WO2017164019A1 - Membrane à fibres creuses - Google Patents

Membrane à fibres creuses Download PDF

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Publication number
WO2017164019A1
WO2017164019A1 PCT/JP2017/010298 JP2017010298W WO2017164019A1 WO 2017164019 A1 WO2017164019 A1 WO 2017164019A1 JP 2017010298 W JP2017010298 W JP 2017010298W WO 2017164019 A1 WO2017164019 A1 WO 2017164019A1
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WO
WIPO (PCT)
Prior art keywords
hollow fiber
fiber membrane
dense layer
less
water
Prior art date
Application number
PCT/JP2017/010298
Other languages
English (en)
Japanese (ja)
Inventor
竜太 田宮
誠之 山田
上野　良之
Original Assignee
東レ株式会社
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Filing date
Publication date
Application filed by 東レ株式会社 filed Critical 東レ株式会社
Priority to JP2017517388A priority Critical patent/JP6973071B2/ja
Priority to CN201780018571.XA priority patent/CN109070011B/zh
Priority to KR1020187026009A priority patent/KR102219541B1/ko
Publication of WO2017164019A1 publication Critical patent/WO2017164019A1/fr

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Classifications

    • 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
    • B01D69/081—Hollow fibre membranes characterised by the fibre diameter
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/02—Hollow fibre modules
    • 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
    • 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
    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
    • 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
    • B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
    • B01D71/441—Polyvinylpyrrolidone
    • 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
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • 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
    • C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
    • 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
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/18—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of unsaturated nitriles, e.g. polyacrylonitrile, polyvinylidene cyanide
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/76—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from other polycondensation products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2201/00—Details relating to filtering apparatus
    • B01D2201/29—Filter cartridge constructions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/022—Asymmetric membranes
    • B01D2325/0232—Dense layer on both outer sides of the membrane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/0283—Pore size
    • B01D2325/02834—Pore size more than 0.1 and up to 1 µm
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2201/00—Apparatus for treatment of water, waste water or sewage
    • C02F2201/002—Construction details of the apparatus
    • C02F2201/006—Cartridges

Definitions

  • the present invention relates to a hollow fiber membrane.
  • Hollow fiber membranes have been widely used in fields ranging from reverse osmosis to microfiltration. As its application, it is widely used for medical applications such as blood purifiers for patients with renal failure and water treatment applications such as for water purifiers.
  • Hydrophobic polymers such as polyethylene and polysulfone are known as materials for hollow fiber membranes, and it is known that hollow fiber membranes using these materials are subjected to a hydrophilic treatment.
  • a hydrophilic treatment a hollow fiber membrane is coated with a hydrophilic polymer after the hollow fiber membrane has been formed, or an injection solution containing a hydrophilic polymer is discharged from a double annular die together with a spinning solution of the hollow fiber membrane to make the hydrophilic There is a method of imparting sex. By performing such a hydrophilic treatment, the water permeability of the hollow fiber membrane is increased.
  • the characteristics required for the cartridge for the water purifier are to have resistance to high water pressure, to have high water permeability, to have high substance removal characteristics, and to have a long cartridge life. Therefore, as a hollow fiber membrane for a water purifier, a hollow fiber membrane having high water permeability and sharp substance fractionation performance has been developed while having strength to withstand water pressure.
  • Patent Document 1 discloses a method of spinning a hollow fiber membrane at a high spinning draft of 100 or 185 in the melt spinning method in order to improve resistance to high water pressure.
  • Patent Document 2 discloses a method of controlling the pore structure of a membrane and increasing the water permeability by controlling the spinning draft rate in a hollow fiber membrane having an asymmetric structure provided with a dense layer.
  • the hollow fiber membrane obtained by the production method disclosed in Patent Document 1 is excellent in resistance to high water pressure, but the cross-sectional structure of the hollow fiber membrane is uniform, that is, there are micropores present in the cross section of the hollow fiber membrane. Since all of them are dense, there is a problem that the water permeability is inferior.
  • As a means for improving the water permeability of the hollow fiber membrane it is conceivable to increase the pore area of the above-mentioned micropores. In this case, however, there is a problem that the hollow fiber membrane is inferior in the fractionation performance.
  • the hollow fiber membrane disclosed in Patent Document 2 has a dense layer and a non-dense layer, and has excellent water permeability by controlling the pore structure, but is resistant to high water pressure. There is a problem that it is inferior.
  • a water purifier cartridge (hereinafter sometimes referred to as a cartridge) provided with a hollow fiber membrane
  • the cartridge is increased in size.
  • challenges Therefore, in order to suppress the enlargement of the cartridge while increasing the membrane area of the hollow fiber membrane, it is conceivable to reduce the diameter of the hollow fiber membrane, in this case, this hollow fiber membrane is inferior in resistance to high water pressure, It tends to be inferior in water permeability.
  • the hollow fiber membrane having a dense layer is reduced in diameter, the resistance of the hollow fiber membrane to high water pressure is further deteriorated.
  • the present invention provides a hollow fiber membrane that is excellent in resistance to high water pressure and excellent in water permeability, and further achieves a long life of a water purifier cartridge equipped with the hollow fiber membrane.
  • the purpose is to do.
  • the present invention is characterized by the following (1) to (5).
  • the hollow fiber membrane according to (1) wherein the dense layer is disposed on an outer surface side of the hollow fiber membrane.
  • (3) The hollow fiber membrane according to (1) or (2), wherein a porosity of the surface of the hollow fiber membrane on which the dense layer is disposed is 15% or more and 45% or less.
  • (4) The hollow fiber membrane according to any one of (1) to (3), comprising a polysulfone-based polymer and polyvinylpyrrolidone.
  • the present invention it is possible to provide a hollow fiber membrane that is excellent in resistance to high water pressure and excellent in water permeability, and can further extend the life of a water purifier cartridge equipped with the hollow fiber membrane.
  • the present inventors have found that the outer diameter, inner diameter and film thickness of the hollow fiber and the structure of the dense layer greatly affect the strength improvement and water permeability of the hollow fiber membrane, and in the longitudinal direction of the hollow fiber membrane.
  • Surface has a plurality of pores, the average pore diameter observed on the hollow fiber membrane surface of the plurality of pores is not less than 0.3 ⁇ m and not more than 0.9 ⁇ m, and the thickness (DT) of the dense layer and the hollow fiber membrane Ratio (DT / WT) to film thickness (WT) is 0.24 or more It has created a hollow fiber membrane of the invention.
  • the outer diameter of the hollow fiber membrane of the present invention is as thin as 350 ⁇ m or less, a large number of the hollow fiber membranes are mounted on a compact hollow fiber membrane module (hereinafter sometimes referred to as a module) or a water purifier cartridge.
  • a module compact hollow fiber membrane module
  • a water purifier cartridge The product life of the module or cartridge can be made excellent.
  • the hollow fiber membrane has a small outer diameter, a large inner diameter, and a thin film thickness. Moreover, from the viewpoint of making the strength of the hollow fiber membrane excellent, it is preferable that the hollow fiber membrane has a large outer diameter, a small inner diameter, and a thick film thickness. In order to satisfy these conflicting conditions, it is important to control the structure of the dense layer. The structure of the dense layer greatly affects the strength retention and water permeability of the membrane.
  • the outer diameter of the hollow fiber membrane is 350 ⁇ m or less, and the lower limit thereof is preferably 190 ⁇ m or more, more preferably 220 ⁇ m or more, and further preferably 260 ⁇ m or more.
  • the upper limit is preferably 330 ⁇ m or less, and more preferably 310 ⁇ m or less.
  • the inner diameter of the hollow fiber membrane is 150 ⁇ m or more, and the lower limit thereof is preferably 155 ⁇ m or more, and more preferably 160 ⁇ m or more.
  • the upper limit is preferably 220 ⁇ m or less, more preferably 210 ⁇ m or less, and even more preferably 200 ⁇ m or less.
  • the film thickness of the hollow fiber membrane is 30 ⁇ m or more and 90 ⁇ m or less, and the lower limit thereof is preferably 40 ⁇ m or more, and more preferably 50 ⁇ m or more.
  • the upper limit is preferably 80 ⁇ m or less, and more preferably 70 ⁇ m or less.
  • the hollow fiber membrane of the present invention has a dense layer, and this dense layer is disposed on the outer surface side or the inner surface side of the hollow fiber membrane.
  • the hollow fiber membrane of the present invention has a plurality of holes on the surface of the hollow fiber membrane on which the dense layer is arranged, and the average pore diameter observed on the hollow fiber membrane surface of the plurality of holes is 0.3 ⁇ m or more. For this reason, the water permeability of the hollow fiber membrane is extremely excellent.
  • the average pore diameter observed on the hollow fiber membrane surface of the above pores is 0.9 ⁇ m or less, the strength of the hollow fiber membrane can be improved, and the turbidity removal performance such as bacteria and fine particles can be removed. Can be increased.
  • the lower limit of the average pore diameter of the plurality of holes is preferably 0.35 ⁇ m or more, and more preferably 0.40 ⁇ m or more.
  • the upper limit of the average pore diameter of the plurality of holes is preferably 0.85 ⁇ m or less, and more preferably 0.80 ⁇ m or less.
  • the dense layer means that when a cross section perpendicular to the longitudinal direction of the hollow fiber membrane is observed with a scanning electron microscope (SEM), the presence of pores having a pore area exceeding 0.28 ⁇ m 2 is not observed. , Refers to a layer having only pores with a pore area of 0.28 ⁇ m 2 or less.
  • the macro void and the finger void are not formed in the membrane cross section.
  • the hollow fiber membrane of the present invention has a ratio (DT / WT) of the dense layer thickness (DT) and the hollow fiber membrane thickness (WT) of 0.24 or more. It can be maintained sufficiently, and not only the resistance of the hollow fiber membrane to high water pressure but also excellent workability and handling properties required for modularization can be achieved.
  • the thickness of the dense layer can be measured by the method described in the examples.
  • the dense layer of the hollow fiber membrane is disposed on the surface of the hollow fiber membrane in contact with the water to be treated.
  • the dense layer of the hollow fiber membrane is disposed on the surface of the hollow fiber membrane in contact with the water to be treated.
  • the hollow fiber membrane of the present invention has a plurality of holes on the surface of the hollow fiber membrane on which the dense layer is arranged, and the porosity on this surface is preferably 15% or more and 45% or less.
  • a porosity of 15% or more on the surface on the dense layer side of the hollow fiber membrane is preferable because the water permeability is excellent.
  • the hole area ratio on the surface of the dense layer side of the hollow fiber membrane is 45% or less, the strength and removal performance can be sufficiently maintained.
  • the lower limit of the open area ratio is more preferably 18% or more, and further preferably 21% or more.
  • the upper limit of the open area ratio is more preferably 42% or less, and further preferably 39% or less.
  • the dry part atmosphere is adjusted and the phase separation rate of the polymer is controlled.
  • the phase separation rate of the polymer examples include adjusting the content of the hydrophilic polymer.
  • the hollow fiber membrane of the present invention preferably contains a hydrophilic polymer.
  • the reason for this is that by imparting hydrophilicity to the membrane surface, it is possible to improve the water permeability and to prevent turbidity from adhering to the membrane.
  • the content of the hydrophilic polymer is large, the hydrophilic polymer itself retains water, so that it becomes a permeation resistance and water permeability decreases. Therefore, the upper limit of the content of the hydrophilic polymer is preferably 20 parts by mass or less and more preferably 15 parts by mass or less with respect to the mass of the entire hollow fiber membrane.
  • the lower limit is preferably 3 parts by mass or more, and more preferably 5 parts by mass or more.
  • the ratio of the hydrophilic polymer to the hydrophobic polymer (hydrophilic polymer / hydrophobic polymer) on the surface of the hollow fiber membrane where the dense layer is present is preferably 0.80 or less, and more preferably 0.70.
  • the ratio of the hydrophilic polymer to the hydrophobic polymer (hydrophilic polymer / hydrophobic polymer) on the surface opposite to the surface of the hollow fiber membrane where the dense layer exists is also 0. 80 or less is preferable, and 0.70 or less is more preferable.
  • the hydrophilic polymer means a water-soluble polymer compound or a polymer compound that interacts with water molecules by electrostatic interaction or hydrogen bonding even if it is water-insoluble.
  • polyalkylene oxide such as polyethylene oxide and polypropylene oxide, polyvinyl alcohol, polyvinyl pyrrolidone (hereinafter sometimes referred to as PVP), polyvinyl acetate, polydimethylmethoxy acrylate, polydimethylacrylamide, and vinyl pyrrolidone.
  • Nonionic hydrophilic polymers such as copolymers with acrylic acid, copolymers of vinyl acetate and vinylpyrrolidone, anionic hydrophilic polymers such as polyacrylic acid, polyvinyl sulfate, carboxymethyl cellulose, polyallylamine, polylysine, chitosan, poly [ Cationic hydrophilic polymers such as methacrylic acid ⁇ 2 (dimethylamino) ethyl ⁇ ], polymethacryloyloxyethyl phosphorylcholine, polymethacryloyloxyethyldimethylan Zwitterionic hydrophilic polymers such as niobium propionate and the like. Two or more hydrophilic polymers may be contained in the hollow fiber membrane. In particular, from the viewpoint of suppressing adhesion of turbidity, nonionic hydrophilic polymers and zwitterionic hydrophilic polymers are preferably used.
  • a hydrophobic polymer As a material (component) constituting the substrate of the hollow fiber membrane, a hydrophobic polymer is preferable.
  • the hydrophobic polymer include polysulfone (hereinafter sometimes referred to as PSF), polyethersulfone, and polyarylate.
  • PSF polysulfone
  • Polysulfone polymers such as polyvinylidene fluoride, fluororesins such as polyvinylidene fluoride, cellulose resins such as cellulose triacetate and cellulose diacetate, polymethyl methacrylate, polyacrylonitrile, polyamide, etc. are preferably used. From the viewpoints of strength and water permeability, polysulfone polymers are preferably used. It is particularly preferable to add PVP to a spinning dope composed of a polysulfone polymer from the viewpoint of easy control of the membrane structure of the present invention.
  • composition ratio of the hollow fiber membrane is preferably a mass ratio (%), and the polysulfone polymer is 5 to 20% with respect to all the components of the hollow fiber membrane.
  • the hollow fiber membrane preferably contains polyvinyl pyrrolidone in addition to the polysulfone polymer.
  • Polyvinylpyrrolidone having various molecular weights can be used, but K90 (trade name, manufactured by ISP, weight average molecular weight 1.3 million), K60 (trade name, manufactured by Tokyo Chemical Industry Co., Ltd., weight average molecular weight). 160,000), K30 (trade name, manufactured by BASF, weight average molecular weight 40,000), K17 (trade name, manufactured by ISP, weight average molecular weight 10,000), and other commercially available products can be used conveniently. You may superpose
  • the components of the hollow fiber membrane such as polysulfone polymer and PVP are dissolved in a solvent to obtain a spinning dope.
  • the solvent is preferably a high boiling polar solvent such as dimethylacetamide (hereinafter abbreviated as DMAc) or N-methylpyrrolidone, but other combinations can be used as long as they can be dissolved uniformly.
  • the water permeability of the hollow fiber membrane of the present invention is preferably 30 ml / Pa / hr / m 2 or more, more preferably 35 ml / Pa / hr / m 2 or more, and 40 ml / Pa / hr. / M 2 or more is more preferable.
  • the upper limit of the water permeability of the hollow fiber membrane is not particularly limited, but if the water permeability is too high, the fractionation performance may be lowered.
  • the upper limit of the water permeability of the hollow fiber membrane is 120 ml / Pa / It is preferably hr / m 2 or less, more preferably 110 ml / Pa / hr / m 2 or less, and even more preferably 100 ml / Pa / hr / m 2 or less.
  • the removal rate of latex bead particles having a particle diameter of 0.2 ⁇ m is preferably 80% or more, and more preferably 90% or more.
  • the hollow fiber membrane of the present invention comprises the composition of the spinning dope and the composition of the injection solution, the discharge linear velocity and the injection solution discharge linear velocity when discharging the spinning dope from the die, the dew point / temperature of the cold air in the dry part after discharge, and the cold air velocity. It can be obtained by controlling the draft ratio, the coagulation bath temperature, the washing conditions and the like when discharging the spinning dope.
  • the hollow fiber membrane of the present invention is not particularly limited, but using an orifice type double ring cap, a spinning stock solution containing a polymer as a material for the hollow fiber membrane is fed from the outer annular slit, and the injected liquid is fed to the inner central pipe.
  • the hollow fiber membrane having an asymmetric structure can be formed by discharging each, passing through the dry part, and then coagulating in a coagulating solution, followed by washing with warm water.
  • the spinning draft rate when producing the hollow fiber membrane of the present invention is preferably 2 or more and 6 or less.
  • the spinning draft rate is a ratio between the discharge linear velocity of the film-forming composition from the outer peripheral slit portion of the double ring die and the winding speed of the hollow fiber membrane, and the winding speed is defined as the film-forming composition. It shows the value divided by the discharge linear velocity.
  • the discharge linear velocity is a linear velocity when the film-forming composition is discharged from the outer peripheral slit of the double ring die, and is a value obtained by dividing the discharge flow rate by the outer slit sectional area.
  • the spinning draft rate By setting the spinning draft rate to 2 or more, the water permeability of the hollow fiber membrane is improved. On the other hand, by setting the spinning draft rate to 6 or less, the spinning stability can be improved and the yarn breakage frequency can be reduced.
  • the spinning fiber draft is high when the hollow fiber membrane has a thin yarn diameter (outer diameter)
  • the outer surface of the hollow fiber membrane is affected by the spinning draft when the injected liquid has non-coagulation properties. The smoothness is lost, a pleated structure is formed, and the dense layer tends to be thin.
  • the thickness of the dense layer is reduced, the fractionation performance of the hollow fiber membrane is reduced, and the resistance of the hollow fiber membrane to high water pressure (hereinafter sometimes referred to as pressure resistance) is reduced. There is concern to cause.
  • the viscosity of the spinning dope is preferably 2 Pa ⁇ s or more and 11 Pa ⁇ s or less.
  • the viscosity of the spinning dope is preferably 2 Pa ⁇ s or more and 11 Pa ⁇ s or less.
  • the liquid to be injected into the center pipe of the double ring cap can be appropriately selected from solid or non-solid according to the desired form of the hollow fiber membrane.
  • This coagulation value represents the added mass of the injected liquid when the injection solution is added little by little with respect to 50 g of 1% by mass of the main polymer constituting the membrane, and the inside of the system becomes cloudy. It shows that the solidification property of injection
  • a solidifying liquid When a solidifying liquid is used as the injection liquid, since solidification starts from the inner surface, a dense layer is formed on the inner surface side of the hollow fiber membrane.
  • a non-solidifying liquid when used, solidification starts from the outer surface by the coagulation bath provided on the downstream side, so that a dense layer is formed on the outer surface side of the hollow fiber membrane. Therefore, in the case of the water purifier use used by the flow filtered from the outer surface side to the inner surface side of the hollow fiber membrane, a non-solidifying liquid is particularly preferably used.
  • the absolute value of the discharge linear velocity of the spinning dope is preferably 0.05 m / s or more, and more preferably 0.1 m / s or more. On the other hand, it is preferably 0.3 m / s or less, and more preferably 0.25 m / s or less.
  • the absolute value of the discharge linear velocity of the injected liquid is preferably 0.05 m / s or more, and more preferably 0.1 m / s or more. On the other hand, it is preferably 0.5 m / s or less, and more preferably 0.3 m / s or less.
  • the relative value of the discharge linear velocity of the spinning dope and the injected liquid is preferably 0.5 or more, and more preferably 0.6 or more. On the other hand, it is preferably 2.0 or less, and more preferably 1.5 or less.
  • the outer diameter variation of the hollow fiber membrane is preferably 15% or less, more preferably 10% or less.
  • the outer diameter variation was evaluated by the method described in the examples. As a means for setting the outer diameter variation of the hollow fiber membrane within the above range, there is control of the size of the annular slit of the double ring cap or the pressure loss of the central pipe of the double ring cap.
  • the hollow fiber membrane In the spinning process of the hollow fiber membrane, when the phase separation of the hollow fiber membrane is induced by heat, the hollow fiber membrane is cooled in a dry part and then rapidly cooled in a coagulation bath to be solidified.
  • the spinning solution When inducing hollow fiber membrane phase separation with a poor solvent in the spinning process of the hollow fiber membrane, the spinning solution is discharged in contact with a coagulation liquid containing the poor solvent and solidified in a coagulation bath comprising the poor solvent. .
  • the poor solvent is supplied into the hollow fiber membrane by diffusion, so that the supply amount of the poor solvent changes in the thickness direction of the hollow fiber membrane.
  • the hole diameter of the cross section in the film thickness direction of the hollow fiber membrane increases from one surface of the hollow fiber membrane toward the other surface. Therefore, it is preferable to contact the coagulating liquid containing the poor solvent and the spinning dope immediately after discharge. If the concentration is adjusted by using the coagulation liquid as a mixture of a poor solvent and a good solvent, the coagulation property is changed, and the minor diameter of the pores on the surface in contact with the coagulation liquid and the thickness of the dense layer can be controlled.
  • the passage time of the dry part is preferably 0.02 seconds or more, more preferably 0.14 seconds or more.
  • 0.40 second or less is preferable, and 0.35 second or less is more preferable.
  • the poor solvent concentration in the coagulation bath is preferably 30 parts by mass or more, more preferably 50 parts by mass or more, and still more preferably 80 parts by mass or more with respect to the entire coagulation liquid.
  • the temperature of the coagulation bath since the temperature of the coagulation bath is high, solvent exchange in the coagulation bath is likely to occur, and the amount of residual solvent in the hollow fiber membrane can be reduced. Is more preferable, and 70 ° C. or higher is more preferable.
  • the discharge temperature of the spinning dope is preferably 25 ° C. or higher.
  • the discharging temperature of the spinning solution is preferably 70 ° C. or less, and more preferably 55 ° C. or less.
  • the concentration of the coagulation bath changes over time depending on the supply of the solvent from the spinning dope and the coagulation solution. For this reason, it is preferable to suppress the change in concentration by increasing the amount of the coagulation bath, or to adjust the concentration as needed by monitoring the concentration.
  • the dry section it is also effective to control the opening of the hollow fiber membrane by providing a traveling section in which the temperature and humidity are more positively controlled, and variation in the performance of the obtained hollow fiber membrane can be reduced.
  • the dry section although not particularly limited, in order to more actively control the humidity of the dry section atmosphere, it is possible to provide a cold wind tube on both sides of the spinning stock solution discharged from the double ring mouthpiece or from the double ring mouthpiece. It is conceivable to surround the discharged spinning stock solution with an annular cold wind tube.
  • a method of supplying cold air from one side of the cold air tube and exhausting cold air from the other side, or a method of supplying cold air from both sides it is preferable because the humidity of the dry part atmosphere can be more positively controlled.
  • the periphery of the spinning dope discharged from the double ring die is surrounded by an annular cold wind tube, it is preferable because the dry part is less affected by outside air and the performance variation of the obtained hollow fiber membrane can be reduced.
  • the dew point of the dry part is preferably 18 ° C. or higher, and more preferably 21 ° C. or higher.
  • the wind speed of the cold air in the dry part is preferably 0.1 m / s or more, and more preferably 0.5 m / s or more.
  • the wind speed of the dry part is preferably 10 m / s or less, more preferably 5 m / s or less. preferable.
  • the length of the dry part is preferably 10 to 200 mm in order to make the hole diameter on the surface of the hollow fiber membrane suitable, while preventing the yarn from shaking during film formation.
  • the poor solvent is a solvent that does not dissolve the polymer that mainly forms the structure of the hollow fiber membrane at the film forming temperature.
  • the poor solvent may be appropriately selected according to the type of polymer, but water is preferably used.
  • the good solvent may be appropriately selected according to the type of polymer, but N, N-dimethylacetamide is preferably used when the polymer that forms the structure of the hollow fiber membrane is a polysulfone polymer.
  • the hollow fiber membrane can be obtained in a wet state, but since the water permeability of the hollow fiber membrane is unstable as it is, drying of moisture and crosslinking reaction of a hydrophilic polymer (PVP, etc.) Is required.
  • a hydrophilic polymer such as PVP
  • hydrophilicity can be imparted to the hollow fiber membrane, and water permeability can be improved and turbidity can be prevented from adhering to the membrane.
  • the hydrophilic polymer remaining in the film may be slightly eluted. This is undesirable in medical and food industry applications.
  • ⁇ -ray irradiation is effective for vinyl-based hydrophilic polymers.
  • the hydrophilic polymer when it is polyvinylpyrrolidone, it can be crosslinked by heating.
  • the drying temperature is preferably 100 ° C. or higher because water is evaporated.
  • the heat treatment temperature for crosslinking is preferably about 5 hours at 170 ° C., about 2.5 hours at 180 ° C., and about 1.5 hours at 190 ° C. If the temperature is further increased, the processing time is shortened accordingly. At 150 ° C. or lower, the treatment time is too long and is not practical.
  • the hydrophilic polymer is unevenly distributed on the surface of the hollow fiber membrane. Since the water permeation performance of the membrane and the filtration flow rate when modularized are lowered, it is preferable to wash the obtained hollow fiber membrane with warm water as a pretreatment. As temperature of warm water, 60 ° C or more is preferred, 70 ° C or more is more preferred, and 80 ° C or more is still more preferred. Moreover, it is preferable that it is 99 degrees C or less.
  • the mass of the hydrophilic polymer after washing with warm water is preferably 3 parts by mass or more and 20 parts by mass or less, and more preferably 5 parts by mass or more and 10 parts by mass or less with respect to the mass of the entire film.
  • the hollow fiber membrane of the present invention can be suitably used for a cartridge for a water purifier.
  • the conventionally used method can be employ
  • the SEM image was binarized to obtain an image in which the pores were black and the structural polymer portion was white.
  • the total area S ( ⁇ m 2 ) of the holes and the number of black holes (hereinafter referred to as the total number of openings) were read, and the average hole area ( ⁇ m 2 ) was calculated by the following formula. Further, the average pore diameter ( ⁇ m) was calculated from the average pore area ( ⁇ m 2 ). In addition, this calculation was performed assuming that the hole shape is a perfect circle.
  • Average pore area ( ⁇ m 2 ) S ( ⁇ m 2 ) / total number of apertures
  • Average pore diameter ( ⁇ m) 2 ⁇ ⁇ (average pore area / ⁇ )
  • the hollow fiber membrane was soaked in water for 5 minutes, then frozen with liquid nitrogen, quickly folded, and perpendicular to the longitudinal direction of the hollow fiber membrane as a cross-sectional observation sample
  • the cross section is observed with SEM (S-5500, manufactured by Hitachi High-Technologies Corporation) at a magnification of 3000 times.
  • the surface of the denser structure is the left side of the image, and the structure is rough.
  • the image was captured in a computer so that the front side of the image was placed on the right side of the image.
  • a hollow fiber membrane in which the structure portion is dense on the outer surface side and the structure portion is rough on the inner surface side is described as an example.
  • the image is cut out at the same contrast part and binarized, and then connected together as before. Returned to the image.
  • the image analysis may be performed by painting other than the structure portion in black.
  • the hole area was obtained by analyzing the portion displayed in black by the above-described binarization processing of the image, that is, the area of a single hole portion by image processing software.
  • the number of pixels of the scale bar indicating a known length in the image was measured, and the length per pixel number ( ⁇ m) was calculated.
  • the size of the captured image was 42.38 ⁇ m wide ⁇ 31.79 ⁇ m long.
  • holes with a pore area exceeding 0.28 ⁇ m 2 are painted in a fluorescent color, and a layer having no pores with a pore area exceeding 0.28 ⁇ m 2 is used as a dense layer in the direction from the outer surface to the inner surface of the hollow fiber membrane.
  • the thickness of the dense layer was measured.
  • pores having a pore area exceeding 0.28 ⁇ m 2 may be observed near the dense layer surface.
  • a plurality of holes having a hole area of 0.28 ⁇ m 2 or less are recognized as one hole in the vicinity of the dense layer surface, and the hole area exceeds 0.28 ⁇ m 2.
  • the fluorescent color may be filled.
  • the thickness of the dense layer was measured as follows. First, a straight line perpendicular to the outer surface was drawn in the thickness direction of the hollow fiber membrane, that is, in the direction from the outer surface to the inner surface of the hollow fiber membrane. From the holes existing on this straight line, a hole having a hole area closest to the outer surface exceeding 0.28 ⁇ m 2 was searched for. Of the intersection points between the holes and the straight line, an intersection point closer to the outer surface was selected, and the distance between the intersection point and the outer surface was taken as the thickness of the dense layer.
  • the above image was divided into three in the lengthwise direction, and three images having a field of view 42.38 ⁇ m ⁇ length 10.6 ⁇ m were obtained.
  • the thickness of the dense layer at the vertical midpoint of each field of view was measured as described above.
  • the thickness of the dense layer was determined from each of the three divided fields of view, and the same measurement was performed from the 20 captured images to obtain a total of 60 measurement data of the thickness of the dense layer.
  • the average value of 60 measurement data was calculated and defined as the thickness (DT) of the dense layer having only pores having a pore area of 0.28 ⁇ m 2 or less.
  • the ratio of hydrophilic polymer to hydrophobic polymer (hydrophilic polymer / hydrophobic polymer) contained on the surface was obtained.
  • the measurement method will be described in detail by exemplifying a case where PVP is used as the hydrophilic polymer and PSF is used as the hydrophobic polymer.
  • the area of the absorption peak of the PSF from the benzene ring C C in the vicinity of 1580 cm -1 (Acc), derived from amide bonds PVP near 1650 cm -1
  • the area (Aco) of the absorption peak was calculated, and the ratio (Aco) / (Acc) of the peak areas was determined.
  • the peak area ratio is obtained by the same method, the average value of the measurement data of the total 30 is calculated, and the ratio of PVP to PSF on the surface to be measured of the hollow fiber membranes (PVP / PSF) and did.
  • Rejection rate 1-Cp / Cf
  • Cp Concentration on the transmission side
  • Cf Concentration on the supply side
  • the relationship between the absorbance at 260 nm and the latex bead concentration was measured in advance, and the concentration was determined by measuring the absorbance of the suspension on the transmission side. Absorbance was measured using a spectrophotometer (manufactured by Hitachi, Ltd., U-5100).
  • Ratio of dense layer thickness (DT) to film thickness (WT) (DT / WT) From the thickness (DT) of the dense layer calculated in (4) above and the film thickness (WT) of the hollow fiber membrane calculated in (7) above, the thickness (DT) of the dense layer and the film thickness (WT) of the hollow fiber membrane are calculated. The ratio (DT / WT) was calculated.
  • Example 1 15 parts by weight of a hydrophobic polymer (PSF (Udelpolysulfone (registered trademark) P-3500) manufactured by Solvay), 7 parts by weight of a hydrophilic polymer (PVP (K90 manufactured by ISP)) and N, N-dimethylacetamide ( DMAc) 75 parts by mass and 3.0 parts by mass of water were dissolved and stirred to prepare a spinning dope.
  • This spinning dope had a viscosity at 37 ° C. of 5.0 Pa ⁇ s. This spinning dope was discharged from the annular slit of the double ring die.
  • a non-solidifying liquid consisting of 55 parts by mass of DMAc, 30 parts by mass of polyvinyl pyrrolidone (BASF K30, weight average molecular weight 40,000) and 15 parts by mass of glycerin was discharged from the center pipe.
  • the base was kept at 37 ° C.
  • a cold air cylinder was installed in the dry section, and a predetermined dry length was allowed to pass while flowing cold air gas from both sides of the spinning dope.
  • the dry part dew point during spinning was as shown in Table 1.
  • the spinning stock solution that has passed through the dry section is solidified by immersing it in an 80 ° C. coagulation bath containing 90 parts of water and 10 parts of DMAc mixed solution.
  • a hollow fiber membrane wound up and wet was obtained.
  • the wound hollow fiber membrane had an outer diameter of 300 ⁇ m, an inner diameter of 180 ⁇ m, and a film thickness of 60 ⁇ m.
  • the obtained hollow fiber membrane was cut into 30 cm in the longitudinal direction and washed with hot water at 90 ° C. for 3 hours.
  • the hollow fiber membrane was dried in a dry heat dryer and heat-treated at 160 ° C. or higher to obtain a dry hollow fiber membrane.
  • the 1994 hollow fiber membranes in the dry state were folded in a U shape, inserted into a cylindrical case (inner diameter 26 mm, length 45 mm), and the opening was fixed with polyurethane resin to obtain a hollow fiber membrane module.
  • Tables 1 and 2 show the configuration and various performances of the obtained hollow fiber membrane, the hollow fiber membrane module filtration flow rate, the water purifier cartridge turbid filtration capacity, and the like.
  • Example 2 A wet hollow fiber membrane was obtained in the same manner as in Example 1. The obtained hollow fiber membrane was cut into 30 cm in the longitudinal direction, the hollow fiber membrane was dried in a dry heat drier, and heat-treated at 160 ° C. or higher to obtain a dry hollow fiber membrane.
  • the 1994 hollow fiber membranes in the dry state were folded in a U shape, inserted into a cylindrical case (inner diameter 26 mm, length 45 mm), and the opening was fixed with polyurethane resin to obtain a hollow fiber membrane module.
  • Tables 1 and 2 show the configuration and various performances of the obtained hollow fiber membrane, the hollow fiber membrane module filtration flow rate, the water purifier cartridge turbid filtration capacity, and the like.
  • Example 3 A wet hollow fiber membrane was obtained in the same manner as in Example 1. The obtained hollow fiber membrane was cut into 30 cm in the longitudinal direction and washed with hot water at 90 ° C. for 3 hours. The hydrophilic polymer in the hollow fiber membrane was crosslinked by gamma ray irradiation (25 kGy).
  • Tables 1 and 2 show the configuration and various performances of the obtained hollow fiber membrane, the hollow fiber membrane module filtration flow rate, the water purifier cartridge turbid filtration capacity, and the like.
  • Example 1 The same method as in Example 1 except that the spinning dope is discharged from the annular slit of the double ring die at a discharge linear velocity of 0.003 m / s and the injection liquid is discharged from the injection liquid pipe at a discharge linear velocity of 0.04 m / s. As a result, a dry hollow fiber membrane was obtained.
  • the yarn diameter of the hollow fiber membrane was an outer diameter of 300 ⁇ m, an inner diameter of 180 ⁇ m, and a film thickness of 60 ⁇ m.
  • the 1994 hollow fiber membranes in the dry state were folded in a U shape, inserted into a cylindrical case (inner diameter 26 mm, length 45 mm), and the opening was fixed with polyurethane resin to obtain a hollow fiber membrane module.
  • Tables 1 and 2 show the configuration and various performances of the obtained hollow fiber membrane, the hollow fiber membrane module filtration flow rate, the water purifier cartridge turbid filtration capacity, and the like.
  • SEM S-5500, manufactured by Hitachi High-Technologies Corporation
  • the membrane structure of the outer surface was stretched in the longitudinal direction to form a pleated structure. Therefore, the thickness of the dense layer in the hollow fiber membrane was reduced, and a hollow fiber membrane having low pressure resistance was obtained.
  • Example 2 The hollow fiber membrane was wound around the skein frame by the same operation as in Example 1 except that the viscosity of the spinning dope was set to 1.5 Pa ⁇ s and discharged from the annular slit of the double ring die. The yarn breakage between the base and the coagulation bath repeatedly occurred, making it difficult.
  • the evaluation results of the hollow fiber membrane are shown in Tables 1 and 2.
  • the hollow fiber membrane that was partially collected had a thin dense layer and a very large ROD of 27%. Since the ROD was large, the performance of the hollow fiber membrane became unstable, and the quality of the hollow fiber membrane deteriorated. In addition, the quality of the hollow fiber membrane of the comparative example 2 was inferior, and this hollow fiber membrane could not be bundled into a U shape. Therefore, a hollow fiber membrane module cannot be produced to evaluate the module filtration flow rate, and in the hollow fiber membrane of Comparative Example 2, the hollow fiber membrane module filtration flow rate and the water purifier cartridge turbidity filtration ability can be evaluated. I could not do it.
  • Example 3 The same method as in Example 1 except that the spinning dope is discharged from the annular slit of the double ring die at a discharge linear velocity of 0.28 m / s and the injection liquid is discharged from the injection liquid pipe at a discharge linear velocity of 0.22 m / s.
  • the hollow fiber membrane had an outer diameter of 360 ⁇ m, an inner diameter of 220 ⁇ m, and a film thickness of 70 ⁇ m.
  • hollow fiber membranes in the dry state were folded in a U shape, inserted into a cylindrical case (inner diameter 26 mm, length 45 mm), and the opening was fixed with polyurethane resin to obtain a hollow fiber membrane module.
  • Tables 1 and 2 show the configuration and various performances of the obtained hollow fiber membrane, the hollow fiber membrane module filtration flow rate, the water purifier cartridge turbid filtration capacity, and the like.
  • the present invention can be used as a hollow fiber membrane applicable to a hollow fiber membrane module or a water purifier cartridge in the field of water treatment.
  • a water purifier it can also be used for medical applications such as a plasma separation membrane.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)
  • Textile Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Water Supply & Treatment (AREA)
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Abstract

La membrane à fibres creuses de l'invention est équipée d'une couche compacte possédant uniquement des orifices dont la surface d'ouverture est inférieure ou égale à ０,２８μｍ２, dans des conditions d'observation selon un plan transversal perpendiculaire dans la direction longitudinale de la membrane à fibres creuses. La couche compacte est placée côté surface externe ou côté surface interne de la membrane à fibres creuses. La membrane à fibres creuses présente un diamètre externe inférieur ou égal à 350μｍ, un diamètre interne supérieur ou égal à 150μｍ, et une épaisseur supérieure ou égale à 30 μｍ et inférieure ou égale à 90 μｍ. La surface de la membrane à fibres creuses sur laquelle est placée la couche compacte, possède une pluralité d'orifices dont le diamètre moyen dans une observation de ceux-ci depuis la surface de la membrane à fibres creuses, est supérieur ou égal à 0,3 μｍ et inférieur ou égal à 0,9 μｍ. Le rapport (DT/WT) de l'épaisseur (DT) de la couche compacte et de l'épaisseur (WT) de la membrane à fibres creuses, est supérieur ou égal à 0,24.
PCT/JP2017/010298 2016-03-22 2017-03-15 Membrane à fibres creuses WO2017164019A1 (fr)

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CN114452844A (zh) * 2022-01-29 2022-05-10 杭州科百特过滤器材有限公司 一种用于生物大分子纯化的pes中空纤维膜及其制备方法与应用
CN114618321A (zh) * 2020-12-11 2022-06-14 中国科学院大连化学物理研究所 一种中空纤维膜及制备和在液压油脱气中的应用
US20230110094A1 (en) * 2021-10-13 2023-04-13 Full Sun International Co., Ltd. Hollow fiber filtration cartridge and methods thereof

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WO2003026779A1 (fr) * 2001-08-01 2003-04-03 Asahi Kasei Kabushiki Kaisha Film microporeux multicouches
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CN114618321B (zh) * 2020-12-11 2023-07-25 中国科学院大连化学物理研究所 一种中空纤维膜及制备和在液压油脱气中的应用
US20230110094A1 (en) * 2021-10-13 2023-04-13 Full Sun International Co., Ltd. Hollow fiber filtration cartridge and methods thereof
CN114452844A (zh) * 2022-01-29 2022-05-10 杭州科百特过滤器材有限公司 一种用于生物大分子纯化的pes中空纤维膜及其制备方法与应用
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