WO2003097221A1 - Membrane en fibre creuse renforcee, procede de fabrication et filiere - Google Patents

Membrane en fibre creuse renforcee, procede de fabrication et filiere Download PDF

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Publication number
WO2003097221A1
WO2003097221A1 PCT/KR2003/000966 KR0300966W WO03097221A1 WO 2003097221 A1 WO2003097221 A1 WO 2003097221A1 KR 0300966 W KR0300966 W KR 0300966W WO 03097221 A1 WO03097221 A1 WO 03097221A1
Authority
WO
WIPO (PCT)
Prior art keywords
hollow fiber
fiber membrane
reinforcing support
spinneret
nozzle
Prior art date
Application number
PCT/KR2003/000966
Other languages
English (en)
Inventor
Ho Sung Yoon
Su Young Han
Jung Wook Lee
Sang Woo Park
Chan Woo Lee
Original Assignee
Para Limited
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from KR10-2002-0027315A external-priority patent/KR100485620B1/ko
Application filed by Para Limited filed Critical Para Limited
Priority to AU2003230426A priority Critical patent/AU2003230426A1/en
Publication of WO2003097221A1 publication Critical patent/WO2003097221A1/fr

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Classifications

    • 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
    • B01D67/0011—Casting solutions therefor
    • B01D67/00111—Polymer pretreatment in the casting solutions
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/24—Formation of filaments, threads, or the like with a hollow structure; Spinnerette packs therefor
    • 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
    • B01D67/0011—Casting solutions 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
    • 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
    • B01D69/085—Details relating to the spinneret
    • 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
    • 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
    • B01D2323/00—Details relating to membrane preparation
    • B01D2323/06—Specific viscosities of materials involved
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/40—Fibre reinforced membranes

Definitions

  • the present invention relates to a hollow fiber membrane having reinforcing supports, which has excellent intensity and is easy to control the inner and outer surfaces of the membrane, the size of the inner pore and the diameter of the membrane, preparation thereof and spinneret for preparing the same .
  • olefin-based hollow fiber membrane has more excellent ductility or intensity than a hollow fiber membrane prepared through wet spinning as it has its own physical properties due to spinning through melt spinning.
  • the olefin-based hollow fiber membrane is not easy to control the pore size or provide hydrophilic property, which is one of important properties of membrane.
  • the hollow fiber membrane prepared through dry and wet spinning or wet spinning is deteriorated in the physical properties of polymer material itself and generally has a low intensity, and the intensity of the hollow fiber membrane is influenced by the pore size or the compactness inside the membrane, as it is prepared through a sedimentation process after polymer is melted in a solvent.
  • the hollow fiber membrane is used in the form of a module without using the hollow fiber membrane in itself.
  • a method to increase the flow rate of treated water inside the module or a method to shake the hollow fiber membrane is used to minimize pollution of membrane.
  • the above methods have several restrictions on module- oriented or systemized hollow fiber membrane.
  • U.S. Patent No. 5,472,607 discloses a method for coating braid with selectively permeable membrane thinly to reinforce intensity of the membrane.
  • the method has a disadvantage in that it is difficult to control the pore size inside the membrane or the diameter of the membrane as internal coagulating solution is not used when the hollow fiber membrane is prepared, thereby reducing the merit of the hollow fiber membrane to expand the sectional area inside the module.
  • the selectively permeable membrane thin-coated on braid is come off partially, and the preparing expenses are high as expensive braid woven with grey yarn is used.
  • the present invention is directed to a hollow fiber membrane that substantially obviates one or more problems due to limitations and disadvantages of the related art.
  • An object of the present invention is to provide a hollow fiber membrane which has excellent intensity and is easy to control the inner and outer surfaces of the membrane, the size of the inner pore and the diameter of the membrane, and of which the preparing expenses are low.
  • Another object of the present invention is to provide a method for preparing the hollow fiber membrane.
  • a further object of the present invention is to provide a spinneret for preparing the hollow fiber membrane.
  • the present invention relates to a hollow fiber membrane having reinforcing supports, to which a conventional method for preparing the hollow fiber membrane is applied as it is.
  • a conventional method for preparing the hollow fiber membrane is applied as it is.
  • the present invention can control the size and structure of pore of the membrane. That is, in U.S. Patent No. 5,472,607, composition, temperature and humidity of polymer solution can be a variable for control as it uses only the polymer solution, but the present invention can easily control the size and structure of pore of the membrane as it uses both the polymer solution and the internal coagulating solution and has a lot of variables for control .
  • the present invention can increase the occupied area of the membrane within a predetermined volume as the diameter of the membrane can be reduced. That is, U.S. Patent No. 5,472,607 is not easy to prepare braid of diameter of l,000 ⁇ m or less as the braid is woven with grey yarn in the form of a circle, but, the present invention is easy to prepare braid of small diameter up to 200 ⁇ m, that is, the diameter for preparing the hollow fiber membrane.
  • the present invention can save expenses as it can increase the spinning speed (preparing speed) for preparing the hollow fiber membrane and the number of pieces of strand prepared on a production base. That is, U.S. Patent No. 5,472,607 has restrictions in increase of the spinning speed as it uses the braid of large diameter, and in the number of the prepared pieces of strand as a space occupied by the braid on the production base is wide.
  • the present invention is easy to increase the spinning speed using properties of the polymer solution and the internal coagulating solution, and can save the preparing expenses in an aspect of a prepared amount by unit time as it can prepare a lot of pieces of strand owing to the small diameter of the membrane.
  • U.S. Patent No. 5,472,607 needs additional processes to prepare braid with gray yarn, but the present invention can reduce the preparing expenses as it directly uses yarns of various kinds including the gray yarn without additional processes.
  • the thin-coated layer according to U.S. Patent No. 5,472,607 can be come off due to weak adhesive force between the coated layer and the braid, which is a supporter, as the membrane is made in such a manner to coat the braid with polymer.
  • the hollow fiber membrane according to the present invention can maintain the properties of the membrane as they are regardless of using methods or washing methods as the hollow fiber membrane has the structure that the gray yarn is embedded inside the membrane to prevent separation of the gray yarn from the membrane .
  • the present invention uses spun undiluted solution, internal coagulating solution and reinforcing supports, and discharges the spun undiluted solution, the internal coagulating solution and the reinforcing supports through a spinneret of the present invention at the same time. It is the core of the present invention.
  • the conventional method only the spun undiluted solution and the internal coagulating solution are used to prepare the hollow fiber membrane, and only the spun undiluted solution and the supporter are used when the membrane using the braid is prepared.
  • the present invention relates to a hollow fiber membrane, which has excellent intensity and is easy to control the inner and outer surfaces of the membrane, the size of the inner pore and the diameter of the membrane, and of which the preparing expenses are low, and a method for preparing the hollow fiber membrane includes the steps of: injecting spun undiluted solution forming a separate filter layer, internal coagulating solution forming a hollow area, and reinforcing support for supporting the separate filter layer into a spun undiluted solution nozzle, an internal coagulating solution nozzle and a reinforcing support nozzle; and simultaneously discharging the spun undiluted solution, the internal coagulating solution and the reinforcing support to external coagulating solution to form hollow fiber membrane.
  • the method for discharging the ingredients from the triple-tube type spinneret is divided into two according to the arrangement order of nozzles; one being that the reinforcing support is discharged from the center, the spun undiluted solution is discharged from the outermost edge, and the internal coagulating solution is discharged between the reinforcing support and the spun undiluted solution; the other being that the internal coagulating solution is discharged from the center, the spun undiluted solution is discharged from the outermost edge, and the reinforcing support is discharged between the internal coagulating solution and the spun undiluted solution.
  • the reinforcing supports are discharged by 1-50 pieces of string.
  • the discharged number of the reinforcing supports can be controlled according to kinds and thickness of applied yarn, and preferably 1-50 pieces of string.
  • the discharged number of the reinforcing supports exceeds 50, the occupied area of a portion, where provides the reinforcing supports, of the spinneret becomes too large, and conditions for preparing hollow fiber membrane of high- intensity become complicated.
  • the number of the nozzles of the reinforcing supports is determined according to the number of the discharged reinforcing supports.
  • the spun undiluted solution used in the present invention is made of polymer, additive and solvent.
  • the polymer is selected from polyacrylo nitrile, polyacrylo nitrile copolymer, polysulfone, sulfonated polysulfone, polyether sulfone, cellulose acetate, cellulose triacetate, polymethyl methacrylate, and groups made of mixture of the above ingredients.
  • the additive is selected from water, methyl alcohol, ethyl alcohol, ethylene glycol, polyethylene glycol, propylene glycol, polypropylene glycol, glycerin, PVP (Poly-vinyl Pyrrolidone) , and groups made of mixture of the above ingredients.
  • the solvent is selected from NMP(N-methyl-2-pyrrolidone) , DMF(dimethyl formamide) , DMAc (dimethyl acetamide), chloroform, tetrahydrofuran, and groups made of mixture of the above ingredients.
  • the internal coagulating solution used in the present invention is selected from water, NMP (N-methyl-2- pyrrolidone) , DMF (dimethyl formamide), chloroform, tetrahydrofuran, polyethylene glycol, propylene glycol, ethylene glycol, and groups made of mixture of the above ingredients.
  • the reinforcing support used in the present invention is yarn, and made of one olefin-based, PET (polyethylene terephthalate) -based and nylon-based materials, which are not melted in the above solvent .
  • the yarn is one of draw twisting yarn (DTY), drawn yarn (FLAT), trigonal-lobal yarn, and trilobal cross section yarn, preferably DTY having excellent bulkiness and lots of crimps.
  • the hollow fiber membrane having the reinforcing support prepared according to the above method includes a separate filter layer, reinforcing supports and a hollow.
  • the hollow fiber membrane having reinforcing support the hollow fiber membrane includes: a tubular separate filter layer having hollow yarn; reinforcing supports distributed and adhered inside the separate filter layer uniformly, the reinforcing supports for supporting the separate filter layer; and a hollow formed among the reinforcing supports.
  • the hollow fiber membrane having reinforcing support includes: a tubular separate filter layer having hollow yarn; reinforcing supports included and adhered inside the separate filter layer, the reinforcing supports for supporting the separate filter layer; and a hollow formed among the reinforcing supports.
  • the separate filter layer has the width of 50 ⁇ 2,000 ⁇ m and the outer surface of 0.05 ⁇ 30 ⁇ m, the outer surface of the edge serving to provide an actual separation function.
  • the adhered rate of the reinforcing supports is 3-100%, preferably, 10-95%.
  • the adhered rate means that the reinforcing support is adhered on the inside or wall surface of the hollow fiber membrane to how much percent, and the supporter and hollow yarn of the prepared membrane are separated from each other during the use and intensity of the membrane is lowered if the adhered rate is low.
  • the intensity of the hollow fiber membrane is increased as the adhered rate becomes higher, but, water-permeability of the membrane can be deteriorated as the hollow portion of hollow yarn is formed little if the adhered rate is too high.
  • the average outer diameter of the reinforcing support is more than 3% of the whole outer diameter of the membrane. If the outer diameter of the reinforcing support is less than 3% of the whole outer diameter of the membrane, the membrane is not proper to use as separate film of high- intensity as the supporter is too thin and the intensity is lowered. On the other hand, if the outer diameter of the reinforcing support is more than 50% of the whole outer diameter of the membrane, it can damage the separate filter layer, which is the outer surface of the hollow fiber membrane .
  • the intensity of the hollow fiber membrane according to the present invention is more excellent than that of the conventional hollow fiber membrane.
  • the cutting load of the hollow fiber membrane according to the present invention is twice or more as much as that of the conventional hollow fiber membrane, which does not have the reinforcing support, in more detail, 15 ⁇ 150kN.
  • the spinneret used in the present invention includes a spun undiluted solution nozzle, an internal coagulating solution nozzle, and reinforcing support nozzles, and is divided into two types according to the number of outlets; a double-tube type and a triple-tube type.
  • the double-tube type spinneret has at least two outlets, and the outlet of the internal coagulating solution nozzle or the outlet of the reinforcing support nozzle communicates with the central side of the corresponding nozzle to join the internal coagulating solution and the reinforcing support.
  • the triple-tube type spinneret has at least three outlets, and the internal coagulating solution nozzle, the reinforcing support nozzle and the spun undiluted solution nozzle are formed independently.
  • the triple- tube type spinneret includes the reinforcing support nozzle formed along the vertical axis of the spinneret, the internal coagulating solution nozzle being at an interval from the outer surface of the reinforcing support nozzle, and the spun undiluted solution nozzle being at an interval from the outer surface of the internal coagulating solution nozzle .
  • the triple-tube type spinneret includes the internal coagulating solution nozzle formed along the vertical axis of the spinneret, the reinforcing support nozzle being at an interval from the outer surface of internal coagulating solution nozzle, and the spun undiluted solution nozzle being at an interval from the outer surface of the internal coagulating solution nozzle at a discharge area.
  • the spinneret of the present invention may have a number of reinforcing support nozzles.
  • the number of the reinforcing support nozzles can be varied according to kinds and thickness of applied yarn, and it is preferable that the number of the reinforcing support nozzles are 1-50. If the number of the reinforcing supports exceeds 50, the occupied area of a portion, where provides the reinforcing supports, of the spinneret becomes too large, and conditions for preparing hollow fiber membrane of high- intensity become complicated.
  • FIG. 1 is a sectional view of a double-tube type spinneret for preparing hollow fiber membrane having reinforcing supports according to the present invention
  • FIG. 2 is a sectional view of a triple-tube type spinneret for preparing hollow fiber membrane having reinforcing supports according to the present invention
  • FIG. 3 is a sectional view of the hollow fiber membrane according to the present invention
  • FIG. 4 is a vertically sectional view of the triple- tube type spinneret according to another embodiment of the present invention.
  • FIG. 5 is a horizontally sectional view of a bottom outlet portion of the triple-tube type spinneret of FIG. 4;
  • FIG. 6 is a sectional view of the hollow spinneret manufactured through the spinneret of FIG. 4.
  • Dope which is spun undiluted solution, is prepared by melting polymer, such as polyacrylo mitrile, polyacrylo nitrile copolymer, polysulfone, sulfonated polysulfone, polyether sulfone, cellulose acetate, cellulose triacetate or polymethyl methacrylate, in solvent, such as NMP(N- methyl-2-pyrrolidone) , DMF(dimethyl formamide), DMAc (dimethyle acetamide), chloroform or tetrahydrofuran.
  • polymer such as polyacrylo mitrile, polyacrylo nitrile copolymer, polysulfone, sulfonated polysulfone, polyether sulfone, cellulose acetate, cellulose triacetate or polymethyl methacrylate
  • solvent such as NMP(N- methyl-2-pyrrolidone) , DMF(dimethyl formamide), DMAc (dimethyle acetamide), chloroform or
  • additive such as water, methyl alcohol, ethyl alcohol, ethylene glycol, propylene glycol, polypropylene glycol, glycerin and PV (Poly-vinyl Pyrrolidone) , is added.
  • the viscosity of the spun undiluted solution is about 500-50, OOOcps at the temperature of 25°C, preferably, 800-30 , OOOcps, and the viscosity is controlled to provide membrane properties appropriate to applicable fields.
  • the viscosity of the spun undiluted solution As too high or low viscosity of the spun undiluted solution may deteriorate the working efficiency in the spinneret and have a bad influence on the membrane property, the viscosity of the spun undiluted solution of 0.5 to lOOcps at the temperature of 25°C is good, and it is preferable to control the viscosity to provide membrane properties suitable for applicable fields.
  • the spun undiluted solution and the internal coagulating solution prepared by the above are discharged through the spinneret, and at this time, the reinforcing support is applied to increase the intensity of the hollow fiber membrane.
  • the reinforcing support is yarn of high quality capable of being bought from general manufacturers or markets.
  • the reinforcing support is flown into or discharged from the spinneret independently from the spun undiluted solution and the internal coagulating solution, or discharged together with the internal coagulating solution at the same time. Furthermore, the reinforcing support can be discharged simultaneously with or independently from the spun undiluted solution after being flown inside independently from the spun undiluted solution and the internal coagulating solution. In this case, the reinforcing support is contacted with the internal coagulating solution after the reinforcing support is first contacted with the spun undiluted solution at an end of the spinneret .
  • Such reinforcing support is made of one of olefin- based, PET (polyethylene terephthalate) -based and nylon- based materials, and not made of materials melted in the above solvents.
  • Yarn of all kinds can be used for the reinforcing support, and particularly, it is good to use draw twisting yarn (DTY) having excellent bulkiness and lots of crimps.
  • DTY draw twisting yarn
  • the bulkiness means how much volume gray yarn occupies actually, and large bulkiness means that the volume of the selected gray yarn is larger than other gray yarn.
  • the crimps means a rate of the number of wrinkles (winding) to the unit length of the gray yarn, and lots of crimps means that the rate of the number of wrinkles to the unit length is high.
  • the thickness of the reinforcing support formed inside the hollow fiber membrane is 3 to 90% of the inner diameter of the hollow fiber membrane, and preferably, 30 to 80%.
  • the average outer diameter of the reinforcing support is 3% or more of the outer diameter of the entire membrane.
  • FIG. 1 is a sectional view of a double-tube type spinneret for preparing hollow fiber membrane having a reinforcing support according to the present invention.
  • an internal coagulating solution nozzle 1 extends in a vertical direction of the central axis of a spinneret 4 formed by coupling of upper and lower spinneret couplers 4a and 4b, and an outlet 2b of a reinforcing support nozzle 2 communicates with the central side of the internal coagulated nozzle 1 to join the internal coagulating solution and the reinforcing support.
  • a spun undiluted solution nozzle 3 is at an interval of a partition from the internal coagulating solution nozzle 1, and has a tube-type fluid channel to form a separate filter layer of the hollow fiber membrane.
  • the internal coagulated-solution is flown into an inlet la of the internal coagulating solution nozzle 1, and the reinforcing support is flown into an inlet 2b of the reinforcing support nozzle 2.
  • the internal coagulating solution and the reinforcing support meet together at the central portion of the internal coagulated-solution nozzle 1, and are discharged to an outlet lb of the internal coagulating solution nozzle 1.
  • the spun undiluted solution is flown into an inlet 3a of the spun undiluted solution nozzle 3, independently spun along the tubular fluid channel, and discharged together with the internal coagulating solution and the reinforcing support to an outlet 3b of the spun undiluted solution nozzle 3 at the same time.
  • FIG. 2 is a sectional view of a triple-tube type spinneret for preparing the hollow fiber membrane having the reinforcing support according to the present invention.
  • an internal coagulating solution nozzle 6, a reinforcing support nozzle 7 and a spun undiluted solution nozzle 8 are formed independently.
  • the reinforcing support nozzle 7 is formed along the vertical axis of the spinneret 9 made by coupling of upper and lower spinneret couplers 9a and 9b
  • the internal coagulating solution nozzle 6 is at an interval of a partition from the outer surface of the reinforcing support nozzle 7 and forms a tubular flow channel
  • the spun undiluted solution nozzle 8 is at an interval of a partition from the outer surface of the internal coagulating solution nozzle 6 and forms a tubular flow channel to form a separate filter layer of the hollow fiber membrane.
  • the internal coagulating solution is flown into an inlet 6a of the internal coagulating solution nozzle 6, the reinforcing support is flown into an inlet 7a of the reinforcing support nozzle 7, and the spun undiluted solution is flown into an inlet 8a of the spun undiluted solution nozzle 8 at the same time.
  • the internal coagulating solution, the reinforcing support and the spun undiluted solution are respectively and independently discharged to an outlet 6b of the internal coagulating solution nozzle 6, an outlet 7b of the reinforcing support nozzle 7 and an outlet 8b of the spun undiluted solution nozzle 8.
  • the internal coagulating solution is discharged to the outside of the reinforcing support to form hollow.
  • the spinning speed for preparing the hollow fiber membrane is about 5 to 130m/min, preferably, 10 to lOOm/min.
  • the reinforcing support must be provided with small tension to maintain its bulkiness and crimps, and it can be changed according to gray yarn to be used. If the bulkiness is lost due to application of tension, intensity of the membrane is reduced and the use purpose of the membrane is restricted as the rate that the reinforcing support is adhered on the inside of the hollow fiber membrane is reduced. Particularly, tension over 170g per a piece of string is applied to the reinforcing support, the reinforcing support and the spinneret can be damaged.
  • the discharged spun body forms hollow fiber membrane in a coagulating tub, which contains external coagulating solution, through a coagulating process.
  • various conditions i.e., discharge temperature of the spun undiluted solution and external coagulating solution, temperature and humidity from the outlet of the spun undiluted solution nozzle to the water surface of the external coagulating solution, temperature of the external coagulating tub, and so on, can become variables for controlling performance of membrane.
  • the hollow fiber membrane first prepared through the coagulating process becomes the final product after passing through washing and drying processes .
  • FIG. 3 is a sectional view of the hollow fiber membrane prepared according to the present invention.
  • the outer surface 18 of the separate filter layer serves to provide an actual separate filtering function, and the thickness of the outer surface 18 is 0.05 ⁇ 30 ⁇ m, and preferably, 0.1 ⁇ 10 ⁇ m.
  • the thickness of the whole separate filter layer is a distance between the inner surface 17 and the outer surface 18, 50--2, OOO ⁇ m, and preferably, 60 ⁇ 800 ⁇ m.
  • Each filament of reinforcing supports 19 is in the form of a circle or a polygon, and a hollow 20 is formed among the reinforcing supports 19 inside the membrane.
  • FIG. 4 is vertically sectional view of the triple-tube type spinneret according to another embodiment of the present invention.
  • an internal coagulating nozzle 20, a reinforcing support nozzle 22 and a spun undiluted solution nozzle 23 are formed independently, and the triple-tube type spinneret of FIG. 4 has a different structure from the triple-tube type spinneret of FIG. 3.
  • the internal coagulating solution nozzle 20 is formed along the vertical axis of a spinneret 21, the reinforcing support nozzle 22 is at an interval of a partition 27 from the outer surface of the internal coagulating solution nozzle 20 and has a number of nozzles, and the spun undiluted solution nozzle 23 is adjacent to the outer surface of the reinforcing support nozzle 22 at a discharge area.
  • the internal coagulating solution is flown into an inlet 20a of the internal coagulating solution nozzle 20, the reinforcing support is flown into an inlet 22a of the reinforcing support nozzle 22, and the spun undiluted solution is flown into an inlet 23a of the spun undiluted solution nozzle 23, and then, they are respectively and independently spun along the tubular flow channels.
  • the internal coagulating solution is discharged to an outlet 20b of the internal coagulating solution nozzle 20
  • the reinforcing support is discharged to outlets 22b of the reinforcing support nozzles 22, and the spun undiluted solution is discharged to an outlet 23b of the spun undiluted solution nozzle 23 independently and at the same time.
  • the reinforcing support is discharged adjacently to the spun undiluted solution, and contacted with the internal coagulating solution after first contacting with the spun undiluted solution in the outlet 23b of the spinneret 21.
  • FIG. 5 is a horizontally sectional view of the bottom outlet area of the triple-tube type spinneret of FIG. 4.
  • the round type outlet 20b of the internal coagulating solution nozzle 20 is formed at the center.
  • the outlet 23b of the spun undiluted solution nozzle 23 is formed on the edge of the spinneret, and a number of the outlets 22b of the reinforcing support nozzles 22 are formed adjacently to the outlet 23b of the spun undiluted solution nozzle 23.
  • three reinforcing support nozzles 22 are shown, but the number of the reinforcing support nozzles 22 can be selected from 1-50 according to kinds and thickness of applied yarn.
  • FIG. 6 is a sectional view of hollow fiber membrane prepared through the spinneret of FIG. 4.
  • the hollow fiber membrane prepared according to a further embodiment of the present invention includes a round type separate filter layer 28 formed on the edge of the hollow fiber membrane, a hollow 29 formed inside the membrane, and reinforcing supports 30 included and adhered in the separate filter layer 28.
  • the reinforcing supports 19 are partially adhered to the inner surface of the filtering layer to support filtering layer, and the space formed among the reinforcing support 19 becomes the hollow 20.
  • the reinforcing support 30 are included in the separate filter layer 28 to support the separate filter layer, and the whole inside space of the separate filter layer 28 becomes the hollow 29.
  • the reinforcing supports a number of bundles of filaments, and the number of the bundles corresponds to the number of reinforcing support nozzles.
  • Each filament of the reinforcing support is in the form of a circle or a polygon, and it would be appreciated that mono filament is used.
  • the spun undiluted solution was prepared by melting polyether sulfone as polymer and PVP (poly-vinyl pyrrolidone) as additive in NMP (N-methyl-2-pyrrolidone) solvent.
  • the viscosity of the prepared spun undiluted solution was 2, OOOcps at the temperature of 25 °C.
  • Mixture of water and NMP was used as the internal coagulating solution, and the reinforcing supports were not used.
  • the spun undiluted solution and the internal coagulating solution were discharged to the external coagulating solution, which was the mixture of water and NMP, through the double-tube type spinneret so as to prepare hollow fiber membrane.
  • the diameters of the internal coagulating solution nozzle and the spun undiluted solution nozzle of the spinneret were respectively ⁇ 400 ⁇ m and ⁇ l,200 ⁇ m on the basis of the outlet, the distance between the spinneret and the external coagulating solution was 10cm, and the temperature of the coagulating tub was 30 °C.
  • Embodiment 1 The spun undiluted solution was prepared by melting polyether sulfone as polymer and PVP (poly-vinyl pyrrolidone) as additive in NMP (N-methyl-2-pyrrolidone) solvent.
  • the viscosity of the prepared spun undiluted solution was 2, OOOcps at the temperature of 25°C.
  • Mixture of water and NMP was used as the internal coagulating solution, and the DTY was used as the reinforcing support.
  • the spun undiluted solution, the internal coagulating solution and the reinforcing support were simultaneously discharged to the external coagulating solution, to which the mixture of water and NMP was used, through the double- tube type spinneret of FIG. 1 so as to prepare hollow fiber membrane.
  • the diameters of the internal coagulating solution nozzle and the spun undiluted solution nozzle of the spinneret were respectively ⁇ 400 ⁇ m and ⁇ l,200 ⁇ m on the basis of the outlet, and the diameter of the inlet of the reinforcing support nozzle was ⁇ 300 ⁇ m.
  • the distance between the spinneret and the external coagulating solution was 10cm, and the temperature of the coagulating tub was 30°C.
  • the spun undiluted solution was prepared by melting polyacrylo nitrile as polymer and polyethylene glycol 200 as additive in DMF (dimethyl formamide) solvent.
  • the viscosity of the prepared spun undiluted solution was
  • the spun undiluted solution was prepared by melting polysulfone as polymer and PVP (poly-vinyl pyrrolidone) and glycerin as additive in DMAc (dimethyl acetamide) solvent.
  • the viscosity of the prepared spun undiluted solution was 800cps at the temperature of 25 °C.
  • Mixture of water and propylene glycol was used as the internal coagulating solution, and trigonal-lobal yarn was used as the reinforcing support.
  • the spun undiluted solution, the internal coagulating solution and the reinforcing support were simultaneously discharged to the external coagulating solution, to which the mixture of water and DMAc was used, through the double-tube type spinneret of FIG. 1 so as to prepare hollow fiber membrane.
  • the diameters of the internal coagulating solution nozzle and the spun undiluted solution nozzle of the spinneret were respectively ⁇ OO ⁇ m and ⁇ 2,000 ⁇ m on the basis of the outlet, and the diameter of the inlet of the reinforcing support nozzle was ⁇ 500 ⁇ m.
  • the distance between the spinneret and the external coagulating solution was 5cm.
  • Embodiment 4 The spun undiluted solution was prepared by melting sulfonated polysulfone as polymer and water as additive in NMP solvent. The viscosity of the prepared spun undiluted solution was 8,100cps at the temperature of 25 °C. Mixture of water and ethylene glycol was used as the internal coagulating solution, and modified cross-section fiber was used as the reinforcing support. The spun undiluted solution, the internal coagulating solution and the reinforcing support were simultaneously discharged to the external coagulating solution, to which the mixture of water and NMP was used, through the triple-tube type spinneret of FIG. 2 so as to prepare hollow fiber membrane.
  • the diameters of the reinforcing support nozzle, the internal coagulating solution nozzle and the spun undiluted solution nozzle were respectively ⁇ 300 ⁇ m, ⁇ 500 ⁇ m and ⁇ 800 ⁇ m on the basis of the outlet, and the distance between the spinneret and the external coagulating solution was 3cm.
  • the spun undiluted solution was prepared by melting polysulfone as polymer and PVP as additive in NMP solvent.
  • the viscosity of the prepared spun undiluted solution was 2, OOOcps at the temperature of 25 °C.
  • Mixture of water and NMP was used as the internal coagulating solution, and the reinforcing support was not used.
  • the spun undiluted solution and the internal coagulating solution were discharged to the external coagulating solution, which was the mixture of water and NMP, through the double-tube type spinneret so as to prepare hollow fiber membrane.
  • the diameters of the internal coagulating solution nozzle and the spun undiluted solution nozzle of the spinneret were respectively ⁇ 400 ⁇ m and ⁇ l,200 ⁇ m on the basis of the outlet, the distance between the spinneret and the external coagulating solution was ' 5cm, and the temperature of the coagulating tub was 30 °C.
  • the spun undiluted solution was prepared by melting polysulfone as polymer and PVP as additive in NMP solvent.
  • the viscosity of the prepared spun undiluted solution was 2, OOOcps at the temperature of 25 °C.
  • Mixture of water and NMP was used as the internal coagulating solution, and the DTY was used as the reinforcing support.
  • the spun undiluted solution, the internal coagulating solution and the reinforcing support were simultaneously discharged to the external coagulating solution, which was the mixture of water and NMP, through the triple-tube type spinneret of FIG. 4 so as to prepare hollow fiber membrane.
  • the diameters of the internal coagulating solution nozzle and the spun undiluted solution nozzle of the spinneret were respectively ⁇ 400 ⁇ m and ⁇ l,200 ⁇ m on the basis of the outlet, and three reinforcing support nozzles of diameter of ⁇ 200 ⁇ m were disposed.
  • the distance between the spinneret and the external coagulating solution was 5cm, and the temperature of the coagulating tub was 30 °C.
  • the spun undiluted solution was prepared by melting polyether sulfone as polymer and polyethylene glycol 200 as additive in DMF (dimethyl formamide) solvent.
  • the viscosity of the prepared spun undiluted solution was 4,500cps at the temperature of 25 °C.
  • Mixture of water and polyethylene glycol 200 was used as the internal coagulating solution, and FLAT yarn was used as the reinforcing support .
  • the spun undiluted solution, the internal coagulating solution and the reinforcing support were simultaneously discharged to the external coagulating solution, to which the mixture of water and DMF was used, through the triple-tube type spinneret of FIG. 4 so as to prepare hollow fiber membrane.
  • the diameters of the internal coagulating solution nozzle and the spun undiluted solution nozzle of the spinneret were respectively ⁇ 400 ⁇ m and ⁇ l,500 ⁇ m on the basis of the outlet, and three reinforcing support nozzles of diameter of ⁇ 200 ⁇ m were disposed.
  • the distance between the spinneret and the external coagulating solution was 1cm.
  • the spun undiluted solution was prepared by melting polyacrylo nitrile as polymer and mixture of PVP and glycerin as additive in DMAc solvent .
  • the viscosity of the prepared spun undiluted solution was 800cps at the temperature of 25 °C.
  • Mixture of water and propylene glycol was used as the internal coagulating solution, and trigonal-lobal yarn was used as the reinforcing support.
  • the spun undiluted solution, the internal coagulating solution and the reinforcing support were simultaneously discharged to the external coagulating solution, to which the mixture of water and DMAc was used, through the triple- tube type spinneret of FIG. 4 so as to prepare hollow fiber membrane.
  • the diameters of the internal coagulating solution nozzle and the spun undiluted solution nozzle of the spinneret were respectively ⁇ 400 ⁇ m and ⁇ 2,500 ⁇ m on the basis of the outlet, and three reinforcing support nozzles of diameter of ⁇ 300 ⁇ m were disposed.
  • the distance between the spinneret and the external coagulating solution was 1cm.
  • Embodiment 8 The spun undiluted solution was prepared by melting sulfonated polysulfone as polymer and water as additive in NMP solvent. The viscosity of the prepared spun undiluted solution was 8,100cps at the temperature of 25°C. Mixture of water and ethylene glycol was used as the internal coagulating solution, and modified cross-section fiber was used as the reinforcing support. The spun undiluted solution, the internal coagulating solution and the reinforcing support were simultaneously discharged to the external coagulating solution, to which the mixture of water and NMP was used, through the triple-tube type spinneret of FIG. 4 so as to prepare hollow fiber membrane.
  • the diameters of the internal coagulating solution nozzle and the spun undiluted solution nozzle of the spinneret were respectively ⁇ 400 ⁇ m and ⁇ 2,000 ⁇ m on the basis of the outlet, and three reinforcing support nozzles of diameter of ⁇ 200 ⁇ m were disposed.
  • the distance between the spinneret and the external coagulating solution was 3cm.
  • Table 1 shows features of the hollow fiber membrane prepared by the comparison 1 and the first to fourth embodiments
  • Table 2 shows features of the hollow fiber membrane prepared by the comparison 2 and the fifth to eighth embodiments.
  • the average pore size of the outer layer of membrane is the pore size of the outer layer of the separate filter layer serving to provide separation function of contamination, and was measured with SEM.
  • the present invention can prepare hollow fiber membranes having various pore sizes of the outer layer.
  • the thickness of the membrane is the distance from the outer surface 18 to the inner surface 17 of the separate filter layer in FIG. 3 and is the width of the separate filter layer 28 in FIG. 6, and measured with SEM.
  • the present invention can prepare hollow fiber membranes having various thicknesses.
  • the thickness of the membrane can be controlled by controlling the size of the spinneret and spinning conditions, and can be selected according to the use purpose.
  • the content of the reinforcing support means an adhered rate, that is, an area rate of the filaments, which are adhered on the inside or the wall surface of the hollow fiber membrane, of the entire area of the supporter, and was measured with SEM.
  • the present invention can prepare the hollow fiber membranes having various contents of the reinforcing support, and the present invention is more useful as the adhered rate is greater.
  • the intensity of the hollow fiber membrane was measured through cutting load using a load measuring device.
  • a load measuring device When one end of fiber of a predetermined length is fixed and load is applied to the other end, the fiber extends, but, if it reaches the limitation of the load, the fiber is broken due to unbearable load.
  • power necessary to cut the fiber is called cutting load N, and a value dividing the cutting load by woven level of the used fiber, that is, the cutting load to unit fineness, is called intensity.
  • the unit of intensity is indicated as gram (or N) per denier (g/d) or gram (or N) per tex (g/tex) .
  • the cutting load of the hollow fiber membrane prepared according to the present invention is seven to seventeen times as much as the conventional hollow fiber membrane, which does not use the reinforcing support.
  • the hollow fiber membrane according to the present invention has higher intensity than the conventional hollow fiber membrane.
  • the manufacturing expenses of the hollow fiber membrane having the reinforcing support according to the present invention are similar to that of the conventional hollow fiber membrane.
  • the production speed and the braid cost of the hollow fiber membrane according to the present invention are ten times as low as that of U.S. Patent No. 5,472,607 using braid. Therefore, the present invention can prepare the hollow fiber membrane having more excellent intensity and properties than the conventional hollow fiber membrane at the expenses similar with the conventional hollow fiber membrane .
  • the hollow fiber membrane prepared according to the present invention has excellent intensity as having the reinforcing supports and can control the inner pore size and the diameter of the membrane by using the internal coagulating solution. Furthermore, the present invention can increase the spinning speed, reduce the diameter of the membrane, and save the manufacturing cost by using the reinforcing supports of various yarn conditions .

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Dispersion Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)

Abstract

Cette invention concerne une membrane en fibre creuse renforcée par un matériau support, son procédé de fabrication et la filière utilisée à cette fin. La membrane en fibre creuse présente des creux obtenus à l'aide d'une solution coagulante interne et des supports de renforcement supportant une couche filtrante distincte qui constitue la surface extérieure. La filière utilisée pour la fabrication de la membrane à fibres creuses comprend une buse de filage pour solution non diluée, une buse pour solution coagulante interne et un buse pour support de renforcement. Pour fabriquer la membrane en fibre creuse, on décharge simultanément la solution de filage non diluée, la solution coagulante interne et le support de renforcement de la filière dans la solution coagulante externe. Cette membrane en fibre creuse présente une remarquable densité par suite du support de renforcement, la solution coagulante interne permettant de contrôler la taille intérieure des pores et le diamètre de la membrane. Par ailleurs, il est possible d'accroître la vitesse de filage, de réduire le diamètre de la membrane, de comprimer le coût de fabrication grâce au support de renforcement, et de produire des fils de types divers.
PCT/KR2003/000966 2002-05-17 2003-05-16 Membrane en fibre creuse renforcee, procede de fabrication et filiere WO2003097221A1 (fr)

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AU2003230426A AU2003230426A1 (en) 2002-05-17 2003-05-16 Hollow fiber membrane having supporting material for reinforcement, preparation thereof and spinneret for preparing the same

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KR10-2002-0027315 2002-05-17
KR10-2002-0027315A KR100485620B1 (ko) 2002-01-15 2002-05-17 보강용 지지체를 가진 중공사막, 그 제조방법 및 이를제조하기 위한 방사구금

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WO2010148517A1 (fr) 2009-06-26 2010-12-29 Asteia Technology Inc. Membrane de fibre creuse renforcée par du textile non tressé
WO2011051273A3 (fr) * 2009-10-29 2011-11-24 Basf Se Procédé pour la préparation de fibres creuses hyperramifiées
CN101766960B (zh) * 2008-12-31 2012-06-06 中国纺织科学研究院 一种复合中空纤维膜及其制备方法
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JP2014213234A (ja) * 2013-04-23 2014-11-17 Nok株式会社 繊維強化多孔質中空糸膜
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WO2014204403A3 (fr) * 2013-06-19 2016-07-14 National University Of Singapore Fibres creuses composites à couche mince permettant de générer un pouvoir osmotique
EP2644757A4 (fr) * 2010-11-24 2017-01-04 Mitsubishi Rayon Co., Ltd. Buse d'extrusion de membrane de fibres creuses, et procédé de fabrication de membrane de fibres creuses
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US9861940B2 (en) 2015-08-31 2018-01-09 Lg Baboh2O, Inc. Additives for salt rejection enhancement of a membrane
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CN108479399A (zh) * 2018-04-09 2018-09-04 天津工业大学 一种纤维增强型三醋酸纤维素反渗透膜及其制备方法
US10155203B2 (en) 2016-03-03 2018-12-18 Lg Nanoh2O, Inc. Methods of enhancing water flux of a TFC membrane using oxidizing and reducing agents
CN109957899A (zh) * 2017-12-25 2019-07-02 宁波斯宾拿建嵘精密机械有限公司 一种新型的内衬增强型中空钎维膜喷丝头
WO2023082538A1 (fr) * 2021-11-12 2023-05-19 创脉医疗科技(上海)有限公司 Filament de membrane à fibres creuses et son procédé de préparation, et membrane d'oxygénation

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EP2316561A1 (fr) 2004-11-19 2011-05-04 Vlaamse Instelling voor Technologisch Onderzoek (VITO) Membranes capillaires autoportantes avec renfort longitudinal et leur fabrication
EP1658889A1 (fr) * 2004-11-19 2006-05-24 "VLAAMSE INSTELLING VOOR TECHNOLOGISCH ONDERZOEK", afgekort "V.I.T.O." Membranes capillaires autoportantes avec renfort longitudinal et leur fabrication
US8596467B2 (en) 2006-10-18 2013-12-03 Gambro Lundia Ab Hollow fiber membrane and method for manufacturing thereof
US9156005B2 (en) 2006-10-18 2015-10-13 Gambro Lundia Ab Hollow fiber membrane and method for manufacturing thereof
US9744499B2 (en) 2008-04-15 2017-08-29 Lg Nanoh2O, Inc. Hybrid nanoparticle TFC membranes
US9254465B2 (en) 2008-04-15 2016-02-09 Lg Nanoh2O, Inc. Hybrid nanoparticle TFC membranes
WO2010043705A1 (fr) 2008-10-17 2010-04-22 Solvay Advanced Polymers, L.L.C. Fibre ou feuille composée de polymères à haute tg et son processus de fabrication
US8637583B2 (en) 2008-10-17 2014-01-28 Solvay Advanced Polymers, L.L.C. Fiber or foil from polymers with high Tg and process for their manufacture
CN101766960B (zh) * 2008-12-31 2012-06-06 中国纺织科学研究院 一种复合中空纤维膜及其制备方法
US9132390B2 (en) 2009-03-26 2015-09-15 Bl Technologies Inc. Non-braided reinforced holow fibre membrane
WO2010148517A1 (fr) 2009-06-26 2010-12-29 Asteia Technology Inc. Membrane de fibre creuse renforcée par du textile non tressé
US9061250B2 (en) 2009-06-26 2015-06-23 Bl Technologies, Inc. Non-braided, textile-reinforced hollow fiber membrane
CN102713029A (zh) * 2009-10-29 2012-10-03 巴斯夫欧洲公司 制备超支化中空纤维的方法
JP2013509502A (ja) * 2009-10-29 2013-03-14 ビーエーエスエフ ソシエタス・ヨーロピア ハイパーブランチ中空繊維の製造方法
WO2011051273A3 (fr) * 2009-10-29 2011-11-24 Basf Se Procédé pour la préparation de fibres creuses hyperramifiées
US9234302B2 (en) 2009-10-29 2016-01-12 Basf Se Process for the preparation of hyperbranched hollow fibers
US9221020B2 (en) 2010-09-15 2015-12-29 Bl Technologies, Inc. Method to make yarn-reinforced hollow fiber membranes around a soluble core
US9597642B2 (en) 2010-11-10 2017-03-21 Lg Nanoh2O, Inc. Hybrid TFC RO membranes with non-metallic additives
EP2644757A4 (fr) * 2010-11-24 2017-01-04 Mitsubishi Rayon Co., Ltd. Buse d'extrusion de membrane de fibres creuses, et procédé de fabrication de membrane de fibres creuses
US10046281B2 (en) 2011-04-26 2018-08-14 Lotte Chemical Corporation Monofilament-reinforced hollow fiber membrane with scalloped lumen
WO2012148068A1 (fr) 2011-04-26 2012-11-01 제일모직 주식회사 Membrane à fibre creuse ayant un monofilament renforcé
US10737223B2 (en) 2011-04-26 2020-08-11 Lotte Chemical Corporation Monofilament-reinforced hollow fiber membrane with scalloped lumen
US9561475B2 (en) 2011-04-26 2017-02-07 Lotte Chemical Corporation Monofilament-reinforced hollow fiber membrane
US8827085B2 (en) 2011-04-26 2014-09-09 Cheil Industries Inc. Monofilament-reinforced hollow fiber membrane
US9321014B2 (en) 2011-12-16 2016-04-26 Bl Technologies, Inc. Hollow fiber membrane with compatible reinforcements
US9643129B2 (en) 2011-12-22 2017-05-09 Bl Technologies, Inc. Non-braided, textile-reinforced hollow fiber membrane
US20160184777A1 (en) * 2011-12-22 2016-06-30 Bl Technologies, Inc. Non-braided, textile-reinforced hollow fiber membrane
US9022229B2 (en) 2012-03-09 2015-05-05 General Electric Company Composite membrane with compatible support filaments
WO2013142000A1 (fr) * 2012-03-22 2013-09-26 General Electric Company Dispositif et procédé de production d'une membrane de fibre creuse renforcée
CN104203376A (zh) * 2012-03-22 2014-12-10 通用电气公司 用于生产加强中空纤维膜的装置和方法
US8999454B2 (en) 2012-03-22 2015-04-07 General Electric Company Device and process for producing a reinforced hollow fibre membrane
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US9227362B2 (en) 2012-08-23 2016-01-05 General Electric Company Braid welding
JP2014213234A (ja) * 2013-04-23 2014-11-17 Nok株式会社 繊維強化多孔質中空糸膜
EP2990100A4 (fr) * 2013-04-23 2017-01-25 NOK Corporation Membrane poreuse à fibres creuses renforcée par des fibres
US10434477B2 (en) 2013-04-23 2019-10-08 Nok Corporation Fiber-reinforced porous hollow fiber membrane
WO2014204403A3 (fr) * 2013-06-19 2016-07-14 National University Of Singapore Fibres creuses composites à couche mince permettant de générer un pouvoir osmotique
US10987846B2 (en) 2013-06-19 2021-04-27 National University Of Singapore Thin film composite hollow fiber membranes for osmotic power generation
CN103710766A (zh) * 2013-12-12 2014-04-09 北京化工大学 一种可调节中空芯管的中空纤维喷头
CN104725748A (zh) * 2014-08-22 2015-06-24 赵杰 超惰性纤维增强复合材料及制备方法
CN104474913A (zh) * 2014-12-04 2015-04-01 云南城投碧水源水务科技有限责任公司 一种抗污染中空纤维内压增强膜、其制备方法及实现所述制备方法的喷丝板
US9861940B2 (en) 2015-08-31 2018-01-09 Lg Baboh2O, Inc. Additives for salt rejection enhancement of a membrane
US9737859B2 (en) 2016-01-11 2017-08-22 Lg Nanoh2O, Inc. Process for improved water flux through a TFC membrane
US10155203B2 (en) 2016-03-03 2018-12-18 Lg Nanoh2O, Inc. Methods of enhancing water flux of a TFC membrane using oxidizing and reducing agents
WO2017162554A1 (fr) * 2016-03-21 2017-09-28 Basf Se Procédé, filière et système de fabrication de membranes multicouches
US11247180B2 (en) 2016-03-21 2022-02-15 Dupont Safety & Construction, Inc. Method, spinneret and system for fabricating multilayer membranes
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CN109957899B (zh) * 2017-12-25 2024-01-12 宁波斯宾拿建嵘精密机械有限公司 一种新型的内衬增强型中空纤维膜喷丝头
CN108479399A (zh) * 2018-04-09 2018-09-04 天津工业大学 一种纤维增强型三醋酸纤维素反渗透膜及其制备方法
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