JP5030182B2 - Electric deionized liquid production equipment - Google Patents

Description

  The present invention uses an ion exchange membrane used in various industries such as semiconductor manufacturing industry, pharmaceutical industry, food industry, power plant, laboratory, etc. using deionized liquid or manufacturing sugar solution, juice, wine, etc. The present invention relates to an electric deionized liquid production apparatus having a simplified apparatus structure.

  Japanese Patent Application Laid-Open No. 2006-159064 discloses a desalting region filled with an ion exchanger, and a liquid permeable region through which a part of the liquid to be processed disposed adjacent to the ion exclusion side of the desalting region passes. An electrode disposed on both sides of the desalting region and the liquid permeation region, a treatment liquid inflow pipe through which the treatment liquid flows, and an electrode chamber or a concentration for discharging the liquid permeated from the liquid permeation region A deionizing solution outflow pipe for discharging a desalting solution from the desalting region, wherein the liquid permeable region is loaded with a porous ion exchanger. An apparatus is disclosed.

  The organic porous ion exchanger used in the desalting region and the liquid permeation region of this electric deionizing liquid production apparatus has a continuous macropore and a mesopore having an average diameter of 1-1000 μm in the wall of the macropore. It has a cell structure, has a total pore volume of 1 to 50 ml / g, has ion exchange groups uniformly distributed, and has an ion exchange capacity of 0.5 mg equivalent / g or more of a dry porous body. The details of the method for producing the organic porous ion exchanger having the above-mentioned open cell structure are disclosed in JP-A-2002-306976. According to this electric deionized liquid production apparatus, the structure of the apparatus can be further simplified than the conventional one without using an ion exchange membrane, and the permeation of the permeated film in the liquid permeation region. Generation of scale can be prevented by the dilution effect of the treatment liquid.

Japanese Patent Laid-Open No. 2006-159064 JP 2002-306976 A JP 2009-62512 A JP 2009-67982 A

  However, the organic porous ion exchangers described in JP-A-2006-159064 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 around 20 μm, the total pore volume also increases accordingly, so that the ion exchange capacity per volume decreases, and thus the quality of treated water and the power consumption increase. There was a problem. In addition, in the monolith loaded in the demineralization chamber of the electric deionized water production apparatus described in Japanese Patent Application Laid-Open No. 2006-159064, the appearance of a monolith having a new structure different from the open cell structure (continuous macropore) is also desired. It was.

  Therefore, the object of the present invention is to maintain the advantage that the ion exchange membrane of the electrodeionization liquid production apparatus disclosed in Japanese Patent Application Laid-Open No. 2006-159064 can be omitted, while the strength of the monolith ion exchanger is high, and the pressure during water flow An object of the present invention is to provide an electric deionized liquid production apparatus that can reduce loss, facilitates the removal of adsorbed ions by further speeding the movement of adsorbed ionic impurities, has 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 obtained in a desalination region of an electric deionization liquid production apparatus in which the installation of an ion exchange membrane is omitted. Or, if used in the permeation region, the movement of the adsorbed ionic impurities can be accelerated to facilitate the removal of the adsorbed ions, the strength of the monolith ion exchanger is high, and the pressure loss during water flow can be reduced. Can, expediting further movement of adsorbed ionic impurities to facilitate the elimination of adsorbed ions, the treated water quality is found such that the good and the power consumption is small, and have completed the present invention.

  That is, the present invention provides a desalting region filled with the first ion exchanger and a second ion exchanger through which a part of the liquid to be treated disposed adjacent to the ion exclusion side of the desalting region passes. A liquid permeation area filled with a liquid, an electrode disposed on both sides of the desalting area and the liquid permeation area, a liquid inflow pipe to be treated for passing the liquid to be treated, and a liquid permeated from the liquid permeation area An electrode chamber or a concentrating chamber for discharging the desalting solution, and a desalting solution outflow pipe for discharging the desalting solution from the desalting region, wherein the first ion exchanger has a continuous skeletal 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 It is a composite structure with a large number of protrusions, and has an average pore diameter of 10 to 150 μm and a total pore volume of 0. A monolithic organic porous ion exchanger having an ion exchange capacity per volume of 0.2 mg equivalent / ml or more in a water-wet state, or the monolithic organic porous ion exchanger It is a mixed ion exchanger with a granular ion exchange resin, and the water resistance of the second ion exchanger is larger than the water resistance of the first ion exchanger. A device is provided.

  The present invention also provides a desalting region filled with the first ion exchanger, and a second ion exchanger through which a part of the liquid to be treated disposed adjacent to the ion exclusion side of the desalting region permeates. A liquid permeation area filled with a liquid, an electrode disposed on both sides of the desalting area and the liquid permeation area, a liquid inflow pipe to be treated for passing the liquid to be treated, and a liquid permeated from the liquid permeation area An electrode chamber or a concentrating chamber for discharging the desalting solution, and a desalting solution outflow pipe for discharging the desalting solution from the desalting region, wherein the second ion exchanger has a continuous skeletal 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 It is a composite structure with a large number of protrusions, and has an average pore diameter of 0.01 to 150 μm and a total pore volume of 0. A monolithic organic porous ion exchanger having an ion exchange capacity of 0.2 mg equivalent / ml or more per volume in a water-wet state, wherein the water resistance of the first ion exchanger is The present invention provides an apparatus for producing an electrical deionized liquid, which is smaller than the water flow resistance of the second ion exchanger.

  The present invention also provides a desalting region filled with the first ion exchanger, and a second ion exchanger through which a part of the liquid to be treated disposed adjacent to the ion exclusion side of the desalting region permeates. A liquid permeation area filled with a liquid, an electrode disposed on both sides of the desalting area and the liquid permeation area, a liquid inflow pipe to be treated for passing the liquid to be treated, and a liquid permeated from the liquid permeation area An electrode chamber or a concentrating chamber for discharging the desalting solution, and a desalting solution outflow pipe for discharging the desalting solution from the desalting region, wherein the first ion exchanger and the second ion exchanger are the same The desalting area and the liquid permeation area are formed of a single monolith, and a flow rate adjusting means is disposed in the flow path of the effluent that has permeated from the liquid permeation area. The monolith 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 of a large number of μm particles or a large number of projections 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 It is a monolithic organic porous ion exchanger having 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. An electrical deionized liquid manufacturing apparatus is provided.

  According to the present invention, the monolithic ion exchanger having a novel structure can be suitably used in a desalting region or a permeation region of an electric deionized liquid production apparatus that omits the installation of an ion exchange membrane. That is, the electric deionized liquid production apparatus of the present invention has high monolithic ion exchanger strength, can reduce pressure loss during water flow, further accelerates the movement of adsorbed ionic impurities, Ease of removal, good quality of treated water and low power consumption.

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 deionization liquid manufacturing apparatus of the 1st Example of this invention. It is a schematic diagram which shows the structure of the electric deionization liquid manufacturing apparatus of the 2nd Example of this invention. It is a schematic diagram which shows the structure of the electrical deionization liquid manufacturing apparatus of the 3rd Embodiment of this invention. It is a schematic diagram which shows the structure of the electric deionization liquid manufacturing apparatus of the 4th Example of this invention. It is a figure explaining the filling state of the deionization area | region and liquid permeation | transmission area | region used with the electrical deionization liquid manufacturing apparatus of FIG. FIG. 3 is a schematic diagram showing the structure of an electrical deionized liquid production apparatus of Example 2. It is a figure explaining the filling state of the deionization area | region and liquid permeation | transmission area | region used with the electrical deionization liquid manufacturing apparatus of FIG. It is typical sectional drawing of a protrusion.

  The basic structure of the electric deionizing liquid production apparatus (hereinafter also simply referred to as “EDI”) of the present invention is a demineralized region filled with the first ion exchanger and adjacent to the ion exclusion side of the demineralized region. A liquid permeable region filled with a second ion exchanger through which a part of the liquid to be treated is disposed, electrodes disposed on both sides of the desalting region and the liquid permeable region, A treatment liquid inflow pipe for passing the liquid, an electrode chamber or a concentration chamber for discharging the liquid permeated from the liquid permeation area, and a desalting liquid outflow pipe for discharging the desalting liquid from the desalination area. Is. In a first aspect of the present invention, the first ion exchanger is a composite monolith ion exchanger, and in a second aspect of the invention according to claim 2, the second ion exchanger is a composite monolith ion exchanger, In a third invention according to Item 3, the single monolith is a composite monolith ion exchanger.

<First invention>
In the EDI of the first invention, the first ion exchanger filled in the desalting region is a composite monolith ion exchanger described later, or mixed ion exchange between the composite monolith ion exchanger and the granular ion exchange resin. Is the body. A well-known thing can be used for a granular ion exchange resin. In the case of a mixed ion exchanger, the mixing ratio (volume ratio) of the composite monolith ion exchanger and the granular ion exchange resin is 1: 0.1 to 1:10, preferably 1: 0.2 to 1: 5. is there. In addition, the liquid flow resistance of the first ion exchanger is made smaller than the liquid flow resistance of the second ion exchanger filled in the liquid permeable region. Thereby, it is easy to reduce the flow resistance of the desalting region with respect to the second ion exchanger loaded in the liquid permeation region, and it is not necessary to provide a separate special channel distribution means. Most of the liquid to be treated that flows into the region flows out from the desalting region as a deionized liquid from the desalting region, and a part of the liquid to be treated permeates into the liquid permeation region.

  The liquid permeation region is loaded with the second ion exchanger, and is disposed adjacent to the ion rejection side of the desalting region, so that a part of the liquid to be treated permeates and is electrophoretically excluded. This is a region through which ionic impurities are transmitted. Examples of the second ion exchanger loaded in the liquid permeation region include a monolith having an open cell structure, a fibrous porous ion exchanger, a particle agglomerated porous ion exchanger, and the like. Monoliths are preferred because the ion exchange groups are uniformly distributed and ion exclusion is performed promptly.

  As the monolith having an open-cell structure as the second ion exchanger, a known one produced from a water-in-oil emulsion can be used. For example, the average diameter is 1 to 20 μm, preferably 1 μm in the wall of the macropore and the macropore. Above, having a common opening (mesopore) of less than 10 μm, total pore volume of 1 to 50 ml, ion exchange groups are uniformly distributed, ion exchange capacity is 0.5 mg equivalent / g dry porous body or more And an organic porous ion exchanger having a three-dimensional network structure. In such a monolith having an open cell structure, the opening forming the flow path is smaller than the opening of the monolith of the first ion exchanger, and the liquid flow resistance becomes high. Such a monolith having an open cell structure and a method for producing the same are disclosed in, for example, Japanese Patent Application Laid-Open No. 2003-334560. In the monolith disclosed in Japanese Patent Application Laid-Open No. 2003-334560, a monolith having a small mesopore average diameter can be obtained by a method such as increasing the amount of the surfactant added or increasing the agitation during the production. Moreover, a well-known thing can also be used for a fibrous porous ion exchanger and a particle aggregation type porous ion exchanger, respectively.

  In the first invention, the flow rate adjusting means may or may not be installed in the permeate flow path. If the flow rate adjusting means is installed, the liquid flow resistance of the first ion exchanger can be surely made smaller than the liquid flow resistance of the second ion exchanger filled in the liquid permeation region. Further, the flow rates of the permeate and deionized liquid can be adjusted to a desired ratio. The flow rate ratio of the permeate passing through the liquid permeation region to the flow rate of the liquid to be processed is, for example, 2 to 30%, preferably 4 to 30%. If this ratio is less than 2%, it becomes difficult to prevent the occurrence of scale by reducing the dilution effect, and if it exceeds 30%, it is not preferable in that the yield of the desalted solution is reduced. Examples of the flow rate adjusting means include a flow rate adjusting valve, Arifis and the like.

  The form in which the liquid permeation region is disposed adjacent to the ion rejection side of the desalting region is not particularly limited, but the form in which the monoliths are disposed adjacent to each other is preferable in terms of quick ion exclusion. . When the monoliths are disposed adjacent to each other, the monolith for the desalting region and the monolith for the liquid permeation region are disposed in close contact with each other in the electric field application direction. Moreover, since the monolith and the ion exchange resin mixture in the desalting region are sponge-like, they can form respective phases without being mixed.

  In the first invention, in the case of an anion cell or a cation cell, it is disposed adjacent to the side opposite to the ion exclusion side of the desalting region. It may have the same structure as the liquid permeable region, or may be a conventional ion exchange membrane. When this liquid permeable region is provided, the liquid that has permeated from this liquid permeable region flows into the electrode chamber or the concentration chamber. Thereby, since an ion exchange membrane becomes completely unnecessary, the device structure can be simplified and the manufacturing cost can be reduced. Further, when an ion exchange membrane is provided, an electrode solution or a concentrated solution is separately supplied to an electrode chamber or a concentrating chamber adjacent to the ion exchange membrane, similarly to the conventional EDI. Examples of the ion exchanger loaded in the other liquid permeable region include the same ion exchanger as the second ion exchanger loaded in the liquid permeable region.

<Second invention>
Next, the second invention will be described mainly with respect to differences from the first invention. In the EDI of the second invention, the second ion exchanger filled in the transmission region is a composite monolith ion exchanger. Further, the flow resistance of the second ion exchanger is made larger than that of the first ion exchanger filled in the desalting region. As a result, it is easy to reduce the flow resistance of the desalting region with respect to the second ion exchanger loaded in the liquid permeation region, and it is not necessary to provide a separate special channel distribution means. Most of the liquid can flow to the desalting zone.

  In the EDI of the second invention, the first ion exchanger used in the desalting region is a granular ion exchange resin or a mixed ion exchanger of a granular ion exchange resin and a composite monolith ion exchanger. A well-known thing can be used for a granular ion exchange resin. In the case of a mixed ion exchanger, the mixing ratio (volume ratio) of the composite monolith ion exchanger and the granular ion exchange resin is 1: 0.1 to 1:10, preferably 1: 0.2 to 1: 5. In addition, the liquid flow resistance of the first ion exchanger is made smaller than the liquid flow resistance of the second ion exchanger filled in the liquid permeable region. As a result, it is easy to reduce the liquid flow resistance with respect to the second ion exchanger loaded in the liquid permeation region, and it is not necessary to provide a separate special channel distribution means, and most of the liquid to be processed is It can flow to the desalting zone.

  In the second invention, the flow rate adjusting means may or may not be installed in the permeate flow path. If the flow rate adjusting means is installed, the flow resistance of the first ion exchanger can be surely made smaller than the flow resistance of the second ion exchanger filled in the liquid permeation region, as in the first invention. wear.

  Next, regarding the third invention, differences from the first invention will be mainly described. That is, in the third invention, the first ion exchanger and the second ion exchanger are the same, that is, the desalting region and the liquid permeation region are formed of a single composite monolith ion exchanger and permeate from the liquid permeation region. A flow rate adjusting means is disposed in the flow path of the effluent. This is advantageous in that it is not necessary to separately manufacture the desalination zone monolith and the liquid permeation zone monolith. A single monolith is a composite monolith ion exchanger. In the third invention, if there is no flow rate adjusting means, the flow rate flowing in the liquid permeation region increases, and the yield of the desalted liquid is reduced. Further, the flow rate ratio of the permeated liquid that permeates the liquid permeation region to the flow rate of the liquid to be processed may be the same as in the first invention. Examples of the flow rate adjusting means include a flow rate adjusting valve, Arifis and the like.

  Next, the monolithic organic porous ion exchanger having a composite structure used in the EDI of the present invention will be described. In the description of the composite monolithic ion exchanger, “monolithic organic porous body” is simply “composite monolith”, “monolithic organic porous ion exchanger” is simply “composite monolithic ion exchanger”, and “monolithic The “organic porous intermediate” is also simply referred to as “monolith intermediate”.

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

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

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

  In the case of the first organic porous ion exchanger, in the case of using a desalting region and using a single monolith, the organic porous body has bubble-like macropores overlapped with each other, and the overlapping portion is in a wet state with an average diameter of 30. It is a continuous macropore structure which becomes an opening (mesopore) of ˜150 μm. The average diameter of the opening of the composite monolith ion exchanger is larger than the average diameter of the opening of the composite monolith in a dry state because the entire composite monolith swells when an ion exchange group is introduced into the monolith. If the average diameter of the openings is less than 30 μm, the pressure loss at the time of water flow is increased, which is not preferable. If the average diameter of the openings is too large, contact between the fluid and the monolith ion exchanger becomes insufficient. As a result, the ion exchange characteristics deteriorate, which is not preferable.

  In the present invention, the average diameter of the openings of the dry monolith intermediate, the average diameter of the pores or openings of the dry composite monolith, and the average diameter of the holes or openings of the dry composite monolith ion exchanger are: It is a value measured by the mercury intrusion method. In the present invention, the average diameter of the pores or openings of the composite monolith ion exchanger in the wet state is calculated by multiplying the average diameter of the pores or openings of the composite monolith ion exchanger in the dry state by the swelling rate. Value. Specifically, the diameter of the composite monolith ion exchanger in the water wet state is x1 (mm), the diameter of the composite monolith ion exchanger in the dry state obtained by drying the composite monolith ion exchanger in the water wet state. And y1 (mm), and the average diameter of the pores or openings when the dry monolithic ion exchanger is measured by mercury porosimetry is z1 (μm) The average diameter (μm) of the holes or openings of the exchanger is calculated by the following formula “average diameter of holes or openings (μm) = z1 × (x1 / y1) of the composite monolith ion exchanger in a water-wet state”. The Also, the average diameter of the pores or openings of the dry composite monolith before introduction of the ion exchange group, and the water-wetting composite monolith ion relative to the dry composite monolith when the ion exchange group is introduced into the dry composite monolith When the swelling ratio of the exchanger is known, the average diameter of the pores or openings of the composite monolith in the dry state is multiplied by the swelling ratio to calculate the average diameter of the pores of the composite monolith ion exchanger in the water wet state. You can also.

  In the case of the second organic porous material ion exchanger, the organic porous material using a desalted region and a single monolith is a three-dimensional one having an average diameter (thickness) of 1 to 60 μm in a wet state. And a co-continuous structure having three-dimensionally continuous pores having an average diameter of 10 to 100 μm, preferably 10 to 90 μm in a water-wet state between the skeletons. If the diameter of the three-dimensionally continuous pores is less than 10 μm, the pressure loss during fluid permeation increases, which is not preferable. If the diameter exceeds 100 μm, contact between the water to be treated and the composite monolith ion exchanger is not preferable. As a result, the ion exchange characteristics become non-uniform, which is not preferable.

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

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

  A preferable value of the average diameter of the pores in the wet state of the composite monolith ion exchanger used in the desalting region 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.

  When used in the liquid permeation region, the average diameter of the pores in the wet state of the composite monolith ion exchanger is 0.01 to 150 μm, preferably 0.1 to 150 μm, particularly preferably 0.1 to 50 μm. When the organic porous body constituting the composite monolith ion exchanger is the first organic porous body when used in the liquid permeation region, the opening diameter of the composite monolith ion exchanger is 0.01 to 150 μm. When the organic porous body constituting the composite monolith ion exchanger is the second organic porous body, preferably 0.1 to 150 μm, particularly preferably 0.1 to 50 μm, the pore diameter of the composite monolith ion exchanger is 0.01-100 μm, preferably 0.1-50 μm, particularly preferably 0.1-30 μm. If one having a small pore diameter is used in the liquid permeation region, the water flow resistance can be increased. In addition, in the case of the 2nd organic porous body used for a liquid permeation | transmission area | region, the average diameter (thickness) of the three-dimensionally continuous frame | skeleton is 1-60 micrometers in a water wet state.

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

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

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

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

  The composite monolith ion exchanger of the present invention has an ion exchange capacity per volume in a water-wet state of 0.2 mg equivalent / ml or more, preferably 0.3 to 1.8 mg equivalent / ml. If the ion exchange capacity per volume is less than 0.2 mg equivalent / ml, the 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.

  In addition, the monolith intermediate has an average diameter of openings (mesopores) that are the overlapping portions of macropores and macropores, in the case of use in a desalted region, 5 to 150 μm in a dry state, and in the case of use in a liquid permeation region It is 0.005-150 μm in a dry state. In the case of use in a desalting region, if the average diameter of the openings is less than 5 μm, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes small, and the pressure loss during passing water becomes large. It is not preferable. On the other hand, if it exceeds 150 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.

  Further, in the case of the first organic porous body of the composite monolith ion exchanger, the monolith intermediate has an average diameter of openings (mesopores) where macropores overlap with macropores. 20 to 150 μm in the state, and 0.005 to 150 μm in the dry state when used in the liquid permeation region. In the case of the second organic porous body of the composite monolith ion exchanger, the monolith intermediate has an average diameter of three-dimensionally continuous pores of 5 to 5 in a dry state when used in a desalting region. In the case of use in a liquid permeation region, it is 0.005 to 100 μm in a dry state.

(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.

  In the continuous macropore structure, 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 co-continuous structure has an average thickness of 0. It is composed of a three-dimensionally continuous skeleton of 8 to 40 μm 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.

  Next, an example of the electric deionized liquid production apparatus in the first embodiment of the present invention will be described with reference to FIG. FIG. 17 is a schematic diagram of a two-cell type EDI using a cation cell ((A) in the figure) for removing cationic impurities in the liquid to be treated and an anion cell ((B) in the figure) for removing anionic impurities. FIG.

  In FIG. 17, the electric deionized liquid production apparatus 10 includes a cation cell 10a and an anion cell 10b. The cation cell 10a is a liquid permeable region through which a part of the liquid to be treated that is disposed adjacent to the decation region 1a filled with the monolith cation exchanger and the ion exclusion side (cathode side) of the decation region 1a passes. A region 2a, a liquid permeable region 3a through which another part of the liquid to be treated disposed adjacent to the anode side of the decationized region 1a passes, a decationized region 1a, a liquid permeable region 2a, and a liquid permeable region 3a An anode 4a and a cathode 4b disposed on both sides of the substrate, a treatment liquid inflow pipe 11 for passing the treatment liquid through the decation region 1a, a cathode chamber 6 into which the liquid permeated from the liquid permeation region 2a flows, The anode chamber 7 into which the liquid which permeate | transmitted from the liquid permeation | transmission area | region 3 flows in, and the decation liquid outflow pipe 12 which discharges a decation liquid from the decation area 1a are provided.

In the cation cell 10a, the flow resistance of the cation exchanger forming the liquid permeable region 2a and the liquid permeable region 3a is larger than the liquid resistance of the monolith cation exchanger filled in the decation region 1a. The liquid to be treated is introduced from the vicinity of the cathode side of the decation region 1a, and the treatment liquid is excluded from flowing out from the vicinity of the anode side of the decation region 1a substantially diagonally to the inlet of the liquid to be treated. And the flow direction of the liquid to be treated in the decationization region 1a are opposite to each other, which is preferable in that a monolith cation exchanger is effectively used and a treatment liquid free from leakage of the cationic impurity X ⁺ is obtained.

  In the anion cell 10b of FIG. 17B, the same components as those of the cation cell 10a of FIG. 17A are denoted by the same reference numerals, description thereof will be omitted, and different points will be described. That is, the anion cell 10b is different from the cation cell 10a in that the desalting region is filled with a monolith anion exchanger, and the liquid permeation region 2b and the liquid permeation region 3b are filled with an anion exchanger. The treatment liquid is introduced from the vicinity of the anode side of the deanion region 1b, and the treatment liquid is caused to flow out from the vicinity of the cathode side of the deanion region 1b on a substantially diagonal line of the inlet of the liquid to be treated. And the decation liquid outflow pipe 12 of the cation cell 10a and the to-be-processed liquid inflow pipe 13 of the anion cell 10b are connected. Similar to the cation cell 10a, the anion cell 10b has a very simple structure.

Next, the manufacturing method of the desalination liquid using the electric deionization liquid manufacturing apparatus 10 is demonstrated. The liquid to be treated is caused to flow from the liquid inlet 11 for the liquid to be treated into the decation region 1a. The liquid to be treated that has flowed into the decationization region 1a has a liquid passage resistance of the cation exchanger that forms the liquid permeation region 2a and the liquid permeation region 3a due to the liquid passage resistance of the monolith cation exchanger filled in the decation region 1a. Since it is large, most of the liquid to be treated flows through the decationization region 1a, and a part thereof passes through the liquid permeation region 2a and the liquid permeation region 3a. The permeated liquid that has passed through the liquid permeable region 2a is discharged as a catholyte into the cathode chamber 6 together with the cationic impurities X ⁺ that are electrophoretically excluded. In the liquid permeation region 2a, a part of the liquid to be treated is always transmitted, and scale generation is prevented by the dilution effect. In addition, the permeated liquid that has permeated through the liquid permeable region 3 a is discharged into the anode chamber 7 as an anolyte. In the drawing, the flow path 17 in the decationization region 1a is schematically shown, but the actual flow is also generally such a flow.

Next, the liquid to be treated from which the cationic impurities have been removed is caused to flow from the liquid to be treated inlet 13 into the deanion region 1b. The liquid to be treated that has flowed into the deanion region 1b has a liquid resistance of the anion exchanger that forms the liquid permeation region 2b and the liquid permeation region 3b due to the liquid resistance of the monolith anion exchanger filled in the deanion region 1b. Since it is large, most of the liquid to be treated flows through the deanion region 1b, and a part thereof passes through the liquid permeation region 2b and the liquid permeation region 3b. The permeated liquid that has passed through the liquid permeable region 2b is discharged as an anolyte into the anode chamber 7 together with the anionic impurity Y ⁻ that is electrophoretically excluded. In the liquid permeation region 2b, like the cation cell 10a, a part of the liquid to be treated is always permeating, and scale generation is prevented by the dilution effect. Further, the permeated liquid that has passed through the liquid permeable region 3 b is discharged into the cathode chamber 6 as a catholyte. In the figure, the flow path 18 in the deanion region 1b is schematically shown, but the actual flow is also generally such a flow.

  According to the two-cell type electric deionized liquid production apparatus 10 composed of the cation cell 10a and the anion cell 10b, neither the cation cell 10a nor the anion cell 10b uses an ion exchange membrane at all, so the apparatus structure is extremely simple. Manufacturing costs can be reduced. Further, in the liquid permeable region 2a on the cathode side of the cation cell 10a and the liquid permeable region 2b on the anode side of the anion cell 10b, the generation effect of the scale that cannot be avoided by conventional EDI is diluted. Can be prevented. In addition, the monolith ion exchanger used in the desalting region has high strength, and since the openings and pores forming the flow path are large, the pressure loss during water flow can be reduced, and the ion exchange capacity per volume can be reduced. Since it is large, conductivity and treated water quality can be improved.

  Next, an example of an electrical deionized liquid production apparatus according to the second embodiment of the present invention will be described with reference to FIG. FIG. 18 shows another two-cell type using a cation cell 20a ((A) in the figure) for removing cationic impurities in the liquid to be treated and an anion cell 20b ((B) in the figure) for removing anionic impurities. It is a schematic diagram of EDI. 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 is different from FIG. 17 in that, in the cation cell 20a, the cation exchange membrane 5 is provided on the anode side of the decation region 1a, and the permeation of the liquid is performed between the decation region 1a and the anode chamber 7. In the anion cell 20b, a cation exchange membrane 5 is provided on the cathode side of the deanion region 1b so that no liquid permeates between the deanion region 1b and the cathode chamber 6. .

  According to the two-cell type electric deionized liquid production apparatus 20 comprising the cation cell 20a and the anion cell 20b, although the ion exchange membrane is used in part, the same effect as the electric deionized liquid production apparatus 10 is obtained. Play.

  Next, an example of an electric deionized liquid production apparatus according to the third embodiment of the present invention will be described with reference to FIG. FIG. 19 is a schematic diagram of one-cell type EDI that simultaneously removes cationic impurities and anionic impurities. 19, the same components as those in FIG. 17 are denoted by the same reference numerals, description thereof is omitted, and different points will be mainly described. That is, FIG. 19 differs from FIG. 17 in that the cell structure is a cation / anion cell 30 having a single cell structure, and in the desalted region 1c, a mixed monolith ion exchanger of a cation exchanger and an anion exchanger is used. The cation exchanger is loaded on the cathode side liquid permeable region 2a of the desalting region 1c, and the anion exchanger is loaded on the anode side liquid permeable region 3b of the desalting region 1c. is there. Examples of the mixed monolith ion exchanger include a laminated structure of a cation monolith and an anion monolith. The lamination direction of the laminated structure may be either the direction in which the processing liquid flows or the direction perpendicular to the direction in which the processing liquid flows.

Next, a method for producing a desalting solution using the cation / anion cell 30 will be described. The liquid to be processed which has flowed into the desalting region 1c through the processing liquid inflow pipe 11 has a resistance to flow of the cation exchanger and the anion exchanger forming the liquid permeation region 2a and the liquid permeation region 3b. Therefore, most of the liquid to be treated flows through the desalting region 1c, and part of the liquid passes through the liquid permeation region 2a and the liquid permeation region 3b. The permeated liquid that has passed through the liquid permeable region 2a is discharged as a catholyte into the cathode chamber 6 together with the cationic impurities X ⁺ that are electrophoretically excluded. Further, the permeated liquid that has passed through the liquid permeable region 3 b is discharged into the anode chamber 7 as an anolyte. In the liquid permeation region 2a and the liquid permeation region 3b, a part of the liquid to be treated is always transmitted, and scale generation is prevented by the dilution effect. In the figure, the flow path 17 in the desalting region 1c is schematically shown, but the actual flow is also generally such a flow.

  According to the 1-cell type electric deionized liquid manufacturing apparatus 30, the same effects as the 2-cell type electric deionized liquid manufacturing apparatus 20 are obtained.

Next, an example of an electrical deionized liquid production apparatus in the fourth embodiment of the present invention will be described with reference to FIG. FIG. 20 is a schematic diagram of EDI in which a plurality of desalting chambers for simultaneously removing cationic impurities and anionic impurities are arranged in parallel. In FIG. 20, the same components as those in FIG. 17 are denoted by the same reference numerals, description thereof will be omitted, and different points will be mainly described. That is, FIG. 20 is different from FIG. 17 in that the basic structure of the desalting cell disposed between the electrodes is different. That is, between the anode chamber 7 and the cathode chamber 6, desalting chambers 1 d, 1 d partitioned on the anode side by an anion exchanger 2 b which is a liquid permeable region and on the cathode side by a monolith cation exchanger 2 a which is a liquid permeable region. And an EDI having a concentration chamber 9 which is partitioned by a cation exchanger which is a liquid-permeable region and whose cathode side is partitioned by an anion exchanger which is a liquid-permeable region. In the electric deionized liquid production apparatus 40, the number of installed desalting chambers 1d and 1d is not limited to this, and may be one or three or more.

Next, a method for producing a desalting solution using the electric deionizing solution production apparatus 40 will be described. The liquid to be processed is caused to flow into the desalting regions 1d and 1d from the liquid inlet pipe 11 to be processed. The liquid to be treated that has flowed into the desalting regions 1d and 1d is a monolith mixed ion exchanger in which the resistance of the ion exchanger forming the liquid permeable region 2a and the liquid permeable region 2b is filled in the desalting regions 1d and 1d. Therefore, most of the liquid to be treated flows through the desalting regions 1d and 1d, and part of the solution passes through the liquid permeable region 2a and the liquid permeable region 2b. The permeated liquid that has passed through the liquid permeable region 2a is discharged as a catholyte and a concentrated liquid into the cathode chamber 6 and the concentrating chamber 9 together with the cationic impurities X ⁺ that are electrophoretically excluded. The permeated liquid that has passed through the liquid permeable region 2b is discharged as an anolyte and a concentrated liquid into the anode chamber 7 and the concentrating chamber 9 together with the anionic impurity Y ⁻ that is electrophoretically excluded. In the liquid permeation area 2a and the liquid permeation area 2b, a part of the liquid to be treated is always transmitted, and scale generation is prevented by the dilution effect. In the figure, the flow path 17 in the desalting region 1d is schematically shown, but the actual flow is also generally such a flow.

  According to the electric deionization liquid production apparatus 40 arranged in parallel with the desalting chamber, the same effects as those of the one-cell type electric deionization liquid production apparatus 30 and the two-cell type electric deionization liquid production apparatus 20 are obtained.

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

Reference example 1
(Step I; production of monolith intermediate)
9.28 g of styrene, 0.19 g of divinylbenzene, 0.50 g of sorbitan monooleate (hereinafter abbreviated as SMO) and 0.26 g of 2,2′-azobis (isobutyronitrile) were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / SMO / 2,2′-azobis (isobutyronitrile) mixture is added to 180 g of pure water, and a vacuum stirring defoaming mixer (manufactured by EM Corp.) which is a planetary stirring device. Was used under reduced pressure in a temperature range of 5 to 20 ° C. to obtain a water-in-oil emulsion. The emulsion was immediately transferred to a reaction vessel, and after sealing, it was allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the content was taken out, extracted with isopropanol, and then dried under reduced pressure to produce a monolith intermediate having a continuous macropore structure. The average diameter of the openings (mesopores) where the macropores and macropores of the monolith intermediate were measured by mercury porosimetry was 40 μm, and the total pore volume was 15.8 ml / g.

(Manufacture of composite monolith)
Next, 36.0 g of styrene, 4.0 g of divinylbenzene, 60 g of 1-decanol, and 0.4 g of 2,2′-azobis (2,4-dimethylvaleronitrile) were mixed and dissolved uniformly (step II). The 10-hour half-life temperature of 2,2′-azobis (2,4-dimethylvaleronitrile) used as the polymerization initiator was 51 ° C. The amount of divinylbenzene used is 6.6 mol% with respect to the total amount of styrene and divinylbenzene used in Step II, while the crosslink density of the monolith intermediate is 1.3 mol%, and the crosslink density ratio is 5.1 times. Met. Next, the monolith intermediate was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 20 mm, and 3.2 g was collected. The separated monolith intermediate is placed 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 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 FIG. 1 to FIG. 3 have different magnifications, and are images at arbitrary positions on a cut surface obtained by cutting a monolith at an arbitrary position. As apparent from FIGS. 1 to 3, the composite monolith has a continuous macropore structure, and the surface of the skeletal phase constituting the continuous macropore structure is coated with particles having an average particle diameter of 4 μm. The particle coverage of the skeleton surface by the body and the like was 80%. Moreover, the ratio for which the particle body with a particle size of 3-5 micrometers occupied to the whole particle body was 90%.

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

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

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

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

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

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

Reference Example 6
(Manufacture of composite monolith)
Table 1 shows the type and amount of vinyl monomer used, amount of crosslinking agent used, type and amount of organic solvent, monolith intermediate porous structure coexisting during polymerization in step III, crosslinking density and amount used. A monolith was produced in the same manner as in Reference Example 1 except for the change. The results are shown in Tables 1 and 2. Moreover, the result of having observed the internal structure of composite monolith (dry body) by SEM is shown in FIGS. What adhered to the skeleton surface of the composite monolith of Reference Example 6 was a protrusion. In the monolith of Reference Example 6, the average diameter of the maximum diameter of the protrusions formed on the surface was 10 μm, and the particle coverage of the skeletal surface with all the particulates was 100%. Moreover, the ratio for which the particle body with a particle size of 6-12 micrometers occupied to the whole particle body was 80%.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Reference Example 13 (known cationic monolith)
46.3 g of styrene, 2.4 g of divinylbenzene, 0.3 g of azobisisobutyronitrile and 3.1 g of sorbitan monooleate were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / azobisisobutyronitrile / sorbitan monooleate mixture is added to 180 ml of pure water, and (revolution / spinning) = (1800 rpm / 600 rpm) using a planetary stirrer. Stirring for a minute gave a water-in-oil emulsion. After completion of emulsification, the resulting product was sufficiently substituted with nitrogen, sealed, and allowed to polymerize at 60 ° C. for 24 hours. After the completion of the polymerization, the contents were taken out and subjected to Soxhlet extraction with isopropanol for 12 hours to remove unreacted monomers and sorbitan monooleate. Then, it dried under reduced pressure at 85 degreeC all day and night. The porous body containing 3.3 mol% of the crosslinking component composed of the styrene / divinylbenzene copolymer thus obtained was cut and 16.6 g was sampled, 900 ml of dichloromethane was added thereto, and 1 ml at 35 ° C. was added. After heating for hours, the mixture was ice-cooled to 0 ° C., 88.0 g of chlorosulfonic acid was gradually added, and after the addition of chlorosulfonic acid, the temperature was raised and reacted at 35 ° C. for 24 hours. Thereafter, the reaction product was washed with methanol and washed with water to obtain a porous cation exchanger. The ion exchange capacity of this porous body is 4.5 mg equivalent / g in terms of dry porous body, and sulfonic acid groups are uniformly introduced into the porous body by mapping of sulfur atoms using EPMA. It was confirmed. Moreover, as a result of SEM observation, the internal structure of the porous body (cationic monolith for liquid permeation region) has an open cell structure, and most of the macropores having an average diameter of 30.0 μm overlap each other. When the average value of the diameters of the mesopores formed by the overlap was determined by the mercury intrusion method, the average value of the diameters was 8.5 μm and the total pore volume was 2.7 ml / g.

Reference Example 14 (known cationic monolith)
19.2 g of styrene, 1.0 g of divinylbenzene, 0.3 g of azobisisobutyronitrile and 1.1 g of sorbitan monooleate were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / azobisisobutyronitrile / sorbitan monooleate mixture is added to 180 ml of pure water, and (revolution / spinning) = (1000 rpm / 330 rpm) 2 using a planetary stirrer. Stirring for a minute gave a water-in-oil emulsion. After completion of emulsification, the resulting product was sufficiently substituted with nitrogen, sealed, and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the contents were taken out and subjected to Soxhlet extraction with isopropanol for 12 hours to remove unreacted monomers and sorbitan monooleate. Then, it dried under reduced pressure at 85 degreeC all day and night. The porous body containing 3.3 mol% of the crosslinking component composed of the styrene / divinylbenzene copolymer thus obtained was cut and 7.9 g was collected, 900 ml of dichloromethane was added, and the mixture was heated at 35 ° C. for 1 hour. After cooling to 0 ° C., 42.0 g of chlorosulfonic acid was gradually added. After completion of the addition of chlorosulfonic acid, the temperature was raised and reacted at 35 ° C. for 24 hours. Thereafter, the reaction product was washed with methanol and washed with water to obtain a porous cation exchanger. The ion exchange capacity of this porous material was 4.6 mg equivalent / g in terms of dry porous material. As a result of SEM observation, the internal structure of the porous body had an open-cell structure, and had a structure in which most of the macropores having an average diameter of 100 μm overlapped. When the average value of the diameter of the mesopore formed by the overlap of the macropore and the macropore was determined by the mercury intrusion method, the average value of the diameter was 29.0 μm and the total pore volume was 8.6 ml / g.

Reference Example 15 (known anionic monolith)
Instead of 46.3 g of styrene, 27.4 g of p-chloromethylstyrene is used, and 1.6 g of divinylbenzene, 0.3 g of azobisisobutyronitrile, and 2.0 g of sorbitan monooleate are mixed and dissolved uniformly. It was. Next, the p-chloromethylstyrene / divinylbenzene / azobisisobutyronitrile / sorbitan monooleate mixture is added to 180 ml of pure water, and (revolution / spinning) = (1800 rpm /) using a planetary stirrer. (600 rpm) for 5 minutes to obtain a water-in-oil emulsion. After completion of emulsification, the resulting product was sufficiently substituted with nitrogen, sealed, and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the contents were taken out and subjected to Soxhlet extraction with isopropanol for 12 hours to remove unreacted monomers and sorbitan monooleate. Then, it dried under reduced pressure at 85 degreeC all day and night. 10.7 g of the porous body containing 5.0 mol% of the cross-linking component composed of the p-chloromethylstyrene / divinylbenzene copolymer thus obtained was cut and sampled, and 900 g of tetrahydrofuran was added at 60 ° C. After heating for 1 hour, the mixture was cooled to room temperature, 58.8 g of a trimethylamine (30%) aqueous solution was gradually added, and after completion of the addition of the trimethylamine aqueous solution, the temperature was raised and reacted at 60 ° C. for 6 hours. After completion of the reaction, the porous body was taken out, washed with methanol, washed with water, and dried to obtain a porous anion exchanger. The ion exchange capacity of this porous material was 3.6 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. As a result of SEM observation, the internal structure of the porous body had an open-cell structure, and had a structure in which most macropores having an average diameter of 30 μm overlapped. When the average value of the diameter of the mesopore formed by the overlap of the macropore and the macropore was determined by the mercury intrusion method, the average value of the diameter was 7.8 μm and the total pore volume was 4.0 ml / g.

Reference Example 16 (known anionic monolith)
Instead of 19.2 g of styrene, 19.2 g of p-chloromethylstyrene is used and 1.0 g of divinylbenzene, 0.3 g of azobisisobutyronitrile and 2.0 g of sorbitan monooleate are mixed and dissolved uniformly. It was. Next, the p-chloromethylstyrene / divinylbenzene / azobisisobutyronitrile / sorbitan monooleate mixture is added to 180 ml of pure water, and (revolution / spinning) = (1000 rpm /) using a planetary stirrer. (330 rpm) for 2 minutes to obtain a water-in-oil emulsion. After completion of emulsification, the resulting product was sufficiently substituted with nitrogen, sealed, and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the contents were taken out and subjected to Soxhlet extraction with isopropanol for 12 hours to remove unreacted monomers and sorbitan monooleate. Then, it dried under reduced pressure at 85 degreeC all day and night. The porous body containing 5.0 mol% of the cross-linking component made of the p-chloromethylstyrene / divinylbenzene copolymer thus obtained was cut and 6.8 g was sampled, and 900 g of tetrahydrofuran was added thereto. After heating at 0 ° C. for 1 hour, the mixture was cooled to room temperature, 43.1 g of a trimethylamine (30%) aqueous solution was gradually added, and after completion of the addition of the aqueous trimethylamine solution, the temperature was raised and reacted at 60 ° C. for 6 hours. After completion of the reaction, the porous body was taken out, washed with methanol, washed with water, and dried to obtain a porous anion exchanger. The ion exchange capacity of this porous material was 3.7 mg equivalent / g in terms of dry porous material. As a result of SEM observation, the internal structure of the porous body had an open-cell structure, and had a structure in which most macropores having an average diameter of 70 μm overlapped. When the average value of the diameter of the mesopore formed by the overlap of the macropore and the macropore was determined by the mercury intrusion method, the average value of the diameter was 21.0 μm and the total pore volume was 8.4 ml / g.

(Preparation of cation cell)
The monolith cation exchanger of Reference Example 13 was used as the cation monolith for the liquid permeation region, and the monolith cation exchanger of Reference Example 2 was used as the cation monolith for the decation region. Then, in order to produce an electric deionized liquid production apparatus 20 as shown in FIG. 18, a cation cell 20a as shown in FIG. 21 was first produced. From the obtained cation monolith for liquid permeation region and cation monolith for decation region, two rectangular parallelepipeds 2a each having a longitudinal (H) of 50 mm, a lateral (W) of 40 mm, and a thickness (L ₁ ) of 20 mm in a pure water wet state, 11a was cut out to obtain a filler for stacking and filling the decation chamber. Next, in order from the cathode chamber (on the left side in the figure), the cell monolith 2a and the cation monolith 11a for the decation region are in close contact and loaded into the cell container 201, and the anode of the cation monolith 11a for the decation region The adjacent space on the side was filled with 80 ml capacity of cation exchange resin 12a (Amberlite IR120B, manufactured by Rohm and Haas). In the figure, the cell container 201 is provided with a treatment liquid inflow pipe 11 on the bottom surface where the cation monolith 11a for the decationization region is located, and a treatment liquid outflow pipe 12 is attached on the upper surface on the anode side where the cation exchange resin 12a is located. Has been. Next, a cathode chamber was formed on the cathode side of the cell container 201, and a SUS304 cathode was disposed on the outer surface of the cathode chamber. A cation exchange membrane (Nafion 350; manufactured by DuPont) is disposed in close contact with the anode side of the cation exchange resin 12a, and an anode made of a platinum-coated titanium substrate is disposed on the outer surface of the cation exchange membrane. A cation cell 20a was prepared by appropriately providing nozzles and lead wire outlets. For simplification, the description of the cation exchange membrane, the electrode chamber, and the electrode is omitted in FIG.

(Preparation of anion cell)
The monolith anion exchanger of Reference Example 15 was used as the anion monolith for the liquid permeation region, and the monolith anion exchanger of Reference Example 7 was used as the anion monolith for the deanion region. From the obtained anion monolith for liquid permeation region and anion monolith for deionization region, two rectangular parallelepipeds 2b each having a longitudinal (H) 50 mm, a lateral (W) 40 mm, and a thickness (L ₁ ) 20 mm in a pure water wet state, 11b was cut out to obtain a filler for stacking and filling the deanion chamber. Next, in the cell container 202, the anion monolith 2b for liquid permeation region and the anion monolith 11b for deanion region are in close contact with each other in order from the anode chamber (left side in FIG. 21). An adjacent space on the cathode side was filled with 80 ml capacity of anion exchange resin 12b (Amberlite IRA402BL, manufactured by Rohm and Haas). The cell container 202 is provided with a liquid to be treated (decationization liquid) inflow pipe 13 on the bottom surface where the anion monolith 11b for the deionization region is located in the figure, and desalting on the upper surface on the cathode side where the anion exchange resin 12b is located. A liquid outflow pipe 14 is attached. Next, an anode chamber was formed on the anode side of the cell container 202, and an anode made of a platinum-coated titanium substrate was disposed on the outer surface of the anode chamber. Further, a cation exchange membrane (Nafion 350; manufactured by DuPont) is disposed in close contact with the cathode side of the anion exchange resin 12b, and a SUS304 cathode is disposed on the outer surface of the cation exchange membrane. An anion cell 20b was prepared by providing a lead wire outlet.

(Preparation of electric deionized liquid manufacturing apparatus 20)
The treatment liquid outflow pipe 12 of the obtained cation cell 20a and the liquid inflow pipe 13 to be treated of the anion cell 20b are connected, and a part of the permeated liquid that has passed through the other two electrode chambers is supplied to the two electrode chambers. I tried to do it.

(Manufacture of deionized liquid)
The electric deionized liquid production apparatus 20 thus obtained was continuously supplied with water having a conductivity of 130 μS / cm as a liquid to be treated at a flow rate of 15 l / h, and a direct current of 2.5 A was serially connected from the cation cell to the anion cell. When energized, an operation voltage was 98 V, and a treatment liquid having an electric conductivity of 0.65 μS / cm was obtained at a flow rate of 13 l / h. The flow rate of the permeate (catholyte) permeated through the cation cell 20a and the flow rate of the permeate (anolyte) permeated through the anion cell 20b were 1 l / h, respectively.

Comparative Example 1
Instead of the monolith cation exchanger of Reference Example 2, instead of the monolith cation exchanger of Reference Example 14 and the monolith anion exchanger of Reference Example 7 instead of the monolith anion exchanger of Reference Example 7, The same method as in Example 1 was used. The obtained electric deionized liquid production apparatus 20 was continuously supplied with water having a conductivity of 130 μS / cm as a liquid to be treated at a flow rate of 15 l / h, and a direct current of 2.5 A was serially connected from the cation cell to the anion cell. When energized, an operating voltage was 110 V, and a treatment liquid having an electrical conductivity of 1 μS / cm was obtained at a flow rate of 10 l / h. The flow rate of the permeate (catholyte) permeated through the cation cell 20a and the flow rate of the permeate (anolyte) permeated through the anion cell 20b were 2.5 l / h, respectively.

<Liquid Permeation Side Cationic Monolith (Production Example 1)>
(Manufacture of monolith intermediates)
19.85 g of styrene, 0.40 g of divinylbenzene, 1.07 g of sorbitan monooleate (hereinafter abbreviated as SMO) and 0.26 g of 2,2′-azobis (isobutyronitrile) were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / SMO / 2,2′-azobis (isobutyronitrile) mixture is added to 180 g of pure water, and a vacuum stirring defoaming mixer (manufactured by EM Corp.) which is a planetary stirring device. Was used under reduced pressure in a temperature range of 5 to 20 ° C. to obtain a water-in-oil emulsion. The emulsion was immediately transferred to a reaction vessel, and after sealing, it was allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the content was taken out, extracted with isopropanol, and then dried under reduced pressure to produce a monolith intermediate having a continuous macropore structure. The average diameter of the opening (mesopore) where the macropores and macropores of the monolith intermediate overlap was 20 μm, and the total pore volume was 8.5 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 8.4 g was collected. The separated monolith intermediate is placed 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).

  As a result of observing the internal structure of the composite monolith (dried body) comprising the styrene / divinylbenzene copolymer thus obtained by SEM, the composite monolith has a continuous macropore structure. The surface of the skeletal phase constituting the particle was coated with particles having an average particle diameter of 4 μm, and the particle coverage of the skeleton surface by all particles 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 7 μm, and the total pore volume was 2.1 ml / g.

(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 21.9 g. To this, 1500 ml of dichloromethane was added and heated at 35 ° C. for 1 hour, then cooled to 10 ° C. or lower, 122.7 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 1.22 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 is 9 μm as estimated from the value of the organic porous body and the swelling ratio of the cation exchanger in the water-wet state, and is obtained by the same method as for the monolith. The particle coverage of the skeletal surface with all particles was 80%, the average particle size of the coated particles was 5 μm, and the total pore volume was 2.1 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, was 0.31 MPa / m · LV.

<Liquid Permeation Side Anionic Monolith (Production Example 2)>
(Manufacture of composite monolith)
39.4 g of vinylbenzyl chloride, 0.6 g of divinylbenzene, 60 g of 1-butanol, 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. Next, the monolith intermediate obtained in Production Example 1 was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 20 mm, and 8.1 g was obtained. The separated monolith intermediate is put in a reaction vessel having an inner diameter of 73 mm, immersed in the styrene / divinylbenzene / 1-butanol / 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).

  As a result of observing the internal structure of the composite monolith (dry body) composed of the vinylbenzyl chloride / divinylbenzene copolymer thus obtained by SEM, the composite monolith has a continuous macropore structure. The surface of the skeletal phase constituting the structure was covered with protrusions having an average of 5 μm, and the coverage of the skeleton surface with all particles and the like was 100%. Moreover, the ratio for which the projection body with a particle size of 3-7 micrometers occupied to the whole projection body was 80%. Moreover, the average diameter of the opening of the composite monolith measured by the mercury intrusion method was 8 μm, and the total pore volume was 1.8 ml / g.

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

  The swelling rate before and after the reaction of the obtained composite anion exchanger was 2.0 times, and the ion exchange capacity per volume was 0.63 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 16 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 10 μm, the coverage of the skeletal surface with all particles was 100%, and the total pore volume was 1.8 ml / g. The differential pressure coefficient, which is an index of pressure loss when water is permeated, was 0.20 MPa / m · LV. Further, the ratio of the protrusions having a particle diameter of 6 to 14 μm to the entire protrusions was 80%.

(Preparation of cation cell)
A cation cell was prepared in the same manner as in Example 1 except that the monolith cation exchanger of Reference Example 13 was used instead of the monolith cation exchanger of Reference Example 13 as the cation monolith for the liquid permeation region. .

(Preparation of anion cell)
An anion cell was prepared in the same manner as in Example 1, except that the monolith anion exchanger obtained in Production Example 2 was used instead of the monolith anion exchanger of Reference Example 15 as the anion monolith for the liquid permeation region. .

(Production of electric deionized liquid production apparatus 20 and production of deionized liquid)
The same method as in Example 1 was used. As a result, an operation voltage was 94 V, and a treatment liquid having an electric conductivity of 0.65 μS / cm was obtained at a flow rate of 13 l / h.

(Preparation of cation cell)
As the cation monolith for the desalting region, a cation cell was prepared in the same manner as in Example 2 except that the cation exchange resin 12a was used alone instead of the mixture of the monolith cation exchanger of Reference Example 2 and the cation exchange resin 12a. Was made.

(Preparation of anion cell)
The anion cell was prepared in the same manner as in Example 2, except that the anion monolith for the desalting region was replaced with the mixture of the monolith anion exchanger and the anion exchange resin 12b of Reference Example 7 and the anion exchange resin 12b was used alone. Was made.

(Production of electric deionized liquid production apparatus 20 and production of deionized liquid)
An electric deionized liquid production apparatus 20 was produced in the same manner as in Example 1. The electric deionized liquid production apparatus 20 thus obtained was continuously supplied with water having a conductivity of 130 μS / cm as a liquid to be treated at a flow rate of 15 l / h, and a direct current of 2.5 A was serially connected from the cation cell to the anion cell. When energized, an operation voltage was 116 V, and a treatment liquid having an electric conductivity of 2 μS / cm (inlet; 130 μS / cm) was obtained at a flow rate of 14 l / h.

(Preparation of cation cell)
As the cation monolith for the desalting region, the same as Example 1 except that the monolith cation exchanger of Reference Example 2 was used alone instead of the mixture of the monolith cation exchanger of Reference Example 2 and the cation exchange resin 12a. A cation cell was prepared by this method. However, the electric deionized liquid production apparatus was of a different form. That is, in order to produce the electrical deionized liquid production apparatus 10 as shown in FIG. From the obtained cation monolith for liquid permeation region, it was purified from two cuboids of length (H) 50 mm, width (W) 40 mm, thickness (L ₁ ) 20 mm in a pure water wet state, from the cation monolith for decation region. A rectangular parallelepiped having a length (H) of 50 mm, a width (W) of 40 mm, and a thickness (L ₁ ) of 40 mm, respectively, was cut out in a wet state of water to obtain a filler for stacking and filling the decation chamber. Next, in the cell container, a cation monolith for liquid permeation region, a cation monolith for decation region, and a cation monolith for liquid permeation region were loaded in close contact from the cathode chamber. In the cell container, an inflow pipe to be treated is provided in the vicinity of the cation monolith for the cathode side liquid permeation region where the cation monolith for the decation region is located, and the cation monolith for the anode side liquid permeable region where the cation monolith for the decation region is located. A treatment liquid outflow pipe was attached in the vicinity. A cathode chamber was formed on the cathode side of the cell container, and a SUS304 cathode was disposed on the outer surface of the cathode chamber. An anode chamber was formed on the anode side of the cell container, an anode made of a platinum-coated titanium substrate was disposed outside the anode chamber, and a nozzle and a lead wire outlet were appropriately provided to produce a cation cell.

(Preparation of anion cell)
As the anion monolith for the desalting region, the same as Example 1 except that the monolith anion exchanger of Reference Example 7 was used alone instead of the mixture of the monolith anion exchanger of Reference Example 7 and the anion exchange resin 12b. An anion cell was prepared by this method. However, the electric deionized liquid production apparatus was of a different form. That is, an anion cell was produced in order to produce the electric deionized liquid production apparatus 10 as shown in FIG. From the obtained anion monolith for liquid permeation region, pure water from two rectangular parallelepipeds of 50 mm in length (H), 40 mm in width (W) and 20 mm in thickness (L ₁ ) in a pure water wet state, anion monolith for deionization region A rectangular parallelepiped having a length (H) of 50 mm, a width (W) of 40 mm, and a thickness (L ₁ ) of 40 mm, respectively, was cut out in a wet state of water to obtain a filler for stacking and filling the deanion chamber. Next, an anion monolith for liquid permeation region, an anion monolith for deionization region, and an anion monolith for liquid permeation region were in close contact with each other in order from the anode chamber. In the cell container, an inflow pipe for the liquid to be treated (decation liquid) is located in the vicinity of the anion monolith for the liquid permeation area on the anode side where the cation monolith for the deanion area is located, and a liquid on the cathode side where the anion monolith for the deanion area is located. A treatment liquid outflow pipe was provided in the vicinity of the anion monolith for the permeation region. A cathode chamber was formed on the cathode side of the cell container, and a SUS304 cathode was disposed on the outer surface of the cathode chamber. An anode chamber was formed on the anode side of the cell container, and an anode made of a platinum-coated titanium substrate was disposed outside the anode chamber, and a nozzle and a lead wire outlet were appropriately provided to produce an anion cell.

(Production of electric deionized liquid production apparatus 10 and production of deionized liquid)
An electric deionized liquid production apparatus 10 as shown in FIG. 17 was produced. The electric deionized liquid production apparatus 10 thus obtained was continuously supplied with water having a conductivity of 130 μS / cm as a liquid to be treated at a flow rate of 11 l / h, and a direct current of 2.5 A was serially connected from the cation cell to the anion cell. When energized, an operation voltage was 88 V, and a treatment liquid having a conductivity of 0.57 μS / cm was obtained.

(Preparation of cation cell)
As the cation monolith for the desalting region, the same as Example 2 except that the monolith cation exchanger of Reference Example 2 was used alone instead of the mixture of the monolith cation exchanger of Reference Example 2 and the cation exchange resin 12a. A cation cell was prepared by this method. However, since the electrical deionized liquid production apparatus used the same electrical deionized liquid production apparatus 10 as shown in FIG. 17 as in Example 4, a cation cell suitable for it was produced in the same manner as in Example 4. .

(Preparation of anion cell)
As the anion monolith for the desalting region, the same as Example 2 except that the monolith anion exchanger of Reference Example 7 was used alone instead of the mixture of the monolith anion exchanger of Reference Example 7 and the anion exchange resin 12b. An anion cell was prepared by this method. However, since the electrical deionized liquid production apparatus used the same electrical deionized liquid production apparatus 10 as shown in FIG. 17 as in Example 4, a cation cell suitable for it was produced in the same manner as in Example 4. .

(Production of electric deionized liquid production apparatus 10 and production of deionized liquid)
An electric deionized liquid production apparatus 10 as shown in FIG. 17 was produced. The electric deionized liquid production apparatus 10 thus obtained was continuously supplied with water having a conductivity of 130 μS / cm as a liquid to be treated at a flow rate of 11 l / h, and a direct current of 2.5 A was serially connected from the cation cell to the anion cell. When energized, an operation voltage was 85 V, and a treatment liquid having a conductivity of 0.57 μS / cm was obtained.

(Cation cell)
The same monolith cation exchanger of Reference Example 2 was used for both the cation monolith for the desalting region and the cation monolith for the liquid permeation region. That is, a cation cell filled with a single monolith cation exchanger was used.

(Anion cell)
The same monolith anion exchanger of Reference Example 7 was used for both the anion monolith for the desalting region and the anion monolith for the liquid permeation region. That is, an anion cell filled with a single monolith anion exchanger was used.

(Production of electric deionized liquid production apparatus 10 and production of deionized liquid)
An electric deionized liquid production apparatus 10 as shown in FIG. 17 was produced. In addition, a flow control valve was installed in the middle of the permeate outflow piping provided in the four liquid permeation regions, and the flow rate of the water to be treated was adjusted to a flow rate of 11 l / h depending on the opening of the valve. . The electric deionized liquid production apparatus 10 thus obtained was continuously supplied with water having a conductivity of 130 μS / cm as a liquid to be treated at a flow rate of 11 l / h, and a direct current of 2.5 A was serially connected from the cation cell to the anion cell. When energized, an operation voltage was 85 V, and a treatment liquid having a conductivity of 0.57 μS / cm was obtained.

DESCRIPTION OF SYMBOLS 1a Decation area | region 1b Deionization area | region 1c Desalination area | region 1d Desalination room | chamber 2a, 2b, 3a, 3b Liquid permeable area | region 4a Anode 4b Cathode room 6 Cathode room 7 Anode room 9 Desalination room 10, 20, 30, 30a, 40 Electricity Deionized liquid production apparatus 10a Cation cell 10b Anion cell 11, 13 Liquid to be treated inflow pipe 12 Decationized liquid outflow pipe 14 Desalted liquid outflow pipe 15 Flow control valve
17, 18 flow path

Claims (3)

A desalting region filled with a first ion exchanger;
A liquid permeable region filled with a second ion exchanger through which a part of the liquid to be treated is disposed adjacent to the ion exclusion side of the desalting region;
Electrodes disposed on both sides of the desalting region and the liquid-permeable region;
A treatment liquid inlet pipe for passing the treatment liquid;
An electrode chamber or a concentration chamber for discharging the liquid that has permeated from the liquid-permeable region;
A desalting solution outlet pipe for discharging the desalting solution from the desalting region,
The first 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 organic porous body A composite structure with a large number of protrusions having a size of 4 to 40 μm formed on the surface of the skeleton, and having an average pore diameter of 10 to 150 μm and a total pore volume of 0.5 to 5 ml / in a wet state or a monolithic organic porous ion exchanger having an ion exchange capacity of 0.2 mg equivalent / ml or more per volume in a water-wet state, or the monolithic organic porous ion exchanger and granular ion exchange A mixed ion exchanger with resin,
An apparatus for producing an electrical deionized liquid, wherein the flow resistance of the second ion exchanger is greater than the flow resistance of the first ion exchanger. A desalting region filled with a first ion exchanger;
A liquid permeable region filled with a second ion exchanger through which a part of the liquid to be treated is disposed adjacent to the ion exclusion side of the desalting region;
Electrodes disposed on both sides of the desalting region and the liquid-permeable region;
A treatment liquid inlet pipe for passing the treatment liquid;
An electrode chamber or a concentration chamber for discharging the liquid that has permeated from the liquid-permeable region;
A desalting solution outlet pipe for discharging the desalting solution from the desalting region,
The second 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 organic porous body A composite structure with a large number of protrusions having a size of 4 to 40 μm formed on the surface of the skeleton, and having an average pore diameter of 0.01 to 150 μm and a total pore volume of 0.5 to 5 ml / g, a monolithic organic porous ion exchanger having an ion exchange capacity per volume of 0.2 mg equivalent / ml or more in a wet state of water,
The apparatus for producing an electrical deionized liquid, wherein the water resistance of the first ion exchanger is smaller than the water resistance of the second ion exchanger. A desalting region filled with a first ion exchanger;
A liquid permeable region filled with a second ion exchanger through which a part of the liquid to be treated is disposed adjacent to the ion exclusion side of the desalting region;
Electrodes disposed on both sides of the desalting region and the liquid-permeable region;
A treatment liquid inlet pipe for passing the treatment liquid;
An electrode chamber or a concentration chamber for discharging the liquid that has permeated from the liquid-permeable region;
A desalting solution outlet pipe for discharging the desalting solution from the desalting region,
The first ion exchanger and the second ion exchanger are the same, the desalting region and the liquid permeation region are formed of a single monolith, and in the flow path of the effluent that has permeated from the liquid permeation region, The flow rate adjusting means is disposed, and the single monolith has an organic porous body composed of a continuous skeleton phase and a continuous pore phase, and a diameter of 4 to 40 μm fixed to the skeleton surface of the organic porous body. A composite structure with a large number of particles or a large number of protrusions having a size of 4 to 40 μm formed on the skeleton surface of the organic porous body, and having an average pore diameter of 10 to 150 μm in a water-wet state, Electricity characterized by being a monolithic organic porous ion exchanger having 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 Type deionized liquid production equipment.