JP5586979B2 - Electric deionized water production apparatus and operation method thereof - Google Patents

Description

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

  Japanese Patent Application Laid-Open No. 2008-55388 includes a desalting chamber filled with an ion exchanger in which the anode side is partitioned by an anion exchange membrane and the cathode side is partitioned by a cation exchange membrane. And allowing ions in the water to be treated to flow into the concentrated water flowing outside the ion exchange membranes by causing a DC electric field to act perpendicularly to the flow of the water to be treated through the both ion exchange membranes. In the electrically deionized water production apparatus that electrically excludes, the ion exchanger has mesopores having an average diameter of 1 to 1000 μm in which bubble-like macropores overlap each other and the overlapping portions form a common opening, An open cell structure in which bubbles formed by macropores and mesopores serve as flow paths, the total pore volume is 1 ml / g to 50 ml / g, ion exchange groups are uniformly distributed, and ion exchange capacity An electric deionized water production apparatus is disclosed which is a mixed ion exchanger of a monolithic organic porous ion exchanger having a quantity of 0.5 mg equivalent / g dry porous body or more and a granular ion exchange resin. The details of the method for producing a monolithic organic porous ion exchanger used in this electric deionized water production apparatus are disclosed in JP-A-2002-306976.

  According to this electric deionized water production apparatus, since a monolith is used as a part of the ion exchanger filled in the vertical demineralization chamber, (1) the volume due to the swelling and shrinkage reaction of the monolith and the granular ion exchange resin. The change can be buffered by the physical stretchability of the monolith, and the filling state in the desalting chamber can be kept uniform. In addition, it is possible to prevent a single flow due to expansion and contraction associated with the ion exchange reaction and poor contact with the ion exchange membrane, and a high voltage is not required, and the current use efficiency is increased. (2) Compared to granular ion exchange resins, monoliths have faster ion migration speed and shorter ion exchanger lengths, so monoliths placed near the treated water outlet suppress leakage of trace ions in dilute concentrations. High-purity treated water can be obtained. For this reason, (3) the ion exchanger filling height can be lowered and the apparatus can be made compact, or (4) a large flow rate treatment can be performed while maintaining the ion exchanger filling height. In addition, (5) by disposing a monolith in the vicinity of the inlet of the water to be treated in the demineralization chamber, the removal rate of hardness components such as calcium is improved in the decation chamber, and in the deanion chamber, carbonic acid, silica and the like Ion elimination rate is improved. In addition, (6) when one desalination chamber is filled with the granular anion exchange resin and the zwitterion monolith in this order from the treated water inflow side to the outflow side, for example, it is far more than the horizontal desalination chamber. Cations and anions can be removed with a low applied voltage, and reverse osmosis membrane-treated water having a particularly high carbonic acid ratio can be made highly purified water.

JP 2008-555388 A JP 2002-306976 A JP 2009-62512 A JP 2009-67982 A

  However, the organic porous ion exchangers described in JP-A-2008-555388 and JP-A-2002-306976 have a common monolithic opening (mesopore) of 1 to 1,000 μm, For monoliths with a small pore volume of 5 ml / g or less in pore volume, it is necessary to reduce the amount of water droplets in the water-in-oil emulsion, so the common aperture is small, and the average diameter of the aperture is substantially 20 μm or more. Cannot be manufactured. For this reason, there existed a problem that the pressure loss at the time of water flow was large. In addition, when the average diameter of the openings is about 20 μm, the total pore volume is increased accordingly, so that the strength is low and the ion exchange capacity per volume is reduced, and thus the quality of treated water is reduced, and There was a problem of large power consumption. In addition, in the monolith loaded in the vertical demineralization chamber of the electric deionized water production apparatus, the appearance of a monolith having a new structure different from the open cell structure (continuous macropore) has been desired.

  Therefore, the object of the present invention is to maintain the advantages of a mixed ion exchanger of a monolith filled with a vertical desalting chamber and a granular ion exchange resin, while maintaining high monolith strength and low pressure loss during water flow. An object of the present invention is to provide an electric deionized water production apparatus (hereinafter, also simply referred to as “EDI”) and a method for operating the same, with good quality of treated water and low power consumption.

  Under such circumstances, the present inventors have conducted intensive studies, and as a result, obtained a monolithic organic porous body (intermediate) having a relatively large pore volume obtained by the method described in JP-A-2003-334560. If the vinyl monomer and the crosslinking agent are allowed to stand and polymerize in an organic solvent under specific conditions in the presence, a large number of particles having a diameter of 2 to 20 μm are fixed on the surface of the skeleton constituting the organic porous body, or a protrusion. A monolith having a composite structure in which an ion exchange group is introduced into the composite monolith is used as part of a mixed ion exchanger of EDI having a vertical desalination chamber. While maintaining the advantages of the mixed ion exchanger of monolith and granular ion exchange resin filled in the vertical desalination chamber, the monolith strength is high, pressure loss during water flow is kept low, and the quality of treated water is good And it found such that power consumption is small, and have completed the present invention.

  That is, the present invention includes a desalting chamber filled with an ion exchanger that is partitioned by an anion exchange membrane on the anode side and partitioned by a cation exchange membrane on the cathode side, and allows water to be treated to pass through the ion exchanger. A DC electric field is applied in a direction perpendicular to the flow of the water to be treated through both ion exchange membranes to electrically exclude ions in the water to be treated in the concentrated water flowing outside the ion exchange membranes. In the electric deionized water production apparatus, the ion exchanger is a mixed ion exchanger of a monolithic organic porous ion exchanger and a granular ion exchange resin, and the monolithic organic porous ion exchanger is a continuous skeleton. An organic porous body composed of a phase and a continuous pore phase, and a large number of particles having a diameter of 4 to 40 μm fixed on the skeleton surface of the organic porous body or a size formed on the skeleton surface of the organic porous body 4-40μm A composite structure with a large number of protrusions, having an average pore diameter of 10 to 150 μm in a water wet state and a total pore volume of 0.5 to 5 ml / g, and ion exchange per volume in a water wet state An electric deionized water production apparatus having a capacity of 0.2 mg equivalent / ml or more is provided.

Further, the present invention is to further disposed intermediate ion exchange membrane between the cation exchange membrane disposed on an anion exchange membrane on the cathode side which is disposed on the anode side, the anion exchange membrane and the intermediate ion exchange A first small desalting chamber filled with a first ion exchanger partitioned by a membrane, and a second small desalting chamber filled with a second ion exchanger partitioned by the intermediate ion exchange membrane and the cation exchange membrane And water to be treated is passed in series in this order through the first small desalting chamber and the second small desalting chamber, or the second small desalting chamber and the first small desalting chamber The treated water is passed in series in this order, and a direct current electric field is applied to the treated water flow through the ion exchange membrane in a direction perpendicular to the outside of the anion exchange membrane and the cation exchange membrane. In an electric deionized water production system that electrically excludes ions in the water to be treated from the flowing concentrated water. Any one or both of the first and second ion exchangers are a mixed ion exchanger of a monolithic organic porous ion exchanger and a granular ion exchange resin, and the monolithic organic porous ion exchanger is 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 skeleton surface of the organic porous body It is a composite structure with a large number of protrusions having a size of 4 to 40 μm, and has an average pore diameter of 10 to 150 μm in a water wet state and a total pore volume of 0.5 to 5 ml / g. An ion-exchange capacity per volume of 0.2 mg equivalent / ml or more is provided.

  The present invention also provides an organic porous body composed of a continuous skeleton phase and a continuous pore phase, the anode side being partitioned by an anion exchange membrane and the cathode side being partitioned by a cation exchange membrane, and the skeleton surface of the organic porous body. A composite structure comprising a large number of particles having a diameter of 4 to 40 μm or a large number of protrusions having a size of 4 to 40 μm formed on the skeleton surface of the organic porous body, Monolithic organic porous ion exchanger and granular ions having a diameter of 10 to 150 μm, a total pore volume of 0.5 to 5 ml / g, and an ion exchange capacity of 0.2 mg equivalent / ml or more per volume in a water-wet state Using an electric deionized water production apparatus that encloses a demineralization chamber filled with a mixed ion exchanger of the exchange resin, water to be treated is passed through the mixed ion exchanger, and the deionized water is passed through the both ion exchange membranes. Perpendicular to treated water flow A method for operating an electric deionized water production apparatus is provided, in which a direct current electric field is applied to electrically remove ions in the water to be treated from the concentrated water flowing outside the ion exchange membranes. To do.

  The present invention also includes an anion exchange membrane on the anode side, a cation exchange membrane on the cathode side, an anion exchange membrane located between the anion exchange membrane and the cation exchange membrane, and the anion exchange membrane and the intermediate The second ion exchanger is filled in the gap formed by the first small desalting chamber in which the first ion exchanger is filled in the gap formed by the ion exchange membrane, the intermediate ion exchange membrane, and the cation exchange membrane. Using an electric deionized water production apparatus including a second small desalting chamber, water to be treated is passed in series through the first small desalting chamber and the second small desalting chamber in this order, or The treated water is passed through the second small desalting chamber and the first small desalting chamber in series in this order, and is perpendicular to the flow of treated water through the anion exchange membrane or the cation exchange membrane. A direct current electric field is applied to the anion exchange membrane and the outside of the cation exchange membrane. A method for electrically removing ions in the water to be treated from the concentrated water, wherein either or both of the first ion exchanger and the second ion exchanger are monolithic organic porous ion exchangers And a granular ion exchange resin, wherein the monolithic organic porous ion exchanger has an organic porous body composed of a continuous skeleton phase and a continuous pore phase, and a skeleton surface of the organic porous body. A composite structure of a large number of particles having a diameter of 4 to 40 μm to be fixed or a large number of protrusions having a size of 4 to 40 μm formed on the skeleton surface of the organic porous body, Electrodeionization having an average diameter of 10 to 150 μm, a total pore volume of 0.5 to 5 ml / g, and an ion exchange capacity of 0.2 mg equivalent / ml or more per volume in a water-wet state Providing operation method of water production equipment It is.

  According to the present invention, the monolith strength is high while maintaining the advantages of the mixed ion exchanger of the monolith and the granular ion exchange resin filled in the vertical desalting chamber, and the pressure loss during water flow is suppressed to a low level. Water quality is good and power consumption is low.

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 which shows the structure of the electrical deionized water manufacturing apparatus of the embodiment of this invention. It is a schematic diagram which shows the structure of the electrical deionized water manufacturing apparatus of the other embodiment of this invention. It is typical sectional drawing of a protrusion.

  The electric deionized water production apparatus of the present invention includes a demineralization chamber filled with an ion exchanger in which the anode side is partitioned by an anion exchange membrane and the cathode side is partitioned by a cation exchange membrane, and the ion exchanger is treated. While allowing water to pass through, a direct current electric field is applied to the flow of water to be treated through both ion exchange membranes in a direction perpendicular to the flow of water to be treated. An apparatus for electrically removing ions (first apparatus), or an intermediate ion exchange membrane is further provided between the anion exchange membrane and the cation exchange membrane, and the anion exchange membrane and the intermediate ion exchange membrane Forming a first small desalting chamber filled with a partitioned first ion exchanger and a second small desalting chamber filled with a second ion exchanger partitioned by the intermediate ion exchange membrane and the cation exchange membrane; The first small desalting chamber and the second small desalting chamber are treated. Are passed in series in this order, or treated water is passed in series in this order through the second small desalting chamber and the first small desalting chamber, and the treated water is passed through the ion exchange membrane. A device (second device) for electrically removing ions in the water to be treated in the concentrated water flowing outside the anion exchange membrane and the cation exchange membrane by applying a direct current electric field in a direction perpendicular to the flow of water ). The basic structure of the first device is, for example, that shown in FIG. 5, which is a conventional example in JP-A-2001-239270, and the basic structure of the second device is described in JP-A-2001-239270. This is the same as the device according to the invention.

  The monolithic organic porous body ion exchanger which is a part of the mixed ion exchanger filled in either or both of the desalting chamber and the small desalting chamber of the electric deionized water production apparatus of the present invention is a composite. It is a monolithic porous ion exchanger having a 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. Is a composite structure with a large number of protrusions having a thickness of 4 to 40 μm, and has 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. 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 material, 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 with an average thickness of 1 to 60 μm in a water-filled state, and a three-dimensional continuous with an average diameter of 10 to 100 μm in a water-filled 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 overlap each other, and the overlapping portion forms an opening (mesopore) having an average diameter of 30 to 150 μm in a water-filled 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 water 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 state is x1 (mm), and the diameter of the composite monolith ion exchanger in the dry state obtained by drying the water-soluble composite monolith ion exchanger. Y1 (mm), and when the average diameter of the pores or openings when the dry monolithic ion exchanger is measured by the mercury intrusion method is z1 (μm), the monolithic monolithic ion in the water state The average diameter (μm) of the holes or openings of the exchanger is calculated by the following formula: “Average diameter of holes or openings of the composite monolith ion exchanger in the water state (μm) = z1 × (x1 / y1)” The In addition, the average diameter of the pores or openings of the dry composite monolith before the introduction of the ion exchange group, and the composite monolith ion in the water state 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 water state of the pores of the composite monolith ion exchanger. You can also.

  In the case of the second organic porous body ion exchanger, the organic porous body has a three-dimensional continuous skeleton with an average diameter of 1 to 60 μm in a water-filled state, and an average diameter between the skeletons in a water-filled 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 at the time of fluid permeation increases, which is not preferable. If it exceeds 100 μm, the contact between the water to be treated and the organic porous ion exchanger Becomes unsatisfactory, and as a result, the ion exchange characteristics become non-uniform.

  The average diameter of the co-continuous structure pores in the water-filled 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 state is x2 (mm), and the diameter of the composite monolith ion exchanger in the dry state obtained by drying the water-soluble composite monolith ion exchanger. 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 state is calculated by the following formula: “average diameter (μm) of water state in the pores of the composite monolith ion exchanger = z2 × (x2 / y2)”. In addition, the average diameter of the pores of the composite monolith in the dry state before the introduction of the ion exchange group, and the composite monolith ion exchanger in the water state relative to the dry composite monolith when the ion exchange group is introduced into the composite monolith in the dry state Can be calculated by multiplying the average diameter of the pores of the composite monolith in the dry state by the swelling ratio. Further, the average thickness of the skeleton of the co-continuous structure in the water state is obtained 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 state is x3 (mm), the diameter of the composite monolith ion exchanger in the dry state obtained by drying the water-soluble composite monolith ion exchanger. 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). For example, the average thickness (μm) of the skeleton of the continuous structure of the composite monolith ion exchanger in the water state is expressed by the following formula: “average thickness of the hydrated state of the skeleton of the continuous structure of the composite monolith ion exchanger” (Μm) = z3 × (x3 / y3) ”. In addition, the average thickness of the skeleton of the dry composite monolith before introduction of the ion exchange groups, and the water-soluble composite monolith ion exchanger 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, and calculating the average thickness of the hydrated 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 deionization 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. 19 shows a schematic cross-sectional view of the protrusion. As shown in FIGS. 19A to 19E, the protrusions protruding from the skeleton surface 61 are protrusions 62. The protrusions 62 are like the protrusions 62a shown in FIG. 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 or the like 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 at the time of water flow is increased, which is not preferable. On the other hand, if the total pore volume exceeds 5 ml / g, the ion exchange capacity per volume is not preferable. Is unfavorable because it decreases. Note that the total pore volume of the composite monolith (monolith intermediate, composite monolith, composite monolith ion exchanger) is the same in both the dry state and the water 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 desalting efficiency is lowered, 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.

  In the present invention, the mixed ion exchanger of the composite monolith ion exchanger and the granular ion exchange resin has a two-layer structure in which the granular ion exchange resin and the composite monolith ion exchanger are laminated in this order with respect to the water flow direction. Or a repetitive three-layer or four-layer structure of the laminated structure, or a two-layer structure in which a composite monolith ion exchanger and a granular ion exchange resin are laminated in this order with respect to the direction of water flow, Or the thing of the repeating 3 layer or 4 layer structure of this laminated structure is mentioned. Since the composite monolith ion exchanger is a sponge-like integral structure, the laminate of the composite monolith ion exchanger and the granular ion exchange resin is not mixed with the granular ion exchange resin and is perpendicular to the water flow direction in the room. It can be filled in phase without using a partition member extending in the direction. The volume ratio of the composite monolith ion exchanger phase and the granular ion exchange resin phase in the laminate is not particularly limited and is appropriately determined depending on the type of ion exchange group, the purpose of treatment of the water to be treated, etc. The exchanger phase is 10 to 90% by volume, preferably 10 to 50% by volume in the mixed ion exchanger.

  Composite monolithic ion exchangers include composite monolithic organic porous cation exchangers (cationic monoliths) and composite monolithic organic porous anion exchangers (anionic monoliths), and granular ion exchange resins include granular cation exchange resins. , Granular anion exchange resin, and mixed resin (granular mix exchange resin) of granular cation exchange resin and granular anion exchange resin.

  The ionic form of the mixed monolith ion exchanger and ion exchange resin mixed ion exchanger is not particularly limited, but the salt form and regenerated mixed ion exchanger can alleviate swelling and shrinkage associated with the ion exchange reaction. preferable. In the present invention, the swelling / shrinkage relaxation effect of the mixed monolith ion exchanger and the ion exchange resin alone is not sufficient, and the physical expansion / contraction effect of the composite monolith ion exchanger is added to this. Adhesion in the desalting chamber can be ensured.

  When the desalting chamber is a cation cell that removes cations in the water to be treated, or when the desalting chamber is an anion cell that removes anions in the water to be treated, the granular ion exchange resin → composite monolith ion in order from the treated water inflow side A laminated structure of the exchanger or a laminated structure of a composite monolith ion exchanger → a granular ion exchange resin in order from the treated water inflow side. Among these, in the case of a laminated structure of granular ion exchange resin → composite monolith ion exchanger in order from the treated water inflow side, the composite monolith ion exchanger of the present invention has an ion exchange zone length as compared with the conventional monolith ion exchanger. Therefore, the monolith arranged in the vicinity of the treated water outlet can suppress the leakage of a trace amount of ions in a dilute concentration region and obtain high-purity treated water. For this reason, the ion exchanger filling height can be lowered, the apparatus can be made compact, or a large flow rate treatment can be performed while the ion exchanger filling height is maintained.

  In the case of an amphoteric cell in which one desalting chamber removes both cations and anions in the water to be treated, a first form that adopts a combination of a granular cation exchange resin and an anionic monolith, or a combination of a granular anion exchange resin and a cation monolith, a cation A second form employing a combination of a monolith and anion monolith laminate structure and a granular ion exchange resin, a monopolar monolith ion exchanger or a monopolar granular ion exchange resin in order from the treated water inflow side, and amphoteric granules A third form that employs a mix exchange resin or a combination of a laminated structure of a cation monolith and an anion monolith can be mentioned. Among these, in the first apparatus, when the laminated structure of the granular anion exchange resin, the cation monolith and the anion monolith is filled in this order from the treated water inflow side to the outflow side of the desalination chamber, or the second apparatus In the apparatus configuration in which the treated water is passed through the first small desalting chamber and the second small desalting chamber in series in this order, the first small desalting chamber is granular in order from the treated water inflow side. In the case of a laminated structure of an anion exchange resin, an anionic monolith, and a laminated structure of a granular mix exchange resin, a cationic monolith and an anionic monolith in order from the first small desalting chamber treated water inflow side to the second small desalting chamber In both cases, cations and anions can be removed at a much lower applied voltage than in the horizontal desalting chamber, and the reverse osmosis membrane treated water having a particularly high carbonic acid ratio can be made highly purified water. Further, in the second apparatus in which the first small desalting chamber has a laminated structure of a granular anion exchange resin and an anionic monolith, granular cations are sequentially introduced into the second small desalting chamber from the treated water inflow side of the first small desalting chamber. It is good also as a laminated structure of the laminated structure of an exchange resin and a cation monolith. In the present invention, one desalting chamber in the second device refers to a first small desalting chamber or a second small desalting chamber.

  Moreover, in the second apparatus, the ion exchanger filled in the first small desalting chamber and the second small desalting chamber is not limited to the above-described form, and complex monolith ion exchange is performed in the first small desalting chamber. When the mixed ion exchanger of the body and the granular ion exchange resin is used, the ion exchanger filled in the second small desalting chamber is not particularly limited. For example, a known monolithic ion exchanger single bed, a granular ion exchange resin single A bed, a mixed ion exchanger of a known monolithic ion exchanger and a granular ion exchange resin, a composite monolith ion exchanger single bed, or the like can be used. Further, when a mixed monolith ion exchanger and a granular ion exchange resin mixed ion exchanger are used in the second small desalting chamber, the ion exchanger charged in the first small desalting chamber is not particularly limited. A monolith ion exchanger single bed, a granular ion exchange resin single bed, a known monolith ion exchanger and a granular ion exchange resin mixed ion exchanger, or a composite monolith ion exchanger single bed can be used.

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

  In the electric deionized water production apparatus of the present invention, as a method of filling a mixed monolith ion exchanger and a granular ion exchange resin in a cell frame forming a desalting chamber, a composite monolith ion exchanger is used. It is preferable to cut it into a size slightly larger than the cell frame, fill it so as to be pushed into a predetermined position of the cell frame, and then fill the space other than the composite monolith ion exchanger with the granular ion exchange resin. In the desalination chamber filled with the mixed ion exchanger in this way, even if the granular ion exchange resin contracts, the composite monolith ion exchanger pushes back like a sponge to close the gap, while the granular ion exchange resin expands. However, the composite monolithic ion exchanger shrinks and absorbs in a sponge form, preventing damage to the cell frame and peeling of the ion exchange membrane. Therefore, the filling state of the mixed ion exchanger in the cell can always be kept constant, and single flow, electrical resistance, and current bias can be prevented. In addition, by combining the composite monolith ion exchanger and the granular ion exchange resin, it is possible to install a partition member that is arranged to extend in the vertical direction with respect to the flow direction of the conventional vertical treated water. Can be omitted.

  As an operating method of the electric deionized water production apparatus of the present invention, the first apparatus is used to pass the water to be treated through the ion exchanger and to the flow of the water to be treated through the both ion exchange membranes. On the other hand, by applying a DC electric field in the vertical direction to electrically exclude ions in the water to be treated from the concentrated water flowing outside the two ion exchange membranes, the second apparatus is used to The treated water is passed in series in this order through the desalting chamber and the second small desalting chamber, or the treated water is serially connected in this order to the second small desalting chamber and the first small desalting chamber. And is treated in the concentrated water flowing outside the anion exchange membrane and the cation exchange membrane by causing a direct current electric field to act perpendicularly to the flow of the treatment water through the ion exchange membrane. An operation method in which ions in water are electrically excluded can be mentioned.

  Next, an example of the electric deionized water production apparatus and the operation method thereof according to the present invention will be described with reference to FIG. FIG. 17 is a schematic view showing the structure of the electric deionized water production apparatus of this example. In the electric deionized water production apparatus 10 of FIG. 17, the cation exchange membranes 1 and the anion exchange membranes 2 are alternately arranged apart from each other, and every other in the space formed by the cation exchange membrane 1 and the anion exchange membrane 2. An ion exchanger is filled to form a desalting chamber 4. A portion not filled with the ion exchanger formed by the anion exchange membrane 2 and the cation exchange membrane 1 located next to each of the desalting chambers 4 is a concentration chamber 5 through which concentrated water flows.

  Further, in the cation exchange membrane 1 and the anion exchange membrane 2 and in the inside thereof, a mixed bed (MB) 45, which is a mixture of an anion exchange resin (AER) and a cation exchange resin (CER), and a cation monolith along the water flow direction. A repetitive structure having a laminated structure of 42 and anion monolith 43 forms a desalting module 40 in which two layers are laminated in this order. FIG. 17 shows a state in which a plurality of desalting modules 40 are provided with a spacer not shown in the figure interposed therebetween, and the cathode 8 is disposed on one end side of the desalting module 40 provided, An anode 7 is disposed on the other end side. In addition, the position which pinched | interposed the spacer is the concentration chamber 5, and both the electrodes separated by the diaphragm 21 are provided with a simple membrane (partition membrane) 21 having no ion exchange property, for example, on both outer sides of the concentration chambers 5 at both ends. The portions in contact with each other are defined as a cathode chamber 81 and an anode chamber 71, respectively.

  Next, in order to process treated water and produce treated water by the electric deionized water production apparatus 10, the following operations are performed. In addition, the to-be-processed water demonstrates the case of reverse osmosis membrane permeated water. That is, a direct current is passed between the cathode 8 and the anode 7, electrode water is passed through the electrode chambers 71 and 81, and concentrated water is passed through the concentration chamber 5. When the water to be treated flows down the desalting chambers 4 and passes through the ion exchangers 41 and 42, the anion component and the cation component are removed, and treated water is obtained from the desalting chambers. The concentrated water flows down the concentration chamber 5, receives impurity ions moving through both ion exchange membranes, and flows out from the concentration chamber 5 as concentrated water in which the impurity ions are concentrated. By the above operation, impurity ions in the permeated water of the reverse osmosis membrane device are electrically removed, and highly purified treated water (pure water) can be obtained.

  Next, another example of the electric deionized water production apparatus and the operation method thereof according to the present invention will be described with reference to FIG. FIG. 18 is a schematic diagram showing the structure of another example of an electrical deionized water production apparatus. In FIG. 18, the same components as those in FIG. 17 are denoted by the same reference numerals, description thereof is omitted, and different points are mainly described. That is, FIG. 18 differs from FIG. 17 in the desalination chamber structure and the flow direction of the water to be treated. The demineralized structure of the electrical deionized water production apparatus 10a has an intermediate ion exchange membrane 9 disposed between the anion exchange membrane 2 and the cation exchange membrane 1, and is partitioned by the anion exchange membrane 2 and the intermediate ion exchange membrane 9. The first small desalting chamber 4a filled with the first ion exchanger to be prepared, the second small desalting chamber 4b filled with the second ion exchanger partitioned by the intermediate ion exchange membrane 9 and the cation exchange membrane 1 are provided. Formed. The intermediate ion exchange membrane 9 is a cation exchange membrane.

  Next, in order to process treated water and produce treated water by the electric deionized water production apparatus 10a, the following operations are performed. In addition, the to-be-processed water demonstrates the case of the permeated water of a reverse osmosis membrane apparatus similarly to the above. That is, a direct current is passed between the cathode 8 and the anode 7, electrode water is passed through the electrode chambers 71 and 81, and concentrated water is passed through the concentration chamber 5. The water to be treated is passed in series in the order of the first small desalting chamber 4a and the second small desalting chamber 4b, and two layers of an anion exchange resin 41 and an anionic monolith (AMo) 43 in the first small desalting chamber 4a. When passing through the packed bed, carbonate ions and other anion components that are difficult to remove by the reverse osmosis membrane device are removed, and then two layers of cation exchange resin 44 and cation monolith (CMo) 42 in the second small desalting chamber 4b. When passing through the packed bed, the remaining anion components are removed, and treated water is obtained from the desalting chamber 4. The concentrated water flows down the concentration chamber 5, receives impurity ions moving through the anion exchange membrane 2 and the cation exchange membrane 1, and flows out from the concentration chamber 5 as concentrated water in which the impurity ions are concentrated. Through the above operation, the impurity ions of the permeated water are electrically removed, and treated water (pure water) can be obtained. According to the operation method of the electrical deionized water production apparatus 10a, the same effect as that of the electrical deionized water production apparatus 10 can be obtained.

  In the electric deionized water production apparatus 10a of FIG. 18, the first small demineralization chamber 4a is a mixed ion exchanger of the anion exchange resin 41 and the anion monolith 43, and the second small demineralization chamber 4b is a single bed of cation exchange resin or The second small desalting chamber 4b can be a mixed ion exchanger of the cation exchange resin 44 and the cation monolith 42, and the second small desalting chamber 4a can be an anion exchange resin single bed or an anion. It can also be a monolith single floor.

  Next, the present invention will be described more specifically with reference to examples. However, this is merely an example and does not limit the present invention.

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. This emulsion was quickly 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 And 1 ° C. lower than the 10-hour half-life temperature of the polymerization initiator). 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, stirred at 20,000 rpm for 2 minutes using a homogenizer, and a water-in-oil emulsion. Got. After emulsification, the water-in-oil emulsion was transferred to a stainless steel autoclave, sufficiently substituted with nitrogen, sealed, and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the content was taken out, extracted with Soxhlet for 18 hours with isopropanol, unreacted monomer and sorbitan monooleate were removed, and dried under reduced pressure at 40 ° C. overnight. 5 g of a porous material containing 14 mol% of a crosslinking component composed of a styrene / divinylbenzene copolymer obtained in this manner was collected, 500 g of tetrachloroethane was added, and the mixture was heated at 60 ° C. for 30 minutes, and then to room temperature. After cooling, 25 g of chlorosulfuric acid was gradually added and reacted at room temperature for 24 hours. Thereafter, acetic acid was added, the reaction product was poured into a large amount of water, washed with water and dried to obtain a porous cation exchanger. The ion exchange capacity of this porous material is 4.0 mg equivalent / g in terms of dry porous material, and sulfonic acid groups are uniformly introduced into the porous material by mapping of sulfur atoms using EPMA. It was confirmed. Further, as a result of SEM observation (not shown), the internal structure of the porous body has an open cell structure, and most of the macropores having an average diameter of 30 μm are overlapped, and the mesopores formed by the overlap of the macropores and the macropores. The average diameter was 5 μm and the total pore volume was 10.1 ml / g. The porous body was cut out to a thickness of 10 mm, and the water permeation rate was measured. As a result, it was 14,000 l / min · m ² · MPa.

Reference Example 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.

  The demineralization chamber structure is a vertical type of the electrical deionized water production apparatus shown in FIG. 17, and the water to be treated is treated under the following operating conditions in the flow shown in FIG. did. In FIG. 17, “C” indicates a cationic monolith, and “A” indicates an anionic monolith.

<Electrical deionized water production device>
・ Electric deionized water production equipment; EDI (manufactured by Organo)
・ Desalination chamber: Width 55mm, Height 230mm, Thickness 8mm
-Volume ratio MB of the mixed ion exchanger (IRA402BL: IR120B = 1: 1): cationic monolith (CMo): anionic monolith (AMo); 4: 1: 1
Cation monolith (CMo) used in mixed ion exchanger; Reference Example 2
Anion monolith (AMo) used in the mixed ion exchanger; Reference Example 7
・ Flow rate of water to be treated: 30 l / h
・ Flow rate of concentrated water: 10 l / h

  In the mixed ion exchanger, the monolith has a laminated structure of two layers so as to be CMo, AMo, CMo, and AMo along the water flow direction. Moreover, all the mixed ion exchangers were regenerated and filled while crushing the monolith so that the total volume was 1.05 times the desalting chamber volume.

The water to be treated is the permeated water of the reverse osmosis membrane device and has a carbonic acid concentration of 3.8 mg CO ₂ / l and a silica concentration of 500 μg SiO ₂ / l. As a result, the average applied voltage for obtaining treated water having a resistivity of 17.9 MΩ-cm at an operation time of 1000 hours was 35 V, and the current was 0.3 A. The water differential pressure was 43 kPa.
Comparative Example 1

  The same as Example 1 except that the cationic monolith of Reference Example 13 was used instead of the cationic monolith of Reference Example 2, and the anionic monolith of Reference Example 14 was used instead of the anionic monolith of Reference Example 7. EDI was obtained and operated. As a result, the average applied voltage was 40 V and the current was 0.3 A to obtain treated water having a resistivity of 17.9 MΩ-cm at an operation time of 1000 hours. Moreover, the water flow differential pressure was 320 kPa. In addition, when the same operation as described above was performed at an average applied voltage of 36 V, the resistivity was 15 MΩ-cm.

  The demineralization chamber structure is the vertical type of the electric deionized water production apparatus shown in FIG. 18, and the water to be treated is treated under the following operating conditions in the flow shown in FIG. The procedure was the same as in Example 1 except that. As a result, the average applied voltage for obtaining treated water having a resistivity of 17.9 MΩ-cm at an operation time of 1000 hours was 26 V, and the current was 0.3 A. The water flow differential pressure was 37 kPa.

<Electrical deionized water production device>
・ Electric deionized water production equipment; D2EDI (organo)
・ 1st small desalination chamber; width 55mm, height 230mm, thickness 8mm
-Volume ratio of mixed ion exchanger in the first small desalting chamber (AER: AMo); 2: 1
AMO of mixed ion exchanger in the first small desalting chamber; Reference Example 7
・ Second small desalination chamber; width 55mm, height 230mm, thickness 8mm
-Volume ratio of mixed ion exchanger in the second small desalting chamber (CER: CMo); 2: 1
-CMo of the mixed ion exchanger in the second small desalting chamber; Reference Example 2
・ Flow rate of water to be treated: 20 l / h
・ Flow rate of concentrated water: 7.5 l / h

Comparative Example 2
(Production of electric deionized water production equipment)
The same as Example 2 except that the cationic monolith of Reference Example 13 was used instead of the cationic monolith of Reference Example 2, and the anionic monolith of Reference Example 14 was used instead of the anionic monolith of Reference Example 7. EDI was obtained and operated. As a result, the average applied voltage was 30 V and the current was 0.3 A in order to obtain treated water having a resistivity of 17.9 MΩ-cm at an operation time of 1000 hours. Moreover, the water flow differential pressure was 210 kPa. In addition, when the same operation as described above was performed at an average applied voltage of 27 V, the resistivity was 15 MΩ-cm.

  The electric deionized water production apparatus of the present invention is used in various industries such as semiconductor manufacturing industry, pharmaceutical industry, food industry, power plant, laboratory, etc. using deionized water, or production of sugar solution, juice, wine, etc. In particular, it is suitable for the treatment of the permeated water of the reverse osmosis membrane device.

DESCRIPTION OF SYMBOLS 1 Cation exchange membrane 2 Anion exchange membrane 4 Desalination chamber 4a 1st small desalination chamber 4b 2nd small desalination chamber 5 Concentration chamber 7 Anode 8 Cathode 9 Intermediate ion exchange membrane 10, 10a, 10b Electric deionized water production apparatus 15 Desalination chamber 41 Granular anion exchange resin 42 Cationic monolith 43 Anionic monolith 44 Granular cationic resin 45 Mixed resin of granular cationic resin and granular anionic resin

Claims (10)

  It contains a desalting chamber filled with an ion exchanger that is partitioned by an anion exchange membrane on the anode side and partitioned by a cation exchange membrane on the cathode side, allowing water to be treated to pass through the ion exchanger, An electric deionized water that causes a DC electric field to act in a direction perpendicular to the flow of the water to be treated and electrically removes ions in the water to be treated in the concentrated water flowing outside the ion exchange membranes. In the production apparatus, the ion exchanger is a mixed ion exchanger of a monolithic organic porous ion exchanger and a granular ion exchange resin, and the monolithic organic porous ion exchanger has 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 4 to 40 μm formed on the skeleton surface of the organic porous body. Multiple protrusions The composite structure has an average pore diameter of 10 to 150 μm in a water wet state, a total pore volume of 0.5 to 5 ml / g, and an ion exchange capacity of 0.2 mg equivalent / ml per volume in the water wet state. An electric deionized water production apparatus characterized by the above.   The desalting chamber has a structure in which the granular ion exchange resin and the monolithic organic porous ion exchanger are laminated in this order along the water flow direction, or is a repeating structure of the laminated structure. The electric deionized water production apparatus according to claim 1.   The desalting chamber has a structure in which a monolithic organic porous ion exchanger and a granular ion exchange resin are laminated in this order along the water flow direction, or a repeating structure of the laminated structure. The electric deionized water production apparatus according to claim 1.   4. The electricity according to claim 2 or 3, wherein the monolithic organic porous ion exchanger has a structure in which a cation exchanger and an anion exchanger are laminated along a water flow direction or a repeating structure of the laminated structure. Type deionized water production equipment. An intermediate ion exchange membrane is further disposed between the anion exchange membrane disposed on the anode side and the cation exchange membrane disposed on the cathode side , and is partitioned by the anion exchange membrane and the intermediate ion exchange membrane. Forming a first small desalting chamber filled with one ion exchanger, a second small desalting chamber filled with a second ion exchanger partitioned by the intermediate ion exchange membrane and the cation exchange membrane, The treated water is passed in series in this order through the 1 small desalting chamber and the second small desalting chamber, or the treated water is passed in this order in the second small desalting chamber and the first small desalting chamber. In the concentrated water flowing outside the anion exchange membrane and the cation exchange membrane by passing a DC electric field in a direction perpendicular to the flow of water to be treated through the ion exchange membrane. In the electric deionized water production apparatus for electrically removing ions in the water to be treated, the first and first Either one or both of the ion exchangers is a mixed ion exchanger of a monolithic organic porous ion exchanger and a granular ion exchange resin, and the monolithic organic porous ion exchanger has a continuous skeleton phase and continuous pores. An organic porous body composed of phases 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 size of 4 to 40 μm formed on the skeleton surface of the organic porous body A composite structure with a large number of protrusions, having an average pore diameter of 10 to 150 μm in a water-wet state, a total pore volume of 0.5 to 5 ml / g, and an ion exchange capacity per volume in a water-wet state An electric deionized water production apparatus characterized by being 0.2 mg equivalent / ml or more.   The first small desalting chamber has a structure in which the granular ion exchange resin and the monolithic organic porous ion exchanger are laminated in this order from the treated water inflow side to the outflow side, or the laminated structure 6. The electric deionized water production apparatus according to claim 5, which has a repeating structure.   The second small desalting chamber has a structure in which the granular ion exchange resin and the monolithic organic porous ion exchanger are laminated in this order from the treated water inflow side to the outflow side, or the laminated structure 6. The electric deionized water production apparatus according to claim 5, which has a repeating structure.   The treated water is passed in series in this order through the first small desalting chamber and the second small desalting chamber, and the first small desalting chamber extends from the treated water inflow side to the outflow side. The second small desalting chamber has a structure in which the granular anion exchange resin and the monolithic organic porous anion exchanger are laminated in this order, and the second small desalting chamber has an outlet side from the treated water inflow side of the first small desalting chamber. 6. The apparatus for producing electric deionized water according to claim 5, wherein the structure is such that a granular cation exchange resin and a monolithic organic porous cation exchanger are laminated in this order.   An organic porous body composed of a continuous skeleton phase and a continuous pore phase, the anode side being partitioned by an anion exchange membrane and the cathode side being partitioned by a cation exchange membrane, and a large number of 4 to 40 μm in diameter fixed to the skeleton surface of the organic porous body A composite structure with a large number of protrusions having a size of 4 to 40 μm formed on the surface of the skeleton of the particle body or the organic porous body, and having an average pore diameter of 10 to 150 μm in the wet state. Mixed ion exchange of a monolithic organic porous ion exchanger having a pore volume of 0.5 to 5 ml / g and an ion exchange capacity of 0.2 mg equivalent / ml or more per volume in a water-wet state and a granular ion exchange resin Using an electric deionized water production apparatus containing a desalting chamber filled with a body, the water to be treated is passed through the mixed ion exchanger and the flow of the water to be treated through the both ion exchange membranes. Direct electric field in the vertical direction Then, the operation method of the electric deionized water production apparatus is characterized in that ions in the water to be treated are electrically excluded from the concentrated water flowing outside the ion exchange membranes.   An anion exchange membrane on the anode side, a cation exchange membrane on the cathode side, an anion exchange membrane located between the anion exchange membrane and the cation exchange membrane, and formed by the anion exchange membrane and the intermediate ion exchange membrane And a second small desalting chamber in which a second ion exchanger is filled in a gap formed by the intermediate ion exchange membrane and the cation exchange membrane. The demineralized water production apparatus containing the water to be treated is passed through the first small desalting chamber and the second small desalting chamber in series in this order, or the second small desalting chamber And the first small demineralization chamber are passed through the treated water in series in this order, and a DC electric field is applied in a direction perpendicular to the flow of the treated water through the anion exchange membrane or the cation exchange membrane. Concentrated water flowing outside the anion exchange membrane and the cation exchange membrane A method for electrically removing ions in water to be treated, wherein one or both of the first ion exchanger and the second ion exchanger are a monolithic organic porous ion exchanger and a granular ion exchange resin. A mixed ion exchanger of the above, wherein the monolithic organic porous ion exchanger has an organic porous body composed of a continuous skeleton phase and a continuous pore phase, and a diameter of 4 to 4 fixed to the skeleton surface of the organic porous body. A composite structure comprising a large number of particles having a size of 40 μm or a large number of protrusions having a size of 4 to 40 μm formed on the skeleton surface of the organic porous material, and having an average pore diameter of 10 to 10 in a wet state Operation of an electric deionized water production apparatus characterized by having a total pore volume of 0.5 to 5 ml / g, 150 μm, and an ion exchange capacity of 0.2 mg equivalent / ml or more per volume in a wet state of water. Method.