KR930007497A - Method for producing hollow fiber membrane for ultrafiltration - Google Patents

Method for producing hollow fiber membrane for ultrafiltration Download PDF

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KR930007497A
KR930007497A KR1019910017321A KR910017321A KR930007497A KR 930007497 A KR930007497 A KR 930007497A KR 1019910017321 A KR1019910017321 A KR 1019910017321A KR 910017321 A KR910017321 A KR 910017321A KR 930007497 A KR930007497 A KR 930007497A
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fiber membrane
hollow fiber
polysulfone
stock solution
spinning
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KR1019910017321A
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KR950006518B1 (en
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이규호
김정훈
박유인
노일준
최수명
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채영복
재단법인 한국화학연구소
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    • 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
    • B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
    • B01D61/14—Ultrafiltration; Microfiltration
    • B01D61/145—Ultrafiltration
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
    • B01D67/0002—Organic membrane manufacture
    • B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
    • B01D67/0016—Coagulation
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    • 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
    • B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
    • B01D67/0025—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching
    • B01D67/0027—Organic membrane manufacture by inducing porosity into non porous precursor membranes by mechanical treatment, e.g. pore-stretching by stretching
    • 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
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    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D69/1216—Three or more layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D71/06—Organic material
    • B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
    • B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
    • B01D71/421—Polyacrylonitrile
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D71/06—Organic material
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    • B01D71/522—Aromatic polyethers
    • B01D71/5222—Polyetherketone, polyetheretherketone, or polyaryletherketone
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    • B01D71/06—Organic material
    • B01D71/56—Polyamides, e.g. polyester-amides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D71/06—Organic material
    • B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
    • B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
    • B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
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    • B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
    • B01D71/06—Organic material
    • B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
    • B01D71/68—Polysulfones; Polyethersulfones
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2323/15—Use of additives
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    • B01D2323/2181—Inorganic additives
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    • B01D2323/22—Specific non-solvents or non-solvent system
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/02—Details relating to pores or porosity of the membranes
    • B01D2325/021—Pore shapes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
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    • B01D2325/0283—Pore size
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/04—Characteristic thickness

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Water Supply & Treatment (AREA)
  • Manufacturing & Machinery (AREA)
  • Dispersion Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Artificial Filaments (AREA)

Abstract

이 발명은 투수성과 기계작 특성이 우수하여 외압방식의 한외 여과 목적에 적합한 방향족 폴리 설폰 중공 섬유막 및 그 제조 방법에 관한 것이다.The present invention relates to an aromatic polysulfone hollow fiber membrane and a method for producing the same, which are excellent in permeability and mechanical properties, and are suitable for the purpose of external filtration by ultrafiltration.

이 발명에서의 폴리 설폰 중공 섬유막은, 외표면은 미세한 기공의 치밀한 스킨층과 이에 인접하여 내측으로 기공의 크기가 증가하는 지상구조가 발달되어 있으며, 내표면은 슬리트형의 기공이 개공되어 있고 그에 인접하여 다공상 망상지지체가 지상구조와 연결되어 있는 구조를 하고 있다. 이 발명의 중공 섬유막에서의 기계작 강도는 인장강도 0.3∼0.5g/denier, 내압성 3∼6기압이고 투수성은 최고 4,000×10-3g/cm3·atm·min이다.In the polysulfone hollow fiber membrane of the present invention, the outer surface has a dense skin layer having fine pores and a ground structure in which the pore size increases inward adjacent to the inner surface, and the inner surface has pores of slit type and Adjacent porous network supports are connected to the ground structure. The mechanical strength in the hollow fiber membrane of this invention is 0.3-0.5 g / denier in tensile strength, 3-6 atmospheres of pressure resistance, and water permeability is up to 4,000x10 <-3> g / cm <3> atm * min.

상기 구조의 중공섬유막은 폴리설폰수지, 첨가제, 유기용매를 이루어진 방사원액을 이중관형 노즐에서 압출할 때 내부응고액과 같이 공기중 또는 외부 응고액조에 방출함으로써 제조한다.The hollow fiber membrane of the above structure is produced by releasing a spinning stock solution consisting of polysulfone resin, an additive, and an organic solvent into an air or external coagulation bath such as an internal coagulation solution when extruding from a double tube nozzle.

Description

방향족 폴리 설폰 중공 섬유막 및 그 제조 방법Aromatic polysulfone hollow fiber membrane and its manufacturing method

본 내용은 요부공개 건이므로 전문내용을 수록하지 않았음Since this is an open matter, no full text was included.

제1도 가), 나)는 이 발명의 각 실시예에 의하여 얻어진 중공 섬유막의 단면 확대 사진.1) a), b) are enlarged cross-sectional photographs of the hollow fiber membranes obtained by the examples of the present invention.

제2도 가), 나)는 이 발명의 각 실시예에 의하여 얻어지 중공 섬유막의 내부 표면 확대 사진.2), b) is an enlarged photograph of the inner surface of the hollow fiber membrane obtained by each embodiment of the present invention.

제3도는 이 발명의 중공 섬유막의 막두께에 따른 투수성에 대한 상관 관계도.3 is a correlation diagram of water permeability according to the film thickness of the hollow fiber membrane of the present invention.

Claims (19)

막 표면에 미세한 공정을 같은 치밀한 스킨층과 이에 인접하여 외측에서 내측으로 공경이 연속적으로 커지는 지상구조가 내표면의 슬리트 형이 기공으로 이루어진 다공성 망상 지지층과 연결되는, 스킨층, 지상구조, 다공성 망상 지지층의 3중 구조로 구성되는 것을 특징으로 하는 폴리 설폰 중공 섬유막.Skin layer, ground structure, porous Polysulfone hollow fiber membrane, characterized in that consisting of a triple structure of the network support layer. 제1항에 있어서, 스킨층은 0.01㎛ 미만의 미세한 공경의 기공으로 이루어진 것을 특징으로 하는 섬유막.The fiber membrane of claim 1, wherein the skin layer is formed of pores having a fine pore diameter of less than 0.01 μm. 제1항에 있어서, 지상구조는 상기의 스킨층과 인접하여 외측에서 내측으로 공경이 연속적으로 증가하는 테이퍼(taper)상의 구조를 갖고 내측에 다공성 망상 지지체와 연결된?? 것을 특징으로 하는 중공 섬유막.The ground structure of claim 1, wherein the ground structure has a tapered structure in which the pore continuously increases from the outside to the inside adjacent to the skin layer and is connected to the porous network support on the inside thereof. Hollow fiber membrane, characterized in that. 제1항 또는 제3항에 있어서, 지상구조는 외표면측에서 0.01㎛이하의 공경을 갖고 내부측에서는 수㎛의 공경을 갖는 특징으로 하는 중공 섬유막.The hollow fiber membrane according to claim 1 or 3, wherein the ground structure has a pore diameter of 0.01 mu m or less on the outer surface side and a pore diameter of several mu m on the inner side. 제1항에 있어서, 내표면의 다공성 지지체는 폭 0.01∼5㎛, 길이 0.02∼10㎛의 슬릿트상 기공이 개공률 40∼80%로 존재하는 내표면과 이에 인접하여 0.01∼10㎛의 열린 기공(open pore)으로 이루어진 다공성 망상 지지층이 전체 막 두께의 1/10이상 차지하는 것을 특징으로 하는 중공 섬유막.The porous support of claim 1, wherein the porous support on the inner surface has a slit-like pore having a width of 0.01 to 5 µm and a length of 0.02 to 10 µm having an opening ratio of 40 to 80% and an open pore of 0.01 to 10 µm adjacent thereto. Hollow fiber membrane, characterized in that the porous network support layer made of (open pore) occupy more than 1/10 of the total film thickness. 폴리 설폰 수지와 첨가제 및 이들의 공통 용매를 이루어진 방사 원액을 이중 관형 노즐에서 압출시키는 동시에 노즐 내부의 홀에 내부 응고액을 주입시켜, 공기중으로 방사한 다음 외부 응고 욕조에서 응고시키거나, 직접 외부 응고 욕조를 방사형 응고시킨 후, 수세하는 것을 특징으로 하는 폴리설폰 중공 섬유막 제조 방법.The spinning stock solution consisting of polysulfone resin and additives and their common solvents is extruded from a double tubular nozzle while injecting internal coagulant into the hole inside the nozzle, spinning into the air and then coagulating in an external coagulation bath, or directly external coagulation. A method for producing a polysulfone hollow fiber membrane, wherein the tub is radially solidified and then washed with water. 제6항에 있어서, 폴리 설폰 수지는 방향족 폴리 설폰 중합체, 방향족 폴리 에테설폰계 중합체 또는 이들의 화학적 변성 중합체 중에서 선택하여 사용되는 것을 특징으로 하는 방법.The method according to claim 6, wherein the poly sulfone resin is selected from an aromatic poly sulfone polymer, an aromatic polyethesulfone polymer or a chemically modified polymer thereof. 제6항에 있어서, 폴리 설폰 수지는 방사원액 중에서 10∼25중량 %의 농도인 것을 특징으로 하는 방법.The method according to claim 6, wherein the poly sulfone resin is at a concentration of 10 to 25% by weight in the spinning solution. 제6항에 있어서, 방사 원액의 요앰는 비등점 100℃ 이상의 난휘발성 유기 용매로서 폴리 설폰에 대하여 양용매(good solbent)인 것을 특징으로 하는 방법.7. The method according to claim 6, wherein the yoam of the spinning stock solution is a good solbent against polysulfone as a nonvolatile organic solvent having a boiling point of 100 ° C or higher. 제6항 또는 제9항에 있어서 방사 원액의 용매는 디메틸 아세트아마이드, 디메틸 포름아미드, N-메틸-2-피롤리돈, 디메틸 설폰사이드, 2-피리딘 중에서 1종이상 선택되어 상용되는 것을 특징으로 하는 방법.The method of claim 6 or 9, wherein the solvent of the spinning stock solution is selected from one or more of dimethyl acetamide, dimethyl formamide, N-methyl-2-pyrrolidone, dimethyl sulfonide, 2-pyridine, and is commercially available. How to. 제6항에 있어서, 첨가제는 무기염, 알콜화합물, 수용성 고분자로서 적어도 1종 이상의 방사 원액에 첨가되는 것을 특징으로 하는 방법.7. The method according to claim 6, wherein the additive is added to at least one spinning stock solution as an inorganic salt, an alcohol compound, or a water-soluble polymer. 제11항에 있어서, 무기염은 탄산칼슘, 염화아연 폴 방사원액에 0∼7 중량% 농도로 첨가되는 것을 특징으로 하는 방법.12. The method according to claim 11, wherein the inorganic salt is added to the calcium carbonate and zinc chloride pole spinning solution at a concentration of 0 to 7% by weight. 제11항에 있어서, 알콜 화합물은, 메탄올, 에탄올 등의 1가 알콜 또는 이들의 유도체 중에서 1종 이상 선택하여 방사원액 중에서 0∼35중량 %농도를 첨가되는 것을 특징으로 하는 방법.The method according to claim 11, wherein the alcohol compound is selected from monohydric alcohols such as methanol and ethanol or derivatives thereof, and a concentration of 0 to 35% by weight is added in the spinning solution. 제11항에 있어서, 수용성 고분자는 폴리에틸렌클리콜, 폴리 비닐 알콜, 폴리 비닐 피론리돈 중에서 선택하여 방사원액 중에서 0∼35중량%농도로 첨가되는 것을 특징으로 하는 방법.The method of claim 11, wherein the water-soluble polymer is selected from polyethylene glycol, polyvinyl alcohol, polyvinyl pyrrolidone and added at a concentration of 0 to 35% by weight in the spinning stock solution. 제6항에 있어서, 방사원액이 점도는 2,000∼60,000 센터포아스인 것을 특징으로 하는 방법.The method of claim 6, wherein the spinning stock solution has a viscosity of 2,000 to 60,000 center pore. 제6항에 있어서, 내부 응고액은 폴리설폰에 피하여 양용매(good solvent)와 저점토, 저응고가의 비용매(poor solvent) 및 고점토, 고응고가의 비용매의 3성분으로 혼합되는 것을 특징으로 하는 방법.The method of claim 6, wherein the internal coagulation solution is mixed with three components of good solvent, low clay, low coagulation nonsolvent and high clay, high coagulation nonsolvent, avoiding polysulfone. Characterized in that the method. 제6항에 있어서, 외부 응고액은 물, 또는 폴리 설폰에 대하여 양용매와 저점도 저 응고가의 비용매의 혼합 용매인 것을 특징으로 하는 방법.7. The method according to claim 6, wherein the external coagulation liquid is a mixed solvent of a good solvent and a low viscosity low coagulation nonsolvent with respect to water or polysulfone. 제6항 또는 제17항에서 외부 응고액의 온도는 0℃∼100℃인 것을 특징으로 하는 방법.18. The method of claim 6 or 17, wherein the temperature of the external coagulation liquid is 0 ° C to 100 ° C. 제6항에 있어서, 방사 높이는 0∼1m인 것을 특징으로 하는 방법.7. The method of claim 6 wherein the radiation height is 0-1 m. ※ 참고사항 : 최초출원 내용에 의하여 공개하는 것임.※ Note: The disclosure is based on the initial application.
KR1019910017321A 1991-10-02 1991-10-02 The manufacturing method for ultrafiltration film KR950006518B1 (en)

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