WO2013073828A1 - Membrane de séparation en fibre creuse à base de polyfluorure de vinylidène hydrophile et procédé pour la fabrication de ladite membrane - Google Patents

Membrane de séparation en fibre creuse à base de polyfluorure de vinylidène hydrophile et procédé pour la fabrication de ladite membrane Download PDF

Info

Publication number
WO2013073828A1
WO2013073828A1 PCT/KR2012/009591 KR2012009591W WO2013073828A1 WO 2013073828 A1 WO2013073828 A1 WO 2013073828A1 KR 2012009591 W KR2012009591 W KR 2012009591W WO 2013073828 A1 WO2013073828 A1 WO 2013073828A1
Authority
WO
WIPO (PCT)
Prior art keywords
polyvinylidene fluoride
hollow fiber
membrane
weight
hydrophilic
Prior art date
Application number
PCT/KR2012/009591
Other languages
English (en)
Korean (ko)
Inventor
이수민
이창호
오현환
박주영
이준석
김민정
Original Assignee
엘지전자 주식회사
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 엘지전자 주식회사 filed Critical 엘지전자 주식회사
Priority to CN201280048355.7A priority Critical patent/CN103857462B/zh
Publication of WO2013073828A1 publication Critical patent/WO2013073828A1/fr

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
    • B01D69/08—Hollow fibre membranes
    • 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
    • B01D69/04—Tubular membranes
    • 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
    • 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
    • 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
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/24—Mechanical properties, e.g. strength

Definitions

  • the present invention relates to a method for producing a hydrophilic polyvinylidene fluoride-based (PVDF) hollow fiber separator, and more specifically, to prepare a spinning solution containing polyvinylidene fluoride (PVDF), a hydrophilic polymer, a specific poor solvent,
  • PVDF polyvinylidene fluoride
  • the present invention relates to a PVDF hollow fiber membrane prepared by spinning and inducing heat-induced phase transition and a method of manufacturing the same.
  • a polymer solution containing a polyvinylidene fluoride resin and a good solvent and a pore-forming agent is cast and extruded at a temperature lower than the melting point of the polyvinylidene fluoride resin.
  • Non-solvent-induced phase separation in which a porous structure is formed by spinning and solidifying in a non-solvent, is generally used.
  • the non-solvent induced phase separation method has an advantage of freely controlling the pore size, but the mechanical strength of the membrane is weak, and the surface characteristics are hydrophobic, so it is vulnerable to membrane contamination.
  • the thermally induced phase separation method is a method of manufacturing a separation membrane by using a vinylidene fluoride-based resin and a poor solvent, spinning at a temperature raised to the melting point of the polyvinylidene fluoride-based resin, cooling and solidifying.
  • Asahi Kasehi prepared a fine filtration membrane by adding inorganic fine particles as a pore-forming agent, but it is troublesome to extract the inorganic fine particles after spinning and undergo a hydrophilization process.
  • Toray is a non-solvent for preparing polyvinylidene fluoride-based ultrafiltration membranes having a double layer structure using a thermally induced phase separation method to form an inner support layer and a hydrophilic polymer solution containing a hydrophilic polymer in the outer membrane active layer. It is prepared using induction phase separation.
  • the Toray ultrafiltration membrane has a double layer structure, so that a high-strength high-molecular separation membrane can be obtained.
  • the manufacturing cost of the Toray ultrafiltration membrane is very high by using both a thermally induced phase separation method and a non-solvent induced phase separation method.
  • the Korea Research Institute of Chemical Technology Patent No.
  • 10-2009-0011655 uses a polyvinylidene fluoride-based resin containing polyacrylonitrile as a hydrophilic polymer in the method of manufacturing a polyvinylidene difluoride hollow fiber membrane, and has a tubular polymer support layer (polyester ) By using non-solvent induction phase separation method.
  • the coating film of the Korea Research Institute of Chemical Technology can produce a high strength separation membrane by using an inner support layer, but the peeling phenomenon of the coating layer occurs in the use of the separation membrane, and when the manufacture without the support layer has a disadvantage in that the strength is very weak.
  • PVDF polyvinylidene fluoride
  • Another object of the present invention is to provide a hydrophilic PVDF hollow fiber membrane having excellent mechanical strength, pore size, permeation flux and membrane fouling resistance prepared by the above method.
  • Another object of the present invention to provide a composition that can be used for the production of the hydrophilic polyvinylidene fluoride-based hollow fiber membrane.
  • One aspect of the present invention is (i) 10 to 60% by weight of polyvinylidene fluoride resin (PVDF); 5-30% by weight of a hydrophilic resin selected from the group consisting of polyetherimide (PEI), polyimide (PI), polyamide (PA) and cellulose acetate (CA); And obtaining a spinning solution containing 20 to 85 wt% of a poor solvent (poor-solvent), and (ii) spinning the spinning solution to prepare a hollow fiber membrane. It provides a method for producing a four separation membrane.
  • PVDF polyvinylidene fluoride resin
  • a hydrophilic resin selected from the group consisting of polyetherimide (PEI), polyimide (PI), polyamide (PA) and cellulose acetate (CA)
  • the PVDF is preferably used 10 to 50% by weight based on the total weight of the polymer resin, more preferably 20 to 40% by weight. If the amount of PVDF is less than 10% by weight, the strength of the hollow fiber membrane may be weakened. If the amount of the PVDF exceeds 50% by weight, the viscosity of the polymer solution may be too high, making it difficult to form the hollow fiber membrane through spinning.
  • the hydrophilic polymer is preferably used 5 to 30% by weight based on the total weight of the polymer resin, more preferably 10 to 25% by weight.
  • the hydrophilic polymer is less than 5% by weight, the membrane fouling resistance of the prepared membrane is insufficient, and when the amount of the hydrophilic polymer exceeds 30% by weight, the proportion of the hydrophilic polymer in the total polymer weight is high and the particles of the hydrophilic polymer increase. It is not preferable that the voids are small.
  • the hydrophilic polymer is preferably used at least one selected from polyetherimide (PEI), polyimide (PI), polyamide (PA) and cellulose acetate (CA). More preferably, one or more selected from the group consisting of polyetherimide (PEI), polyimide (PI) and polyamide (PA) can be used.
  • PEI polyetherimide
  • PI polyimide
  • PA polyamide
  • CA cellulose acetate
  • hydrophilic polymer having a weight average molecular weight of 100,000 to 500,000.
  • the poor solvent is preferably used 20 to 85% by weight based on the total weight of the polymer resin, more preferably 35 to 70% by weight.
  • the poor solvent can dissolve the resin at least 5% by weight at a low temperature of 60 ° C or lower, but may be used without limitation as long as it can dissolve 5% or more in the high temperature range of 60 ° C or higher and below the melting point of the resin. It is preferable to use any one or more selected from ⁇ -butyrolactone (lactone), cyclohexanone, acetophenone, and isophorone.
  • a method of manufacturing a PVDF hollow fiber separator using the polymer resin for preparing the PVDF separator is as follows.
  • step is to obtain a spinning solution, for example, 10 to 60% by weight of polyvinylidene fluoride resin (PVDF); 5-30% by weight of hydrophilic resin and at least one solvent selected from the group consisting of polyetherimide (PEI), polyimide (PI), polyamide (PA) and cellulose acetate (CA) 20-85
  • PVDF polyvinylidene fluoride resin
  • hydrophilic resin at least one solvent selected from the group consisting of polyetherimide (PEI), polyimide (PI), polyamide (PA) and cellulose acetate (CA) 20-85
  • PEI polyetherimide
  • PI polyimide
  • PA polyamide
  • CA cellulose acetate
  • the method of uniformly melting the polymer resin for PVDF separator production is not particularly limited, but for example, a method is prepared by adding a uniform spinning solution to a continuous resin kneading apparatus such as a screw extruder or having a stirrer having a predetermined size. Uniform spinning solution can be prepared in the working liquid preparation device. At this time, the temperature of each device is preferably maintained at 120 ⁇ 180 °C.
  • the spinning solution is discharged by moving the fixed amount to the nozzle with a gear pump, and preferably cooled and solidified in the phase change tank.
  • the transfer line from the polymer resin production apparatus to the gear pump and the gear pump to the nozzle is preferably heated to reduce the heat loss of the polymer resin.
  • Next step (ii) is to spin the spinning solution to prepare a hollow fiber membrane.
  • step (ii) may be carried out by a thermally induced phase separation method.
  • the spinning solution and the internal coagulation bath may be spun from the same nozzle, thereby cooling and solidifying the spinning solution in a phase-transfer bath to prepare a hollow fiber separator.
  • the internal coagulation bath and the phase transfer bath may be used by mixing a poor solvent or a good solvent in a poor solvent or water.
  • the poor solvent is not particularly limited, but ⁇ -butyrolactone (lactone) and cyclohexanone ( It is preferable to use any one or more selected from cyclohexanone, acetophenone, and isophorone, and the good solvent is dimethylformamide, n-methyl-2-pyrrolidone, dimethylacetamide and dimethyl sulfoxide. It is preferable to use any one or more selected from.
  • the temperature of the internal coagulation bath and the phase transition bath is 0 to 80 °C and more preferably 10 to 50 °C.
  • the solidification phenomenon occurs on the surface of the hollow fiber membrane so that it is difficult to impart porosity of the hollow fiber membrane.
  • the temperature exceeds 80 ° C. the solidification occurs too slowly. As the polymer crystals become larger, the pore size may increase, and the mechanical strength may be weakened.
  • the method further comprises stretching the separator prepared in step (ii) above.
  • the drawing may be performed by drawing through a drawing machine to produce a final hollow fiber separator.
  • the stretching machine is not particularly limited to a method of increasing the mechanical strength of the hollow fiber membrane and increasing the pure water flux.
  • the moist heat stretching proceeds with rotating rolls at the front and rear ends of the stretching period, and each roll can control the rotational speed.
  • the stretching machine can use water or steam, and the temperature is preferably maintained at 80 to 90 ° C. Do.
  • the drawing step may be performed by a local drawing method in which an external stress is concentrated at a specific portion of the separator, and the stress concentration is repeated to allow the drawing operation to proceed according to hysteresis, between the seaweed bobbin and the winding bobbin. It may also be carried out by a cyclic stretching method after phase separation which is continuously circulated in the forward and reverse directions.
  • a cyclic stretching method after phase separation when the external stress acts perpendicular to the growth direction of the lamellae on the unstretched hollow fiber membrane without any external stress, the fibril structure appears in the polymer lean region and further external stress is applied. Increasing the length of the ground fibrils may increase the distance between the lamellar regions.
  • fibril may be generated at the end of the polymer chain inside the lamellae.
  • the method of the present invention is characterized in that after step (ii), the process does not include a process for coating the surface of the prepared membrane, a surface hydrophilization treatment process or a porosity imparting after treatment process.
  • the hollow fiber membrane manufactured by the method of the present invention is prepared by using a spinning solution containing a specific hydrophilic polymer and a poor solvent, and coats the surface of the separator prepared for the purpose of hydrophilization, porosity, and strength.
  • the mechanical strength is excellent on its own, the pore size is small, the permeation flow rate is high, and at the same time the membrane fouling resistance is very excellent.
  • the hollow fiber membrane after the step (ii), the hollow fiber membrane, characterized in that it does not include the step of coating the surface of the prepared membrane, the surface hydrophilization treatment process or the porous end treatment process
  • a manufacturing method is provided, which is economical and efficient by excluding certain coating, surface treatment and post treatment processes.
  • Another aspect of the present invention is to provide a hydrophilic polyvinylidene fluoride-based hollow fiber separator prepared by the above method.
  • PVDF hollow fiber membrane prepared by the above manufacturing method has excellent mechanical strength by itself, without any specific porosity post-treatment, surface treatment, or coating treatment, while having small pore size, high permeate flow rate, and very high membrane fouling resistance. great.
  • Hydrophilic PVDF hollow fiber membrane prepared by the method of the present invention is excellent in mechanical strength by forming a spherorite structure without a macrovoid as a cross-sectional structure of the membrane, the outer diameter of the hollow fiber membrane is in the range of 1 ⁇ 5 mm, the inner diameter is It has a range of 0.6 to 4.8 mm, has an average pore size of 0.1 to 0.02 ⁇ m, a pure permeate flow rate of 200 to 1200 L / m 2 hr (-500 mmHg), and a porosity of 60% or more, and exhibits excellent membrane fouling resistance.
  • PVDF polyvinylidene fluoride resin
  • hydrophilic resin selected from the group consisting of polyetherimide (PEI), polyimide (PI), polyamide (PA) and cellulose acetate (CA); And it provides a composition for producing a hydrophilic polyvinylidene fluoride-based hollow fiber membrane comprising 20 to 85% by weight of a poor solvent (poor-solvent).
  • composition for producing a hollow fiber membrane of the present invention is not used for the purpose of surface modification treatment or post-treatment, and has the use of producing the hollow fiber membrane support structure itself.
  • the composition of the present invention is 10 to 60% by weight of polyvinylidene fluoride resin (PVDF); 5-30% by weight of hydrophilic resin and at least one solvent selected from the group consisting of polyetherimide (PEI), polyimide (PI), polyamide (PA) and cellulose acetate (CA) 20-85 It is obtained by the method of mixing the weight percent, and the mixture is melted uniformly and spun to give excellent porosity and small pore size by itself, without the need for specific porosity post-treatment, surface treatment, or coating treatment.
  • a hydrophilic polyvinylidene fluoride-based hollow membrane having a high permeation flow rate and excellent membrane fouling resistance can be produced.
  • the hydrophilic resin is one or more selected from the group consisting of polyetherimide (PEI), polyimide (PI) and polyamide (PA).
  • the hydrophilic resin is preferably a weight average molecular weight of 100,000 to 500,000.
  • the poor solvent may be one or more selected from the group consisting of ⁇ - butyrolactone (lactone), cyclohexanone (cyclohexanone), acetophenone (Acetophenone) and isophorone (isophorone).
  • the present invention is prepared by using a spinning solution containing a specific hydrophilic polymer and a poor solvent by supplementing the disadvantages of the conventional non-solvent induced phase separation method and the thermally induced phase separation method of the polyvinylidene fluoride-based membrane manufacturing process and the characteristics of the prepared membrane.
  • the present invention provides a hydrophilic polyvinylidene fluoride-based hollow fiber membrane having excellent porosity, small pore size, high permeate flow rate, and high membrane fouling resistance.
  • the hydrophilic polyvinylidene fluoride-based hollow fiber membrane prepared by the method of the present invention has excellent properties in all aspects of pore size, permeate flow rate, hydrophilicity, and strength without a separate post-treatment process. It is economical and efficient because it can exclude the hydration post-treatment process.
  • FIG. 1 is a view of the film thickness, pore size and cross section of the hollow fiber membrane prepared by the method of the present invention observed with a scanning electron microscope (SEM).
  • Figure 2 is a state observed the surface state of the hollow fiber membrane prepared by the method of the present invention by a scanning electron microscope (Scanning Electron Microscope, SEM).
  • PVDF polyvinylidene fluoride resin
  • GBL ⁇ -butyrolactone
  • PEI polyetherimide
  • SABIC innovation plasitics After stirring for 12 hours in a 170 °C reactor filled with gas was transferred to a stabilizer in the same state to stabilize for 12 hours to prepare a spinning composition. Thereafter, the spinning composition and the internal coagulation bath (GBL 80% by weight, water 20% by weight) are simultaneously discharged through a nozzle to form a hollow fiber, which is immersed in the non-solvent contained in the external coagulation bath (phase transfer bath). Formed a desert.
  • the rate of pumping of the internal coagulation bath was 4.5 ml / min and the temperature was 25 ° C.
  • the discharge pressure was set to 5 kgf / cm 2 or more in the reactor, the production solution transfer pump was maintained at 30 rpm, and the gap between the nozzle and the non-solvent of the phase transfer tank was fixed at 10 cm. It was.
  • the thickness, pore size, cross section and surface state of the hollow fiber membrane prepared by the above method were measured by scanning electron microscope (Scanning Electron Microscope, SEM), and are shown in FIGS. 1 and 2, and spherical spherical lights were connected. It could be confirmed that the appearance.
  • SEM scanning Electron Microscope
  • a hollow fiber separator was manufactured in the same manner as in Example 1, except that polyimide (PI, Matrimid 5218, manufactured by Ciba Polymer, Inc.) was used instead of the polyetherimide of Example 1.
  • polyimide PI, Matrimid 5218, manufactured by Ciba Polymer, Inc.
  • a hollow fiber separator was manufactured in the same manner as in Example 1, except that polyamide (PA, Grivory G16 of EMS-Grivory Co., Ltd.) was used instead of the polyetherimide of Example 1.
  • a hollow fiber separator was manufactured in the same manner as in Example 1, except that cellulose triacetate (CTA, CA-436-80S, manufactured by EASTMAN) was used instead of the polyetherimide of Example 1.
  • CTA cellulose triacetate
  • CA-436-80S manufactured by EASTMAN
  • a hollow fiber membrane was prepared in the same manner as in Example 1, except that Acetophenone was used instead of ⁇ -butylolactone (GBL) of Example 1.
  • GBL ⁇ -butylolactone
  • a hollow fiber membrane was prepared in the same manner as in Example 1, except that isophorone was used instead of ⁇ -butylolactone (GBL) of Example 1.
  • GBL ⁇ -butylolactone
  • a hollow fiber separator was manufactured in the same manner as in Example 1, except that polyacrylonitrile (PAN, Aldrich) was used instead of the polyetherimide of Example 1.
  • PAN polyacrylonitrile
  • a hollow fiber separator was prepared in the same manner as in Example 1, but the composition was prepared by mixing 40% by weight of polyvinylidene fluoride-based resin and 60% by weight of ⁇ -butylolactone (GBL) without using a hydrophilic polymer.
  • GBL ⁇ -butylolactone
  • the hollow fiber membranes were prepared in the same manner as in Comparative Example 1 except that n-methyl-2-pyrrolidone (NMP) was stirred at 150 ° C. instead of ⁇ -butylolactone (GBL) in comparison with Comparative Example 2. Prepared.
  • a hollow fiber separator was prepared in the same manner as in Comparative Example 2, except that dimethylacetamide (DMAc) was used instead of ⁇ -butylolactone (GBL) in comparison with Comparative Example 2.
  • DMAc dimethylacetamide
  • GBL ⁇ -butylolactone
  • the hollow fiber membranes prepared in Examples 1 to 6 and Comparative Examples 1 to 3 produced a module having a constant length and number of strands, and pure water was out at room temperature under a pressure of 1 kgf / cm 2 of TMP (Trans Membrane Pressure). Pressurized using a pressure pump in the -In method was measured.
  • TMP Trans Membrane Pressure
  • the hollow fiber membranes prepared in Examples 1 to 6 and Comparative Examples 1 to 3 were measured using a capillary flow porometer.
  • the hollow fiber separators prepared in Examples 1 to 6 and Comparative Examples 1 to 3 were measured at a dynamic contact angle using KRSS K100 Tensiometers.
  • Tensile strength of the hollow fiber membrane prepared in Examples 1 to 6 and Comparative Examples 1 to 3 was measured using a micro-forcing tester.
  • Examples 1-6 secured excellent properties in all aspects of pore size, permeation flow rate, contact angle, and breaking strength, and in particular, Examples 1-3 and 5-6 were excellent.

Landscapes

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

Abstract

En général, un procédé de fabrication pour une membrane de séparation à base de polyfluorure de vinylidène et une membrane fabriquée en utilisant ce procédé font appel à un procédé de séparation de phases non induit par solvant et un procédé de séparation de phases induit thermiquement. Toutefois, la membrane de séparation en fibre creuse à base de polyfluorure de vinylidène hydrophile selon la présente invention est fabriquée en utilisant une solution de filage qui contient un polymère hydrophile prédéterminé et un mauvais solvant pour une excellente résistance mécanique, et a de petits pores, un débit de perméation élevé, et une résistance élevée à la contamination de la membrane. De même, quand une membrane de séparation pour le traitement de l'eau est fabriquée, les procédés de posttraitement prédéterminés pour fournir la porosité et l'hydrophilicité sont éliminés, si bien que la membrane de séparation peut être fabriquée de manière économique et efficace.
PCT/KR2012/009591 2011-11-16 2012-11-14 Membrane de séparation en fibre creuse à base de polyfluorure de vinylidène hydrophile et procédé pour la fabrication de ladite membrane WO2013073828A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201280048355.7A CN103857462B (zh) 2011-11-16 2012-11-14 亲水性聚偏氟乙烯系中空纤维分离膜及其制造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
KR1020110119649A KR101462939B1 (ko) 2011-11-16 2011-11-16 친수성 폴리불화비닐리덴계 중공사 분리막 및 이의 제조방법
KR10-2011-0119649 2011-11-16

Publications (1)

Publication Number Publication Date
WO2013073828A1 true WO2013073828A1 (fr) 2013-05-23

Family

ID=48429841

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/KR2012/009591 WO2013073828A1 (fr) 2011-11-16 2012-11-14 Membrane de séparation en fibre creuse à base de polyfluorure de vinylidène hydrophile et procédé pour la fabrication de ladite membrane

Country Status (3)

Country Link
KR (1) KR101462939B1 (fr)
CN (1) CN103857462B (fr)
WO (1) WO2013073828A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103495347A (zh) * 2013-10-15 2014-01-08 山东招金膜天有限责任公司 一种连续的热致相分离法成膜装置及成膜工艺
CN103861481A (zh) * 2014-04-03 2014-06-18 陕西科技大学 一种制备聚偏氟乙烯多孔膜的方法
US9492785B2 (en) 2013-12-16 2016-11-15 Sabic Global Technologies B.V. UV and thermally treated polymeric membranes
US9522364B2 (en) 2013-12-16 2016-12-20 Sabic Global Technologies B.V. Treated mixed matrix polymeric membranes
CN106637493A (zh) * 2016-09-23 2017-05-10 江西师范大学 尼龙66/pvdf/peo/硼酸复合纳米纤维及其制备方法
CN111013400A (zh) * 2019-12-30 2020-04-17 安徽普朗膜技术有限公司 一种低温热致相法制备聚偏氟乙烯管式膜的方法

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101661671B1 (ko) * 2013-06-28 2016-09-30 제일모직 주식회사 나노증기를 이용한 이차 전지용 다공성 분리막의 제조 방법, 이를 이용해 제조된 분리막, 및 이차 전지
CN104209016B (zh) * 2014-07-30 2017-02-08 昆明理工大学 一种磁性电滤膜及其制备方法
CN104857866B (zh) * 2015-05-18 2017-06-16 上海交通大学 一种制备亲水改性聚偏氟乙烯膜的方法
EP3427818B1 (fr) * 2016-03-09 2023-01-04 Asahi Kasei Kabushiki Kaisha Membrane poreuse à fibres creuses, son procédé de production, et procédé de filtration
KR102281508B1 (ko) 2016-06-24 2021-07-26 도레이 카부시키가이샤 복합 다공질 중공사막, 복합 다공질 중공사막의 제조 방법, 복합 다공질 중공사막 모듈 및 복합 다공질 중공사막 모듈의 운전 방법
TWI740635B (zh) 2020-09-09 2021-09-21 財團法人工業技術研究院 聚偏氟乙烯薄膜組成物及聚偏氟乙烯隔離膜
CN112316756A (zh) * 2020-11-12 2021-02-05 艾克飞膜材(嘉兴)有限公司 一种高强度、高截留tips中空纤维膜及其制备方法
CN114849500B (zh) * 2022-05-17 2023-02-10 江苏艾乐膜科技有限公司 一种基于tips法的亲水化改性中空纤维超滤膜的制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002515322A (ja) * 1998-05-18 2002-05-28 ユーエスエフ・フィルトレイション・アンド・セパレイションズ・グループ・インコーポレイテッド 高多孔性のポリ二弗化ビニリデン膜
KR20080057637A (ko) * 2006-12-20 2008-06-25 에스케이케미칼주식회사 폴리비닐리덴플루오라이드 중공사막의 제조방법 및이로부터 제조된 중공사막
KR20090037963A (ko) * 2006-08-10 2009-04-16 가부시키가이샤 구라레 불화비닐리덴계 수지로 이루어지는 다공막 및 그 제조 방법
JP2010094670A (ja) * 2008-09-19 2010-04-30 Toray Ind Inc ポリフッ化ビニリデン系複合膜およびその製造方法
KR20100114808A (ko) * 2009-04-16 2010-10-26 주식회사 파라 비대칭 다공성 중공사 분리막의 제조 방법
KR20110052244A (ko) * 2009-11-12 2011-05-18 한국화학연구원 신규한 ｐｖｄｆ 중공사막 제조용 고분자 수지, 막오염 저항성이 우수한 ｐｖｄｆ 중공사막, 및 이의 제조방법

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3724412B2 (ja) * 2001-11-02 2005-12-07 東レ株式会社 中空糸膜の製造方法および中空糸膜モジュール
US7338692B2 (en) * 2003-09-12 2008-03-04 3M Innovative Properties Company Microporous PVDF films
JP4623626B2 (ja) * 2004-01-30 2011-02-02 日東電工株式会社 多孔質膜およびその製造方法
CN1281301C (zh) * 2004-09-30 2006-10-25 浙江大学 用熔纺－拉伸法制备聚偏氟乙烯中空纤维膜的方法
CN101269302B (zh) * 2008-05-06 2011-08-31 南京奥特高科技有限公司 非结晶型永久亲水聚偏氟乙烯膜材料及其制备方法
CN101342468B (zh) * 2008-08-22 2011-09-14 清华大学 一种β晶相聚偏氟乙烯中空纤维多孔膜的制备方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002515322A (ja) * 1998-05-18 2002-05-28 ユーエスエフ・フィルトレイション・アンド・セパレイションズ・グループ・インコーポレイテッド 高多孔性のポリ二弗化ビニリデン膜
KR20090037963A (ko) * 2006-08-10 2009-04-16 가부시키가이샤 구라레 불화비닐리덴계 수지로 이루어지는 다공막 및 그 제조 방법
KR20080057637A (ko) * 2006-12-20 2008-06-25 에스케이케미칼주식회사 폴리비닐리덴플루오라이드 중공사막의 제조방법 및이로부터 제조된 중공사막
JP2010094670A (ja) * 2008-09-19 2010-04-30 Toray Ind Inc ポリフッ化ビニリデン系複合膜およびその製造方法
KR20100114808A (ko) * 2009-04-16 2010-10-26 주식회사 파라 비대칭 다공성 중공사 분리막의 제조 방법
KR20110052244A (ko) * 2009-11-12 2011-05-18 한국화학연구원 신규한 ｐｖｄｆ 중공사막 제조용 고분자 수지, 막오염 저항성이 우수한 ｐｖｄｆ 중공사막, 및 이의 제조방법

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103495347A (zh) * 2013-10-15 2014-01-08 山东招金膜天有限责任公司 一种连续的热致相分离法成膜装置及成膜工艺
CN103495347B (zh) * 2013-10-15 2016-05-25 山东招金膜天有限责任公司 一种连续的热致相分离法成膜装置及成膜工艺
US9492785B2 (en) 2013-12-16 2016-11-15 Sabic Global Technologies B.V. UV and thermally treated polymeric membranes
US9522364B2 (en) 2013-12-16 2016-12-20 Sabic Global Technologies B.V. Treated mixed matrix polymeric membranes
CN103861481A (zh) * 2014-04-03 2014-06-18 陕西科技大学 一种制备聚偏氟乙烯多孔膜的方法
CN106637493A (zh) * 2016-09-23 2017-05-10 江西师范大学 尼龙66/pvdf/peo/硼酸复合纳米纤维及其制备方法
CN106637493B (zh) * 2016-09-23 2018-11-09 江西师范大学 尼龙66/pvdf/peo/硼酸复合纳米纤维及其制备方法
CN111013400A (zh) * 2019-12-30 2020-04-17 安徽普朗膜技术有限公司 一种低温热致相法制备聚偏氟乙烯管式膜的方法

Also Published As

Publication number Publication date
KR101462939B1 (ko) 2014-11-19
KR20130053933A (ko) 2013-05-24
CN103857462A (zh) 2014-06-11
CN103857462B (zh) 2016-08-24

Similar Documents

Publication Publication Date Title
WO2013073828A1 (fr) Membrane de séparation en fibre creuse à base de polyfluorure de vinylidène hydrophile et procédé pour la fabrication de ladite membrane
JP4050977B2 (ja) 編物により補強された複合中空糸膜
KR102031395B1 (ko) 상용성 브레이드화 지지체 필라멘트를 갖는 복합 중공 섬유 막
US7455772B2 (en) Hollow-fiber porous water filtration membrane of vinylidene fluoride resin and process for producing the same
WO2010021474A2 (fr) Membrane poreuse et procédé de préparation correspondant
WO2011037354A2 (fr) Membrane à fibres creuses à base de fluor et procédé pour sa production
US20080156722A1 (en) Porous hollow-yarn membrane of vinylidene fluoride resin
KR20070113375A (ko) 비대칭 폴리불화비닐리덴계 다공성 중공사막 및 이의제조방법
WO2012177058A2 (fr) Module de membrane à fibres creuses pressurisé
KR20090013643A (ko) 수처리용 폴리불화비닐리덴계 중공사막 및 이의 제조방법
KR101494053B1 (ko) 비대칭성 중공사막의 제조방법 및 이에 의해 제조된 비대칭성 중공사막
WO2011126001A1 (fr) Procédé de production de membrane poreuse
WO2014112689A1 (fr) Procédé de fabrication de membrane à fibres creuses rendue hydrophile par un processus continu à l'aide d'une extrudeuse
WO2012074222A2 (fr) Procédé de préparation d'une membrane à fibres creuses pour un traitement de l'eau à l'aide d'une résine à base de cellulose
WO2016072554A1 (fr) Membrane à fibres creuses poreuse et son procédé de fabrication
WO2014098322A1 (fr) Membrane à fibres creuses ayant une structure innovante et son procédé de production
KR20160081612A (ko) 다공성 pvdf 중공사막 및 이의 제조방법
CN101890303B (zh) 一种具有非对称结构的中空纤维膜及制法
KR20070113374A (ko) 고분자 나노섬유를 함유한 구형입자로 구성된폴리불화비닐리덴계 다공성 중공사막 및 이의 제조방법
KR20070103187A (ko) 폴리불화비닐리덴계 다공성 중공사막 및 이의 제조방법
KR20100079630A (ko) 투수도 및 기계적 강도가 개선된 한외여과막 및 그의 제조방법
KR20070102011A (ko) 고수투과성 폴리불화비닐리덴계 다공성 중공사막 및 이의제조방법
WO2013147525A1 (fr) Membrane poreuse et son procédé de fabrication
KR101556009B1 (ko) 강도 및 내열성이 향상된 다층 중공사막 및 이의 제조 방법
KR20130040625A (ko) 이차저지층을 갖는 수처리용 폴리불화비닐리덴 중공사막 및 그 제조방법

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12848903

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12848903

Country of ref document: EP

Kind code of ref document: A1