a monolithic intermediate having a continuous macroporous structure is present in the polymerization system as in the present invention, the monolithic structure after polymerization changes rapidly, and the particle agglomerated structure disappears, and the monolithic monolith is obtained. The reason for this has not been explained in detail. It is considered that in the case where a monolithic intermediate is not present, the crosslinked polymer produced by the polymerization forms a particle agglomerated structure by precipitation and precipitation, and in this case, in the polymerization system. When a porous body (intermediate) is present, the vinyl monomer and the crosslinking agent are adsorbed or distributed to the skeleton portion of the porous body by the liquid phase, and are polymerized in the porous body to obtain a monolithic skeleton. Further, although the opening diameter is narrowed by the progress of polymerization, since the total pore volume of the single intermediate body is large, for example, even if the skeleton is a rough frame, an opening diameter of an appropriate size can be obtained.

The internal volume of the reaction vessel is not particularly limited as long as the size of the monolithic intermediate is present in the reaction vessel, and may be a gap around the monolith when viewed from the top when the monolithic intermediate is placed in the reaction vessel. Alternatively, the monolithic intermediate may be placed in the reaction vessel without a gap. Among them, the aggregated monolithic block is not pressed into the reaction vessel without being pressed by the inner wall of the container, and is not strained on the single block, and the reaction raw material is not wasted, and the efficiency is better. Further, even when the internal volume of the reaction vessel is large and there is a gap around the monolith after polymerization, since the vinyl monomer or the crosslinking agent is adsorbed and distributed in the monolith intermediate, it is not in the reaction vessel. A particle agglomerate structure is formed in the gap portion.

In the step III, in the reaction vessel, the monolithic intermediate system is placed in a state of being impregnated with the mixture (solution). The compounding ratio of the mixture obtained in the step II to the monolithic intermediate is as described above, and is suitably formulated so as to be 3 to 40 times, preferably 4 to 30 times by weight based on the weight of the vinyl monomer relative to the monolithic intermediate. Thereby, a monolith having a moderate opening diameter and having a rough skeleton can be obtained. In the reaction vessel, the vinyl monomer and the crosslinking agent in the mixture are adsorbed and distributed on the standing monolithic intermediate skeleton, and polymerization is carried out in the skeleton of the monolithic intermediate.

The polymerization conditions can be selected depending on the type of the monomer and the type of the initiator. For example, using 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), benzammonium peroxide, laurel peroxide When potassium persulfate or the like is used as a starter, it may be heated and polymerized at 30 to 100 ° C for 1 to 48 hours in a sealed container under an inert gas atmosphere. By heating polymerization, the vinyl monomer adsorbed and distributed on the monolithic intermediate skeleton and the crosslinking agent are polymerized in the skeleton to thicken the skeleton. After completion of the polymerization, the contents are taken out, and the unreacted vinyl monomer and the organic solvent are removed for extraction with a solvent such as acetone to obtain a monolithic monolith.

Next, a method of introducing an ion exchange group after the monolith is produced by the above method is preferable because the porous structure of the obtained monolithic ion exchanger can be closely controlled.

The method of introducing the 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, for example, a monoblock is a styrene-divinylbenzene copolymer, and a method of sulfonating using chlorosulfuric acid, concentrated sulfuric acid, or fuming sulfuric acid; a method of uniformly introducing a radical starting group or a chain moving group into the surface of the skeleton and the inside of the skeleton to carry out graft polymerization of sodium styrene sulfonate or acrylamide-2-methylpropanesulfonic acid; A method in which a glycidyl acrylate is graft-polymerized, and a sulfonic acid group is introduced by functional group conversion. In addition, as a method of introducing a quaternary ammonium group, for example, when a monolith is a styrene-divinylbenzene copolymer, a chloromethyl group is introduced by chloromethyl methyl ether or the like, and then reacted with a tertiary amine. Method for producing a monolith by copolymerization of chloromethylstyrene and divinylbenzene, and reacting with a tertiary amine; uniformly introducing a radical starting group or a chain moving group into a skeleton in a monolith a method of graft-polymerizing N,N,N-trimethylammonium acrylate or N,N,N-trimethylammonium propyl decylamine on the surface and the inside of the skeleton; A method in which a propyl ester is subjected to graft polymerization, and a quaternary ammonium group is introduced by a functional group conversion. In addition, as a beet For example, a method in which a tertiary amine is introduced into a monolith by the above method, a monoiodoacetic acid is reacted and introduced, and the like can be mentioned. Among these methods, as for the method of introducing a sulfonic acid group, from the viewpoint of uniformly and quantitatively introducing an ion-exchange group, it is preferred to introduce a sulfonic acid into the styrene-divinylbenzene copolymer using chlorosulfuric acid. The method of introducing a quaternary ammonium group is a method of reacting with a tertiary amine by introducing a chloromethyl group by using chloromethyl methyl ether or the like in a styrene-divinylbenzene copolymer, or by borrowing chlorine A method of copolymerizing methyl styrene and divinyl benzene to produce a monolith and reacting with a tertiary amine. Further, examples of the ion-exchange group to be introduced include a cation exchange group such as a carboxylic acid group, an iminodiacetate group, a sulfonic acid group, a phosphoric acid group, or a phosphate group; a quaternary ammonium group, a tertiary amino group, and An anion exchange group of a primary amino group, a primary amino group, a polyethylenediimide group, a third fluorenyl group, a fluorenyl group or the like.

Since the first monolithic ion exchanger introduces an ion exchange group into the monolithic monolith, it is greatly swollen to, for example, 1.4 to 1.9 times the bulk of the monolith. That is, the degree of swelling is greatly increased as compared with the introduction of the ion exchange group into the conventional monolith described in Japanese Patent Laid-Open Publication No. 2002-306976. Therefore, even if the opening diameter of the rough monolith is small, the opening diameter of the monolithic ion exchanger becomes larger depending on the above magnification. Further, even if the opening diameter becomes large due to swelling, the total pore volume does not change. Therefore, the first monolithic ion exchange system has a large mechanical strength regardless of the large diameter of the opening.

<Description of the second monolithic ion exchanger>

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

The second monolithic ion exchange system is a three-dimensional continuous skeleton having an average thickness of the introduced ion exchange group of 1 to 60 μm, preferably 3 to 58 μm in a wet state of water, and an average diameter between the skeletons in a wet state of water. A co-continuous structure composed of three-dimensional continuous pores of 10 to 100 μm, preferably 15 to 90 μm, and particularly preferably 20 to 80 μm. That is, the co-continuous structure is shown in the schematic view of Fig. 6, and the continuous skeleton phase 1 is entangled with the continuous pore phase 2, and the two together have a three-dimensional continuous structure 10. Compared with the conventional continuous bubble type monolithic or particle agglutination type monolith, the continuous pores 2 have high porosity continuity and no deviation in size, so that extremely uniform ion adsorption behavior can be achieved. Moreover, since the skeleton is thick, the mechanical strength is high.

The skeleton thickness and pore diameter of the second monolithic ion exchanger are such that when the ion exchange group is introduced into a single block, the bulk of the single block is swollen, so that the thickness and the diameter of the single skeleton are larger than that of the single block. . Compared with the conventional continuous-bubble monolithic organic porous ion exchanger or the particle agglomerated monolithic organic porous ion exchanger, the continuous pores have high porosity continuity and no deviation in size, so A very uniform ion adsorption behavior is achieved. When the diameter of the three-dimensional continuous pores is less than 10 μm, the pressure loss due to the passage of the fluid becomes large, which is not preferable. If the diameter exceeds 100 μm, the contact between the treated water and the organic porous ion exchanger is insufficient, and as a result, ion exchange characteristics are obtained. The unevenness, that is, the length of the ion exchange belt becomes long, and it is easy to cause a slight leakage of the adsorbed ions, which is not preferable. Further, when the skeleton thickness is less than 1 μm, the ion exchange capacity per unit volume is lowered, and the mechanical strength is lowered, which is not preferable. On the other hand, if the skeleton thickness is too large, the uniformity of ion exchange characteristics is lost. The length of the ion exchange belt becomes long, so it is not good.

The average diameter of the pores of the continuous structure in a wet state of water is measured by a known mercury intrusion method, and the average diameter of the pores of the monolithic ion exchanger in a dry state is multiplied by the swelling ratio. Specifically, the diameter of the monolithic ion exchanger in a water-wet state is set to x2 (mm), and the monolithic ion exchanger in the wet state is dried, and the diameter of the monolithic ion exchanger obtained in the dried state is set. When the average diameter of the pores in the dry state of the monolithic ion exchanger by the mercury intrusion method is z2 (μm), the pores of the monolithic ion exchanger are wetted by water. The lower average diameter (μm) is calculated by the following formula "average diameter (μm) = z2 × (x2 / y2) of the pores of the monolithic ion exchanger in the wet state of water". Further, the average diameter of the pores in the dry state before the introduction of the ion exchange group and the drying of the monolithic ion exchanger in the water-wet state with respect to the introduction of the ion exchange group in the monolith in the dry state are known. In the case of the swelling ratio of the monolith of the state, the average diameter of the pores in the dry state is multiplied by the swelling ratio, and the average diameter of the pores of the monolithic ion exchanger in the wet state of water can also be calculated. Further, the average thickness of the skeleton of the continuous structure in a wet state of water is observed by SEM of a monolithic ion exchanger at least three times in a dry state, and the skeleton thickness in the obtained image is measured, and the average value is multiplied. The value calculated from the swelling rate. Specifically, the diameter of the monolithic ion exchanger in a water-wet state is set to x3 (mm), and the monolithic ion exchanger in the wet state is dried, and the diameter of the monolithic ion exchanger obtained in the dried state is set. For y3 (mm), at least three times of SEM observation of the monolithic ion exchanger in the dry state, and measuring the skeleton thickness in the obtained image, and setting the average value to z3 (μm), the monolithic ion exchanger The average thickness (μm) of the continuous structure skeleton in a water-wet state is the average thickness (μm) of the continuous structure skeleton of the monolithic ion exchanger in the wet state of water = z3 × (x3/y3) )" calculated. Further, the average thickness of the monolith skeleton in the dry state before the introduction of the ion exchange group and the dry state of the monolithic ion exchanger in the water-wet state with respect to the ion exchange group introduced into the monolith in the dry state are known. In the case of the swelling ratio of the monolith, the average roughness of the monolithic skeleton in the dry state is multiplied by the swelling ratio, and the average thickness of the skeleton of the monolithic ion exchanger in the wet state of water can also be calculated. Further, although the skeleton has a rod shape and a circular cross-sectional shape, it may have a different diameter cross section such as a circular cross-sectional shape. The thickness at this time is the average of the short diameter and the long diameter.

In the second monolithic ion exchanger, when the thickness of the three-dimensional continuous rod-shaped skeleton is less than 10 μm, the ion exchange capacity per unit volume is lowered, which is not preferable, and if it exceeds 100 μm, the uniformity of ion exchange characteristics is lost. Not good. The wall portion definition and measurement method of the monolithic ion exchanger are the same as those of the monolith.

Further, the second monolith ion exchange system has a total pore volume of 0.5 to 5 ml/g. When the total pore volume is less than 0.5 ml/g, the pressure loss at the time of fluid permeation becomes large, which is not preferable. Further, the amount of permeated fluid per unit sectional area becomes small, and the treatment ability is lowered, which is not preferable. On the other hand, if the total pore volume exceeds 5 ml/g, the ion exchange capacity per unit volume is lowered, which is not preferable. When the three-dimensional continuous pore size and the total pore volume are in the above range, the contact with the fluid is uniform and the contact area is large, so that the length of the ion exchange belt is shortened, and a small amount of leakage of the adsorbed ions is less likely to occur. Further, since the fluid can be transmitted under a low pressure loss, it is excellent in performance as an ion-adsorbing material. Further, the total pore volume of a monolith (monolithic monolith, monolithic, monolithic ion exchanger) is the same regardless of the dry state or the water wet state.

In addition, the pressure loss when the water passes through the second monolithic ion exchanger is the pressure loss when the water is passed through the water column at a water velocity (LV) of 1 m/h for a column filled with a porous body of 1 m (hereinafter The "pressure difference coefficient" is preferably in the range of 0.001 to 0.5 MPa/m ‧ LV, and particularly preferably 0.001 to 0.1 MPa / m ‧ LV. When the transmission speed and the total pore volume are in this range, when it is used as an ion-adsorbing material, the contact area with the water to be treated can be increased, and the water to be treated can be smoothly circulated, and sufficient mechanical strength can be obtained. Therefore, it is better.

In the second monolithic ion exchanger, the material constituting the skeleton of the co-continuous structure is an aromatic vinyl having a crosslinked structural unit of 0.3 to 5 mol%, more preferably 0.5 to 3.0 mol%, based on the total constituent unit. Base polymer and is hydrophobic. When the crosslinked structural unit is less than 0.3 mol%, the mechanical strength is insufficient, and if it exceeds 5 mol%, the structure of the porous body is likely to be separated from the co-continuous structure. The type of the aromatic vinyl polymer is not particularly limited, and examples thereof include polystyrene, poly(α-methylstyrene), polyvinyltoluene, polyvinylbenzyl chloride, and polyvinylbiphenyl. Polyvinyl naphthalene and the like. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, or a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, and It may be a blend of two or more polymers. Among these organic polymer materials, the ease of formation by the co-continuous structure, the ease of introduction of the ion exchange group and the height of the mechanical strength, and the height of the stability of the acid and alkali are preferably styrene-two. Vinyl benzene copolymer or vinyl benzyl chloride-divinyl benzene copolymer.

The second monolith ion exchanger has an ion exchange capacity of 0.3 to 5 mg equivalent/ml per unit volume in a water-wet state. In the conventional monolithic organic porous ion exchanger having a continuous macroporous structure different from the present invention as described in JP-A-2002-306976, in order to achieve a practically required low pressure loss When the opening diameter is increased, the total pore volume is also increased, so the ion exchange capacity per unit volume is lowered, and if the total pore volume is reduced in order to increase the exchange capacity per unit volume, the opening diameter becomes small. There are disadvantages of increased pressure loss. On the other hand, the continuity or uniformity of the three-dimensional continuous pores of the monolithic ion exchange system of the present invention is high, so that the pressure loss is not increased even if the total pore volume is lowered. Therefore, the ion exchange capacity per unit volume can be dramatically increased while suppressing the pressure loss to be low, and the exchange frequency of the module can be reduced. Further, the ion exchange capacity per unit weight of the second monolithic ion exchanger in the dry state is not particularly limited, but the ion exchange group is uniformly introduced into the skeleton surface of the porous body and the inside of the skeleton, and is 3~ 5 mg equivalent / g. Further, the ion exchange capacity of the porous body in which only the ion exchange group is introduced on the surface of the skeleton cannot be determined depending on the type of the porous body or the ion exchange group, but is approximately 500 μg equivalent/g.

The ion exchange group as the second monolith ion exchanger is the same as the ion exchange group of the first monolith ion exchanger, and the description thereof will be omitted. In the second monolithic ion exchanger, the introduced ion exchange groups are not only distributed on the surface of the porous body but also uniformly distributed 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 monolithic ion exchanger.

(Method for producing second monolithic ion exchanger)

The second monolithic ion exchange system is obtained by preparing a water-drop type emulsion in an oil by stirring a mixture of an oil-soluble monomer, a surfactant, and water which does not contain an ion exchange group, and then is made into an oil. The water-repellent emulsion is polymerized to obtain a monolithic organic porous intermediate having a continuous pore volume of more than 16 ml/g and 30 ml/g or less, and a step of preparing a monolithic organic porous intermediate; a cross-linking agent having at least two or more vinyl groups in the molecule of 0.3 to 5 mol% in the total oil-soluble monomer, and dissolving the aromatic vinyl monomer or the cross-linking agent but not dissolving to make the aromatic vinyl single Step II of the mixture of the organic solvent of the polymer formed by the bulk polymerization and the polymerization initiator; the mixture obtained in the step II is allowed to stand, and the monolithic organic porous intermediate obtained in the step I is In the presence of polymerization, a III step of obtaining a co-continuous structure; and an IV step of introducing an ion exchange group into the co-continuous structure obtained in the step III.

The first step of obtaining a monolithic intermediate of the second monolithic ion exchanger may be carried out according to the method described in JP-A-2002-306976.

In other words, the oil-soluble monomer which does not contain an ion-exchange group in the first step may, for example, be an ion-exchange group which does not contain a carboxylic acid group, a sulfonic acid group or a quaternary ammonium group, and has low solubility in water and is a pro- Oily monomer. Specific examples of such monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride, vinylbiphenyl, and vinylnaphthalene; Alpha-olefin such as ethylene, propylene, 1-butene or isobutylene; diene monomer such as butadiene, isoprene or chloropentadiene; vinyl chloride, vinyl bromide, vinylidene chloride and tetrafluoroethylene Halogenated olefin such as ethylene; nitrile monomer such as acrylonitrile or methacrylonitrile; vinyl ester such as vinyl acetate or vinyl propionate; methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethyl acrylate Hexyl hexyl ester, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate A (meth)acrylic monomer such as glycidyl methacrylate. Among these monomers, preferred are aromatic vinyl monomers, and examples thereof include styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride, and divinylbenzene. These monomers may be used alone or in combination of two or more. Among them, from the viewpoint of obtaining necessary mechanical strength when a large number of ion-exchange groups are introduced in the subsequent step, it is preferred to select a cross-linking single such as divinylbenzene or ethylene glycol dimethacrylate. The body is at least one component of the oil-soluble monomer, and the content thereof is 0.3 to 5 mol%, preferably 0.3 to 3 mol%, based on the total oil-soluble monomer.

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

Further, in the first step, when a water-drop type emulsion is formed in the oil, a polymerization initiator may be used as needed. The polymerization initiator is preferably a compound which generates a radical by heat and light irradiation. The polymerization initiator may be water-soluble or oil-soluble, and may, for example, be 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2 , 2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azo double Dimethyl isobutyrate, 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexane-1-carbonitrile), benzammonium peroxide, Peroxidic lauryl sulfonate, potassium persulfate, ammonium persulfate, tetramethylammonium thioformate, etc., hydrogen peroxide-ferric chloride, sodium persulfate-acid sodium sulfite, and the like.

As a method of mixing the oil-soluble monomer, the surfactant, the water, and the polymerization initiator which do not contain the ion-exchange group to form a water-drop type emulsion in the oil, in the first step of the first monolithic ion exchanger The mixing method is the same, and the description thereof is omitted.

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

The type of the polymer material of the monolithic intermediate is the same as the type of the polymer material of the monolithic intermediate of the first monolithic ion exchanger, and the description thereof is omitted.

The total pore volume of the monolithic intermediate is more than 16 ml/g and 30 ml/g or less, preferably 6 to 25 ml/g. That is, the monolithic intermediate is basically a continuous macroporous structure, but since the opening (gap hole) of the overlapping portion of the macropore and the macropore is particularly large, the skeleton having the monolithic structure is infinitely close to the two-dimensional wall surface. The construction of a one-dimensional rod-shaped skeleton. When it coexists in a polymerization system, a monolithic intermediate structure is used as a mold to form a porous body having a co-continuous structure. If the total pore volume is too small, the monolith structure obtained by polymerizing the vinyl monomer changes from a co-continuous structure to a continuous macroporous structure, which is not preferable. On the other hand, when the total pore volume is too large, the mechanical strength of the monolith obtained by polymerizing the vinyl monomer is lowered, or the ion exchange capacity per unit volume is lowered, which is not preferable. When the total pore volume of the monolith intermediate is set to a specific range of the second monolith ion exchanger, the ratio of the monomer to water can be set to about 1:20 to 1:40.

Further, in the monolith intermediate body, the average diameter of the opening (gap hole) belonging to the overlapping portion of the macropore and the macropore is 5 to 100 μm in the dry state. When the average diameter of the openings is less than 5 μm, the opening diameter of the monolith obtained by polymerizing the vinyl monomer becomes small, and the pressure loss at the time of water passage becomes large, which is not preferable. On the other hand, when it exceeds 100 μm, the opening diameter of the monolith obtained by polymerizing the vinyl monomer becomes too large, and the contact between the water to be treated and the monolithic ion exchanger is insufficient, and as a result, the adsorption property or the ion exchange property is lowered. Not good. The monolithic intermediate is preferably a structure in which the macropore size or the opening diameter is uniform, but is not limited thereto. In the uniform structure, uneven macropores having a larger size than the uniform macropores may be present in a dot shape.

In the method for producing a second monolithic ion exchanger, the second step is to prepare an aromatic vinyl monomer having at least two or more vinyl groups in one molecule and 0.3 to 5 mol% in the total oil-soluble monomer. The crosslinking agent is a step of dissolving an aromatic vinyl monomer or a crosslinking agent without dissolving a mixture of an organic solvent and a polymerization initiator which polymerizes the aromatic vinyl monomer. Further, the steps I and II are not in the order, and the step II can be performed after the step I, or the step I can be performed after the step II.

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

The amount of the aromatic vinyl monomer to be added is 5 to 50 times, preferably 5 to 40 times by weight based on the weight of the monolith intermediate which is present during the polymerization. When the amount of the aromatic vinyl monomer added is less than 5 times with respect to the porous body, the rod-shaped skeleton becomes too coarse, and the ion exchange capacity per unit volume after the introduction of the ion-exchange group becomes small, and the superior ion cannot be exhibited. Exchange ability.

The crosslinking agent used in the second step is suitably used in those having at least two polymerizable vinyl groups in the molecule and having high solubility in an organic solvent. Specific examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, and butanediol diacrylic acid. Ester and the like. These crosslinking agents can be used alone or in combination of two or more. The preferred crosslinking agent is an aromatic polyvinyl compound such as divinylbenzene, divinylnaphthalene or divinylbiphenyl, depending on the height of the mechanical strength and the stability to hydrolysis. The amount of the crosslinking agent used is preferably 0.3 to 5 mol%, particularly preferably 0.3 to 3 mol%, based on the total amount of the vinyl monomer and the crosslinking agent (total oil-soluble monomer). If the amount of the crosslinking agent used is less than 0.3 mol%, the mechanical strength of the monolith is insufficient, which is not preferable. On the other hand, if it is too much, the embrittlement of a monolith will proceed, and the softness will be lost, and the introduction amount of an ion-exchange group will fall, and it is unpreferable. Further, the amount of the crosslinking agent to be used is preferably such that it is almost equal to the crosslinking density of the monolithic intermediate which coexists when the vinyl monomer/crosslinking agent is polymerized. If the difference in the amount of use between the two is too large, the deviation of the crosslink density distribution occurs in the generated monolith, and cracks are likely to occur at the time of introduction of the ion exchange group into the reaction.

The organic solvent used in the second step is an organic solvent which dissolves the aromatic vinyl monomer or the crosslinking agent but does not dissolve the polymer formed by polymerizing the aromatic vinyl monomer, in other words, for the aromatic vinyl monomer. The polymer formed by the bulk polymerization is a poor solvent. The organic solvent is largely different depending on the type of the aromatic vinyl monomer. Therefore, it is difficult to cite a general example. However, when the aromatic vinyl monomer is styrene, methanol or ethanol is used as an organic solvent. Alcohols such as propanol, butanol, hexanol, cyclohexanol, octanol, 2-ethylhexanol, decyl alcohol, dodecanol, propylene glycol, butylene glycol; diethyl ether, butyl race Chain (poly)ethers such as sulphate, polyethylene glycol, polypropylene glycol, polybutylene glycol, etc.; chain saturated hydrocarbons such as hexane, heptane, octane, isooctane, decane, dodecane, etc. Ethyl acetate, isopropyl acetate, celecoxib acetate, ethyl propionate and the like. Again, even if it is like two A good solvent for alkane or THF or toluene-like polystyrene can be used as an organic solvent when used together with the above-mentioned poor solvent and used in a small amount. The amount of the organic solvent used is preferably such that the aromatic vinyl monomer concentration is 30 to 80% by weight. When the amount of the organic solvent used is out of the above range and the aromatic vinyl monomer concentration is less than 30% by weight, the polymerization rate is lowered, or the monolithic structure after polymerization is out of the range of the present invention, which is not preferable. On the other hand, when the aromatic vinyl monomer concentration exceeds 80% by weight, there is a possibility that the polymerization is out of control, which is not preferable.

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

In the method for producing the second monolithic ion exchanger, in the third step, the mixture obtained in the second step is subjected to polymerization under the conditions of standing, and the monolith intermediate obtained in the first step is polymerized to obtain the monolithic intermediate. The continuous macroporous structure changes to a co-continuous structure, and a step of obtaining a monolithic frame of the skeleton is obtained. The monolithic intermediate used in the third step plays a very important role in creating a monolithic structure having a novel structure in the present invention. When the vinyl monomer and the crosslinking agent are allowed to stand in a specific organic solvent in the absence of a monolithic intermediate, as disclosed in Japanese Patent Laid-Open No. Hei 7-501140, a single particle agglutination type can be obtained. Bulk organic porous body. 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 monolith structure after polymerization changes rapidly, and the particle aggregation structure disappears. A monomer that is continuously constructed. The reason for this has not been explained in detail. It is considered that in the case where a monolithic intermediate is not present, the crosslinked polymer produced by the polymerization forms a particle agglomerated structure by precipitation and precipitation, and in this case, in the polymerization system. When a porous body (intermediate) having a large total pore volume is present, the vinyl monomer and the crosslinking agent are adsorbed or distributed to the skeleton portion of the porous body by a liquid phase, and polymerization is carried out in the porous body to form a composition. The skeleton of the monolithic structure is changed from a two-dimensional wall surface to a one-dimensional rod-shaped skeleton to form a monolithic organic porous body having a co-continuous structure.

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

In the step III, in the reaction vessel, the monolithic intermediate system is placed in a state of being impregnated with the mixture (solution). The compounding ratio of the mixture obtained in the step II to the monolithic intermediate is as described above, and is suitably formulated so as to be 5 to 50 times, preferably 5 to 40 parts by weight based on the weight of the aromatic vinyl monomer relative to the monolithic intermediate. Times. Thereby, a monolithic structure in which the pores of a moderate size are three-dimensionally continuous and the rough skeleton is three-dimensionally continuous can be obtained. In the reaction vessel, the aromatic vinyl monomer and the crosslinking agent in the mixture are adsorbed and distributed on the standing monolithic intermediate skeleton, and polymerization is carried out in the skeleton of the monolithic intermediate.

The basic structure of a monolith having a co-continuous structure is a three-dimensional continuous skeleton having an average thickness of 0.8 to 40 μm in a dry state, and a three-dimensional continuous pore having a diameter of 8 to 80 μm between the skeletons. The average diameter of the three-dimensional continuous pores is determined by mercury intrusion method, and can be obtained according to the maximum value of the pore distribution curve. The thickness of the monolithic skeleton was measured by at least three SEM observations, and the average thickness of the skeleton in the obtained image was measured. Further, the monolithic structure having a co-continuous structure has a total pore volume of 0.5 to 5 mg/g.

The polymerization conditions are the same as those of the polymerization conditions of the first step of the first monolithic ion exchanger, and the description thereof is omitted.

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

Since the second monolithic ion exchanger introduces an ion exchange group into a monolithic structure, it is greatly swollen to, for example, 1.4 to 1.9 times the monolith. Further, even if the pore diameter becomes large due to swelling, the total pore volume does not change. Therefore, the second monolithic ion exchange system is extremely large in size regardless of the three-dimensional continuous pore size, and has high mechanical strength due to the thick skeleton. Further, since the skeleton is thick, the ion exchange capacity per unit volume in the wet state is increased, and the water to be treated can be passed through water for a long time according to the low pressure and the large flow rate, and can be suitably used as an ion adsorption module.

[Invention (A2)]

In the ion adsorption module according to the embodiment of the invention (A2), the third monolithic ion exchanger is filled in the container. In the specification of the invention (A2), the "monolithic organic porous body" may be simply referred to as "composite monolithic body", and the "monolithic organic porous ion exchanger" may be simply referred to as "composite monolithic ion exchange". The "monolithic organic porous intermediate" is simply referred to as "monolithic intermediate".

<Description of composite monolithic ion exchanger>

The composite monolithic ion exchange system is obtained by introducing an ion exchange group into a composite monolith, and is an organic porous body composed of a continuous skeleton phase and a continuous pore phase, and is adhered to the surface of the organic porous skeleton. a composite structure of a plurality of particle bodies having a diameter of 4 to 40 μm; or an organic porous body composed of a continuous skeleton phase and a continuous pore phase, and a size formed on the surface of the organic porous skeleton skeleton is 4~ a composite structure of a plurality of protrusions of 40 μm; the average diameter of the pores in the wet state of water is 10 to 150 μm, the total pore volume is 0.5 to 5 ml/g, and the ion exchange capacity per unit volume in the wet state is 0.2 mg. Above the equivalent/ml, the ion exchange groups are uniformly distributed in the composite structure. Further, in the present invention (A2), the "particle body" and the "protrusion body" may be collectively referred to as "particle body or the like".

The continuous framework phase of the organic porous body and the continuous pore phase (dry body) can be observed by SEM image. The basic structure of the organic porous body may, for example, be a continuous macroporous structure or a co-continuous structure. The skeleton phase of the organic porous body is a columnar continuous body, a concave wall surface continuous body or a composite of these, and has a shape which is significantly different from a particle shape or a protrusion shape.

A preferred structure of the organic porous material is, for example, a bubble-like macropores which overlap with each other in a wetted state, and a continuous macroporous structure having an opening having an average diameter of 30 to 150 μm and an average of water wet state. A three-dimensional continuous skeleton having a thickness of 1 to 60 μm and a co-continuous structure composed of three-dimensional continuous pores having an average diameter of 10 to 100 μm in a water-wet state between the skeletons.

The average opening diameter of the composite monolithic ion exchanger having a continuous macroporous structure is obtained by introducing an ion exchange group into the composite monolith, and since the composite monolith is swollen as a whole, the average diameter of the composite monolith is larger than that of the dry composite. The opening has a large average diameter. If the average diameter of the opening is less than 30 μm, the pressure loss during the passage of water becomes large, which is not preferable. If the average diameter of the opening is too large, the contact between the fluid and the monolithic ion exchanger is insufficient, and as a result, the ion exchange characteristics are lowered. It is not good.

In a composite monolithic ion exchanger having a co-continuous structure, if the diameter of the three-dimensional continuous pores is less than 10 μm, the pressure loss during fluid permeation becomes large, which is not preferable, and if it exceeds 100 μm, the fluid exchanges with the composite monolith. Insufficient contact between the bodies, as a result, the ion exchange characteristics are not uniform, that is, the length of the ion exchange band becomes long, and the adsorbed ions are liable to cause a small amount of leakage, which is not preferable.

In the composite monolithic ion exchanger having a co-continuous structure, if the average diameter of the three-dimensional continuous skeleton is less than 1 μm, the ion exchange capacity per unit volume is lowered, which is not preferable, and if it exceeds 60 μm, the ion exchange property is lost. Uniformity, so it is not good.

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

The average diameter of the pores of the composite monolithic ion exchanger in the wet state of water is preferably from 10 to 120 μm. When the organic porous body constituting the composite monolithic ion exchanger is a continuous macroporous structure, the pore diameter of the composite monolithic ion exchanger is preferably from 30 to 120 μm, and the organic porous body constituting the composite monolithic ion exchanger In the case of a continuous continuous structure, the pore diameter of the composite monolithic ion exchanger is preferably from 10 to 90 μm.

In the composite monolithic ion exchanger of the invention (A2), the particle diameter and the size of the protrusion in the water-wet state are 4 to 40 μm, preferably 4 to 30 μm, and particularly preferably 4 to 20 μm. Further, in the invention (A2), in the case where both the particle body and the protrusion are observed on the surface of the skeleton, a person who observes the granular shape is referred to as a particle body, and a person who cannot be called a granular shape is referred to as a protrusion. . Fig. 29 is a schematic cross-sectional view showing a projection. As shown in (A) to (E) of FIG. 29, the protrusions protruding from the skeleton surface 61 are the protrusions 62, and the protrusions 62 may be, for example, as close as the protrusions 62a shown in (A). The shape of the protrusion 62b is a hemispherical shape as shown in (B); the protrusion 62c as shown in (C) is raised like a skeleton surface. Further, as in the case of the protrusion 61, as shown by the protrusion 62d shown in (D), the plane direction of the skeleton surface 61 is longer in the vertical direction with respect to the skeleton surface 61, or as (E) The protrusion 62e shown has a shape that protrudes in the plural direction. Further, the size of the protrusions was judged by the SEM image at the time of SEM observation, and the width in the SEM image of each protrusion means the length of the largest portion.

In the composite monolithic ion exchanger of the invention (A2), the proportion of the particles or the like in the water-wet state in the composite monolithic ion exchanger is 70% or more, preferably 80% or more. In the total particle size, the proportion of the particles in the wet state of 4 to 40 μm is a particle size of 4 to 40 μm in the wet state. Number ratio. Further, 40% or more, preferably 50% or more of the surface of the skeleton phase is covered with the total particles or the like. Further, the particle body is equal to the coating ratio of the surface of the skeleton layer, and refers to the ratio of the area on the SEM image when the surface is observed by SEM, that is, the ratio of the area with respect to the surface when viewed from the top. When the size of the particles covering the wall surface or the skeleton is out of 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 becomes small, which is not preferable. In addition, the total particle body and the like also include particles and protrusions in a size range other than the particle body of 4 to 40 μm in a wet state, and all the particle bodies and protrusions formed on the surface of the skeleton layer.

The particle body attached to the surface of the skeleton of the composite monolithic ion exchanger is equal to the diameter or size in the wet state of water, and is the diameter or size of the particle body or the like obtained by SEM image observation of the composite monolithic ion exchanger in a dry state. The value calculated by multiplying the swelling ratio when the dry state is in a wet state, or the diameter or size of the particle body or the like obtained by observing the SEM image of the composite monolith in a dry state before introduction of the ion exchange group, multiply the ion The value calculated by the swelling ratio before and after the introduction of the exchange group. Specifically, the composite monolithic ion exchanger having a water-wet state is set to x4 (mm), and the composite monolithic ion exchanger in a water-wet state is dried, and the obtained composite monolithic ion exchanger in a dry state is obtained. The diameter of the composite monolithic ion exchanger in the dry state is set to z4 (μm) in the SEM image when the diameter or size of the particle body in the SEM image is observed by SEM, and the composite form of the water-wet state is y4 (mm). The diameter or size (μm) of the bulk ion exchanger is calculated from the following formula "diameter or size (μm) = z4 × (x4 / y4) of the particle body of the composite monolithic ion exchanger in a water-wet state. Further, the diameter or size of all the particles and the like observed in the SEM image of the composite monolithic ion exchanger in a dry state was measured, and based on this value, the total particle size in the SEM image of one field of view was calculated to be equal to the diameter in the wet state of water. Or size. The SEM observation of the composite monolithic ion exchanger in this dry state was carried out at least three times, and the total particle size in the SEM image was calculated to be equal to the diameter or size in the wet state of the water in the SEM image, and it was confirmed whether the diameter or the size was observed to be 4~. When the 40 μm particle body or the like is confirmed in the total field of view, it is determined that a particle body having a diameter or a size of 4 to 40 μm in a water-wet state is formed on the skeleton surface of the composite monolith ion exchanger. Further, the total particle size in the SEM image per one field of view is equal to the diameter or size in the wet state of the water, and the particle body of 4 to 40 μm in the wet state of water is obtained in the total particle body or the like in each of the fields of view. In the total particle size, when the ratio of the particles of 4 to 40 μm in the wet state of water is 70% or more, it is judged to be formed in the composite monolithic ion exchanger. In the total particle body or the like on the surface of the skeleton, the proportion of the particles of 4 to 40 μm in the wet state of water is 70% or more. Further, according to the above, the ratio of the total particle body in the SEM image on the surface of the skeleton layer in each field of view is obtained, and when the total particle size is equal to or greater than 40% of the surface of the skeleton layer in the total field of view, it is judged The ratio of the surface of the skeleton layer of the composite monolithic ion exchanger to the total particle body or the like is 40% or more. Further, it is known that the diameter or size of the particle body of the composite monolith in a dry state before introduction of the ion exchange group, and the composite monolithic ion exchanger in a water-wet state are introduced into the composite monolith in a dry state thereof. In the case of the swelling ratio of the composite monolith in the dry state at the time of exchange, the diameter or the size of the particle body of the composite monolith in the dry state is multiplied by the swelling ratio, and the particles of the composite monolithic ion exchanger in the water wet state are calculated. The diameter or size of the body; as described above, the diameter or size of the particle body of the composite monolithic ion exchanger in the wet state of water, and the particle body of 4 to 40 μm in the wet state of the water can be occupied in the total particle body or the like. The proportion of the particle body is equal to the proportion of the surface of the skeleton layer.

If the coating ratio of the particle body to the surface of the skeleton phase is less than 40%, the effect of improving the contact efficiency between the fluid and the skeleton interior and the skeleton surface of the composite monolithic ion exchanger is small, and the uniformity of the ion exchange behavior is impaired. Not good. As a method of measuring the coverage of the above-mentioned particle body or the like, for example, a method of analyzing an image of a SEM image of a composite monolith (dry body) can be mentioned.

In addition, the total pore volume of the composite monolithic ion exchanger is the same as the total pore volume of the composite monolith. That is, even if the opening diameter is increased by the introduction of the ion exchange group in the composite monolith, the pore diameter is hard, and the total pore volume is hardly changed. When the total pore volume is less than 0.5 ml/g, the pressure loss at the time of water passing becomes large, which is not preferable. On the other hand, when the total pore volume exceeds 5 ml/g, the ion exchange capacity per unit volume is lowered, which is not preferable. Further, the total pore volume of the composite monolith (monolithic intermediate, composite monolith, composite monolithic ion exchanger) is the same regardless of the dry state or the water wet state.

The composite monolithic 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 unit volume in a water-wet state. If the ion exchange capacity per unit volume is less than 0.2 mg equivalent/ml, the amount of treated water to be treated before the failure becomes small, and the exchange frequency of the module becomes high, which is not preferable. Further, the ion exchange capacity per unit weight of the composite monolithic ion exchanger of the present invention (A2) in a dry state is not particularly limited, but the ion exchange group is uniformly introduced into the skeleton surface and the skeleton inside the composite monolith. And it is 3~5mg equivalent/g. Further, the ion exchange capacity of the organic porous material in which only the ion exchange group is introduced on the surface of the skeleton cannot be determined depending on the type of the organic porous material or the ion exchange group, but is approximately 500 μg equivalent/g.

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

In the composite monolithic ion exchanger of the invention (A2), the introduced ion exchange group, the definition of the uniform distribution, the distribution of the ion exchange group, and the technical significance of the ion exchange group uniformly distributed inside the skeleton phase are The same as the invention (A1).

The composite monolithic ion exchange system of the present invention (A2) has a thickness of 1 mm or more and is distinguished from a film-like porous body. If the thickness is less than 1 mm, the ion exchange capacity per sheet of the porous body is extremely lowered, which is not preferable. The thickness of the composite monolithic ion exchanger is preferably from 3 mm to 1000 mm. Further, the composite monolithic ion exchange system skeleton of the present invention has a basic structure of a continuous pore structure, and thus has high mechanical strength.

The composite monolithic ion exchange system of the invention (A2) comprises the steps of: stirring an oil-soluble monomer not containing an ion exchange group, a first crosslinking agent having at least two vinyl groups in one molecule, and an interface; A mixture of an active agent and water is used to prepare a water-drop type emulsion in oil, and then a water-drop type emulsion in the oil is polymerized to obtain a monolithic organic porous intermediate having a continuous pore structure of a total pore volume of 5 to 30 ml/g. I step; preparing a second monomer having a vinyl monomer, a second crosslinking agent having at least two or more vinyl groups in one molecule, dissolving the vinyl monomer or the second crosslinking agent, but not dissolving to polymerize the vinyl monomer And a step of the mixture of the organic solvent of the polymer and the polymerization initiator; the mixture obtained in the step II is allowed to stand, and in the presence of the monolithic organic porous intermediate obtained in the step I Step III of carrying out the polymerization; and IV step of introducing an ion exchange group into the monolithic organic porous body obtained in the step III; in the production of the monolithic organic porous body, by the following (1)~( 5), in the condition of satisfying at least 1 condition Step II or III be obtained by:

(1) The polymerization temperature in the step III is a temperature at least 5 ° C lower than the 10-hour half-life temperature of the polymerization initiator;

(2) The mole % of the second crosslinking agent used in the second step is twice or more the mole % of the first crosslinking agent used in the step I;

(3) The vinyl single system used in the step II and the oil-soluble monomer used in the first step are vinyl monomers of different configurations;

(4) The organic solvent used in the step II is a polyether having a molecular weight of 200 or more;

(5) The concentration of the vinyl monomer used in the step II is 30% by weight or less in the mixture of the step II.

(Manufacturing method of monolithic intermediate)

In the method for producing a composite monolith according to the invention (A2), the first step is by stirring an oil-soluble monomer which does not contain an ion exchange group, and a first crosslinking agent having at least two or more vinyl groups in one molecule, and an interface. A mixture of an active agent and water is used to prepare a water-drop type emulsion in oil, and then a water-drop type emulsion in the oil is polymerized to obtain a monolithic intermediate having a continuous pore structure of a total pore volume of 5 to 30 ml/g. The first step of obtaining a monolithic intermediate can be carried out according to the method described in JP-A-2002-306976.

The oil-soluble monomer which does not contain an ion-exchange group is, for example, a monomer which does not contain an ion exchange group such as a carboxylic acid group, a sulfonic acid group or a quaternary ammonium group, and has low solubility in water and is lipophilic. Preferred examples of such monomers include styrene, α-methylstyrene, vinyltoluene, vinylbenzyl chloride, divinylbenzene, ethylene, propylene, isoprene, and dibutyl. Alkene, ethylene glycol dimethacrylate, and the like. These monomers may be used alone or in combination of two or more.

The first crosslinking agent having at least two or more vinyl groups in one molecule may, for example, be divinylbenzene, divinylnaphthalene, divinylbiphenyl or ethylene glycol dimethacrylate. These crosslinking agents may be used alone or in combination of two or more. The preferred first crosslinking agent is an aromatic polyvinyl compound such as divinylbenzene, divinylnaphthalene or divinylbiphenyl from the viewpoint of mechanical strength. The amount of the first crosslinking agent used is 0.3 to 10 mol%, preferably 0.3 to 5 mol%, more preferably 0.3 to 3 mol%, based on the total amount of the vinyl monomer and the first crosslinking agent. . When 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, when it exceeds 10 mol%, the embrittlement of a monolith proceeds, the flexibility is lost, and the introduction amount of the ion exchange group is reduced, which is not preferable.

The surfactant is not particularly limited as long as it forms a water-drop type (W/O) emulsion when the oil-soluble monomer having no ion-exchange group is mixed with water, and sorbitan monooleate can be used. , sorbitan monolaurate, sorbitan monostearate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene nonylphenyl ether, polyoxyethylene stearyl a nonionic surfactant such as ether or polyoxyethylene sorbitan monooleate; an anionic surfactant such as potassium oleate, sodium dodecylbenzenesulfonate or dioctylsulfonate succinate; a cationic surfactant such as stearyl dimethyl ammonium chloride; lauryl dimethyl beet Etc. Sexual surfactants. These surfactants can be used alone or in combination of two or more. Moreover, the water-drop type emulsion in oil refers to an emulsion in which an oil phase is a continuous phase in which water droplets are dispersed. The amount of the surfactant added is greatly changed depending on the type of the oil-soluble monomer and the target size of the emulsified particles (macropores), so that it cannot be said to be inferior to the oil-soluble monomer and interface. The total amount of active agents is selected in the range of about 2 to 70%.

Further, in the first step, when a water-drop type emulsion is formed in the oil, a polymerization initiator may be used as needed. The polymerization initiator is preferably a compound which generates a radical by heat and light irradiation. The polymerization initiator may be water-soluble or oil-soluble, and may, for example, be 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2 , 2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azo double Dimethyl isobutyrate, 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexane-1-carbonitrile), benzammonium peroxide, Peroxidic lauryl sulfonate, potassium persulfate, ammonium persulfate, hydrogen peroxide-ferric chloride, sodium persulfate-acid sodium sulfite, and the like.

The method of mixing the oil-soluble monomer, the first crosslinking agent, the surfactant, the water, and the polymerization initiator which do not contain an ion-exchange group to form a water-drop type emulsion is not particularly limited, and can be used. a method of mixing all the components at one time; water-soluble monomer, first crosslinking agent, surfactant, oil-soluble component belonging to oil-soluble polymerization initiator, water-soluble or water-soluble polymerization initiator A method in which the components are uniformly dissolved, and the components are mixed. The mixing device for forming the emulsion is not particularly limited, and a suitable apparatus for obtaining the particle size of the target emulsion may be selected using a usual mixer, homogenizer, high-pressure homogenizer or the like. Further, the mixing conditions are not particularly limited, and the number of stirring rotations or the stirring time at which the target emulsion particle diameter can be obtained can be arbitrarily set.

The monolithic intermediate system obtained in the I step has a continuous macropore structure. When it is coexisted in the polymerization system, the monolithic intermediate structure is used as a mold to form a particle body or the like on the surface of the skeleton phase of the continuous macroporous structure, or to form a particle body on the surface of the skeleton phase of the co-continuous structure. . Further, the monolithic intermediate system has an organic polymer material having a crosslinked structure. The crosslinking density of the polymer material is not particularly limited, and is preferably from 0.3 to 10 mol%, more preferably from 0.3 to 5 mol%, based on the total constituent unit of the polymer material. If the crosslinked structural unit is less than 0.3 mol%, it is not good because of insufficient mechanical strength. On the other hand, when it exceeds 10 mol%, the embrittlement of the porous body proceeds, and the softness is lost, which is not preferable.

The total pore volume of the monolithic intermediate is 5 to 30 ml/g, preferably 6 to 28 ml/g. When the total pore volume is too small, the total pore volume of the monolith obtained by polymerizing the vinyl monomer becomes too small, and the pressure loss at the time of fluid permeation becomes large, which is not preferable. On the other hand, when the total pore volume is too large, the structure of the monolith obtained by polymerizing the vinyl monomer tends to be uneven, and the structure collapses as the case may be, which is not preferable. When the total pore volume of the monolith intermediate is set to the above numerical range, the ratio (weight) of the monomer to water can be set to about 1:5 to 1:35.

If the ratio of the monomer to water is about 1:5 to 1:20, a continuous macroporous structure having a total pore volume of 5 to 16 ml/g for a single intermediate can be obtained, and can be obtained via III. The organic monolithic body of the composite monolith obtained in the step is a continuous macroporous structure. Further, when the blending ratio is set to about 1:20 to 1:35, a continuous pore structure having a total pore volume of a single intermediate of more than 16 ml/g and 30 ml/g or less can be obtained, and is obtained by III. The composite monolithic organic porous body obtained in the step is a co-continuous structure.

Further, the average diameter of the opening (gap hole) in which the monolithic intermediate system belongs to the overlapping portion of the macropore and the macropore is 20 to 100 μm in the dry state. When the average diameter of the openings is less than 20 μm, the opening diameter of the monolith obtained by polymerizing the vinyl monomer becomes too small, and the pressure loss at the time of water passage becomes large, which is not preferable. On the other hand, when it exceeds 100 μm, the opening diameter of the monolith obtained by polymerizing the vinyl monomer becomes too large, and the contact between the water to be treated and the monolithic ion exchanger is insufficient, and as a result, the removal efficiency of the ion component is lowered. Not good. The monolithic intermediate is preferably a structure in which the macropore size or the opening diameter is uniform, but is not limited thereto. In the uniform structure, uneven macropores having a larger size than the uniform macropores may be present in a dot shape.

(Manufacturing method of composite monolith)

The second step is a method of preparing a vinyl monomer, a second crosslinking agent having at least two or more vinyl groups in one molecule, and dissolving the vinyl monomer or the second crosslinking agent without dissolving the vinyl monomer. A step of forming a mixture of an organic solvent of a polymer and a polymerization initiator. Further, the steps I and II are not in the order, and the step II can be performed after the step I, or the step I can be performed after the step II.

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

The amount of the vinyl monomer added is 3 to 40 times, preferably 4 to 30 times by weight based on the monolithic intermediate which is present during the polymerization. When the amount of the vinyl monomer added is less than 3 times that of the porous body, the particle body cannot be formed on the formed monolith skeleton, and the ion exchange capacity per unit volume after the introduction of the ion exchange group becomes small, so good. On the other hand, when the amount of the vinyl monomer added exceeds 40 times, the opening diameter becomes small, and the pressure loss at the time of water passage becomes large, which is not preferable.

The second crosslinking agent used in the second step is suitably used in those having at least two polymerizable vinyl groups in the molecule and having high solubility in an organic solvent. Specific examples of the second crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, and butylene glycol. Diacrylate and the like. These second crosslinking agents may be used alone or in combination of two or more. The second crosslinking agent is preferably an aromatic polyvinyl compound such as divinylbenzene, divinylnaphthalene or divinylbiphenyl, depending on the height of the mechanical strength and the stability to hydrolysis. The amount of the second crosslinking agent used is preferably from 0.3 to 20 mol%, particularly preferably from 0.3 to 10 mol%, based on the total amount of the vinyl monomer and the second crosslinking agent. If the amount of the crosslinking agent used is less than 0.3 mol%, the mechanical strength of the monolith is insufficient, which is not preferable. On the other hand, when it exceeds 20 mol%, the embrittlement of a monolith is lost and the flexibility is lost, and the problem that the introduction amount of the ion exchange group is reduced is not preferable.

The organic solvent used in the second step is an organic solvent which dissolves the vinyl monomer or the second crosslinking agent but does not dissolve the polymer formed by polymerizing the vinyl monomer, in other words, polymerizes the vinyl monomer to form The polymer is a poor solvent. The organic solvent is largely different depending on the type of the vinyl monomer. Therefore, it is difficult to cite a general specific example. However, when the vinyl monomer is styrene, methanol, ethanol, propanol or butyl as an organic solvent is exemplified. Alcohols such as alcohol, hexanol, cyclohexanol, octanol, 2-ethylhexanol, decyl alcohol, dodecanol, propylene glycol, butylene glycol; diethyl ether, butyl 赛路苏, poly Chain (poly)ethers such as diol, polypropylene glycol, polybutylene glycol, etc.; chain saturated hydrocarbons such as hexane, heptane, octane, isooctane, decane, dodecane, etc.; ethyl acetate , esters of isopropyl acetate, celecoxib acetate, ethyl propionate, and the like. Again, even if it is like two A good solvent for alkane or THF or toluene-like polystyrene can be used as an organic solvent when used together with the above-mentioned poor solvent and used in a small amount. The amount of the organic solvent used is preferably such that the concentration of the vinyl monomer is 5 to 80% by weight. When the amount of the organic solvent used is out of 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 concentration of the vinyl monomer exceeds 80% by weight, there is a possibility that the polymerization is out of control, which is not preferable.

As the polymerization initiator, a compound which generates a radical by heat and light irradiation is suitably used. The polymerization initiator is preferably oil-soluble. Specific examples of the polymerization initiator used in the present invention include 2,2'-azobis(isobutyronitrile) and 2,2'-azobis(2,4-dimethylvaleronitrile). , 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-even Dimethyl bis-isobutyrate, 4,4'-azobis(4-cyanovaleric acid), 1,1'-azobis(cyclohexane-1-carbonitrile), benzammonium peroxide Base, peroxidic lauryl sulfhydryl, tetramethylammonium sulfonate disulfide, and the like. The amount of the polymerization initiator to be used varies greatly depending on the type of the monomer, the polymerization temperature, and the like, and can be used in a range of about 0.01 to 5% based on the total amount of the vinyl monomer and the second crosslinking agent.

The third step is a step of obtaining a composite monoblock by subjecting the mixture obtained in the second step to a static state and carrying out polymerization in the presence of the monolith intermediate obtained in the first step. The monolithic intermediate used in the third step plays a very important role in creating a monolith having a novel structure in the invention (A2). Particle agglutination can be obtained by static polymerization of a vinyl monomer and a second crosslinking agent in a specific organic solvent in the absence of a monolithic intermediate as disclosed in Japanese Patent Laid-Open No. Hei 7-501140. A monolithic organic porous body of the type. On the other hand, when a monolithic intermediate having a continuous macroporous structure is present in the polymerization system as in the present invention, the monolithic structure after polymerization changes rapidly, and the particle agglomerate structure disappears, and the monolith having the specific skeleton structure is obtained. .

The internal volume of the reaction vessel is not particularly limited as long as the size of the monolithic intermediate is present in the reaction vessel, and may be a gap around the monolith when viewed from the top when the monolithic intermediate is placed in the reaction vessel. Alternatively, the monolithic intermediate may be placed in the reaction vessel without a gap. Wherein, the composite monolith after polymerization is not pressed into the reaction vessel without being pressed by the inner wall of the container, and the strain is not generated on the composite monolith, and the reaction raw material is not wasted, and the efficiency is better. Further, even when the internal volume of the reaction vessel is large and there is a gap around the composite monolith after polymerization, since the vinyl monomer or the crosslinking agent is adsorbed and distributed in the monolith intermediate, it is not in the reaction vessel. The gap portion generates a particle agglomerate structure.

In the step III, in the reaction vessel, the monolithic intermediate system is placed in a state of being impregnated with the mixture (solution). The compounding ratio of the mixture obtained in the step II to the monolith intermediate is as described above, and is suitably formulated to be 3 to 40 times, preferably 4 to 30 times by weight based on the weight of the vinyl monomer. . Thereby, a monolith having a moderate opening diameter and having a specific skeleton can be obtained. In the reaction vessel, the vinyl monomer and the crosslinking agent in the mixture are adsorbed and distributed on the standing monolithic intermediate skeleton, and polymerization is carried out in the skeleton of the monolithic intermediate.

The polymerization conditions can be selected depending on the type of the monomer and the type of the initiator. For example, using 2,2'-azobis(isobutyronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), benzammonium peroxide, laurel peroxide When it is used as a starter, it can be heated and polymerized at 20 to 100 ° C for 1 to 48 hours in a sealed container under an inert gas atmosphere. By heating polymerization, a vinyl monomer adsorbed and distributed on a single intermediate skeleton and a crosslinking agent are polymerized in the skeleton to form the specific skeleton structure. After the completion of the polymerization, the content is taken out, and the unreacted vinyl monomer and the organic solvent are removed for extraction with a solvent such as acetone to obtain a monolith having a specific skeleton structure.

In the production of the above composite monolith, the characteristic structure belonging to the present invention (A2) can be produced by performing the second step or the third step under the conditions of the following (1) to (5) under at least one condition. A composite monolith such as a particle body is formed on the surface of the skeleton.

(1) The polymerization temperature in the step III is a temperature at least 5 ° C lower than the 10-hour half-life temperature of the polymerization initiator;

(2) The mole % of the second crosslinking agent used in the second step is twice or more the mole % of the first crosslinking agent used in the step I;

(3) The vinyl single system used in the step II and the oil-soluble monomer used in the first step are vinyl monomers of different configurations;

(4) The organic solvent used in the step II is a polyether having a molecular weight of 200 or more;

(5) The concentration of the vinyl monomer used in the step II is 30% by weight or less in the mixture of the step II.

(Description of (1) above)

The 10-hour half-life temperature is the characteristic value of the polymerization initiator, and if the polymerization initiator used is determined, the 10-hour half-life temperature is known. Further, if there is a required half-time half-life temperature, a polymerization initiator equivalent thereto can be selected. In the third step, by lowering the polymerization temperature, the polymerization rate can be lowered, and a particle body or the like can be formed on the surface of the skeleton phase. The reason for this is considered to be that the monomer concentration inside the skeleton phase of the monolithic intermediate is slowed down, and the distribution speed of the monomer from the liquid phase portion to the monolithic intermediate is lowered, so that the remaining monomer is in the skeleton layer of the monolithic intermediate. The vicinity of the surface is concentrated and polymerized there.

The preferred polymerization temperature is a temperature 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. However, the lower the temperature, the lower the polymerization rate, and the polymerization time is longer than practically unacceptable. Therefore, it is preferred to set the polymerization temperature to a half-life temperature of 10 hours. Low range of 5~20 °C.

(Description of (2))

When the molar % of the second crosslinking agent used in the second step is set to be twice or more the molar % of the first crosslinking agent used in the first step, the composite monolith of the present invention can be obtained. The reason for this is considered to be that the polymer formed by the impregnation polymerization is excluded from the surface of the skeleton phase of the monolithic intermediate because phase separation occurs due to a decrease in the compatibility between the monolith intermediate and the polymer formed by the impregnation polymerization. Concavities and convexities such as particle bodies are formed on the surface of the skeleton phase. Further, the molar % of the crosslinking agent is the crosslinking density molar %, which means the amount of the crosslinking agent (% by mole) based on the total amount of the vinyl monomer and the crosslinking agent.

The upper limit of the second crosslinking agent molar % used in the second step is not particularly limited, and if the second crosslinking agent molar % is remarkably large, cracks in the monolith after polymerization and embrittlement of the monolith are caused. The loss of flexibility and the reduction of the introduction amount of the ion exchange group are not preferable. Preferably, the second crosslinking agent is in a multiple of 2 to 10 times the mole %. On the other hand, even if the second crosslinking agent mol% used in the second step is set to be twice or more the molar ratio of the first crosslinking agent used in the first step, no particles are formed on the surface of the skeleton phase. The composite monolith of the present invention could not be obtained.

(Description of (3))

When the vinyl monomer used in the second step is a vinyl monomer having a different structure from the oil-soluble monomer used in the first step, the composite monolith of the invention (A2) can be obtained. For example, styrene and vinylbenzyl chloride, even if the structure of the vinyl monomer is only slightly different, a composite monolith having a particle body or the like formed on the surface of the skeleton phase is formed. In general, the two homopolymers obtained from two monomers which are only slightly different in construction are incompatible with each other. Therefore, if a monomer having a different structure from the monomer used in the formation of the monolith intermediate in the I step, that is, a monomer other than the monomer used in the formation of the monolith intermediate in the first step, is used in the step II, And the polymerization is carried out in the third step. Although the monomers used in the step II are uniformly distributed or impregnated in the monolith intermediate, when the polymerization is carried out to form a polymer, the formed polymer is incompatible with the monolith intermediate. Therefore, phase separation occurs, and the generated polymer is excluded to the vicinity of the surface of the skeleton phase of the monolithic intermediate, and irregularities such as particle bodies are formed on the surface of the skeleton phase.

(Description of (4))

When the organic solvent used in the second step is a polyether having a molecular weight of 200 or more, the composite monolith of the present invention can be obtained. The affinity between the polyether and the monolith intermediate is high, especially the low molecular weight cyclic polyether is a good solvent for polystyrene, while the low molecular weight chain polyether is not a good solvent but still has considerable affinity. Sex. However, when the molecular weight of the polyether is increased, the affinity with the monolith intermediate is rapidly lowered, and the affinity with the monolith intermediate is hardly exhibited. If such a solvent lacking in affinity is used in an organic solvent, the diffusion of the monomer into the interior of the monolithic intermediate skeleton is hindered, and as a result, the monomer is polymerized only in the vicinity of the surface of the monolithic intermediate skeleton, so that the surface of the skeleton phase A particle body or the like is formed, and irregularities are formed on the surface of the skeleton.

When the molecular weight of the polyether is 200 or more, the upper limit thereof is not particularly limited. If the molecular weight is too high, the viscosity of the mixture prepared in the second step becomes high, and it is difficult to impregnate the inside of the monolithic intermediate, which is not preferable. The preferred molecular weight of the polyether is preferably from 200 to 100,000, particularly preferably from 200 to 10,000. Further, the terminal structure of the polyether may be an unmodified hydroxyl group, may be etherified with an alkyl group such as a methyl group or an ethyl group, or may be esterified with acetic acid, oleic acid, lauric acid, stearic acid or the like.

(Description of (5))

When the concentration of the vinyl monomer used in the second step is 30% by weight or less in the mixture of the second step, the composite monolith of the invention (A2) can be obtained. When the monomer concentration is lowered by the second step, the polymerization rate is lowered. For the same reason as in the above (1), a particle body or 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. The lower the monomer concentration, the lower the polymerization rate, and the polymerization time becomes longer than practically unacceptable. Therefore, it is preferred to set the monomer concentration to 10 to 30 weight. %.

The composite monolith obtained in the third step is an organic porous body composed of a continuous skeleton phase and a continuous pore phase, and a plurality of particle bodies fixed on the surface of the skeleton of the organic porous body or formed on the organic porous material. A composite structure of a plurality of protrusions on the surface of a skeleton of a body. The continuous framework phase and continuous pore phase of the organic porous body can be observed by SEM image. The basic structure of the organic porous body is a continuous macroporous structure or a co-continuous structure.

The continuous macroporous structure in the composite monolith has a bubble-like macropores which overlap with each other. The overlapping portion becomes an opening having an average diameter of 20 to 100 μm in a dry state, and the co-continuous structural system of the composite monolith has an average thickness of A three-dimensional continuous skeleton of 0.8 to 40 μm in a dry state; and a three-dimensional continuous pore having an average diameter of 8 to 80 μm under drying between the skeletons.

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

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

[Common Description of Invention (A1) and Invention (A2)]

The ion adsorption module according to the embodiment of the present invention includes a container having at least an opening into which the water to be treated flows, a first monolithic ion exchanger filled in the container, and a second monolithic ion exchanger or 3 monolithic ion exchanger. If the container has only an opening for allowing the water to be treated to flow in, the container can be applied to a batch processing method in which the ion adsorption module is put into water in a storage container or a storage tank to purify the water, and The water to be treated in which the water to be treated flows in flows into the pipe, and the treated water from which the treated water flows out flows out of the pipe, and can be applied to a conventional continuous water treatment method generally used. The contact form of the water to be treated and the ion-adsorbing module is not particularly limited as long as the water to be treated is in contact with the monolithic ion exchanger, and it is exemplified by rising in a simple cylindrical or polygonal columnar layer. a method of passing water through a flow or a descending flow; an external pressure method of passing water from the outer side in the circumferential direction toward the inner cylinder in the cylindrical filling layer, or an internal pressure method of passing water in the opposite direction; A plurality of plastids are filled, a tube method for passing water according to internal pressure type or external pressure type, a flat film method using a sheet-like filling layer, and a folding plate method for forming a flat film into a folded shape.

Further, the shape of the monolithic ion exchanger to be filled is a block shape, a sheet shape, a plate shape, a column shape, a cylindrical shape or the like, depending on the shape of the container of the module in the above-described adsorption mode. Further, the monolithic ion exchanger may be formed into spherical or amorphous granular pieces of 0.1 mm to 10 mm, and the small pieces may be filled in a container to form a packed layer. As a method of forming the monolithic ion exchanger of various shapes, for example, a method of cutting by a bulk monolithic ion exchanger can be mentioned.

The type and filling form of the monolithic ion exchanger filled in the container are not particularly limited, and may be arbitrarily determined depending on the purpose of use or the type of ionic impurities to be adsorbed. Specifically, for example, a monolithic cation exchanger or a monolithic anion exchanger may be placed in a container alone or in a mixture. Further, as a form in which a single ion exchanger is mixed, for example, a form in which a block, a sheet, a plate, or a column is formed into a block shape, a sheet shape, a plate shape, or a column shape, and a layer is formed in a water-passing direction; The form in which the block ion exchangers are mixed and filled. Among them, the lamination of a monolithic cation exchanger and a monolithic anion exchanger is preferred from the ease of preparation and filling of the monolithic ion exchanger into the container.

Further, as another aspect of the ion exchange module of the present invention, for example, a granular ion exchange resin-filled layer and the monolithic ion exchanger packed layer are laminated in this order from the upstream side; The ion adsorption module filled with the monolithic ion exchanger is disposed on the downstream side of the ion adsorption module filled with the granular ion exchange resin. Compared with the latter form, the former form can omit the connecting pipe. By disposing the conventional granular ion exchange resin in the upstream portion and disposing the monolithic ion exchanger in the downstream portion, the ionic impurities can be removed in a large amount, and the residual ionic impurities can be removed with high efficiency. The reduction of the total ion exchange zone length, the low capacity of the ion adsorption column, and the adsorption efficiency at high flow rates are achieved. The granular ion exchange resin on the upstream side is preferably a mixed ion exchange resin of a cation exchange resin and an anion exchange resin, and the monolithic ion exchanger on the downstream side is preferably a laminated layer of a monolithic cation exchanger and a monolithic anion exchanger. .

The shape of the ion exchange module used in the present invention is not particularly limited, and examples thereof include a columnar shape, a flat shape, and a tower shape having a mirror plate portion at a lower portion. The flat (small drum) ion exchange module is characterized in that the ion exchange filling layer is shorter in the water passing direction and longer in the direction of the vertical water passing direction (diameter), and is suitable for water passage in a short time. Water treatment method with regeneration. Further, a so-called ion exchange column having a mirror plate portion in the lower portion is used in the case where the granular ion exchange resin and the monolithic ion exchanger are filled in the above-described other forms. In other words, a so-called ion exchange column having a mirror plate portion at a lower portion is provided from the upstream side toward the downstream side, and is provided with a desalting portion filled with a granular ion exchange resin, and is provided with or filled with a mesh plate or has a distributor function. The mirror plate portion of the pebble (Tekapoa), in the case of the ion exchange module of this example, can replace the monolithic ion exchanger with the mesh plate or the pumice (Tekapoa) of the mirror plate portion, thereby enabling high flow rate The adsorption efficiency of the ionic impurities is increased, and the single-piece ion exchanger has the function of a distributor, so that the components in the tower can be reduced, and in the regeneration of the upward flow, there is no need to move the filling layer to improve the regeneration efficiency. . Further, according to the ion adsorption module of the present invention, the monolithic ion exchanger can be obtained by, for example, a block shape embedded in a filling container, and the filling is easy.

The water treatment method of the present invention is a method of adsorbing and removing ionic impurities in the water to be treated by contacting the water to be treated with the monolithic ion exchanger (water treatment first method), and by being treated The first treated water obtained by contacting the water with the particulate ion exchange resin is further contacted with the monolithic ion exchanger to obtain a second treated water (water treatment second method). In the first method of the water treatment, the content of the ionic impurities in the water to be treated is a small amount. For example, when the water to be treated having a conductivity of 0.1 to 100 mS/m is treated, the filling of the single ion exchanger is easy. It is suitable for use in a water treatment method that uses a small device and performs frequent regeneration. Further, even at a high flow rate, the length of the ion exchange belt can be kept short, and the volume reduction of the ion exchanger device can be achieved. According to the second method of water treatment, the ionic impurities have a high adsorption rate even in a small amount, and the adsorbed ions are less likely to leak. That is, since the particle size of the granular ion exchange resin is 0.2 to 0.5 mm, the diffusion rate inside the particle and the particle is greatly different, and if the flow rate is increased, it is a mixed region between the ion-adsorbed portion and the unadsorbed portion. The length of the ion exchange belt becomes long, and although a small amount of leakage of the adsorbed ions is likely to occur, since the total exchange vessel is large, the extraction of ions can be performed. On the other hand, since the monolithic ion exchanger has a small variation in the diffusion speed, the length of the ion exchange zone can be kept short even at a high flow rate. Therefore, by providing the granular ion exchange resin on the upstream side and the monolithic ion exchanger on the downstream side, the ionic substance can be removed in a large amount, and then the residual ions can be removed with high efficiency, and the total ion exchange band can be realized. The reduction in length, the low capacity of the ion adsorption tower, and the increase in adsorption efficiency at high flow rates. Therefore, the ion adsorption module can be used as a substitute for a purifier of the type used in a subsidiary system of a conventional ultrapure water production apparatus.

The water treatment method of the present invention may also use the monolithic ion exchanger as an ion shape having a lower adsorption selectivity than the target ion to be treated, and then pass the treated water to the target ion in the treated water. It is adsorbed and removed, and the ions having low adsorption selectivity are released into the water to be treated. Specifically, in the case where the target ion is removed from calcium ions or magnesium ions, sodium ions having a lower adsorption selectivity are adsorbed on the monolith ion exchanger, and are used for water treatment. This method is suitable in the case of inexpensive and safely recyclable in the case of, for example, boiler feed water to prevent the adhesion of scale to the main water treatment purpose, since it is not necessary to remove all ions. Further, in the water treatment method of the present invention, the monolithic ion exchanger may be a cation exchanger, and the cation exchanger may be made into a sodium form, and then the water to be treated may be passed through water, and the hardness component of the water to be treated may be exchanged with sodium. Softening treatment method. According to this method, the hardness component of the water to be treated can be easily removed.

Since the monolithic ion exchanger used in the ion exchange module and the water treatment method of the present invention is repeatedly used in the ion adsorption removal treatment, it is possible to use a reconstitution treatment by means of a drug. The regeneration treatment method is, for example, a method in which an ionic substance adsorbed on the monolithic ion exchanger is detached by bringing an acid into contact with a monolithic cation exchanger and contacting the base with a monolithic anion exchanger. Examples of the acid include hydrochloric acid, sulfuric acid, and nitric acid. Examples of the alkali include caustic soda. Further, the method of contacting the drug with the monolithic ion exchanger is not particularly limited as long as it is an ascending flow or a descending flow, and when other ion exchangers such as a granular ion exchange resin are mixed, it is not necessary to carry out each ion. The operation of the exchange body separation.

(Example)

The present invention will now be described in more detail by way of examples, but by way of illustration only and not limitation. Hereinafter, Reference Examples 1 to 25, Examples 1 and 2, and Comparative Examples 1 and 2 (A1), Reference Examples 26 to 36, and Example 3 and Comparative Examples 3 and 4 are Inventions (A2).

<Manufacture of the first monolithic ion exchanger (Reference Example 1)> (I step: manufacture of a single 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 uniformly dissolved. Next, the styrene/divinylbenzene/SMO/2,2'-azobis(isobutyronitrile) mixture was added to 180 g of pure water containing 1.8 ml of THF, and vacuum stirring was carried out using a planetary stirring device. The bubble mixer (manufactured by EME Co., Ltd.) was stirred under reduced pressure in a temperature range of 5 to 20 ° C to obtain a water-drop type emulsion in oil. The emulsion was quickly transferred to a reaction vessel, and after sealing, it was polymerized at 60 ° C for 24 hours under standing. After completion of the polymerization, the content was taken out, extracted with isopropyl alcohol, and dried under reduced pressure to produce a monolithic intermediate having a continuous macroporous structure. The opening (gap hole) of the portion where the macropores and the macropores of the monolith intermediate portion were measured by the mercury intrusion method had an average diameter of 56 μm and a total pore volume of 7.5 ml/g.

(Manufacture of single block)

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

The internal structure of a monolith (dry body) containing 1.3 mol% of a cross-linking component composed of the styrene/divinylbenzene copolymer obtained as described above was observed by SEM, and the results are shown in Fig. 1 . The SEM image of Fig. 1 is an image of an arbitrary position of a cut section obtained by cutting a single piece at an arbitrary position. As is apparent from Fig. 1, the monolith has a continuous macropore structure, and the skeleton constituting the continuous macroporous structure is much thicker than that of Fig. 12 of the comparative example, and the wall portion constituting the skeleton is thick.

Next, in the obtained monolith, the thickness of the wall portion and the cross section of the skeleton portion shown in the SEM image were measured at two points in the SEM image obtained by cutting off at a position different from the above position, and three points as the case may be. The area. The thickness of the wall portion is an average value of 8 points obtained by one SEM photograph, and the area of the skeleton portion is obtained by image analysis. Further, the wall portion is defined as above. Further, the skeleton portion area is represented by an average of three SEM images. As a result, the average thickness of the wall The degree was 30 μm, and the area of the cross section of the skeleton shown in the SEM image was 28% in the SEM image. Further, the average diameter of the opening of the monolith measured by the mercury intrusion method was 31 μm, and the total pore volume was 2.2 ml/g. The results are shown in Tables 1 and 2. In Table 1, the filling column sequentially shows, from left to right, the vinyl monomer used in the step II, the crosslinking agent, the monolith intermediate obtained in the first step, and the organic solvent used in the second step.

(Manufacture of monolithic 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 is 27 g. 1500 ml of dichloromethane was added thereto, and the mixture was heated at 35 ° C for 1 hour, and then cooled to 10 ° C or lower. 145 g of sulfuric acid sulfuric acid was gradually added thereto, and the mixture was heated and reacted at 35 ° C for 24 hours. Thereafter, methanol was added to quench the remaining chlorinated sulfuric acid, and then washed with methanol to remove dichloromethane, followed by washing with pure water to obtain a monolithic cation exchanger having a continuous macroporous structure.

The swelling ratio of the obtained cation exchanger before and after the reaction was 1.7 times, and the ion exchange capacity per unit volume was 0.67 mg equivalent/ml in a water-wet state. The average diameter of the opening of the organic porous ion exchanger in the water-wet state was estimated from the value of the organic porous body and the swelling ratio of the cation exchanger in the water-wet state, and found to be 54 μm, which was obtained by the same method as the monolith. The wall portion constituting the skeleton had an average thickness of 50 μm, the skeleton portion area was 28% in the photograph area of the SEM photograph, and the total pore volume was 2.2 ml/g. Further, the length of the ion exchange band with respect to sodium ions in the monolithic cation exchanger was 22 mm at LV = 20 m/h. Also, it belongs to the pressure loss when water is transmitted. The standard differential pressure coefficient is 0.016 MPa/m‧LV. The results are shown in Table 2.

Next, in order to confirm the distribution state of the sulfonic acid group in the monolithic cation exchanger, the distribution state of the sulfur atom was observed by EPMA. The results are shown in Fig. 2 and Fig. 3. Fig. 2 shows a distribution state of a sulfur atom on the surface of a cation exchanger, and Fig. 3 shows a distribution state of a sulfur atom in a cross section (thickness) direction of a cation exchanger. 2 and 3, the sulfonic acid groups were uniformly introduced into the skeleton surface of the cation exchanger and the inside of the skeleton (cross-sectional direction).

<Manufacture of the first monolithic ion exchanger (Reference Examples 2 to 11)> (Manufacture of single block)

In addition to the amount of styrene used, the type and amount of the crosslinking agent, the type and amount of the organic solvent, the porous structure of the monolithic intermediate coexisting in the impregnation polymerization of styrene and divinylbenzene, and the crosslinking density and A monolith was produced in the same manner as in Reference Example 1 except that the amount of use was changed to the amount shown in Table 1. The results are shown in Tables 1 and 2. Further, from the SEM images (not shown) of Reference Examples 2 to 11 and Table 2, the average diameter of the openings of the single blocks of Reference Examples 2 to 11 was as large as 22 to 70 μm , and the average thickness of the wall portion constituting the skeleton was also Thick to 25~50 μm , the frame area is 26~44% of the rough monoblock in the SEM image area.

(Manufacture of monolithic cation exchanger)

The monoliths produced by the above method were reacted with chlorinated sulfuric acid in the same manner as in Reference Example 1 to produce a monolithic cation exchanger having a continuous macroporous structure. The results are shown in Table 2. The average diameter of the openings of the monolithic cation exchangers of Reference Examples 2 to 11 is 46 to 138 μm , the average thickness of the wall portion constituting the skeleton is 45 to 110 μm, and the area of the skeleton is 26 to 44 in the SEM image area. %. The ion exchange band length is also shorter than the conventional one, and the differential pressure coefficient also shows a lower value. Further, the mechanical properties of the monolithic cation exchanger of Reference Example 8 were also evaluated.

(Evaluation of mechanical properties of monolithic cation exchangers)

The monolithic cation exchanger obtained in Reference Example 8 was cut into a short sheet of 4 mm × 5 mm × 10 mm in a water-wet state, and was used as a test piece for a tensile strength test. The test piece was attached to a tensile tester, the speed of the slider was set to 0.5 mm/min, and the test was carried out in water at 25 °C. As a result, the tensile strength and the tensile modulus of elasticity were 45 kPa and 50 kPa, respectively, and showed an extremely large value compared to the conventional monolithic cation exchanger. Further, the tensile breaking elongation is 25%, which is a larger value than the conventional monolithic cation exchanger.

<Reference Examples 12 and 13> (Manufacture of single block)

The same composition as in Reference Example 4 was produced in the same manner as in Reference Example 1 except that the amount of styrene used, the amount of the crosslinking agent used, and the amount of the organic solvent used were changed to those shown in Table 1. Piece. Further, Reference Example 13 was carried out in the same manner as in Reference Example 12 except that a reaction vessel having an inner diameter of 75 mm was used instead of the reaction vessel having an inner diameter of 110 mm. The results are shown in Tables 1 and 2.

(Manufacture of monolithic anion exchanger)

The monolith produced by the above method was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 15 mm. 1400 ml of dimethoxymethane and 20 ml of tin tetrachloride were added thereto, and 560 ml of sulfuric acid sulfuric acid was added dropwise under ice cooling. After completion of the dropwise addition, the mixture was heated and reacted at 35 ° C for 5 hours to introduce a chloromethyl group. After completion of the reaction, the mother liquid was extracted by a siphon method, washed with a mixed solution of THF/water = 2/1, and then washed with THF. To the chloromethylated monolithic organic porous body, 1000 ml of THF and 600 ml of a 30% aqueous solution of trimethylamine were added, and the mixture was reacted at 60 ° C for 6 hours. After completion of the reaction, the product was washed with a methanol/water mixed solvent, and then washed with pure water to separate.

The ion exchange capacity per unit volume of the anion exchanger of Reference Example 12 and Reference Example 13 and the average diameter of the opening of the organic porous ion exchanger in the wet state of water were determined by the same method as that of the monolith. The average thickness of the wall portion of the skeleton, the area of the skeleton portion (the proportion in the photograph field of the SEM photograph), the total pore volume, the length of the ion exchange belt, and the pressure difference coefficient are shown in Table 2.

Next, in order to confirm the distribution state of the quaternary ammonium group 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 the chlorine atoms was observed by EPMA. As a result, the chlorine atoms were not only distributed on the surface of the skeleton of the anion exchanger, but also uniformly distributed inside the skeleton, and it was confirmed that the quaternary ammonium group was uniformly introduced into the anion exchanger.

<Manufacture of second monolithic ion exchanger (Reference Example 14)> (I step: manufacture of a single 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 uniformly dissolved. Next, the styrene/divinylbenzene/SMO/2,2'-azobis(isobutyronitrile) mixture was added to 180 g of pure water using a vacuum stirring defoaming mixer (EME) belonging to a planetary stirring device. The company made a stirring under reduced pressure in a temperature range of 5 to 20 ° C to obtain a water-drop type emulsion in oil. The emulsion was quickly transferred to a reaction vessel, and after sealing, it was polymerized at 60 ° C for 24 hours under standing. After completion of the polymerization, the content was taken out, extracted with methanol, and dried under reduced pressure to produce a monolithic intermediate having a continuous macroporous structure. The internal structure of the monolithic intermediate (dried body) thus obtained was observed by the SEM image (Fig. 7). As a result, although the wall portion of the two adjacent macropores was separated into a very thin rod shape, it had a continuous bubble structure. The opening (gap hole) of the portion where the macropores and the macropores were overlapped by the mercury intrusion method had an average diameter of 70 μm and a total pore volume of 21.0 ml/g.

(Manufacture of a continuous continuous monolith)

Next, 76.0 g of styrene, 4.0 g of divinylbenzene, 120 g of 1-nonanol, and 0.8 g of 2,2'-azobis(2,4-dimethylvaleronitrile) were mixed to uniformly dissolve them (Step II) ). Next, the above-mentioned monolithic intermediate was cut into a disk shape having a diameter of 70 mm and a thickness of about 40 mm, and 4.1 g was taken. The separated monolithic intermediate was placed in a reaction vessel having an inner diameter of 75 mm and immersed in the styrene/divinylbenzene/1-nonanol/2,2'-azobis (2,4- In the dimethylvaleronitrile mixture, after defoaming in a decompression chamber, the reaction vessel was sealed and polymerized at 60 ° C for 24 hours under standing. After completion of the polymerization, a monolithic content having a thickness of about 60 mm was taken out, and subjected to Soxler extraction with propanol, followed by drying under reduced pressure at 85 ° C overnight (Step III).

The internal structure of a monolith (dry body) containing 3.2 mol% of a cross-linking component composed of the styrene/divinylbenzene copolymer obtained as described above was observed by SEM, and as a result, the monolithic skeleton and empty The holes are respectively in a three-dimensional continuous, co-continuous configuration in which the two phases are entangled with each other. Further, the skeleton thickness measured by SEM image was 10 μm. Further, the three-dimensional continuous pore size of the monolith measured by the mercury intrusion method was 17 μm, and the total pore volume was 2.9 ml/g. The results are shown in Tables 3 and 4. In Table 4, the skeleton thickness is represented by the skeleton diameter.

(Manufacture of a continuous 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 is 18g. 1500 ml of dichloromethane was added thereto, and the mixture was heated at 35 ° C for 1 hour, and then cooled to 10 ° C or lower. 99 g of sulfuric acid sulfuric acid was gradually added thereto, and the mixture was heated and reacted at 35 ° C for 24 hours. Thereafter, methanol was added to quench the remaining chlorinated sulfuric acid, and then washed with methanol to remove dichloromethane, followed by washing with pure water to obtain a monolithic cation exchanger having a co-continuous structure.

A part of the obtained cation exchanger was cut out and dried, and the internal structure was observed by SEM. As a result, it was confirmed that the monolithic cation maintained a co-continuous structure. The SEM image thereof is shown in Fig. 8. Further, the cation exchange rate of the cation exchanger before and after the reaction was 1.4 times, and the ion exchange capacity per unit volume was 0.74 mg equivalent/ml in a water-wet state. From the value of the monolith and the swelling ratio of the cation exchanger in the water-wet state, the continuous pore size of the monolith in the water-wet state was estimated to be 24 μm, the skeleton diameter was 14 μm, and the total pore volume was 2.9 ml/g.

Further, the pressure difference coefficient belonging to the pressure loss index when water is transmitted is 0.052 MPa/m‧LV. Further, the length of the ion exchange band of the sodium ion in the monolithic cation exchanger was measured, and as a result, the ion exchange band length at LV = 20 m/h was 16 mm, compared to the commercially available strong acid cation exchange resin Amberlite IR120B. The value (320 mm) of (manufactured by Rohm and Haas Co., Ltd.) is not only overwhelmingly shorter, but also has a shorter value than the conventional monolithic porous ion exchanger having an open cell structure. The results are shown in Table 4.

Next, in order to confirm the distribution state of the sulfonic acid group in the monolithic cation exchanger, the distribution state of the sulfur atom was observed by EPMA. The results are shown in Fig. 9 and Fig. 10. 9 and 10 correspond to the left and right photos, respectively. Fig. 9 shows a distribution state of a sulfur atom on the surface of a cation exchanger, and Fig. 10 shows a distribution state of a sulfur atom in a cross section (thickness) direction of a cation exchanger. In the photograph on the left side of Fig. 9, the skeleton portion is obliquely extended to the left and right, and in the photograph on the left side of Fig. 10, the two circular shapes are skeleton cross sections. As is apparent from Fig. 9 and Fig. 10, the sulfonic acid groups were uniformly introduced into the skeleton surface of the cation exchanger and the inside of the skeleton (cross-sectional direction).

<Manufacture of the second monolithic ion exchanger (Reference Examples 15 to 17)> (Manufacture of monoliths with a co-continuous structure)

In addition to the amount of styrene used, the amount of crosslinking agent used, the amount of organic solvent used, and the porous structure, crosslinking density, and amount of use of the monolithic intermediates coexisting during styrene and divinylbenzene impregnation polymerization, A monolith having a co-continuous structure was produced in the same manner as in Reference Example 14 except for the amount shown in Table 3. Further, Reference Example 17 was carried out in the same manner as in Reference Example 14 except that a reaction vessel having an inner diameter of 75 mm was used instead of the reaction vessel having an inner diameter of 110 mm. The results are shown in Tables 3 and 4.

(Manufacture of monoliths with a co-continuous structure)

In addition to the amount of styrene used, the amount of crosslinking agent used, the type and amount of organic solvent, the porous structure of the monolithic intermediate coexisting in the impregnation polymerization of styrene and divinylbenzene, the crosslinking density and the amount of use A monolith having a co-continuous structure was produced in the same manner as in Reference Example 14 except that the amount shown in Table 4 was changed. The results are shown in Tables 3 and 4.

(Manufacture of a monolithic cation exchanger having a co-continuous structure)

The monoliths produced by the above method were reacted with chlorinated sulfuric acid in the same manner as in Reference Example 14 to produce a monolithic cation exchanger having a co-continuous structure. The results are shown in Table 4. Further, the internal structure of the monolithic cation exchanger having a co-continuous structure obtained is shown by an SEM image (not shown) and Table 4, and the monolithic cation exchangers obtained in Reference Examples 15 to 17 show a small differential pressure coefficient per The superior capacity of the exchange volume per unit volume and the short length of the ion exchange belt. Further, the mechanical properties of the monolithic cation exchanger of Reference Example 15 were also evaluated.

(Evaluation of mechanical properties of monolithic cation exchangers)

The monolithic cation exchanger obtained in Reference Example 15 was cut into a short sheet of 4 mm × 5 mm × 10 mm in a water-wet state, and was used as a test piece for a tensile strength test. The test piece was attached to a tensile tester, the speed of the slider was set to 0.5 mm/min, and the test was carried out in water at 25 °C. As a result, the tensile strength and the tensile modulus of elasticity were 23 kPa and 15 kPa, respectively, and the value was exceptionally large compared to the conventional monolithic cation exchanger. Further, the tensile breaking elongation is 50%, which is a larger value than the conventional monolithic cation exchanger.

<Reference Examples 18 and 19> (Manufacture of monoliths with a co-continuous structure)

In addition to the amount of styrene used, the amount of crosslinking agent used, the amount of organic solvent used, and the porous structure, crosslinking density, and amount of use of the monolithic intermediates coexisting during styrene and divinylbenzene impregnation polymerization, A monolith having a co-continuous structure was produced in the same manner as in Reference Example 14 except for the amount shown in Table 4. Further, Reference Example 19 was carried out in the same manner as in Reference Example 18 except that a reaction vessel having an inner diameter of 75 mm was used instead of the reaction vessel having an inner diameter of 110 mm. The results are shown in Tables 3 and 4.

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

The monolith produced by the above method was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 15 mm. 1400 ml of dimethoxymethane and 20 ml of tin tetrachloride were added thereto, and 560 ml of sulfuric acid sulfuric acid was added dropwise under ice cooling. After completion of the dropwise addition, the mixture was heated and reacted at 35 ° C for 5 hours to introduce a chloromethyl group. After completion of the reaction, the mother liquid was extracted by a siphon method, washed with a mixed solvent of THF/water = 2/1, and then washed with THF. To the chloromethylated monolithic organic porous body, 1000 ml of THF and 600 ml of a 30% aqueous solution of trimethylamine were added, and the mixture was reacted at 60 ° C for 6 hours. After completion of the reaction, the product was washed with a methanol/water mixed solvent, and then washed with pure water to separate.

The ion exchange capacity per unit volume of the anion exchanger of Reference Example 18 and Reference Example 19, and the average diameter of the continuous pores of the organic porous ion exchanger in the wet state of water were determined by the same method as that of the monolith. The integration of the skeleton thickness, total pore volume, ion exchange zone length, and differential pressure coefficient are shown in Table 4. Further, the internal structure of the obtained monolithic 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 group in the monolithic anion exchanger, the anion exchanger was treated with an aqueous hydrochloric acid solution to form a chloride form, and then the distribution state of the chlorine atoms was observed by EPMA. As a result, not only the chlorine atoms were distributed on the surface of the anion exchanger but also uniformly distributed inside, and it was confirmed that the quaternary ammonium group was uniformly introduced into the anion exchanger.

<Reference Example 20> (Manufacture of monolithic organic porous body (known material) having a continuous macroporous structure)

According to the production method described in Japanese Laid-Open Patent Publication No. 2002-306976, a monolithic organic porous body having a continuous macroporous structure is produced. Namely, 19.2 g of styrene, 1.0 g of divinylbenzene, 1.0 g of SMO, and 0.26 g of 2,2'-azobis(isobutyronitrile) were mixed and uniformly dissolved. Next, the styrene/divinylbenzene/SMO/2,2'-azobis(isobutyronitrile) mixture was added to 180 g of pure water using a vacuum stirring defoaming mixer (EME) belonging to a planetary stirring device. The company made a stirring under reduced pressure in a temperature range of 5 to 20 ° C to obtain a water-drop type emulsion in oil. The emulsion was quickly transferred to a reaction vessel, and after sealing, it was polymerized at 60 ° C for 24 hours under standing. After completion of the polymerization, the content was taken out, extracted with isopropyl alcohol, and dried under reduced pressure to produce a monolithic organic porous body having a continuous macroporous structure.

The SEM showing the internal structure of the organic porous body containing 3.3 mol% of the cross-linking component composed of the styrene/divinylbenzene copolymer obtained as described above was the same as that of Fig. 12 . As is apparent from Fig. 12, the organic porous body has a continuous macroporous structure, and the thickness of the wall portion constituting the skeleton of the continuous macroporous structure is thinner than that of the embodiment, and the average thickness of the wall portion measured by the SEM image is 5 μm. The area of the skeleton is 10% of the area of the SEM image. Further, the organic porous body having an average opening diameter of 29 μm and a total pore volume of 8.6 ml/g as measured by a mercury intrusion method. The results are shown in Table 5. In Tables 1, 2 and 5, the clearance hole diameter represents the average diameter of the opening. Further, in Tables 1 to 5, the values of the thickness, the skeleton diameter, and the voids respectively represent the average.

(Manufacture of monolithic organic porous cation exchanger (known material) having a continuous macroporous structure)

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 body was 6 g. After adding 1000 ml of dichloromethane thereto, the mixture was heated at 35 ° C for 1 hour, and then cooled to 10 ° C or lower. 30 g of sulfuric acid sulfuric acid was gradually added thereto, and the mixture was heated and reacted at 35 ° C for 24 hours. Thereafter, methanol was added to quench the remaining chlorinated sulfuric acid, and then washed with methanol to remove methylene chloride, followed by washing with pure water to obtain a monolithic porous cation exchanger having a continuous macroporous structure. The swelling ratio of the obtained cation exchanger before and after the reaction was 1.6 times, and the ion exchange capacity per unit volume was 0.22 mg equivalent/ml in a water-wet state, showing a value smaller than that of Reference Example 1. The average pore diameter of the organic porous ion exchanger in the water-wet state was estimated from the value of the organic porous material and the swelling ratio of the cation exchanger in the water-wet state, and as a result, it was 46 μm, and the average thickness of the wall portion constituting the skeleton was 8 μm. The area of the skeleton was 10% in the SEM image area, and the total pore volume was 8.6 ml/g. Further, the pressure difference coefficient belonging to the pressure loss index when water is transmitted is 0.013 MPa/m‧LV. The results are shown in Table 5. Further, the monolithic cation exchanger obtained in Reference Example 20 was also evaluated for mechanical properties.

(Evaluation of mechanical properties of a conventional monolithic cation exchanger)

With respect to the monolithic cation exchanger obtained in Reference Example 20, a tensile test was carried out in the same manner as in the evaluation method of Reference Example 8. As a result, the tensile strength and the tensile elastic modulus were 28 kPa and 12 kPa, respectively, which were lower than those of the monolithic cation exchanger of Reference Example 8. Further, the tensile breaking elongation was 17%, which was a smaller value than the monolithic cation exchanger of the present invention.

<Reference Example 21~23> (Manufacture of monolithic organic porous bodies having a continuous macroporous structure) In addition to changing the amount of styrene used, the amount of divinylbenzene used, and the amount of SMO to the amount shown in Table 5, the same method as in Reference Example 20 was used to manufacture continuous macropores by the conventional technique. A monolithic organic porous body constructed. The results are shown in Table 5. Further, the monolithic internal structure of Reference Example 23 was observed by an SEM not shown. Further, Reference Example 23 is a condition in which the total pore volume is minimized, and when the amount of the oil phase portion or water is equal to or less than this, the opening cannot be formed. The monoliths of the reference examples 21 to 23 each have an opening diameter as small as 9 to 18 μm, and the average thickness of the wall portion constituting the skeleton is also as thin as 15 μm, and the skeleton portion is as small as 22% in the SEM image region. (Manufacture of monolithic organic porous cation exchanger having a continuous macroporous structure)

The organic porous body produced by the above method was reacted with chlorinated sulfuric acid in the same manner as in Reference Example 20 to produce a monolithic porous cation exchanger having a continuous macroporous structure. The results are shown in Table 5. If the diameter of the opening is to be increased, the thickness of the wall portion becomes small and the skeleton becomes thin. On the other hand, if the wall portion is to be thickened or the skeleton is thickened, the opening diameter tends to decrease. As a result, when the differential pressure coefficient is suppressed to be low, the ion exchange capacity per unit volume is decreased, and when the ion exchange capacity is increased, the differential pressure coefficient is increased.

<Reference Example 24>

In addition to changing the type of organic solvent used in step II to the second solvent belonging to polystyrene Except for the alkane, the other attempts were made to produce a monolith in the same manner as in Reference Example 1. However, the isolated product was transparent, showing that the collapse of the porous structure disappeared. SEM observation was performed for confirmation, but only a dense structure was observed, and the continuous macropore structure disappeared.

<Reference Example 25> (Manufacture 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 to uniformly dissolve them. Next, the styrene/divinylbenzene/azobisisobutyronitrile/sorbitan monooleate mixture was added to 450 ml of pure water, and stirred by a homogenizer at 20,000 rotations/min for 2 minutes to obtain an oil. Medium drop type emulsion. After completion of the emulsification, the water-drop type emulsion in the oil was transferred to an autoclave made of stainless steel, sufficiently substituted with nitrogen, sealed, and polymerized at 60 ° C for 24 hours under standing. After completion of the polymerization, the contents were taken out and subjected to Soxler extraction with isopropyl alcohol for 18 hours, and the unreacted monomer and sorbitan monooleate were removed, and then dried under reduced pressure at 40 ° C for a day and night. 5 g of the porous body containing 14 mol% of the cross-linking component composed of the styrene/divinylbenzene copolymer thus obtained was taken out, 500 g of tetrachloroethane was added, and the mixture was heated at 60 ° C for 30 minutes, and then cooled to a chamber. While warm, 25 g of chlorinated sulfuric acid was slowly added and reacted at room temperature for 24 hours. Thereafter, acetic acid was added, and the reactant was poured into a large amount of water, washed with water, and dried to obtain a porous cation exchanger. The ion exchange capacity of the porous material was 4.0 mg equivalent/g in terms of dry porous material, and it was confirmed by using a map of sulfur atoms of EPMA that the sulfonic acid group was uniformly introduced into the porous body. 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 overlap, and the interstitial pores 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. Further, the porous body was cut into a thickness of 10 mm, and the water permeation rate was measured, and it was 14,000 l/min. ‧ m ² ‧ MPa.

Further, regarding the monolithic ion exchangers produced in Reference Examples 1 to 11 and Reference Examples 20 to 23, the relationship between the pressure difference coefficient and the ion exchange capacity per unit volume is shown in Fig. 4 . As is apparent from Fig. 4, in the reference examples 1 to 11, the well-known reference examples 20 to 23 have poor balance between the differential pressure coefficient and the ion exchange capacity. On the other hand, the ion exchange capacity per unit volume of Reference Examples 1 to 11 was large, and the differential pressure coefficient was also low.

(Example 1)

The column having an inner diameter of 57 mm filled with the ion exchanger was passed through the water so that the raw water was flowed downward from the upper side to the lower side, and the sodium concentration in the treated water was measured to be more than 1 μg/l. In addition, the water pressure difference in the water is also measured. The water passing experimental conditions are as follows. As a result, the time during which the sodium concentration in the treated water exceeded 1 μg/l was 114 days. Moreover, the water pressure difference is 24 kPa.

(water conditions)

‧ Ion exchanger: The upstream side is a mixed resin of a granular cation exchange resin and an anion exchange resin (mixing ratio = 1:1 (filling volume ratio), resin layer height: 300 mm) and the downstream side is a single piece (diameter 57 mm, 40mm high layered body

‧Cation exchange resin: IR120B (trade name)

‧ Anion exchange resin: IRA402BL (trade name)

‧ Raw water: NaCl aqueous solution, sodium concentration 80μg / l

‧Flow: 120l/h

‧ Monolith: Reference monolithic cation exchanger of Example 8

The cation exchange resin was once Na-formed with sodium chloride, and then regenerated with 1% hydrochloric acid at a regeneration rate of 99%, and then sufficiently washed with ultrapure water to be used as a regenerated shape. Further, the regeneration rate means the capacity ratio of the H type which can be adsorbed on the resin.

(Example 2)

The same procedure as in Example 1 was carried out except that the monolithic cation exchanger of Reference Example 8 was used instead of the monolithic cation exchanger of Reference Example 17. As a result, the time during which the sodium concentration in the treated water exceeded 1 μg/l was 147 days. Moreover, the water pressure difference is 18 kPa.

(Comparative Example 1)

The same procedure as in Example 1 was carried out except that the monolithic cation exchanger of Reference Example 8 was used instead of the monolithic cation exchanger of Reference Example 25. As a result, the time during which the sodium concentration in the treated water exceeded 1 μg/l was 21 days. Moreover, the water pressure difference is 230 kPa.

(Comparative Example 2)

The same procedure as in Example 1 was carried out except that a mixed resin of a granular cation exchange resin and an anion exchange resin (resin layer height: 340 mm) was used as the ion exchanger. That is, in Comparative Example 2, a monolith was used as the ion exchanger, and the granular ion exchange resin was 100%. As a result, the time during which the sodium concentration in the treated water exceeds 1 μg/l is 0 days, that is, the sodium concentration in the treated water from the first day of water passing exceeds 1 μg/l. Moreover, the water pressure difference is 230 kPa.

Compared with Comparative Examples 1 and 2, the ions adsorbed in Examples 1 and 2 leaked slowly. Therefore, the exchange frequency of the ion exchange module can be reduced. Moreover, since the water pressure difference is low, water can be supplied at a low pressure.

<Manufacture of the third monolithic ion exchanger (Reference Example 26)> (I step: manufacture of a single 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 uniformly dissolved. Next, the styrene/divinylbenzene/SMO/2,2'-azobis(isobutyronitrile) mixture was added to 180 g of pure water using a vacuum stirring defoaming mixer (EME) belonging to a planetary stirring device. The company made a stirring under reduced pressure in a temperature range of 5 to 20 ° C to obtain a water-drop type emulsion in oil. The emulsion was quickly transferred to a reaction vessel, and after sealing, it was polymerized at 60 ° C for 24 hours under standing. After completion of the polymerization, the content was taken out, extracted with isopropyl alcohol, and dried under reduced pressure to produce a monolithic intermediate having a continuous macroporous structure. The opening (gap hole) of the portion where the macropores and the macropores of the monolith intermediate portion were measured by the mercury intrusion method had an average diameter of 40 μm and a total pore volume of 15.8 ml/g.

(manufacturing of composite monoliths)

Next, 36.0 g of styrene, 4.0 g of divinylbenzene, 60 g of 1-nonanol, and 0.4 g of 2,2'-azobis(2,4-dimethylvaleronitrile) were mixed to uniformly dissolve them (Step II). ). The 10 hour half-life temperature of 2,2'-azobis(2,4-dimethylvaleronitrile) used as a polymerization initiator was 51 °C. The cross-linking density of the monolithic intermediate is 1.3 mol%, and the amount of divinylbenzene used in the second step is 6.6 mol% relative to the total amount of styrene and divinylbenzene, and the crosslinking density ratio is It is 5.1 times. Next, the monolithic 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 taken. The separated monolithic intermediate was placed in a reaction vessel having an inner diameter of 73 mm and immersed in the styrene/divinylbenzene/1-nonanol/2,2'-azobis (2,4- In the dimethylvaleronitrile mixture, after defoaming in a decompression chamber, the reaction vessel was sealed and polymerized at 60 ° C for 24 hours under standing. After completion of the polymerization, a monolithic content having a thickness of about 30 mm was taken out, and subjected to Soxler extraction with propanol, followed by drying under reduced pressure at 85 ° C overnight (Step III).

The internal structure of the composite monolith (dry body) composed of the styrene/divinylbenzene copolymer obtained as described above was observed by SEM, and the results are shown in Figs. 13 to 15 . The SEM images of FIGS. 13 to 15 are images of arbitrary positions of the cut sections obtained by cutting a single piece at an arbitrary position. As apparent from Fig. 13 to Fig. 15, the composite monolith has a continuous macroporous structure, and the surface of the skeleton phase constituting the continuous macroporous structure is covered by a particle having an average particle diameter of 4 μm, and the total particle volume is equal to the particle coverage of the skeleton surface. It is 80%. Further, the proportion of the particle body having a particle diameter of 3 to 5 μm in the entire particle body was 90%.

Further, the average diameter of the opening of the composite monolith measured by the mercury intrusion method was 16 μm, and the total pore volume was 2.3 ml/g. The results are shown in Tables 6 and 7. In Table 6, the filling column sequentially shows the vinyl monomer, the crosslinking agent, the organic solvent, and the monolith intermediate obtained in the first step from the left to the right. Further, the particle body or the like is represented by particles.

(Manufacture of composite monolithic 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. 1500 ml of dichloromethane was added thereto, and the mixture was heated at 35 ° C for 1 hour, and then cooled to 10 ° C or lower. Then, 98.9 g of sulfuric acid sulfuric acid was gradually added thereto, and the mixture was heated and reacted at 35 ° C for 24 hours. Thereafter, methanol was added to quench the remaining chlorinated sulfuric acid, and then washed with methanol to remove dichloromethane, followed by washing with pure water to obtain a composite monolithic cation exchanger.

The swelling ratio of the obtained cation exchanger before and after the reaction was 1.3 times, and the ion exchange capacity per unit volume was 1.11 mg equivalent/ml in a water-wet state. The average opening diameter of the organic porous ion exchanger in the water-wet state was estimated from the value of the organic porous material and the swelling ratio of the cation exchanger in the water-wet state, and as a result, it was 21 μm, and the average of the coated particles obtained by the same method was obtained. The particle size was 5 μm. Further, the total particle volume was equal to the particle coverage of the skeleton surface of 80%, and the total pore volume was 2.3 ml/g. Further, the proportion of the particle body having a particle diameter of 4 to 7 μm in the entire particle body was 90%. Further, the pressure difference coefficient belonging to the pressure loss index when water is transmitted is 0.057 MPa/m‧LV, which is a low pressure loss smaller than the pressure loss required in practical use. Furthermore, the length of the ion exchange strip was 9 mm, showing a significantly shorter value. The results are shown in Table 7.

Next, in order to confirm the distribution state of the sulfonic acid group in the composite monolithic cation exchanger, the distribution state of the sulfur atom was observed by EPMA. The results are shown in Fig. 16 and Fig. 17. 16 and 17 correspond to the left and right photos, respectively. Fig. 16 shows a distribution state of a sulfur atom on the surface of a cation exchanger, and Fig. 17 shows a distribution state of a sulfur atom in a cross section (thickness) direction of a cation exchanger. 16 and 17, the sulfonic acid groups were uniformly introduced into the skeleton surface of the cation exchanger and the inside of the skeleton (cross-sectional direction).

<Reference Example 27~30> (manufacturing of composite monoliths)

In addition to the amount of the vinyl monomer used, the amount of the crosslinking agent used, the type and amount of the organic solvent, the porous structure of the monolithic intermediate which coexists in the polymerization in the III step, the crosslinking density and the amount used, and the polymerization temperature The monolith was produced in the same manner as in Reference Example 26 except that the amount shown in Table 6 was changed. The results are shown in Tables 6 and 7. Moreover, the internal structure of the composite monolith (dry body) was observed by SEM, and the results are shown in FIGS. 18 to 25. 18 to 25 are reference examples 27, 21 and 22 are reference examples 28, 23 are reference examples 29, and Figs. 24 and 25 are reference examples 30. Further, these were produced under the following conditions satisfying the production conditions of the present invention: Reference Example 27 is a crosslinking density ratio (2.5 times), Reference Example 28 is a type of organic solvent (PEG; molecular weight 400), and Reference Example 29 is The vinyl monomer concentration (28.0%), Reference Example 30 is the polymerization temperature (40 ° C; 11 ° C lower than the 10-hour half-life temperature of the polymerization initiator). From Fig. 18 to Fig. 25, those attached to the surface of the composite monolithic skeleton in Reference Examples 28 to 30, rather than the particle body, should be protrusions. The "average particle diameter" of the protrusion is the average diameter of the size (maximum diameter) of the protrusion. From Figs. 18 to 25 and Table 7, the average diameter of the particles attached to the surface of the single skeleton in Reference Examples 27 to 31 was 3 to 8 μm, and the total particle size was equal to the particle coverage of the skeleton surface of 50 to 95%. Further, in Reference Example 27, the ratio of the particle body having a particle diameter of 3 to 6 μm to the entire particle body was 80%, and the ratio of the protrusion having a particle diameter of 3 to 10 μm in the reference example 28 to the entire particle body was 80. %, in the reference example 29, the particle body having a particle diameter of 3 to 5 μm is occupied by 90% in the entire particle body, and in the reference example 30, the particle body having a particle diameter of 3 to 7 μm is occupied by 90% in the entire particle body. %.

(Manufacture of composite monolithic cation exchanger)

The composite monoliths produced by the above method were reacted with chlorinated sulfuric acid in the same manner as in Reference Example 26 to produce a composite monolithic cation exchanger. The results are shown in Table 7. In the reference examples 27 to 30, the average pore diameter of the composite monolithic cation exchanger is 21 to 52 μm, the average diameter of the particles attached to the surface of the skeleton is 5 to 13 μm, and the total particle volume is equal to the particle coverage of the skeleton surface. 50~95%, the differential pressure coefficient is also as small as 0.010~0.057MPa/m‧LV. In addition, the ion exchange band length is also significantly smaller than 8~12mm. Further, the particle body having a particle diameter of 5 to 10 μm accounts for 90% of the total particle body.

<Reference Example 31> (manufacturing of composite monoliths)

In addition to the type and amount of the vinyl monomer used, the amount of the crosslinking agent used, the type and amount of the organic solvent, and the porous structure of the monolithic intermediate which is present during the polymerization in the third step, the crosslinking density and the amount of use are changed. A monolith was produced in the same manner as in Reference Example 26 except that the amount shown in Table 6 was used. The results are shown in Tables 6 and 7. Moreover, the internal structure of the composite monolith (dry body) was observed by SEM, and the results are shown in FIGS. 26 to 28. In Reference Example 31, those attached to the surface of the composite monolithic skeleton were protrusions. In the monolith of the reference example 31, the average diameter of the largest diameter of the protrusions formed on the surface was 10 μm, and the total particle volume was equal to 100% of the particle coverage of the skeleton surface. Further, the proportion of the particle body having a particle diameter of 6 to 12 μm in the entire particle body was 80%.

(Manufacture of composite monolithic 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. 1500 ml of tetrahydrofuran was added thereto, and the mixture was heated at 40 ° C for 1 hour, and then cooled to 10 ° C or lower. Then, 114.5 g of a trimethylamine 30% aqueous solution was gradually added thereto, and the mixture was heated and reacted at 40 ° C for 24 hours. After completion of the reaction, the mixture was washed with methanol to remove tetrahydrofuran, and then washed with pure water to obtain a monolithic anion exchanger.

The swelling ratio of the obtained composite anion exchanger before and after the reaction was 2.0 times, and the ion exchange capacity per unit volume was 0.32 mg equivalent/ml in a water-wet state. The average pore diameter of the organic porous ion exchanger in the water-wet state was estimated from the value of the monolith and the swelling ratio of the monolithic anion exchanger in the water-wet state, and the result was 58 μm, and the protrusions obtained by the same method were obtained. The average diameter was 20 μm, the total particle volume was equal to 100% of the particle surface coverage, and the total pore volume was 2.1 ml/g. Also, the ion exchange tape length shows a very short value of 16 mm. Further, the pressure difference coefficient belonging to the pressure loss index when water is transmitted is 0.041 MPa/m‧LV, which is a low pressure loss smaller than the pressure loss required in practical use. Further, the proportion of the particle body having a particle diameter of 12 to 24 μm in the entire particle body was 80%. The results are shown in Table 7.

Next, in order to confirm the distribution state of the quaternary ammonium group 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 the chlorine atoms was observed by EPMA. As a result, the chlorine atoms were not only distributed on the surface of the anion exchanger but also uniformly distributed inside the skeleton, and it was confirmed that the quaternary ammonium group was uniformly introduced into the anion exchanger.

<Reference Example 32> (Manufacture of single block)

The amount of the vinyl monomer used, the amount of the crosslinking agent used, the type and amount of the organic solvent, and the amount of the monolith intermediate used in the polymerization in the third step were changed to the amounts shown in Table 6. The rest was produced in the same manner as in Reference Example 26. The results are shown in Tables 6 and 7. Further, from the SEM photograph (not shown), no formation of particles or protrusions was observed on the surface of the skeleton. It can be seen from Tables 6 and 7 that if a single piece is produced under the conditions deviating from the specific manufacturing conditions of the present invention, that is, under the conditions of the above (1) to (5), it cannot be seen on the surface of the single skeleton. Particle generation.

(Manufacture of monolithic cation exchanger)

The monolith produced by the above method was reacted with chlorinated sulfuric acid in the same manner as in Reference Example 26 to produce a monolithic cation exchanger. The results are shown in Table 7. The resulting ion exchange zone of the monolithic cation exchanger had a length of 26 mm, which was a larger value than Reference Examples 26 to 31.

<Reference Example 33~35> (Manufacture of single block)

In addition to changing the amount of the vinyl monomer used, the amount of the crosslinking agent used, the type and amount of the organic solvent, and the porous structure, crosslinking density, and amount of use of the monolithic intermediate which are present during the polymerization in the third step, A monolith was produced in the same manner as in Reference Example 26 except for the blending amount shown in FIG. The results are shown in Tables 6 and 7. Further, these were produced under the following conditions which did not satisfy the production conditions of the present invention: Reference Example 33 is a crosslinking density ratio (0.2 times), and Reference Example 34 is a type of organic solvent (2-(2-methoxy B) Ethoxy)ethanol; molecular weight 120), Reference Example 35 is the polymerization temperature (50 ° C; 1 ° C lower than the 10-hour half-life temperature of the polymerization initiator). The results are shown in Table 7. In the monoliths of Reference Examples 33 and 35, no particle formation was observed on the skeleton surface. Further, the product isolated in Reference Example 34 was transparent, and the porous structure collapsed and disappeared.

(Manufacture of monolithic cation exchanger)

The organic porous body produced by the above method was reacted with chlorinated sulfuric acid in the same manner as in Reference Example 32 except for Reference Example 34 to produce a monolithic cation exchanger. The results are shown in Table 7. The resulting ion exchange zone of the monolithic cation exchanger has a length of 23 to 26 mm, which is a larger value than the reference examples 26 to 31.

<Reference Example 36> (Manufacture of single block)

The amount of the vinyl monomer used, the amount of the crosslinking agent used, the amount of the organic solvent used, and the porous structure and the amount of the monolithic intermediate which were coexisted during the polymerization in the third step were changed to the amounts shown in Table 1. Except for the same procedure as Reference Example 32, a monolith was produced. The results are shown in Tables 6 and 7. However, when a monolith was produced without departing from the specific production conditions of the present invention, particle formation was not observed on the surface of the monolith skeleton.

(Manufacture of monolithic anion exchanger)

The monolith produced by the above method was cut into a disk shape having a diameter of 70 mm and a thickness of about 15 mm. 1400 ml of dimethoxymethane and 20 ml of tin tetrachloride were added thereto, and 560 ml of sulfuric acid sulfuric acid was added dropwise under ice cooling. After completion of the dropwise addition, the mixture was heated and reacted at 35 ° C for 5 hours to introduce a chloromethyl group. After completion of the reaction, the mother liquid was extracted by siphoning, washed with a mixed solvent of THF/water = 2/1, and then washed with THF. To the chloromethylated monolith, 1000 ml of THF and 600 ml of a 30% aqueous solution of trimethylamine were added, and the mixture was reacted at 60 ° C for 6 hours. After completion of the reaction, the product was washed with a methanol/water mixed solvent, and then washed with pure water to separate. The results are shown in Table 7. The length of the ion exchange zone of the obtained monolithic anion exchanger was 47 mm, which was a value larger than that of Reference Examples 6 to 7. In Tables 6 and 7, the values of the clearance hole diameter and the pore diameter indicate the average value, respectively.

<Reference Example 37> (Manufacture of monolithic organic porous 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 to uniformly dissolve them. Next, the styrene/divinylbenzene/azobisisobutyronitrile/sorbitan monooleate mixture was added to 450 ml of pure water, and stirred by a homogenizer at 20,000 rotations/min for 2 minutes to obtain an oil. Medium drop type emulsion. After completion of the emulsification, the water-drop type emulsion in the oil was transferred to an autoclave made of stainless steel, sufficiently substituted with nitrogen, sealed, and polymerized at 60 ° C for 24 hours under standing. After completion of the polymerization, the contents were taken out and subjected to Soxler extraction with isopropyl alcohol for 18 hours, and the unreacted monomer and sorbitan monooleate were removed, and then dried under reduced pressure at 40 ° C for a day and night. 11.5 g of an organic porous body containing 14 mol% of a cross-linking component composed of a styrene/divinylbenzene copolymer thus obtained was taken out, and 800 ml of tetrachloroethane was added thereto, and the mixture was heated at 60 ° C for 30 minutes, and then cooled. To room temperature, 59.1 g of chlorinated sulfuric acid was slowly added, and the mixture was reacted at room temperature for 24 hours. Thereafter, acetic acid was added, and the reactant was poured into a large amount of water, washed with water, and dried to obtain a porous cation exchanger. The ion exchange capacity of the porous body was 4.4 mg equivalent/g in terms of dry porous substance, and was 0.32 mg equivalent/ml in terms of wet volume, and the sulfonic acid was confirmed by using a sulfur atom of EPMA. The groups are uniformly introduced into the porous body. Further, as a result of SEM observation, the internal structure of the organic porous body has an open cell structure, and most of the macropores having an average diameter of 30 μm overlap, and the pores formed by the overlap of the macropores and the macropores have a pore diameter of 5 μm. The total pore volume was 10.1 ml/g, and the BET specific surface area was 10 m ² /g.

(Example 3)

The inner diameter of the composite monolithic ion exchanger was filled with a 57 mm inner diameter column, and the raw water was passed from the upper side toward the lower side to pass the water, and the sodium concentration in the treated water was measured to be more than 1 μg/l. In addition, the water pressure difference in the water is also measured. The water passing experimental conditions are as follows. As a result, the time during which the sodium concentration in the treated water exceeded 1 μg/l was 190 days. Moreover, the water pressure difference is 37 kPa.

(water conditions)

‧ Ion exchanger: The upstream side is a mixed resin of a granular cation exchange resin and an anion exchange resin (mixing ratio = 1:1 (filling volume ratio), resin layer height: 300 mm) and the downstream side is a single piece (diameter 57 mm, 40mm high layered body

‧Cation exchange resin: IR120B (trade name)

‧ Anion exchange resin: IRA402BL (trade name)

‧ Raw water: NaCl aqueous solution, sodium concentration 80μg / l

‧Flow: 120l/h

‧ Monolith: Reference monolithic cation exchanger of Example 27

The cation exchange resin was once Na-formed with sodium chloride, and then regenerated with 1% hydrochloric acid at a regeneration rate of 99%, and then sufficiently washed with ultrapure water to be used as a regenerated shape. Further, the regeneration rate means the capacity ratio of the H type which can be adsorbed on the resin.

(Comparative Example 3)

The same procedure as in Example 3 was carried out except that the monolithic cation exchanger of Reference Example 27 was used instead of the monolithic cation exchanger of Reference Example 37. As a result, the time during which the sodium concentration in the treated water exceeded 1 μg/l was 21 days. Moreover, the water pressure difference is 230 kPa.

(Comparative Example 4)

The same procedure as in Example 3 was carried out except that a mixed resin of a granular cation exchange resin and an anion exchange resin (resin layer height: 340 mm) was used as the ion exchanger. That is, in Comparative Example 4, a monolith was used as the ion exchanger, and the ion exchange resin in a granular form was 100%. As a result, the time during which the sodium concentration in the treated water exceeded 1 μg/l was 0 days. That is, the sodium concentration in the treated water from the first day of watering is more than 1 μg/l. Moreover, the water pressure difference is 230 kPa.

The leakage of ions adsorbed in Example 3 was slower than in Comparative Examples 3 and 4. Therefore, the exchange frequency of the ion exchange module can be reduced. Moreover, since the water pressure difference is low, water can be supplied at a low pressure.

(industrial availability)

According to the present invention, the monolithic porous ion exchanger can be easily formed into, for example, a block shape embedded in a filling container, and the filling is also easy. Further, it can be applied to any of the continuous water-passing method generally employed in the conventional module and the batch processing method which is carried out in the water in the storage container or the storage tank.

1‧‧‧Desalting room

2‧‧‧Concentration room

10‧‧‧Separation sub-module

11‧‧‧Area

12‧‧‧ Skeleton Department

13‧‧‧ giant hole

61‧‧‧ skeleton phase

62a, 62b, 62c, 62d, 62e‧‧ ‧ protrusions

Figure 1 is an SEM image of a single block in a first monolithic ion exchanger.

Figure 2 is an EPMA image showing the distribution of sulfur atoms in the surface of the monolith of Figure 1.

Fig. 3 is an EPMA image showing the distribution of sulfur atoms in the cross section (thickness) direction of the monolith of Fig. 1.

4 is a graph showing the correlation between the differential pressure coefficient of Reference Examples 1 to 13 and Reference Examples 20 to 23 and the ion exchange capacity per unit volume.

Fig. 5 is a view showing the manual transfer of the skeleton portion shown by the SEM image section of Fig. 1.

Fig. 6 is a view schematically showing a co-continuous structure of a second monolithic ion exchanger;

Figure 7 is an SEM image of a monolithic intermediate in a co-continuous construction.

Figure 8 is an SEM image of a monolithic cation exchanger having a co-continuous structure.

Figure 9 is an EPMA image showing the distribution of sulfur atoms on the surface of a monolithic cation exchanger having a co-continuous structure.

Figure 10 is an EPMA image showing the distribution of sulfur atoms in the cross-sectional (thickness) direction of a monolithic cation exchanger having a co-continuous structure.

Figure 11 is an SEM image of another monolithic cation exchanger having a co-continuous configuration.

Fig. 12 is a SEM photograph of an organic porous body of a conventional (Japanese Patent Laid-Open Publication No. 2002-306976).

Fig. 13 is an SEM image of a magnification of 100 of the monolith obtained in Reference Example 26.

14 is an SEM image of a magnification of 300 of the monolith obtained in Reference Example 26.

Fig. 15 is an SEM image of a magnification of 3000 of the monolith obtained in Reference Example 26.

Fig. 16 is an EPMA image showing the distribution of sulfur atoms on the surface of the monolithic cation exchanger obtained in Reference Example 26.

Fig. 17 is an EPMA image showing the distribution of sulfur atoms in the cross-sectional (thickness) direction of the monolithic cation exchanger obtained in Reference Example 26.

18 is an SEM image of a magnification of 100 of the monolith obtained in Reference Example 27.

19 is an SEM image of a magnification of 600 of the monolith obtained in Reference Example 27.

20 is an SEM image of a magnification of 3000 of the monolith obtained in Reference Example 27.

21 is an SEM image of a magnification of 600 of the monolith obtained in Reference Example 28.

22 is an SEM image of a magnification of 3000 of the monolith obtained in Reference Example 28.

23 is an SEM image of a magnification of 3000 of the monolith obtained in Reference Example 29.

24 is an SEM image of a magnification of 100 of the monolith obtained in Reference Example 30.

25 is an SEM image of a magnification of 3000 of the monolith obtained in Reference Example 30.

26 is an SEM image of a magnification of 100 of the monolith obtained in Reference Example 31.

27 is an SEM image of a magnification of 600 of the monolith obtained in Reference Example 31.

28 is an SEM image of a magnification of 3000 of the monolith obtained in Reference Example 31.

Figure 29 is a schematic cross-sectional view of a protrusion.

Claims (15)

An ion adsorption module comprising: a container having at least an opening into which water to be treated flows, and a monolithic organic porous ion exchanger filled in the container; wherein the monolithic organic The porous pores of the porous ion exchange system overlap each other, and the overlapping portion becomes a continuous macroporous structure having an opening of an average diameter of 30 to 300 μm in a wet state of water; the total pore volume is 0.5 to 5 ml/g, and the water is wet. The ion exchange capacity per unit volume in the state is 0.4 to 5 mg equivalent/ml, and the ion exchange group is uniformly distributed in the porous ion exchanger, and the SEM image of the cut section of the continuous macroporous structure (dry body) The area of the cross section of the skeleton shown in the SEM image is 25 to 50% in the image area. An ion adsorption module comprising a container having at least an opening into which water to be treated flows, and a monolithic organic porous ion exchanger filled in the container; wherein the monolithic organic porous ion The exchange system belongs to a three-dimensional continuous skeleton formed by an aromatic vinyl polymer having 0.3 to 5.0 mol% of a crosslinked structural unit in a total constituent unit of the ion exchange group, and having a thickness of 1 to 60 μm. a co-continuous structure composed of three-dimensional continuous pores having a diameter of 10 to 100 μm; the total pore volume is 0.5 to 5 ml/g, and the ion exchange capacity per unit volume in the water-wet state is 0.3 to 5 mg equivalent. /ml, the ion exchange group is uniformly distributed in the porous ion exchanger. An ion adsorption module having at least a flow of water to be treated An open container and a monolithic organic porous ion exchanger filled in the container; wherein the monolithic organic porous ion exchange system comprises an organic porous body having a continuous skeleton phase and a continuous pore phase And a composite body having a diameter of 4 to 40 μm adhered to the surface of the skeleton of the organic porous body or a plurality of protrusions having a size of 4 to 40 μm formed on the surface of the skeleton of the organic porous body; The pores have an average diameter of 10 to 150 μm in a wet state of water, a total pore volume of 0.5 to 5 ml/g, and an ion exchange capacity per unit volume in a wet state of water of 0.2 mg equivalent/ml or more. The ion adsorption module according to claim 3, wherein the porous pores of the organic porous system overlap each other, and the overlapping portion is a continuous macroporous structure having an opening having an average diameter of 30 to 150 μm in a wet state of water. body. The ion adsorption module according to claim 3, wherein the organic porous system has a three-dimensional continuous skeleton having an average thickness of 1 to 60 μm in a wet state of water, and a diameter between the skeleton and a water wet state. It is a co-continuous structure composed of three-dimensional continuous pores of 10 to 100 μm. The ion-adsorbing module according to any one of claims 1 to 3, wherein the container is provided with a water to be treated which is connected to an opening through which the water to be treated flows, and a treated water outflow pipe. The ion adsorption module according to any one of claims 1 to 3, wherein the monolithic organic porous ion exchange system organic porous cation exchanger and the organic porous anion exchanger, and the organic porous Quality The ion exchanger and the organic porous anion exchanger are laminated and filled. An ion adsorption module characterized in that the following structures are sequentially stacked from the upstream side: a granular ion exchange resin filling layer; and an organic porous ion exchange filling layer, a bubble-like macropores Coincidentally overlapping, and the overlapping portion is a continuous macroporous structure having an opening of an average diameter of 30 to 300 μm in a wet state of water; the total pore volume is 0.5 to 5 ml/g, and the ion exchange capacity per unit volume in a wet state of water 0.4 to 5 mg equivalent/ml, the ion exchange group is uniformly distributed in the porous ion exchanger, and in the SEM image of the cut section of the continuous macroporous structure (dry body), the skeleton portion shown in the SEM image The area of the section is 25 to 50% of the image area. An ion adsorption module characterized in that the following structures are sequentially stacked from the upstream side: a granular ion exchange resin filling layer; and an organic porous ion exchange filling layer, which belongs to the introduction a three-dimensional continuous skeleton having a thickness of 1 to 60 μm formed by an aromatic vinyl polymer having a crosslinked structural unit of 0.3 to 5.0 mol% of the total constituent unit of the ion exchange group, and a diameter of 10 to 10 between the skeletons a co-continuous structure composed of three-dimensional continuous pores of 100 μm; the total pore volume is 0.5 to 5 ml/g, and the ion exchange capacity per unit volume in the wet state of water is 0.3 to 5 mg equivalent/ml, and the ion exchange group is uniform. Distributed in the porous ion exchanger. An ion adsorption module characterized in that the following structures are sequentially stacked from the upstream side: a granular ion exchange resin filling layer; and an organic porous ion exchange filling layer containing a continuous skeleton phase and The organic porous body of the continuous pore phase and the majority of the particles having a diameter of 4 to 40 μm adhered to the surface of the skeleton of the organic porous body or the surface of the skeleton of the organic porous body are 4 to 40 μm. a composite structure of a plurality of protrusions; the average diameter of the pores in the wet state of water is 10 to 150 μm, the total pore volume is 0.5 to 5 ml/g, and the ion exchange capacity per unit volume in the wet state is 0.2 mg. Equivalent / ml or more. The ion adsorption module according to any one of claims 1 to 3, wherein the ion adsorption module is disposed on a downstream side of the ion adsorption module filled with the granular ion exchange resin. A water treatment method characterized in that an ionic impurity in the water to be treated is adsorbed and removed by contacting an organic porous ion exchanger with water to be treated; the bubble-like pores of the organic porous ion exchange system coincide with each other And the superposed portion is a continuous macroporous structure having an opening with an average diameter of 30 to 300 μm in a wet state of water, and the total pore volume is 0.5 to 5 ml/g, and the ion exchange capacity per unit volume in the water wet state is 0.4. ~5mg equivalent/ml, the ion exchange group is uniformly distributed in the porous ion exchanger, and the cross section of the skeleton portion shown in the SEM image is in the SEM image of the cut section of the continuous macroporous structure (dry body) The area is 25~50% in the image area. A water treatment method characterized in that an ionic impurity in a water to be treated is adsorbed and removed by contacting an organic porous ion exchanger with water to be treated; the organic porous ion exchange system belongs to an ion exchange introduced therein a three-dimensional continuous skeleton having a thickness of 1 to 60 μm formed by an aromatic vinyl polymer having a crosslinked structural unit of 0.3 to 5.0 mol% in the total constituent unit, and a diameter of 10 to 100 μm between the skeletons A co-continuous structure composed of three-dimensional continuous pores has a total pore volume of 0.5 to 5 ml/g, and an ion exchange capacity per unit volume in a wet state of water is 0.3 to 5 mg equivalent/ml, and ion exchange groups are uniformly distributed in In the porous ion exchanger. A water treatment method characterized in that an ionic impurity in a water to be treated is adsorbed and removed by contacting an organic porous ion exchanger with water to be treated; the organic porous ion exchange system containing a continuous skeleton phase and continuous space The organic porous body of the pore phase, and a plurality of particle bodies having a diameter of 4 to 40 μm adhered to the surface of the skeleton of the organic porous body or a size of 4 to 40 μm formed on the surface of the skeleton of the organic porous body The composite structure of the protrusions has an average diameter of pores of 10 to 150 μm in a wet state of water, a total pore volume of 0.5 to 5 ml/g, and an ion exchange capacity per unit volume in a wet state of water of 0.2 mg equivalent / More than ml. The water treatment method according to any one of claims 12 to 14, wherein the water to be treated is treated water previously treated with a particulate ion exchange resin.