JP5431194B2 - Electric deionized water production equipment - Google Patents

Description

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

  As a method for producing deionized water, there is conventionally known a method in which deionized water is passed through an ion exchange resin to be treated. In this method, regeneration is performed with a drug when the ion exchange resin is saturated with ions. In order to eliminate such disadvantages in processing operations, a method for producing deionized water by an electric deionization method which does not require any regeneration by a chemical agent has been established and has been put into practical use.

  Japanese Patent Application Laid-Open No. 2003-334560 has an open cell structure having macropores connected to each other and mesopores having an average diameter of 1 to 1000 μm in the walls of the macropores, and the total pore volume is 1 ml / g to 50 ml / g. And having a deionization chamber in which the ion exchange groups are uniformly distributed and the ion exchange capacity is filled with an organic porous ion exchanger having a dry porous body of 0.5 mg equivalent / g or more, and is passed through the deionization chamber. Water, remove ionic impurities in the water to produce deionized water, and apply a DC electric field to the deionization chamber to remove ionic impurities adsorbed on the organic porous ion exchanger out of the system In the electric deionized water production apparatus, the application of the DC electric field is performed so that the ions to be excluded migrate in the direction opposite to the water flow direction in the organic porous ion exchanger. Apparatus is disclosed.

  According to this electric deionized water production apparatus, it is possible to accelerate the movement of ions in the porous ion exchanger and facilitate the removal of adsorbed ions. Further, it is not necessary to divide the deionization chamber into a large number and arrange them in parallel, simplifying the structure of the apparatus, and reducing material costs, processing costs, and assembly costs. In addition, there is no generation of scale such as calcium carbonate and magnesium hydroxide, and no pretreatment such as primary desalting or softening is required. Furthermore, it is possible to obtain treated water with stable water quality at a low voltage.

JP 2003-334560 A

  However, the organic porous ion exchanger described in Japanese Patent Application Laid-Open No. 2003-334560 describes a monolith common opening (mesopore) of 1 to 1,000 μm, but has a total pore volume of 5 ml / g or less. For monoliths with a small pore volume, the amount of water droplets in the water-in-oil emulsion needs to be reduced, so that the common opening becomes small, and those having an average diameter of 20 μm or more cannot be manufactured. For this reason, there existed a problem that the pressure loss at the time of water flow was large. In addition, when the average diameter of the openings is around 20 μm, the total pore volume also increases accordingly, so that the ion exchange capacity per volume decreases, so that the treated water quality decreases and the power consumption increases. There was a problem.

  Therefore, the object of the present invention is to accelerate the movement of the adsorbed ionic impurities to facilitate the removal of the adsorbed ions, to increase the strength of the ion exchanger, and to reduce the pressure loss during water flow. Is to provide an electric deionized water production apparatus with good power consumption and low power consumption.

  Under such circumstances, the present inventors have conducted intensive studies, and as a result, obtained a monolithic organic porous body (intermediate) having a relatively large pore volume obtained by the method described in JP-A-2003-334560. In the presence, if the vinyl monomer and the crosslinking agent are allowed to stand and polymerize in a specific organic solvent, a thick monolith having a larger skeleton than the skeleton of the intermediate organic porous body can be obtained. When an ion exchange group is introduced into a thick monolith, the swelling is large due to the thick bone, and therefore the opening can be further increased. When used as an ion exchanger in an electrical deionized water production apparatus, the ion exchanger can be easily removed by accelerating the movement of the adsorbed ionic impurities. A high strength of the ion exchanger, it is possible to reduce the pressure loss during water flow, the treated water quality is good, and power consumption found such that little, and have completed the present invention.

  In addition, as a result of intensive studies, the present inventors have found that an aromatic monolith-like organic porous material intermediate having a large pore volume obtained by the method described in JP-A-2003-334560 is aromatic. If a vinyl monomer and a crosslinking agent are allowed to stand in a specific organic solvent, they are composed of a three-dimensionally continuous aromatic vinyl polymer skeleton and three-dimensionally continuous pores between the skeleton phases. It is possible to obtain an intertwined, hydrophobic monolith with a continuous structure, this monocontinuous structure has a high continuity of pores, is not biased in size, and has a low pressure loss during fluid permeation. Since the skeleton of the co-continuous structure is thick, if an ion exchange group is introduced, a monolithic organic porous ion exchanger having a large ion exchange capacity per volume can be obtained, and the monolithic organic porous ion exchanger (hereinafter, “ Second When used as an ion exchanger of an electrical deionized water production apparatus, the “noris ion exchanger” can be used to accelerate the movement of adsorbed ionic impurities as in the case of the first monolith ion exchanger. It was found that the ion exchanger was easy to remove, the strength of the ion exchanger was high, the pressure loss during water flow could be reduced, the quality of the treated water was good and the power consumption was low, and the present invention was completed. It was.

  That is, the present invention is a continuous macropore structure in which bubble-like macropores overlap each other, and the overlapping portion is an opening having an average diameter of 30 to 300 μm in a water-wet state, and has a total pore volume of 0.5 to 5 ml / g, The ion exchange capacity per volume in a wet state of water is 0.4 to 5 mg equivalent / ml, the ion exchange groups are uniformly distributed in the porous ion exchanger, and the continuous macropore structure (dried body) In the SEM image of the cut surface of), water is passed through a deionization chamber filled with an organic porous ion exchanger having an area of 25 to 50% of the image area in the image area to remove ionic impurities in water. In the electric deionized water producing apparatus for producing deionized water and applying a DC electric field to the deionized chamber to exclude ionic impurities adsorbed on the organic porous ion exchanger out of the system, The application of the DC electric field is to provide an electric deionized water production apparatus characterized in that the ions to be excluded migrate so as to migrate in the direction opposite to the direction of water flow in the organic porous ion exchanger. is there.

  The present invention also provides a three-dimensional thickness of 1 to 60 μm in thickness composed of an aromatic vinyl polymer containing 0.3 to 5.0 mol% of a crosslinked structural unit among all the structural units into which ion exchange groups have been introduced. A co-continuous structure composed of a continuous skeleton and three-dimensionally continuous pores having a diameter of 10 to 100 μm between the skeletons, and has a total pore volume of 0.5 to 5 ml / g, Deionization packed with an organic porous ion exchanger in which the ion exchange capacity per volume in a wet state is 0.3 to 5 mg equivalent / ml and the ion exchange groups are uniformly distributed in the porous ion exchanger Water is passed through the chamber to remove ionic impurities in the water to produce deionized water, and a DC electric field is applied to the deionization chamber to remove the ionic impurities adsorbed on the organic porous ion exchanger. In the electric deionized water production apparatus excluded outside, the direct The application of an electric field provides an electric deionized water production apparatus characterized in that the ions to be excluded migrate so as to migrate in the direction opposite to the direction of water flow in the organic porous ion exchanger. .

  The present invention also includes a decation chamber formed by filling an organic porous cation exchanger in a deionization chamber partitioned by an ion exchange membrane on one side and a cation exchange membrane on the other side, An anode disposed outside the ion exchange membrane, a cathode disposed outside the other cation exchange membrane, and disposed in the vicinity of the other cation exchange membrane in the decation chamber. An electric decationized water production apparatus comprising: a first treated water introduction / distribution unit; and a first treated water collecting unit disposed in the vicinity of an ion exchange membrane on one side of the decationization chamber, A deionization chamber formed by filling a deionization chamber partitioned by an anion exchange membrane on one side and an ion exchange membrane on the other side with an organic porous anion exchanger, and the outside of the anion exchange membrane on the one side An anode disposed on the other side, a cathode disposed outside the ion exchange membrane on the other side, and a first treatment of the electric decationized ion water production apparatus. A second treated water introduction / distribution unit disposed in the vicinity of the anion exchange membrane on one side in the deanion ion chamber connected to the water collecting unit by a communication pipe; and the other side in the deanion ion chamber An electrodeionized ion water production apparatus having a second treated water collection part disposed in the vicinity of the ion exchange membrane, the organic porous cation exchanger and the organic porous The anion exchanger is a continuous macropore structure in which bubble-like macropores overlap each other, and this overlapping portion is an opening having an average diameter of 30 to 300 μm in a water-wet state, with a total pore volume of 0.5 to 5 ml / g, The ion exchange capacity per volume in a wet state of water is 0.4 to 5 mg equivalent / ml, the ion exchange groups are uniformly distributed in the porous ion exchanger, and the continuous macropore structure (dried body) ) In the SEM image of the cut surface Area, and provides an electrodeionization water producing apparatus, characterized in that from 25 to 50% in image area.

The present invention also includes a decation chamber formed by filling an organic porous cation exchanger in a deionization chamber partitioned by an ion exchange membrane on one side and a cation exchange membrane on the other side, An anode disposed outside the ion exchange membrane, a cathode disposed outside the other cation exchange membrane, and disposed in the vicinity of the other cation exchange membrane in the decation chamber. An electric decationized water production apparatus comprising: a first treated water introduction / distribution unit; and a first treated water collecting unit disposed in the vicinity of an ion exchange membrane on one side of the decationization chamber, A deionization chamber formed by filling a deionization chamber partitioned by an anion exchange membrane on one side and an ion exchange membrane on the other side with an organic porous anion exchanger, and the outside of the anion exchange membrane on the one side An anode disposed on the other side, a cathode disposed outside the ion exchange membrane on the other side, and a first treatment of the electric decationized ion water production apparatus. A second treated water introduction / distribution unit disposed in the vicinity of the anion exchange membrane on one side in the deanion ion chamber connected to the water collecting unit by a communication pipe; and the other side in the deanion ion chamber An electrical deionized ion water production apparatus having a second treated water collection unit disposed in the vicinity of the ion exchange membrane,
An aromatic vinyl polymer in which the organic porous cation exchanger and the organic porous anion exchanger contain 0.3 to 5.0 mol% of a crosslinked structural unit in all the structural units into which an ion exchange group is introduced. A co-continuous structure comprising a three-dimensionally continuous skeleton having a thickness of 1 to 60 μm and three-dimensionally continuous pores having a diameter of 10 to 100 μm between the skeletons, The volume is 0.5 to 5 ml / g, the ion exchange capacity per volume in a wet state of water is 0.3 to 5 mg equivalent / ml, and the ion exchange groups are uniformly distributed in the porous ion exchanger. An electrical deionized water production apparatus is provided.

In addition, the present invention provides a first detachment partitioned by a cation exchange membrane on one side and an intermediate cation exchange membrane formed between the cation exchange membrane on one side and the anion exchange membrane on the other side. An organic porous anion is formed in a decation chamber in which an ion chamber is filled with an organic porous cation exchanger, and a second deionization chamber defined by the other anion exchange membrane and the intermediate cation exchange membrane. A deanion chamber filled with an ion exchanger, a cathode disposed outside the cation exchange membrane on one side, an anode disposed outside the anion exchange membrane on the other side, A first treated water introduction / distribution unit disposed in the vicinity of the cation exchange membrane on one side in the decation chamber, and a first disposed in the vicinity of the intermediate cation exchange membrane in the decation chamber. A treated water collection unit is disposed in the vicinity of the anion exchange membrane on the other side in the deionization chamber connected to the first treated water collection unit through a communication pipe. A second processed water inlet distribution unit, there is provided a second processing water catchment portion which is disposed in the intermediate cation exchange membrane vicinity in dehydration anion chamber, and
The organic porous cation exchanger and the organic porous anion exchanger are continuous macropore structures in which bubble-shaped macropores overlap each other, and the overlapping portions form an opening having an average diameter of 30 to 300 μm in a wet state. The total pore volume is 0.5 to 5 ml / g, the ion exchange capacity per volume in a wet state of water is 0.4 to 5 mg equivalent / ml, and the ion exchange groups are uniformly distributed in the porous ion exchanger. In addition, in the SEM image of the cut surface of the continuous macropore structure (dry body), the skeleton part area that appears in the cross section is 25 to 50% in the image region, A device is provided.

In addition, the present invention provides a first detachment partitioned by a cation exchange membrane on one side and an intermediate cation exchange membrane formed between the cation exchange membrane on one side and the anion exchange membrane on the other side. An organic porous anion is formed in a decation chamber in which an ion chamber is filled with an organic porous cation exchanger, and a second deionization chamber defined by the other anion exchange membrane and the intermediate cation exchange membrane. A deanion chamber filled with an ion exchanger, a cathode disposed outside the cation exchange membrane on one side, an anode disposed outside the anion exchange membrane on the other side, A first treated water introduction / distribution unit disposed in the vicinity of the cation exchange membrane on one side in the decation chamber, and a first disposed in the vicinity of the intermediate cation exchange membrane in the decation chamber. A treated water collection unit is disposed in the vicinity of the anion exchange membrane on the other side in the deionization chamber connected to the first treated water collection unit through a communication pipe. A second processed water inlet distribution unit, there is provided a second processing water catchment portion which is disposed in the intermediate cation exchange membrane vicinity in dehydration anion chamber, and
An aromatic vinyl polymer in which the organic porous cation exchanger and the organic porous anion exchanger contain 0.3 to 5.0 mol% of a crosslinked structural unit in all the structural units into which an ion exchange group is introduced. A co-continuous structure comprising a three-dimensionally continuous skeleton having a thickness of 1 to 60 μm and three-dimensionally continuous pores having a diameter of 10 to 100 μm between the skeletons, The volume is 0.5 to 5 ml / g, the ion exchange capacity per volume in a wet state of water is 0.3 to 5 mg equivalent / ml, and the ion exchange groups are uniformly distributed in the porous ion exchanger. An electrical deionized water production apparatus is provided.

The present invention also provides a first deionization chamber defined by an ion exchange membrane on one side and an intermediate cation exchange membrane formed between the ion exchange membrane on the one side and the ion exchange membrane on the other side. A decation chamber filled with an organic porous cation exchanger, the intermediate cation exchange membrane, and an intermediate anion exchange membrane formed between the intermediate cation exchange membrane and the other side ion exchange membrane And a deionization chamber formed by filling an organic porous anion exchanger in a second deionization chamber partitioned by the ion exchange membrane on the other side and the intermediate anion exchange membrane. An anode disposed outside the ion exchange membrane on one side, a cathode disposed outside the ion exchange membrane on the other side, and an intermediate cation exchange membrane in the decation chamber. A first treated water introduction / distribution section provided, and a first disposed in the vicinity of the ion exchange membrane on one side in the decation chamber. A treated water collection section, a second treated water introduction / distribution section disposed in the vicinity of the intermediate anion exchange membrane in the deanion ion chamber connected to the first treated water collection section by a communication pipe, A second treated water collecting section disposed near the ion exchange membrane on the other side in the deanion ion chamber,
The organic porous cation exchanger and the organic porous anion exchanger are continuous macropore structures in which bubble-shaped macropores overlap each other, and the overlapping portions form an opening having an average diameter of 30 to 300 μm in a wet state. The total pore volume is 0.5 to 5 ml / g, the ion exchange capacity per volume in a wet state of water is 0.4 to 5 mg equivalent / ml, and the ion exchange groups are uniformly distributed in the porous ion exchanger. In addition, in the SEM image of the cut surface of the continuous macropore structure (dry body), the skeleton part area that appears in the cross section is 25 to 50% in the image region, A device is provided.

The present invention also provides a first deionization chamber defined by an ion exchange membrane on one side and an intermediate cation exchange membrane formed between the ion exchange membrane on the one side and the ion exchange membrane on the other side. A decation chamber filled with an organic porous cation exchanger, the intermediate cation exchange membrane, and an intermediate anion exchange membrane formed between the intermediate cation exchange membrane and the other side ion exchange membrane And a deionization chamber formed by filling an organic porous anion exchanger in a second deionization chamber partitioned by the ion exchange membrane on the other side and the intermediate anion exchange membrane. An anode disposed outside the ion exchange membrane on one side, a cathode disposed outside the ion exchange membrane on the other side, and an intermediate cation exchange membrane in the decation chamber. A first treated water introduction / distribution section provided, and a first disposed in the vicinity of the ion exchange membrane on one side in the decation chamber. A treated water collection section, a second treated water introduction / distribution section disposed in the vicinity of the intermediate anion exchange membrane in the deanion ion chamber connected to the first treated water collection section by a communication pipe, A second treated water collecting section disposed near the ion exchange membrane on the other side in the deanion ion chamber,
An aromatic vinyl polymer in which the organic porous cation exchanger and the organic porous anion exchanger contain 0.3 to 5.0 mol% of a crosslinked structural unit in all the structural units into which an ion exchange group is introduced. A co-continuous structure comprising a three-dimensionally continuous skeleton having a thickness of 1 to 60 μm and three-dimensionally continuous pores having a diameter of 10 to 100 μm between the skeletons, The volume is 0.5 to 5 ml / g, the ion exchange capacity per volume in a wet state of water is 0.3 to 5 mg equivalent / ml, and the ion exchange groups are uniformly distributed in the porous ion exchanger. An electrical deionized water production apparatus is provided.

  According to the present invention, the movement of adsorbed ionic impurities can be accelerated to facilitate the removal of adsorbed ions, the ion exchanger has high strength, the pressure loss during water flow can be reduced, and the quality of treated water is good. And low power consumption.

It is a SEM image of the monolith in the 1st monolith ion exchanger. It is an EPMA image which showed the distribution state of the sulfur atom in the surface of the monolith of FIG. 2 is an EPMA image showing a distribution state of sulfur atoms in the cross-section (thickness) direction of the monolith of FIG. It is a figure which shows the correlation of the differential pressure | voltage coefficient of the reference examples 1-11 and the reference examples 20-23, and the ion exchange capacity per volume. It is a manual transfer of the skeleton part that appears as a cross section of the SEM image of FIG. It is the figure which showed typically the co-continuous structure of the 2nd monolith ion exchanger. It is a SEM image of the monolith intermediate in a bicontinuous structure. It is a SEM image of the monolith cation exchanger which has a bicontinuous structure. It is the EPMA image which showed the distribution state of the sulfur atom in the surface of the monolith cation exchanger which has a bicontinuous structure. It is the EPMA image which showed the distribution state of the sulfur atom in the cross section (thickness) direction of the monolith cation exchanger which has a bicontinuous structure. It is a SEM image of the other monolith cation exchanger which has a bicontinuous structure. It is the SEM photograph of the organic porous body of the former (Unexamined-Japanese-Patent No. 2002-306976). It is a schematic diagram which shows the structure of the electrical deionized water manufacturing apparatus of the 1st Example of this invention. It is a schematic diagram which shows the structure of the electrical deionized water manufacturing apparatus of the 2nd Example of this invention. It is a schematic diagram which shows the structure of the electrical deionized water manufacturing apparatus of the 3rd Example of this invention. It is the figure which illustrated the groove part of the surface of the porous ion exchanger used as a to-be-processed water introduction distribution part or a treated water collection part.

  The electric deionized water production apparatus of the present invention passes through a deionization chamber filled with an organic porous ion exchanger having a specific structure, and removes ionic impurities in the water to produce deionized water. In an apparatus for applying a DC electric field to a deionization chamber to exclude ionic impurities adsorbed on the organic porous ion exchanger out of the system, the application of the DC electric field is such that the ions to be excluded are the organic porous ions. It is performed so as to migrate in the opposite direction to the direction of water flow in the exchanger. That is, the basic structure of the electric deionized water production apparatus of the present invention is to form a deionization chamber by filling an organic porous ion exchanger into a deionization chamber partitioned by ion exchange membranes on both sides, An electrode for applying a DC electric field is disposed outside the membrane, and the application of the DC electric field is performed in a specific manner as described above. In the present invention, the water flow direction in the organic porous ion exchanger means the water flow direction in the organic porous ion exchanger having a specific open cell structure, that is, organic porous ions having a specific open cell structure. This refers to the average diffusion direction of ions derived from the direction of water flow in the exchanger, and the first and second treated water introduction and distribution separately disposed or processed in the organic porous ion exchanger as described later. It does not mean the direction of water flow in the section or in the first and second treated water collecting sections.

  The organic porous ion exchanger filled in the deionization chamber is the first monolith ion exchanger or the second monolith ion exchanger. In the present specification, “monolithic organic porous body” is simply “monolith”, “monolithic organic porous ion exchanger” is simply “monolith ion exchanger”, and “monolithic organic porous intermediate”. Is also simply referred to as “monolith intermediate”.

<Description of the first monolith ion exchanger>
The first monolith ion exchanger is obtained by introducing an ion exchange group into a monolith. Bubble-shaped macropores are overlapped with each other, and the overlapping portion is in a wet state with an average diameter of 30 to 300 μm, preferably 30. A continuous macropore structure having an opening (mesopore) of ˜200 μm, particularly 35 to 150 μm, and an average pore diameter of 5 to 800 nm, preferably 2 to 500 nm, on the inner wall of the cell structure formed by the macropore and the mesopore. It is a continuous macropore structure which may have micropores which are non-continuous pores. The average diameter of the opening of the monolith ion exchanger is larger than the average diameter of the opening of the monolith because the entire monolith swells when an ion exchange group is introduced into the monolith. If the average diameter of the openings is less than 30 μm, the pressure loss at the time of water flow is increased, which is not preferable. If the average diameter of the openings is too large, contact between the fluid and the monolith ion exchanger becomes insufficient. As a result, the ion exchange characteristics deteriorate, which is not preferable. In the present invention, the average diameter of the opening of the monolith intermediate in the dry state, the average diameter of the opening of the monolith in the dry state, and the average diameter of the opening of the monolith ion exchanger in the dry state are values measured by a mercury intrusion method. It is. Further, the average diameter of the openings of the monolith ion exchanger in the wet state is a value calculated by multiplying the average diameter of the openings of the monolith ion exchanger in the dry state by the swelling rate. Specifically, the water-wet monolith ion exchanger has a diameter of x1 (mm), the water-wet monolith ion exchanger is dried, and the resulting dried monolith ion exchanger has a diameter of y1 ( mm), and the average diameter of the opening of the monolith ion exchanger in the dry state measured by the mercury intrusion method was z1 (μm), the average diameter of the opening of the monolith ion exchanger in the water wet state ( μm) is calculated by the following formula: “average diameter of openings of monolith ion exchanger in water wet state (μm) = z1 × (x1 / y1)”. In addition, the average diameter of the opening of the dried monolith before introduction of the ion exchange group, and the swelling ratio of the monolith ion exchanger in the water wet state relative to the dried monolith when the ion exchange group is introduced into the dried monolith. In this case, the average diameter in the water-wet state of the pores of the monolith ion exchanger can also be calculated by multiplying the average diameter of the opening of the monolith in the dry state by the swelling rate.

  In the first monolith ion exchanger, in the SEM image of the cut surface of the continuous macropore structure, the skeleton part area appearing in the cross section is 25 to 50%, preferably 25 to 45% in the image region. If the area of the skeleton part appearing in the cross section is less than 25% in the image region, it becomes a thin skeleton, which is not preferable because the ion exchange capacity per volume decreases, and if it exceeds 50%, the skeleton becomes too thick. Since the uniformity of ion exchange characteristics is lost, it is not preferable. In addition, the monolith described in JP-A-2002-346392 actually has a limit to the blending ratio in order to ensure a common opening even if the blending ratio of the oil phase part with respect to water is increased to make the skeleton portion thick. Yes, the maximum value of the skeleton part area appearing in the cross section cannot exceed 25% in the image region.

  The conditions for obtaining the SEM image may be any conditions as long as the skeleton part that appears in the cross section of the cut surface appears clearly. For example, the magnification is 100 to 600, and the photographic area is about 150 mm × 100 mm. SEM observation is preferably performed on three or more images, preferably five or more images, taken at arbitrary locations on an arbitrary cut surface of the monolith excluding subjectivity and at different locations. The monolith to be cut is in a dry state for use in an electron microscope. The skeleton part of the cut surface in the SEM image will be described with reference to FIGS. FIG. 5 is a transcribed skeleton that appears as a cross section of the SEM photograph of FIG. In FIGS. 1 and 5, what is generally indeterminate and shown in cross section is the “skeleton portion (reference numeral 12)” in the present invention, the circular hole shown in FIG. 1 is an opening (mesopore), and A relatively large curvature or curved surface is a macropore (reference numeral 13 in FIG. 5). The skeleton area shown in the cross section of FIG. 5 is 28% in the rectangular photographic region 11. Thus, the skeleton can be clearly determined.

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

  The first monolith ion exchanger has a total pore volume of 0.5 to 5 ml / g, preferably 0.8 to 4 ml / g. If the total pore volume is less than 0.5 ml / g, the pressure loss during water passage is increased, which is not preferable. On the other hand, if the total pore volume exceeds 5 ml / g, the ion exchange capacity per volume decreases, which is not preferable. Since the monolith of the present invention has an average diameter and total pore volume of openings in the above ranges and is a thick skeleton, when it is used as an ion exchanger of an electric deionized water production apparatus, the strength is high. The water flow differential pressure is small, and the conductivity and the quality of treated water are improved. In the present invention, the total pore volume of the monolith (monolith intermediate, monolith, monolith ion exchanger) is a value measured by a mercury intrusion method. In addition, the total pore volume of the monolith (monolith intermediate, monolith, monolith ion exchanger) is the same both in the dry state and in the water wet state.

  In addition, the pressure loss at the time of making water permeate | transmit the 1st monolith ion exchanger is the pressure loss at the time of letting water flow through the column filled with 1 m of the porous body at a water flow rate (LV) of 1 m / h (hereinafter referred to as “pressure loss”). , “Differential pressure coefficient”), it is preferably in the range of 0.001 to 0.1 MPa / m · LV, more preferably 0.001 to 0.05 MPa / m · LV. If the permeation rate and the total pore volume are within this range, when this is used as an ion exchanger in an electrical deionized water production apparatus, pressure loss during water flow is suppressed and the quality of treated water is improved. It is preferable because it has sufficient mechanical strength.

  The first monolith ion exchanger has an ion exchange capacity of 0.4 to 5 mg equivalent / ml per volume in a water-wet state. In the conventional monolithic organic porous ion exchanger having a continuous macropore structure different from the present invention as described in JP-A-2003-334560, in order to achieve a low pressure loss that is practically required, When the opening diameter is increased, the total pore volume is increased accordingly, so that the ion exchange capacity per volume is decreased, and the total pore volume is decreased to increase the exchange capacity per volume. In addition, since the opening diameter is reduced, the pressure loss increases. On the other hand, the monolith ion exchanger of the present invention can further increase the aperture diameter and thicken the skeleton of the continuous macropore structure (thicken the skeleton wall), so that the pressure loss during permeation can be reduced. Desalination performance can be dramatically increased while keeping it low. If the ion exchange capacity per volume is less than 0.4 mg equivalent / ml, the desalting performance is lowered, which is not preferable. The ion exchange capacity per weight of the monolith ion exchanger of the present invention is not particularly limited. However, since the ion exchange groups are uniformly introduced to the surface of the porous body and the inside of the skeleton, 3 to 5 mg equivalent / g It is. The ion exchange capacity of a porous body in which ion exchange groups are introduced only on the surface cannot be determined unconditionally depending on the type of the porous body or ion exchange groups, but is at most 500 μg equivalent / g.

  In the first monolith ion exchanger, the material constituting the skeleton of the continuous macropore structure is an organic polymer material having a crosslinked structure. Although the crosslinking density of the polymer material is not particularly limited, it contains 0.3 to 50 mol%, preferably 0.3 to 5 mol% of crosslinked structural units with respect to all structural units constituting the polymer material. It is preferable. If the cross-linking structural unit is less than 0.3 mol%, it is not preferable because the mechanical strength is insufficient. On the other hand, if it exceeds 50 mol%, the porous body becomes brittle and the flexibility is lost. In particular, in the case of an ion exchanger, the amount of ion exchange groups introduced is decreased, which is not preferable. The type of the polymer material is not particularly limited, and examples thereof include aromatic vinyl polymers such as polystyrene, poly (α-methylstyrene), polyvinyl toluene, polyvinyl benzyl chloride, polyvinyl biphenyl, and polyvinyl naphthalene; polyolefins such as polyethylene and polypropylene; Poly (halogenated polyolefin) such as vinyl chloride and polytetrafluoroethylene; Nitrile-based polymer such as polyacrylonitrile; Cross-linking weight of (meth) acrylic polymer such as polymethyl methacrylate, polyglycidyl methacrylate, and polyethyl acrylate Coalescence is mentioned. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or a blend of two or more types of polymers. It may be what was done. Among these organic polymer materials, the cross-linking weight of the aromatic vinyl polymer is high due to the ease of forming a continuous macropore structure, the ease of introducing ion-exchange groups and the high mechanical strength, and the high stability to acids and alkalis. A styrene-divinylbenzene copolymer and a vinylbenzyl chloride-divinylbenzene copolymer are particularly preferable materials.

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

  In the first monolith ion exchanger, the introduced ion exchange groups are uniformly distributed not only on the surface of the porous body but also within the skeleton of the porous body. If the distribution of ion exchange groups is non-uniform, the movement of ions in the porous ion exchanger becomes non-uniform, which is not preferable because rapid removal of the adsorbed ions is impeded. Here, “ion exchange groups are uniformly distributed” means that the distribution of ion exchange groups is uniformly distributed on the surface and inside the skeleton in the order of at least μm. The distribution of ion exchange groups can be confirmed relatively easily by using EPMA or the like. In addition, if the ion exchange groups are uniformly distributed not only on the surface of the monolith but also within the skeleton of the porous body, the physical and chemical properties of the surface and the interior can be made uniform, so that the swelling and shrinkage can be achieved. The durability against is improved.

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

  In the first method for producing a monolith ion exchanger, the step I may be performed in accordance with the methods described in JP-A Nos. 2003-334560 and 2002-306976.

  In the production of the monolith intermediate of step I, the oil-soluble monomer that does not contain an ion exchange group includes, for example, an ion exchange group such as a carboxylic acid group, a sulfonic acid group, and a quaternary ammonium group, and is soluble in water. Low and lipophilic monomers may be mentioned. Preferable examples of these monomers include styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, divinyl benzene, ethylene, propylene, isobutene, butadiene, ethylene glycol dimethacrylate, and the like. These monomers can be used alone or in combination of two or more. However, a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate is selected as at least one component of the oil-soluble monomer, and the content thereof is 0.3 to 50 mol%, preferably 0.3 to the total oil-soluble monomer. 5 mol% is preferable in that the mechanical strength necessary for introducing a large amount of ion-exchange groups in a later step can be obtained.

  The surfactant is not particularly limited as long as it can form a water-in-oil (W / O) emulsion when an oil-soluble monomer containing no ion exchange group and water are mixed, and sorbitan monooleate, Nonionic surfactants such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene nonylphenyl ether, polyoxyethylene stearyl ether, polyoxyethylene sorbitan monooleate; potassium oleate Anionic surfactants such as sodium dodecylbenzenesulfonate and dioctyl sodium sulfosuccinate; cationic surfactants such as distearyldimethylammonium chloride; amphoteric surfactants such as lauryldimethylbetaine can be used . These surfactants can be used alone or in combination of two or more. The water-in-oil emulsion refers to an emulsion in which an oil phase is a continuous phase and water droplets are dispersed therein. The amount of the surfactant added may vary depending on the type of oil-soluble monomer and the size of the target emulsion particles (macropores), but it cannot be generally stated, but the total amount of oil-soluble monomer and surfactant Can be selected within a range of about 2 to 70%.

  In Step I, a polymerization initiator may be used as necessary when forming a water-in-oil emulsion. As the polymerization initiator, a compound that generates radicals by heat and light irradiation is preferably used. The polymerization initiator may be water-soluble or oil-soluble. For example, azobisisobutyronitrile, azobiscyclohexanenitrile, azobiscyclohexanecarbonitrile, benzoyl peroxide, potassium persulfate, ammonium persulfate, Examples thereof include hydrogen oxide-ferrous chloride, sodium persulfate-sodium acid sulfite, and tetramethylthiuram disulfide.

  The mixing method for mixing the oil-soluble monomer not containing an ion exchange group, a surfactant, water, and a polymerization initiator to form a water-in-oil emulsion is not particularly limited. Method of mixing at once, oil-soluble monomer, surfactant and oil-soluble polymerization initiator oil-soluble component and water or water-soluble polymerization initiator water-soluble component separately and uniformly dissolved, A method of mixing the components can be used. There is no particular limitation on the mixing apparatus for forming the emulsion, and a normal mixer, homogenizer, high-pressure homogenizer, or the like can be used, and an appropriate apparatus may be selected to obtain the desired emulsion particle size. Moreover, there is no restriction | limiting in particular about mixing conditions, The stirring rotation speed and stirring time which can obtain the target emulsion particle size can be set arbitrarily.

  The monolith intermediate obtained in Step I has a continuous macropore structure. When this coexists in the polymerization system, a porous structure having a thick skeleton is formed using the structure of the monolith intermediate as a template. The monolith intermediate is an organic polymer material having a crosslinked structure. Although the crosslinking density of the polymer material is not particularly limited, it contains 0.3 to 50 mol%, preferably 0.3 to 5 mol% of crosslinked structural units with respect to all the structural units constituting the polymer material. Is preferred. When the cross-linking structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable. In particular, when the total pore volume is as large as 10 to 16 ml / g, in order to maintain a continuous macropore structure, it is preferable to contain 2 mol% or more of cross-linked structural units. On the other hand, if it exceeds 50 mol%, the porous body becomes brittle and the flexibility is lost.

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

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

  Moreover, the average diameter of the opening (mesopore) which is an overlap part of a macropore and a macropore is 20-200 micrometers in a monolith intermediate body in a dry state. When the average diameter of the openings is less than 20 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes small, and the pressure loss at the time of passing water becomes large, which is not preferable. On the other hand, if it exceeds 200 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes too large, and the contact between the water to be treated and the monolith ion exchanger becomes insufficient, resulting in a decrease in desalting efficiency. This is not preferable. Monolith intermediates preferably have a uniform structure with uniform macropore size and aperture diameter, but are not limited to this, and the uniform structure is dotted with nonuniform macropores larger than the size of the uniform macropore. You may do.

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

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

  The added amount of these vinyl monomers is 3 to 40 times, preferably 4 to 30 times, by weight with respect to the monolith intermediate coexisting at the time of polymerization. If the amount of vinyl monomer added is less than 3 times that of the porous material, the resulting monolith skeleton (the thickness of the monolith skeleton wall) cannot be made thick, and the adsorption capacity per volume and the volume after introduction of ion exchange groups. This is not preferable because the ion exchange capacity per unit becomes small. On the other hand, when the addition amount of vinyl monomer exceeds 40 times, the opening diameter becomes small, and the pressure loss at the time of passing water becomes large.

  As the crosslinking agent used in step II, a crosslinking agent containing at least two polymerizable vinyl groups in the molecule and having high solubility in an organic solvent is preferably used. Specific examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol diacrylate, and the like. These crosslinking agents can be used singly or in combination of two or more. Preferred cross-linking agents are aromatic polyvinyl compounds such as divinylbenzene, divinylnaphthalene and divinylbiphenyl because of their high mechanical strength and stability to hydrolysis. The amount of the crosslinking agent used is preferably 0.3 to 50 mol%, particularly 0.3 to 5 mol%, based on the total amount of the vinyl monomer and the crosslinking agent. When the amount of the crosslinking agent used is less than 0.3 mol%, the mechanical strength of the monolith is insufficient, which is not preferable. On the other hand, if it exceeds 50 mol%, the brittleness of the monolith proceeds and the flexibility is lost, and the introduction amount of ion exchange groups is reduced. It is preferable to use it so as to be approximately equal to the crosslinking density of the monolith intermediate coexisting during the polymerization of the vinyl monomer / crosslinking agent. If the amounts used of both are too large, the crosslink density distribution is biased in the produced monolith, and cracks are likely to occur during the ion exchange group introduction reaction.

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

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

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

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

  In step III, the monolith intermediate is placed in a reaction vessel impregnated with the mixture (solution). As described above, the blending ratio of the mixture obtained in Step II and the monolith intermediate is 3 to 40 times by weight, preferably 4 to 30 times by weight, relative to the monolith intermediate. It is suitable to mix. Thereby, it is possible to obtain a monolith having a thick skeleton while having an appropriate opening diameter. In the reaction vessel, the vinyl monomer and the crosslinking agent in the mixture are adsorbed and distributed on the skeleton of the monolith intermediate that has been allowed to stand, and polymerization proceeds in the skeleton of the monolith intermediate.

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

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

  There is no restriction | limiting in particular as a method to introduce | transduce an ion exchange group into the said monolith, Well-known methods, such as a polymer reaction and graft polymerization, can be used. For example, as a method of introducing a sulfonic acid group, if the monolith is a styrene-divinylbenzene copolymer, etc., a method of sulfonation using chlorosulfuric acid, concentrated sulfuric acid or fuming sulfuric acid; A method of grafting a sodium styrenesulfonate or acrylamido-2-methylpropanesulfonic acid by introducing a mobile group into the skeleton surface or inside the skeleton; Similarly, after graft polymerization of glycidyl methacrylate, a sulfonic acid group is introduced by functional group conversion. And the like. As a method for introducing a quaternary ammonium group, if the monolith is a styrene-divinylbenzene copolymer or the like, a method of introducing a chloromethyl group with chloromethyl methyl ether or the like and then reacting with a tertiary amine; A method in which chloromethylstyrene and divinylbenzene are produced by copolymerization and reacted with a tertiary amine; N, N, N-trimethylammonium is introduced into the monolith by introducing radical initiation groups and chain transfer groups uniformly into the skeleton surface and inside the skeleton. Examples include a method of graft polymerization of ethyl acrylate and N, N, N-trimethylammoniumpropylacrylamide; a method of grafting glycidyl methacrylate in the same manner and then introducing a quaternary ammonium group by functional group conversion. Examples of the method for introducing betaine include a method in which a tertiary amine is introduced into a monolith by the above method and then introduced by reacting with monoiodoacetic acid. Among these methods, the method of introducing a sulfonic acid group includes a method of introducing a sulfonic acid group into a styrene-divinylbenzene copolymer using chlorosulfuric acid, and a method of introducing a quaternary ammonium group includes styrene. -Introducing a chloromethyl group into the divinylbenzene copolymer with chloromethyl methyl ether, etc., then reacting with a tertiary amine, or producing a monolith by copolymerization of chloromethylstyrene and divinylbenzene and reacting with a tertiary amine The method is preferable in that the ion exchange group can be introduced uniformly and quantitatively. The ion exchange groups to be introduced include cation exchange groups such as carboxylic acid groups, iminodiacetic acid groups, sulfonic acid groups, phosphoric acid groups, and phosphoric ester groups; quaternary ammonium groups, tertiary amino groups, and secondary amino groups. Groups, primary amino groups, polyethyleneimine groups, tertiary sulfonium groups, phosphonium groups and the like.

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

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

  The second monolith ion exchanger has a three-dimensional continuous skeleton having an average thickness of 1 to 60 μm, preferably 3 to 58 μm in a water-wet state in which ion-exchange groups are introduced, and an average diameter between the skeletons. It is a co-continuous structure composed of three-dimensionally continuous pores of 10 to 100 μm, preferably 15 to 90 μm, particularly 20 to 80 μm in a wet state. That is, as shown in the schematic diagram of FIG. 6, the co-continuous structure is a structure 60 in which a continuous skeleton phase 61 and a continuous vacancy phase 62 are intertwined and each of them is three-dimensionally continuous. The continuous vacancies 62 have higher continuity of vacancies than the conventional open-cell monolith and particle agglomeration monolith, and the size of the vacancies is not biased. Therefore, an extremely uniform ion adsorption behavior can be achieved. Moreover, since the skeleton is thick, the mechanical strength is high.

  The skeleton thickness and pore diameter of the second monolith ion exchanger are larger than the monolith skeleton thickness and pore diameter because the entire monolith swells when an ion exchange group is introduced into the monolith. It becomes. These continuous pores have higher continuity of pores and are not biased in size compared to conventional open-cell monolithic organic porous ion exchangers and particle-aggregated monolithic organic porous ion exchangers. Therefore, extremely uniform ion adsorption behavior can be achieved. If the diameter of the three-dimensionally continuous pores is less than 10 μm, the pressure loss when passing through the fluid increases, which is not preferable. Becomes unsatisfactory, and as a result, the ion exchange characteristics become non-uniform. In addition, if the thickness of the skeleton is less than 1 μm, it is not preferable because the ion exchange capacity per volume decreases and the mechanical strength decreases. This is not preferable because the uniformity of the exchange characteristics is lost.

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

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

  The second monolith ion exchanger has a total pore volume of 0.5 to 5 ml / g. If the total pore volume is less than 0.5 ml / g, the pressure loss at the time of fluid permeation increases, which is not preferable. Further, the amount of permeated fluid per unit cross-sectional area decreases, and the processing capacity decreases. Therefore, it is not preferable. On the other hand, if the total pore volume exceeds 5 ml / g, the ion exchange capacity per volume decreases, which is not preferable. If the size of the three-dimensionally continuous pores and the total pore volume are in the above ranges, the contact with the fluid is extremely uniform and the contact area is large, so the ion exchange zone length is short and low pressure loss Become. The total pore volume of the monolith (monolith intermediate, monolith, monolith ion exchanger) is the same in the dry state and in the water wet state.

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

  In the second monolith ion exchanger, the material constituting the skeleton of the co-continuous structure is 0.3 to 5 mol%, preferably 0.5 to 3.0 mol% of the crosslinked structural unit in all the structural units. It is an aromatic vinyl polymer containing and is hydrophobic. If the cross-linking structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, if it exceeds 5 mol%, the structure of the porous body tends to deviate from the bicontinuous structure. There is no restriction | limiting in particular in the kind of this aromatic vinyl polymer, For example, a polystyrene, poly ((alpha) -methylstyrene), polyvinyl toluene, polyvinyl benzyl chloride, polyvinyl biphenyl, polyvinyl naphthalene etc. are mentioned. The polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or a blend of two or more types of polymers. It may be what was done. Among these organic polymer materials, a styrene-divinylbenzene copolymer is used because of its ease of forming a co-continuous structure, ease of introduction of ion exchange groups, high mechanical strength, and high stability against acids and alkalis. And vinylbenzyl chloride-divinylbenzene copolymer is preferred.

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

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

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

  What is necessary is just to perform the I process of obtaining the monolith intermediate body in a 2nd monolith ion exchanger based on the method of Unexamined-Japanese-Patent No. 2002-306976.

  That is, in the step I, as the oil-soluble monomer not containing an ion exchange group, for example, it does not contain an ion exchange group such as a carboxylic acid group, a sulfonic acid group, and a quaternary ammonium group, has low solubility in water, and is lipophilic. These monomers are mentioned. Specific examples of these monomers include aromatic vinyl monomers such as styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, vinyl biphenyl and vinyl naphthalene; α-olefins such as ethylene, propylene, 1-butene and isobutene; butadiene Diene monomers such as vinyl chloride, vinyl bromide, vinylidene chloride and tetrafluoroethylene; nitrile monomers such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate and vinyl propionate Methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethyl methacrylate Sill, cyclohexyl methacrylate, benzyl methacrylate, and (meth) acrylic monomer of glycidyl methacrylate. Among these monomers, preferred are aromatic vinyl monomers such as styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, divinyl benzene and the like. These monomers can be used alone or in combination of two or more. However, a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate is selected as at least one component of the oil-soluble monomer, and its content is 0.3 to 5 mol%, preferably 0.3 to the total oil-soluble monomer. 3 mol% is preferable in that a mechanical strength necessary for introducing a large amount of ion-exchange groups in a later step can be obtained.

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

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

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

  In the second method for producing a monolith ion exchanger, the monolith intermediate obtained in the step I is an organic polymer material having a crosslinked structure, preferably an aromatic vinyl polymer. Although the crosslinking density of the polymer material is not particularly limited, it contains 0.3 to 5 mol%, preferably 0.3 to 3 mol% of crosslinked structural units with respect to all structural units constituting the polymer material. Is preferred. When the cross-linking structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, if it exceeds 5 mol%, the structure of the monolith tends to deviate from the co-continuous structure, which is not preferable. In particular, when the total pore volume is as small as 16 to 20 ml / g in the present invention, the cross-linking structural unit is preferably less than 3 mol in order to form a co-continuous structure.

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

  The total pore volume of the monolith intermediate is more than 16 ml / g and not more than 30 ml / g, preferably 6-25 ml / g. In other words, this monolith intermediate basically has a continuous macropore structure, but the opening (mesopore) that is the overlapping part of the macropore and the macropore is remarkably large. It has a structure as close as possible to the original rod-like skeleton. When this coexists in the polymerization system, a porous body having a co-continuous structure is formed using the structure of the monolith intermediate as a template. If the total pore volume is too small, the structure of the monolith obtained after polymerizing the vinyl monomer is not preferable because it changes from a co-continuous structure to a continuous macropore structure. On the other hand, if the total pore volume is too large, This is not preferable because the mechanical strength of the monolith obtained after polymerizing the vinyl monomer is lowered and the ion exchange capacity per volume is lowered. In order to make the total pore volume of the monolith intermediate within a specific range of the second monolith ion exchanger, the ratio of monomer to water may be approximately 1:20 to 1:40.

  Moreover, the average diameter of the opening (mesopore) which is an overlap part of a macropore and a macropore is a monolith intermediate body is 5-100 micrometers in a dry state. If the average diameter of the openings is less than 5 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes small, and the pressure loss during water passage becomes large, which is not preferable. On the other hand, if it exceeds 100 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes too large, and the contact between the fluid and the monolith ion exchanger becomes insufficient, resulting in a decrease in ion exchange characteristics. Therefore, it is not preferable. Monolith intermediates preferably have a uniform structure with uniform macropore size and aperture diameter, but are not limited to this, and the uniform structure is dotted with nonuniform macropores larger than the size of the uniform macropore. You may do.

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

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

  The amount of these aromatic vinyl monomers added is 5 to 50 times, preferably 5 to 40 times, by weight with respect to the monolith intermediate coexisting during polymerization. If the amount of aromatic vinyl monomer added is less than 5 times that of the porous material, the rod-like skeleton cannot be thickened, and the ion exchange capacity per volume after introduction of ion exchange groups is reduced, resulting in conductivity and treated water quality. Can not be increased.

  As the crosslinking agent used in step II, a crosslinking agent containing at least two polymerizable vinyl groups in the molecule and having high solubility in an organic solvent is preferably used. Specific examples of the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol diacrylate, and the like. These crosslinking agents can be used singly or in combination of two or more. Preferred cross-linking agents are aromatic polyvinyl compounds such as divinylbenzene, divinylnaphthalene and divinylbiphenyl because of their high mechanical strength and stability to hydrolysis. The amount of the crosslinking agent used is 0.3 to 5 mol%, particularly 0.3 to 3 mol%, based on the total amount of vinyl monomer and crosslinking agent (total oil-soluble monomer). When the amount of the crosslinking agent used is less than 0.3 mol%, the mechanical strength of the monolith is insufficient, which is not preferable. This is not preferable because a problem arises in that the amount of introduction of is reduced. In addition, it is preferable to use the said crosslinking agent usage-amount so that it may become substantially equal to the crosslinking density of the monolith intermediate body coexisted at the time of vinyl monomer / crosslinking agent polymerization. If the amounts used of both are too large, the crosslink density distribution is biased in the produced monolith, and cracks are likely to occur during the ion exchange group introduction reaction.

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

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

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

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

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

  The basic structure of a monolith having a co-continuous structure is a three-dimensional continuous skeleton having an average thickness of 0.8 to 40 μm in a dry state and a three-dimensional continuous sky having a diameter of 8 to 80 μm between the skeletons. This is a structure in which holes are arranged. The average diameter of the three-dimensionally continuous pores can be obtained as a maximum value of the pore distribution curve by measuring the pore distribution curve by the mercury intrusion method. The thickness of the skeleton of the monolith may be calculated by performing SEM observation at least three times and measuring the average thickness of the skeleton in the obtained image. A monolith having a co-continuous structure has a total pore volume of 0.5 to 5 ml / g.

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

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

  Since the ion exchange group is introduced into the bilithic monolith, the second monolith ion exchanger swells greatly, for example, 1.4 to 1.9 times that of the monolith. Further, the total pore volume does not change even if the pore diameter becomes larger due to swelling. Therefore, the second monolith ion exchanger has a high mechanical strength because it has a thick bone skeleton even though the size of three-dimensionally continuous pores is remarkably large. Moreover, since the skeleton is thick, the ion exchange capacity per volume in a water-wet state can be increased, and the conductivity and the quality of treated water can be improved.

  In the present invention, the water to be treated is intended for deionization treatment and is not particularly limited as long as it does not contain turbidity. For example, industrial water or city water having a turbidity of about 1 degree or less. Can be mentioned.

  Next, the electric deionized water production apparatus according to the first embodiment of the present invention will be described with reference to FIG. FIG. 13 is a schematic view showing the structure of the electric deionized water production apparatus of this example. An electric deionized water production apparatus 20A in FIG. 13 removes cationic impurities from the water to be treated, and an anion from the treated water of the electric decation water production apparatus 20a. It comprises an electric deionized water production apparatus 20b that removes ionic impurities. The electric decationized water production apparatus 20a is formed by filling an organic porous cation exchanger 15 in a deionization chamber partitioned by an ion exchange membrane 17 on one side and a cation exchange membrane 1 on the other side. The ion chamber 6, the anode 10 disposed outside the ion exchange membrane 17 on one side, the cathode 9 disposed outside the cation exchange membrane 1 on the other side, and the other in the decation chamber 6 The first treated water introduction / distribution portion 3a disposed in the vicinity of the cation exchange membrane 1 on the side, and the first treated water collection disposed in the vicinity of the ion exchange membrane 17 on the one side in the decation chamber 6. And a water portion 4a. That is, the water flow direction in the porous cation exchanger 15 of the electrical decationized water production apparatus 20a is from the bottom to the top, which is the solid arrow direction in FIG.

  On the other hand, the electrical deanion water production apparatus 20b is formed by filling an organic porous anion exchanger 16 in a deionization chamber partitioned by an anion exchange membrane 2 on one side and an ion exchange membrane 17 on the other side. A deionization chamber 7, an anode 10 disposed outside the anion exchange membrane 2 on one side, a cathode 9 disposed outside the ion exchange membrane 17 on the other side, and electrical decationized water Second treated water introduction / distribution unit 3b disposed in the vicinity of the anion exchange membrane 2 on one side in the deanion ion chamber 7 connected to the first treated water collecting unit 4a of the production apparatus 20a by the communication pipe 5a. And a second treated water collecting portion 4b disposed in the vicinity of the ion exchange membrane 17 on the other side in the deanion ion chamber 7. That is, the water flow direction in the porous anion exchanger 16 of the electric decationized water production apparatus 20b is from the top to the bottom, which is the solid arrow direction in FIG.

  The organic porous cation exchanger 15 filled in the decation chamber 6 of the electric decation water production apparatus 20a of this example is the above-mentioned organic porous cation exchanger, and the electric deanion water. The organic porous anion exchanger 16 filled in the deanion chamber 7 of the production apparatus 20b is the aforementioned organic porous anion exchanger. Further, the shape of the decation ion chamber 6 and the deionization ion chamber 7 is such that an electric field can be applied so that ions to be excluded migrate in the direction opposite to the water flow direction in the porous ion exchanger. Although not particularly limited, for example, a cylindrical shape or a rectangular parallelepiped shape is preferable from the viewpoint of ease of manufacture of the constituent members. The distance that the water to be treated moves, that is, the effective thickness of the porous ion exchanger packed layer constituting the decation ion chamber 6 and the deanion chamber 7 is 20 to 600 mm, preferably 30 to 300 mm. It is preferable in that the deionization treatment can be reliably performed while suppressing the electric resistance value and the water flow differential pressure to a low value. The method of filling the organic ion exchanger in the deionization chamber partitioned by the ion exchange membranes on both sides is not particularly limited. For example, a porous ion exchanger having a shape matched to the deionization chamber can be produced and used as it is. It may be filled, or a layered organic porous ion exchanger divided into a plurality of layers may be stacked and filled.

The cation exchange membrane is not particularly limited as long as it can permeate only cations and sequester water on both sides thereof. For example, a strongly acidic cation exchange membrane in which a —SO ₃ ^— group is introduced into a fluororesin matrix. (For example, Nafion 117 and Nafion 350 (manufactured by DuPont)) and strongly acidic cation exchange membranes (for example, Neocepta CMX (manufactured by Tokuyama Soda Co., Ltd.)) in which a —SO ₃ ^— group is introduced into a styrene-divinylbenzene copolymer matrix. Can be mentioned. The anion exchange membrane is not particularly limited as long as it can permeate only anions and isolate water on both sides thereof. For example, an anion exchange membrane in which an anion exchange group is introduced into a fluororesin matrix (for example, TOSFLEX) IE-SA, TOSFLEX IE-DF, TOSFLEX IE-SF (manufactured by Tosoh Corporation)) and anion exchange membranes in which anion exchange groups are introduced into a styrene-divinylbenzene copolymer matrix (for example, Neocepta AMH (manufactured by Tokuyama Soda Co., Ltd.)) ) And the like. Moreover, either the cation exchange membrane or the anion exchange membrane can be used for the ion exchange membrane 17 used with the electric deionized water production apparatus 20A of this example.

Moreover, as the cathode 9 and the anode 10, a conductive material such as a metal, an alloy, a metal oxide, any one of these plated or coated as a substrate, and sintered carbon can be used. Plates, punching metals, meshes, and the like can be used. In particular, as the material of the anode 10, for example, Pt, Pd, Ir, β-PbO ₂ , NiFe ₂ O _{4 and the} like are preferable because they have excellent acid resistance and are not easily oxidized. Moreover, as a material of the cathode 9, for example, Pt, Pd, Au, carbon steel, stainless steel, Ag, Cu, graphite, vitreous carbon, and the like are preferable in terms of excellent alkali resistance.

  The arrangement of the electrode and the ion exchange membrane is preferably such that the electrode and the ion exchange membrane are in direct contact with each other because the voltage during operation can be lowered and the power consumption can be reduced. When the electrode and the ion exchange membrane are brought into direct contact, particularly on the anode side, it is necessary to prevent deterioration of the ion exchange membrane due to a strong oxidizing action by using an ion exchange membrane of a fluororesin matrix. When using an ion exchange membrane other than the fluororesin matrix, inserting a non-conductive spacer such as a polyolefin mesh between the electrode and the ion exchange membrane avoids direct contact between the electrode and the ion exchange membrane. Is preferable in that it can be protected from deterioration. However, even in the case of an ion exchange membrane made of a fluororesin matrix, the anion exchange membrane 2 into which an anion exchange group such as a quaternary ammonium group is introduced and the anode 10 are arranged like the anode side of the deanion chamber 7. When installed, inserting a non-conductive spacer such as a polyolefin mesh between the positive electrode 10 and the anion exchange membrane 2 prevents oxidation of the anion exchange groups and protects the ion exchange membrane from deterioration. This is preferable in that it can be performed.

  In the electric deionized water production apparatus 20A, the first and second treated water introduction / distribution units 3a and 3b and the first and second treated water collecting units 4a and 4b are treated equally in, for example, the deionized chamber. A method of embedding distribution pipes and water collection pipes having pores in the pipes in a concentric or equidistant parallel line in the porous ion exchanger so as to form a water flow, and Examples include a method in which grooves are formed in the treated water introduction / distribution section and the treated water collection section of the porous ion exchanger, and the treated water distribution and treated water collection functions are provided in the porous ion exchanger itself. In addition, the method of giving the treated water distribution and treated water collecting function to the porous ion exchanger itself is preferable in that it can be easily produced without preparing a separate piping member.

  In the electric deionized water production apparatus 20A of the present example, as a direct current arrangement form, a method of independently energizing each chamber of the decation ion chamber 6 and the deanion ion chamber 7 with individual power supplies, or An example is a method in which the decation ion chamber 6 and the deanion ion chamber 7 are connected in series using a single DC power source and energized. In the method of conducting electricity by connecting the decation chamber 6 and the deionization chamber 7 in parallel, the electric resistance values of the deionization chambers are generally different. This is not preferable because there is a risk of inhibiting the sufficient discharge of the water.

  In the electric deionized water production apparatus 20A of this example, as a method of energizing the direct current, the voltage value is automatically changed in accordance with the change in the electrical resistance value of the porous ion exchanger caused by the change in the ion composition or the like. The constant current operation is preferable in that the ion load that flows in can be efficiently eliminated. The required current value is determined by the amount of ions to be excluded, that is, the quality of the water to be treated and the treatment flow rate. Further, in the case of intermittent operation, the required current value varies depending on the water flow time and the stop time in addition to the quality of the water to be treated and the treatment flow rate. In this way, the required current value varies depending on various conditions, so it is difficult to determine it in general, but the value obtained by adding a safety factor in anticipation of water quality fluctuations to the current efficiency in the electric deionized water production system And a value obtained by multiplying the necessary minimum current value obtained by the following equation.

Necessary minimum current value in the decation chamber Imin (A) = McQF / (60 ² × 10 ³ ); Necessary minimum current value in the deanion chamber Imin (A) = MaQF / (60 ² × 10 ³ ); , Mc is the total cation (meq / l) of water to be treated, Ma is the total anion (meq / l), Q is the treatment flow rate (l / h), and F is the Faraday constant (C / mol). The current efficiency is the rate at which the current is used to exclude ions, and is 95 to 100% in the electric deionized water production apparatus of the present invention.

  In addition, the operation method of the electric deionized water production apparatus 20A of this example may be either continuous operation or intermittent operation. For example, the continuous operation method by continuous water flow and continuous energization of the water to be treated and the treatment target. It is also possible to adopt an intermittent operation method in which the water flow is stopped for a certain period of time, and a direct current is applied only during the water flow stop time or both the water flow stop time and the water flow time.

In the electrical decationized water production apparatus 20a, the water to be treated is introduced from the cathode 9 side of the decationization chamber 6 and is evenly distributed to the porous cation exchanger 15 by the first treated water introduction / distribution unit 3a. The Next, the water to be treated moves to the anode 10 side while adsorbing and removing the cation X ⁺ in the porous cation exchanger 15, becomes acidic soft water, is collected by the first treated water collecting section 4 a and is first collected. It is discharged from the decation chamber 6 as treated water. Next, the acidic soft water is introduced to the anode 10 side in the deanion 7 chamber by the communication pipe 5a, and is equally distributed to the porous anion exchanger 16 by the second treated water introduction / distribution unit 3b. Next, the first treated water, which is the treated water, moves to the cathode 9 side while adsorbing and removing the anions Y ⁻ in the porous anion exchanger 16, and is collected by the second treated water collecting section 4b. 2 is discharged from the deanion chamber 7 as treated water.

On the other hand, the cation X ⁺ adsorbed by the organic porous cation exchanger 15 in the decation chamber 6 is a direct current applied between the cathode 9 and the anode 10 disposed at both ends of the decation chamber 6. , And passes through the cation exchange membrane 1 on the cathode 9 side and is discharged to the cathode chamber 12. Similarly, the anion Y ⁻ adsorbed on the organic porous anion exchanger 16 in the deanion chamber 7 is a direct current applied between the cathode 9 and the anode 10 disposed at both ends of the deanion chamber 7. Electrophoresis is caused by the electric current, passes through the anion exchange membrane 2 on the anode 10 side, and is discharged to the anode chamber 13.

  Impurity cations discharged into the cathode chamber 12 flow in from the electrode chamber inlet C, are taken into the electrode water flowing out from the electrode chamber outlet c, and are discharged out of the system. Similarly, impurity anions discharged into the anode chamber 13 flow in from the electrode chamber inlet D, are taken into the electrode water flowing out from the electrode chamber outlet d, and are discharged out of the system. The electrode water may be made to flow partially in the four electrode chambers by branching off a part of the water to be treated, or may be allowed to flow in two systems of an anodic water system and a cathodic water system, respectively. Moreover, electrode water may be always flowed and may be appropriately flowed intermittently.

  By this operation, the concentration distribution of adsorbed impurity ions in the porous ion exchanger is always high on the treated water inflow side and low on the outflow side. For this reason, since the porous ion exchanger in the vicinity of the treated water collecting section 4 is maintained in a substantially completely regenerated form, it is possible to adsorb impurity ions in the treated water to a low concentration, and high purity deionization. Water can be stably supplied to use points. In addition, since the impurity cation and the impurity anion are separately discharged outside the apparatus, they are not mixed in the apparatus unlike conventional electric deionized water production apparatuses, and calcium or Even when a hardness component such as magnesium is contained, no scale is generated in the apparatus.

  In addition to the above, as a water passing method of the electric deionized water production apparatus 20A, for example, the treated water is treated by the electric deionized water production apparatus 20b, and then the treatment by the electric deionized water production apparatus 20b. The method of processing water with the electric decation water production apparatus 20a can be taken. This method can be applied to water to be treated which does not contain hardness components such as calcium and magnesium like soft water. However, when water other than soft water is treated, the flow sequence of the water to be treated can be changed from the decation chamber 6 to the deanion chamber 7 when the flow sequence is reversed. This is preferable in that precipitation of hardness components in the deionization chamber 7 can be prevented.

  Next, an electric deionized water production apparatus according to the second embodiment of the present invention will be described with reference to FIG. FIG. 14 is a schematic diagram showing the structure of the electric deionized water production apparatus of this example. In FIG. 14, the same components as those in FIG. 13 are denoted by the same reference numerals, description thereof is omitted, and different points are mainly described. The electric deionized water production apparatus 20B of FIG. 14 is different from FIG. 13 in that one set of electrodes is omitted and a decation ion chamber and a deanion chamber are provided between the one set of electrodes. That is, the electric deionized water production apparatus 20B of the present example includes a cation exchange membrane 1 on one side, and an intermediate cation formed between the cation exchange membrane 1 on one side and the anion exchange membrane 2 on the other side. A decation chamber 6 in which a first deionization chamber partitioned by an ion exchange membrane 1 is filled with an organic porous cation exchanger 15, an anion exchange membrane 2 on the other side, and an intermediate cation exchange membrane 1. A deionization chamber 7 formed by filling the second deionization chamber with an organic porous anion exchanger 16, a cathode 9 disposed outside the cation exchange membrane 1 on one side, and the like. An anode 10 disposed outside the anion exchange membrane 2 on the side, a first treated water introduction / distribution portion 3a disposed in the vicinity of the cation exchange membrane 1 on the one side in the decation chamber 6, A first treated water collection section 4a and a first treated water collection section 4a disposed near the intermediate cation exchange membrane 1 in the decation chamber 6. The second treated water introduction / distribution part 3b disposed in the vicinity of the anion exchange membrane 2 on the other side in the deanion chamber 7 connected by the communication pipe 5b, and the intermediate cation exchange in the deanion chamber 7 And a second treated water collecting part 4b disposed in the vicinity of the membrane 1.

In the electric deionized water production apparatus 20B, as in the electric deionized water production apparatus 20A, the water to be treated is introduced from the cathode 9 side of the decation chamber 6 and is porous by the first treated water introduction / distribution unit 3a. The cation exchanger 15 is evenly distributed. Next, the water to be treated moves to the intermediate cation exchange membrane 1 side while adsorbing and removing the cation X ⁺ in the porous cation exchanger 15, and becomes acidic soft water and collected by the first treated water collecting section 4a. Water is discharged from the decation chamber 6 as first treated water. Next, the first treated water is introduced to the anode 10 side in the deanion chamber 7 through the communication pipe 5b, and is equally distributed to the porous anion exchanger 16 by the second treated water introduction / distribution unit 3b. . Next, the first treated water, which is the treated water, moves to the intermediate cation exchange membrane 1 side while adsorbing and removing the anions Y ⁻ in the porous anion exchanger 16, and the second treated water collecting section 4 b. Water is collected and discharged from the deanion chamber 7 as second treated water.

On the other hand, the cation X ⁺ adsorbed on the organic porous cation exchanger 15 in the decation chamber 6 is electrically converted by a direct current applied between the cathode 9 and the anode 10 disposed at both ends of the apparatus 20B. Electrophoretic migration passes through the cation exchange membrane 1 on the cathode 9 side and is discharged to the cathode chamber 12. Similarly, the anion Y ⁻ adsorbed on the organic porous anion exchanger 16 in the deanion chamber 7 is also electrophoresed by the direct current applied between the cathode 9 and the anode 10, and the anode 10 It passes through the anion exchange membrane 2 on the side and is discharged to the anode chamber 13. According to the electric deionized water production apparatus 20B of the second embodiment, the same effect as the electric deionized water production apparatus 20A of the first embodiment is obtained, and one set of electrodes is omitted. Thus, the device can be reduced in size and simplified.

  Next, an electric deionized water production apparatus according to a third embodiment of the present invention will be described with reference to FIG. FIG. 15 is a schematic view showing the structure of the electric deionized water production apparatus of this example. In FIG. 15, the same components as those in FIG. The electric deionized water production apparatus 20C in FIG. 15 differs from that in FIG. 13 in that one set of electrodes is omitted, and a decation ion chamber and a deanion chamber are provided between one set of electrodes and ions to be excluded. It is in the point which made it the structure which collects in the concentration chamber provided in the center. That is, the electric deionized water production apparatus 20C of this example includes an ion exchange membrane 17 on one side and an intermediate cation exchange membrane formed between the ion exchange membrane 17 on one side and the ion exchange membrane 17 on the other side. 1, a decation chamber 6 in which an organic porous cation exchanger 15 is packed in a first deionization chamber partitioned by 1, an intermediate cation exchange membrane 1, an intermediate cation exchange membrane 1, and the other side A concentration chamber 11 defined by the intermediate anion exchange membrane 2 formed between the ion exchange membranes 17 and a second deionization chamber defined by the other side ion exchange membrane 17 and the intermediate anion exchange membrane 2. Deionization chamber 7 filled with organic porous anion exchanger 16, anode 10 disposed outside ion exchange membrane 17 on one side, and outside ion exchange membrane 17 on the other side. Disposed near the intermediate cation exchange membrane 1 in the cathode 9 and the decation chamber 6. A first treated water collection section 3a, a first treated water collection section 4a disposed in the vicinity of the ion exchange membrane 17 on one side in the decation chamber 6; a first treated water collection section 4a; A second treated water introduction / distribution portion 3b disposed in the vicinity of the intermediate anion exchange membrane 2 in the deanion ion chamber 7 connected by the communication pipe 5b, and an ion exchange membrane on the other side in the deanion ion chamber 7 17 is provided with a second treated water collecting portion 4b disposed in the vicinity of 17.

In the electric deionized water production apparatus 20C of the present example, the direction of water to be treated in the decation chamber 6 is the direction from the central concentration chamber 11 side to the anode 10 side, and is excluded from the cations X ^+. Is the opposite direction. Further, the flow direction of the water to be treated in the deanion chamber 7 is the direction from the central concentration chamber 11 side to the cathode 9 side, and the anion Y ⁻ to be excluded is the opposite direction. Impurity ions that have flowed into the concentration chamber 11 flow in from the concentration chamber inlet B, are taken into the concentrated water flowing out from the concentration chamber outlet b, and are discharged out of the system. For example, a part of the water to be treated can be used as the concentrated water flowing through the concentration chamber 11. According to the electric deionized water production apparatus 20C, the same effects as the electric deionized water production apparatus 20B can be obtained. However, since cations such as calcium ions and magnesium ions and anions such as carbonate ions are mixed in the concentration chamber 11, there is a possibility that scale is generated on the surface of the anion exchange membrane 2 in the concentration chamber 11. Therefore, it is desirable to install a pretreatment means for performing softening, primary desalting or the like in the front part of the electric deionized water production apparatus 20C.

  In the electric deionized water production apparatus of the present invention, a small amount of gas such as oxygen and chlorine is generated at the anode and a small amount of gas such as hydrogen is generated at the cathode by the electrode reaction. For this reason, gas-liquid separation means and exhaust gas piping are provided in the middle of each electrode chamber or electrode water piping, and the generated gas is exhausted constantly or intermittently, and after appropriate processing according to the type of gas, the system Release outside. Similarly, a metal such as calcium may be precipitated by the electrode reaction, particularly at the cathode. In this case, the electrode function can be obtained by a method of reversing the polarity of the electrode every fixed operation time, a method of performing acid cleaning by passing an acid such as about 1 mol / l of nitric acid through the electrode water pipe, or a method of combining these. Is preferably maintained.

  The electric deionized water production apparatus of the present invention can be applied and combined in the same way as a conventional ion exchange apparatus. By attaching a vessel, the quality of the treated water can be further increased.

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

<Production of first monolithic ion exchanger (Reference Example 1)>
(Step I; production of monolith intermediate)
19.2 g of styrene, 1.0 g of divinylbenzene, 1.0 g of sorbitan monooleate (hereinafter abbreviated as SMO) and 0.26 g of 2,2′-azobis (isobutyronitrile) were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / SMO / 2,2′-azobis (isobutyronitrile) mixture is added to 180 g of pure water containing 1.8 ml of THF, and a vacuum stirring defoaming mixer which is a planetary stirring device. (EM Co., Ltd.) was used and stirred under reduced pressure in a temperature range of 5 to 20 ° C. to obtain a water-in-oil emulsion. The emulsion was immediately transferred to a reaction vessel, and after sealing, it was allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the content was taken out, extracted with isopropanol, and then dried under reduced pressure to produce a monolith intermediate having a continuous macropore structure. The average diameter of the openings (mesopores) where the macropores and macropores of the monolith intermediate were measured by mercury porosimetry was 56 μm, and the total pore volume was 7.5 ml / g.

(Manufacture of monoliths)
Next, 49.0 g of styrene, 1.0 g of divinylbenzene, 50 g of 1-decanol, and 0.5 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and dissolved uniformly (step II). Next, the monolith intermediate was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 20 mm, and 7.6 g was collected. The separated monolith intermediate is put in a reaction vessel having an inner diameter of 90 mm, immersed in the styrene / divinylbenzene / 1-decanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture, and removed in a vacuum chamber. After bubbling, the reaction vessel was sealed and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the monolith-like contents having a thickness of about 30 mm were taken out, subjected to Soxhlet extraction with acetone, and then dried under reduced pressure at 85 ° C. overnight (step III).

  FIG. 1 shows the result of observing the internal structure of the monolith (dry body) containing 1.3 mol% of the crosslinking component composed of the styrene / divinylbenzene copolymer obtained by SEM as described above. The SEM image in FIG. 1 is an image at an arbitrary position on a cut surface obtained by cutting a monolith at an arbitrary position. As is clear from FIG. 1, the monolith has a continuous macropore structure, and the skeleton constituting the continuous macropore structure is much thicker than that of the comparative example of FIG. The thickness of the part was thick.

  Next, the thickness of the wall part and the area of the skeleton part appearing in the cross section were measured from two SEM images obtained by cutting the obtained monolith at a position different from the above position, excluding subjectivity. The wall thickness was an average of 8 points obtained from one SEM photograph, and the skeleton area was determined by image analysis. The wall portion has the above definition. Moreover, the skeleton part area was shown by the average of three SEM images. As a result, the average thickness of the wall portion was 30 μm, and the area of the skeleton portion represented by the cross section was 28% in the SEM image. Moreover, the average diameter of the opening of the monolith measured by mercury porosimetry was 31 μm, and the total pore volume was 2.2 ml / g. The results are summarized in Tables 1 and 2. In Table 1, the preparation column shows, in order from the left, the vinyl monomer used in Step II, the crosslinking agent, the monolith intermediate obtained in Step I, and the organic solvent used in Step II.

(Production of monolith cation exchanger)
The monolith produced by the above method was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 15 mm. The weight of the monolith was 27 g. To this, 1500 ml of dichloromethane was added and heated at 35 ° C. for 1 hour, then cooled to 10 ° C. or lower, 145 g of chlorosulfuric acid was gradually added, and the temperature was raised and reacted at 35 ° C. for 24 hours. Thereafter, methanol was added to quench the remaining chlorosulfuric acid, which was then washed with methanol to remove dichloromethane and further washed with pure water to obtain a monolith cation exchanger having a continuous macropore structure.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Reference Example 20
(Manufacture of monolithic organic porous material having a continuous macropore structure (known product))
A monolithic organic porous body having a continuous macropore structure was produced according to the production method described in JP-A-2002-306976. That is, 19.2 g of styrene, 1.0 g of divinylbenzene, 1.0 g of SMO and 0.26 g of 2,2′-azobis (isobutyronitrile) were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / SMO / 2,2′-azobis (isobutyronitrile) mixture is added to 180 g of pure water, and a vacuum stirring defoaming mixer (manufactured by EM Corp.) which is a planetary stirring device. Was used under reduced pressure in a temperature range of 5 to 20 ° C. to obtain a water-in-oil emulsion. The emulsion was immediately transferred to a reaction vessel, and after sealing, it was allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the content was taken out, extracted with isopropanol, and then dried under reduced pressure to produce a monolithic organic porous body having a continuous macropore structure.

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

(Production of monolithic organic porous cation exchanger having a continuous macropore structure (known product))
The organic porous body produced by the above method was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 15 mm. The weight of the organic porous material was 6 g. To this was added 1000 ml of dichloromethane, and the mixture was heated at 35 ° C. for 1 hour, then cooled to 10 ° C. or less, 30 g of chlorosulfuric acid was gradually added, and the temperature was raised and reacted at 35 ° C. for 24 hours. Thereafter, methanol was added to quench the remaining chlorosulfuric acid, which was washed with methanol to remove dichloromethane and further washed with pure water to obtain a monolithic porous cation exchanger having a continuous macropore structure. The swelling rate before and after the reaction of the obtained cation exchanger was 1.6 times, and the ion exchange capacity per volume was 0.22 mg equivalent / ml in a water-wet state, which was a small value compared to Reference Examples 1-19. Indicated. The average diameter of the mesopores of the organic porous ion exchanger in the water wet state was 46 μm as estimated from the value of the organic porous body and the swelling ratio of the cation exchanger in the water wet state. The average thickness was 8 μm, the skeleton part area was 10% in the SEM image area, and the total pore volume was 8.6 ml / g. The differential pressure coefficient, which is an index of pressure loss when water is permeated, was 0.013 MPa / m · LV. The results are summarized in Table 5. The monolith cation exchanger obtained in Reference Example 20 was also evaluated for mechanical properties.

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

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

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

Reference Example 24
(Production of monolithic organic cation exchanger having a continuous macropore structure)
83.1 g of styrene, 20.7 g of divinylbenzene, 0.42 g of azobisisobutyronitrile and 11.4 g of sorbitan monooleate were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / azobisisobutyronitrile / sorbitan monooleate mixture is added to 1350 ml of pure water and stirred for 2 minutes at 20,000 rpm using a homogenizer, and a water-in-oil emulsion. Got. After emulsification, the water-in-oil emulsion was transferred to a stainless steel autoclave, sufficiently substituted with nitrogen, sealed, and allowed to polymerize at 60 ° C. for 24 hours. After the completion of the polymerization, the contents were taken out, extracted with Soxhlet for 24 hours with isopropanol to remove unreacted monomers and sorbitan monooleate, and then dried under reduced pressure at 40 ° C. overnight. 1500 g of tetrachloroethane was added to the porous body containing 14 mol% of the crosslinking component composed of the styrene / divinylbenzene copolymer thus obtained, heated at 60 ° C. for 30 minutes, cooled to room temperature, 75 g of sulfuric acid was gradually added and reacted at room temperature for 24 hours. Thereafter, acetic acid was added, the reaction product was poured into a large amount of water, washed with water and dried to obtain a porous cation exchanger. The ion exchange capacity of this porous material is 4.0 mg equivalent / g in terms of dry porous material, and sulfonic acid groups are uniformly introduced into the porous material by mapping of sulfur atoms using EPMA. It was confirmed. Moreover, as a result of SEM observation, the internal structure of this porous body has an open cell structure, most of the macropores having an average diameter of 30 μm overlap, and the average diameter of the mesopores formed by the overlap of the macropores and the macropores. The value was 5 μm and the total pore volume was 10.1 ml / g.

Reference Example 25
(Production of monolithic organic anion exchanger having continuous macropore structure)
Similar to the production of the porous cation exchanger, except that 54.0 g of p-chloromethylstyrene was used instead of 83.1 g of styrene, and 51.9 g of divinylbenzene and 0.78 g of azobisisobutyronitrile were used. A water-in-oil emulsion was polymerized to produce a porous body containing 50 mol% of a cross-linking component composed of a p-chloromethylstyrene / divinylbenzene copolymer. To this porous body, 1500 g of dioxane was added and heated at 80 ° C. for 30 minutes, then cooled to room temperature, 195 g of an aqueous solution of trimethylamine (30%) was gradually added, reacted at 50 ° C. for 3 hours, and then allowed to stand at room temperature for a whole day and night. did. After completion of the reaction, the porous body was taken out, washed with acetone, washed with water, and dried to obtain a porous anion exchanger. The ion exchange capacity of this porous material was 2.5 mg equivalent / g in terms of dry porous material, and it was confirmed by SIMS that trimethylammonium groups were uniformly introduced into the porous material. Moreover, as a result of SEM observation, the internal structure of this porous body has an open cell structure, most of the macropores having an average diameter of 30 μm overlap, and the average diameter of the mesopores formed by the overlap of the macropores and the macropores. The value was 4 μm and the total pore volume was 9.9 ml / g.

  In addition, about the monolith ion exchanger manufactured by Reference Examples 1-11 and Reference Examples 20-23, the relationship between a differential pressure coefficient and the ion exchange capacity per volume was shown in FIG. As is clear from FIG. 4, it can be seen that the known reference examples 20 to 23 have a poor balance between the differential pressure coefficient and the ion exchange capacity with respect to the reference examples 1 to 11. On the other hand, it is understood that Reference Examples 1 to 11 have a large ion exchange capacity per volume and a low differential pressure coefficient.

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

(Production of electric decationized water production apparatus A)
In order to produce an electric deionized water production apparatus 20A as shown in FIG. 13, first, an electric deionized water production apparatus 20a was produced. From the porous cation exchanger of Reference Example 8, deionized by cutting out 5 cuboids 100 mm long, 100 mm wide, 10 mm thick and 2 cuboids 100 mm long, 100 mm wide, 5 mm thick in a pure water wet state. A filler for laminating and filling the chamber was obtained. Next, a plurality of longitudinal grooves 21 having a spacing (w) of 10 mm and a width (s) of 2 mm as shown in FIG. 16 are provided on one side of two fillers having a thickness of 5 mm and two fillers having a thickness of 10 mm. A horizontal groove 22 that connects one end of the vertical groove 21 and an introduction groove 23 that is connected to an external pipe (not shown) were formed by cutting. Next, a filler having a thickness of 5 mm was arranged so that the groove portion 24 faced the inside of the apparatus to be an uppermost part and a lowermost part, and five fillers having a thickness of 10 mm were laminated therebetween. At this time, among the filler having a thickness of 10 mm, the upper and lower fillers are arranged so that the groove portion 24 faces the groove portion 24 of the filler having a thickness of 5 mm, and the treated water introduction / distribution portion 3 and the treated water collection are collected. Water part 4 was formed. The block-shaped porous cation exchanger 15 thus produced has a length of 100 mm, a width of 100 mm, and a total packed bed height of 60 mm. From the center of the treated water introduction / distribution unit 3 to the center of the treated water collection unit 4 The effective ion exchanger layer height was 50 mm. Next, a cation exchange membrane (Nafion 350; manufactured by DuPont) is disposed on the other side of the block-shaped porous cation exchanger 15, and a cation exchange membrane (Nafion 350; manufactured by DuPont) is disposed on the one side. Set up. Further, a platinum mesh anode 10 was disposed on the outer surface of the cation exchange membrane, and a platinum mesh cathode 9 was disposed on the outer surface of the cation exchange membrane. The obtained structure was appropriately constructed in a case made of polyvinyl chloride having a nozzle and a lead wire outlet, and an electric decationized water production apparatus 20a was produced.

(Preparation of electric deanion water production apparatus A)
About the porous anion exchanger of Reference Example 13, a filler is obtained by the same method as described above, and the treated water introduction / distribution part 3 and the treated water collecting part 4 are formed to form a block-like porous anion exchanger. 16 was obtained. Next, an anion exchange membrane 2 (Neocepta AMH; manufactured by Tokuyama Soda Co., Ltd.) is adhered to one side of the block-shaped porous anion exchanger 16, and a cation exchange membrane (Nafion 350; manufactured by DuPont) is adhered to the other side. Arranged. Further, a platinum mesh anode 10 was disposed on the outer surface of the anion exchange membrane 2, and a platinum mesh cathode 9 was disposed on the outer surface of the cation exchange membrane. A polytetrafluoroethylene mesh was interposed between the anode 10 and the anion exchange membrane 2. The obtained structure was appropriately constructed in a case made of polyvinyl chloride having a nozzle and a lead wire outlet, and an electrical deionized water production apparatus 20b was produced.

(Production of electric deionized water production apparatus A)
The opening of the treated water collecting section 4 of the obtained electrical decationized water production apparatus 20a and the opening of the treated water introduction / distribution section 3 of the electrical deionized water production apparatus 20b are connected by a communication pipe 5a. A part of the water to be treated was supplied to each of the electrode chambers independently. In addition, a single DC power source was used as a power source, and the decation ion chamber and the deanion chamber were wired in series to obtain an electric deionized water production apparatus 20A.

(Production of electric decationized water production apparatus B)
In place of the porous cation exchanger of Reference Example 8 except that the porous cation exchanger of Reference Example 17 was used, the electric decation water production apparatus A was manufactured by the same method as that of the electric decation water production apparatus A. A deionized water production apparatus B was prepared.

(Production of electric deanion water production apparatus B)
A method similar to the method for producing the electric deanion water production apparatus A, except that the porous anion exchanger of Reference Example 19 was used instead of the porous anion exchanger of Reference Example 13, Formula deionized water production apparatus B was produced.

(Preparation of electric deionized water production apparatus B)
Except for using the electrical decationized water production apparatus B as the electrical decationized water production apparatus 20a and using the electrical deanion water production apparatus B as the electrical deionization water production apparatus 20b, An electric deionized water production apparatus B was produced by the same method as the electric deionized water production apparatus A.

(Operation of electric deionized water production apparatus A)
The obtained electric deionized water production apparatus A (reference numeral 20A in the figure) was continuously treated with city water having a conductivity of 120 μS / cm as treated water at a flow rate of 100 l / h, and a direct current of 4.5 A was supplied. When energized, the operation voltage was 29 V, and treated water having an electrical conductivity of 0.055 μS / cm was obtained, indicating that pure water with high purity was produced by the electric deionized water production apparatus of the present invention. Further, the water flow differential pressure was 9.0 kPa.

(Operation of electric deionized water production apparatus B)
The electric deionized water production apparatus B (20A in the figure) was continuously passed at a flow rate of 100 l / h with city water having a conductivity of 120 μS / cm as the treated water, and a direct current of 4.5 A was supplied. When energized, the operation voltage was 28 V, and treated water having an electrical conductivity of 0.055 μS / cm was obtained, indicating that pure water with high purity was produced by the electric deionized water production apparatus of the present invention. Moreover, the water flow differential pressure was 7.5 kPa.

Comparative Example 1
(Production of electric decationized water production apparatus C)
In place of the porous cation exchanger of Reference Example 8 and using the porous cation exchanger of Reference Example 24, the electric decation water production apparatus A was manufactured by the same method as that of the electric decationized water production apparatus A. A decationized water production apparatus C was prepared.

(Preparation of electric deanion water production apparatus C)
A method similar to the method for producing the electric deanion water production apparatus A, except that the porous anion exchanger of Reference Example 25 was used instead of the porous anion exchanger of Reference Example 13, A type deionized water production apparatus C was prepared.

(Preparation of electric deionized water production apparatus C)
Except for using the electric decationized water production apparatus C as the electric decationized water production apparatus 20a and using the electric deanion water production apparatus C as the electric deionization water production apparatus 20b, An electric deionized water production apparatus C was produced in the same manner as the electric deionized water production apparatus A.

(Operation of electric deionized water production apparatus C)
The obtained electric deionized water production apparatus C (20A in the figure) was continuously treated with city water having a conductivity of 120 μS / cm as the water to be treated at a flow rate of 100 l / h, and a direct current of 4.5 A was supplied. When energized, the operation voltage was 36 V, and treated water having an electrical conductivity of 0.1 μS / cm was obtained, indicating that pure water with high purity was produced by the electric deionized water production apparatus of the present invention. Moreover, the water flow differential pressure was 120 kPa.

DESCRIPTION OF SYMBOLS 1,101 Cation exchange membrane 2,102 Anion exchange membrane 3a, 3b 1st, 2nd to-be-processed water introduction distribution part 4a, 4b 1st, 2nd treated water collection part 5a, 5b Communication pipe 6 Decation Chamber 7 Deanion chamber 9, 109 Cathode 10, 110 Anode 11, 105 Concentration chamber 12, 112 Cathode chamber 13, 113 Anode chamber 15 Porous cation exchanger 16 Porous anion exchanger 17, 117 Cation exchange membrane Or anion exchange membranes 20A to 20C Electric deionized water production device 24 Groove 61 Skeletal phase 62 Hole phase 104 Deionization chamber 106 Deionization module 107 Frame 108 Rib 111 Partition membrane B Concentrated water inlet b Concentrated water outlet C , D Electrode water inlet c, d Electrode water outlet

Claims (8)

  Bubble-shaped macropores overlap each other, and the overlapping portion is a continuous macropore structure having an opening with an average diameter of 30 to 300 μm in a water-wet state. SEM of the cut surface of the continuous macropore structure (dried body) having an ion exchange capacity of 0.4 to 5 mg equivalent / ml, an ion exchange group uniformly distributed in the porous ion exchanger In the image, water is passed through a deionization chamber filled with an organic porous ion exchanger having a skeleton area of 25 to 50% in the image area in the image area, and ionic impurities in the water are removed to remove deionized water. In the electrical deionized water production apparatus that applies a direct current electric field to the deionization chamber and excludes ionic impurities adsorbed on the organic porous ion exchanger out of the system, the direct current electric field is applied to , Dividing the ions are organic porous electrodeionization water producing apparatus which is characterized in that to migrate in the opposite direction to the water flow direction in the ion-exchange body.   A three-dimensionally continuous skeleton having a thickness of 1 to 60 μm composed of an aromatic vinyl polymer containing 0.3 to 5.0 mol% of a crosslinked structural unit among all the structural units having an ion exchange group introduced therein; A co-continuous structure comprising three-dimensionally continuous pores having a diameter of 10 to 100 μm between the skeletons, the total pore volume being 0.5 to 5 ml / g, Water is passed through a deionization chamber filled with an organic porous ion exchanger in which the ion exchange capacity is 0.3 to 5 mg equivalent / ml, and the ion exchange groups are uniformly distributed in the porous ion exchanger, An electric system that removes ionic impurities in water to produce deionized water and applies a DC electric field to the deionization chamber to exclude ionic impurities adsorbed on the organic porous ion exchanger out of the system In the deionized water production apparatus, the application of the DC electric field is Dividing the ions are organic porous electrodeionization water producing apparatus which is characterized in that to migrate in the opposite direction to the water flow direction in the ion-exchange body. A decation chamber formed by filling an organic porous cation exchanger in a deionization chamber partitioned by an ion exchange membrane on one side and a cation exchange membrane on the other side; and on the outside of the ion exchange membrane on the one side An anode to be disposed; a cathode disposed outside the cation exchange membrane on the other side; and a first treated water disposed in the vicinity of the cation exchange membrane on the other side in the decation chamber. An electric decationized water production apparatus having an introduction / distribution unit and a first treated water collecting unit disposed in the vicinity of an ion exchange membrane on one side in the decation chamber, and anion exchange on one side A deionization chamber formed by filling a deionization chamber partitioned by a membrane and an ion exchange membrane on the other side with an organic porous anion exchanger, and an anode disposed outside the one side anion exchange membrane A cathode disposed outside the ion exchange membrane on the other side, and a first treated water collecting part of the electric decationized ion water production apparatus A second treated water introduction / distribution unit disposed near one anion exchange membrane in the deanion chamber connected by the first and second ion exchange membranes near the other ion exchange membrane in the deanion chamber. An electrical deionized water production apparatus having a second treated water collection unit installed,
The organic porous cation exchanger and the organic porous anion exchanger are continuous macropore structures in which bubble-shaped macropores overlap each other, and the overlapping portions form an opening having an average diameter of 30 to 300 μm in a wet state. The total pore volume is 0.5 to 5 ml / g, the ion exchange capacity per volume in a wet state of water is 0.4 to 5 mg equivalent / ml, and the ion exchange groups are uniformly distributed in the porous ion exchanger. In addition, in the SEM image of the cut surface of the continuous macropore structure (dry body), the skeleton part area that appears in the cross section is 25 to 50% in the image region, apparatus. A decation chamber formed by filling an organic porous cation exchanger in a deionization chamber partitioned by an ion exchange membrane on one side and a cation exchange membrane on the other side; and on the outside of the ion exchange membrane on the one side An anode to be disposed; a cathode disposed outside the cation exchange membrane on the other side; and a first treated water disposed in the vicinity of the cation exchange membrane on the other side in the decation chamber. An electric decationized water production apparatus having an introduction / distribution unit and a first treated water collecting unit disposed in the vicinity of an ion exchange membrane on one side in the decation chamber, and anion exchange on one side A deionization chamber formed by filling a deionization chamber partitioned by a membrane and an ion exchange membrane on the other side with an organic porous anion exchanger, and an anode disposed outside the one side anion exchange membrane A cathode disposed outside the ion exchange membrane on the other side, and a first treated water collecting part of the electric decationized ion water production apparatus A second treated water introduction / distribution unit disposed near one anion exchange membrane in the deanion chamber connected by the first and second ion exchange membranes near the other ion exchange membrane in the deanion chamber. An electrical deionized water production apparatus having a second treated water collection unit installed,
An aromatic vinyl polymer in which the organic porous cation exchanger and the organic porous anion exchanger contain 0.3 to 5.0 mol% of a crosslinked structural unit in all the structural units into which an ion exchange group is introduced. A co-continuous structure comprising a three-dimensionally continuous skeleton having a thickness of 1 to 60 μm and three-dimensionally continuous pores having a diameter of 10 to 100 μm between the skeletons, The volume is 0.5 to 5 ml / g, the ion exchange capacity per volume in a wet state of water is 0.3 to 5 mg equivalent / ml, and the ion exchange groups are uniformly distributed in the porous ion exchanger. An electrical deionized water production apparatus. Organic porous material in a first deionization chamber defined by a cation exchange membrane on one side and an intermediate cation exchange membrane formed between the cation exchange membrane on one side and the anion exchange membrane on the other side An organic porous anion exchanger is filled in a decation chamber filled with a cation exchanger, and a second deion chamber partitioned by the anion exchange membrane on the other side and the intermediate cation exchange membrane. A deionization chamber, a cathode disposed outside the cation exchange membrane on one side, an anode disposed outside the anion exchange membrane on the other side, and the decationization chamber A first treated water introduction / distribution unit disposed near the cation exchange membrane on one side, and a first treated water collection unit disposed near the intermediate cation exchange membrane in the decation chamber The second treated water conduit disposed near the anion exchange membrane on the other side in the deionization chamber connected to the first treated water collecting section by a communication pipe A distribution unit, there is provided a second processing water catchment portion which is disposed in the intermediate cation exchange membrane vicinity in dehydration anion chamber, and
The organic porous cation exchanger and the organic porous anion exchanger are continuous macropore structures in which bubble-shaped macropores overlap each other, and the overlapping portions form an opening having an average diameter of 30 to 300 μm in a wet state. The total pore volume is 0.5 to 5 ml / g, the ion exchange capacity per volume in a wet state of water is 0.4 to 5 mg equivalent / ml, and the ion exchange groups are uniformly distributed in the porous ion exchanger. In addition, in the SEM image of the cut surface of the continuous macropore structure (dry body), the skeleton part area that appears in the cross section is 25 to 50% in the image region, apparatus. Organic porous material in a first deionization chamber defined by a cation exchange membrane on one side and an intermediate cation exchange membrane formed between the cation exchange membrane on one side and the anion exchange membrane on the other side An organic porous anion exchanger is filled in a decation chamber filled with a cation exchanger, and a second deion chamber partitioned by the anion exchange membrane on the other side and the intermediate cation exchange membrane. A deionization chamber, a cathode disposed outside the cation exchange membrane on one side, an anode disposed outside the anion exchange membrane on the other side, and the decationization chamber A first treated water introduction / distribution unit disposed near the cation exchange membrane on one side, and a first treated water collection unit disposed near the intermediate cation exchange membrane in the decation chamber The second treated water conduit disposed near the anion exchange membrane on the other side in the deionization chamber connected to the first treated water collecting section by a communication pipe A distribution unit, there is provided a second processing water catchment portion which is disposed in the intermediate cation exchange membrane vicinity in dehydration anion chamber, and
An aromatic vinyl polymer in which the organic porous cation exchanger and the organic porous anion exchanger contain 0.3 to 5.0 mol% of a crosslinked structural unit in all the structural units into which an ion exchange group is introduced. A co-continuous structure comprising a three-dimensionally continuous skeleton having a thickness of 1 to 60 μm and three-dimensionally continuous pores having a diameter of 10 to 100 μm between the skeletons, The volume is 0.5 to 5 ml / g, the ion exchange capacity per volume in a wet state of water is 0.3 to 5 mg equivalent / ml, and the ion exchange groups are uniformly distributed in the porous ion exchanger. An electrical deionized water production apparatus. Organic porous cation exchange in a first deionization chamber partitioned by an ion exchange membrane on one side and an intermediate cation exchange membrane formed between the ion exchange membrane on one side and the ion exchange membrane on the other side Concentration partitioned by a decation chamber filled with a body, the intermediate cation exchange membrane, and an intermediate anion exchange membrane formed between the intermediate cation exchange membrane and the ion exchange membrane on the other side A deionization chamber formed by filling an organic porous anion exchanger in a second deionization chamber partitioned by the chamber, the ion exchange membrane on the other side and the intermediate anion exchange membrane, and the ion on the one side An anode disposed outside the exchange membrane, a cathode disposed outside the ion exchange membrane on the other side, and a first coating disposed in the vicinity of the intermediate cation exchange membrane in the decation chamber. A treated water introduction / distribution section, and a first treated water collection section disposed in the vicinity of the ion exchange membrane on one side in the decation chamber. A second treated water introduction / distribution unit disposed in the vicinity of the intermediate anion exchange membrane in the deanion chamber connected to the first treated water collecting unit by a communication pipe; A second treated water collection section disposed near the ion exchange membrane on the other side,
The organic porous cation exchanger and the organic porous anion exchanger are continuous macropore structures in which bubble-shaped macropores overlap each other, and the overlapping portions form an opening having an average diameter of 30 to 300 μm in a wet state. The total pore volume is 0.5 to 5 ml / g, the ion exchange capacity per volume in a wet state of water is 0.4 to 5 mg equivalent / ml, and the ion exchange groups are uniformly distributed in the porous ion exchanger. In addition, in the SEM image of the cut surface of the continuous macropore structure (dry body), the skeleton part area that appears in the cross section is 25 to 50% in the image region, apparatus. Organic porous cation exchange in a first deionization chamber partitioned by an ion exchange membrane on one side and an intermediate cation exchange membrane formed between the ion exchange membrane on one side and the ion exchange membrane on the other side Concentration partitioned by a decation chamber filled with a body, the intermediate cation exchange membrane, and an intermediate anion exchange membrane formed between the intermediate cation exchange membrane and the ion exchange membrane on the other side A deionization chamber formed by filling an organic porous anion exchanger in a second deionization chamber partitioned by the chamber, the ion exchange membrane on the other side and the intermediate anion exchange membrane, and the ion on the one side An anode disposed outside the exchange membrane, a cathode disposed outside the ion exchange membrane on the other side, and a first coating disposed in the vicinity of the intermediate cation exchange membrane in the decation chamber. A treated water introduction / distribution section, and a first treated water collection section disposed in the vicinity of the ion exchange membrane on one side in the decation chamber. A second treated water introduction / distribution unit disposed in the vicinity of the intermediate anion exchange membrane in the deanion chamber connected to the first treated water collecting unit by a communication pipe; A second treated water collection section disposed near the ion exchange membrane on the other side,
An aromatic vinyl polymer in which the organic porous cation exchanger and the organic porous anion exchanger contain 0.3 to 5.0 mol% of a crosslinked structural unit in all the structural units into which an ion exchange group is introduced. A co-continuous structure comprising a three-dimensionally continuous skeleton having a thickness of 1 to 60 μm and three-dimensionally continuous pores having a diameter of 10 to 100 μm between the skeletons, The volume is 0.5 to 5 ml / g, the ion exchange capacity per volume in a wet state of water is 0.3 to 5 mg equivalent / ml, and the ion exchange groups are uniformly distributed in the porous ion exchanger. An electrical deionized water production apparatus.