JP5497468B2 - Electric deionized water production equipment - Google Patents

Description

  The present invention relates to an electric deionized water production apparatus that prevents generation of power-saving scale and is used in various industries or laboratory facilities such as semiconductor manufacturing field, pharmaceutical manufacturing field, power generation field such as nuclear power and thermal power, food industry, etc. Is.

  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.

  In this electric deionized water production apparatus, one demineralization chamber defined by one side cation exchange membrane and the other side anion exchange membrane is filled with an ion exchanger to form a demineralization chamber. Concentration chambers are provided on both sides of the desalting chamber via an exchange membrane and an anion exchange membrane, and these desalting chambers and concentration chambers are arranged between an anode chamber equipped with an anode and a cathode chamber equipped with a cathode. In addition, the water to be treated flows into the desalting chamber while applying a voltage, and the concentrated water flows into the concentration chamber to remove impurity ions in the water to be treated, thereby obtaining deionized water.

  However, the conventional electric deionized water production apparatus has a problem that the electric resistance value of the concentrating chamber is large, so that the voltage required to pass the rated current increases, resulting in increased power consumption. As described above, in the electric deionized water production apparatus, regeneration with a chemical solution is unnecessary, and thus the operating cost is determined by power consumption. Except for the rectification loss when converting alternating current to direct current, the power consumption in the electrical deionized water production apparatus is expressed as direct current x voltage between the electrodes.

  Here, the direct current is determined by the amount and type of ions contained in the water to be treated and the required quality of the treated water. That is, in the electric deionized water production apparatus, it is necessary to continuously discharge ions captured by the ion exchanger in the desalting chamber to the concentrated water side by electrophoretic migration, which is necessary for causing ions to migrate. The above current is indispensable for the electric deionized water production apparatus to exhibit its performance normally. Therefore, in the normal case, the electric deionized water production apparatus performs constant current operation that maintains a constant current value that exceeds the minimum current value required under the operation conditions, and this is reduced to reduce power consumption. There is no saving.

  On the other hand, the voltage is the sum of the potential differences generated by the electric resistance of the electrode chamber, the concentrating chamber, the desalting chamber, and the ion-exchange membrane that separates these electrodes between the two electrodes. It depends on the performance of the exchanger and ion exchange membrane, the type of counter ion, and the type and amount of ions contained in the indoor water. Especially, the electrical resistance of a concentration chamber is large compared with the component of other electric deionized water manufacturing apparatuses. That is, there is usually only one electrode chamber at both ends of the apparatus, and the ionic strength inside thereof is relatively high, and a plurality of ion exchange membranes and desalting chambers are usually provided between the two electrodes. Since the ion exchange membrane itself is a conductive solid having an ion exchange group, and the desalting chamber is filled with an ion exchanger which is a conductive solid, the electrical resistance due to these is relatively small. On the other hand, a plurality of concentrating chambers are disposed between both electrodes, and in the conventional electric deionized water production apparatus, the concentrating chamber is not filled with a conductive filler. The electric resistance is large because it is based only on the ions held by water, and this is the main cause of the increase in the electric resistance of the entire apparatus.

  Further, in the conventional electric deionized water production apparatus, when the hardness of the incoming water to be treated is high, there is a problem that scales such as calcium carbonate and magnesium hydroxide are generated in the concentration chamber of the electric deionized water production apparatus. there were. When the scale occurs, the electrical resistance at that portion increases, and current does not flow easily. That is, in order to pass the same current as when no scale is generated, it is necessary to increase the voltage, resulting in an increase in power consumption. In addition, depending on the place where the scale is attached, the current density differs in the concentration chamber, and current non-uniformity occurs in the desalting chamber. Moreover, when the amount of scale adhesion further increases, the water flow differential pressure increases and the voltage further increases. When the maximum voltage value of the apparatus is exceeded, the current value decreases. In this case, a current of a magnitude necessary for ion removal cannot be flowed, and the quality of treated water is deteriorated. Furthermore, the grown scale erodes into the ion exchange membrane and eventually breaks the ion exchange membrane.

  Japanese Patent Laid-Open No. 2003-230886 is filled with an organic porous ion exchanger having an open-cell structure in the concentrating chamber in order to reduce the electric resistance value derived from the concentrating chamber and prevent the generation of scale. An electrical deionized water production apparatus has been proposed.

  In the electric deionized water production apparatus in which these concentrating chambers are filled with an organic porous ion exchanger having an open cell structure, the electrical resistance is reduced due to the conductivity of the organic porous ion exchanger, and the concentrating chamber Since local mixing at a concentration exceeding the solubility product of calcium ions and magnesium ions, and carbonate ions and hydroxide ions due to the uneven distribution of ions in can be avoided, scale generation can be prevented. Details of the production of the organic porous ion exchanger used in the electric deionized water production apparatus disclosed in Japanese Patent Application Laid-Open No. 2003-230886 are disclosed in Japanese Patent Application Laid-Open No. 2002-306976.

JP 2003-230886 A JP 2002-306976 A JP 2009-62512 A JP 2009-67982 A

  However, the organic porous ion exchanger described in Japanese Patent Application Laid-Open No. 2003-230886 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. Further, when the average diameter of the openings is around 20 μm, the total pore volume is increased accordingly, so that there is a problem that the ion exchange capacity per volume is lowered and the conductivity becomes insufficient.

  If the conductivity is insufficient, the effect of reducing the electrical resistance is not sufficient, so that the thickness of the concentration chamber needs to be set small, and there is a problem that the scale prevention effect cannot be obtained sufficiently. The scale prevention mechanism when the concentration chamber is filled with an ion exchanger is as follows. That is, in the anion exchanger packed region in the concentration chamber, the anion that has permeated through the anion exchange membrane does not move into the concentrated water, passes through the highly conductive anion exchanger, and moves to the cation exchange membrane. Move to. Similarly, in the cation exchanger packed region, cations that have permeated through the cation exchange membrane do not move to the concentrated water, pass through the highly conductive cation exchanger, and move to the anion exchange membrane. To do. For this reason, calcium ions, magnesium ions, etc. in the liquid that cause scale generation in the concentration chamber, and high-concentration regions such as carbonate ions and hydroxide ions are separated from both ends of the concentration chamber by anion exchange membranes and cations. In the vicinity of the exchange membrane, mixing at a concentration exceeding the solubility product is avoided, and scale generation can be prevented. As is clear from the above scale prevention mechanism, in order to obtain a sufficient scale prevention effect in the concentration chamber, the distance between the anion exchange membrane and the cation exchange membrane separated at both ends of the concentration chamber, that is, the thickness of the concentration chamber is sufficiently large. I need to take it. However, in the conventional ion exchanger having an open cell structure filled in the concentration chamber, the effect of reducing the electric resistance is not sufficient as described above, and therefore the thickness of the concentration chamber cannot be made sufficiently large. There was a problem that the prevention effect could not be sufficiently obtained. In addition, in the monolith loaded in the concentrating chamber, the appearance of a monolith with a new structure different from the open cell structure (continuous macropore) has been desired.

  Accordingly, an object of the present invention is to solve the problem of reduction of electric resistance or generation of scale from the structural aspect of the concentration chamber of an electric deionized water production apparatus (hereinafter also simply referred to as “EDI”). An object of the present invention is to provide an electric deionized water production apparatus that can be reduced and that does not generate scale in the concentrating chamber even during long-term continuous operation.

  Under such circumstances, the present inventors have conducted intensive studies, and as a result, have obtained a monolithic organic material having a relatively large pore volume obtained by the methods described in JP2003-230886A and JP2002-306976A. If the vinyl monomer and the crosslinking agent are allowed to stand in an organic solvent under specific conditions in the presence of the porous body (intermediate), a large number of 2 to 20 μm in diameter is formed on the surface of the skeleton constituting the organic porous body. If a monolith having a composite structure in which the particle bodies are fixed or a protrusion is formed is obtained, and the composite monolith ion exchanger having ion exchange groups introduced into the composite monolith is used as a packing in the EDI concentration chamber The electric resistance at the time of EDI operation can be sufficiently reduced, so that the voltage can be lowered, the power consumption, that is, the operation cost can be reduced, and the water flow differential pressure can be further reduced. Which resulted in the completion of the invention.

That is, the present invention provides a desalination chamber in which a chamber partitioned by a cation exchange membrane disposed on the cathode side and an anion exchange membrane disposed on the anode side is filled with an ion exchanger, Concentration chambers are provided on both sides of the desalting chamber via a membrane and an anion exchange membrane, and these desalting chambers and concentrating chambers are arranged between an anode chamber having an anode and a cathode chamber having a cathode. In the deionized water production apparatus, the concentrating chamber includes an organic porous body composed of a continuous skeleton phase and a continuous pore phase, and a large number of particles having a diameter of 4 to 40 μm fixed to the skeleton surface of the organic porous body. A composite structure of a large number of protrusions having a size of 4 to 40 μm formed on the skeleton surface of the organic porous body, and having an average pore diameter of 10 to 150 μm and a total pore volume of 0 in a wet state of water. .5-5 ml / g, ion exchange per volume in water-wet condition There is provided an electrodeionization water production apparatus characterized in that it is formed by filling only monolithic organic porous ion exchanger is capacity 0.2mg equivalent / ml or more.

Further, the present invention is partitioned by a cation exchange membrane disposed on the cathode side , an anion exchange membrane disposed on the anode side, and an intermediate ion exchange membrane located between the cation exchange membrane and the anion exchange membrane 2 A small desalting chamber is filled with an ion exchanger to form a desalting chamber, and a concentration chamber is provided on both sides of the desalting chamber via the cation exchange membrane and anion exchange membrane. In an electric deionized water production apparatus comprising an anode chamber having an anode and a cathode chamber having a cathode, wherein the concentrating chamber has an organic porous body composed of a continuous skeleton phase and a continuous pore phase. And a large number of particles having a diameter of 4 to 40 μm fixed to the skeleton surface of the organic porous body or a large number of protrusions having a size of 4 to 40 μm formed on the skeleton surface of the organic porous body A structure having an average pore diameter of 10 to 15 in a wet state with water Filled only with monolithic organic porous ion exchanger with 0 μm, total pore volume of 0.5-5 ml / g and ion exchange capacity per volume in water-wet state of 0.2 mg equivalent / ml or more An electric deionized water production apparatus is provided.

  According to the present invention, due to the high conductivity of the organic porous ion exchanger, the electrical resistance derived from the concentration chamber is reduced, the voltage during operation of the device is reduced, the power consumption is reduced, and the operating cost is reduced. I can do it. Moreover, the water flow differential pressure can be lowered.

4 is a SEM image of a monolith obtained in Reference Example 1 at a magnification of 100. FIG. 3 is a SEM image of a monolith obtained in Reference Example 1 at a magnification of 300. 3 is an SEM image of the monolith obtained in Reference Example 1 at a magnification of 3000. 2 is an EPMA image showing the distribution state of sulfur atoms on the surface of the monolith cation exchanger obtained in Reference Example 1. FIG. 2 is an EPMA image showing a distribution state of sulfur atoms in the cross-section (thickness) direction of the monolith cation exchanger obtained in Reference Example 1. FIG. 10 is a SEM image of a monolith obtained in Reference Example 2 at a magnification of 100. 6 is an SEM image of a monolith obtained in Reference Example 2 at a magnification of 600. 4 is an SEM image of the monolith obtained in Reference Example 2 at a magnification of 3000. 10 is an SEM image of a monolith obtained in Reference Example 3 at a magnification of 600. 10 is an SEM image of the monolith obtained in Reference Example 3 at a magnification of 3000. 10 is a SEM image of the monolith obtained in Reference Example 4 at a magnification of 3000. 10 is an SEM image of a monolith obtained in Reference Example 5 at a magnification of 100. 10 is a SEM image of the monolith obtained in Reference Example 5 at a magnification of 3000. 10 is a SEM image of a monolith obtained in Reference Example 6 at a magnification of 100. 10 is an SEM image of a monolith obtained in Reference Example 6 at a magnification of 600. 10 is an SEM image of the monolith obtained in Reference Example 6 at a magnification of 3000. It is a schematic diagram of the electric deionized water manufacturing apparatus in embodiment of this invention. It is a figure explaining the structure of a desalination chamber module and a concentration chamber. It is the figure which showed simply the electric-type deionized water manufacturing apparatus. It is a figure explaining the movement of the impurity ion in a concentration chamber. It is a figure which shows concentration distribution of the impurity ion in a concentration chamber. It is a figure which shows the density | concentration distribution of the impurity ion in the concentration chamber (conventional type) without an organic porous ion exchanger filling. It is a schematic diagram of the electric deionized water manufacturing apparatus in other embodiment of this invention. It is typical sectional drawing of a protrusion.

The electric deionized water production apparatus in the present embodiment will be described with reference to FIG. FIG. 17 is a schematic view showing an example of an electrical deionized water production apparatus. As shown in FIG. 17, the cation exchange membrane 3, the intermediate ion exchange membrane 5, and the anion exchange membrane 4 are alternately arranged apart from each other, and ion exchange is performed in the space formed by the cation exchange membrane 3 and the intermediate ion exchange membrane 5. The first small desalting chambers d ₁ , d ₃ , d ₅ , and d ₇ are formed by filling the body 8, and the space formed by the intermediate ion exchange membrane 5 and the anion exchange membrane 4 is filled with the ion exchanger 8. Thus, the second small desalting chambers d ₂ , d ₄ , d ₆ , and d ₈ are formed, and the first small desalting chamber d ₁ and the second small desalting chamber d _{2 form} the desalting chamber D ₁ , first small Desalination chamber D ₃ and second small desalination chamber d ₄ are desalted chamber D ₂ , and first small desalination chamber d ₅ and second small desalination chamber d ₆ are desalted chamber D ₃ and first small desalination chamber _6. The chamber d _{7 is} the second small desalting chamber d ₈ and is designated as the desalting chamber D ₄ . The portion filled with the ion exchanger 8a formed by the anion exchange membrane 4 and the cation exchange membrane 3 located next to each of the desalting chambers D ₂ and D ₃ is a concentration chamber 1 for flowing concentrated water. Drawing sequentially features this depletion chamber _{D 1} from the left, concentrating chamber 1, desalting _{D 2,} concentrating chamber 1, depletion chamber _{D 3,} concentrating chamber 1, to form a depletion chamber _{D 4.} Further, the cathode chamber 2a through the cation exchange membrane 3 to the left of the depletion chamber D _1, provided respectively anode chamber 2b through the anion exchange membrane 4 to the right of the depletion chamber D _4. Further, in two small desalting chambers adjacent via the intermediate ion exchange membrane 5, the treated water outflow line 12 of the second small desalting chamber is connected to the treated water inflow line 13 of the first small desalting chamber. Yes.

  As shown in FIG. 18, such a demineralization chamber includes a deionization module 20 formed by two frames 21 and 22 and three ion exchange membranes 3, 5, and 4. That is, the cation exchange membrane 3 is sealed on one surface of the first frame body 21, the internal space of the first frame body 21 is filled with an ion exchanger, and then the other surface of the first frame body 21 is filled. The intermediate ion exchange membrane 5 is sealed to form a first small desalting chamber. Next, the second frame 22 is sealed so as to sandwich the intermediate ion exchange membrane 5, the ion exchanger is filled in the internal space of the second frame 22, and then the other surface of the second frame 22 is filled with an anion. The exchange membrane 4 is sealed to form a second small desalting chamber. The ion exchanger filled in the first desalting chamber and the second small desalting chamber is not particularly limited, but the second small desalting chamber into which treated water first flows is filled with an anion exchanger, Next, the first small desalting chamber into which the effluent of the second small desalting chamber flows is filled with a mixed ion exchanger of an anion exchanger and a cation exchanger. It is preferable in that the water to be treated containing a large amount of weak acid components such as silica and carbonic acid can be sufficiently treated. Reference numeral 23 denotes a rib for reinforcing the frame.

  In the present invention, the EDI concentration chamber 1 is filled with a monolithic organic porous ion exchanger having a composite structure. In this specification, “monolithic organic porous body” is simply “composite monolith”, “monolithic organic porous ion exchanger” is simply “composite monolithic ion exchanger”, and “monolithic organic porous intermediate”. "Body" is also simply called "monolith intermediate".

<Description of composite monolith ion exchanger>
A composite monolith ion exchanger is obtained by introducing an ion exchange group into a composite monolith, and is fixed to an organic porous body composed of a continuous skeleton phase and a continuous pore phase, and the skeleton surface of the organic porous body. An organic porous body consisting of a continuous skeleton phase and a continuous pore phase, and a size formed on the skeleton surface of the organic porous body. A composite structure with a large number of protrusions having a thickness of 4 to 40 μm, and having an average pore diameter of 10 to 150 μm and a total pore volume of 0.5 to 5 ml / g in a water wet state, The ion exchange capacity per volume is 0.2 mg equivalent / ml or more, and the ion exchange groups are uniformly distributed in the composite structure. In the present specification, “particle bodies” and “projections” may be collectively referred to as “particle bodies”.

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

  As a preferable structure of the organic porous body, a continuous macropore structure (hereinafter referred to as “first organic porous ion”) in which bubble-shaped macropores overlap each other, and the overlapping portion becomes an opening having an average diameter of 30 to 150 μm in a wet state. And a three-dimensional continuous skeleton having an average thickness of 1 to 60 μm in a water-wet state, and three-dimensional continuous having an average diameter of 10 to 100 μm in a water-wet state between the skeletons. A co-continuous structure (hereinafter, also referred to as “second organic porous ion exchanger”).

  In the case of the first organic porous ion exchanger, the organic porous body is a continuous macropore structure in which bubble-shaped macropores are overlapped with each other, and the overlapping portions form openings (mesopores) having an average diameter of 30 to 150 μm in a wet state. It is. The average diameter of the opening of the composite monolith ion exchanger is larger than the average diameter of the opening of the composite monolith in a dry state because the entire composite 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 openings of the dry monolith intermediate, the average diameter of the pores or openings of the dry composite monolith, and the average diameter of the holes or openings of the dry composite monolith ion exchanger are: It is a value measured by the mercury intrusion method. In the present invention, the average diameter of the pores or openings of the composite monolith ion exchanger in the wet state is calculated by multiplying the average diameter of the pores or openings of the composite monolith ion exchanger in the dry state by the swelling rate. Value. Specifically, the diameter of the composite monolith ion exchanger in the water wet state is x1 (mm), the diameter of the composite monolith ion exchanger in the dry state obtained by drying the composite monolith ion exchanger in the water wet state. And y1 (mm), and the average diameter of the pores or openings when the dry monolithic ion exchanger is measured by mercury porosimetry is z1 (μm) The average diameter (μm) of the holes or openings of the exchanger is calculated by the following formula “average diameter of holes or openings (μm) = z1 × (x1 / y1) of the composite monolith ion exchanger in a water-wet state”. The Also, the average diameter of the pores or openings of the dry composite monolith before introduction of the ion exchange group, and the water-wetting composite monolith ion relative to the dry composite monolith when the ion exchange group is introduced into the dry composite monolith When the swelling ratio of the exchanger is known, the average diameter of the pores or openings of the composite monolith in the dry state is multiplied by the swelling ratio to calculate the average diameter of the pores of the composite monolith ion exchanger in the water wet state. You can also.

  In the case of the second organic porous body ion exchanger, the organic porous body has a three-dimensionally continuous skeleton having an average diameter of 1 to 60 μm in a water-wet state, and an average diameter between the skeletons in a water-wet state. It is a co-continuous structure having three-dimensionally continuous pores of 10 to 100 μm. If the diameter of the three-dimensionally continuous pores is less than 10 μm, the pressure loss during fluid permeation increases, which is not preferable. If the diameter exceeds 100 μm, contact between the concentrated water and the organic porous ion exchanger is not preferable. As a result, the ion exchange characteristics become non-uniform, which is not preferable.

  The average diameter of the co-continuous structure pores in the water-wet state is a value calculated by multiplying the average diameter of the pores of the composite monolith ion exchanger in the dry state measured by a known mercury intrusion method and the swelling ratio. It is. Specifically, the diameter of the composite monolith ion exchanger in the water wet state is x2 (mm), the diameter of the composite monolith ion exchanger in the dry state obtained by drying the composite monolith ion exchanger in the water wet state. Is y2 (mm), and the average diameter of the pores when the dried monolithic ion exchanger is measured by mercury porosimetry is z2 (μm), the pores of the composite monolith ion exchanger The average diameter (μm) in the water-wet state is calculated by the following formula: “Average diameter (μm) of the pores of the composite monolith ion exchanger in the water-wet state = z2 × (x2 / y2)”. In addition, the average diameter of the pores of the dry composite monolith before introduction of the ion exchange group, and the water-wet composite monolith ion exchanger with respect to the dry composite monolith when the ion exchange group is introduced into the dry composite monolith Can be calculated by multiplying the average diameter of the pores of the composite monolith in the dry state by the swelling ratio to calculate the average diameter of the pores of the composite monolith ion exchanger in the water-wet state. The average thickness of the skeleton of the co-continuous structure in the wet state is determined by performing SEM observation of the composite monolith ion exchanger in the dry state at least three times and measuring the thickness of the skeleton in the obtained image. The average value is calculated by multiplying the swelling ratio. Specifically, the diameter of the composite monolith ion exchanger in the water wet state is x3 (mm), the diameter of the composite monolith ion exchanger in the dry state obtained by drying the composite monolith ion exchanger in the water wet state. Y3 (mm), SEM observation of this dried composite monolith ion exchanger was performed 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 composite monolith ion exchanger in the water-wet state is expressed by the following formula: “average thickness of the skeleton of the continuous structure of the composite monolith ion exchanger in the water-wet state” (Μm) = z3 × (x3 / y3) ”. Further, the average thickness of the skeleton of the dry composite monolith before the introduction of the ion exchange groups, and the water-wet composite monolith ion exchanger with respect to the dry composite monolith when the ion exchange groups are introduced into the dry composite monolith Can be calculated by multiplying the average thickness of the skeleton of the composite monolith in the dry state by the swell ratio to the water-wet state of the skeleton of the composite monolith ion exchanger. The skeleton forming the co-continuous structure is rod-shaped and has a circular cross-sectional shape, but may have a cross-section with different diameters such as an elliptical cross-sectional shape. The thickness in this case is the average of the minor axis and the major axis.

  Further, if the average diameter of the three-dimensionally continuous skeleton is less than 1 μm, it is not preferable because the ion exchange capacity per volume decreases, and if it exceeds 60 μm, the uniformity of ion exchange characteristics is lost. Absent.

  A preferable value of the average diameter of the pores of the composite monolith ion exchanger in a wet state with water is 10 to 120 μm. When the organic porous body constituting the composite monolith ion exchanger is the first organic porous body, the preferred pore diameter of the composite monolith ion exchanger is 30 to 120 μm, and the organic porous body constituting the composite monolith ion exchanger In the case of the second organic porous body, a preferable value of the pore diameter of the composite monolith ion exchanger is 10 to 90 μm.

  In the composite monolith ion exchanger according to the present invention, the diameter of the particles and the size of the protrusions in a wet state are 4 to 40 μm, preferably 4 to 30 μm, and particularly preferably 4 to 20 μm. In the present invention, both the particles and the protrusions are observed as protrusions on the surface of the skeleton, and the particles observed are referred to as particles, and the protrusions that are not granular are protrusions. Called the body. FIG. 24 shows a schematic cross-sectional view of the protrusion. As shown to (A)-(E) in FIG. 24, the protrusion-shaped thing protruded from the skeleton surface 61 is the protrusion 62, and the protrusion 62 is like the protrusion 62a shown to (A). The shape close to a granular shape, a hemispherical shape like a projection 62b shown in (B), and a swell of the skeleton surface like a projection 62c shown in (C). In addition, the protrusion 61 has a shape that is longer in the direction perpendicular to the skeleton surface 61 than in the plane direction of the skeleton surface 61, like the protrusion 62d shown in FIG. There is a thing of the shape which protruded in the several direction like the protrusion 62e shown to (E). Further, the size of the protrusions is determined by the SEM image when observed by SEM, and indicates the length of the portion where the width of each protrusion is the largest in the SEM image.

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

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

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

  The total pore volume of the composite monolith ion exchanger is the same as the total pore volume of the composite monolith. That is, even when the ion exchange group is introduced into the composite monolith to swell and increase the opening diameter, the total pore volume hardly changes because the skeletal phase is thick. If the total pore volume is less than 0.5 ml / g, the pressure loss during fluid permeation increases, 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. Note that the total pore volume of the composite monolith (monolith intermediate, composite monolith, composite monolith ion exchanger) is the same both in the dry state and in the water wet state.

  Note that the pressure loss when water is permeated through the composite monolith ion exchanger is the same as the pressure loss when water is permeated through the composite monolith.

  The composite monolith ion exchanger of the present invention has an ion exchange capacity per volume in a water-wet state of 0.2 mg equivalent / ml or more, preferably 0.3 to 1.8 mg equivalent / ml. If the ion exchange capacity per volume is less than 0.2 mg equivalent / ml, the conductivity decreases and the electrical resistance increases, which is not preferable. In addition, the ion exchange capacity per weight in the dry state of the composite monolith ion exchanger of the present invention is not particularly limited, but since the ion exchange groups are uniformly introduced to the skeleton surface and the skeleton inside the composite monolith, 5 mg equivalent / g. The ion exchange capacity of the organic porous material in which the ion exchange group is introduced only on the surface of the skeleton cannot be determined depending on the kind of the organic porous material or the ion exchange group, but is 500 μg equivalent / g at most.

  Examples of the ion exchange group to be introduced into the composite monolith of the present invention 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 composite monolith ion exchanger of the present invention, the introduced ion exchange groups are uniformly distributed not only on the surface of the skeleton of the composite monolith but also inside the skeleton phase. Here, “the ion exchange groups are uniformly distributed” means that the distribution of the ion exchange groups is uniformly distributed at least on the order of μm on the surface of the skeleton phase and inside the skeleton phase. The distribution of ion exchange groups can be confirmed relatively easily by using EPMA or the like. In addition, when the ion exchange groups are uniformly distributed not only on the surface of the composite monolith but also inside the skeleton phase, the physical and chemical properties of the surface and the interior can be made uniform, so that the swelling and shrinkage can be prevented. Durability is improved.

  The composite monolith ion exchanger of the present invention has a thickness of 1 mm or more, and is distinguished from a membrane-like porous body. When the thickness is less than 1 mm, the ion exchange capacity per porous body is extremely reduced, which is not preferable. The thickness of the composite monolith ion exchanger is preferably 3 mm to 1000 mm. In addition, the composite monolith ion exchanger of the present invention has high mechanical strength because the basic structure of the skeleton is a continuous pore structure.

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

(Method for producing monolith intermediate)
In the method for producing a monolith according to the present invention, in the step I, an oil-soluble monomer not containing an ion exchange group, a first crosslinking agent having at least two or more vinyl groups in one molecule, a mixture of a surfactant and water are stirred. In this step, a water-in-oil emulsion is prepared, and then the water-in-oil emulsion is polymerized to obtain a monolith intermediate having a continuous macropore structure having a total pore volume of 5 to 30 ml / g. The step I for obtaining the monolith intermediate may be performed according to the method described in JP-A-2002-306976.

  Examples of the oil-soluble monomer that does not contain an ion exchange group include an oleophilic monomer that does not contain an ion exchange group such as a carboxylic acid group, a sulfonic acid group, and a quaternary ammonium group, has low solubility in water. Preferable examples of these monomers include styrene, α-methylstyrene, vinyl toluene, vinyl benzyl chloride, divinyl benzene, ethylene, propylene, isobutene, butadiene, ethylene glycol dimethacrylate, and the like. These monomers can be used alone or in combination of two or more.

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

  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, 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, hydrogen peroxide-ferrous chloride, sodium persulfate- Examples include acidic sodium sulfite.

  There is no particular limitation on the mixing method when mixing the oil-soluble monomer containing no ion exchange group, the first cross-linking agent, the surfactant, water and the polymerization initiator to form a water-in-oil emulsion, A method of mixing components all at once, an oil-soluble monomer, a first crosslinking agent, a surfactant, an oil-soluble component that is an oil-soluble polymerization initiator, and a water-soluble component that is water or a water-soluble polymerization initiator For example, a method in which each component is mixed after being uniformly dissolved separately can be used. 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, particles or the like are formed on the surface of the skeleton phase of the continuous macropore structure using the structure of the monolith intermediate as a template, or particles or the like are formed on the surface of the skeleton phase of the co-continuous structure. Or The monolith intermediate is an organic polymer material having a crosslinked structure. Although the crosslinking density of the polymer material is not particularly limited, it contains 0.3 to 10 mol%, preferably 0.3 to 5 mol% of crosslinked structural units with respect to all the structural units constituting the polymer material. Is preferred. When the cross-linking structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, if it exceeds 10 mol%, the porous body becomes brittle and the flexibility is lost, which is not preferable.

  The total pore volume of the monolith intermediate is 5-30 ml / g, preferably 6-28 ml / g. If the total pore volume is too small, the total pore volume of the monolith obtained after polymerizing the vinyl monomer becomes too small, and the pressure loss during fluid permeation increases, which is not preferable. On the other hand, if the total pore volume is too large, the structure of the monolith obtained after polymerizing the vinyl monomer tends to be non-uniform, and in some cases, the structure collapses, which is not preferable. In order to set the total pore volume of the monolith intermediate in the above numerical range, the ratio (weight) of the monomer to water may be set to approximately 1: 5 to 1:35.

  When the ratio of this monomer to water is approximately 1: 5 to 1:20, a monolith intermediate having a total pore volume of 5 to 16 ml / g and a continuous macropore structure can be obtained and obtained through Step III. The obtained composite monolithic organic porous body is the first organic porous body. Further, if the blending ratio is approximately 1:20 to 1:35, a monolith intermediate having a total pore volume of more than 16 ml / g and a continuous macropore structure of 30 ml / g or less can be obtained. The organic porous body of the composite monolith obtained through the above is obtained as the second organic porous body.

  Moreover, the average diameter of the opening (mesopore) which is an overlap part of a macropore and a macropore is 20-100 micrometers in a dry state in a monolith intermediate. When the average diameter of the openings is less than 20 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes small, and the pressure loss at the time of passing water becomes large, which is not preferable. On the other hand, if it exceeds 100 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes too large, and it becomes difficult to form a water flow path uniformly. Monolith intermediates preferably have a uniform structure with uniform macropore size and aperture diameter, but are not limited to this, and the uniform structure is dotted with nonuniform macropores larger than the size of the uniform macropore. You may do.

(Production method of composite monolith)
Step II is an organic solvent in which a vinyl monomer, a second cross-linking agent having at least two vinyl groups in one molecule, a vinyl monomer or a second cross-linking agent dissolves, but a polymer formed by polymerization of the vinyl monomer does not dissolve. And a step of preparing a mixture comprising a polymerization initiator. In addition, there is no order of I process and II process, II process may be performed after I process, and I process may be performed after II process.

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

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

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

  The organic solvent used in step II is an organic solvent that dissolves the vinyl monomer and the second cross-linking agent but does not dissolve the polymer formed by polymerization of the vinyl monomer, in other words, a poor solvent for the polymer formed by polymerization of the vinyl monomer. It is. Since the organic solvent varies greatly depending on the type of vinyl monomer, it is difficult to list general specific examples. For example, when the vinyl monomer is styrene, the organic solvent includes methanol, ethanol, propanol, butanol, Alcohols such as hexanol, cyclohexanol, octanol, 2-ethylhexanol, decanol, dodecanol, propylene glycol, tetramethylene glycol; chain (poly) ethers such as diethyl ether, butyl cellosolve, polyethylene glycol, polypropylene glycol, polytetramethylene glycol Chain saturated hydrocarbons such as hexane, heptane, octane, isooctane, decane, dodecane, etc .; Ethyl acetate, isopropyl acetate, cellosolve acetate, ethyl propionate, etc. Ethers, and the like. Moreover, even if it is a good solvent of polystyrene like a dioxane, THF, and toluene, when it is used with the said poor solvent and the usage-amount is small, it can be used as an organic solvent. These organic solvents are preferably used so that the concentration of the vinyl monomer is 5 to 80% by weight. If the amount of the organic solvent used deviates from the above range and the vinyl monomer concentration is less than 5% by weight, the polymerization rate is lowered, which is not preferable. On the other hand, if the vinyl monomer concentration exceeds 80% by weight, the polymerization may run away, which is not preferable.

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

  In step III, the mixture obtained in step II is allowed to stand, and in the presence of the monolith intermediate obtained in step I, polymerization is performed to obtain a composite monolith. 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 second cross-linking agent are allowed to stand in a specific organic solvent in the absence of a monolith intermediate, a particle aggregation type monolithic organic material is obtained. A porous body is obtained. On the other hand, when a monolith intermediate having a continuous macropore structure is present in the polymerization system as in the present invention, the structure of the monolith after polymerization changes dramatically, the particle aggregation structure disappears, and the specific skeleton described above is lost. A monolith having a structure is obtained.

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

  In step III, the monolith intermediate is placed in a reaction vessel impregnated with 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 specific skeleton while having an appropriate opening diameter. In the reaction vessel, the vinyl monomer and the crosslinking agent in the mixture are adsorbed and distributed on the skeleton of the monolith intermediate that has been allowed to stand, and polymerization proceeds in the skeleton of the monolith intermediate.

  Various polymerization conditions can be selected depending on the type of monomer and the type of initiator. For example, when 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, or the like is used as an initiator, an inert atmosphere What is necessary is just to heat-polymerize at 20-100 degreeC for 1 to 48 hours in the lower sealed container. By heat polymerization, the vinyl monomer adsorbed and distributed on the skeleton of the monolith intermediate and the crosslinking agent are polymerized in the skeleton to form the specific skeleton structure. After completion of the polymerization, the content is taken out and extracted with a solvent such as acetone for the purpose of removing unreacted vinyl monomer and organic solvent to obtain a monolith having a specific skeleton structure.

  When the above-mentioned composite monolith is produced, the skeleton, which is the characteristic structure of the present invention, is obtained by performing the II step or the III step under the conditions satisfying at least one of the following conditions (1) to (5). A composite monolith having particles or the like formed on the surface can be produced.

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

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

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

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

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

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

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

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

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

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

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

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

  The method for introducing an ion exchange group into the composite monolith is not particularly limited, and a known method such as polymer reaction or graft polymerization can be used. For example, as a method of introducing a sulfonic acid group, if the composite monolith is a styrene-divinylbenzene copolymer, etc., a method of sulfonation using chlorosulfuric acid, concentrated sulfuric acid, or fuming sulfuric acid; radical initiating groups uniformly on the composite monolith And a method of grafting sodium styrene sulfonate or acrylamido-2-methylpropane sulfonic acid by introducing a chain transfer group into the skeleton surface or inside the skeleton; Similarly, after graft polymerization of glycidyl methacrylate, the sulfonic acid group is converted by functional group conversion. The method etc. which introduce | transduce are mentioned. In addition, as a method of introducing a quaternary ammonium group, if the composite 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 of producing monolith by copolymerization of chloromethylstyrene and divinylbenzene and reacting with a tertiary amine; uniformly introducing a radical initiating group or chain transfer group into the monolith on the skeleton surface and inside the skeleton, and N, N, N- Examples include a method of graft polymerization of trimethylammonium ethyl acrylate or N, N, N-trimethylammonium propylacrylamide; a method of grafting glycidyl methacrylate in the same manner and then introducing a quaternary ammonium group by functional group conversion. Among these methods, the method of introducing a sulfonic acid group includes a method of introducing a sulfonic acid group into a styrene-divinylbenzene copolymer using chlorosulfuric acid, and a method of introducing a quaternary ammonium group includes styrene. -Introducing a chloromethyl group into the divinylbenzene copolymer with chloromethyl methyl ether, etc., then reacting with a tertiary amine, or producing a monolith by copolymerization of chloromethylstyrene and divinylbenzene and reacting with a tertiary amine The method is preferable in that the ion exchange group can be introduced uniformly and quantitatively. The ion exchange groups to be introduced include cation exchange groups such as carboxylic acid groups, iminodiacetic acid groups, sulfonic acid groups, phosphoric acid groups, and phosphoric ester groups; quaternary ammonium groups, tertiary amino groups, and secondary amino groups. Groups, primary amino groups, polyethyleneimine groups, tertiary sulfonium groups, phosphonium groups and the like.

  The method for filling the concentrating chamber with the composite monolith ion exchanger is not particularly limited, and the anion exchanger single bed, the cation exchanger single bed, the anion exchanger single bed and the cation exchanger single bed are concentrated water. A double bed in which two or more beds are alternately stacked in the inflow direction, and a row bed in which an anion exchanger single bed and a cation exchanger single bed are alternately stacked in the direction perpendicular to the concentrated water inflow direction. Among them, among these, a double bed in which two or more anion exchanger single beds and cation exchanger single beds are alternately stacked in the concentrated water inflow direction is a scale as described later. It is preferable at the point from which it becomes a structure which does not generate | occur | produce easily. The concentrating chamber 1 shown in FIG. 18 is produced by sandwiching organic porous ion exchangers 81 and 82 cut into regular dimensions between an anion exchange membrane 4 on one side and a cation exchange membrane 3 on the other side. In FIG. 18, the organic porous ion exchanger is composed of two laminated beds 8 a, an upper organic porous anion exchanger 81 and a lower organic porous cation exchanger 82. That is, one organic porous cation exchanger 81 and one organic porous anion having the same size as the organic porous cation exchanger 81 are placed in the concentrating chamber of a flat plate type electric deionized water production apparatus. When two beds of ion bodies 82 are stacked and packed, the vertical and horizontal dimensions of the organic porous ion exchanger formed of the two beds are substantially the same as the ion exchange membranes 3 and 4 on both sides, and the thickness dimension w is the thickness in the concentration chamber. It becomes. In addition, when the packing form of the organic porous ion exchanger is a multiple bed, the order of the organic porous ion exchanger to be stacked and packed in the inflow / outflow direction of the concentration chamber is not particularly limited. To an organic porous cation exchanger and an organic porous anion exchanger, or vice versa. In addition, end surfaces of different ion exchangers are stacked and filled so that the end surfaces are in contact with or close to each other unless a large gap is generated. In this way, if the organic porous ion exchanger is uniformly stacked and packed in the concentration chamber, electrical conduction between the ion exchange membranes on both sides that define the concentration chamber is obtained, and ions are transferred and concentrated. The ion concentration gradient in water can be reduced. Further, the shape of these organic porous ion exchangers is not limited to the above-mentioned plate-like material, and a combination of one or two or more block-like materials and irregular shapes can be used. Among these, a plate-like object or a block-like object is preferable in that it can reliably achieve low electrical resistance and can be easily manufactured.

  The composite monolith ion exchanger may have a flow path that is formed separately from a porous structure composed of a continuous skeleton phase and a continuous pore phase. That is, the first monolith ion exchanger can be further provided with a separate flow path different from the open cells formed by the macropores and the openings (mesopores) to reduce the water flow differential pressure in the concentration chamber. . Further, the second monolith ion exchanger can be further provided with a separate flow path different from the co-continuous structure to reduce the water flow differential pressure in the concentration chamber. The separate flow path is not particularly limited, and for example, it is formed of one or more through-hole-shaped flow paths formed in parallel with the concentrated water inflow direction, or continuous grooves parallel or perpendicular to the concentrated water inflow direction. Comb-shaped flow paths, zigzag flow paths having no directivity so that concentrated water meanders in the concentration chamber, and mesh-shaped flow paths. These flow paths may be continuous from the concentrated water inlet to the concentrated water outlet or may be discontinuous. These flow paths can be formed by selecting a container shape at the time of polymerization for forming an open cell structure, and can also be formed by processing the open cell structure after polymerization. The diameter or gap size of the flow channel is usually about 1 to 5 mm. Furthermore, in order to reinforce the physical strength of the organic porous ion exchanger having a separate flow path, that is, a gap and having an open cell structure, an oblique network of polyolefin-based polymer is used as the organic porous ion. It may be filled together with the exchanger.

  The thickness of the concentration chamber is 0.2 to 15 mm, preferably 0.5 to 12 mm, and more preferably 3 to 10 mm. Conventionally, in the case where the concentration chamber is not filled with an ion exchanger, the thickness of the concentration chamber cannot be taken large because the electric resistance is large, and the upper limit value is at most 2 to 3 mm. Since the thickness of several times can be taken, generation | occurrence | production of a scale can be suppressed reliably. If the thickness of the concentration chamber is less than 0.2 mm, for example, even if an anion exchanger single bed of an organic porous ion exchanger having an open cell structure and a mesh-like cation exchanger single bed are filled, the scale Occurrence prevention effects are difficult to obtain, and the water flow differential pressure tends to increase. Moreover, when it exceeds 15 mm, the thickness of the whole apparatus becomes large and is not preferable.

The electric deionized water production apparatus is usually operated as follows. That is, a direct current is passed between the cathode 6 and the anode 7, and water to be treated flows from the treated water inflow line 11, and concentrated water flows from the concentrated water inflow line 15, and the cathode water inflow line 17 a and the anode water Cathode water and anode water flow in from the inflow line 17b, respectively. To-be-treated water flowing from the to-be-treated water inflow line 11 flows down the second small desalination chambers d ₂ , d ₄ , d ₆ and d ₈ , and impurity ions are removed when passing through the packed bed of the ion exchanger 8. Is done. Furthermore, the effluent water that has passed through the treated water inflow line 12 of the second small desalting chamber passes through the treated water inflow line 13 of the first small desalting chamber, and thus the first small desalting chamber d ₁ d ₃ d ₅ d. ₇ flows down, and again, when passing through the packed bed of the ion exchanger 8, impurity ions are removed and deionized water is obtained from the deionized water outflow line. Concentrated water that has flowed in from the concentrated water inflow line 15 rises in each concentration chamber 1 and moves through the cation exchange membrane 3 and the anion exchange membrane 4, as well as in the concentration chamber, as will be described later. Cathode water that has received impurity ions moving through the organic porous ionic body, flows out from the concentration chamber outflow line 16 as concentrated water enriched with impurity ions, and further flows in from the cathode water inflow line 17a is the cathode water outflow line. The anode water that has flowed out of 18a and has flowed in from the anode water inflow line 17b flows out of the anode water outflow line 18b. By the above operation, impurity ions in the water to be treated are electrically removed.

Next, the scale generation preventing effect in the concentration chamber of the electric deionized water production apparatus of the present invention will be described with reference to FIGS. 19 is a diagram showing the electric deionized water production apparatus of FIG. 17 in a simplified manner, and FIGS. 20 and 21 are diagrams for explaining the movement of impurity ions in the concentration chamber of the electric deionized water production apparatus of FIG. Respectively. In FIG. 19, the second small desalting chambers d ₂ , d ₄ , and d ₆ into which treated water first flows are filled with an anion exchanger (A), and the effluent from the second small desalting chamber flows. The first small desalting chambers d ₁ , d ₃ , and d ₅ are filled with a mixed ion exchanger (M) of a cation exchanger and an anion exchanger, and the four concentration chambers 1 are arranged along the flow direction of the concentration chamber. In order from the outflow side to the inflow side, the organic porous cation exchanger single bed (C) having the same open cell structure as the organic porous anion exchanger single bed (A) having a three-dimensional network-like open cell structure Are alternately packed in 4 beds.

  In FIG. 20, in the porous anion exchanger single-bed region 1a of the concentration chamber 1, anions such as carbonate ions that have permeated through the anion exchange membrane a do not move into the concentrated water, and the organic porous anion having high conductivity. It moves through the exchanger A to the cation exchange membrane c, and moves into the concentrated water for the first time at the contact portion 101 between the organic porous anion exchanger A and the cation exchange membrane c (the arrow pointing to the right in FIG. 20). For this reason, anions such as carbonate ions are discharged from the concentration chamber 1 in a state of being electrically attracted to the cation exchange membrane c. That is, for anions such as carbonate ions in the organic porous anion exchanger single bed region 1a, the concentration gradient in the concentrated water is distributed as shown in FIG. On the other hand, in the organic porous anion exchanger single bed region 1a, cations such as calcium ions that have permeated the cation exchange membrane c move in the concentrated water. For this reason, in the part where the calcium ion concentration is the highest, the carbonate ion, which is the counter ion forming the scale, moves through the organic porous anion exchanger single-bed part, so that it is difficult to generate scale.

  Similarly, in the organic porous cation exchanger single-bed region 1b of the concentration chamber 1, cations such as calcium ions that have permeated the cation exchange membrane c do not move into the concentrated water, and highly conductive organic porous cation exchange. It moves to the anion exchange membrane a through the body C, and moves into the concentrated water for the first time at the contact portion 102 between the organic porous cation exchanger C and the anion exchange membrane a (left arrow in FIG. 20). For this reason, cations such as calcium ions are discharged from the concentration chamber 1 in a state of being electrically attracted to the anion exchange membrane a. That is, the concentration in the concentrated water is distributed as shown in FIG. 21 for cations such as calcium ions in the organic porous cation exchanger single bed region 1b. On the other hand, anions such as carbonate ions that have passed through the anion exchange membrane a move in the concentrated water. For this reason, in the part where the density | concentration of a carbonate ion becomes the highest, since the calcium ion which is a counter ion which forms a scale moves the organic porous cation exchanger single bed part, it is hard to generate | occur | produce a scale. Such ion transfer is the same for magnesium ions, hydrogen ions, and hydroxide ions. In addition, by laminating the organic porous anion exchanger single bed region 1a and the organic porous cation exchanger single bed region 1b in the concentration chamber, the organic porous cation exchanger is moved to a portion filled with the organic porous cation exchanger. Rather than moving through concentrated water with low conductivity, the anion travels through the highly conductive anion exchange membrane and reaches the organic porous anion exchanger 1a, where the highly porous organic porous anion exchanger. To move. This ion movement is the same for cations. That is, almost no ions move to the vicinity of the facing ion exchange membrane through the concentrated water, and most of the ions pass through the organic porous cation exchanger, the organic porous anion exchanger and the vicinity of the facing ion exchange membrane. Move up.

  Conventionally, in an electric deionized water production apparatus when the concentration chamber is not filled with an ion exchanger, the current applied for the purpose of regenerating the ion exchanger promotes the electrolysis of water, and the ion exchanger is not filled. A pH shift is caused on the surface of the ion exchange membrane in the concentrating chamber, the pH is high near the anion exchange membrane, the pH is low near the cation exchange membrane, and both the carbonate ion and calcium ion have a high concentration gradient as shown in FIG. Therefore, the scale is easily generated on the surface of the anion exchange membrane on the concentration chamber side. However, in this example, as described above, the concentrated water near the surface of the anion exchange membrane a which seems to have the highest cation concentration in the concentrated water does not contain anions such as carbonate ions with high concentration. Carbonate ions and calcium ions do not combine to produce calcium carbonate (see FIG. 21). Therefore, even if the electric deionized water production apparatus of this example is continuously operated for a long time, scale does not occur in the concentration chamber. Further, since the concentration chamber 1 is filled with an organic porous ion exchanger having a dense ion exchange group uniformly throughout the packed bed, the conductivity is increased, and the operating voltage can be reduced to save power consumption.

  In the present invention, the flow direction in the first small desalination chamber and the second small desalination chamber of the water to be treated is not particularly limited, and in addition to the above embodiment, the first small desalination chamber and the second small desalination chamber. The flow direction in the salt chamber may be different. In addition to the above embodiment, the small desalination chamber into which the water to be treated flows first flows the water to be treated into the first small desalination chamber and flows down, and then the effluent from the first small desalination chamber. May flow into the second small desalting chamber. Further, the flow direction of the concentrated water is also appropriately determined.

  Another electric deionized water production apparatus in the embodiment of the present invention will be described with reference to FIG. The electric deionized water production apparatus 100 in FIG. 23 is a conventional EDI without an intermediate ion exchange membrane in the improved electric deionized water production apparatus 10 shown in FIG. 17, and the flow of water to be treated in the demineralization chamber. Is one pass. That is, in the electrical deionized water production apparatus 100, a chamber partitioned by the cation exchange membrane 101 on one side and the anion exchange membrane 102 on the other side is filled with the ion exchanger 103 to form the demineralization chamber 104. Concentration chambers 105 are provided on both sides of the desalting chamber 104 via the cation exchange membrane 101 and the anion exchange membrane 102. The desalting chamber 104 and the concentration chamber 105 are provided with an anode chamber provided with an anode 110 and a cathode provided with a cathode 109. The water to be treated flows into the desalting chamber 104 while applying voltage, and then the concentrated water flows into the concentration chamber 105 to remove impurity ions in the water to be treated. In the obtaining method, the concentrating chamber 105 has the same function and effect by adopting the same configuration as in the above embodiment. In addition, the code | symbol 111 shows a to-be-processed water inflow line, 114 is a deionized water outflow line, 115 is a concentrated water inflow line, 116 is a concentrated water outflow line, 117 is an electrode water inflow line, 118 is an electrode water outflow line. In addition, the form of the electric deionized water production apparatus of the present invention is not particularly limited, and examples thereof include a spiral type, a concentric cylindrical type, and a flat plate laminated type.

  The treated water used in the deionized water production method of the present invention is not particularly limited. For example, well water, tap water, sewage, industrial water, river water, washing waste water or concentration chambers for semiconductor devices in a semiconductor manufacturing factory, etc. Permeated water obtained by treating the recovered water from the reverse osmosis membrane, or recovered water used at a point of use such as a semiconductor manufacturing plant, which is not subjected to the reverse osmosis membrane treatment. When a part of the treated water supplied in this way is also used as concentrated water, it is scaled to use the treated water supplied to the desalting chamber and the concentrated water supplied to the concentrating chamber after softening. It is preferable in that generation can be further suppressed. The softening method is not particularly limited, but a softener using a sodium ion exchange resin or the like is suitable.

(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.

Reference example 1
(Step I; production of monolith intermediate)
9.28 g of styrene, 0.19 g of divinylbenzene, 0.50 g of sorbitan monooleate (hereinafter abbreviated as SMO) and 0.26 g of 2,2′-azobis (isobutyronitrile) were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / SMO / 2,2′-azobis (isobutyronitrile) mixture is added to 180 g of pure water, and a vacuum stirring defoaming mixer (manufactured by EM Corp.) which is a planetary stirring device. Was 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 monolith intermediate having a continuous macropore structure. The average diameter of the openings (mesopores) where the macropores and macropores of the monolith intermediate were measured by mercury porosimetry was 40 μm, and the total pore volume was 15.8 ml / g.

(Manufacture of composite monolith)
Next, 36.0 g of styrene, 4.0 g of divinylbenzene, 60 g of 1-decanol, and 0.4 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and dissolved uniformly (step II). The 10-hour half-life temperature of 2,2′-azobis (2,4-dimethylvaleronitrile) used as the polymerization initiator was 51 ° C. The amount of divinylbenzene used is 6.6 mol% with respect to the total amount of styrene and divinylbenzene used in Step II, while the crosslink density of the monolith intermediate is 1.3 mol%, and the crosslink density ratio is 5.1 times. Met. Next, the monolith intermediate was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 20 mm, and 3.2 g was collected. The separated monolith intermediate is put in a reaction vessel having an inner diameter of 73 mm, and the styrene / divinylbenzene / 1-
After immersing in a decanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture and degassing in a vacuum chamber, the reaction vessel was sealed and 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).

  The results of observing the internal structure of the composite monolith (dried body) composed of the styrene / divinylbenzene copolymer thus obtained by SEM are shown in FIGS. The SEM images in FIGS. 1 to 3 are different in magnification, and are images at arbitrary positions on a cut surface obtained by cutting a monolith at an arbitrary position. As apparent from FIGS. 1 to 3, the composite monolith has a continuous macropore structure, and the surface of the skeletal phase constituting the continuous macropore structure is coated with particles having an average particle diameter of 4 μm. The particle coverage of the skeleton surface by the body and the like was 80%. Moreover, the ratio for which the particle body with a particle size of 3-5 micrometers occupied to the whole particle body was 90%.

  Moreover, the average diameter of the opening of the composite monolith measured by mercury porosimetry was 16 μm, and the total pore volume was 2.3 ml / g. The results are summarized in Tables 1 and 2. In Table 1, the preparation column shows the vinyl monomer, the crosslinking agent, the organic solvent used in Step II, and the monolith intermediate obtained in Step I in order from the left. Further, the particle bodies and the like are shown as particles.

(Production of complex monolith cation exchanger)
The composite monolith produced by the above method was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 15 mm. The weight of the monolith was 19.6 g. To this, 1500 ml of dichloromethane was added and heated at 35 ° C. for 1 hour, then cooled to 10 ° C. or less, 98.9 g of chlorosulfuric acid was gradually added, and the temperature was raised and reacted at 35 ° C. for 24 hours. Thereafter, methanol was added to quench the remaining chlorosulfuric acid, which was then washed with methanol to remove dichloromethane and further washed with pure water to obtain a composite monolith cation exchanger.

  The swelling rate before and after the reaction of the obtained cation exchanger was 1.3 times, and the ion exchange capacity per volume was 1.11 mg equivalent / ml in a water wet state. The average diameter of the openings of the organic porous ion exchanger in the water wet state was 21 μm as estimated from the value of the organic porous body and the swelling ratio of the cation exchanger in the water wet state. The average particle size of the particles was 5 μm. The particle coverage of the skeletal surface with all particles was 80%, and the total pore volume was 2.3 ml / g. Moreover, the ratio for which the particle body of 4-7 micrometers of particle | grains accounts to the whole particle body was 90%. The differential pressure coefficient, which is an index of pressure loss when water is permeated, is 0.057 MPa / m · LV, which is a lower pressure loss than that required for practical use. It was. Further, the length of the ion exchange zone was 9 mm, showing a remarkably short value. The results are summarized in Table 2.

  Next, in order to confirm the distribution state of the sulfonic acid group in the composite monolith cation exchanger, the distribution state of sulfur atoms was observed by EPMA. The results are shown in FIGS. 4 and 5, the left and right photographs correspond to each other. FIG. 4 shows the distribution of sulfur atoms on the surface of the cation exchanger, and FIG. 5 shows the distribution of sulfur atoms in the cross-section (thickness) direction of the cation exchanger. 4 and 5, it can be seen that the sulfonic acid groups are uniformly introduced on the skeleton surface of the cation exchanger and inside the skeleton (cross-sectional direction).

Reference Examples 2-5
(Manufacture of composite monolith)
The amount of vinyl monomer used, the amount of crosslinking agent used, the type and amount of organic solvent used, the porous structure of the monolith intermediate that coexists during polymerization in step III, the crosslinking density and the amount used, and the polymerization temperature are shown in Table 1. 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. Moreover, the result of having observed the internal structure of composite monolith (dry body) by SEM is shown in FIGS. 6 to 8 are of Reference Example 2, FIGS. 9 and 10 are of Reference Example 3, FIG. 11 is of Reference Example 4, and FIGS. 12 and 13 are of Reference Example 5. For Reference Example 2, the crosslinking density ratio (2.5 times), for Reference Example 3, the type of organic solvent (PEG; molecular weight 400), for Reference Example 4, the vinyl monomer concentration (28.0%), Reference Example For No. 5, the polymerization temperature (40 ° C .; 11 ° C. lower than the 10-hour half-life temperature of the polymerization initiator) was produced under conditions satisfying the production conditions of the present invention. From FIG. 6 to FIG. 13, what adhered to the skeleton surface of the composite monoliths of Reference Examples 3 to 5 were protrusions rather than particles. The “particle average diameter” of the protrusion is the average diameter of the protrusions (maximum diameter). From FIG. 6 to FIG. 13 and Table 2, the average diameter of the particles adhering to the surface of the monolith skeleton of Reference Examples 2 to 6 is 3 to 8 μm, and the particle coverage of the skeleton surface by all particles is 50 to 95%. there were. In addition, the proportion of Reference Example 2 in which particles having a particle diameter of 3 to 6 μm occupy the entire particle body is 80%, and the ratio of Reference Example 3 in which protrusions having a particle diameter of 3 to 10 μm occupy the entire particle is 80%. In Reference Example 4, the proportion of particles having a particle diameter of 3 to 5 μm in the total particle body was 90%, and in Reference Example 5, the proportion of particles having a particle diameter of 3 to 7 μm in the entire particle body was 90%. .

(Production of complex monolith cation exchanger)
The composite monolith produced by the above method was reacted with chlorosulfuric acid in the same manner as in Reference Example 1 to produce a composite monolith cation exchanger. The results are shown in Table 2. The average diameter of the continuous pores of the composite monolith cation exchanger in Reference Examples 2 to 5 is 21 to 52 μm, the average diameter of the particles attached to the skeleton surface is 5 to 13 μm, the skeleton surface due to all the particles, etc. The particle coverage was as high as 50 to 95%, the differential pressure coefficient was as small as 0.010 to 0.057 MPa / m · LV, and the ion exchange zone length was as extremely small as 8 to 12 mm. Moreover, the ratio for which the particle body with a particle size of 5-10 micrometers occupied to the whole particle body was 90%.

Reference Example 6
(Manufacture of composite monolith)
Table 1 shows the type and amount of vinyl monomer used, amount of crosslinking agent used, type and amount of organic solvent, monolith intermediate porous structure coexisting during polymerization in step III, crosslinking density and 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. Moreover, the result of having observed the internal structure of composite monolith (dry body) by SEM is shown in FIGS. What adhered to the skeleton surface of the composite monolith of Reference Example 6 was a protrusion. In the monolith of Reference Example 6, the average diameter of the maximum diameter of the protrusions formed on the surface was 10 μm, and the particle coverage of the skeletal surface with all the particulates was 100%. Moreover, the ratio for which the particle body with a particle size of 6-12 micrometers occupied to the whole particle body was 80%.

(Production of complex monolith anion exchanger)
The composite monolith produced by the above method was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 15 mm. The weight of the composite monolith was 17.9 g. To this was added 1500 ml of tetrahydrofuran, heated at 40 ° C. for 1 hour, cooled to 10 ° C. or lower, gradually added 114.5 g of a 30% trimethylamine aqueous solution, heated to react at 40 ° C. for 24 hours. After completion of the reaction, the resultant was washed with methanol to remove tetrahydrofuran, and further washed with pure water to obtain a monolith anion exchanger.

  The obtained composite anion exchanger had a swelling ratio of 2.0 times before and after the reaction, and the ion exchange capacity per volume was 0.32 mg equivalent / ml in a water-wet state. The average diameter of the continuous pores of the organic porous ion exchanger in the water wet state was 58 μm as estimated from the value of the monolith and the swelling ratio of the monolith anion exchanger in the water wet state. The average diameter of the body was 20 μm, the particle coverage of the skeletal surface with all particles was 100% and the total pore volume was 2.1 ml / g. The ion exchange zone length was as short as 16 mm. The differential pressure coefficient, which is an index of pressure loss when water is permeated, is 0.041 MPa / m · LV, which is a lower pressure loss than that required for practical use. It was. Moreover, the ratio for which the particle body with a particle size of 12-24 micrometers occupied to the whole particle body was 80%. The results are summarized in Table 2.

  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.

Reference Example 7
(Manufacture of monolith intermediates)
A monolith intermediate was obtained in the same manner as in Reference Example 1.

(Manufacture of composite monolith)
38.0 g of styrene, 2.0 g of divinylbenzene, 60 g of 1-decanol, and 0.4 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and dissolved uniformly (step II). The 10-hour half-life temperature of 2,2′-azobis (2,4-dimethylvaleronitrile) used as the polymerization initiator was 51 ° C. The amount of divinylbenzene used is 3.3 mol% with respect to the total amount of styrene and divinylbenzene used in Step II, with a crosslink density ratio of 2.5 times the crosslink density of the monolith intermediate of 1.3 mol%. Met. Next, the monolith intermediate was cut into a disk shape having a diameter of 70 mm and a thickness of about 30 mm to obtain 3.3 g. The separated monolith intermediate is put in a reaction vessel having an inner diameter of 73 mm, immersed in the styrene / divinylbenzene / 1-decanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture, and removed in a vacuum chamber. After bubbling, the reaction vessel was sealed and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the monolith-like contents having a thickness of about 30 mm were taken out, subjected to Soxhlet extraction with acetone, and then dried under reduced pressure at 85 ° C. overnight (step III).

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

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

  The swelling ratio of the obtained monolith anion exchanger before and after the reaction was 1.5 times, and the anion exchange capacity per volume was 0.72 mg equivalent / ml in a water-wet state. The average diameter of the openings of the monolith anion exchanger in the water wet state was estimated to be 53 μm from the value of the monolith and the swelling ratio of the monolith anion exchanger in the water wet state, and the average particle diameter of the coated particles determined by the same method The diameter was 8 μm. In addition, the particle | grain coverage of the frame | skeleton surface by all the particle bodies etc. was 50%, and the total pore volume was 3.8 ml / g. Moreover, the ratio for which the particle diameter of 4-8 micrometers was occupied to the whole particle body was 90%.

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

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

Reference Example 8
(Manufacture of monoliths)
Except for changing the usage amount of the vinyl monomer, the usage amount of the crosslinking agent, the type and usage amount of the organic solvent, and the usage amount of the monolith intermediate coexisting during the polymerization in Step III to the blending amounts shown in Table 1, Example 1 and A monolith was produced in a similar manner. The results are shown in Tables 1 and 2. From the SEM photograph (not shown), the formation of particles and protrusions was not observed at all on the skeleton surface. From Table 1 and Table 2, when a monolith is produced under conditions deviating from the specific production conditions of the present invention, that is, conditions deviating from the requirements (1) to (5) above, particle formation on the surface of the monolith skeleton is caused. It turns out that it is not recognized.

(Production of monolith cation exchanger)
The monolith produced by the above method was reacted with chlorosulfuric acid in the same manner as in Reference Example 1 to produce a monolith cation exchanger. The results are shown in Table 2. The obtained monolith cation exchanger had an ion exchange zone length of 26 mm, which was a large value as compared with Reference Examples 1-7.

Reference Examples 9-11
(Manufacture of monoliths)
The amount of vinyl monomer used, the amount of crosslinking agent used, the type and amount of organic solvent used, the porous structure of the monolith intermediate that coexists during polymerization in step III, the crosslinking density, and the amount used were changed to the amounts shown in Table 1. Produced a monolith in the same manner as in Reference Example 1. The results are shown in Tables 1 and 2. For Reference Example 9, the crosslinking density ratio (0.2 times), for Reference Example 10, the type of organic solvent (2- (2-methoxyethoxy) ethanol; molecular weight 120), and for Reference Example 11, the polymerization temperature (50 C .: 1 ° C. lower than the 10-hour half-life temperature of the polymerization initiator) was produced under conditions that did not satisfy the production conditions of the present invention. The results are shown in Table 2. For the monoliths of Reference Examples 9 and 11, there was no particle formation on the skeleton surface. In Reference Example 10, the isolated product was transparent, and the porous structure was collapsed and disappeared.

(Production of monolith cation exchanger)
Except for Reference Example 10, the organic porous material produced by the above method was reacted with chlorosulfuric acid in the same manner as in Reference Example 8 to produce a monolith cation exchanger. The results are shown in Table 2. The obtained monolith cation exchanger had an ion exchange zone length of 23 to 26 mm, which was a large value as compared with Reference Examples 1 to 7.

Reference Example 12
(Manufacture of monoliths)
Reference Example 8 except that the use amount of the vinyl monomer, the use amount of the crosslinking agent, the use amount of the organic solvent, the porous structure and the use amount of the monolith intermediate coexisting during the polymerization in Step III were changed to the blending amounts shown in Table 1. A monolith was produced in the same manner as described above. The results are shown in Tables 1 and 2, and it can be seen that when a monolith is produced outside the specific production conditions of the present invention, no particle formation is observed on the surface of the monolith skeleton.

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

Reference Example 13
(Production of porous cation exchanger (known))
27.7 g of styrene, 6.9 g of divinylbenzene, 0.14 g of azobisisobutyronitrile and 3.8 g of sorbitan monooleate were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / azobisisobutyronitrile / sorbitan monooleate mixture is added to 450 ml of pure water and stirred for 2 minutes at 20,000 rpm with a homogenizer, and a water-in-oil emulsion. Got. After emulsification, the water-in-oil emulsion was transferred to a stainless steel autoclave, sufficiently substituted with nitrogen, sealed, and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the content was taken out, extracted with Soxhlet for 18 hours with isopropanol, unreacted monomer and sorbitan monooleate were removed, and dried under reduced pressure at 40 ° C. overnight. 5 g of a porous material containing 14 mol% of a crosslinking component composed of a styrene / divinylbenzene copolymer obtained in this manner was collected, 500 g of tetrachloroethane was added, and the mixture was heated at 60 ° C. for 30 minutes, and then to room temperature. After cooling, 25 g of chlorosulfuric acid was gradually added and reacted at room temperature for 24 hours. Thereafter, acetic acid was added, the reaction product was poured into a large amount of water, washed with water and dried to obtain a porous cation exchanger. The ion exchange capacity of this porous material is 4.0 mg equivalent / g in terms of dry porous material, and sulfonic acid groups are uniformly introduced into the porous material by mapping of sulfur atoms using EPMA. It was confirmed. Further, as a result of SEM observation (not shown), the internal structure of the porous body has an open cell structure, and most of the macropores having an average diameter of 30 μm are overlapped, and the mesopores formed by the overlap of the macropores and the macropores. The average diameter was 5 μm and the total pore volume was 10.1 ml / g. The porous body was cut out to a thickness of 10 mm, and the water permeation rate was measured. As a result, it was 14,000 l / min · m ² · MPa.

Reference Example 14
(Production of porous anion exchanger (known))
A water-in-oil emulsion similar to that of Example 1 except that 18.0 g of p-chloromethylstyrene was used instead of 27.7 g of styrene, and 17.3 g of divinylbenzene and 0.26 g of azobisisobutyronitrile were used. Polymerization was performed to produce a porous body containing 50 mol% of a cross-linking component composed of a p-chloromethylstyrene / divinylbenzene copolymer. After separating 5 g of this porous material, adding 500 g of dioxane and heating at 80 ° C. for 30 minutes, the mixture was cooled to room temperature, 65 g of a trimethylamine (30%) aqueous solution was gradually added, and reacted at 50 ° C. for 3 hours. It was left overnight at room temperature. After completion of the reaction, the porous body was taken out, washed with acetone, washed with water, and dried to obtain a porous anion exchanger. The ion exchange capacity of this porous material was 2.5 mg equivalent / g in terms of dry porous material, and it was confirmed by SIMS that trimethylammonium groups were uniformly introduced into the porous material. Moreover, as a result of SEM observation, the internal structure of this porous body has an open cell structure, most of the macropores having an average diameter of 30 μm overlap, and the average diameter of the mesopores formed by the overlap of the macropores and the macropores. The value was 4 μm and the total pore volume was 9.9 ml / g. The porous body was cut out to a thickness of 10 mm, and the water permeation rate was measured. As a result, it was 12,000 l / min · m ² · MPa.

In the following apparatus specifications and operating conditions, an electric deionized water production apparatus configured by arranging six deionization modules in parallel with the same configuration as in FIG. 23 was used. The treated water was industrial water reverse osmosis membrane permeated water, and its hardness was 200 μg CaCO ₃ / l. Moreover, some treated water was used as concentrated water and electrode water. The operation time is 4000 hours, and Table 3 shows the operation conditions for obtaining treated water having a resistivity of 17.9 MΩ-cm and the water flow differential pressure (kPa) of concentrated water.

<Operating conditions>
・ Electric deionized water production equipment; prototype EDI
・ Desalination chamber: width 300mm, height 300mm, thickness 3mm
-Ion exchange resin filled in the desalting chamber; mixed ion exchange resin of anion exchange resin (A) and cation exchange resin (C) (mixing ratio is A: C = 1: 1 by volume)
・ Concentration chamber: width 300mm, height 300mm, thickness 5mm
-Concentrated chamber filled ion exchanger; the organic porous anion exchanger single bed of Reference Example 7 and the organic porous cation exchanger single bed of Reference Example 2 were alternately stacked along the flow direction of concentrated water 4 Flow rate of the entire floor and equipment; 0.5 m ³ / h
・ Flow rate of the entire concentration chamber: 50 L / h

In the apparatus specifications and operating conditions, an electric deionized water production apparatus comprising three deionization modules (six small demineralization chambers) arranged in parallel with the same configuration as in FIG. 17 was used. The treated water was industrial water reverse osmosis membrane permeated water, and its hardness was 200 μg CaCO ₃ / l. Moreover, some treated water was used as concentrated water and electrode water. The operation time was 4000 hours, and the occurrence of scale in the concentration chamber after 4000 hours was observed. In addition, Table 3 shows operating conditions for obtaining treated water having a resistivity of 17.9 MΩ-cm at the same time and a water flow differential pressure (kPa) of concentrated water.

<Operating conditions>
・ Electric deionized water production equipment; prototype EDI
・ Intermediate ion exchange membrane; anion exchange membrane ・ first small desalination chamber; width 300 mm, height 300 mm, thickness 3 mm
-Ion exchange resin filled in the first small desalting chamber; mixed ion exchange resin of anion exchange resin (A) and cation exchange resin (C) (mixing ratio is A: C = 1: 1 by volume)
・ Second small desalination chamber: width 300mm, height 300mm, thickness 8mm
・ Second small desalination chamber filled ion exchange resin; anion exchange resin ・ concentration chamber; width 300 mm, height 300 mm, thickness 5 mm
-Concentrated chamber filled ion exchanger; the organic porous anion exchanger single bed of Reference Example 7 and the organic porous cation exchanger single bed of Reference Example 2 were alternately stacked along the flow direction of concentrated water 4 Flow rate of the entire floor and equipment; 0.5 m ³ / h
・ Flow rate of the entire concentration chamber: 50 L / h

Comparative Example 1
It replaced with the organic porous anion exchanger of the reference example 7, and it was set as the organic porous anion exchanger of the reference example 14, it replaced with the organic porous cation exchanger single bed of the reference example 2, and reference example 13 The same procedure as in Example 1 was performed except that the organic porous cation exchanger was used. The results are shown in Table 3.

Comparative Example 2
It replaced with the organic porous anion exchanger of the reference example 7, and it was set as the organic porous anion exchanger of the reference example 14, it replaced with the organic porous cation exchanger single bed of the reference example 2, and reference example 13 The same procedure as in Example 2 was performed except that the organic porous cation exchanger was used. The results are shown in Table 3.

D, D _{1 to} D ₄ , 104 Desalination chamber d ₁ , d ₃ , d ₅ , d ₇₇ First small desalination chamber d ₂ , d ₄ , d ₆ , d ₈ Second small desalination chamber ₁ , 105 Concentration Chamber 2 Electrode chamber 3, 101 Cation membrane 4, 102 Anion membrane 5 Intermediate ion exchange membrane 6, 109 Cathode 7, 110 Anode 8, 103 Ion exchanger 8a Organic porous cation exchanger single bed and organic porous anion exchanger single Laminated floors 10, 100 Electric deionized water production apparatus 11, 111 To-be-treated water inflow line 12 To-be-treated water inflow line 13 to the first small demineralization chamber 13, 114 Deionized water outflow lines 15, 115 Concentrated water inflow lines 16, 116 Concentrated water outflow lines 17a, 17b, 117 Electrode water inflow lines 18a, 18b, 118 Electrode water outflow line 20 Deionization module 101 Carbonate ions are concentrated Point 102 that moves for the first time in condensed water 102 Point that calcium ion moves for the first time in concentrated water

Claims (7)

A chamber defined by a cation exchange membrane disposed on the cathode side and an anion exchange membrane disposed on the anode side is filled with an ion exchanger to form a desalting chamber, and the cation exchange membrane and the anion exchange membrane are An electric deionized water production apparatus in which concentrating chambers are provided on both sides of a desalting chamber, and these desalting chambers and concentrating chambers are disposed between an anode chamber having an anode and a cathode chamber having a cathode. The concentration chamber comprises an organic porous body composed of a continuous skeleton phase and a continuous pore phase, and a large number of particles having a diameter of 4 to 40 μm fixed to the skeleton surface of the organic porous body or the organic porous body. A composite structure with a large number of protrusions having a size of 4 to 40 μm formed on the surface of the skeleton, and having an average pore diameter of 10 to 150 μm and a total pore volume of 0.5 to 5 ml / g in a wet state Ion exchange capacity per volume in a water-wet state 0.2 mg equivalent / An electric deionized water production apparatus characterized in that it is formed by filling only a monolithic organic porous ion exchanger of ml or more. Two small desalination chambers partitioned by a cation exchange membrane disposed on the cathode side , an anion exchange membrane disposed on the anode side, and an intermediate ion exchange membrane located between the cation exchange membrane and the anion exchange membrane An ion exchanger is filled to form a desalting chamber, and concentration chambers are provided on both sides of the desalting chamber via the cation exchange membrane and anion exchange membrane, and the desalting chamber and the concentration chamber are provided with an anode. In an electric deionized water production apparatus arranged between an anode chamber and a cathode chamber provided with a cathode, the concentration chamber includes an organic porous body composed of a continuous skeleton phase and a continuous pore phase, and the organic porous body A composite structure with a large number of particles having a diameter of 4 to 40 μm fixed to the surface of the body skeleton or a large number of protrusions having a size of 4 to 40 μm formed on the skeleton surface of the organic porous body, The average pore diameter in the water-wet state is 10 to 150 μm and the total pore volume A 0.5 to 5 ml / g, and being formed by filling only monolithic organic porous ion exchanger is an ion-exchange capacity 0.2mg equivalent / ml or more per volume of water wet Electric deionized water production equipment. The ion exchanger filled in one small desalting chamber partitioned by the intermediate ion exchange membrane and the anode side anion exchange membrane is an anion exchanger, and the cathode side cation exchange membrane and the intermediate ion 3. The apparatus for producing electric deionized water according to claim 2, wherein the ion exchanger filled in the other small demineralization chamber partitioned by the exchange membrane is a mixture of a cation exchanger and an anion exchanger. .   The organic porous body is a continuous macropore structure in which bubble-shaped macropores overlap each other, and the overlapping portion forms an opening having an average diameter of 30 to 150 µm in a wet state. The electric deionized water production apparatus according to claim 1.   The organic porous body is a three-dimensionally continuous skeleton having an average thickness of 1 to 60 μm in a water-wet state, and a three-dimensionally continuous skeleton having an average diameter of 10 to 100 μm in a water-wet state between the skeletons. It is a co-continuous structure which consists of a void | hole, The electrical deionized water manufacturing apparatus of any one of Claims 1-3 characterized by the above-mentioned.   The monolithic organic porous ion exchanger is a laminate of an organic porous cation exchanger and an organic porous anion exchanger, and the organic porous cation exchanger and the organic porous anion exchanger are The electric deionized water production apparatus according to any one of claims 1 to 5, wherein the apparatus is formed by alternately laminating and filling the concentrated water in and out.   The monolithic organic porous ion exchanger has a channel formed separately from an organic porous body structure composed of the continuous skeleton phase and the continuous pore phase. The electric deionized water production apparatus according to any one of the above.