WO2018159724A1 - Mélange organique-inorganique, son utilisation et son procédé de production - Google Patents

Mélange organique-inorganique, son utilisation et son procédé de production Download PDF

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WO2018159724A1
WO2018159724A1 PCT/JP2018/007656 JP2018007656W WO2018159724A1 WO 2018159724 A1 WO2018159724 A1 WO 2018159724A1 JP 2018007656 W JP2018007656 W JP 2018007656W WO 2018159724 A1 WO2018159724 A1 WO 2018159724A1
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organic
compound
adsorbent
group
inorganic mixture
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Japanese (ja)
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隆一郎 平鍋
竜馬 宮本
智子 金森
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東レ株式会社
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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    • B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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    • B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
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    • B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
    • B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
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    • B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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    • B01J20/28016—Particle form
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    • B01J20/28023—Fibres or filaments
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    • 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
    • B01J20/2803—Sorbents comprising a binder, e.g. for forming aggregated, agglomerated or granulated products
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3007—Moulding, shaping or extruding
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/3042—Use of binding agents; addition of materials ameliorating the mechanical properties of the produced sorbent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3202—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the carrier, support or substrate used for impregnation or coating
    • B01J20/3206—Organic carriers, supports or substrates
    • B01J20/3208—Polymeric carriers, supports or substrates
    • B01J20/3212—Polymeric carriers, supports or substrates consisting of a polymer obtained by reactions otherwise than involving only carbon to carbon unsaturated bonds
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    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
    • B01J20/3234—Inorganic material layers
    • B01J20/3236—Inorganic material layers containing metal, other than zeolites, e.g. oxides, hydroxides, sulphides or salts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/30—Processes for preparing, regenerating, or reactivating
    • B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
    • B01J20/3291—Characterised by the shape of the carrier, the coating or the obtained coated product
    • B01J20/3293—Coatings on a core, the core being particle or fiber shaped, e.g. encapsulated particles, coated fibers
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L29/00—Compositions 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 alcohol, ether, aldehydo, ketonic, acetal or ketal radical; Compositions of hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Compositions of derivatives of such polymers
    • C08L29/02—Homopolymers or copolymers of unsaturated alcohols
    • C08L29/04—Polyvinyl alcohol; Partially hydrolysed homopolymers or copolymers of esters of unsaturated alcohols with saturated carboxylic acids
    • 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
    • B01J2220/00—Aspects relating to sorbent materials
    • B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
    • B01J2220/46—Materials comprising a mixture of inorganic and organic materials
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • 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
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/103—Arsenic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/105—Phosphorus compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/108—Boron compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • C02F2101/14—Fluorine or fluorine-containing compounds

Definitions

  • the present invention is an organic-inorganic mixture capable of adsorbing boron, arsenic, fluorine and phosphorus suitable for various water treatments such as drinking water production, industrial water production, water purification treatment, wastewater treatment, seawater desalination, industrial water production, etc. About.
  • Patent Documents 1 and 2 have not obtained a removal rate sufficient for practical use for removing boron in seawater desalination.
  • This invention makes it a subject to provide the technique for implement
  • the present inventors have found that a mixture of hydrous oxide and crosslinked polyvinyl alcohol (hereinafter referred to as PVA) becomes an adsorbent with a high removal rate. That is, the present invention has any one of the following configurations (1) to (12).
  • the ratio of the mass of the compound (M) to the sum of the masses of the compound (M) and the crosslinked polyvinyl alcohol (P) is 50% by mass or more and 90% by mass or less. Inorganic mixture.
  • the cross-linking agent is selected from a compound having two or more functional groups selected from the group consisting of an epoxy group, an aldehyde group, a methylol group, and a halogen group, and a compound containing at least one of titanium or zirconium.
  • the organic-inorganic mixture according to (1) or (2) which is at least one kind of compound.
  • Substrate (X) and adsorption layer (Y) containing the organic-inorganic mixture according to any one of (1) to (3), Having a sheet.
  • the sheet according to (4), wherein the adsorption layer (Y) has a thickness of 1 ⁇ m or more and 25 ⁇ m or less.
  • thermoplasticity The sheet according to any one of (4) to (6), wherein the substrate (X) has thermoplasticity.
  • an adsorbent having a high removal rate for specific ions and a method for producing the same are provided.
  • FIG. 1 is a schematic cross-sectional view of a sheet-like adsorbent in an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view of the core fiber of the fibrous adsorbent in the embodiment of the present invention.
  • FIG. 3 is a schematic cross-sectional view of the fibrous adsorbent in the embodiment of the present invention.
  • FIG. 4 is a schematic cross-sectional view of a laminate in the embodiment of the present invention.
  • 5 is a view showing a photograph of the surface of the adsorbent in Example 1.
  • FIG. 6 is a view showing a photograph of a cross section of the adsorbent in Example 1.
  • FIG. 1 is a schematic cross-sectional view of a sheet-like adsorbent in an embodiment of the present invention.
  • FIG. 2 is a schematic cross-sectional view of the core fiber of the fibrous adsorbent in the embodiment of the present invention.
  • FIG. 3 is a schematic cross-
  • Organic-inorganic mixture contains at least one compound (M) selected from the group consisting of metal oxides, hydroxides and hydrated oxides.
  • M metal oxides
  • As the metal at least one element selected from the group consisting of aluminum, iron, titanium, tin, silicon, zirconium or cerium is employed. These metal oxides, hydroxides, and hydrated oxides are preferable because they have a large adsorption capacity for boron, arsenic, fluorine, and phosphorus. Zirconium and cerium have particularly large adsorption capacities.
  • the organic-inorganic mixture preferably contains the compound (M) as particles. When the organic-inorganic mixture includes particles, the particles may be either primary particles or secondary particles.
  • primary particles and secondary particles are used as terms having a general meaning in the field of metals. Specifically, primary particles are particles generated by the growth of a single crystal nucleus, and secondary particles are particles formed by coalescence, aggregation, or consolidation of primary particles.
  • the average particle size is preferably 80 ⁇ m or less, more preferably 8 ⁇ m or less, and even more preferably 3 ⁇ m or less.
  • the organic-inorganic mixture of the present invention is a mixture of PVA and particles. That is, since PVA plays the role of a binder, it can be said that it is a useful technique when a fine hydrous oxide that is difficult to handle is advantageous.
  • the particle diameter is preferably 0.05 ⁇ m or more, 0.1 ⁇ m or more, or 1 ⁇ m or more.
  • the organic-inorganic mixture of the present invention contains crosslinked polyvinyl alcohol (PVA) (P).
  • Crosslinking is formed by a bond between a hydroxy group of PVA and a crosslinking agent.
  • Crosslinked PVA (P) is insoluble in water.
  • the organic / inorganic mixture has a high removal rate because the compound (M) is supported (specifically dispersed) in the crosslinked PVA (P) as a binder. Function as.
  • boron will be described as an example of an adsorption target, but the same description applies to arsenic, fluorine, phosphorus, and the like.
  • an adsorbent having a porous body and a metal oxide supported on the porous body has been proposed. Therefore, in the conventional adsorbent, an aqueous solution containing boron (hereinafter referred to as mixed water) is adsorbed by the metal oxide by contacting the metal oxide while moving through the pores of the porous body. The Therefore, boron is preferentially adsorbed on the metal oxide on the surface of the adsorbent, and the metal oxide in the central portion of the adsorbent is not fully utilized.
  • Patent Document 1 in addition to forming a porous adsorbent with ethylene vinyl alcohol by a phase separation method, the water-soluble polymer polybilylpyrrolidone is eluted after molding so that the surface layer (surface and its vicinity) Devised measures such as enlarging the opening. That is, in Patent Document 1, an attempt is made to shorten the time for the mixed water to reach the central portion of the metal oxide. However, it takes time for the mixed water to reach the metal oxide at the center of the adsorbent through the fine porous portion. Moreover, when the pores are formed by the phase separation method, the size and number of the holes are likely to be non-uniform, and macropores called macrovoids are generated.
  • the organic / inorganic mixture of the present invention has a high ability to remove boron.
  • PVA is a polyhydric alcohol, so that it can adsorb boron and that PVA can diffuse boron. That is, even if the adsorbent to which the organic-inorganic mixture of the present invention is applied is not porous, boron can move in the adsorbent by PVA.
  • boron adsorbed on the compound (M) on the surface layer of the adsorbent moves from the surface layer to the inside by diffusing through the surrounding cross-linked PVA.
  • the amount of boron decreases in the surface layer of the adsorbent, it becomes possible to adsorb boron from the mixed water that newly contacts the adsorbent.
  • boron can be continuously adsorbed on the surface in this way, a higher adsorption rate can be obtained as compared with conventional porous bodies.
  • an adsorbent having a high adsorption rate is used, a high removal rate can be maintained even if the water flow rate is high. That is, the higher the adsorption speed, the higher the removal rate.
  • a high removal rate can be realized, and an adsorption capacity equal to or higher than that of the conventional product can be obtained.
  • the ratio represented by (mass of compound (M)) / (mass of compound (M) + mass of crosslinked PVA (P)) ⁇ 100 is preferably 10% by mass or more. 50% by mass or more is more preferable, and 60% by mass or more is more preferable. A favorable adsorption capacity is obtained because the content is within these ranges.
  • the ratio is preferably 90% by mass or less, more preferably 80% by mass or less, and further preferably 75% by mass or less. By the said ratio being in this range, the deformation
  • the proportion of the mass of the crosslinked PVA (P) is preferably 90% by mass or more, 95% by mass or more, or 100% by mass. It may be.
  • the crosslinked PVA (P) is removed by heating to 400 ° C. or higher in an electric furnace, and the mass of the residue is regarded as the mass of the compound (M).
  • a method of dividing by the mass of the mixture is mentioned.
  • the polyvinyl alcohol constituting the crosslinked PVA (P) in the organic-inorganic mixture of the present invention contains a vinyl alcohol unit as a main constituent component.
  • the proportion of vinyl alcohol units in the crosslinked PVA is preferably 80 mol% or more, more preferably 90 mol% or more, and still more preferably 95% or more.
  • a high adsorption capacity can be obtained when the proportion of vinyl alcohol units is in the above range.
  • components other than the vinyl alcohol unit contained in the crosslinked PVA include vinyl acetate, vinyl butyral, vinyl acetal, N-vinylacetamide, polyethylene, polypropylene, and a modified polyvinyl alcohol copolymer.
  • modified polyvinyl alcohol copolymer examples include block copolymers and graft copolymers modified with acrylic, urethane, polyester, epoxy, polyethylene, polypropylene, etc., or carboxyl groups, sulfonic acid groups, amino groups, phosphorus Examples include acid groups, isocyanate groups, oxazoline groups, methylol groups, nitrile groups, acetoacetyl groups, cationic groups, aldehyde groups, alkoxide groups, and modified products with halogen atoms.
  • the structure of the crosslinking is not particularly limited, but it is preferably formed by a bond between the hydroxyl group of PVA and a crosslinking agent.
  • the crosslinking agent include compounds having two or more functional groups selected from the group consisting of epoxy groups, aldehyde groups, methylol groups, and halogen groups (halogen atoms), and metal compounds.
  • One type of cross-linking agent may be used, or a plurality of types may be used in combination.
  • cross-linking agents having an epoxy group examples include: epoxy chlorohydrin; diepoxy alkane; diepoxy alkene; or (poly) ethylene glycol diglycidyl ether, (poly) propylene glycol diglycidyl ether or (poly) glycerin diglycidyl ether And diglycidyl ether compounds such as ethylene glycol diglycidyl ether are preferred.
  • a dialdehyde compound is mentioned as an example of the crosslinking agent which has an aldehyde group.
  • dialdehyde compound examples include glutaraldehyde, succinaldehyde, malondialdehyde, terephthalaldehyde, and isophthalaldehyde, and glutaraldehyde is particularly preferable.
  • the crosslinking agent which is a metal compound suppresses swelling of the crosslinked PVA due to water, it is suitable for an organic-inorganic mixture used in the presence of water or water vapor.
  • the metal compound at least one of titanium and zirconium is preferable, and a titanium-based crosslinking agent (crosslinking agent which is a titanium compound) is particularly preferable.
  • titanium-based cross-linking agent titanium alkoxide-based cross-linking agents such as titanium diisopropoxybis (triethanolaminate) and titanium lactate ammonium salt are preferable for suppressing swelling.
  • Adsorbent The organic-inorganic mixture described above is applicable to the adsorbent.
  • the shape of the adsorbent include, but are not limited to, a sheet shape, a fiber shape, and a granular shape.
  • the sheet-like adsorbent preferably has a base material (X) and an adsorption layer (Y) that is disposed on at least one side of the base material (X) and contains the above-described organic-inorganic mixture.
  • a fiber-shaped adsorbent has a core fiber and the adsorption layer arrange
  • the sheet-like adsorbent 1 shown in FIG. 1 is a multilayer sheet having a substrate (X) and an adsorbing layer (Y) laminated on one side and having adsorbing performance.
  • the adsorption layer (Y) is the above-described organic-inorganic mixture.
  • the adsorption layer (Y) is preferably a non-porous solid.
  • the thickness of the adsorption layer is preferably small when it is used for continuous water flow and is large when it is intermittent water that allows sufficient diffusion time. Specifically, it is as follows.
  • the thickness of the adsorption layer (Y) is preferably 25 ⁇ m or less, more preferably 15 ⁇ m or less, and even more preferably 10 ⁇ m or less.
  • the lower limit of the thickness is preferably 1 ⁇ m or more, more preferably 2 ⁇ m or more, and further preferably 5 ⁇ m or more.
  • the thickness of the adsorption layer (Y) is related to both the adsorption speed and the adsorption capacity.
  • the volume of the adsorption layer is the same, the surface area can be increased by reducing the thickness, so that the contact area with the mixed water increases. Therefore, the adsorption rate per unit volume is increased. Further, when the thickness is 25 ⁇ m or less, boron easily diffuses throughout the adsorbent and the adsorption capacity increases.
  • the thickness of the adsorption layer (Y) here is the thickness of one layer, and the first adsorption layer (Y), the substrate (X), and the second adsorption layer (Y) are laminated in this order.
  • the thickness of each adsorption layer (Y) is preferably 25 ⁇ m or less.
  • the adsorption capacity can be ensured when the thickness of the adsorption layer (Y) is 1 ⁇ m or more.
  • the adsorbent is a laminate of the base material (X) and the adsorption layer (Y)
  • the base material (X) is preferably a film or a nonwoven fabric, and the material of the base material (X) is thermoplastic. It is preferable to contain a synthetic resin as a main component.
  • a contains B as a main component means that the B content in A is 70% by mass or more, 80% by mass or more, 90% by mass or more, or 95% by mass or more. means.
  • polyolefin resins such as polyethylene, polypropylene and polymethylpentene
  • polyamide resins such as nylon 6 and nylon 66
  • polyethylene terephthalate and polybutylene terephthalate polybutylene terephthalate
  • polyester resins such as polypropylene terephthalate and polyethylene-2,6-naphthalate
  • polyacetal resins polyvinylidene fluoride resins, and polyphenylene sulfide resins
  • the film is preferably a biaxially oriented film. This is because the biaxially oriented film has high toughness. In the biaxially oriented film, the molecules are oriented in two directions perpendicular to each other.
  • a nonwoven fabric is a thin leaf body containing fibers entangled randomly. Typical examples of the nonwoven fabric include a melt blown nonwoven fabric and a spunbond nonwoven fabric. In the nonwoven fabric, natural fibers and chemical fibers may be mixed.
  • the base material (X) is added with various additives such as an antioxidant, a flame retardant, a lubricant, and a colorant within a range that does not impair the physical properties of the base material (X). be able to.
  • the fiber adsorbent will be described.
  • the fiber diameter (diameter) D is preferably 20 ⁇ m or more, more preferably 50 ⁇ m or more, and further preferably 100 ⁇ m or more. When the fiber diameter is 20 ⁇ m or more, a gap can be held between the fibers when the fibers are stacked, so that the water flow resistance can be reduced.
  • the fiber diameter is preferably 1000 ⁇ m or less, more preferably 600 ⁇ m or less, and more preferably 400 ⁇ m or less.
  • the fiber diameter is 1000 ⁇ m or less, the area where the fibrous adsorbent comes into contact with the raw water can be increased, and the adsorption rate can be increased.
  • the fiber diameter D is the maximum diameter of the adsorbent cross section.
  • the fibrous adsorbent may be composed only of an organic / inorganic mixture, or may include a thermoplastic fiber (hereinafter referred to as “core fiber”) as a core and an organic / inorganic mixture coated around the core. But you can.
  • a fibrous adsorbent containing thermoplastic fibers has the advantage of having high strength.
  • thermoplastic fiber synthetic fiber or natural fiber, or a blended yarn or a blended yarn of these can be used.
  • Synthetic fibers include polyolefins such as polyethylene and polypropylene; polyesters such as PET (polyethylene terephthalate) and polycarbonate; polyamides, aromatic polyamides; acrylics, polyacrylonitriles; polyvinyl chloride, PTFE (polytetrafluoroethylene), polyvinylidene fluoride, etc. And halogenated polyolefin.
  • polyamides and polyesters are particularly preferable, and polyamides are particularly nylon and polyesters are particularly preferable PET.
  • Natural fibers include wool, silk, and cotton.
  • the core fiber may be a monofilament, but is preferably a multifilament including a plurality of single fibers. Since the core fiber is a multifilament and the compound (M) and the polymer resin are present in the fiber gap, the total mass of the compound (M) and the polymer resin is sufficiently large relative to the mass of the core fiber. It becomes large and exhibits excellent adsorption performance.
  • the cross-sectional shape of the core fiber is not particularly limited, and examples thereof include a circular cross section and an irregular cross section.
  • a more preferable cross section is an irregular cross section.
  • the core fiber having an irregular cross section has a large specific surface area, and the gap between the core fibers when a plurality of core fibers are bundled increases, so that the amount of resin that can be coated increases. As a result, since the total mass of the compound (M) and the polymer resin is sufficiently large with respect to the mass of the core fiber, excellent adsorption performance is exhibited.
  • the irregular cross section is not particularly limited, and has, for example, a polygonal cross section, a flat cross section, a lens mold cross section, and so-called multi-lobe cross sections such as a three-lobe cross section and a six-lobe cross section, as many as three to eight convex portions. Examples include irregular cross sections and hollow cross sections. Also, other known irregular cross sections may be used.
  • the profile of the fiber cross section is preferably 1.2 or more and 6.0 or less. The degree of irregularity is obtained by dividing the circumscribed circle diameter of the sectional shape by the inscribed circle diameter of the sectional shape (FIG. 2).
  • FIG. 3 shows a cross-sectional view of a fibrous adsorbent 2 having a plurality of core fibers A and an organic-inorganic mixture B existing between and around the core fibers. Since the core fiber A is an island component and the organic-inorganic mixture B is a sea component, this fibrous adsorbent is a sea-island type fiber.
  • the cross-sectional shape of the core fiber is a circular diameter, but the above-described configuration is appropriately employed as the cross-sectional shape of the core fiber and other configurations.
  • the adsorbent of the present invention can be obtained by mixing the compound (M), PVA and its cross-linking agent in a solvent such as water and molding it into a sheet.
  • the detailed method is exemplified by a method of laminating on a PET film to form a sheet, but is not limited to the following method.
  • a predetermined amount of the compound (M), PVA, and its cross-linking agent as raw materials for the adsorption layer (Y) are weighed and mixed with a solvent to obtain an aqueous coating material.
  • the PET pellets which are the raw material of the substrate (X), at 120 to 180 ° C. for 2 to 4 hours under reduced pressure, the PET pellets are supplied to a melt extruder and are fed into a sheet form from a T die die provided in the extruder at 260 to 300 ° C. Then, the casting drum is landed in front of the casting drum while rotating at a constant speed. At this time, the angle between the molten polymer and the casting drum is preferably 0 ° to 90 °, more preferably 10 ° to 60 °.
  • the molten polymer is adhered and solidified by an electrostatic application method and / or an air knife method, and is cooled and solidified to obtain an unoriented (unstretched) film.
  • This unstretched film may be stretched within a range where heat shrinkage is suitable.
  • the unoriented film obtained as needed is stretched with a plurality of roll groups, in the longitudinal direction (referred to as the “longitudinal direction”, indicating the traveling direction of the film) using the peripheral speed difference between the rolls.
  • the stretching temperature is preferably 80 to 170 ° C, more preferably 100 to 160 ° C, and further preferably 120 to 150 ° C.
  • the draw ratio is preferably 1.1 to 4 times, more preferably 1.5 to 3 times.
  • the laminated surface of this film is subjected to corona discharge treatment in air, the wet tension of the surface is set to 47 mN / m or more, and the adjusted aqueous coating is applied to the treated surface.
  • the coated laminated film is gripped with a clip, guided to a drying zone, dried at a temperature lower than Tg of the PET resin constituting the substrate (X), raised to a temperature higher than Tg, and again at a temperature near Tg. dry.
  • the film is stretched 2.5 to 5 times in a transverse direction (referred to as a direction orthogonal to the film traveling direction) in a heating zone at 70 to 150 ° C.
  • PVA is crosslinked by performing a heat treatment for 5 to 300 seconds in a heating zone of 130 to 240 ° C.
  • a sheet-like adsorbent is formed.
  • a 3 to 12% relaxation treatment may be performed as necessary.
  • Biaxial stretching may be longitudinal, transverse sequential stretching, or simultaneous biaxial stretching, and may be re-stretched in either the longitudinal or transverse direction after longitudinal and transverse stretching.
  • the above-described adsorbent can be used in a method for removing a solute from water regardless of a sheet shape, a fiber shape, or the like. Specifically, this removal method includes removing at least one element selected from the group consisting of arsenic, boron, fluorine and phosphorus from water by bringing the adsorbent into contact with water.
  • the adsorbent is applied to various water treatments such as drinking water production, industrial water production, water purification treatment, wastewater treatment, seawater desalination, industrial water production and the like.
  • the sheet-like adsorbent is applied to a laminate including a plurality of sheet-like adsorbents and spacers arranged therebetween. FIG.
  • the laminate 10 includes a plurality of sheet-like adsorbents 1 and spacers 3 arranged therebetween.
  • a member used as a spacer in a conventional water treatment element such as a net, a tricot, and a sheet having unevenness can be used.
  • a spiral-type water treatment apparatus has a rod-shaped or cylindrical core material and the above-described laminate wound around the core material.
  • the material for the core material polyolefin such as polyethylene and polypropylene, and fluororesin such as PTFE and PFA are suitable, but are not limited thereto.
  • the mixed water supplied from one end face of the spiral-type water treatment element passes through the sheet-like channel material and is taken out from the opposite end face. It is preferable to use the fibrous adsorbent by filling the column. The water taken into the inside from one end of the column flows through the gaps between the fibers as the adsorbent, and the solute is removed during that time. Permeate is withdrawn from the other end of the column.
  • Example 1 Polyethylene terephthalate (inherent viscosity 0.65) was dried at 180 ° C. for 3 hours. Then, it supplied to the extruder provided with the T-type nozzle
  • a polyester film was obtained.
  • One side of this biaxially oriented polyester film is subjected to corona discharge treatment in the air, and using an applicator (5 mil setting), the following coating solution 1 is coated on the treated surface of the film as a coating solution and dried at 180 ° C. with hot air Sheet-like adsorbent was obtained by drying in the machine for 180 seconds.
  • the thickness of the adsorption layer (Y) provided by single-sided coating was 25 ⁇ m, and the boron removal rate was 29%.
  • FIG. 5 and FIG. 6 show photographs of the surface and cross section of the obtained adsorbent, respectively.
  • Example 2 A biaxially oriented polyester film was obtained by performing the same operation as in Example 1 except that polypropylene terephthalate (Corterra Bright manufactured by DuPont) was used instead of polyethylene terephthalate. Both sides of this biaxially oriented polyester film are subjected to corona discharge treatment in the air, and the coating liquid 2 is coated on one side of the film using a metalling bar (# 20), in a hot air dryer at 110 ° C. Dried for 60 seconds. Thereafter, the coating liquid 2 was coated on the uncoated surface in the same manner and dried in a hot air dryer at 180 ° C. for 180 seconds, whereby double-side coating was performed to obtain the sheet-like adsorbent of the present invention.
  • the thickness of the adsorption layer (Y) after drying was 15 ⁇ m, respectively, and the boron removal rate was 26%.
  • Example 3 A polyethylene terephthalate raw material (inherent viscosity 0.50) was dried at 180 ° C. for 3 hours. Thereafter, the mixture was supplied to an extruder equipped with a rectangular die having a hole diameter of 0.8 mm and a hole number of 100, and the die temperature was 290 ° C., the hot air temperature was 295 ° C., the hot air speed was 7000 m / min, and the polymer discharge rate was 35 g / min. Spinning, collecting fibers on a net conveyor at a collection distance of 10 cm, and winding them to produce an unstretched nonwoven fabric with a basis weight of 90 g / m 2 .
  • a coating liquid 3 was coated on one side of the corona discharge treatment surface using an applicator (3 mil setting) to obtain a sheet-like adsorbent.
  • the thickness of the adsorption layer (Y) provided by single-side coating was 18 ⁇ m, and the boron removal rate was 27%.
  • Example 4 A polyethylene terephthalate raw material (inherent viscosity 0.50) was dried at 180 ° C. for 3 hours. After that, it is supplied to an extruder equipped with a rectangular die having a hole diameter of 0.8 mm and a hole number of 72, and is spun at a die temperature of 290 ° C. and a polymer discharge rate of 35 g / min, so that the upper end is located at a position of 30 mm on the lower surface of the die. Install a cooling device (chimney), cool the melt with cooling air at 25 ° C. and a wind speed of 1.5 m / sec, converge while applying oil, and wind it up with a winder at a speed of 1500 m / min. A core fiber was prepared.
  • a cooling device chimney
  • a woven fabric was produced using the obtained fibers with a plain weaving machine and the number of warp and weft meshes was 40 (pieces / inch). This fabric is subjected to corona discharge treatment in air, and then dipped in the coating solution 1 described in Example 1, and then the excess coating solution is drained with a mangle so that the fiber shape of the fabric is maintained. did.
  • the fabric with the coating solution adhering to the fibers was fixed to a metal frame, dried at 80 ° C. for 30 minutes, and then subjected to a crosslinking treatment at 160 ° C. for 1 hour to obtain a fibrous adsorbent.
  • the resulting adsorbent had a boron removal rate of 22%.
  • Example 1 One side of the biaxially oriented polyester film obtained in Example 1 was subjected to corona discharge treatment in air, and using an applicator (3 mil setting), the coating liquid 4 was coated on one side of the film, and a cold water bath at 5 ° C.
  • the sheet-like adsorbent on which the porous body was laminated was obtained by allowing it to stay for 20 seconds and solidifying.
  • the thickness of the adsorption layer (Y) provided by single-sided coating was 25 ⁇ m, had many voids, and the boron removal rate was 8%.
  • the organic / inorganic mixture of the present invention is suitable as an adsorbent.
  • ADVANTAGE OF THE INVENTION According to this invention, the adsorption agent with a high removal rate with respect to specific ions, and its manufacturing method are provided.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Analytical Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Water Supply & Treatment (AREA)
  • Environmental & Geological Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Hydrology & Water Resources (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Multicomponent Fibers (AREA)
  • Water Treatment By Sorption (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'objectif de la présente invention est de produire un adsorbant qui présente un taux d'élimination élevé pour des ions spécifiques, et un procédé de production de l'adsorbant. Ce mélange organique-inorganique contient : au moins un composé (M) choisi dans le groupe constitué par des oxydes, des hydroxydes et des oxydes hydratés d'aluminium, de fer, de titane, d'étain, de silicium, de zirconium ou de cérium; et un alcool polyvinylique réticulé (P), le mélange organique-inorganique étant approprié comme adsorbant.
PCT/JP2018/007656 2017-02-28 2018-02-28 Mélange organique-inorganique, son utilisation et son procédé de production WO2018159724A1 (fr)

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JPS58122039A (ja) * 1982-01-18 1983-07-20 Toray Ind Inc 繊維吸着材
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JP2007098363A (ja) * 2005-10-07 2007-04-19 Nippon Sheet Glass Co Ltd 吸着材
JP2010227757A (ja) * 2009-03-26 2010-10-14 Toray Ind Inc 複合分離膜
JP2013002865A (ja) * 2011-06-14 2013-01-07 Dainichiseika Color & Chem Mfg Co Ltd 吸着剤組成物、放射性セシウム吸着剤及びそれを用いた放射性セシウムの分離方法
JP2013193043A (ja) * 2012-03-21 2013-09-30 Osaka Gas Co Ltd 吸水材料組成物および吸水性シート
WO2015159865A1 (fr) * 2014-04-14 2015-10-22 富士フイルム株式会社 Matériau absorbant l'humidité, procédé de production associé et emballage-coque
JP2016215156A (ja) * 2015-05-22 2016-12-22 株式会社クラレ 水処理用安全フィルター

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JPS5281086A (en) * 1975-12-24 1977-07-07 Commw Scient Ind Res Org Composite materials
JPS52123986A (en) * 1976-04-13 1977-10-18 Toray Ind Inc Adsorption of ionic or polar substances
JPS5471091A (en) * 1977-10-07 1979-06-07 Ici Australia Ltd Manufacture of composite matter containing adsorbent
JPS58122039A (ja) * 1982-01-18 1983-07-20 Toray Ind Inc 繊維吸着材
JPS5991603A (ja) * 1982-11-16 1984-05-26 株式会社明電舎 熱伝導性電気絶縁材料及びその製造方法
JP2007098363A (ja) * 2005-10-07 2007-04-19 Nippon Sheet Glass Co Ltd 吸着材
JP2010227757A (ja) * 2009-03-26 2010-10-14 Toray Ind Inc 複合分離膜
JP2013002865A (ja) * 2011-06-14 2013-01-07 Dainichiseika Color & Chem Mfg Co Ltd 吸着剤組成物、放射性セシウム吸着剤及びそれを用いた放射性セシウムの分離方法
JP2013193043A (ja) * 2012-03-21 2013-09-30 Osaka Gas Co Ltd 吸水材料組成物および吸水性シート
WO2015159865A1 (fr) * 2014-04-14 2015-10-22 富士フイルム株式会社 Matériau absorbant l'humidité, procédé de production associé et emballage-coque
JP2016215156A (ja) * 2015-05-22 2016-12-22 株式会社クラレ 水処理用安全フィルター

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115722202A (zh) * 2022-11-08 2023-03-03 中国科学院上海高等研究院 一种用于去除水中有机膦的钇-锆-对苯二甲酸基复合磁性吸附材料、制备方法及其应用
CN115722202B (zh) * 2022-11-08 2024-03-29 中国科学院上海高等研究院 一种用于去除水中有机膦的钇-锆-对苯二甲酸基复合磁性吸附材料、制备方法及其应用

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