US20120325746A1 - Polymer membrane for water treatment and method for manufacture of same, and water treatment method - Google Patents

Polymer membrane for water treatment and method for manufacture of same, and water treatment method Download PDF

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Publication number
US20120325746A1
US20120325746A1 US13/582,528 US201113582528A US2012325746A1 US 20120325746 A1 US20120325746 A1 US 20120325746A1 US 201113582528 A US201113582528 A US 201113582528A US 2012325746 A1 US2012325746 A1 US 2012325746A1
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Prior art keywords
membrane
water treatment
polymer membrane
resin solution
vinyl chloride
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US13/582,528
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English (en)
Inventor
Toshihiro Tamai
Naotaka Oyabu
Saki Tanimura
Takashi Osugi
Ryuichi Matsuo
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Sekisui Chemical Co Ltd
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Sekisui Chemical Co Ltd
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Assigned to SEKISUI CHEMICAL CO., LTD. reassignment SEKISUI CHEMICAL CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: TAMAI, TOSHIHIRO, MATSUO, RYUICHI, OSUGI, TAKASHI, OYABU, NAOTAKA, TANIMURA, SAKI
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0016—Coagulation
    • B01D67/00165—Composition of the coagulation baths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • B01D69/087—Details relating to the spinning process
    • B01D69/0871—Fibre guidance after spinning through the manufacturing apparatus
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/30—Polyalkenyl halides
    • B01D71/301—Polyvinylchloride
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/001—Combinations of extrusion moulding with other shaping operations
    • B29C48/0022—Combinations of extrusion moulding with other shaping operations combined with cutting
    • 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
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
    • C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/12—Activated sludge processes
    • C02F3/1236—Particular type of activated sludge installations
    • C02F3/1268—Membrane bioreactor systems
    • C02F3/1273—Submerged membrane bioreactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/04—Characteristic thickness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/755—Membranes, diaphragms
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00—Biological treatment of water, waste water, or sewage
    • C02F3/02—Aerobic processes
    • C02F3/12—Activated sludge processes
    • C02F3/1236—Particular type of activated sludge installations
    • C02F3/1268—Membrane bioreactor systems
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/10—Biological treatment of water, waste water, or sewage
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T29/00—Metal working
    • Y10T29/49—Method of mechanical manufacture

Definitions

  • the present invention relates to a polymer membrane for water treatment a method for the manufacture of same, and a water treatment method.
  • polymer membranes for water treatment are used for purifying water, for example, for removing turbidity from river water and groundwater, clarification of industrial water, treatment of wastewater and sewage, and as a pretreatment for seawater desalination, and the like.
  • polystyrene PS
  • PVDF poly(vinylidene fluoride)
  • PE polyethylene
  • CA cellulose acetate
  • PAN polyacrylonitrile
  • PVA poly(vinyl alcohol)
  • PI polyimide
  • polysulfone resins are frequently used due to their superior mechanical and chemical properties such as heat resistance, acid resistance, alkali resistance, and the like, and from the additional perspective of the ease of making a membrane.
  • porous hollow fiber membranes By supplying contaminated water under pressure to micropores, porous hollow fiber membranes can remove contaminating substances from water by capturing only contaminating substances of a certain size or larger.
  • properties that are required in such polymer membranes for water treatment include having superior water permeability and superior physical strength, high stability toward a variety of chemical substances (namely, chemical resistance), less likelihood of adhesion of impurities during filtration (namely, superior antifouling properties), and the like.
  • cellulose acetate fiber hollow-fiber separation membranes have been proposed that have comparatively high water permeability and are less likely to become contaminated even when used for long periods (see Patent Document 1).
  • this cellulose acetate hollow-fiber separation membrane has low mechanical strength and its chemical resistance is inadequate. Consequently, there is a problem in that when the separation membrane becomes contaminated, cleaning employs physical means or chemical means using chemical products and is extremely difficult.
  • polymer membranes for water treatment have been proposed using hollow fiber membranes formed from poly(vinylidene fluoride) resin that have both superior physical strength and chemical resistance (see Patent Document 2).
  • This polymer membrane for water treatment can be used by direct immersion in an aeration tank, and can be cleaned using various chemical agents even when contaminated.
  • poly(vinylidene fluoride) tends to have comparatively weak hydrophilic properties, with low antifouling properties.
  • This submersion-type MBR is a method to obtain treated water by suction filtration using hollow fiber-type or flat-type water treatment membranes immersed in a biological water treatment tank, and the membrane surfaces are cleaned by continuous aeration to prevent the reduction in filtration efficiency when contaminants are deposited on the outer surface of the membrane.
  • water treatment is differentiated into inside-out filtration and outside-in filtration.
  • inside-out filtration is used and high-pressure water is supplied to hollow-fiber membranes with a small inner diameter. In this way, water treatment at a high filtration rate is possible.
  • the operational method used for carrying out the water treatment employs low pressure using either a tubular membrane with a large pore diameter made from a composite material on a support frame or a flat membrane, and either an air flow or water flow is supplied to the membrane outer surface to prevent the deposition of the turbidity components on the membrane surface.
  • an inside-out type (outside the tank type) MBR has been proposed in which bio-treated water flows into a hollow-fiber membrane that is installed in a water bio-treatment tank and the filtration is carried out using internal pressure.
  • a tubular-shaped water treatment membrane with an inner diameter of about 5 to 10 mm is used so that no occlusion will occur due to deposition of solids at the module end surface caused by bio-treated water that contains solids of varying sizes.
  • the treatment rate frequently cannot be accommodated due to problems with pressure resistance with flat-membrane filtration, and equipment other than the raw water pump and energy are required as a solution for preventing the deposition of turbidity components on the membrane surface.
  • a resin solution comprising resin and solvent passes into a double-tube-type mold and a non-solvent is used to direct coagulation water to an interior part that will become a hollow part, and the non-solvent induced phase separation method (NIPS method) is applied to carry out phase separation by immersion of the outer part in a coagulation bath (for example, Patent Document 5).
  • NIPS method non-solvent induced phase separation method
  • the resin solution leaving the mold is once brought into contact with air, and the solvent in the resin solution evaporates to form a skin layer.
  • the resin solution is submersed in the coagulation tank by dropping vertically due to gravity, and thereafter the membrane obtained by coagulation of the resin component in the coagulation tank is passed along a guide such as a roller, transferred to a different machine direction, and finally positioned horizontally in the machine direction and cut.
  • the object of the present invention is to provide a polymer membrane for water treatment that maintains mechanical strength, water permeability, and the like, while increasing the water treatment efficiency, and a method for manufacture of a polymer membrane for water treatment wherein the manufacture is easy and reliable, and a water treatment method that can realize efficient water treatment and maintenance.
  • the present inventors discovered a method by which they could simply and reliably manufacture a membrane that would adequately achieve the abovementioned characteristics in a spinning state under specified conditions and/or with transfer/recovery of the membrane under specified conditions, and thereby accomplished the present invention.
  • polymer membrane for water treatment characterizes in comprising a hollow fiber membrane having a self-supporting design composed of the substantially single principal structural material
  • Such polymer membrane for water treatment preferably has one or more below.
  • the pores with a short axis dimension of 10-100 ⁇ m are 80% or more of the total pore surface area
  • the polymer membrane has the fractionation property of an ultrafiltration membrane or a microfiltration membrane.
  • the polymer membrane has;
  • the main structural material is poly(vinyl chloride), chlorinated poly(vinyl chloride), or a vinyl chloride-chlorinated vinyl chloride copolymer.
  • the degree of polymerization of the vinyl chloride resin is 250-3000.
  • the chlorine content in the vinyl chloride resin is 56.7 to 73.2%.
  • the mass ratio of vinyl chloride monomer units in the vinyl chloride resin amounts to 50-99 mass %.
  • a method for the manufacture of a polymer membrane for water treatment has;
  • Such method for the manufacture preferably has one or more below.
  • the method has
  • a spinneret provided with a discharge port, where the discharge port discharges the resin solution in an immersed state into a coagulation tank that contains a non-solvent.
  • the method further has;
  • the difference in specific gravity between the resin solution and the non-solvent is within 1.0.
  • a method for water treatment of the present invention characterizes that the polymer membrane for water treatment described above is used as a separation membrane or that separating water is performed by passing microbiological treated wastewater using activated sludge inside the polymer membrane for water treatment described above.
  • the present invention is possible to provide a polymer membrane for water treatment that maintains mechanical strength, water permeability, and the like, while increasing the water treatment efficiency.
  • polymer membrane for water treatment can realize efficient water treatment and maintenance.
  • FIG. 1 A schematic diagram that describes a cross-section along the radial direction of a polymer membrane for water treatment of the present invention.
  • FIG. 2 A conceptual diagram that describes an inside-out mode MBR using a water treatment unit equipped with a polymer membrane for water treatment of the present invention.
  • FIG. 3 A schematic diagram that describes the discharge angle for the resin solution in a method for manufacturing a polymer membrane for water treatment of the present invention.
  • FIG. 4 A schematic diagram that describes the steps from discharge of the resin solution to cutting of the membrane in a method for manufacturing a polymer membrane for water treatment of the present invention.
  • FIG. 5 A schematic diagram that describes the take-up of the resin solution in a comparative example.
  • the polymer membrane for water treatment of the present invention is primarily a membrane composed of a hollow-fiber membrane that has a self-supporting structure using a substantially single principal structural material.
  • the polymer membrane for water treatment of the present invention is a hollow-fiber membrane that has a single-layer structure formed with a substantially single principal structural material.
  • a single-layer structure means being formed from a single material.
  • weak materials are not strengthened through the formation of composite materials with structural supporting bodies that are stronger materials (ceramics, nonwoven fabrics, and the like), they cannot be maintained in any desired shape, for example a cylinder, tube, or the like. Consequently, in addition to the materials that form the membrane, to maintain the desirable shape while being used as a water treatment membrane, conventional water treatment membranes with relatively large pore diameters are associated with tubular ceramics, or nonwoven fabrics formed into a tubular shape, or the like, as structural frames to support the membrane.
  • the polymer membrane for water treatment of the present invention is formed only from a hollow-fiber membrane, and is not accompanied by a support frame formed from different ingredients or materials (for example, nonwoven fabric, paper, metal, ceramics, and the like) which do not change a desirable shape such as a tube.
  • this means that the polymer membrane for water treatment of the present invention is formed in a single-layer structure, and a laminated structure using different ingredients or materials is not used. Nevertheless, even such a structure must have sufficient strength to maintain the desired shape such as a cylinder, tube, or the like for use as a water treatment membrane. In other words, it has “a self-supporting property/structure”. Consequently, a support frame-less membrane with large pore diameter can be realized.
  • substantially single principal structural material means that it has been formed from substantially a single material.
  • substantially single material means the principal structural material is of one type.
  • one type of resin means a material accounting for 50 to 99 mass %.
  • the design doesn't include the additives normally used.
  • An example of a hollow-fiber membrane is a membrane with an outer diameter of about 3.6 to 10 mm and a thickness of about 0.15 to 2.4 mm.
  • the strength of a hollow-fiber membrane is determined by various factors such as the material, inner diameter, thickness, circularity, internal structure, and the like, among which the use of the SDR value (value calculated as the ratio of the outer diameter and the thickness) was discovered to be effective.
  • SDR value value calculated as the ratio of the outer diameter and the thickness
  • a design in which the SDR value was reduced was linked to a reduction in the membrane filtration area in the water treatment module. Consequently, from the perspective of ensuring balance therebetween, an SDR of about 3.6 or greater is preferred.
  • about 4.0 or greater is preferred and about 20 or less is preferred, and about 16 or less, or about 11 or less is further preferred.
  • the inner diameter is determined by its outer diameter and thickness, but in the example of about 1.6 to 9.4 mm, 4 mm to 8 mm is suitable, and in this case the thickness is preferably about 0.1 mm to 2 mm.
  • examples include
  • a membrane that comprises a hollow-fiber membrane having a self-supporting structure from using a substantially single principal structural material will have an outer diameter of 3.6 mm to 10 mm and an SDR value of 3.6 to 34.
  • an outer diameter of about 5 to 7 mm and an SDR value of about 6.5 to 11 are preferred.
  • the hollow-fiber membrane maintains its strength when internal or external pressure is applied, and a large inner diameter is maintained and the interior of the hollow fiber does not become occluded when the water through-flow has highly concentrated waste water.
  • the membrane inner and outer diameters, thickness, and the like can be measured from the actual dimensions by using electron microphotography.
  • examples include (2) a membrane that comprises a hollow-fiber membrane having a self-supporting structure from using a substantially single principal structural material will have an inner diameter of 3 to 8 mm and an SDR value of 4 to 13,
  • a membrane that comprises a hollow-fiber membrane having a self-supporting structure from using a substantially single principal structural material will have an inner diameter of 1.6 mm to 9.4 mm, and a thickness of 0.15 mm to 2.4 mm.
  • the polymer membrane for water treatment is preferably a porous membrane having a plurality of micropores in its surface.
  • the average pore diameter of these micropores for example, is about 0.001 to 10 ⁇ m, preferably about 0.01 to 1 ⁇ m.
  • the size and density of micropores in the membrane surface can be suitably adjusted using the abovementioned inner diameter, thickness, the intended characteristics and the like, for example, these can be suitable to achieve enough water permeability as mentioned below.
  • using the micropore size, density, and the like can be adjusted, for example, for the fractionation properties of an ultrafiltration membrane or a microfiltration membrane.
  • ultrafiltration membranes have pore sizes of about 2 to 200 nm, while microfiltration membranes have pore sizes of about 50 nm to 10 ⁇ m.
  • the porosity is, for example, about 10 to 90%, and is preferably about 20 to 80%.
  • porosity means the proportion of the total pore area vs. the total area of the polymer membrane for water treatment from an arbitrary horizontal cross-section (radial cross section of a hollow fiber, same below), for example, determined by a method of calculating the respective areas from a microphotograph of a horizontal cross-section of the membrane.
  • the porosity based on the cross-sectional area of the aforementioned hollow-fiber membrane is preferably about 30 to 85%, and about 50 to 85%, about 40 to 75%, or about 50 to 75% are further preferred.
  • pores with a short axis dimension of 10 to 100 ⁇ m are preferably about 80% or more of the total pore surface area, and about 83% or more, about 85% or more, or about 87% or more, are further preferred.
  • pores 21 are constituted in relatively orderly layers so that the long axis will match the radial orientation, and are respectively arranged/distributed so as to be constituted from innermost layer 20 d , inner layer 20 c , outer layer 20 b , and outermost layer 20 a .
  • the arrangement/distribution in this case can have the various layers clearly separated and can be approximately independent, but pores 21 constituted in one layer can be partially nested to overlap with pores 21 constituted in another layer (see X in FIG. 1 ).
  • Pores 21 d are distributed in innermost layer 20 of a hollow-fiber membrane, likewise pores 21 c in inner layer 20 c , pores 21 b in outer layer 20 b , and pores 21 a in outermost layer 20 a , respectively.
  • As the size of pores 21 in each layer for example, long axis A and/or short axis B as shown in FIG. 1 are preferably relatively aligned for each layer within about ⁇ 30%.
  • the long axis dimension of pores 21 c and 21 b in inner layer 20 c and outer layer 20 b preferably amount to, respectively, about 20 to 50% of the thickness and about 25 to 45% of the thickness.
  • the corresponding average long axis dimension of pores 21 c and 20 b are preferably relatively aligned to about ⁇ 30%, and further preferably about ⁇ 15%. Additionally, the long axis dimension of pores 21 d and 21 a in innermost layer 20 d and outermost layer 20 a preferably amount respectively to about 0 to 20% of the thickness and about 5 to 15% of the thickness. The corresponding average long axis dimension of pores 21 d and 20 a , for example, are preferably relatively aligned to about ⁇ 30%, and further preferably about ⁇ 15%.
  • the polymer membrane for water treatment of the present invention is formed from a substantially single principal structural material, and ingredients and materials used in the art can be employed as this principal structural material, among these, vinyl chloride resins are suitable.
  • vinyl chloride resins include vinyl chloride homopolymers, copolymers of vinyl chloride monomer with copolymerizable monomers that have an unsaturated bond, graft copolymers wherein vinyl chloride monomer is graft copolymerized onto a polymer, (co)polymers derived by chlorination of the vinyl chloride monomer units of such materials, and the like. These can be used singly, or two or more types can be combined for use. In particular, to improve the antifouling properties, it is suitable for a hydrophilic monomer to be copolymerized.
  • Chlorination of the vinyl chloride monomer units can be carried out before the polymerization or after the polymerization.
  • the content of monomer units other than vinyl chloride monomer units (including chlorinated vinyl chloride) is within the range that does not inhibit the primary characteristics, and is 50 mass % or more of vinyl chloride-derived units (including units derived from chlorinated vinyl chloride), for example, a content of 50-99 mass % is preferred (the mass calculation here does not include plasticizers in the vinyl chloride resin or other polymers that are blended into said copolymer resin).
  • the vinyl chloride resin is contained amounts to 50 mass % or more (preferably 60 mass % or more, further preferably 70 mass % or more) based on the total resin constituting the membrane, and the monomer or polymer which is blended in is contained amounts to less than 50 mass % based on the total resin constituting the membrane.
  • (meth)acrylic acid derivatives such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, n-pentyl (meth)acrylate, neopentyl (meth)acrylate, cyclopentyl (meth)acrylate, n-hexyl (meth)acrylate, cyclohexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, n-decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth
  • vinyl esters such as vinyl acetate, vinyl propionate, and the like;
  • vinyl ethers such as butyl vinyl ether, cetyl vinyl ether, and the like;
  • aromatic vinyl compounds such as styrene, ⁇ -methylstyrene, and the like;
  • vinyl halides such as vinylidene chloride, vinylidene fluoride, and the like;
  • N-substituted maleimides such as N-phenylmaleimide, N-cyclohexylmaleimide, and the like;
  • vinyl acetate, acrylic ester, ethylene, propylene, vinylidene fluoride to copolymerize or to blend in order to give further flexibility and anti-pollution characteristics, chemical resistance.
  • polymers that are graft-polymerized with vinyl chloride include ethylene/vinyl acetate copolymers, ethylene/vinyl acetate/carbon monoxide copolymers, ethylene/ethyl acrylate copolymers, ethylene/butyl acetate/carbon monoxide copolymers, ethylene/methyl methacrylate copolymers, ethylene/propylene copolymers, acrylonitrile/butadiene copolymers, polyurethanes, chlorinated polyethylene, chlorinated polypropylene, and the like. These can be used singly, or 2 or more types can be combined for use.
  • crosslinkable monomer can be used as the monomer material constituting the polymer membrane.
  • examples of the crosslinkable monomer include
  • (meth)acrylic esters of the polyol such as ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, 1,2-butylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, glycerin di(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and the like;
  • acrylic amides such as N-methyl allyl acrylic amide, N-vinyl acrylic amide, N,N′-methylene bis(meth)acrylic amide, bisacrylic amide acetate;
  • divinyl compounds such as divinylbenzene, divinyl ether, divinyl ethylene urea, and the like;
  • polyallyl compounds such as diallyl phthalate, diallyl maleate, diallylamine, triallyl amine, triallyl ammonium salt, allyl-etherified compounds of pentaerythritol, allyl-etherified compounds of sucrose which has at least two allyl ether units in the molecule, and the like; and
  • (meth)acrylic esters of unsaturated alcohol such as vinyl (meth)acrylate, allyl (meth)acrylate, 2-hydroxy-3-acryloyloxypropyl (meth)acrylate, 2-hydroxy-3-acryloyloxypropyl (meth)acrylate, and the like.
  • hydrophilic monomers examples include, for examples,
  • cationic group-containing vinyl monomers and/or salts thereof such as amino group, ammonium group, pyridyl group, imino group, betaine structure;
  • non-ionic monomer hydrophilic non-ionic group-containing vinyl monomers and/or salts thereof (hereinafter may be referred to as “non-ionic monomer”) such as hydroxyl group, amido group, ester structure, ether structure;
  • anionic monomer such as carboxyl group, sulfonate group, phosphoric acid group
  • examples of the cationic monomer include (meth)acrylic ester or (meth) acrylic amide which has a dialkyl amino group having carbon number of 2-44 such as dimethylamino ethyl (meth)acrylate, diethylamino ethyl (meth)acrylate, dipropylamino ethyl (meth)acrylate, diisopropyl amino ethyl (meth)acrylate, dibutyl amino ethyl (meth)acrylate, diisobutyl amino ethyl (meth)acrylate, di t-butyl amino ethyl (meth)acrylate, dimethylamino propyl (meth)acrylic amide, diethylamino propyl (meth)acrylic amide, dipropylamino propyl (meth)acrylic amide, diisopropyl amino propyl (meth)acrylic amide, dibutyl amino propyl (meth)
  • styrene having total carbon number of 2-44 dialkyl amino group such as dimethylamino styrene, dimethylamino methyl styrene, and the like;
  • vinyl pyridine such as 2- or 4-vinyl pyridine, and the like
  • N-vinyl heterocyclic compounds such as N-vinyl imidazole, and the like;
  • amino group-containing monomers such as vinyl ether, for example, aminoethyl vinyl ether, dimethylamino ethyl vinyl, or quaternized compounds in which the monomers thereof are quaternized by halogenated alkyl (carbon number of 1-22), halogenated benzyl, alkyl (carbon number of 1-18) or aryl (carbon number of 6-24) sulfonic acid or dialkyl (total carbon number of 2-8) sulfate, and the like;
  • vinyl ether for example, aminoethyl vinyl ether, dimethylamino ethyl vinyl, or quaternized compounds in which the monomers thereof are quaternized by halogenated alkyl (carbon number of 1-22), halogenated benzyl, alkyl (carbon number of 1-18) or aryl (carbon number of 6-24) sulfonic acid or dialkyl (total carbon number of 2-8) sulfate, and the like;
  • vinyl monomers having a diallyl-type quaternized ammonium salt such as dimethyl diallyl ammonium chloride, diethyl diallyl ammonium chloride, and the like, or having a betaine structure such as N-(3-sulfopropyl)-N-(meth)acryloyloxyethyl-N,N-dimethyl ammonium betaine, N-(3-sulfopropyl)-N-(meth)acryloyl amide propyl-N,N-dimethyl ammonium betaine, N-(3-carboxymethyl)-N-(meth)acryloyl amido propyl-N,N-dimethyl ammonium betaine, N-carboxymethyl-N-(meth)acryloyloxyethyl-N,N-dimethyl ammonium betaine, and the like.
  • a diallyl-type quaternized ammonium salt such as dimethyl diallyl ammonium chloride,
  • amino group-containing and ammonium group-containing monomers are preferable.
  • (meth)acrylic ester or (meta) acrylic amide which have a hydroxy alkyl (carbon number of 1-8) such as the N-hydroxypropyl (meth)acrylic amide, hydroxyethyl (meth)acrylate, N-hydroxypropyl (meta)acrylic amide, and the like;
  • polyol (meth)acrylic ester such as polyethylene glycol (meth)acrylate (a degree of polymerization of ethylene glycol: 1-30), and the like;
  • (meth)acrylic amide such as N-methyl (meth)acrylic amide, N-n-propyl (meth)acrylic amide, N-isopropyl (meth)acrylic amide, N-t-butyl (meth)acrylic amide, N-isobutyl (meth)acrylic amide, and the like;
  • dialkyl (total carbon number of 2-8) (meth) acrylic amide such as N,N-dimethyl (meth)acrylic amide, N,N-diethyl (meth)acrylic amide, N,N-dimethyl acrylic amide, N,N-diethyl acrylic amide, and the like;
  • N-vinyl cyclic amide such as N-vinyl pyrrolidone, and the like
  • (meth)acrylic ester having alkyl (carbon number of 1-8) group such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, and the like;
  • (meth)acrylic amide having cyclic amido group such as N-(meth)acryloyl morpholine, and the like.
  • vinyl alcohol (meth) acrylic amide monomer and hydroxy alkyl group (carbon number of 1-8)-containing (meth)acrylic ester described above, (meth) acrylic ester of polyol described above are preferable.
  • carboxylic acid monomer having polymeric unsaturated group such as (meta) acrylic acid, maleic acid, itaconic acid, etc. and/or acid anhydride (in cases where having carboxyl groups more than two in one monomer);
  • sulfonic acid monomer having polymeric unsaturated group such as styrene sulfonic acid, 2-(meth)acrylic amide-2-alkyl (carbon number of 1-4) propanesulfonic acid, and the like;
  • phosphate monomer having polymeric unsaturated group such as vinyl phosphonic acid, (meth)acryloyloxy alkyl (carbon number of 1-4) phosphoric acid, and the like.
  • the anionic group may be neutralized in any neutralization degree by basic substance.
  • all anionic groups or part of anionic group in the polymer produce salts.
  • a positive ion in the salt include ammonium ion, trialkyl ammonium ion having total carbon number of 3-54 (e.g., trimethyl ammonium ion, triethyl ammonium ion), hydroxy alkyl ammonium ion having carbon number of 2-4, dihydroxy alkyl ammonium ion having total carbon number of 4-8, tri hydroxy alkyl ammonium ion having total carbon number of 6-12, alkali metal ions, alkaline earth metals ion, and the like.
  • Neutralization may be performed with a monomer and after making a polymer.
  • monomers may include a monomer having the active site that is hydrogen-bondable such as N-vinyl-2-pyrrolidone, hydroxyethyl methacrylate, hydroxyethyl acrylate, and the like.
  • any desired conventionally-known polymerization method can be employed as the abovementioned method for manufacturing vinyl chloride resins.
  • examples thereof include bulk polymerization, solution polymerization, emulsion polymerization, suspension polymerization, and the like.
  • chlorination methods that can be used include methods that are well known in the art, such as are described in Japanese Published Unexamined Patent Application No. H09-278826, Japanese Published Unexamined Patent Application No. 2006-328165, World Patent WO/2008/62526, and the like.
  • a chlorine content of 56.7 to 73.2% in the vinyl chloride resin is preferred.
  • a chlorine content of 58 to 73.2% in the chlorinated vinyl chloride resin is satisfactory, 60 to 73.2% is preferred, and 67 to 71% is further preferred.
  • the degree of polymerization of the vinyl chloride resin is preferably 250-3000, and further preferably 500-1300. If the degree of polymerization is too low, the solution viscosity during spinning will decrease, which will be problematic for the membrane manufacturing operation, and the water treatment membrane made therefrom will tend to lack strength. On the other hand, a degree of polymerization that is too high will cause the viscosity to be too high and tends to result in residual bubbles in the water treatment membrane that has been manufactured.
  • the degree of polymerization means a measured value that complies with JIS K 6720-2.
  • the polymer membrane for water treatment of the present invention is preferably formed from poly(vinyl chloride) (homopolymer), poly(chlorinated vinyl chloride) (homopolymer), or copolymers of vinyl chloride and chlorinated vinyl chloride.
  • additives such as lubricants, heat stabilizing agents, membrane formation aids, or the like, can also be blended into the vinyl chloride resin constituting the polymer membrane for water treatment of the present invention. These can be used singly, or two or more types can be used in combination.
  • lubricants examples include stearic acid, paraffin wax, and the like.
  • heat stabilizing agents generally used in the formation of vinyl chloride resins include tin, lead, and Ca/Zn stabilizers, and the like.
  • membrane formation aids include hydrophilic polymers such as poly(ethylene glycol), polyvinylpyrrolidone, and the like, with various degrees of polymerization.
  • a pure water flux of about 100 L/(m 2 ⁇ h) or more, or about 200 L/(m 2 ⁇ h) or more is suitable for polymer membranes for water treatment of the present invention, and about 600 L/(m 2 ⁇ h) or more is preferred, about 800 L/(m 2 ⁇ h) or more is further preferred, and about 1000 L/(m 2 ⁇ h) or more is still further preferred.
  • the membrane internal pressure resistance is preferably about 0.3 MPa or more, and about 0.35 MPa or more or about 0.4 MPa or more is further preferred.
  • the external pressure resistance of the membrane is preferably about 0.1 MPa or more, and about 0.15 MPa or more or about 0.2 MPa or more is further preferred.
  • a pure water flux of about 100 L/(m 2 ⁇ h) or more with a membrane internal pressure resistance of preferably about 0.3 MPa or more and external pressure resistance of preferably about 0.1 MPa or more is further preferred.
  • TIPS thermally-induced phase separation method
  • NIPS non-solvent phase separation method
  • drawing method drawing method
  • NIPS method manufacturing by the NIPS method is preferred.
  • the resin solution is prepared from a good solvent and the material (resin) that constitutes the membrane, and optionally includes additives.
  • a suitable choice of a good solvent in this case depends on the type of material (resin) or the like. Examples include dimethyl sulfoxide, N,N-dimethylformamide, tetrahydrofuran, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, and the like.
  • a suitable viscosity is, for example, about 500-4000 mPa ⁇ s, and about 1000-3000 mPa ⁇ s is preferred. In this manner, it is possible to maintain the external circular shape of the hollow-fiber membrane in the spinning line, and a membrane of a uniform gauge and thickness can be manufactured.
  • a preparation exhibiting a difference in specific gravity with a non-solvent mentioned below of within 1.0 is suitable, and it is preferably within 0.8, and further preferably within 0.2. In this manner, with the membrane itself floating or submerged in the coagulation tank, it is possible to effectively prevent the membrane from being flattened while being taken up.
  • coagulation tank 30 As shown in FIG. 4 is used.
  • Coagulation tank 30 is filled with a non-solvent.
  • the spinneret used is equipped a discharge port having a concentrically-arranged double nozzle.
  • This spinneret can be positioned inside or outside the coagulation tank, or extends from outside to inside to be able to spin into coagulation tank 30 .
  • spinneret 31 provided with a discharge port (not shown in the figure) is positioned inside coagulation tank 30 , in other words, immersed in non-solvent.
  • the resin solution does not come into contact with air and is discharged directly into non-solvent, and since a liquid-liquid phase separation is initiated rapidly, giving a porous surface with no dense skin layer is produced on the surface.
  • spinning can be oriented horizontally in the same manner as described in the present invention, and in this case the two procedures below for initiating spinning can be considered.
  • the non-solvent flow and the flow of the resin solution from the discharge port of the spinneret are oriented in opposite directions, and the resin solution discharged from the spinneret discharge port experiences substantial discharge resistance when spinning is initiated. For this reason, congestion of the flow occurs in the vicinity of the spinneret discharge port, and this portion of the resin progressively solidifies, resulting in a high likelihood of occlusion in the spinneret discharge port.
  • the non-solvent in the coagulation tank prior to the start of spinning backwashes the spinneret discharge port through which resin solution should flow, and there is a high likelihood the resin solution will solidify in the spinneret discharge port part when spinning begins.
  • the direction of discharge ( FIG. 3 , 32 ) of the resin solution from spinneret 31 is preferably adjusted to be within ⁇ 30° ( FIG. 3 , 33 ) with respect to bottom 30 a of coagulation tank 30 .
  • the resin solution it is preferable for the resin solution to be discharged such that the direction of discharge is adjusted to be within ⁇ 30° with respect to the ground.
  • the system generally adopted has the resin solution discharged vertically from a spinneret, and since the overall outer diameter is less in the case of conventional hollow-fiber membranes, and conforms relatively flexibly even when the machine direction is changed, and thus doesn't cause deformation of the membrane such as flattening or bending.
  • the present inventors identified the most suitable procedure for carrying out spinning would be when, during the manufacture of the polymer membrane for water treatment shown in the present invention, the resin solution is discharged from a spinneret in a horizontal direction and the spinneret is immersed in a coagulation tank.
  • a single-layer membrane without having a support frame would have superior strength and water permeability, so that a polymer membrane for water treatment could be manufactured wherein the membrane terminus would not become clogged even with highly concentrated wastewater such as in bio-treated wastewater, and spinning can take place in the horizontal direction from a spinneret immersed in water.
  • the non-solvent with which the coagulation tank is filled can be suitably selected according to the abovementioned types of resin solution, for example, having water as a principal ingredient is preferred.
  • the difference in temperature between the resin solution discharged from the discharge port (or spinneret) and the non-solvent is preferably within about 100° C. In this manner, it is possible to avoid clogging in the vicinity of the spinneret discharge port due a sharp decrease in the temperature of the resin solution and a rapid increase in viscosity of the resin solution associated with a sharp decrease in the temperature of the resin solution. Additionally, by keeping the non-solvent at a fixed temperature, it is possible to maintain stable phase separation behavior in the resin solution, which can be manifested in stable properties such as water permeability and strength.
  • the take-up of the membrane during membrane manufacture generally is preferably carried out with a linear orientation.
  • the discharge port within ⁇ 30° of horizontal within the coagulation tank, there will be no change in the membrane take-up direction after the resin solution is discharged, and take-up will be easy while maintaining a fixed speed and uniform load. In this way, it is possible to minimize deformations in the membrane structure.
  • Cutting of the membrane after take-up can be done either inside or outside the coagulation tank.
  • cutting 35 is preferably carried out at cutting position 38 higher than position 37 of the discharge port of spinneret 31 in coagulation tank 30 .
  • flow of the internal coagulation liquid from the tips of the discharged membrane due to siphoning effects will be prevented, which will minimize pressure changes in the internal coagulation liquid inside the membrane, and prevent not only flattening of the membrane shape but also variations in shape, which will have the effect of stabilizing the membrane shape.
  • this cutting position when cutting is carried out inside the coagulation tank, there is no particular limitation concerning this cutting position.
  • the polymer membrane for water treatment of the present invention has a superior balance between water permeability and physical strength. Consequently, when suitably employed as a separation membrane in existing water treatment systems, it enables suitable water treatment with the goal of water purification, and in particular the treatment of highly concentrated waste water.
  • the polymer membrane for water treatment of the present invention having such characteristics can be suitably employed as and ultrafiltration (UF) membrane and a microfiltration (MF) membrane.
  • the water treatment method of the present invention can be realized using any method well known in the art.
  • Examples include the use of immersion MBRs (membrane bioreactor method) that is being increasing adopted in recent years, wherein in this case, wastewater drawn in by pump undergoes biological treatment using activated sludge from an activated sludge treatment tank in units employing a hollow-fiber-shaped water treatment membrane.
  • the flow is introduced to the interior of the polymer membrane for water treatment shown in the present invention that is accommodated inside the unit, and water treatment can take place by inner pressure filtration by applying pressure from the inside of the membrane to the outside.
  • the use of the inside-out-type MBR shown in FIG. 2 is advantageous.
  • the method of separating water by passage of activated sludge through the hollow fibers of a polymer membrane for water treatment can be used.
  • an example of the separation method with activated sludge is shown, wherein wastewater is sequentially fed into anaerobic tank 11 as shown by arrow A and then into activated sludge tank 12 , and after a predetermined purification in activated sludge tank 12 , the activated sludge including the treated water is pumped out as shown by arrow B, and using water treatment module 10 with its ends sealed with sealing material 14 having a multiplicity of hollow-fiber water treatment membranes 13 accommodated in a circular casing, a water flow with a pressure load of 0.3 MPa or more of activated sludge containing treated water passes into the interior of the hollow fibers in hollow-fiber treatment membrane 13 , with the treated water shown by arrow D passing through the hollow-fiber membrane and being
  • the polymer membrane for water treatment according to the present invention will have a large inner diameter compared to conventional hollow-fiber membranes for water treatment while maintaining adequate strength, and when conducting an inside-out filtration of waste water with a comparatively high floc content such as bio-treated wastewater, the membrane end surface, in other words the membrane at the intake port where the wastewater is introduced, cannot become clogged. This is a characteristic that is not observed in conventional hollow-fiber-type membranes for water treatment.
  • the spinning direction of membrane 34 was oriented to the horizontal, and in coagulation tank 30 (filled with water), 10 m was taken up in a straight line along the horizontal direction 36 from the discharge port of spinneret 31 .
  • membrane 34 is raised up about 10 cm by roller 39 , and cutting 35 is made by a cutting machine outside coagulation tank 30 and at cutting position 38 higher than position 37 of the discharge port of spinneret 31 which is inside coagulation tank 30 .
  • the membrane obtained has an outer diameter of 5.4 mm, and SDR value of 18 (inner diameter: 4.8 mm), and is of uniform shape without any cracks, bends, swelling, warping, or uneven thicknesses.
  • the tensile strength was 33 N/fiber, and the tensile elongation at break was 50%.
  • pores in the outermost layer and innermost layer had a width (length along the short axis direction; B in FIG. 1 ) of 10 ⁇ m, and the length (length along the long axis direction; A in FIG. 1 ) was 5% of the thickness.
  • the width was 20 ⁇ m and the length was 40% of the thickness.
  • Such pores in other words, pores with a short axis dimension of 10-100 ⁇ m, will have a sum total of cross-sectional surface area for all pores of about 85%.
  • a hollow-fiber membrane single fiber was used to manufacture a water treatment module as shown in FIG. 2 , and a pure water flux of 200 L/m 2 ⁇ hr ⁇ atm was confirmed.
  • bio-treated water with an MLSS of about 3000 means 3,000 mg/L of activated sludge suspended solids
  • industrial wastewater with an SS of about 50 means 50 mg/L suspended solids.
  • the relative water permeability compared to pure water flux was about 80%.
  • the globulin blocking rate was 99% or greater.
  • the spinning direction of membrane 34 was oriented to the horizontal, and in coagulation tank 30 (filled with water), 10 m was taken up in a straight line along the horizontal direction 36 from the discharge port of spinneret 31 .
  • membrane 34 is raised up about 10 cm by roller 39 , and cutting 35 is made by a cutting machine outside coagulation tank 30 and at cutting position 38 higher than position 37 of the discharge port of spinneret 31 which is inside coagulation tank 30 .
  • the membrane obtained has an outer diameter of 5.1 mm, and SDR value of 8.5, and is of uniform shape without any cracks, bends, swelling, warping, or uneven thicknesses.
  • the tensile strength was 45 N/fiber, and the tensile elongation at break was 50%.
  • a hollow-fiber membrane single fiber was used to manufacture a water treatment module as shown in FIG. 2 , and a pure water flux of 120 L/m 2 ⁇ hr ⁇ atm was confirmed.
  • the relative water permeability compared to pure water flux was about 80%.
  • the globulin blocking rate was 99% or greater.
  • the spinning direction of membrane 34 was oriented to the horizontal, and in coagulation tank 30 (filled with water), 10 m was taken up in a straight line along the horizontal direction 36 from the discharge port of spinneret 31 .
  • membrane 34 is raised up about 10 cm by roller 39 , and cutting 35 is made by a cutting machine outside coagulation tank 30 and at cutting position 38 higher than position 37 of the discharge port of spinneret 31 which is inside coagulation tank 30 .
  • the membrane obtained has an outer diameter of 4.6 mm, and SDR value of 5.8, and is of uniform shape without any cracks, bends, swelling, warping, or uneven thicknesses.
  • the tensile strength was 40 N/fiber, and the tensile elongation at break was 50%.
  • a hollow-fiber membrane single fiber was used to manufacture a water treatment module as shown in FIG. 2 , and a pure water flux of 450 L/m 2 ⁇ hr ⁇ atm was confirmed.
  • the relative water permeability compared to pure water flux was about 80%.
  • the globulin blocking rate was 99% or greater.
  • the spinning direction of membrane 34 was oriented to the horizontal, and in coagulation tank 30 (filled with water) 10 m was taken up in a straight line along the horizontal direction 36 from the discharge port of spinneret 31 .
  • membrane 34 is raised up about 10 cm by roller 39 , and cutting 35 is made by a cutting machine outside coagulation tank 30 and at cutting position 38 higher than position 37 of the discharge port of spinneret 31 which is inside coagulation tank 30 .
  • the membrane obtained has an outer diameter of 5.1 mm, and SDR value of 40, and is of uniform shape without any cracks, bends, swelling, warping, or uneven thicknesses.
  • membrane 40 a is introduced into coagulation tank 30 (filled with water) through a 3 cm air gap, and 1 meter downstream from the spinneret, the machine direction for membrane 40 a is changed by 300° using guide roller 41 , and then again the machine direction of membrane 40 b is changed by 30° using guide roller 42 , and take-up is in a straight line of about 8 m.
  • membrane 34 is raised up about 10 cm by roller 39 , and cutting 35 is made by a cutting machine outside coagulation tank 30 and at cutting position 38 higher than position 37 of the discharge port of spinneret 31 inside coagulation tank 30 .
  • the membrane obtained has an outer diameter of 5.4 mm, and SDR value of 18, and the shape is non-uniform with cracks, bends, swelling, warping, and uneven thicknesses.
  • the spinning direction of membrane 34 was oriented to the horizontal, and in coagulation tank 30 (filled with water), 10 m was taken up in a straight line along the horizontal direction 36 from the discharge port of spinneret 31 .
  • membrane 34 is raised up about 10 cm by roller 39 , and cutting 35 is made by a cutting machine outside coagulation tank 30 and at cutting position 38 higher than position 37 of the discharge port of spinneret 31 which is inside coagulation tank 30 .
  • the membrane obtained has an outer diameter of 5.6 mm, and SDR value of 11.2, and is of uniform shape without any cracks, bends, swelling, warping, or uneven thicknesses.
  • a hollow-fiber membrane single fiber was used to manufacture a water treatment module as shown in FIG. 2 , and a pure water flux of 300 L/m 2 ⁇ hr ⁇ atm was confirmed.
  • the relative water permeability compared to pure water flux was about 80%.
  • the globulin blocking rate was 99% or greater.
  • the spinning direction of membrane 34 was oriented to the horizontal, and in coagulation tank 30 (filled with water), 10 m was taken up in a straight line along the horizontal direction 36 from the discharge port of spinneret 31 .
  • membrane 34 is raised up about 10 cm by roller 39 , and cutting 35 is made by a cutting machine outside coagulation tank 30 and at cutting position 38 higher than position 37 of the discharge port of spinneret 31 which is inside coagulation tank 30 .
  • the membrane obtained has an outer diameter of 5.6 mm, and SDR value of 11.2, and is of uniform shape without any cracks, bends, swelling, warping, or uneven thicknesses.
  • a hollow-fiber membrane single fiber was used to manufacture a water treatment module as shown in FIG. 2 , and a pure water flux of 700 L/m 2 ⁇ hr ⁇ atm was confirmed.
  • the relative water permeability compared to pure water flux was about 80%.
  • the globulin blocking rate was 99% or greater.
  • the spinning direction of membrane 34 was oriented to the horizontal, and in coagulation tank 30 (filled with water), 10 m was taken up in a straight line along the horizontal direction 36 from the discharge port of spinneret 31 .
  • membrane 34 is raised up about 10 cm by roller 39 , and cutting 35 is made by a cutting machine outside coagulation tank 30 and at cutting position 38 higher than position 37 of the discharge port of spinneret 31 which is inside coagulation tank 30 .
  • the membrane obtained has an outer diameter of 5.6 mm, and SDR value of 11.2, and is of uniform shape without any cracks, bends, swelling, warping, or uneven thicknesses.
  • a hollow-fiber membrane single fiber was used to manufacture a water treatment module as shown in FIG. 2 , and a pure water flux of 300 L/m 2 ⁇ hr ⁇ atm was confirmed.
  • the relative water permeability compared to pure water flux was about 80%.
  • the globulin blocking rate was 99% or greater.
  • the spinning direction of membrane 34 was oriented to the horizontal, and in coagulation tank 30 (filled with water), 10 m was taken up in a straight line along the horizontal direction 36 from the discharge port of spinneret 31 .
  • membrane 34 is raised up about 10 cm by roller 39 , and cutting 35 is made by a cutting machine outside coagulation tank 30 and at cutting position 38 higher than position 37 of the discharge port of spinneret 31 which is inside coagulation tank 30 .
  • the membranes obtained have an outer diameter of 3.8-10 mm, and SDR value of 7-16, and is of uniform shape without any cracks, bends, swelling, warping, or uneven thicknesses.
  • a hollow-fiber membrane single fiber was used to manufacture a water treatment module as shown in FIG. 2 , and a pure water flux of 300 L/m 2 ⁇ hr ⁇ atm was confirmed for all membranes.
  • a hollow-fiber membrane was manufactured using the same method as in Working Example 1 except that after take-up of the membrane in the horizontal direction, the height of the membrane was not changed but remained as is for the cutting made by the cutting machine in the coagulation tank.
  • a hollow-fiber membrane was manufactured using the same method as in Working Example 1 except that the membrane spinning direction was upward 20°, the membrane was taken up in a straight line, and the cutting was made in the coagulation tank without changing the existing orientation or height. The results were confirmed as exhibiting substantially the same characteristics as in Working Example 1.
  • a hollow-fiber membrane was manufactured using the same method as in Working Example 1 except that membrane spinning direction was downward 20°, the membrane was taken up in a straight line, and the cutting was made in the coagulation tank without changing the existing orientation or height. The results were confirmed as exhibiting substantially the same characteristics as in Working Example 1.
  • a hollow-fiber membrane was manufactured using the same method as in Working Example 1 except that membrane spinning direction was upward 45°, the membrane was taken up in a straight line, and the cutting was made in the coagulation tank without changing the existing orientation or height.
  • the membrane obtained has the shape that is non-uniform with swelling, warping, and uneven thicknesses relative to Working Example 1.
  • a hollow-fiber membrane was manufactured using the same method as in Working Example 1 except that membrane spinning direction was downward 45°, the membrane was taken up in a straight line, and the cutting was made in the coagulation tank without changing the existing orientation or height.
  • the membrane obtained has the shape that is non-uniform with swelling, warping, and uneven thicknesses relative to Working Example 1.
  • the present invention can be widely-used as a membrane for water treatment and a microfiltration membrane for purifying water, such as for removing turbidity from river water and groundwater, clarification of industrial water, treatment of wastewater and sewage, and as a pretreatment for seawater desalination, and the like, in particular, it is used with advantage for MBR.

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US10596524B2 (en) 2013-12-20 2020-03-24 Lg Chem, Ltd. Hollow fiber membrane
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JP2013086042A (ja) * 2011-10-20 2013-05-13 Sekisui Chem Co Ltd 高分子水処理膜
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