WO2014175282A1 - Procédé de production d'une membrane poreuse à fibres creuses renforcée par un filé - Google Patents

Procédé de production d'une membrane poreuse à fibres creuses renforcée par un filé Download PDF

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Publication number
WO2014175282A1
WO2014175282A1 PCT/JP2014/061326 JP2014061326W WO2014175282A1 WO 2014175282 A1 WO2014175282 A1 WO 2014175282A1 JP 2014061326 W JP2014061326 W JP 2014061326W WO 2014175282 A1 WO2014175282 A1 WO 2014175282A1
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WO
WIPO (PCT)
Prior art keywords
spun yarn
fiber membrane
nozzle
hollow fiber
spinning
Prior art date
Application number
PCT/JP2014/061326
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English (en)
Japanese (ja)
Inventor
波形　和彦
孝利 佐藤
正崇 近藤
Original Assignee
Nok株式会社
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
Application filed by Nok株式会社 filed Critical Nok株式会社
Publication of WO2014175282A1 publication Critical patent/WO2014175282A1/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
    • 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
    • B01D71/70—Polymers having silicon in the main chain, with or without sulfur, nitrogen, oxygen or carbon only
    • 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
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/40—Fibre reinforced membranes
    • 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
    • D01D11/00—Other features of manufacture
    • D01D11/06—Coating with spinning solutions or melts
    • 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
    • D01D5/28—Formation of filaments, threads, or the like while mixing different spinning solutions or melts during the spinning operation; Spinnerette packs therefor
    • D01D5/30—Conjugate filaments; Spinnerette packs therefor
    • D01D5/34—Core-skin structure; Spinnerette packs therefor

Definitions

  • the present invention relates to a method for producing a spun yarn reinforced porous hollow fiber membrane. More specifically, the present invention relates to a method for producing a spun yarn reinforced porous hollow fiber membrane excellent in mechanical strength.
  • Porous hollow fiber membranes are used in various fields such as water purification treatment by membrane filtration, wastewater treatment, dehumidification or humidification.
  • PVDF membranes prepared by thermally induced phase separation have a strength of about 8-22 MPa, and among them, many are about 11 MPa in practical use, although some strength is shown, Compared with a membrane prepared by a non-solvent induced phase separation method, it does not necessarily have sufficient strength.
  • the thermally induced phase separation method has a complicated process and requires cleaning with a large number of solvents, so that it is difficult to say that it is expensive and environmentally friendly.
  • a membrane module membrane area of about 10 to 100 m 2
  • a structure in which polysulfone, PVDF, etc., prepared using a non-solvent-induced phase separation method are fixed in a resin case with an adhesive is also used for wastewater treatment and water purification treatment. Many are used.
  • Such a membrane module is supplied with water in an amount of several tens of liters to several hundreds of liters per minute. At that time, since the chemical cleaning or peristaltic cleaning for the purpose of recovering the flow rate is periodically performed, the hollow fiber membrane may be broken during use or cleaning.
  • the method of dehumidifying or humidifying by the hollow fiber membrane method has many advantages such as not requiring maintenance but not requiring a power source for driving.
  • a dehumidifying film or humidifying film a film-forming resin material such as polyimide, polysulfone, or polyphenylsulfone is used (for example, Patent Document 3).
  • dehumidifying membranes using these materials are used in many industrial fields, they are porous, so the absolute strength of the membrane is weak. There is a possibility that the hollow fiber membrane is broken.
  • a porous membrane in which spun yarn as a reinforcing material is embedded in the membrane has been proposed as means for preventing the hollow fiber membrane from being broken and improving the mechanical strength (Patent Document 4).
  • a method for embedding the spun yarn in the hollow fiber membrane a method for producing a porous hollow fiber membrane by a production method using a known double annular nozzle by mixing a reinforcing material in the spinning dope can be considered.
  • the air contained in the reinforcing material such as spun yarn is gradually accumulated in the spinning dope inside the nozzle, and as a result of entraining the bubbles during spinning, the film shape is deformed as shown in the comparative example described later. Or pinholes, and therefore, the membrane may be cut.
  • An object of the present invention is a porous hollow fiber membrane in which all or a part of the spun yarn is embedded in the membrane, and improves the mechanical strength without impairing the original function of the porous hollow fiber membrane.
  • An object of the present invention is to provide a method for producing a spun yarn-reinforced porous hollow fiber membrane with a reduced defect rate.
  • the object of the present invention is to discharge the core liquid from the inner nozzle of the double annular nozzle and the spinning stock solution from the outer nozzle, respectively, and perform spinning inside the outer nozzle that discharges the spinning stock solution when performing wet spinning or dry-wet spinning. This is achieved by a method for producing a spun yarn-reinforced porous hollow fiber membrane by simultaneously supplying yarn from a spun yarn introduction pipe.
  • a spun yarn reinforced porous hollow fiber membrane is produced by simultaneously supplying spun yarn to a spinning dope using a spun yarn pipe, the spun yarn which is an aggregate of short fibers, That is, the air contained between the fibers is discharged outside through the spun yarn introduction pipe, so that it is not caught in the spinning dope, and as a result, the spinning failure caused by the air in the spun yarn or There exists an effect of avoiding the defect of the obtained hollow fiber membrane.
  • FIG. 1 is a schematic half-cut sectional view showing an example of a double annular nozzle used in a method for producing a spun yarn-reinforced porous hollow fiber membrane according to the present invention.
  • the core liquid is discharged from the inner nozzle of the double annular nozzle, and the spinning solution is discharged from the outer nozzle, and the spun yarn is spun inside the outer nozzle that discharges the spinning solution. It is performed by supplying simultaneously from the yarn introduction pipe.
  • the double annular nozzle a known one that has been used conventionally, that is, an inner nozzle and an outer nozzle having a diameter corresponding to a desired hollow fiber membrane size are arranged so as to be double. It can be used without particular limitation.
  • a double annular nozzle 1 comprising an annular body 3 provided with a spinning dope 6, an inner nozzle 2 and a hollow fiber membrane discharge port 7 is preferably used. It is done.
  • the annular body 3 having the hollow fiber membrane discharge port 7 constitutes the outer nozzle of the double annular nozzle 1, and the hollow fiber membrane discharge port 7 and the tip of the inner nozzle 2 Are arranged so as to form a double tubular shape capable of forming a hollow fiber membrane having a desired film thickness.
  • a spun yarn introduction pipe 4 for introducing the spun yarn 9 into the spinning dope is disposed in a state of penetrating the side surface portion of the outer nozzle 3.
  • the spun yarn introduction pipe 4 penetrates the side surface of the outer nozzle 3 so that one end located outside the outer nozzle 3 is located above the upper portion of the outer nozzle 3 and the other end is located inside the outer nozzle 3.
  • the spinning dope is fed from the spun yarn introduction port of the spun yarn introduction pipe 4. This is because it will overflow.
  • the spun yarn introduction pipe 4 has an inner diameter of 1.5 to 2.0 times, preferably 1.6 to 1.8 times the outer diameter (thickness) of the spun yarn. Since the spinning dope is pressurized in the outer nozzle (annular body 3 in FIG. 1), if the inner diameter of the spun yarn introduction pipe 4 is smaller than this, the air discharged from the spun yarn is not properly discharged, and bubbles are generated in the nozzle. If the inner diameter of the spun yarn introduction pipe 4 is larger than this, the spinning dope will flow backward through the spun yarn introduction pipe and will be outside as a result. It may leak out of the nozzle.
  • the length of the spun yarn introduction pipe 4 is not particularly limited because the position of the spinning stock solution changes depending on the thickness of the spun yarn, the diameter of the spun yarn introduction pipe, and the viscosity of the spinning stock solution, but generally the outer diameter of the spun yarn ( The thickness is about 200 to 250 times, preferably about 220 to 230 times.
  • the inner nozzle 2 is filled with the core liquid supplied from the core liquid inlet 5 and the outer nozzle 3 is filled with the spinning raw liquid and pressurized, and the spun yarn is fed from the spun yarn introduction pipe 4.
  • a porous hollow fiber membrane in which all or part of the spun yarn is buried can be obtained by a wet spinning method or a dry-wet spinning method by simultaneously discharging the spinning stock solution while supplying it to the inside of the outer nozzle 3.
  • FIG. 1 only one spun yarn introduction pipe 4 is used, but a plurality of spun yarn introduction pipes 4 can be used. Generally, 1 to 8 spun yarn introduction pipes 4 are provided.
  • a mode in which a double annular nozzle is arranged on the circumference and equidisposed is also included.
  • the spun yarn can be used without particular limitation as long as it is a commonly used spun yarn, and a spun yarn such as polyethylene terephthalate or polyphenylene sulfide is preferably used.
  • the outer diameter is 0.1 to Those having a thickness of 0.5 mm, preferably 0.25 to 0.35 mm are used.
  • the spinning dope includes a material for producing a hollow fiber membrane and a solvent.
  • a manufacturing material of the hollow fiber membrane any of known hollow fiber membrane-forming materials (polymers) can be used, for example, cellulose-based materials such as cellulose acetate, cellulose propionate, cellulose butyrate, regenerated cellulose, or a mixture thereof, Examples thereof include hydrophobic polymers such as polysulfone resins, polyethersulfone resins, polyvinylidene fluoride resins, polyacrylonitrile resins, polyimide resins, polyaramid resins, polypropylene resins, and polyethylene resins.
  • an aprotic polar solvent such as alcohol, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, dimethylsulfoxide, N-methyl-2-pyrrolidone is preferably used.
  • the core liquid water or a non-solvent of a film-forming resin is used.
  • the spun yarn 9 is preferably discharged in advance from the hollow fiber membrane discharge port to the outside of the nozzle before discharging the core solution and the spinning stock solution. deep. Further, the core solution and the spinning dope are preferably used after evacuation from the viewpoint of preventing the mixing of unnecessary air.
  • the spun yarn preferably has 50% by volume or more of the cross section of the spun yarn, more preferably 60% by volume or more, particularly preferably 70% by volume or more embedded in the hollow fiber membrane, and the functional layer (workpiece contact side)
  • the mechanical properties can be further improved while keeping the permeation performance and separation performance high.
  • a spun yarn reinforced porous hollow fiber membrane is produced by coagulating, washing, and drying a spun yarn reinforced porous hollow fiber membrane spun by a wet spinning method or a dry wet spinning method using a coagulating liquid. .
  • a polyethylene terephthalate spun yarn as the spun yarn 9 is passed through the inside of the yarn introduction pipe (tube inner diameter: 1.67 times the outer diameter of the spun yarn, pipe length: 225 times the outer diameter of the spun yarn) through the gap between the outer nozzle 3 and the inner nozzle 2.
  • the obtained spun yarn reinforced hollow fiber membrane was washed in a washing tank with a water temperature of 45 ° C., then subjected to high-pressure sterilization treatment at 121 ° C. for 1 hour, and then in a drying furnace with an internal temperature of 40 ° C. And dried for 12 hours or longer to obtain a spun yarn reinforced porous polyetherimide hollow fiber membrane by a wet spinning method.
  • a pinhole inspection and a cross-sectional dimension inspection were performed on the porous hollow fiber membrane, none of the hollow fiber membranes had pinholes or deformation, and the defect rate was 0%.
  • the obtained porous polyetherimide hollow fiber membrane has an outer diameter of 1000 ⁇ m, an inner diameter of 700 ⁇ m, a water vapor transmission rate at 25 ° C.
  • the spun yarn was introduced into the nozzle from the spinning dope introduction port 6 instead of the spun yarn introduction port 8, and the polyethylene terephthalate spun yarn, which is the spun yarn 9, was previously obtained from the gap between the outer nozzle 3 and the inner nozzle 2.
  • a hollow fiber membrane was obtained with about 1 m protruding.
  • one film break and two pinholes core liquid blows out to the outside of the film
  • a large number of bubbles were confirmed in the spinning dope, and it was found that defects occurred due to the bubbles.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Textile Engineering (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)

Abstract

Quand un liquide de cœur et une solution de filage sont éjectés respectivement de la buse intérieure et de la buse extérieure d'une buse annulaire à double paroi pour mettre en œuvre un filage au mouillé ou un filage à sec/au mouillé, un filé est simultanément fourni par un tuyau d'introduction de filé à l'intérieur de la buse extérieure dont est éjectée la solution de filage, de façon à produire une membrane à fibres creuses poreuses renforcée par un filé. Par ce procédé, une membrane poreuse à fibres creuses renforcée par un filé est produite, dans laquelle le filé a été en totalité ou en partie enterré, et qui conserve les fonctions inhérentes à la membrane poreuse à fibres creuses, présente une résistance mécanique améliorée, avec une réduction du taux de rebut.
PCT/JP2014/061326 2013-04-23 2014-04-22 Procédé de production d'une membrane poreuse à fibres creuses renforcée par un filé WO2014175282A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013090708A JP5737319B2 (ja) 2013-04-23 2013-04-23 紡績糸強化多孔質中空糸膜の製造方法
JP2013-090708 2013-04-23

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WO2014175282A1 true WO2014175282A1 (fr) 2014-10-30

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57167414A (en) * 1981-04-03 1982-10-15 Ube Ind Ltd Production of polyimide hollow fiber
JP2003245528A (ja) * 2002-02-26 2003-09-02 Mitsubishi Rayon Co Ltd 繊維強化多孔質中空糸膜の製造方法
JP2006088148A (ja) * 2004-09-20 2006-04-06 Para Ltd 透水性に優れた中空糸膜
WO2009142279A1 (fr) * 2008-05-21 2009-11-26 三菱レイヨン株式会社 Membrane poreuse creuse et son procédé de fabrication
JP2012200635A (ja) * 2011-03-24 2012-10-22 Toray Ind Inc 複合中空糸膜の製造方法
JP2012530594A (ja) * 2009-06-26 2012-12-06 ビーエル・テクノロジーズ・インコーポレイテッド 非編組式織物で強化された中空糸膜

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57167414A (en) * 1981-04-03 1982-10-15 Ube Ind Ltd Production of polyimide hollow fiber
JP2003245528A (ja) * 2002-02-26 2003-09-02 Mitsubishi Rayon Co Ltd 繊維強化多孔質中空糸膜の製造方法
JP2006088148A (ja) * 2004-09-20 2006-04-06 Para Ltd 透水性に優れた中空糸膜
WO2009142279A1 (fr) * 2008-05-21 2009-11-26 三菱レイヨン株式会社 Membrane poreuse creuse et son procédé de fabrication
JP2012530594A (ja) * 2009-06-26 2012-12-06 ビーエル・テクノロジーズ・インコーポレイテッド 非編組式織物で強化された中空糸膜
JP2012200635A (ja) * 2011-03-24 2012-10-22 Toray Ind Inc 複合中空糸膜の製造方法

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JP2014213236A (ja) 2014-11-17
JP5737319B2 (ja) 2015-06-17

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