WO2010104004A1 - Module d'adsorption ionique et procédé de traitement de l'eau - Google Patents

Module d'adsorption ionique et procédé de traitement de l'eau Download PDF

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WO2010104004A1
WO2010104004A1 PCT/JP2010/053642 JP2010053642W WO2010104004A1 WO 2010104004 A1 WO2010104004 A1 WO 2010104004A1 JP 2010053642 W JP2010053642 W JP 2010053642W WO 2010104004 A1 WO2010104004 A1 WO 2010104004A1
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Prior art keywords
monolith
water
ion
ion exchange
skeleton
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PCT/JP2010/053642
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English (en)
Japanese (ja)
Inventor
洋 井上
弘次 山中
陽代 鈴木
理 中森
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オルガノ株式会社
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Priority claimed from JP2009115958A external-priority patent/JP5465463B2/ja
Application filed by オルガノ株式会社 filed Critical オルガノ株式会社
Priority to CN201080011228.0A priority Critical patent/CN102348505B/zh
Publication of WO2010104004A1 publication Critical patent/WO2010104004A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C08J9/283—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum a discontinuous liquid phase emulsified in a continuous macromolecular phase
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
    • B01J20/28011—Other properties, e.g. density, crush strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28042—Shaped bodies; Monolithic structures
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/2805—Sorbents inside a permeable or porous casing, e.g. inside a container, bag or membrane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
    • B01J20/28076—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being more than 1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J47/00—Ion-exchange processes in general; Apparatus therefor
    • B01J47/02—Column or bed processes
    • B01J47/04—Mixed-bed processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J49/00—Regeneration or reactivation of ion-exchangers; Apparatus therefor
    • B01J49/05—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds
    • B01J49/09—Regeneration or reactivation of ion-exchangers; Apparatus therefor of fixed beds of mixed beds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/365—Coating
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
    • C02F2001/425—Treatment of water, waste water, or sewage by ion-exchange using cation exchangers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/02—Homopolymers or copolymers of hydrocarbons
    • C08J2325/04—Homopolymers or copolymers of styrene

Definitions

  • the present invention relates to an ion adsorption module and a water treatment method having a remarkably short ion exchange zone length.
  • ion exchangers are typified by polymer synthetic resins collectively referred to as ion exchange resins, and if classified according to product shape, granular or flake ion exchange resins, membrane ion exchange membranes, and fibrous ion exchange resins It can be classified into ion exchange fibers.
  • ion exchange resins polymer synthetic resins
  • organic porous ion exchangers having continuous pores are also known.
  • Japanese Patent Application Laid-Open No. 2004-82027 discloses a container having at least an opening through which water to be treated flows, a macropore filled in the container, and a mesopore having an average diameter of 1 to 1000 ⁇ m in the wall of the macropore. 3 having an open cell structure, a total pore volume of 1 ml / g to 50 ml / g, an ion exchange group uniformly distributed, and an ion exchange capacity of 0.5 mg equivalent / g dry porous body or more
  • An ion adsorption module comprising an organic porous ion exchanger having a dimensional network structure is disclosed.
  • the filling of the ion exchanger is extremely easy, and the packed bed does not move even in the upward flow. Further, in the water treatment method using this ion adsorption module, the ion exchange zone length can be kept short even when the flow rate is increased, the volume of the ion exchanger device can be reduced, and a small amount of adsorbed ions can be achieved. Since no leakage occurs, the reproduction frequency is reduced and the processing efficiency can be improved.
  • Japanese Patent Laid-Open No. 2002-306976 discloses details of the method for producing the organic porous ion exchanger.
  • JP 2004-82027 A (Claims) JP 2002-306976 A JP 2009-62512 A JP 2009-67982 A
  • the organic porous ion exchanger used in the ion adsorption module of Japanese Patent Application Laid-Open No. 2004-82027 has a common pore (mesopore) of monolith described as 1 to 1,000 ⁇ m, but has a total pore volume of 5 ml.
  • a common pore mepore
  • an object of the present invention is to provide an ion adsorption module that is extremely easy to fill with an ion exchanger. Another object of the present invention is to reduce the water differential pressure and to increase the flow rate even if the flow rate increases.
  • the band length can be kept short, the ion exchange capacity per volume is large, and a minute leak of adsorbed ions does not occur, so the exchange frequency is reduced or the regeneration frequency is lowered, and the processing efficiency can be improved.
  • Another object is to provide an ion adsorption module and a water treatment method.
  • the present inventors have conducted intensive studies, and as a result, the existence of a monolithic organic porous material (intermediate) having a relatively large pore volume obtained by the method described in JP-A-2002-306976.
  • a monolith having a large opening diameter and a thicker skeleton than that of the intermediate organic porous material can be obtained.
  • the ion exchange group is introduced into the monolith, the swelling is large because it is thick. Therefore, the opening can be further increased, and the monolith ion exchanger in which the ion exchange group is introduced into the bone monolith is used as an adsorbent for the ion adsorption module.
  • the differential water flow pressure can be reduced, the ion exchange zone length can be kept short even when the flow rate is increased, and the ion exchange capacity per volume is large. Since trace amounts leak wearing ions does not occur, replacement frequency is reduced or regeneration frequency is lowered, it found such that it is possible to improve the processing efficiency, and have completed the present invention.
  • a monolithic organic porous ion exchanger having a large ion exchange capacity per volume can be obtained by introducing an ion exchange group because the skeleton of the co-continuous structure is thick.
  • the water differential pressure can be reduced, the ion exchange zone length can be kept short even when the flow rate is increased, and the volume per volume can be reduced.
  • the present inventors have found that the ion exchange capacity is large and a minute leak of adsorbed ions does not occur, so that the exchange frequency is reduced or the regeneration frequency is lowered and the processing efficiency can be improved, and the present invention has been completed.
  • the present inventors under the presence of a monolithic organic porous material (intermediate) having a relatively large pore volume obtained by the method described in JP-A-2002-306976, under specific conditions, If the vinyl monomer and the crosslinking agent are allowed to stand in an organic solvent, a large number of particles having a diameter of 2 to 20 ⁇ m are fixed on the surface of the skeleton constituting the organic porous material, or a projection structure is formed.
  • the monolith can be obtained, and the composite monolith ion exchanger in which an ion exchange group is introduced into the composite monolith can be used as an adsorbent for the ion adsorption module.
  • the length can be kept short, the ion exchange capacity per volume is large, and there is no minute leakage of adsorbed ions, so the exchange frequency is reduced or the regeneration frequency is reduced. It found such that it is possible to improve the processing efficiency, and have completed the present invention.
  • the present invention (A1) is an ion adsorption module comprising at least a container having an opening through which water to be treated flows and a monolithic organic porous ion exchanger filled in the container, wherein the monolithic organic
  • the porous ion exchanger is a continuous macropore structure in which bubble-like macropores overlap each other, and the overlapping portion is an opening having an average diameter of 30 to 300 ⁇ m in a wet state of water, and the total pore volume is 0.5 to 5 ml / g.
  • the ion exchange capacity per volume in a wet state of water is 0.4 to 5 mg equivalent / ml, the ion exchange groups are uniformly distributed in the porous ion exchanger, and the continuous macropore structure (dry In the SEM image of the cut surface of the body, the area of the skeleton part appearing in the cross section is 25 to 50% in the image region (hereinafter also referred to as “first monolith ion exchanger”).
  • first monolith ion exchanger dry In the SEM image of the cut surface of the body, the area of the skeleton part appearing in the cross section is 25 to 50% in the image region.
  • the present invention (A1) is an ion adsorption module comprising at least a container having an opening through which water to be treated flows and a monolithic organic porous ion exchanger filled in the container, wherein the monolithic organic
  • the porous ion exchanger is a three-dimensional one having a thickness of 1 to 60 ⁇ m made of an aromatic vinyl polymer containing 0.3 to 5.0 mol% of a crosslinked structural unit among all the structural units into which ion exchange groups are introduced.
  • the ion exchange capacity per volume in a wet state of water is 0.3 to 5 mg equivalent / ml, and the ion exchange groups are uniformly distributed in the porous ion exchanger (hereinafter referred to as “second monolith ion exchange”). It is also called “body”.)
  • second monolith ion exchange porous ion exchanger
  • the present invention (A2) is an ion adsorption module comprising at least a container having an opening through which water to be treated flows and an organic porous ion exchanger filled in the container, wherein the organic porous ion exchange
  • An organic porous body composed of a continuous skeleton phase and a continuous pore phase, a large number of particles having a diameter of 4 to 40 ⁇ m fixed to the skeleton surface of the organic porous body, or a skeleton surface of the organic porous body
  • An ion adsorption module characterized by having an ion exchange capacity per volume in a wet state of 0.2 mg equivalent / ml or more (hereinafter also referred to as “third monolith ion exchanger”)
  • the porous ion exchanger can be easily produced, for example, as a block shape that fits into a filling container, and filling is also easy. Moreover, it can apply to both the continuous water flow processing method generally employ
  • the water differential pressure can be reduced with a compact device, and the ion exchange zone length should be kept short even when the flow rate is increased.
  • the exchange frequency is reduced or the regeneration frequency is lowered, and the processing efficiency can be improved.
  • FIG. 6 is a diagram showing the correlation between the differential pressure coefficient and the ion exchange capacity per volume in Reference Examples 1 to 13 and Reference Examples 20 to 23. It is a manual transfer of the skeleton part that appears as a cross section of the SEM image of FIG. It is the figure which showed typically the co-continuous structure of the 2nd monolith ion exchanger.
  • FIG. 10 is an SEM image of a monolith obtained in Reference Example 26 at a magnification of 100.
  • FIG. 10 is an SEM image of a monolith obtained in Reference Example 26 at a magnification of 300.
  • FIG. 10 is an SEM image of the monolith obtained in Reference Example 26 at a magnification of 3000.
  • 7 is an EPMA image showing a distribution state of sulfur atoms on the surface of the monolith cation exchanger obtained in Reference Example 26.
  • FIG. It is the EPMA image which showed the distribution state of the sulfur atom in the cross section (thickness) direction of the monolith cation exchanger obtained in Reference Example 26.
  • 18 is a SEM image of a monolith obtained in Reference Example 27 at a magnification of 100.
  • FIG. 18 is a SEM image of a monolith obtained in Reference Example 27 at a magnification of 600.
  • 10 is a SEM image of the monolith obtained in Reference Example 27 at a magnification of 3000. It is a SEM image of magnification of 600 of the monolith obtained in Reference Example 28. It is a SEM image of the monolith obtained in Reference Example 28 at a magnification of 3000.
  • 10 is a SEM image of the monolith obtained in Reference Example 29 at a magnification of 3000.
  • 10 is an SEM image of a monolith obtained in Reference Example 30 at a magnification of 100.
  • FIG. 4 is a SEM image of the monolith obtained in Reference Example 30 at a magnification of 3000.
  • FIG. 10 is a SEM image of a monolith obtained in Reference Example 31 at a magnification of 100.
  • FIG. 6 is an SEM image of a monolith obtained in Reference Example 31 at a magnification of 600.
  • FIG. 4 is a SEM image of the monolith obtained in Reference Example 31 at a magnification of 3000. It is typical sectional drawing of a protrusion.
  • the container is filled with the first monolith ion exchanger or the second monolith ion exchanger.
  • “monolithic organic porous body” is simply “monolith”
  • “monolithic organic porous ion exchanger” is simply “monolith ion exchanger”
  • “monolithic The “organic porous intermediate” is also simply referred to as “monolith intermediate”.
  • the first monolith ion exchanger is obtained by introducing an ion exchange group into a monolith. Bubble-shaped macropores are overlapped with each other, and the overlapped portion is in a wet state in water with an average diameter of 30 to 300 ⁇ m, preferably 30. It is a continuous macropore structure having openings (mesopores) of ⁇ 200 ⁇ m, particularly 35 to 150 ⁇ m.
  • the average diameter of the opening of the monolith ion exchanger is larger than the average diameter of the opening of the monolith because the entire monolith swells when an ion exchange group is introduced into the monolith.
  • the average diameter of the openings is less than 30 ⁇ m, 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.
  • the average diameter of the opening of the monolith intermediate in the dry state, the average diameter of the opening of the monolith in the dry state, and the average diameter of the opening of the monolith ion exchanger in the dry state are values measured by a mercury intrusion method. It is.
  • the average diameter of the openings of the monolith ion exchanger in the wet state is a value calculated by multiplying the average diameter of the openings of the monolith ion exchanger in the dry state by the swelling rate.
  • the water-wet monolith ion exchanger has a diameter of x1 (mm)
  • the water-wet monolith ion exchanger is dried
  • the resulting dried monolith ion exchanger has a diameter of y1 ( mm)
  • the average diameter of the opening of the monolith ion exchanger in the dry state measured by the mercury intrusion method was z1 ( ⁇ m)
  • the average diameter of the opening of the dried monolith before introduction of the ion exchange group, and the swelling ratio of the monolith ion exchanger in the water wet state relative to the dried monolith when the ion exchange group is introduced into the dried monolith can also be calculated by multiplying the average diameter of the opening of the monolith in the dry state by the swelling rate.
  • the skeleton part area appearing in the cross section is 25 to 50%, preferably 25 to 45% in the image region. If the area of the skeleton part appearing in the cross section is less than 25% in the image region, it becomes a thin skeleton, which is not preferable because the ion exchange capacity per volume decreases, and if it exceeds 50%, the skeleton becomes too thick. Since the uniformity of ion exchange characteristics is lost, it is not preferable.
  • the monolith described in JP-A-2002-346392 has a limit to the blending ratio in order to ensure a common opening even if the blending ratio of the oil phase part to water is actually increased and the skeleton portion is thickened. Yes, the maximum value of the skeleton part area appearing in the cross section cannot exceed 25% in the image region.
  • the conditions for obtaining the SEM image may be any conditions as long as the skeleton appearing in the cross section of the cut surface appears clearly.
  • the magnification is 100 to 600
  • the photographic area is about 150 mm ⁇ 100 mm.
  • SEM observation is preferably performed on three or more images, preferably five or more images, taken at arbitrary locations on an arbitrary cut surface of the monolith excluding subjectivity and at different locations.
  • the monolith to be cut is in a dry state for use in an electron microscope.
  • FIG. 5 is a transcribed skeleton that appears as a cross section of the SEM photograph of FIG. In FIGS.
  • the skeleton portion (reference numeral 12)” in the present invention
  • the circular hole shown in FIG. 1 is an opening (mesopore)
  • a relatively large curvature or curved surface is a macropore (reference numeral 13 in FIG. 5).
  • the skeleton area shown in the cross section of FIG. 5 is 28% in the rectangular photographic region 11. Thus, the skeleton can be clearly determined.
  • the method for measuring the area of the skeletal part appearing in the cross section of the cut surface is not particularly limited, and after specifying the skeletal part by performing known computer processing or the like, calculation by automatic calculation or manual calculation by a computer or the like A method is mentioned.
  • the manual calculation includes a method in which an indefinite shape is replaced with an aggregate such as a quadrangle, a triangle, a circle, or a trapezoid, and the areas are obtained by stacking them.
  • the first monolith ion exchanger has a total pore volume of 0.5 to 5 ml / g, preferably 0.8 to 4 ml / g. If the total pore volume is less than 0.5 ml / g, the pressure loss during water passage is increased, which is not preferable. On the other hand, if the total pore volume exceeds 5 ml / g, the ion exchange capacity per volume decreases, which is not preferable.
  • the monolith ion exchanger of the present invention (A1) has an average diameter of openings and a total pore volume within the above ranges and is a bone skeleton, when this is used as an ion adsorbent, It has a large contact area and can exhibit excellent adsorption ability.
  • the total pore volume of the monolith is a value measured by a mercury intrusion method.
  • the total pore volume of the monolith is the same both in the dry state and in the water wet state.
  • transmit the 1st monolith ion exchanger is the pressure loss at the time of letting water flow through the column packed with 1 m of the porous body at a water flow velocity (LV) of 1 m / h (hereinafter referred to as the pressure loss) , “Differential pressure coefficient”) is preferably in the range of 0.001 to 0.1 MPa / m ⁇ LV, particularly 0.001 to 0.05 MPa / m ⁇ LV. If the differential pressure coefficient and the total pore volume are within this range, when this is used as an ion adsorbent, the contact area with the water to be treated is large, and smooth circulation of the water to be treated is possible. Since it has sufficient mechanical strength, it is preferable.
  • the first monolith ion exchanger has an ion exchange capacity of 0.4 to 5 mg equivalent / ml per volume when wet in water.
  • the conventional monolithic organic porous ion exchanger having a continuous macropore structure different from the present invention as described in JP-A-2002-306976 in order to achieve a low pressure loss that is practically required, When the opening diameter is increased, the total pore volume is increased accordingly, so that the ion exchange capacity per volume is decreased, and the total pore volume is decreased to increase the exchange capacity per volume. In addition, since the opening diameter is reduced, the pressure loss increases.
  • the monolith ion exchanger of the present invention (A1) can further increase the opening diameter and thicken the skeleton of the continuous macropore structure (thicken the skeleton wall), The ion adsorption performance can be dramatically increased while keeping the pressure loss low. If the ion exchange capacity per volume is less than 0.4 mg equivalent / ml, the amount of treated water to be treated before breakthrough is reduced and the frequency of module exchange is increased, which is not preferable.
  • the ion exchange capacity per weight of the monolith ion exchanger of the present invention (A1) is not particularly limited. However, since the ion exchange groups are uniformly introduced to the surface of the porous body and the inside of the skeleton, 3 to 5 mg Equivalent / g. The ion exchange capacity of a porous body in which ion exchange groups are introduced only on the surface cannot be determined unconditionally depending on the type of the porous body or ion exchange groups, but is at most 500 ⁇ g equivalent / g.
  • the material constituting the skeleton of the continuous macropore structure is an organic polymer material having a crosslinked structure.
  • the crosslink density of the polymer material is not particularly limited, but includes 0.3 to 50 mol%, preferably 0.3 to 5 mol% of cross-linked structural units with respect to all the structural units constituting the polymer material. It is preferable. If the cross-linking structural unit is less than 0.3 mol%, it is not preferable because the mechanical strength is insufficient. On the other hand, if it exceeds 50 mol%, embrittlement of the porous body proceeds and flexibility is lost. In particular, in the case of an ion exchanger, the amount of ion exchange groups introduced is decreased, which is not preferable.
  • the type of the polymer material is not particularly limited, and examples thereof include aromatic vinyl polymers such as polystyrene, poly ( ⁇ -methylstyrene), polyvinyl toluene, polyvinyl benzyl chloride, polyvinyl biphenyl, and polyvinyl naphthalene; polyolefins such as polyethylene and polypropylene; Poly (halogenated polyolefin) such as vinyl chloride and polytetrafluoroethylene; Nitrile-based polymer such as polyacrylonitrile; Cross-linking weight of (meth) acrylic polymer such as polymethyl methacrylate, polyglycidyl methacrylate, and polyethyl acrylate Coalesce is mentioned.
  • aromatic vinyl polymers such as polystyrene, poly ( ⁇ -methylstyrene), polyvinyl toluene, polyvinyl benzyl chloride, polyvinyl biphenyl, and polyvinyl naphthalene
  • the polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or a blend of two or more types of polymers. It may be what was done.
  • the cross-linking weight of the aromatic vinyl polymer is high due to the ease of forming a continuous macropore structure, the ease of introducing ion-exchange groups and the high mechanical strength, and the high stability to acids and alkalis.
  • a styrene-divinylbenzene copolymer and a vinylbenzyl chloride-divinylbenzene copolymer are particularly preferable materials.
  • Examples of the ion exchange group of the first monolith ion exchanger include cation exchange groups such as a sulfonic acid group, a carboxylic acid group, an iminodiacetic acid group, a phosphoric acid group, and a phosphoric acid ester group; a quaternary ammonium group and a tertiary amino group And anion exchange groups such as secondary amino group, primary amino group, polyethyleneimine group, tertiary sulfonium group, and phosphonium group. If the ion exchange group is a cation exchanger, metals that have a particularly adverse effect on semiconductor devices can be effectively removed.
  • 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
  • anion exchange groups such as secondary amino group, primary amino group, polyethyleneimine group, tertiary sulfonium group
  • the introduced ion exchange groups are uniformly distributed not only on the surface of the porous body but also within the skeleton of the porous body.
  • “ion exchange groups are uniformly distributed” means that the distribution of ion exchange groups is uniformly distributed on the surface and inside the skeleton in the order of at least ⁇ m. The distribution of ion exchange groups can be confirmed relatively easily by using EPMA or the like.
  • the ion exchange groups are uniformly distributed not only on the surface of the monolith but also within the skeleton of the porous body, the physical and chemical properties of the surface and the interior can be made uniform, so that the swelling and shrinkage can be achieved. The durability against is improved.
  • the first monolith ion exchanger is prepared by preparing a water-in-oil emulsion by stirring a mixture of oil-soluble monomer, surfactant and water that does not contain ion-exchange groups, and then polymerizing the water-in-oil emulsion.
  • Step I for obtaining a monolithic organic porous intermediate having a continuous macropore structure with a total pore volume of 5 to 16 ml / g, a vinyl monomer, a crosslinking agent having at least two vinyl groups in one molecule, a vinyl monomer
  • Step II for preparing a mixture comprising an organic solvent and a polymerization initiator that dissolves the cross-linking agent but does not dissolve the polymer formed by polymerization of the vinyl monomer.
  • the mixture obtained in Step II is allowed to stand still and in Step I.
  • Polymerization is performed in the presence of the obtained monolithic organic porous intermediate to obtain a thick organic porous body having a skeleton thicker than the skeleton of the organic porous intermediate. It is obtained by performing the IV step of introducing an ion exchange group into the thick organic porous material obtained in the step III.
  • the step I may be performed according to the method described in JP-A-2002-306976.
  • the oil-soluble monomer that does not contain an ion exchange group includes, for example, an ion exchange group such as a carboxylic acid group, a sulfonic acid group, and a quaternary ammonium group, and is soluble in water.
  • Low and lipophilic monomers may be mentioned.
  • Preferable examples of these monomers include styrene, ⁇ -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.
  • a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate is selected as at least one component of the oil-soluble monomer, and the content thereof is 0.3 to 50 mol% in the total oil-soluble monomer, preferably 0.3 to 5 mol% is preferable in that the mechanical strength necessary for introducing a large amount of ion-exchange groups in a later step can be obtained.
  • the surfactant is not particularly limited as long as it can form a water-in-oil (W / O) emulsion when an oil-soluble monomer containing no ion exchange group and water are mixed, and sorbitan monooleate,
  • Nonionic surfactants such as sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan trioleate, polyoxyethylene nonylphenyl ether, polyoxyethylene stearyl ether, polyoxyethylene sorbitan monooleate; potassium oleate
  • Anionic surfactants such as sodium dodecylbenzene sulfonate and dioctyl sodium sulfosuccinate; cationic surfactants such as distearyl dimethyl ammonium chloride; amphoteric surfactants such as lauryl dimethyl betaine can be used.
  • 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%.
  • a polymerization initiator may be used as necessary when forming a water-in-oil emulsion.
  • a compound that generates radicals by heat and light irradiation is preferably used.
  • the polymerization initiator may be water-soluble or oil-soluble.
  • the mixing method for mixing the oil-soluble monomer not containing an ion exchange group, a surfactant, water, and a polymerization initiator to form a water-in-oil emulsion is not particularly limited. Method of mixing at once, oil-soluble monomer, surfactant and oil-soluble polymerization initiator oil-soluble component and water or water-soluble polymerization initiator water-soluble component separately and uniformly dissolved, A method of mixing the components can be used.
  • 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.
  • 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.
  • a porous structure having a thick skeleton is formed using the structure of the monolith intermediate as a template.
  • the monolith intermediate is an organic polymer material having a crosslinked structure.
  • the crosslinking density of the polymer material is not particularly limited, but it contains 0.3 to 50 mol%, preferably 0.3 to 5 mol% of crosslinked structural units with respect to all the structural units constituting the polymer material. Is preferred. When the cross-linking structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable.
  • the total pore volume is as large as 10 to 16 ml / g, it is preferable to contain 2 mol% or more of crosslinked structural units in order to maintain a continuous macropore structure.
  • it exceeds 50 mol% the porous body becomes brittle and the flexibility is lost.
  • the type of polymer material of the monolith intermediate is not particularly limited, and examples thereof include the same materials as the monolith polymer material described above. Thereby, the same polymer can be formed in the skeleton of the monolith intermediate, and the skeleton can be thickened to obtain a monolith having a uniform skeleton structure.
  • the total pore volume of the monolith intermediate is 5 to 16 ml / g, preferably 6 to 16 ml / g. If the total pore volume is too small, the total pore volume of the monolith obtained after polymerizing the vinyl monomer becomes too small, and the pressure loss during water passage becomes large, which is not preferable. On the other hand, if the total pore volume is too large, the structure of the monolith obtained after polymerizing the vinyl monomer deviates from the continuous macropore structure, which is not preferable. In order to make the total pore volume of the monolith intermediate within the above numerical range, the ratio of monomer to water may be about 1: 5 to 1:20.
  • the average diameter of the opening (mesopore) that is the overlapping portion of the macropore and the macropore is 20 to 200 ⁇ m in a dry state.
  • the average diameter of the openings is less than 20 ⁇ m, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes small, and the pressure loss at the time of passing water becomes large, which is not preferable.
  • it exceeds 200 ⁇ m the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes too large, and the contact between the water to be treated and the monolith ion exchanger becomes insufficient.
  • the removal efficiency of ion components Is unfavorable because it decreases.
  • Monolith intermediates preferably have a uniform structure with uniform macropore size and aperture diameter, but are not limited to this, and the uniform structure is dotted with nonuniform macropores larger than the size of the uniform macropore. You may do.
  • Step II consists of a vinyl monomer, a crosslinking agent having at least two vinyl groups in one molecule, an organic solvent and a polymerization initiator that dissolves the vinyl monomer and the crosslinking agent but does not dissolve the polymer formed by polymerization of the vinyl monomer.
  • a step of preparing a mixture of there is no order of I process and II process, II process may be performed after I process, and I process may be performed after II process.
  • the vinyl monomer used in step II is not particularly limited as long as it is a lipophilic vinyl monomer containing a polymerizable vinyl group in the molecule and having high solubility in an organic solvent, but is allowed to coexist in the polymerization system. It is preferred to select a vinyl monomer that produces the same or similar polymer material as the monolith intermediate.
  • vinyl monomers include aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, vinyl toluene, vinyl benzyl chloride, vinyl biphenyl and vinyl naphthalene; ⁇ -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-me
  • the amount of these vinyl monomers added 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 material, the resulting monolith skeleton (the thickness of the monolith skeleton wall) cannot be increased, and the adsorption capacity per volume and the volume after introduction of ion-exchange groups. Since the ion exchange capacity per unit becomes small, it is not preferable. On the other hand, when the addition amount of vinyl monomer exceeds 40 times, the opening diameter becomes small, and the pressure loss at the time of passing water becomes large.
  • crosslinking agent used in Step II a crosslinking agent containing at least two polymerizable vinyl groups in the molecule and having high solubility in an organic solvent is preferably used.
  • the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol diacrylate, and the like. These crosslinking agents can be used singly or in combination of two or more.
  • Preferred cross-linking agents are aromatic polyvinyl compounds such as divinylbenzene, divinylnaphthalene and divinylbiphenyl because of their high mechanical strength and stability to hydrolysis.
  • the amount of the crosslinking agent used is preferably 0.3 to 50 mol%, particularly 0.3 to 5 mol%, based on the total amount of the vinyl monomer and the crosslinking agent.
  • 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.
  • it exceeds 50 mol% the brittleness of the monolith proceeds and the flexibility is lost, and the introduction amount of ion exchange groups is reduced. It is preferable to use it so as to be approximately equal to the crosslinking density of the monolith intermediate coexisting during the polymerization of the vinyl monomer / crosslinking agent. If the amounts used of both are too large, the crosslink density distribution is biased in the produced monolith, and cracks are likely to occur during the ion exchange group introduction reaction.
  • the organic solvent used in Step II is an organic solvent that dissolves the vinyl monomer and the crosslinking agent but does not dissolve the polymer formed by polymerization of the vinyl monomer. In other words, it is a poor solvent for the polymer formed by polymerization of the vinyl monomer. . Since the organic solvent varies greatly depending on the type of vinyl monomer, it is difficult to list general specific examples.
  • the organic solvent includes methanol, ethanol, propanol, butanol, Hexanol, cyclohexanol, octanol, II-ethylhexanol, decanol, dodecanol, alcohols such as ethylene glycol, propylene glycol, tetramethylene glycol, glycerin; diethyl ether, ethylene glycol dimethyl ether, cellosolve, methyl cellosolve, butyl cellosolve, polyethylene glycol, polypropylene Chain (poly) ethers such as glycol and polytetramethylene glycol; hexane, heptane, octane, isooctane, decane, dope
  • Examples include chain saturated hydrocarbons such as decane; esters such as ethyl acetate, isopropyl acetate, cellosolve acetate
  • organic solvent 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.
  • organic solvents are preferably used so that the vinyl monomer concentration is 30 to 80% by weight. If the amount of the organic solvent used deviates from the above range and the vinyl monomer concentration is less than 30% by weight, the polymerization rate is lowered, or the monolith structure after polymerization deviates from the range of the present invention. On the other hand, if the vinyl monomer concentration exceeds 80% by weight, the polymerization may run away, which is not preferable.
  • 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 (A1) 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-cyano (Valeric acid), 1,1′-azobis (cyclohexane-1-carbonitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, ammonium persulfate, tetramethylthiuram disulfide and the like.
  • the amount of the polymerization initiator used varies greatly depending on the type of monomer, polymerization temperature, etc., but can be used in the range of about 0.01 to 5% with respect to the total amount of vinyl monomer and crosslinking agent.
  • step III the mixture obtained in step II is allowed to stand and polymerize in the presence of the monolith intermediate obtained in step I to obtain a thick monolith having a skeleton thicker than the skeleton of the monolith intermediate. It is a process to obtain.
  • the monolith intermediate used in the step III plays a very important role in creating the monolith having the novel structure of the present invention. As disclosed in JP-A-7-501140 and the like, when a vinyl monomer and a crosslinking agent are allowed to stand in a specific organic solvent in the absence of a monolith intermediate, a particle aggregation type monolithic organic porous material is obtained. The body is obtained.
  • the vinyl monomer and the cross-linking agent are adsorbed or distributed from the liquid phase to the skeleton of the porous body, and polymerization proceeds in the porous body to obtain a thick skeleton monolith. It is thought that. Although the opening diameter is narrowed by the progress of the polymerization, since the total pore volume of the monolith intermediate is large, an appropriate opening diameter can be obtained even if the skeleton becomes thick.
  • the internal volume of the reaction vessel is not particularly limited as long as it is large enough to allow the monolith intermediate to exist in the reaction vessel.
  • the monolith intermediate 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.
  • the thick monolith after polymerization is not pressed from the inner wall of the container and enters the reaction container without any gap, and the monolith is not distorted, and the reaction raw materials are not wasted and efficient.
  • 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.
  • step III the monolith intermediate is placed in a reaction vessel impregnated with a mixture (solution).
  • the blending ratio of the mixture obtained in Step II and the monolith intermediate is such that, as described above, the amount of vinyl monomer added is 3 to 40 times, preferably 4 to 30 times, by weight with respect to the monolith intermediate. It is suitable to mix. Thereby, it is possible to obtain a monolith having a thick skeleton while having an appropriate opening diameter.
  • the vinyl monomer and the crosslinking agent in the mixture are adsorbed and distributed on the skeleton of the monolith intermediate that has been allowed to stand, and polymerization proceeds in the skeleton of the monolith intermediate.
  • Various polymerization conditions can be selected depending on the type of monomer and the type of initiator. For example, when 2,2′-azobis (isobutyronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile), benzoyl peroxide, lauroyl peroxide, potassium persulfate, etc. are used as initiators
  • the polymerization may be carried out by heating at 30 to 100 ° C. for 1 to 48 hours in a sealed container under an inert atmosphere. By heat polymerization, the vinyl monomer adsorbed and distributed on the skeleton of the monolith intermediate and the cross-linking agent are polymerized in the skeleton to thicken the skeleton. After completion of the polymerization, the contents are taken out and extracted with a solvent such as acetone for the purpose of removing unreacted vinyl monomer and organic solvent to obtain a thick monolith.
  • a solvent such as acetone
  • a method of introducing an ion exchange group is preferable in that the porous structure of the resulting monolith ion exchanger can be strictly controlled.
  • the method for introducing an ion exchange group into the monolith is not particularly limited, and a known method such as polymer reaction or graft polymerization can be used.
  • a method of introducing a sulfonic acid group if the monolith is a styrene-divinylbenzene copolymer, etc., a method of sulfonation using chlorosulfuric acid, concentrated sulfuric acid or fuming sulfuric acid; A method in which a mobile group is introduced into the skeleton surface and inside the skeleton, and graft polymerization of sodium styrenesulfonate or acrylamido-2-methylpropanesulfonic acid is performed; after glycidyl methacrylate is similarly grafted, a sulfonic acid group is introduced by functional group conversion.
  • a method for introducing a quaternary ammonium group if the monolith is a styrene-divinylbenzene copolymer or the like, a method of introducing a chloromethyl group with chloromethyl methyl ether or the like and then reacting with a tertiary amine; A method in which chloromethylstyrene and divinylbenzene are produced by copolymerization and reacted with a tertiary amine; N, N, N-trimethylammonium is introduced into the monolith by introducing radical initiation groups and chain transfer groups uniformly into the skeleton surface and inside the skeleton.
  • Examples include a method of graft polymerization of ethyl acrylate and N, N, N-trimethylammoniumpropylacrylamide; a method of grafting glycidyl methacrylate in the same manner and then introducing a quaternary ammonium group by functional group conversion.
  • Examples of the method for introducing betaine include a method in which a tertiary amine is introduced into a monolith by the above method and then introduced by reacting with monoiodoacetic acid.
  • 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.
  • the method is preferable in that the ion exchange group can be introduced uniformly and quantitatively.
  • the ion exchange groups to be introduced include cation exchange groups such as carboxylic acid groups, iminodiacetic acid groups, sulfonic acid groups, phosphoric acid groups, and phosphoric ester groups; quaternary ammonium groups, tertiary amino groups, and secondary amino groups. Groups, primary amino groups, polyethyleneimine groups, tertiary sulfonium groups, phosphonium groups and the like.
  • the first monolith ion exchanger swells greatly, for example, 1.4 to 1.9 times that of the thick monolith because the ion exchange group is introduced into the thick monolith. That is, the degree of swelling is much greater than that obtained by introducing an ion exchange group into a conventional monolith described in JP-A No. 2002-306976. For this reason, even if the opening diameter of the thick monolith is small, the opening diameter of the monolith ion exchanger generally increases at the above magnification. In addition, the total pore volume does not change even when the opening diameter increases due to swelling. Therefore, the first monolith ion exchanger has a high mechanical strength because it has a thick bone skeleton despite the remarkably large opening diameter.
  • the second monolith ion exchanger is a tertiary having a thickness of 1 to 60 ⁇ m made of an aromatic vinyl polymer containing 0.3 to 5.0 mol% of a cross-linking structural unit among all the structural units into which ion exchange groups are introduced.
  • a co-continuous structure composed of an originally continuous skeleton and three-dimensionally continuous pores having a diameter of 10 to 100 ⁇ m between the skeletons, with a total pore volume of 0.5 to 5 ml / g
  • the ion exchange capacity per volume in a wet state of water is 0.3 to 5 mg equivalent / ml, and the ion exchange groups are uniformly distributed in the porous ion exchanger.
  • the second monolith ion exchanger has a three-dimensionally continuous skeleton having an average thickness of 1 to 60 ⁇ m, preferably 3 to 58 ⁇ m in a water-wet state in which ion-exchange groups are introduced, and an average diameter between the skeletons.
  • a co-continuous structure composed of three-dimensionally continuous pores of 10 to 100 ⁇ m, preferably 15 to 90 ⁇ m, particularly 20 to 80 ⁇ m in a wet state. That is, as shown in the schematic diagram of FIG. 6, the co-continuous structure is a structure 10 in which a continuous skeleton phase 1 and a continuous vacancy phase 2 are intertwined and each of them is three-dimensionally continuous.
  • the continuous pores 2 have higher continuity of the pores than the conventional open-cell monolith and particle aggregation type monolith, and the size thereof is not biased. Therefore, it is possible to achieve extremely uniform ion adsorption behavior. Moreover, since the skeleton is thick, the mechanical strength is high.
  • the skeleton thickness and pore diameter of the second monolith ion exchanger are larger than the monolith skeleton thickness and pore diameter because the entire monolith swells when an ion exchange group is introduced into the monolith. It becomes.
  • These continuous pores have higher continuity of pores and are not biased in size compared to conventional open-cell monolithic organic porous ion exchangers and particle-aggregated monolithic organic porous ion exchangers. Therefore, extremely uniform ion adsorption behavior can be achieved. If the diameter of the three-dimensionally continuous pores is less than 10 ⁇ m, the pressure loss when passing through the fluid increases, which is not preferable.
  • the ion exchange characteristics are not uniform, that is, the length of the ion exchange zone becomes long, or a small amount of adsorbed ions are likely to leak, which is not preferable.
  • the thickness of the skeleton is less than 1 ⁇ m, it is not preferable because the ion exchange capacity per volume decreases and the mechanical strength decreases, which is not preferable.
  • the skeleton thickness is too large, Since the uniformity of the exchange characteristics is lost and the ion exchange zone length becomes long, it is not preferable.
  • the average diameter of the pores of the continuous structure in the water-wet state is a value calculated by multiplying the average diameter of the pores of the dry monolith ion exchanger measured by a known mercury intrusion method and the swelling ratio. is there.
  • the water-wet monolith ion exchanger has a diameter of x2 (mm)
  • the water-wet monolith ion exchanger is dried
  • the resulting dried monolith ion exchanger has a diameter of y2 ( mm)
  • the average diameter of the pores when the dried monolith ion exchanger was measured by the mercury intrusion method was z2 ( ⁇ m)
  • the average diameter of the pores of the dried monolith before introduction of the ion exchange groups, and the swelling ratio of the water-dried monolith ion exchanger with respect to the dried monolith when the ion exchange groups are introduced into the dried monolith can be calculated by multiplying the average diameter of the pores of the dry monolith by the swelling rate.
  • the average thickness of the skeleton of the continuous structure in the water-wet state is obtained by performing SEM observation of the dried monolith ion exchanger at least three times, and measuring the thickness of the skeleton in the obtained image. It is a value calculated by multiplying the average value by the swelling rate.
  • the water-wet monolith ion exchanger has a diameter of x3 (mm)
  • the water-wet monolith ion exchanger is dried
  • the resulting dried monolith ion exchanger has a diameter of y3
  • the average thickness of the skeleton of the dried monolith before the introduction of the ion exchange group, and the swelling ratio of the monolith ion exchanger in the water wet state relative to the dried monolith when the ion exchange group is introduced into the dried monolith can be calculated by multiplying the average thickness of the skeleton of the monolith in the dry state by the swelling ratio.
  • the skeleton has a rod-like shape and a circular cross-sectional shape, but may have a cross-section with a different diameter such as an elliptical cross-sectional shape. The thickness in this case is the average of the minor axis and the major axis.
  • the second monolith ion exchanger is not preferable because the ion exchange capacity per volume is lowered, and if it exceeds 100 ⁇ m, the ion exchange characteristics This is not preferable because the uniformity of the film is lost.
  • the definition and measurement method of the wall of the monolith ion exchanger are the same as those of the monolith.
  • the second monolith ion exchanger has a total pore volume of 0.5 to 5 ml / g. If the total pore volume is less than 0.5 ml / g, the pressure loss at the time of fluid permeation increases, which is not preferable. Further, the amount of water per unit cross-sectional area decreases, and the processing capacity decreases. It is not preferable. On the other hand, if the total pore volume exceeds 5 ml / g, the ion exchange capacity per volume decreases, which is not preferable.
  • the contact with the fluid is extremely uniform and the contact area is large, so the ion exchange zone length is shortened and the adsorbed ions It is difficult to cause a slight leak.
  • the fluid can be permeated under a low pressure loss, it exhibits excellent performance as an ion adsorbent.
  • the total pore volume of the monolith (monolith intermediate, monolith, monolith ion exchanger) is the same in the dry state and in the water wet state.
  • the pressure loss when water was permeated through the second monolith ion exchanger was the pressure loss when water was passed through a column filled with 1 m of a porous material at a water flow rate (LV) of 1 m / h (hereinafter referred to as “pressure loss”).
  • pressure loss a water flow rate of 1 m / h
  • pressure loss is in the range of 0.001 to 0.5 MPa / m ⁇ LV, particularly 0.001 to 0.1 MPa / m ⁇ LV. If the permeation rate and the total pore volume are within this range, when this is used as an ion adsorbent, the contact area with the water to be treated is large and the water to be treated can be smoothly distributed. It is preferable because of its high mechanical strength.
  • the material constituting the skeleton of the co-continuous structure includes 0.3 to 5 mol%, preferably 0.5 to 3.0 mol% of the crosslinked structural unit in all the structural units. It is an aromatic vinyl polymer containing and is hydrophobic. If the cross-linking structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable. On the other hand, if it exceeds 5 mol%, the structure of the porous body tends to deviate from the bicontinuous structure.
  • polystyrene poly ((alpha) -methylstyrene), polyvinyl toluene, polyvinyl benzyl chloride, polyvinyl biphenyl, polyvinyl naphthalene etc.
  • the polymer may be a polymer obtained by copolymerizing a single vinyl monomer and a crosslinking agent, a polymer obtained by polymerizing a plurality of vinyl monomers and a crosslinking agent, or a blend of two or more types of polymers. It may be what was done.
  • styrene-divinylbenzene copolymer is used because of its ease of forming a co-continuous structure, ease of introduction of ion-exchange groups, high mechanical strength, and high stability against acids and alkalis.
  • vinylbenzyl chloride-divinylbenzene copolymer is preferred.
  • the second monolith ion exchanger has an ion exchange capacity of 0.3 to 5 mg equivalent / ml per volume under water wet condition.
  • the conventional monolithic organic porous ion exchanger having a continuous macropore structure different from the present invention as described in JP-A-2002-306976 in order to achieve a low pressure loss that is practically required, When the opening diameter is increased, the total pore volume is increased accordingly, so that the ion exchange capacity per volume is decreased, and the total pore volume is decreased to increase the exchange capacity per volume. In addition, since the opening diameter is reduced, the pressure loss increases.
  • the monolith ion exchanger of the present invention since the monolith ion exchanger of the present invention has high continuity and uniformity of three-dimensionally continuous pores, the pressure loss does not increase so much even if the total pore volume is reduced. Therefore, the ion exchange capacity per volume can be dramatically increased while keeping the pressure loss low, and the replacement frequency of the module can be reduced.
  • the ion exchange capacity per weight in the dry state of the second monolith ion exchanger is not particularly limited. However, since the ion exchange groups are uniformly introduced to the skeleton surface and inside the skeleton of the porous body, 3 to 5 mg equivalent / g.
  • the ion exchange capacity of a porous body in which ion exchange groups are introduced only on the surface of the skeleton cannot be determined unconditionally depending on the kind of the porous body or ion exchange groups, but is at most 500 ⁇ g equivalent / g.
  • the ion exchange group in the second monolith ion exchanger is the same as the ion exchange group in the first monolith ion exchanger, and the description thereof is omitted.
  • the introduced ion exchange groups are uniformly distributed not only on the surface of the porous body but also inside the skeleton of the porous body.
  • the definition of the uniform distribution is the same as the definition of the uniform distribution of the first monolith ion exchanger.
  • the second monolith ion exchanger prepares a water-in-oil emulsion by stirring a mixture of oil-soluble monomer, surfactant and water that does not contain ion-exchange groups, and then polymerizes the water-in-oil emulsion.
  • Step I for obtaining a monolithic organic porous intermediate having a continuous macropore structure having a total pore volume of more than 16 ml / g and 30 ml / g or less, an aromatic vinyl monomer, and at least two or more vinyl groups in one molecule
  • the cross-linking agent aromatic vinyl monomer and cross-linking agent dissolved in the total oil-soluble monomer, but from the organic solvent and polymerization initiator that does not dissolve the polymer formed by polymerization of the aromatic vinyl monomer
  • Step II for preparing the mixture the mixture obtained in Step II is allowed to stand, and polymerization is performed in the presence of the monolithic organic porous intermediate obtained in Step I. III to obtain a continuous structure, obtained by performing the IV step of introducing ion exchange groups to resulting co-continuous structure in the step III.
  • the I step for obtaining the monolith intermediate in the second monolith ion exchanger may be performed according to the method described in JP-A-2002-306976.
  • the oil-soluble monomer not containing an ion exchange group for example, it does not contain an ion exchange group such as a carboxylic acid group, a sulfonic acid group, a quaternary ammonium group, has low solubility in water, and is lipophilic These monomers are mentioned.
  • these monomers include aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, vinyl toluene, vinyl benzyl chloride, vinyl biphenyl and vinyl naphthalene; ⁇ -olefins such as ethylene, propylene, 1-butene and isobutene; butadiene Diene monomers such as vinyl chloride, vinyl bromide, vinylidene chloride and tetrafluoroethylene; nitrile monomers such as acrylonitrile and methacrylonitrile; vinyl esters such as vinyl acetate and vinyl propionate Methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethyl methacrylate Sill, cyclohexyl methacrylate, benzyl mono
  • aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, vinyl toluene, vinyl benzyl chloride, divinyl benzene and the like.
  • aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, vinyl toluene, vinyl benzyl chloride, divinyl benzene and the like.
  • a crosslinkable monomer such as divinylbenzene or ethylene glycol dimethacrylate is selected as at least one component of the oil-soluble monomer, and its content is 0.3 to 5 mol%, preferably 0.3 to 3 mol% is preferable in that a mechanical strength necessary for introducing a large amount of ion-exchange groups in a later step can be obtained.
  • the surfactant is the same as the surfactant used in step I of the first monolith ion exchanger, and the description thereof is omitted.
  • a polymerization initiator may be used as necessary when forming a water-in-oil emulsion.
  • a compound that generates radicals by heat and light irradiation is preferably used.
  • the polymerization initiator may be water-soluble or oil-soluble.
  • 2,2′-azobis isobutyronitrile
  • 2,2′-azobis (2,4-dimethylvaleronitrile) 2
  • 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile) dimethyl 2,2′-azobisisobutyrate
  • 4,4′-azobis 4-cyanovaleric acid
  • 1,1'-azobis cyclohexane-1-carbonitrile
  • benzoyl peroxide lauroyl peroxide
  • potassium persulfate ammonium persulfate
  • tetramethylthiuram disulfide hydrogen peroxide-ferrous chloride Sodium persulfate-sodium acid sulfite and the like.
  • the monolith intermediate obtained in the step I is an organic polymer material having a crosslinked structure, preferably an aromatic vinyl polymer.
  • the crosslinking density of the polymer material is not particularly limited, but it contains 0.3 to 5 mol%, preferably 0.3 to 3 mol% of crosslinked structural units with respect to all the structural units constituting the polymer material. Is preferred.
  • the cross-linking structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable.
  • the structure of the monolith tends to deviate from the co-continuous structure, which is not preferable.
  • the cross-linking structural unit is preferably less than 3 mol.
  • the type of the polymer material of the monolith intermediate is the same as the type of the polymer material of the monolith intermediate of the first monolith ion exchanger, and the description thereof is omitted.
  • the total pore volume of the monolith intermediate is more than 16 ml / g and not more than 30 ml / g, preferably 6 to 25 ml / g.
  • this monolith intermediate basically has a continuous macropore structure, but the opening (mesopore) that is the overlapping part of the macropore and the macropore is remarkably large, so that the skeleton constituting the monolith structure is primary from the two-dimensional wall surface. It has a structure as close as possible to the original rod-like skeleton.
  • a porous body having a co-continuous structure is formed using the structure of the monolith intermediate as a template.
  • the ratio of monomer to water may be approximately 1:20 to 1:40.
  • the average diameter of openings is 5 to 100 ⁇ m in a dry state. If the average diameter of the openings is less than 5 ⁇ m, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes small, and the pressure loss during water passage becomes large, which is not preferable. On the other hand, if it exceeds 100 ⁇ m, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes too large, and the contact between the water to be treated and the monolith ion exchanger becomes insufficient, resulting in adsorption characteristics and ion exchange. This is not preferable because the characteristics deteriorate.
  • 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.
  • the step II includes 0.3 to 5 mol% of a crosslinking agent in the aromatic vinyl monomer and the total oil-soluble monomer having at least two or more vinyl groups in one molecule.
  • This is a step of preparing a mixture comprising an organic solvent and a polymerization initiator that dissolves the aromatic vinyl monomer and the crosslinking agent but does not dissolve the polymer formed by polymerization of the aromatic vinyl monomer.
  • II process may be performed after I process, and I process may be performed after II process.
  • the aromatic vinyl monomer used in step II includes a lipophilic aromatic vinyl monomer that contains a polymerizable vinyl group in the molecule and has high solubility in an organic solvent. If it is, there is no particular limitation, but it is preferable to select a vinyl monomer that produces the same or similar polymer material as the monolith intermediate coexisting in the polymerization system. Specific examples of these vinyl monomers include styrene, ⁇ -methylstyrene, vinyl toluene, vinyl benzyl chloride, vinyl biphenyl, vinyl naphthalene and the like. These monomers can be used alone or in combination of two or more. Aromatic vinyl monomers preferably used in the present invention are styrene, vinyl benzyl chloride and the like.
  • the amount of these aromatic vinyl monomers added is 5 to 50 times, preferably 5 to 40 times, by weight with respect to the monolith intermediate coexisting during polymerization. If the amount of aromatic vinyl monomer added is less than 5 times that of the porous material, the rod-like skeleton cannot be thickened, the ion exchange capacity per volume after the introduction of ion exchange groups is reduced, and excellent ion exchange capacity is obtained. Cannot be demonstrated.
  • crosslinking agent used in Step II a crosslinking agent containing at least two polymerizable vinyl groups in the molecule and having high solubility in an organic solvent is preferably used.
  • the crosslinking agent include divinylbenzene, divinylnaphthalene, divinylbiphenyl, ethylene glycol dimethacrylate, trimethylolpropane triacrylate, butanediol diacrylate, and the like. These crosslinking agents can be used singly or in combination of two or more.
  • Preferred cross-linking agents are aromatic polyvinyl compounds such as divinylbenzene, divinylnaphthalene and divinylbiphenyl because of their high mechanical strength and stability to hydrolysis.
  • the amount of the crosslinking agent used is 0.3 to 5 mol%, particularly 0.3 to 3 mol%, based on the total amount of vinyl monomer and crosslinking agent (total oil-soluble monomer).
  • amount of the crosslinking agent used is less than 0.3 mol%, it is not preferable because the mechanical strength of the monolith is insufficient.
  • amount is too large, the brittleness of the monolith proceeds and the flexibility is lost. This is not preferable because a problem arises in that the amount of introduction of is reduced.
  • the said crosslinking agent usage-amount so that it may become substantially equal to the crosslinking density of the monolith intermediate body coexisted at the time of vinyl monomer / crosslinking agent polymerization. If the amounts used of both are too large, the crosslink density distribution is biased in the produced monolith, and cracks are likely to occur during the ion exchange group introduction reaction.
  • the organic solvent used in step II is an organic solvent that dissolves the aromatic vinyl monomer and the crosslinking agent but does not dissolve the polymer formed by polymerization of the aromatic vinyl monomer, in other words, is formed by polymerization of the aromatic vinyl monomer. It is a poor solvent for polymers. Since the organic solvent varies greatly depending on the type of the aromatic vinyl monomer, it is difficult to list general specific examples.
  • the organic solvent includes methanol, ethanol, Alcohols such as propanol, butanol, hexanol, cyclohexanol, octanol, 2-ethylhexanol, decanol, dodecanol, propylene glycol, tetramethylene glycol; chain structures such as diethyl ether, butyl cellosolve, polyethylene glycol, polypropylene glycol, polytetramethylene glycol (Poly) ethers; chain saturated hydrocarbons such as hexane, heptane, octane, isooctane, decane, dodecane; ethyl acetate, isopropyl acetate, cellosolve acetate, propionic acid Examples include esters such as ethyl.
  • organic solvent even if it is a good solvent of polystyrene like a dioxane, THF, and toluene, when it is used with the said poor solvent and the usage-amount is small, it can be used as an organic solvent.
  • These organic solvents are preferably used so that the concentration of the aromatic vinyl monomer is 30 to 80% by weight. If the amount of the organic solvent used deviates from the above range and the aromatic vinyl monomer concentration becomes less than 30% by weight, the polymerization rate is lowered, or the monolith structure after polymerization deviates from the scope of the present invention, which is not preferable. On the other hand, if the concentration of the aromatic vinyl monomer exceeds 80% by weight, the polymerization may run away, which is not preferable.
  • the polymerization initiator is the same as the polymerization initiator used in Step II of the first monolith ion exchanger, and the description thereof is omitted.
  • the mixture obtained in the step II is allowed to stand, and polymerization is performed in the presence of the monolith intermediate obtained in the step I.
  • This is a process of changing the continuous macropore structure of the body to a co-continuous structure to obtain a monolith with a bone skeleton.
  • the monolith intermediate used in the step III plays a very important role in creating the monolith having the novel structure of the present invention.
  • JP-A-7-501140 and the like when a vinyl monomer and a crosslinking agent are allowed to stand in a specific organic solvent in the absence of a monolith intermediate, a particle aggregation type monolithic organic porous material is obtained. The body is obtained.
  • the vinyl monomer and the crosslinking agent are adsorbed or distributed from the liquid phase to the skeleton of the porous body, and polymerization proceeds in the porous body. It is considered that the skeleton constituting the monolith structure is changed from a two-dimensional wall surface to a one-dimensional rod-like skeleton to form a monolithic organic porous body having a co-continuous structure.
  • the internal volume of the reaction vessel is the same as the description of the internal volume of the reaction vessel of the first monolith ion exchanger, and the description thereof is omitted.
  • step III the monolith intermediate is placed in a reaction vessel impregnated with a mixture (solution).
  • the blending ratio of the mixture obtained in Step II and the monolith intermediate is 5 to 50 times, preferably 5 to 40 times, by weight of the aromatic vinyl monomer added to the monolith intermediate. It is preferable to blend them as described above. Thereby, it is possible to obtain a monolith having a co-continuous structure in which pores of an appropriate size are three-dimensionally continuous and a thick skeleton is three-dimensionally continuous.
  • the aromatic vinyl monomer and the cross-linking agent in the mixture are adsorbed and distributed on the skeleton of the monolith intermediate that is allowed to stand, and polymerization proceeds in the skeleton of the monolith intermediate.
  • the basic structure of a monolith having a co-continuous structure is a three-dimensional continuous skeleton with an average thickness of 0.8 to 40 ⁇ m in a dry state, and a three-dimensional continuous sky with a diameter of 8 to 80 ⁇ m between the skeletons.
  • This is a structure in which holes are arranged.
  • the average diameter of the three-dimensionally continuous pores can be obtained as a maximum value of the pore distribution curve by measuring the pore distribution curve by the mercury intrusion method.
  • the thickness of the skeleton of the monolith may be calculated by performing SEM observation at least three times and measuring the average thickness of the skeleton in the obtained image.
  • a monolith having a co-continuous structure has a total pore volume of 0.5 to 5 ml / g.
  • Polymerization conditions are the same as the description of the polymerization conditions in the III step of the first monolith ion exchanger, and the description thereof is omitted.
  • the method for introducing an ion exchange group into a monolith having a co-continuous structure is the same as the method for introducing an ion exchange group into a monolith in the first monolith ion exchanger, and the description thereof is omitted.
  • the second monolith ion exchanger swells to a large extent 1.4 to 1.9 times that of the monolith, for example, because the ion exchange group is introduced into the monolith having a co-continuous structure. Further, the total pore volume does not change even if the pore diameter becomes larger due to swelling. Therefore, the second monolith ion exchanger has a high mechanical strength because it has a thick bone skeleton even though the size of three-dimensionally continuous pores is remarkably large. In addition, since the skeleton is thick, it is possible to increase the ion exchange capacity per volume in a wet state of water, and it is possible to pass water to be treated for a long time at a low pressure and a large flow rate. be able to.
  • the third monolith ion exchanger is filled in the container.
  • “monolithic organic porous material” is simply “composite monolith”
  • “monolithic organic porous ion exchanger” is simply “composite monolithic ion exchanger”
  • the “monolithic organic porous intermediate” is also simply referred to as “monolith intermediate”.
  • 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 to the skeleton surface of the organic porous body. Or an organic porous body composed of a continuous skeleton phase and a continuous pore phase and a size formed on the skeleton surface of the organic porous body.
  • 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.
  • a "particle body” and a “projection body” may be collectively called “particle body etc.”
  • 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.
  • bubble-like macropores overlap each other, and the overlapped portion is a continuous macropore structure in which an opening having an average diameter of 30 to 150 ⁇ m is formed in a water wet state, and an average thickness is 1 in a water wet state.
  • Examples thereof include a co-continuous structure comprising a three-dimensionally continuous skeleton of ⁇ 60 ⁇ m and three-dimensionally continuous pores having an average diameter of 10 to 100 ⁇ m in a wet state between the skeletons.
  • the average diameter of the opening of the composite monolith ion exchanger having a continuous macropore structure is larger than the average diameter of the opening of the composite monolith in the dry state because the entire composite monolith swells when an ion exchange group is introduced into the composite monolith. Become. If the average diameter of the openings is less than 30 ⁇ m, 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.
  • the diameter of the three-dimensionally continuous pores is less than 10 ⁇ m, it is not preferable because the pressure loss at the time of fluid permeation increases, and if it exceeds 100 ⁇ m As a result, the contact between the composite monolith ion exchanger and the composite monolith ion exchanger becomes insufficient, and as a result, the ion exchange characteristics are not uniform, that is, the ion exchange zone length becomes long, or a slight leak of adsorbed ions is likely to occur.
  • a composite monolith ion exchanger having a co-continuous structure if the diameter of a three-dimensionally continuous skeleton is less than 1 ⁇ m, it is not preferable because the ion exchange capacity per volume decreases, and if it exceeds 60 ⁇ m, ion exchange Since the uniformity of characteristics is lost, it is not preferable.
  • the average diameter of the openings of the monolith intermediate in the dry state, the average diameter of the pores or openings of the composite monolith in the dry state, and the average of holes or openings of the composite monolith ion exchanger in the dry state The diameter is a value measured by a mercury intrusion method.
  • the average diameter of the pores or openings of the composite monolith ion exchanger in a wet state is the average diameter of the pores or openings of the dry composite monolith ion exchanger. Is a value calculated by multiplying the swelling ratio, and the specific calculation method is the same as the calculation method of the invention (A1).
  • the preferred value of the average diameter of the pores in the wet state of the composite monolith ion exchanger is 10 to 120 ⁇ m.
  • the preferred pore diameter of the composite monolith ion exchanger is 30 to 120 ⁇ m, and the organic porous body constituting the composite monolith ion exchanger is a co-continuous structure.
  • the preferable value of the pore diameter of the composite monolith ion exchanger is 10 to 90 ⁇ m.
  • the diameter of the particles and the size of the protrusions in a wet state of water are 4 to 40 ⁇ m, preferably 4 to 30 ⁇ m, particularly preferably 4 to 20 ⁇ m.
  • 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 cannot be said to be granular A thing is called a protrusion.
  • FIG. 29 shows a schematic cross-sectional view of the protrusion. As shown in FIGS.
  • the protrusions protruding from the skeleton surface 61 are the protrusions 62.
  • the protrusions 62 are like the protrusions 62a shown in FIG.
  • 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.
  • 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.
  • the proportion of 4 to 40 ⁇ m particles in a wet state in water is 70% or more, preferably 80% or more.
  • the ratio of 4 to 40 ⁇ m particles in the wet state in all particles refers to the number ratio of 4 to 40 ⁇ m particles in the wet state in the total number of particles.
  • 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.
  • the total particle body and the like are all the particle bodies formed on the surface of the skeleton layer, including all the particle bodies and protrusions in a size range other than 4 to 40 ⁇ m particle bodies in a 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.
  • the diameter of the composite monolith ion exchanger in the water wet state is x4 (mm)
  • the diameter or size of the particles in the SEM image of the dried composite monolith ion exchanger observed by SEM is z4 ( ⁇ m).
  • 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 the particles in the range of 4 to 40 ⁇ m are observed, and when confirmed in the entire field of view, the diameter or size is 4 to 40 ⁇ m in a wet state on the skeleton surface of the composite monolith ion exchanger.
  • the particle body at is formed.
  • the diameter or size of all particles in the SEM image in the water wet state is calculated for each field of view according to the above, and particles of 4 to 40 ⁇ m in the water wet state occupying the whole particles for each field of view.
  • the proportion of the particles, etc. is 4% to 40 ⁇ m in the wet state in all the particles in the entire visual field is 70% or more
  • the skeleton surface of the composite monolith ion exchanger is obtained. It is determined that the proportion of 4 to 40 ⁇ m particles in the wet state is 70% or more in all particles formed in 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.
  • 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 in the water wet state with respect to the composite monolith in the dry state when the ion exchange group is introduced into the composite monolith in the dry state When the swelling rate of the exchanger is known, the diameter or size of the particle of the composite monolith in the dry state is multiplied by the swelling rate to obtain the diameter or size of the particle of the composite monolith ion exchanger in the 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 particles of 4 to 40 ⁇ m in the water wet state, etc. occupy in the whole particles. It is also possible to determine the ratio, the ratio of the surface of the skeleton layer covered with particles, and the like.
  • 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.
  • the method for measuring the coverage with the particle bodies include an image analysis method using an SEM image of a composite monolith (dry body).
  • the total pore volume of the composite monolith ion exchanger is the same as the total pore volume of the composite monolith. That is, even when the ion exchange group is introduced into the composite monolith to swell and increase the opening diameter, the total pore volume hardly changes because the skeletal phase is thick. If the total pore volume is less than 0.5 ml / g, the pressure loss during water passage is increased, which is not preferable. On the other hand, if the total pore volume exceeds 5 ml / g, the ion exchange capacity per volume decreases, which is not preferable. 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.
  • the composite monolith ion exchanger of the present invention (A2) has an ion exchange capacity of 0.2 mg equivalent / ml or more, preferably 0.3 to 1.8 mg equivalent / ml per volume when wet in water. Have. If the ion exchange capacity per volume is less than 0.2 mg equivalent / ml, the amount of treated water to be treated before breakthrough decreases, and the frequency of module replacement increases, which is not preferable.
  • the ion exchange capacity per weight in the dry state of the composite monolith ion exchanger of the present invention (A2) is not particularly limited, but the ion exchange groups are uniformly introduced to the surface of the composite monolith and the inside of the skeleton. 3-5 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 ⁇ g equivalent / g at most.
  • Examples of the ion exchange group to be introduced into the composite monolith of the present invention (A2) include the same ion exchange groups as those of the invention (A1).
  • the composite monolith ion exchanger of the present invention (A2) 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.
  • 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 stirs 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.
  • Step II for preparing a mixture comprising the following: polymerization in the presence of the mixture obtained in Step II and standing in the presence of the monolithic organic porous intermediate obtained in Step I
  • the following steps (1) to (5) are carried out when the monolithic organic porous material is produced by performing the step III and the IV step of introducing an ion exchange group into the monolithic organic porous material obtained in the step III.
  • 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 .
  • the step I comprises an oil-soluble monomer containing no ion exchange group, a first crosslinking agent having at least two vinyl groups in one molecule, a surfactant and water.
  • 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.
  • oil-soluble monomer that does not contain an ion exchange group examples 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 and has low solubility in water.
  • 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 and has low solubility in water.
  • these monomers include styrene, ⁇ -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.
  • first crosslinking agent having at least two or more vinyl groups in one molecule examples 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.
  • 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 dodecylbenzene sulfonate and dioctyl sodium sulfosuccinate; cationic surfactants such as distearyl dimethyl ammonium chloride; amphoteric surfactants such as lauryl dimethyl betaine can be used.
  • 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%.
  • a polymerization initiator may be used as necessary when forming a water-in-oil emulsion.
  • a compound that generates radicals by heat and light irradiation is preferably used.
  • the polymerization initiator may be water-soluble or oil-soluble.
  • 2,2′-azobis isobutyronitrile
  • 2,2′-azobis (2,4-dimethylvaleronitrile) 2
  • 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
  • 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.
  • mixing apparatus for forming the emulsion
  • 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.
  • an appropriate apparatus may be selected to obtain the desired emulsion particle size.
  • 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.
  • 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.
  • the monolith intermediate is an organic polymer material having a crosslinked structure.
  • the crosslinking density of the polymer material is not particularly limited, but 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.
  • the cross-linking structural unit is less than 0.3 mol%, the mechanical strength is insufficient, which is not preferable.
  • 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 to 30 ml / g, preferably 6 to 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 make the total pore volume of the monolith intermediate within the above numerical range, the ratio of monomer to water (weight) may be set to approximately 1: 5 to 1:35.
  • the ratio of this monomer to water is approximately 1: 5 to 1:20, a monolith intermediate having a total macropore structure of 5 to 16 ml / g and a continuous macropore structure can be obtained and obtained through the step III.
  • the resulting composite monolithic organic porous body has a continuous macropore structure.
  • the blending ratio is approximately 1:20 to 1:35, a monolith intermediate having a total pore volume exceeding 16 ml / g and having 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 a bicontinuous structure.
  • the average diameter of the opening (mesopore) that is the overlapping portion of the macropore and the macropore is 20 to 100 ⁇ m in a dry state.
  • the average diameter of the openings is less than 20 ⁇ m, the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes small, and the pressure loss at the time of passing water becomes large, which is not preferable.
  • it exceeds 100 ⁇ m the opening diameter of the monolith obtained after polymerizing the vinyl monomer becomes too large, and the contact between the water to be treated and the monolith ion exchanger becomes insufficient.
  • the removal efficiency of ion components Is unfavorable because it decreases.
  • Monolith intermediates preferably have a uniform structure with uniform macropore size and aperture diameter, but are not limited to this, and the uniform structure is dotted with nonuniform macropores larger than the size of the uniform macropore. You may do.
  • Step II 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.
  • 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.
  • these vinyl monomers include aromatic vinyl monomers such as styrene, ⁇ -methylstyrene, vinyl toluene, vinyl benzyl chloride, vinyl biphenyl and vinyl naphthalene; ⁇ -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 acryl
  • the amount of these vinyl monomers added 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.
  • the second cross-linking 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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
  • Step III is a step in which the mixture obtained in Step II is allowed to stand still and in the presence of the monolith intermediate obtained in Step I, to obtain a composite monolith.
  • the monolith intermediate used in Step III plays an extremely important role in creating a monolith having a novel structure of the present invention (A2).
  • A2 As disclosed in JP-A-7-501140, etc., when a vinyl monomer and a second crosslinking 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.
  • 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.
  • the monolith intermediate 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.
  • the composite monolith after polymerization does not receive any pressure from the inner wall of the container and enters the reaction container without any gap, so that the composite monolith is not distorted and the reaction raw materials are not wasted and efficient.
  • the vinyl monomer and the cross-linking agent are adsorbed and distributed on the monolith intermediate. A particle aggregate structure is not generated in the gap portion.
  • step III the monolith intermediate is placed in a reaction vessel impregnated with a mixture (solution).
  • the blending ratio of the mixture obtained in Step II and the monolith intermediate is such that, as described above, the amount of vinyl monomer added is 3 to 40 times, preferably 4 to 30 times, by weight with respect 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.
  • 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.
  • a solvent such as acetone
  • the step II or step III is performed under the conditions satisfying at least one of the following conditions (1) to (5), the characteristic structure of the present invention (A2) is obtained.
  • a composite monolith in which particles and the like are formed on the skeleton surface can be produced.
  • 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.
  • 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.
  • 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 organic solvent used in step II is a polyether having a molecular weight of 200 or more.
  • the concentration of the vinyl monomer used in Step II is 30% by weight or less in the mixture of Step II.
  • 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.
  • 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.
  • the lower limit of the polymerization temperature is not particularly limited, but 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 half-temperature of 10 hours. It is preferable to set to a low range.
  • 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.
  • 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.
  • the preferred multiple of the second crosslinker mol% is 2 to 10 times.
  • 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.
  • the composite monolith of the present invention (A2) is obtained.
  • 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.
  • two types of homopolymers obtained from two types of monomers that are slightly different in structure are not compatible with each other.
  • 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.
  • 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. .
  • the affinity with the monolith intermediate dramatically decreases and shows little affinity with the monolith intermediate.
  • 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 preferred polyether has a molecular weight of 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.
  • the composite monolith obtained in the step III includes an organic porous body composed of a continuous skeleton phase and a continuous pore phase, a large number of particles fixed to the skeleton surface of the organic porous body, or a skeleton surface of the organic porous body. It is a composite structure with a number of protrusions formed on it.
  • the continuous skeleton phase and the continuous pore phase of the organic porous body can be observed by SEM images.
  • the basic structure of the organic porous body is a continuous macropore structure or a co-continuous structure.
  • the continuous macropore structure in the composite monolith is such that bubble-shaped macropores overlap each other, and the overlapping portion becomes an opening having an average diameter of 20 to 100 ⁇ m in a dry state.
  • the bicontinuous structure in the composite monolith has an average thickness. Consists of a three-dimensionally continuous skeleton of 0.8 to 40 ⁇ m in a dry state and three-dimensionally continuous pores having an average diameter of 8 to 80 ⁇ m 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 the same as the method for introducing an ion exchange group into the monolith in the invention (A1).
  • An ion adsorption module includes a container having at least an opening through which water to be treated flows, and a first monolith ion exchanger, a second monolith ion exchanger, or a third filled in the container. And a monolith ion exchanger.
  • this container has only an opening through which water to be treated flows, it can be applied to a batch processing method in which the ion adsorption module is put into water in a storage container or storage tank to purify the water.
  • the contact form of the water to be treated and the ion adsorption module is not particularly limited as long as the water to be treated and the monolith ion exchanger are brought into contact with each other, and the upward flow flows into a simple cylindrical or polygonal packed bed.
  • a method of passing water in a downward flow an external pressure method of passing water from the outer circumferential direction to the inner cylinder, an internal pressure method of passing water in the reverse direction, and filling a large number of cylindrical organic porous bodies, an internal pressure method
  • a tubular system that allows water to flow by an external pressure system a flat film system that uses a sheet-like packed bed, a pleat system that is molded into a shape in which the flat film is folded, and the like can be exemplified.
  • a block shape, a sheet shape, a plate shape, a columnar shape, a cylindrical shape, or the like is selected according to the shape of the container of the module taking the adsorption form.
  • the monolith ion exchanger may be formed into a spherical or irregular granular small block of 0.1 mm to 10 mm, and this small block may be filled into a container to form a packed bed. Examples of a method for forming these various types of monolith ion exchangers include a method by cutting from a block monolith ion exchanger.
  • the type and packing form of the monolith ion exchanger filled in the container are not particularly limited, and can be arbitrarily determined depending on the purpose of use and the type of ionic impurities to be adsorbed. Specifically, a form in which a monolith cation exchanger and a monolith anion exchanger are filled alone or mixed in the container can be mentioned.
  • a form to mix the monolith ion exchanger a form formed or processed into a block shape, a sheet shape, a plate shape, or a column shape is laminated in the water flow direction, or a small block monolith ion exchanger is mixed. And filling form.
  • a monolithic cation exchanger and a monolith anion exchanger stacked and filled are preferable because the monolith ion exchanger can be easily produced and filled into a container.
  • a granular ion exchange resin packed layer and the monolith ion exchanger packed layer are laminated in this order from the upstream side, and the monolith ion exchanger
  • the ion adsorption module filled with is arranged downstream of the ion adsorption module filled with a granular ion exchange resin.
  • the former form can omit connection piping compared with the latter form.
  • the granular ion exchange resin on the upstream side is preferably a mixed ion exchange resin of a cation exchange resin and an anion exchange resin
  • the monolith ion exchanger on the downstream side is preferably a stacked packed layer of a monolith cation exchanger and a monolith anion exchanger.
  • the shape of the ion exchange module used in the present invention is not particularly limited, and examples thereof include a column shape, a flat shape, and a tower shape having an end plate portion at a lower portion.
  • a flat (small drum-shaped) ion exchange module is a water treatment method in which the ion exchanger packed layer is short in the direction of water flow and long in the direction (diameter) perpendicular to the direction of water flow, and water flow and regeneration are performed in a short time. Suitable for.
  • a so-called ion exchange tower having an end plate portion in the lower part is used in the case of stacking and filling the granular ion exchange resin and the monolith ion exchanger in the other embodiment.
  • a so-called ion exchange tower having a mirror plate part in a conventional lower part has a desalting part filled with a granular ion exchange resin from the upstream side to the downstream side, and a pumice stone serving as the eyeplate or distributor.
  • the monolith ion exchanger is filled instead of the end plate or pumice (tecapore) of the end plate part, Well, this increases the adsorption efficiency of ionic impurities in high-speed flow, and the monolith ion exchanger serves as a distributor, so that the number of components in the tower can be reduced, and the packed bed moves by regeneration by upward flow. There will be no reproduction efficiency.
  • the monolith ion exchanger can be obtained, for example, in the form of a block that fits into a filling container, and is easily filled.
  • the water treatment method of the present invention comprises a method for adsorbing and removing ionic impurities in the water to be treated by bringing the water to be treated into contact with the monolith ion exchanger (first method of water treatment) and In this method, the first treated water obtained by bringing the ion exchange resin into contact is further brought into contact with the monolith ion exchanger to obtain the second treated water (second water treatment method).
  • first method of water treatment a method for adsorbing and removing ionic impurities in the water to be treated by bringing the water to be treated into contact with the monolith ion exchanger
  • second water treatment method In the first water treatment method, when the water to be treated is treated with a small amount of ionic impurities, for example, conductivity of 0.1 to 100 mS / m, the monolith ion exchanger can be easily filled. Therefore, it is suitable for a water treatment method that uses a small apparatus and regenerates frequently.
  • the ion exchange zone length can be kept short even at a high flow rate, and the volume of the ion exchanger apparatus can be reduced.
  • the adsorption rate is high even if the amount of ionic impurities is very small, and the leak of adsorbed ions hardly occurs. That is, since the particle size of the granular ion exchange resin is 0.2 to 0.5 mm, the diffusion rate inside and outside the particle is greatly different, and when the flow rate is increased, the ion adsorption part and the non-adsorption part are mixed regions.
  • the exchange zone length becomes long and a slight leak of adsorbed ions occurs, the total exchange capacity is large, so that rough ion removal is possible.
  • the ion exchange zone length can be kept short even at a high flow rate. Therefore, by installing the granular ion exchange resin on the upstream side and the monolith ion exchanger on the downstream side, first, a large amount of ionic substances are removed, and then the residual ions are removed with high efficiency. It is possible to reduce the length of the exchange zone, reduce the volume of the ion adsorption tower, and improve the adsorption efficiency at a high flow rate. Therefore, the ion adsorption module can be used as an alternative to a cartridge polisher used in a subsystem of a conventional ultrapure water production apparatus, for example.
  • the monolith ion exchanger is made into an ion form having lower adsorption selectivity than the removal target ions in the treated water, and then the treated water is passed through to adsorb the target ions in the treated water.
  • a method of removing the ions having low adsorption selectivity into the water to be treated may be used.
  • the ions to be removed are calcium ions and magnesium ions
  • sodium ions having a lower selective adsorptivity are adsorbed on the monolith ion exchanger and used for water treatment. This method is preferable in that it is not necessarily required to remove all the ions when scale prevention is the main purpose of water treatment, such as boiler feed water, and it can be safely and inexpensively regenerated.
  • the monolith ion exchanger is a cation exchanger, and after the cation exchanger is made into a sodium form, the water to be treated is passed through and the hardness component in the water to be treated is determined. It may be a softening treatment method that replaces sodium. According to this method, the hardness component in the for-treatment water can be easily removed.
  • the monolith ion exchanger used in the ion exchange module and water treatment method of the present invention is repeatedly used for the ion adsorption removal treatment, it can be regenerated with a chemical.
  • the regeneration treatment method include a method in which an ionic substance adsorbed on the monolith ion exchanger is desorbed by contacting an acid and a monolith cation exchanger or an alkali and a monolith anion exchanger, respectively.
  • the acid include hydrochloric acid, sulfuric acid, and nitric acid
  • examples of the alkali include caustic soda.
  • the method of contacting the drug with the monolithic ion exchanger is not particularly limited to the upward flow or the downward flow, and each ion exchanger is separated even when other ion exchangers such as a granular ion exchange resin are mixed. The operation to do is unnecessary.
  • Step I Production of monolith intermediate
  • 19.2 g of styrene, 1.0 g of divinylbenzene, 1.0 g of sorbitan monooleate (hereinafter abbreviated as SMO) and 0.26 g of 2,2′-azobis (isobutyronitrile) were mixed and dissolved uniformly.
  • SMO sorbitan monooleate
  • 2,2′-azobis 2,2′-azobis (isobutyronitrile)
  • the styrene / divinylbenzene / SMO / 2,2′-azobis (isobutyronitrile) mixture is added to 180 g of pure water containing 1.8 ml of THF, and a vacuum stirring defoaming mixer which is a planetary stirring device.
  • EM Co., Ltd. was used and stirred under reduced pressure in a temperature range of 5 to 20 ° C. to obtain a water-in-oil emulsion.
  • the emulsion was immediately transferred to a reaction vessel, and after sealing, it was allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the content was taken out, extracted with isopropanol, and then dried under reduced pressure to produce a monolith intermediate having a continuous macropore structure.
  • the average diameter of the openings (mesopores) where the macropores and macropores of the monolith intermediate were measured by mercury porosimetry was 56 ⁇ m, and the total pore volume was 7.5 ml / g.
  • the separated monolith intermediate is put in a reaction vessel having an inner diameter of 90 mm, immersed in the styrene / divinylbenzene / 1-decanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture, and removed in a vacuum chamber. After bubbling, the reaction vessel was sealed and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the monolith-like contents having a thickness of about 30 mm were taken out, subjected to Soxhlet extraction with acetone, and then dried under reduced pressure at 85 ° C. overnight (step III).
  • FIG. 1 shows the result of observing the internal structure of a monolith (dry body) containing 1.3 mol% of a cross-linking component composed of a styrene / divinylbenzene copolymer obtained by SEM, as described above.
  • the SEM image in FIG. 1 is an image at an arbitrary position on a cut surface obtained by cutting a monolith at an arbitrary position.
  • the monolith has a continuous macropore structure, and the skeleton constituting the continuous macropore structure is much thicker than that of the comparative example of FIG. The thickness of the part was thick.
  • the thickness of the wall part and the area of the skeleton part appearing in the cross section were measured from two SEM images obtained by cutting the obtained monolith at a position different from the above position, excluding subjectivity, and three convenient points.
  • the wall thickness was an average of 8 points obtained from one SEM photograph, and the skeleton area was determined by image analysis.
  • the wall portion has the above definition.
  • the skeleton part area was shown by the average of three SEM images. As a result, the average thickness of the wall portion was 30 ⁇ m, and the area of the skeleton portion represented by the cross section was 28% in the SEM image.
  • the average diameter of the opening of the monolith measured by mercury porosimetry was 31 ⁇ m, and the total pore volume was 2.2 ml / g.
  • Tables 1 and 2 The results are summarized in Tables 1 and 2.
  • the preparation column shows, in order from the left, the vinyl monomer used in Step II, the crosslinking agent, the monolith intermediate obtained in Step I, and the organic solvent used in Step II.
  • the monolith produced by the above method was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 15 mm.
  • the weight of the monolith was 27 g.
  • 1500 ml of dichloromethane was added and heated at 35 ° C. for 1 hour, then cooled to 10 ° C. or lower, 145 g of chlorosulfuric acid was gradually added, and the temperature was raised and reacted at 35 ° C. for 24 hours.
  • the swelling rate before and after the reaction of the obtained cation exchanger was 1.7 times, and the ion exchange capacity per volume was 0.67 mg equivalent / ml in a water wet state.
  • the average diameter of the openings of the organic porous ion exchanger in the water wet state was estimated from the value of the organic porous body and the swelling ratio of the cation exchanger in the water wet state, and was 54 ⁇ m, and was obtained by the same method as for the monolith.
  • the average thickness of the wall part constituting the skeleton was 50 ⁇ m, the skeleton part area was 28% in the photographic region of the SEM photograph, and the total pore volume was 2.2 ml / g.
  • FIG. 2 shows a distribution state of sulfur atoms on the surface of the cation exchanger
  • FIG. 3 shows a distribution state of sulfur atoms in the cross-section (thickness) direction of the cation exchanger. 2 and 3, it can be seen that the sulfonic acid groups are uniformly introduced into the surface of the cation exchanger and inside the skeleton (cross-sectional direction).
  • Table 1 shows the amount of styrene used, the type and amount of crosslinking agent, the type and amount of organic solvent, the porous structure of the monolith intermediate coexisting during styrene and divinylbenzene impregnation polymerization, the crosslinking density and the amount used.
  • a monolith was produced in the same manner as in Reference Example 1 except for the change. The results are shown in Tables 1 and 2.
  • the average diameter of the openings of the monoliths of Reference Examples 2 to 11 is as large as 22 to 70 ⁇ m, and the average thickness of the walls constituting the skeleton is also 25 to It was as thick as 50 ⁇ m, and the skeletal area was 26-44% in the SEM image area, which was a thick monolith.
  • the monolith produced by the above method was reacted with chlorosulfuric acid in the same manner as in Reference Example 1 to produce a monolith cation exchanger having a continuous macropore structure.
  • the results are shown in Table 2.
  • the average diameter of the openings of the monolith cation exchangers of Reference Examples 2 to 11 is 46 to 138 ⁇ m, the average thickness of the wall portion constituting the skeleton is as large as 45 to 110 ⁇ m, and the skeleton area is 26 to 44% in the SEM image region. Met.
  • the ion exchange zone length was shorter than the conventional one, and the differential pressure coefficient was also low.
  • the monolith cation exchanger of Reference Example 8 was also evaluated for mechanical properties.
  • the monolith cation exchanger obtained in Reference Example 8 was cut into a strip of 4 mm ⁇ 5 mm ⁇ 10 mm in a wet state, and used as a test piece for a tensile strength test.
  • the test piece was attached to a tensile tester, the head speed was set to 0.5 mm / min, and the test was performed at 25 ° C. in water.
  • the tensile strength and the tensile modulus were 45 kPa and 50 kPa, respectively, which were much larger than those of the conventional monolith cation exchanger.
  • the tensile elongation at break was 25%, which was a value larger than that of the conventional monolith cation exchanger.
  • Reference Examples 12 and 13 Manufacture of monoliths
  • a monolith having the same composition and structure as Reference Example 4 was produced in the same manner as Reference Example 1 except that the amount of styrene used, the amount of crosslinking agent used, and the amount of organic solvent used were changed to the amounts shown in Table 1.
  • Reference Example 13 was carried out in the same manner as Reference Example 12 except that a reaction vessel having an inner diameter of 110 mm was used instead of the reaction vessel having an inner diameter of 75 mm. The results are shown in Tables 1 and 2.
  • the monolith produced by the above method was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 15 mm.
  • 1400 ml of dimethoxymethane and 20 ml of tin tetrachloride were added, and 560 ml of chlorosulfuric acid was added dropwise under ice cooling.
  • the temperature was raised and reacted at 35 ° C. for 5 hours to introduce a chloromethyl group.
  • Ion exchange capacity per volume of the anion exchangers of Reference Example 12 and Reference Example 13 average diameter of openings of organic porous ion exchangers in a wet state of water, and walls constituting the skeleton obtained by the same method as that of monolith Table 2 summarizes the average thickness, skeleton area (ratio in the photographic region of the SEM photograph), total pore volume, ion exchange zone length, differential pressure coefficient, and the like.
  • 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.
  • Step I Production of monolith intermediate
  • SMO sorbitan monooleate
  • 2,2′-azobis 2,2′-azobis (isobutyronitrile)
  • SMO sorbitan monooleate
  • 2,2′-azobis 2,2′-azobis
  • the wall portion separating two adjacent macropores was very thin and rod-shaped, but the open cell structure
  • the average diameter of the openings (mesopores) where the macropores overlap with each other as measured by the mercury intrusion method was 70 ⁇ m, and the total pore volume was 21.0 ml / g.
  • the separated monolith intermediate is placed in a reaction vessel having an inner diameter of 75 mm, immersed in the styrene / divinylbenzene / 1-decanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture, and removed in a vacuum chamber. After bubbling, the reaction vessel was sealed and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the monolithic contents having a thickness of about 60 mm were taken out, subjected to Soxhlet extraction with acetone, and then dried under reduced pressure at 85 ° C. overnight (step III).
  • the monolith When the internal structure of the monolith (dry body) containing 3.2 mol% of the crosslinking component composed of the styrene / divinylbenzene copolymer obtained in this way was observed by SEM, the monolith had a skeleton and pores, respectively. It was a three-dimensional continuous structure with both phases intertwined. Moreover, the thickness of the skeleton measured from the SEM image was 10 ⁇ m. Further, the size of the three-dimensionally continuous pores of the monolith measured by mercury porosimetry was 17 ⁇ m, and the total pore volume was 2.9 ml / g. The results are summarized in Tables 3 and 4. In Table 4, the thickness of the skeleton was represented by the diameter of the skeleton.
  • the monolith produced by the above method was cut into a disk shape having a diameter of 75 mm and a thickness of about 15 mm.
  • the weight of the monolith was 18 g.
  • a part of the obtained cation exchanger was cut out and dried, and then its internal structure was observed by SEM. As a result, it was confirmed that the monolith cation body maintained a co-continuous structure.
  • the SEM image is shown in FIG. Moreover, the swelling ratio before and after the reaction of the cation exchanger was 1.4 times, and the ion exchange capacity per volume was 0.74 mg equivalent / ml in a water-wet state.
  • the size of the continuous pores of the monolith in the water wet state was estimated from the value of the monolith and the swelling ratio of the cation exchanger in the water wet state to be 24 ⁇ m, the skeleton diameter was 14 ⁇ m, and the total pore volume was 2. It was 9 ml / g.
  • Amberlite IR120B (a commercially available strong acid cation exchange resin) It was not only overwhelmingly shorter than the value (320 mm) manufactured by Rohm and Haas, but also shorter than the value of the monolithic porous cation exchanger having a conventional open cell structure. The results are summarized in Table 4.
  • FIGS. 9 and 10 show the left and right photographs correspond to each other.
  • FIG. 9 shows a distribution state of sulfur atoms on the surface of the cation exchanger
  • FIG. 10 shows a distribution state of sulfur atoms in the cross-section (thickness) direction of the cation exchanger.
  • a part extending in a horizontal direction is a skeleton part
  • the photograph on the left side of FIG. 9 and 10 it can be seen that the sulfonic acid groups are uniformly introduced into the surface of the cation exchanger and inside the skeleton (cross-sectional direction).
  • the monolith cation exchanger obtained in Reference Example 15 was cut into a strip of 4 mm ⁇ 5 mm ⁇ 10 mm in a wet state of water and used as a test piece for a tensile strength test.
  • the test piece was attached to a tensile tester, the head speed was set to 0.5 mm / min, and the test was performed at 25 ° C. in water.
  • the tensile strength and the tensile modulus were 23 kPa and 15 kPa, respectively, which were significantly larger than the conventional monolith cation exchanger.
  • the tensile elongation at break was 50%, which was a value larger than that of the conventional monolith cation exchanger.
  • Reference Examples 18 and 19 Manufacture of monolith with co-continuous structure Except that the amount of styrene used, the amount of crosslinking agent used, the amount of organic solvent used, the porous structure of the monolith intermediate coexisting during styrene and divinylbenzene impregnation polymerization, the crosslinking density and the amount used were changed to the amounts shown in Table 4.
  • a monolith having a co-continuous structure was produced in the same manner as in Reference Example 14.
  • Reference Example 19 was carried out in the same manner as Reference Example 18 except that a reaction vessel having an inner diameter of 110 mm was used instead of the reaction vessel having an inner diameter of 75 mm. The results are shown in Tables 3 and 4.
  • the monolith produced by the above method was cut into a disk shape having a diameter of 70 mm and a thickness of about 15 mm.
  • 1400 ml of dimethoxymethane and 20 ml of tin tetrachloride were added, and 560 ml of chlorosulfuric acid was added dropwise under ice cooling.
  • the temperature was raised and the reaction was carried out at 35 ° C. for 5 hours to introduce a chloromethyl group.
  • the ion exchange capacity per volume of the anion exchangers of Reference Example 18 and Reference Example 19 the average diameter of the continuous pores of the organic porous ion exchanger in a water-wet state, and the thickness of the skeleton obtained by the same method as that of the monolith Table 4 summarizes the total pore volume, ion exchange zone length, differential pressure coefficient, and the like. Moreover, the internal structure of the obtained monolith anion exchanger having a co-continuous structure was observed by an SEM image (not shown).
  • the anion exchanger was treated with an aqueous hydrochloric acid solution to form a chloride form, and then the distribution state of chlorine atoms was observed by EPMA. As a result, it was confirmed that the chlorine atoms were uniformly distributed not only on the surface of the anion exchanger but also inside, and the quaternary ammonium groups were uniformly introduced into the anion exchanger.
  • Reference Example 20 Manufacture of monolithic organic porous material having a continuous macropore structure (known product)
  • a monolithic organic porous material having a continuous macropore structure was produced according to the production method described in JP-A-2002-306976. That is, 19.2 g of styrene, 1.0 g of divinylbenzene, 1.0 g of SMO and 0.26 g of 2,2′-azobis (isobutyronitrile) were mixed and dissolved uniformly.
  • 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.
  • EM Corp. vacuum stirring defoaming mixer
  • the emulsion was immediately transferred to a reaction vessel, and after sealing, it was allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the content was taken out, extracted with isopropanol, and then dried under reduced pressure to produce a monolithic organic porous body having a continuous macropore structure.
  • the SEM representing the internal structure of the organic porous material containing 3.3 mol% of the cross-linking component made of the styrene / divinylbenzene copolymer thus obtained was the same as that shown in FIG.
  • the organic porous body has a continuous macropore structure, but the thickness of the wall portion constituting the skeleton of the continuous macropore structure is thinner than that of the example, and from the SEM image
  • the measured wall thickness average thickness was 5 ⁇ m, and the skeleton area was 10% in the SEM image area.
  • the average diameter of the opening of the organic porous material measured by mercury porosimetry was 29 ⁇ m, and the total pore volume was 8.6 ml / g.
  • Table 5 the mesopore diameter means the average diameter of the openings.
  • the values of the thickness, the skeleton diameter, and the pores are averages.
  • the organic porous body produced by the above method was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 15 mm.
  • the weight of the organic porous material was 6 g.
  • the average diameter of the mesopores of the organic porous ion exchanger in the water wet state was 46 ⁇ m as estimated from the value of the organic porous body and the swelling ratio of the cation exchanger in the water wet state.
  • the average thickness was 8 ⁇ m
  • the skeleton part area was 10% in the SEM image area
  • the total pore volume was 8.6 ml / g.
  • the differential pressure coefficient which is an index of pressure loss when water is permeated, was 0.013 MPa / m ⁇ LV. The results are summarized in Table 5.
  • the monolith cation exchanger obtained in Reference Example 20 was also evaluated for mechanical properties.
  • Reference Examples 21-23 Manufacture of monolithic organic porous body having continuous macropore structure
  • the body was manufactured. The results are shown in Table 5. Further, the internal structure of the monolith of Reference Example 23 was observed with an SEM (not shown). In addition, Reference Example 23 is a condition for minimizing the total pore volume, and an opening cannot be formed by adding less water to the oil phase part.
  • the opening diameter is small as 9 to 18 ⁇ m
  • the average thickness of the wall portion constituting the skeleton is as thin as 15 ⁇ m
  • the skeleton area is as small as 22% at the maximum in the SEM image region. It was.
  • Reference Example 24 Monolith production was attempted in the same manner as in Reference Example 1, except that the type of organic solvent used in Step II was changed to dioxane, which is a good solvent for polystyrene. However, the isolated product was transparent, suggesting collapse / disappearance of the porous structure. SEM observation was performed for confirmation, but only a dense structure was observed, and the continuous macropore structure disappeared.
  • Reference Example 25 (Production of porous cation exchanger (known)) 27.7 g of styrene, 6.9 g of divinylbenzene, 0.14 g of azobisisobutyronitrile and 3.8 g of sorbitan monooleate were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / azobisisobutyronitrile / sorbitan monooleate mixture is added to 450 ml of pure water, stirred at 20,000 rpm for 2 minutes using a homogenizer, and a water-in-oil emulsion. Got.
  • the water-in-oil emulsion was transferred to a stainless steel autoclave, sufficiently substituted with nitrogen, sealed, and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the content was taken out, extracted with Soxhlet for 18 hours with isopropanol, unreacted monomer and sorbitan monooleate were removed, and dried under reduced pressure at 40 ° C. overnight.
  • the ion exchange capacity of this porous material is 4.0 mg equivalent / g in terms of dry porous material, and sulfonic acid groups are uniformly introduced into the porous material by mapping of sulfur atoms using EPMA. It was confirmed. Further, as a result of SEM observation (not shown), the internal structure of the porous body has an open cell structure, and most of the macropores having an average diameter of 30 ⁇ m are overlapped, and the mesopores formed by the overlap of the macropores and the macropores. The average diameter was 5 ⁇ m and the total pore volume was 10.1 ml / g. The porous body was cut out to a thickness of 10 mm, and the water permeation rate was measured. As a result, it was 14,000 l / min ⁇ m 2 ⁇ MPa.
  • Raw water was passed through a column having an inner diameter of 57 mm packed with an ion exchanger so as to flow downward from above, and the time during which the sodium concentration in the treated water exceeded 1 ⁇ g / l was measured. Moreover, the water flow differential pressure during water flow was also measured. The conditions of this water flow experiment are as follows. As a result, the time when the sodium concentration in the treated water exceeded 1 ⁇ g / l was 114 days. The water flow differential pressure was 24 kPa.
  • the cation exchange resin was once made Na type with sodium chloride, regenerated with 99% regeneration rate with 1N hydrochloric acid, washed thoroughly with ultrapure water and used in a regenerated form.
  • the regeneration rate is the ratio of the H-type capacity among the exchange capacity that can be adsorbed to the resin.
  • Example 17 The same procedure as in Example 1 was performed except that the monolith cation exchanger of Reference Example 17 was used instead of the monolith cation exchanger of Reference Example 8. As a result, the time when the sodium concentration in the treated water exceeded 1 ⁇ g / l was 147 days. Moreover, the water flow differential pressure was 18 kPa.
  • Comparative Example 1 The same procedure as in Example 1 was performed except that the monolith cation exchanger of Reference Example 25 was used instead of the monolith cation exchanger of Reference Example 8. As a result, the time during which the sodium concentration in the treated water exceeded 1 ⁇ g / l was 21 days. Moreover, the water flow differential pressure was 230 kPa.
  • Comparative Example 2 The same procedure as in Example 1 was performed except that the ion exchanger was a mixed resin of a granular cation exchange resin and an anion exchange resin (resin layer height: 340 mm). That is, in Comparative Example 2, a monolith is not used as the ion exchanger, and the granular ion exchange resin is 100%. As a result, the time when the sodium concentration in the treated water exceeded 1 ⁇ g / l was 0 day, that is, the sodium concentration in the treated water exceeded 1 ⁇ g / l from the first day of water flow. Moreover, the water flow differential pressure was 230 kPa.
  • Step I Production of monolith intermediate
  • SMO sorbitan monooleate
  • 2,2′-azobis 2,2′-azobis (isobutyronitrile)
  • SMO sorbitan monooleate
  • 2,2′-azobis 2,2′-azobis
  • step II Manufacture of composite monolith
  • styrene 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.
  • the monolith intermediate was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 20 mm, and 3.2 g was collected.
  • the separated monolith intermediate is put in a reaction vessel having an inner diameter of 73 mm, and the styrene / divinylbenzene / 1- After immersing in a decanol / 2,2′-azobis (2,4-dimethylvaleronitrile) mixture and degassing in a vacuum chamber, the reaction vessel was sealed and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the monolith-like contents having a thickness of about 30 mm were taken out, subjected to Soxhlet extraction with acetone, and then dried under reduced pressure at 85 ° C. overnight (step III).
  • FIGS. 13 to FIG. 15 The results of observing the internal structure of the composite monolith (dried body) made of the styrene / divinylbenzene copolymer thus obtained by SEM are shown in FIGS.
  • the SEM images in FIG. 13 to FIG. 15 have different magnifications and are images at arbitrary positions on the cut surface obtained by cutting the monolith at arbitrary positions.
  • 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 ⁇ m.
  • the particle coverage of the skeleton surface by the body and the like was 80%.
  • the ratio of the particles having a particle diameter of 3 to 5 ⁇ m to the entire particles was 90%.
  • the average diameter of the opening of the composite monolith measured by mercury porosimetry was 16 ⁇ m, and the total pore volume was 2.3 ml / g.
  • Tables 6 and 7. the preparation column shows the vinyl monomer used in Step II, the crosslinking agent, the organic solvent, and the monolith intermediate obtained in Step I in order from the left. Further, the particle bodies and the like are shown as particles.
  • the composite monolith produced by the above method was cut into a disk shape having an outer diameter of 70 mm and a thickness of about 15 mm.
  • the weight of the monolith was 19.6 g.
  • 1500 ml of dichloromethane was added 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 wet state.
  • the average diameter of the openings of the organic porous ion exchanger in the water wet state was 21 ⁇ m 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 ⁇ m.
  • the particle coverage of the skeletal surface with all particles was 80%, and the total pore volume was 2.3 ml / g. Further, the ratio of the particle bodies having a particle diameter of 4 to 7 ⁇ m to the entire particle bodies 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 7.
  • FIGS. 16 and 17 show the left and right photographs correspond to each other.
  • FIG. 16 shows a distribution state of sulfur atoms on the surface of the cation exchanger
  • FIG. 17 shows a distribution state of sulfur atoms in the cross-section (thickness) direction of the cation exchanger. 16 and 17, it can be seen that the sulfonic acid groups are uniformly introduced into the surface of the cation exchanger and inside the skeleton (cross-sectional direction).
  • FIGS. 18 to 25 show the results of observing the internal structure of the composite monolith (dry body) by SEM. 18 to 25 are of Reference Example 27, FIGS. 21 and 22 are of Reference Example 28, FIG. 23 is of Reference Example 29, and FIGS. 24 and 25 are of Reference Example 30.
  • the average diameter of the particles adhering to the monolith skeleton surface of Reference Examples 27 to 31 is 3 to 8 ⁇ m, and the particle coverage of the skeleton surface by all particles is 50 to 95%. there were.
  • the proportion of the particles having a particle size of 3 to 6 ⁇ m accounts for 80%
  • the proportion of the protrusions of the particle size of 3 to 10 ⁇ m accounts for 80%.
  • Reference Example 29 the proportion of particles having a particle size of 3 to 5 ⁇ m accounted for 90%
  • Reference Example 30 the proportion of particles having a particle size of 3 to 7 ⁇ m accounted for 90%. .
  • Table 6 shows the types and amounts of vinyl monomers used, the amounts of crosslinking agents used, the types and amounts of organic solvents used, the porous structure of monolith intermediates that coexist during polymerization in step III, the crosslinking density, and the amounts used.
  • a monolith was produced in the same manner as in Reference Example 26, except for the change. The results are shown in Tables 6 and 7. Further, the results of observing the internal structure of the composite monolith (dry body) by SEM are shown in FIGS. What adhered to the skeleton surface of the composite monolith of Reference Example 31 was a protrusion.
  • the average diameter of the maximum diameter of the protrusions formed on the surface was 10 ⁇ m, and the particle coverage of the skeletal surface with all the particulates was 100%. Further, the ratio of the particle bodies having a particle size of 6 to 12 ⁇ m to the entire particle bodies was 80%.
  • 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.
  • 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 0.32 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 ⁇ m 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 ⁇ m, 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. In addition, the proportion of the particles having a particle size of 12 to 24 ⁇ m in the entire particles was 80%. The results are summarized in Table 7.
  • 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 32 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 6, Reference Example 26 and A monolith was produced in a similar manner. The results are shown in Tables 6 and 7. From the SEM photograph (not shown), the formation of particles and protrusions was not observed at all on the skeleton surface. From Table 6 and Table 7, when the 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.
  • the monolith produced by the above method was reacted with chlorosulfuric acid in the same manner as in Reference Example 26 to produce a monolith cation exchanger.
  • the results are shown in Table 7.
  • the obtained monolith cation exchanger had an ion exchange zone length of 26 mm, which was a large value as compared with Reference Examples 26 to 31.
  • Reference Examples 33-35 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 6.
  • the results are shown in Tables 6 and 7.
  • the crosslinking density ratio (0.2 times)
  • Reference Example 34 the type of organic solvent (2- (2-methoxyethoxy) ethanol; molecular weight 120
  • Reference Example 35 the polymerization temperature (50 C .: 1 ° C.
  • Reference Example 36 Manufacture of monoliths
  • Reference Example 32 Manufacture of monoliths
  • the amount of vinyl monomer used, the amount of crosslinking agent used, the amount of organic solvent used, the porous structure of monolith intermediate coexisting during polymerization in step III and the amount used were changed to those shown in Table 1.
  • a monolith was produced in the same manner as described above. The results are shown in Tables 6 and 7, and it can be seen that when a monolith is produced outside the specific production conditions of the present invention, particle formation on the monolith skeleton surface is not observed.
  • Reference Example 37 (Production of monolithic organic porous cation exchanger (known)) 27.7 g of styrene, 6.9 g of divinylbenzene, 0.14 g of azobisisobutyronitrile (ABIBN) and 3.8 g of sorbitan monooleate were mixed and dissolved uniformly. Next, the styrene / divinylbenzene / azobisisobutyronitrile / sorbitan monooleate mixture is added to 450 ml of pure water, and stirred for 2 minutes at 20,000 rpm with a homogenizer, and a water-in-oil emulsion. Got.
  • the water-in-oil emulsion was transferred to a stainless steel autoclave, sufficiently substituted with nitrogen, sealed, and allowed to polymerize at 60 ° C. for 24 hours. After completion of the polymerization, the content was taken out, extracted with Soxhlet for 18 hours with isopropanol, unreacted monomer and sorbitan monooleate were removed, and dried under reduced pressure at 40 ° C. overnight. After separating 11.5 g of an organic porous material containing 14 mol% of a crosslinking component composed of the styrene / divinylbenzene copolymer thus obtained, 800 ml of dichloroethane was added, and the mixture was heated at 60 ° C.
  • the porous body has an ion exchange capacity of 4.4 mg equivalent / g in terms of dry porous body and 0.32 mg equivalent / ml in terms of wet volume.
  • the internal structure of this organic porous body has an open cell structure, most of the macropores having an average diameter of 30 ⁇ m overlap, and the pore diameter of the mesopore formed by the overlap of the macropores and the macropores is 5 ⁇ m.
  • the total pore volume was 10.1 ml / g, and the BET specific surface area was 10 m 2 / g.
  • Raw water was passed through the column with an inner diameter of 57 mm packed with the composite monolith ion exchanger so as to flow downward from the top to the bottom, and the time during which the sodium concentration in the treated water exceeded 1 ⁇ g / l was measured. Moreover, the water flow differential pressure during water flow was also measured. The conditions of this water flow experiment are as follows. As a result, the time when the sodium concentration in the treated water exceeded 1 ⁇ g / l was 190 days. The water flow differential pressure was 37 kPa.
  • the cation exchange resin was once made Na type with sodium chloride, regenerated with 99% regeneration rate with 1N hydrochloric acid, washed thoroughly with ultrapure water and used in a regenerated form.
  • the regeneration rate is the ratio of the H-type capacity among the exchange capacity that can be adsorbed to the resin.
  • Comparative Example 3 The same procedure as in Example 3 was performed except that the monolith cation exchanger of Reference Example 37 was used instead of the monolith cation exchanger of Reference Example 27. As a result, the time during which the sodium concentration in the treated water exceeded 1 ⁇ g / l was 21 days. Moreover, the water flow differential pressure was 230 kPa.
  • Comparative Example 4 The same procedure as in Example 3 was performed except that the ion exchanger was a mixed resin of a granular cation exchange resin and an anion exchange resin (resin layer height: 340 mm). That is, in Comparative Example 4, a monolith is not used as the ion exchanger, and the granular ion exchange resin is 100%. As a result, the time when the sodium concentration in the treated water exceeded 1 ⁇ g / l was 0 day, that is, the sodium concentration in the treated water exceeded 1 ⁇ g / l from the first day of water flow. Moreover, the water flow differential pressure was 230 kPa.
  • Example 3 the leakage of adsorbed ions is slower than in Comparative Examples 3 and 4. For this reason, the exchange frequency of an ion exchange module can be reduced. Moreover, since the water flow differential pressure is low, water can be fed at a low pressure. Tables 6 and 7 are sequentially shown below in order.
  • the monolithic porous ion exchanger can be easily produced, for example, as a block shape that fits into a filling container, and filling is also easy. Moreover, it can apply to both the continuous water flow processing method generally employ

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Abstract

La présente invention concerne un module d'adsorption ionique équipé d'un bac présentant une ouverture à travers laquelle de l'eau à traiter s'écoule pour y pénétrer et un échangeur d'ions monobloc poreux et organique garnissant le bac, le monobloc étant une structure macroporeuse continue comprenant des macropores alvéolaires se chevauchant, les parties chevauchantes dans un état mouillé par l'eau formant des ouvertures avec un diamètre moyen compris entre 30 et 300 µm, et présentant un volume de pores total de 0,5 à 5 mL/g et une capacité d'échange ionique en l'état mouillé par l'eau de 0,4 à 5 mg-eq/mL. Dans une image d'un microscope électronique à balayage (SEM) d'une section en coupe de la structure macroporeuse continue (à l'état sec), la superficie des parties squelettiques apparaissant dans la section est comprise entre 25 et 50% de la zone d'image. Ce module d'adsorption ionique est efficace pour réduire la pression différentielle entraînée par le passage de l'eau et pour maintenir une longueur minimale de l'échangeur d'ions même lors de l'accroissement du débit. Le module possède une capacité élevée d'échange d'ions par volume unitaire.
PCT/JP2010/053642 2009-03-10 2010-03-05 Module d'adsorption ionique et procédé de traitement de l'eau WO2010104004A1 (fr)

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JP2010234357A (ja) * 2009-03-10 2010-10-21 Japan Organo Co Ltd イオン吸着モジュール及び水処理方法
JP2010264344A (ja) * 2009-05-12 2010-11-25 Japan Organo Co Ltd 超純水製造装置
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CN111902368A (zh) * 2018-05-17 2020-11-06 奥加诺株式会社 超纯水的制造方法、超纯水制造系统和离子交换体填充组件
WO2019221186A1 (fr) * 2018-05-17 2019-11-21 オルガノ株式会社 Procédé d'analyse de contenu d'impuretés métalliques, et kit d'analyse de contenu d'impuretés métalliques
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