WO2015102291A1 - Membrane à fibres creuses composite et procédé pour la fabriquer - Google Patents

Membrane à fibres creuses composite et procédé pour la fabriquer Download PDF

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Publication number
WO2015102291A1
WO2015102291A1 PCT/KR2014/012778 KR2014012778W WO2015102291A1 WO 2015102291 A1 WO2015102291 A1 WO 2015102291A1 KR 2014012778 W KR2014012778 W KR 2014012778W WO 2015102291 A1 WO2015102291 A1 WO 2015102291A1
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Prior art keywords
foam
tubular
polymer
hollow fiber
fiber membrane
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PCT/KR2014/012778
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English (en)
Korean (ko)
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이재훈
문희완
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코오롱인더스트리 주식회사
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Publication of WO2015102291A1 publication Critical patent/WO2015102291A1/fr

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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
    • B01D69/08—Hollow fibre membranes
    • B01D69/087—Details relating to the spinning process
    • 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
    • B01D71/26—Polyalkenes
    • B01D71/262—Polypropylene
    • 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
    • B01D67/0081—After-treatment of organic or inorganic membranes
    • B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
    • 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
    • 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
    • B01D69/088—Co-extrusion; Co-spinning
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/105—Support pretreatment
    • 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
    • B01D69/10—Supported membranes; Membrane supports
    • B01D69/107—Organic support material
    • 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
    • B01D69/12—Composite membranes; Ultra-thin 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1213—Laminated layers
    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1218—Layers having the same chemical composition, but different properties, e.g. pore size, molecular weight or porosity
    • 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
    • B01D71/26—Polyalkenes
    • B01D71/261—Polyethylene
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/08—Specific temperatures applied
    • B01D2323/081—Heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/26—Spraying processes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/60—Co-casting; Co-extrusion
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/28—Degradation or stability over time
    • 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
    • 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
    • B01D71/26—Polyalkenes
    • 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
    • B01D71/32—Polyalkenyl halides containing fluorine atoms
    • B01D71/34—Polyvinylidene fluoride
    • 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
    • B01D71/54—Polyureas; Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/02—Non-contaminated water, e.g. for industrial water supply
    • C02F2103/04—Non-contaminated water, e.g. for industrial water supply for obtaining ultra-pure water
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/42—Nature of the water, waste water, sewage or sludge to be treated from bathing facilities, e.g. swimming pools

Definitions

  • the present invention relates to a composite hollow fiber membrane and a method of manufacturing the same, and more particularly, to a composite hollow fiber membrane and a method for producing the composite hollow fiber membrane having an excellent water permeability and peel strength and minimized the generation of pinholes / defects in the polymer membrane.
  • Separation methods for fluid treatment include separation methods using heating or phase change, separation methods using filtration membranes, and the like.
  • the separation method using the filtration membrane has the advantage of increasing the reliability of the process because the desired water quality can be stably obtained according to the pore size of the filtration membrane. There is an advantage that it can be widely used in the separation process using the available microorganisms.
  • the filtration membrane may be classified into a flat membrane and a hollow fiber membrane according to its shape.
  • Hollow fiber membranes having a lumen therein are advantageous over flat membranes in terms of water treatment efficiency because they have a much larger surface area than flat membranes.
  • Hollow fiber membranes are widely used in the field of precision filtration such as sterile water, drinking water, ultrapure water production, and recently, sewage / wastewater treatment, solid-liquid separation in septic tanks, removal of suspended solids (SS) from industrial wastewater, filtration of river water, Filtration of industrial water, filtration of swimming pool water, and the like have expanded its application range.
  • the filtration membrane In order for the filtration membrane to be applied to water treatment, it should basically have excellent permeation performance, as well as excellent pressure resistance and mechanical strength.
  • the hollow fiber membranes have only insufficient mechanical strength due to the nature of the porous structure.
  • attempts have been made to reinforce hollow fiber membranes using tubular knitted fabrics.
  • U. S. Patent No. 6,354, 444 and U. S. Patent No. 8, 201, 485 disclose a composite hollow fiber membrane prepared by coating a polymer membrane on the outer surface of a tubular knitted fabric as a support.
  • the present invention relates to a composite hollow fiber membrane and a method of manufacturing the same that can prevent problems caused by the above limitations and disadvantages of the related art.
  • One aspect of the present invention is to provide a composite hollow fiber membrane having excellent water permeability and peel strength and at the same time minimizing the generation of pinholes / defects in the polymer membrane.
  • Another aspect of the present invention is to provide a method for producing a composite hollow fiber membrane having excellent water permeability and peel strength and minimizing the occurrence of pinholes / defects in the polymer membrane.
  • the tubular polymer foam ; And a polymer membrane coated on an outer surface of the tubular polymer foam.
  • the tubular polymer foam may be formed of at least one of polyurethane, polyethylene, polypropylene, polystyrene, and polyvinylidene fluoride (PVDF).
  • PVDF polyvinylidene fluoride
  • the tubular polymer foam is a polyurethane foam having a foam ratio of 20 to 80 times, a polyethylene foam having a foam ratio of 10 to 70 times, a polypropylene foam having a foam ratio of 10 to 70 times, a foam ratio of 10 to 60 times Polystyrene foam, and polyvinylidene fluoride foam having a foaming ratio of 5 to 40 times.
  • the tubular polymer foam may have an outer diameter of 1.0 to 2.0 mm and a thickness of 0.1 to 0.7 mm.
  • the polymer membrane may be polysulfone resin, polyethersulfone resin, sulfonated polysulfone resin, polyvinylidene fluoride (PVDF) resin or polyacrylonitrile (PAN) resin, polyimide resin, polyamideimide resin and polyesterimide resin It may include at least one of.
  • preparing a tubular polymer foam provides a method for producing a composite hollow fiber membrane comprising coating a polymer film on the outer surface of the tubular polymer foam.
  • the preparing of the tubular polymer foam may include preparing a first dope comprising a first polymer; Spinning the first dope through a tubular nozzle; And injecting gas into the first dope when the first dope passes through the tubular nozzle.
  • the preparing of the tubular polymer foam may include preparing a first dope comprising a first polymer and a pore former; Spinning the first dope through a tubular nozzle; And removing the pore former from the spun first dope.
  • the preparing of the tubular polymer foam may include preparing a first dope comprising a precursor for the first polymer and a blowing agent; Spinning the first dope through a tubular nozzle; And solidifying the spun first dope.
  • the heat treatment of the tubular polymer foam may be further performed.
  • the heat treatment step may be performed at 50 to 200 °C for 1 to 60 seconds.
  • the polymer film coating step preparing a spinning solution containing a second polymer; Passing the tubular polymeric foam through an inner tube of a double tubular nozzle; And spinning the spinning solution through the outer tube of the double tubular nozzle.
  • the tubular polymer foam may be further passed through an oven maintained at 50 to 200 ° C. before the polymer membrane coating step.
  • the oven passing step and the coating step of the tubular polymer may be performed continuously.
  • the tubular polymer elastomer does not have any wool and / or loops penetrating the polymer membrane coated on its outer surface, leakage point generation can be prevented or minimized, and as a result, the composite hollow fiber membrane It can have excellent pressure resistance and durability.
  • a composite hollow fiber membrane having excellent water permeability can be provided by using a tubular polymer elastic body having a foaming ratio in a predetermined range as a reinforcement.
  • a composite hollow fiber membrane having excellent peel strength may be provided by appropriately heat treating the tubular polymer elastomer before coating the polymer film on the outer surface of the tubular polymer elastomer.
  • Figure 3 schematically shows a method of manufacturing a tubular polymer elastomer according to an embodiment of the present invention
  • Figure 4 schematically shows a method of manufacturing a tubular polymer elastomer according to another embodiment of the present invention
  • Figure 5 schematically shows a method of manufacturing a tubular polymer elastomer according to another embodiment of the present invention
  • Figure 6 schematically shows a method of coating a polymer film on the outer surface of the tubular polymer elastomer according to an embodiment of the present invention.
  • FIG. 2 schematically shows a cross section of a composite hollow fiber membrane according to the invention.
  • the composite hollow fiber membrane 200 of the present invention includes a tubular polymer foam 210 functioning as a reinforcing material and a polymer film 220 coated on a surface thereof.
  • the tubular polymer foam 210 may be formed of at least one of polyurethane, polyethylene, polypropylene, polystyrene, and polyvinylidene fluoride (PVDF).
  • PVDF polyvinylidene fluoride
  • the expansion ratio of the tubular polymer foam 210 is appropriate to each material forming the tubular polymer foam 210 in consideration of the effect on the water permeability of the composite hollow fiber membrane 200 as well as the mechanical strength required for the reinforcement. It must be adjusted.
  • the expansion ratio is calculated by dividing the apparent density of the tubular polymer foam 210 by the density of the polymer before foaming.
  • the expansion ratio for each material of the tubular polymer foam 210 according to the embodiment of the present invention is as follows.
  • polystyrene foam expansion ratio of 10 to 60 times
  • Tubular polymer foam 210 according to an embodiment of the present invention has an outer diameter of 1.0 to 2.0 mm.
  • the outer diameter of the tubular polymer foam 210 is less than 1.0 mm, the inner diameter of the composite hollow fiber membrane 200 is also excessively small, causing too low permeate flow rate.
  • the outer diameter of the tubular polymer foam 210 exceeds 2.0 mm, the membrane area of the bundle of the composite hollow fiber membrane 200 increases significantly when the cross sections of the bundle of the hollow fiber membranes 200 occupy a certain area. Can't be.
  • the thickness ratio of the tubular polymer foam 210 to the outer diameter of the tubular polymer foam 210 is 15 to 35%.
  • the thickness ratio of the tubular polymer foam 210 to the outer diameter of the tubular polymer foam 210 exceeds 35%, that is, if the thickness of the tubular polymer foam 210 is too thick compared to its outer diameter, the tubular polymer foam 210 As the inner diameter of the composite hollow fiber membrane 200 decreases, the flow of the filtered water flowing along the hollow of the composite hollow fiber membrane 200 decreases, and due to the increase in the thickness of the composite hollow fiber membrane 200, the amount of the fluid that penetrates the membrane itself also occurs.
  • the ratio of the thickness of the tubular polymer foam 210 to the outer diameter of the tubular polymer foam 210 is less than 15%, that is, if the thickness of the tubular polymer foam 210 is too thin compared to its outer diameter, the tubular polymer foam is deteriorated due to the decrease in mechanical strength.
  • the function as the reinforcing material of the polymer foam 210 can not be secured.
  • the tubular polymer foam 210 has an outer diameter of 1.0 to 2.0 mm and a thickness of 0.1 to 0.7 mm.
  • the outer diameter, the inner diameter and the thickness of the tubular polymer foam 210 are measured by the following method.
  • the FE-SEM cross section is cut by the tubular polymer foam 210 at any point perpendicular to the longitudinal direction thereof to obtain a cross section sample, and then the cross section is analyzed by FE-SEM.
  • Five samples with a deviation between the longest and shortest lengths of the outer and inner diameters, respectively, within 20% are selected.
  • the outer diameter of each selected sample is determined by the average of the longest outer diameter and the shortest outer diameter
  • the inner diameter is determined by the average of the longest inner diameter and the shortest inner diameter.
  • the thickness (meaning the average thickness) of the tubular polymer foam 210 is the difference between the outer diameter and the inner diameter.
  • the polymer membrane 220 coated on the outer surface of the tubular polymer foam 210 may be polysulfone resin, polyethersulfone resin, sulfonated polysulfone resin, polyvinylidene fluoride (PVDF) resin or polyacrylonitrile ( PAN) resin, polyimide resin, polyamideimide resin and polyesterimide resin may include at least one.
  • the polymer film 220 may be composed of a skin layer having a dense structure and an inner layer having a sponge structure.
  • a skin layer having a dense structure and an inner layer having a sponge structure.
  • micropores having a pore size of 0.01 to 1 ⁇ m are formed, and micropores having a pore diameter of 10 ⁇ m or less, more preferably 5 ⁇ m or less are formed in the inner layer.
  • the inner layer of the polymer membrane 220 of the present invention there are no defects exceeding 10 ⁇ m, that is, micropores having a pore diameter of more than 10 ⁇ m. Filtration reliability can be greatly reduced if there are more than 10 ⁇ m defects in the inner layer. More preferably, the pore diameters of the micropores formed in the inner layer of the sponge structure gradually increase toward the center of the composite hollow fiber membrane 200.
  • the thickness of the polymer film 220 is 0.3 mm or less.
  • the method of manufacturing the composite hollow fiber membrane 200 of the present invention includes preparing a tubular polymer foam 210 and coating the polymer membrane 220 on an outer surface of the tubular polymer foam 210.
  • the tubular polymer foam 210 may be continuously manufactured by extrusion molding.
  • tubular polymer foam 210 according to various embodiments of the present invention will be described in detail with reference to FIGS. 3 to 5.
  • a first dope comprising a first polymer selected from polyethylene, polypropylene, polystyrene, and polyvinylidene fluoride is prepared.
  • the first dope may be prepared by melting the first polymer.
  • the first dope is radiated through the tubular nozzle 330.
  • foaming is performed by injecting a gas, for example, an inorganic gas such as nitrogen gas or carbon dioxide gas, into the first dope.
  • the spun first dope is solidified by air cooling to form a tubular polyurethane foam 210.
  • the expansion ratio of the finally obtained tubular polymer foam 210 may be adjusted.
  • a first dope comprising a first polymer and a pore former selected from polyethylene, polypropylene, polystyrene, and polyvinylidene fluoride is prepared.
  • the first dope may be prepared by melting the first polymer and then adding a pore forming agent.
  • the first dope is radiated through a tubular nozzle 310.
  • the spun first dope passes through the coagulating solution 322 in the coagulation bath 321, the pore former is removed, and the first dope coagulates, thereby forming a tubular polyurethane foam 210.
  • the coagulating solution 322 is preferably a solution suitable for elution of the pore former.
  • the pore former is a polymer such as poly (alkylene carbonate), poly (alkylene oxide), poly (dialkylsiloxane), acrylic resin, or the like
  • the coagulation solution is an organic solvent
  • the pore former is lithium carbonate.
  • alkali metal carbonates such as potassium carbonate, sodium carbonate and lithium chloride, the coagulation may be made through water.
  • the expansion ratio of the finally obtained tubular polymer foam 210 can be controlled.
  • first dope comprising the first polymer precursor and the blowing agent is prepared.
  • the first polymer may be polyurethane.
  • the first dope can be prepared by mixing a polyol, a diisocyanate, a catalyst, a foam stabilizer, a crosslinking agent and a blowing agent.
  • the polyol may be a polyether polyol or a polyester polyol. Specifically, polyethylene oxide (PEO), polyethylene glycol (PEG), polypropylene glycol (PPG) and the like may be used as the polyol.
  • PEO polyethylene oxide
  • PEG polyethylene glycol
  • PPG polypropylene glycol
  • the diisocyanate may be toluene diisocyanate, methylenediphenyl diisocyanate, 1,6-hexamethylene diisocyanate, or isophorone diisocyanate.
  • the polyols and diisocyanates may be used with a percentage index of isocyanate equivalents / polyol equivalents ranging from 60 to 130, preferably from 80 to 120.
  • the catalyst may be an amine catalyst or a mixed catalyst of an amine catalyst and a tin catalyst, and may be included in an amount of 0.2 to 3.5 wt% in the first dope.
  • the foam stabilizer may be a silicone surfactant to lower the surface tension of the foam and increase the mixing property, and may be included in an amount of 0.2 to 3.5 wt% in the first dope.
  • the crosslinking agent may be a diol, a triol, or a diamine to promote a crosslinking reaction for forming a polymer, and may be included in an amount of 0.2 to 3.5 wt% in the first dope.
  • the blowing agent acts to expand the volume by foaming during the urethane reaction process, water, azodicarbonamide (ADCA), methylene chloride, liquid carbon dioxide, n-pentane, isopentane, or hydrofluorocarbon ( hydrogenated chlorofluorocarbon), and may be included in an amount of 0.5 to 20% by weight in the first dope.
  • ADCA azodicarbonamide
  • methylene chloride liquid carbon dioxide
  • n-pentane isopentane
  • hydrofluorocarbon hydrogenated chlorofluorocarbon
  • the first dope is spun through the tubular nozzle 310 and the spun first dope is solidified to form the tubular polymer foam 210.
  • the expansion ratio of the tubular polymer foam 210 may be adjusted by 20 to 80 times.
  • the step of coating the polymer film 220 on its outer surface is performed.
  • the coating step can be performed using a double tubular nozzle.
  • the heat treatment of the tubular polymer foam 210 may be further performed.
  • the heat treatment step may be performed at 50 to 200 °C for 1 to 60 seconds.
  • the second polymer may be polysulfone resin, polyethersulfone resin, sulfonated polysulfone resin, polyvinylidene fluoride (PVDF) resin or polyacrylonitrile (PAN) resin, polyimide resin, polyamideimide resin, or poly Esterimide.
  • PVDF polyvinylidene fluoride
  • PAN polyacrylonitrile
  • the spinning solution is prepared by dissolving an additive polyvinylpyrrolidone and / or a hydrophilic compound together with the second polymer in an organic solvent.
  • the spinning solution may include 10 to 50 wt% of a second polymer, 1 to 30 wt% of an additive (polyvinylpyrrolidone and / or a hydrophilic compound), and 20 to 89 wt% of an organic solvent.
  • Dimethyl acetamide, dimethylformamide or a mixture thereof may be used as the organic solvent.
  • the hydrophilic compound water or a glycol compound, more preferably polyethylene glycol having a molecular weight of 2,000 or less may be used. Since the hydrophilic compound plays a role of reducing the stability of the spinning solution, the possibility of the sponge-like structure being expressed in the polymer membrane 220 is relatively increased. In other words, the higher the stability of the spinning solution, the more the defects (fine pores with a pore diameter exceeding 10 ⁇ m) are formed in the polymer membrane 220, and thus, become a finger-like structure. Thus, water or glycols are added as additives. By adding a hydrophilic compound, such as a compound, the stability of the spinning solution may be lowered and the polymer membrane 220 may be hydrophilized to increase the water permeability of the composite hollow fiber membrane 200.
  • a hydrophilic compound such as a compound
  • the tubular polymer foam 210 was passed through an oven 410 maintained at 50 to 200 ° C. in order to apply the spinning solution on the outer surface of the tubular polymer foam 210. After passing through the inner tube of the double tubular nozzle (420).
  • the spinning solution is radiated through the outer tube of the double tubular nozzle 420 so that the spinning solution becomes the tubular polymer foam 210. It is applied on the outer surface of).
  • the coated spinning solution is discharged into the air from the double tubular nozzle 420 together with the tubular polymer foam 210 and then solidified in the coagulating solution. Subsequently, the washing and drying processes are performed sequentially.
  • Q is the amount of spinning solution supplied per hour
  • ⁇ is the density of spinning solution
  • ⁇ is the advancing speed of the tubular polymer foam
  • D o is the outer diameter of the tubular polymer foam
  • T is the thickness of the spinning solution coated.
  • the thickness of the polymer film 220 may be adjusted using the supply amount of the spinning solution, the density of the spinning solution, the traveling speed of the tubular polymer foam 210, and the like.
  • Passing through the oven 410 of the tubular polymer foam 210 and coating using the double tubular nozzle 420 are preferably performed continuously. Since the polymer membrane 220 is coated on the outer surface immediately after the tubular polymer foam 210 is heat treated at 50 to 200 ° C., the composite hollow fiber membrane 200 of the present invention exhibits a low heat shrinkage of 3% or less. In addition, the adhesion between the tubular polymer foam 210 and the polymer membrane 220 is enhanced to show excellent peel strength of 1 to 5 MPa.
  • the first dope was spun through a tubular nozzle and then solidified in an air-cooled manner to complete a tubular polymer foam having an outer diameter of 1.3 mm, a thickness of 0.2 mm, and a 50 times expansion ratio.
  • the first dope was prepared by melting polyethylene.
  • the first dope was then spun through a tubular nozzle.
  • a foaming process was performed by injecting nitrogen gas into the first dope when the first dope passed through the tubular nozzle. Solidification by air cooling resulted in a tubular polyurethane foam having an outer diameter of 1.4 mm, a thickness of 0.3 mm and a foaming ratio of 50 times.
  • the first dope was prepared by melting polyethylene and then adding lithium chloride as pore former. The first dope was then spun through a tubular nozzle. As the first dope discharged into the air passes through the water, the pore-forming agent is removed and the first dope is solidified, thereby completing a tubular polyurethane foam having an outer diameter of 1.3 mm, a thickness of 0.2 mm and a foaming ratio of 40 times. It became.
  • Yarn was prepared by splicing two fine fine filaments consisting of 200 PET monofilaments having a fineness of 0.31 denier and one medium fine filament consisting of 72 PET monofilaments having a fineness of 2 denier. Using 20 such yarns, a tubular knitted fabric having an outer diameter of 1.7 mm and a thickness of 0.4 mm was prepared.
  • Yarn was prepared by splicing six fine fine filaments consisting of 200 PET monofilaments having a fineness of 0.31 denier. Using 20 such yarns, a tubular knitted fabric having an outer diameter of 1.9 mm and a thickness of 0.6 mm was prepared.
  • PVDF polyvinylidene fluoride
  • organic solvent dimethylformamide
  • the spinning solution was supplied to a double tubular nozzle including an outer tube (diameter: 2.38 mm) of the double tubular nozzle and the tubular polymer foam prepared in Example 1 was passed through the double tubular nozzle inner tube to pass the tubular nozzle.
  • the spinning solution was coated on the outer surface of the polymer foam and then discharged into the air.
  • the speed ratio k of the tubular polymer foam to the feed rate of the spinning solution was set to 750 g / m 2.
  • the hollow fiber membrane was manufactured by sequentially passing the coagulation bath and the cleaning bath at 35 ° C. and winding up.
  • the polymer membrane coated on the tubular polymer foam had a thickness of 0.2 mm.
  • a composite hollow fiber membrane was prepared in the same manner as in Example 4, except that the tubular polymer foam prepared in Example 2 was used instead of the tubular polymer foam prepared in Example 1.
  • a composite hollow fiber membrane was prepared in the same manner as in Example 4, except that the tubular polymer foam prepared in Example 3 was used instead of the tubular polymer foam prepared in Example 1.
  • a composite hollow fiber membrane was prepared in the same manner as in Example 4 except that the heat treatment was performed at 120 ° C. for 30 seconds by passing the oven immediately before passing the tubular polymer foam through the double tubular nozzle inner tube.
  • a composite hollow fiber membrane was prepared in the same manner as in Example 4, except that the tubular knitted fabric prepared in Comparative Example 1 was used instead of the tubular polymer foam prepared in Example 1.
  • a composite hollow fiber membrane was prepared in the same manner as in Example 4, except that the tubular knitted fabric prepared in Comparative Example 2 was used instead of the tubular polymer foam prepared in Example 1.
  • An acrylic tube and a composite hollow fiber membrane 4 strands of 10 mm in diameter and 170 mm in length were prepared.
  • the composite hollow fiber membrane was cut to a length of 160 mm and one end thereof was sealed with an adhesive.
  • the composite hollow fiber membrane was placed in the acrylic tube, and then sealed between one end of the acrylic tube and the composite hollow fiber membrane.
  • pure water was put in an acrylic tube and subjected to nitrogen pressure to measure the amount of pure water penetrating the composite hollow fiber membrane for 1 minute.
  • the unit of water permeability (Lp) is ml / (cm 2 ⁇ min ⁇ kg / cm 2 ).
  • the composite hollow fiber membrane After cutting 500 strands of the composite hollow fiber membrane to a length of 4m, it was maintained in a U-shape to fix the cut portion with an adhesive.
  • the U-shaped hollow fiber membrane was immersed in a water bath. Water was sucked through the cross section of the membrane fixed with adhesive for 30 minutes using a pump, and then nitrogen pressure was applied for 3 minutes while increasing the pressure in 0.1 kg / cm 2 units. At this time, the pressure at which bubbles are generated on the membrane surface was recorded.
  • the load at the instant of the polymer film peeling from the reinforcing material was measured using a tensile tester, and the peel strength was calculated by dividing this by the area (m 2 ) to which the shear force was applied.
  • Specific measurement conditions are as follows.
  • Specimen Prepared by bonding and fixing one strand of composite hollow fiber membrane to a 6mm diameter polypropylene tube with a polyurethane resin so that the length of the adhesive part is 10cm.
  • Peel strength (Pa) load at yield point (kg) / area to which shear force is applied (m 2 )
  • the peel strength is defined as the shear strength per unit area applied to the coated polymer membrane when the specimen is tensioned, and the area (m 2 ) where the shear force is applied is " ⁇ ⁇ outer diameter (m) of the composite hollow fiber membrane ⁇ adhesive part of the composite hollow fiber membrane. Is calculated as " length (m) "

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

L'invention concerne une membrane à fibres creuses composite, qui présente une excellente perméabilité à l'eau et une excellente résistance au décollage et qui présente un nombre réduit de trous d'épingle/défauts à l'intérieur d'une membrane polymère, et un procédé pour la fabriquer. La membrane à fibres creuses composites selon la présente invention comprend : une mousse polymère tubulaire, et une membrane polymère formée en tant que revêtement sur la surface externe de la mousse polymère tubulaire.
PCT/KR2014/012778 2013-12-31 2014-12-24 Membrane à fibres creuses composite et procédé pour la fabriquer WO2015102291A1 (fr)

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KR10-2013-0168102 2013-12-31

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CN111052224A (zh) * 2017-08-25 2020-04-21 京洛株式会社 结构体、车辆用结构体及车辆用空调管道

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CN105080361B (zh) * 2015-08-20 2017-05-10 广州市纳清环保科技有限公司 一种涂覆高分子复合涂层的聚丙烯中空纤维超滤膜
KR101716194B1 (ko) * 2015-12-08 2017-03-28 주식회사 휴비스 난연성이 향상된 코어-쉘 구조의 발포체
KR101942807B1 (ko) * 2018-04-13 2019-04-17 (주)신우엔지니어링 다공성 중공사막 제조용 고분자수지 조성물

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