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WO2017039309A1 - Membrane poreuse à fibres creuses - Google Patents

Membrane poreuse à fibres creuses Download PDF

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Publication number
WO2017039309A1
WO2017039309A1 PCT/KR2016/009712 KR2016009712W WO2017039309A1 WO 2017039309 A1 WO2017039309 A1 WO 2017039309A1 KR 2016009712 W KR2016009712 W KR 2016009712W WO 2017039309 A1 WO2017039309 A1 WO 2017039309A1
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WO
WIPO (PCT)
Prior art keywords
hollow
virtual circle
hollow fiber
fiber membrane
resin
Prior art date
Application number
PCT/KR2016/009712
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English (en)
Korean (ko)
Inventor
장재영
Original Assignee
주식회사 퓨어엔비텍
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 KR1020160110882A external-priority patent/KR101848817B1/ko
Application filed by 주식회사 퓨어엔비텍 filed Critical 주식회사 퓨어엔비텍
Publication of WO2017039309A1 publication Critical patent/WO2017039309A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D63/00—Apparatus in general for separation processes using semi-permeable membranes
    • B01D63/02—Hollow fibre modules
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis

Definitions

  • the present invention relates to a porous hollow fiber membrane, and more particularly, to a porous hollow fiber membrane formed so that a plurality of holes are formed in the cross section of the hollow fiber and have a petal shape on the outer circumferential surface.
  • membrane technology uses selective permeability of a polymer material, etc., and is commercialized while being applied to a desalination process in the United States in the 1960s.
  • the membrane separation process to which the separation membrane is applied does not have a phase change, thereby saving energy and having a relatively simple process, so that the space occupied by the device is small. Therefore, the separator is widely applied to the reverse osmosis (RO) separation process, ultrafiltration (UF), microfiltration (MF) and nanofiltration (NF) separation process.
  • RO reverse osmosis
  • UF ultrafiltration
  • MF microfiltration
  • NF nanofiltration
  • membranes have various shapes such as spiral wound, tubular, hollow fiber, plate and frame, among which hollow fiber has a diameter of 0.2 ⁇ 2mm Since the shape of the hollow tube, the area ratio per unit volume of the hollow yarn has the advantage of obtaining high productivity compared to the spiral wound, tubular, and plate-shaped.
  • a hollow fiber membrane having a unique structure has been developed compared to a commercially available hollow fiber membrane, and Inge of Germany has seven independent capillaries in rigid single fibers having a circular outer circumferential surface.
  • Formed porous membrane Multibore® membrane
  • the hollow fiber membrane is applied to the ultrafiltration process for water treatment, the separation performance is superior to that of a conventional single-bore hollow fiber membrane in which only one capillary (hollow) is formed in the conventional short fibers, and has excellent mechanical properties and chemical stability.
  • the membrane fouling (fouling) effect such as excellent, but there is still room for improvement in order to maximize the permeation performance, filtration efficiency and membrane fouling prevention performance.
  • the present inventors have conducted a study on the hollow fiber membrane for water treatment having a new structure, and have formed a channel having a plurality of holes (multi-bore, hollow) in the short fibers constituting the hollow fiber, but the holes (multi- When the outer circumferential surface of the short fibers including bore, hollow) is designed in the shape of petals with a pattern of concave and convex portions not circular, the outer circumferential surface of the short fibers increases the filling density and specific surface area compared to the circular shape, and thus the filtration efficiency is increased.
  • the present invention has been made in view of the fact that the permeation performance can be further improved, and the membrane fouling prevention performance can be greatly improved.
  • An object of the present invention is to increase the filling density and specific surface area to improve the filtration efficiency and permeability, as well as to prevent membrane fouling, and to form a plurality of hollows (holes) in the short fibers forming hollow fibers, It is to provide a porous hollow fiber membrane formed in the shape of a petal of the concave portion and the convex portion repeated pattern on the outer peripheral surface of the hollow fiber short fiber comprising.
  • the first hollow is formed in the center of the cross-section, is arranged so as to uniformly radiate with respect to the center to form N (N is a natural number of 3 or more) second hollows
  • N is a natural number of 3 or more
  • the outer peripheral surface of the cross section is formed with N concave portions for integrally connecting between the second hollow and the second hollow.
  • the concentric circle of the first hollow is defined as the first virtual circle
  • the diameter is larger than the second hollow
  • the concentric circle of the second hollow is defined as the second virtual circle
  • the second virtual circle is preferably formed to circumscribe the first virtual circle.
  • first virtual circle radius is formed to the same size as the second virtual circle radius.
  • first virtual circle radius may be larger than the second virtual circle radius.
  • the first virtual circle radius is formed smaller than the second virtual circle radius.
  • the porous hollow fiber membrane is made of polyethylene (PE) resin, polypropylene (PP) resin, ethylene chloro trifluoro ethylene resin (ECTFE), polyvinyl chloride (PVC) resin, polysulfone resin, polyether sulfone At least one selected from the group consisting of resins, sulfonated polysulfone resins, polyvinylidene fluoride (PVDF) resins, polyacrylonitrile (PAN) resins, polyimide resins, polyamideimide resins and polyetherimides is suitable. .
  • PE polyethylene
  • PP polypropylene
  • ECTFE ethylene chloro trifluoro ethylene resin
  • PVDF polyvinyl chloride
  • PVDF polysulfone resin
  • PAN polyacrylonitrile
  • porous hollow fiber membrane is preferably prepared by conventional non-solvent-induced phase transition (NIPS) or heat-induced phase transition (TIPS).
  • NIPS non-solvent-induced phase transition
  • TIPS heat-induced phase transition
  • porous hollow fiber membrane is preferably applied to the microfiltration membrane, the ultrafiltration membrane, the degassing membrane, and the pervaporation membrane.
  • Porous hollow fiber membranes according to an embodiment of the present invention as compared to the conventional mono- or porous hollow fiber membranes by increasing the mechanical strength of the membrane or increase the packing density and specific surface area not only improves the filtration efficiency, permeation performance, but also prevents membrane fouling. It is excellent in effect and can be applied to microfiltration and ultrafiltration separation process for water treatment.
  • FIG. 1 is a perspective view of a porous hollow fiber membrane according to an embodiment of the present invention.
  • FIG 2 is an exemplary cross-sectional view of the first virtual circle diameter and the second virtual circle diameter of the porous hollow fiber membrane according to an embodiment of the present invention.
  • FIG. 3 is an exemplary view showing the form of FIG.
  • Figure 4 is an exemplary cross-sectional view of the first virtual circle diameter of the porous hollow fiber membrane is formed larger than the second virtual circle diameter in accordance with an embodiment of the present invention.
  • FIG. 5 is an exemplary view showing the form of FIG.
  • FIG. 6 is a cross-sectional view illustrating a first virtual circle diameter of the porous hollow fiber membrane smaller than the second virtual circle diameter in accordance with an embodiment of the present invention.
  • FIG. 7 is an exemplary view showing the form of FIG.
  • FIG. 1 is a perspective view of a porous hollow fiber membrane according to an embodiment of the present invention
  • Figure 2 is a cross section in which the first virtual circle diameter and the second virtual circle diameter of the porous hollow fiber membrane according to an embodiment of the present invention are the same
  • 3 is an exemplary view showing the form of Figure 2
  • Figure 4 is a cross-sectional view of the first virtual circle diameter of the porous hollow fiber according to an embodiment of the present invention is formed larger than the second virtual circle diameter
  • FIG. 6 is a cross-sectional view illustrating a first virtual circle diameter of the porous hollow fiber membrane smaller than the second virtual circle diameter according to an embodiment of the present invention
  • 7 is an exemplary view showing the form of FIG.
  • the porous hollow fiber according to an embodiment of the present invention, the first hollow 100 is formed in the center of the cross-section, N is formed so as to uniformly radiate with respect to the center (N is a natural number of 3 or more) two second hollows 200 are formed, and N concave portions for integrally connecting the second hollows 200 and the second hollows 200 are formed on the outer circumferential surface of the cross section. do.
  • the porous hollow fiber membrane 10 is formed in a pillar shape in which a first hollow 100 is formed at a central portion thereof.
  • the first hollow 100 serves as a passage through which foreign matter or purified material moves.
  • the second hollow 200 is uniformly formed at the back radial position with respect to the center of the first hollow 100. That is, it is appropriate that the second hollow 200 is formed with N (N is a natural number of 3 or more) of the first hollow 100.
  • the porous hollow fiber membrane 10 has a first virtual circle 310 and a second hollow formed larger than the first hollow radius a1 based on the center of the first hollow 100.
  • the second virtual circle 330 formed larger than the second hollow radius b1 based on the center of the concentric circle of 200 and the second virtual circle 330 are in contact with the inside from the center of the concentric circle of the first hollow 100.
  • the third virtual circle 350 is included.
  • the first virtual circle 310 is larger than the radius a1 of the first hollow and formed around the concentric circle of the first hollow 100.
  • the first virtual circle 310 is formed such that the second virtual circle 330 is circumscribed.
  • the first virtual circle 310 is disposed at a position where the second hollow 200 is uniformly radiated.
  • the second virtual circle 330 is larger than the second hollow radius b1 and is formed around the concentric circles of the second hollow 200.
  • the second virtual circle 330 is formed to circumscribe the first virtual circle 310.
  • the second virtual circle 330 is in contact with N (N is a natural number of 3 or more) centering on the first virtual circle 310. That is, the second hollow 200 is formed to be spaced apart from the first hollow 100 in an equal radial shape, and the second hollow 200 is formed of N (N is a natural number of 3 or more).
  • the third virtual circle 350 is formed to be in contact with the second virtual circle 330 at the center of the first hollow 100. That is, the third virtual circle 350 is formed to have a size of the outer circumferential surface of the porous hollow fiber membrane 10 at the center of the first hollow 100.
  • Unevenness is formed on the outer circumferential surface of the porous hollow fiber membrane 10.
  • the bending of the unevenness 110 is formed corresponding to the number of the second hollow 200 is arranged. That is, the unevenness 110 may be divided into the concave portion 111 and the convex portion 113.
  • Such unevenness 110 is preferably formed in the shape of a petal with respect to the cross section of the porous hollow fiber membrane 10.
  • Porous hollow fiber membrane 10 is improved in bending strength and mechanical strength than the conventional circular. That is, the porous hollow fiber membrane 10 serves to withstand the air injected vertically when installed in the filtration device. Many air pressure is formed on the surface of the porous hollow fiber 10 has the effect of improving the filtration efficiency.
  • Concave-convex 110 is a convex portion 113 is formed in a portion formed by extending the second hollow 200 in the circumferential direction.
  • the concave-convex 110 includes a concave portion 111 at a portion connecting the second hollow 200 and the second hollow 200 in the circumferential direction.
  • the convex portion 113 of the concave-convex 110 is formed to contact the inner side of the third virtual circle 350, and the concave portion 111 of the concave-convex 110 is the second hollow 200 and the second hollow 200. It is formed between. That is, the recess 111 has a space close to the space between the second hollow 200 and the second hollow 200 is formed.
  • the unevenness 110 is formed on the outer circumferential surface of the porous hollow fiber membrane 10, thereby improving the specific surface area and filtration efficiency.
  • the concave-convex 110 forms a concave portion 111 on the outer circumferential surface of the porous hollow fiber membrane 10, so that the concave-convex 110 reduces the raw materials used in manufacturing, thereby improving economic efficiency.
  • the unevenness 110 serves to ensure uniform permeability and uniform reliability of the product as compared to the conventional hollow fiber membrane by making the distance between the second hollow 200 and the convex portion 113 constant.
  • the concave portion 111 is formed to be closer to the first hollow 100. That is, the second hollows 200 are provided.
  • the concave portion 111 is in contact with the first virtual circle 310.
  • the concave portion 111 is necessarily formed in contact with the first virtual circle 310. That is, it is revealed that the recess 111 is formed near the first virtual circle 310.
  • the porous hollow fiber membrane 10 is formed such that when the second hollow 200 increases by one, the concave portion 111 moves away from the first hollow 100 direction. That is, when four or more second hollows 200 are formed, it can be seen that the concave portion 111 is far from the first virtual circle 310. That is, the concave portion 111 is formed to be closer to the direction of the third virtual circle 350 while gradually moving away from the vicinity of the first virtual circle 310 when the second hollow 200 increases. That is, the recess 111 is formed near the first virtual circle 310 as shown in FIG. 3A, and the recess 111 is formed near the third virtual circle 350 as shown in FIG. 3H. can confirm. do.
  • the porous hollow fiber membrane 10 has a radius a2 of the first virtual circle 310 and a radius b2 of the second virtual circle having the same size.
  • the porous hollow fiber membrane 10 may be made of a hydrophobic polymer including a vinyl polymer and an olefin polymer.
  • a hydrophobic polymer polyethylene (PE) resin, polypropylene (PP) resin, ethylene chloro trifluoro ethylene resin (ECTFE), polyvinyl chloride (PVC) resin, polysulfone resin, polyethersulfone resin, sulfonated polysulfone resin
  • PVC polyvinyl chloride
  • PVDF polysulfone resin
  • PAN polyacrylonitrile
  • polyimide resin polyamideimide resin
  • polyetherimide polyetherimide.
  • fluorine-containing hydrophobic polymers such as polyvinylidene fluoride (PVDF) homopolymers or copolymers thereof are more preferably used in view of chemical stability.
  • the porous hollow fiber membrane 10 according to the present invention is obtained by dissolving the above-mentioned hydrophobic polymer in a solvent or a solvent containing a non-solvent or an additive, if necessary, to obtain a spinning solution, the spinning solution and the internal coagulant to the spinning nozzle After discharging, supplying and spinning through a conventional nonsolvent induced phase separation method (NIPS) or thermally induced phase separation method (TIPS) to form a hollow fiber completely phase-transferred by an external coagulant It can be manufactured by.
  • NIPS nonsolvent induced phase separation method
  • TIPS thermally induced phase separation method
  • the porous hollow fiber membrane 10 according to the second exemplary embodiment of the present invention omits the same components as those of the first exemplary embodiment, and the radius a2 of the first virtual circle 310 is set to the first.
  • the case in which the virtual circle 330 is formed larger than the radius b2 will be described in detail.
  • Unevenness is formed on the outer circumferential surface of the porous hollow fiber membrane 10.
  • the bending of the unevenness 110 is formed corresponding to the number of the second hollow 200 is arranged. That is, the concave-convex 110 may be divided into the concave portion 111 and the convex portion 113 (see FIG. 4).
  • Concave-convex 110 is a convex portion 113 is formed in a portion formed by extending the second hollow 200 in the circumferential direction.
  • the concave-convex 110 includes a concave portion 111 at a portion connecting the second hollow 200 and the second hollow 200 in the circumferential direction.
  • the convex portion 113 of the concave-convex 110 is formed to contact the inner side of the third virtual circle 350, and the concave portion 111 of the concave-convex 110 is the second hollow 200 and the second hollow 200. It is formed between. That is, the recess 111 has a space close to the space between the second hollow 200 and the second hollow 200 is formed.
  • the recess 111 has a depth of “v” shape in the direction of the first hollow 100.
  • the porous hollow fiber membrane 10 is increased by one second hollow 200.
  • the concave portion 111 is formed one by one between the second hollow 200 and the second hollow 200, the concave portion 111 is formed to move away from the first hollow 100 direction. That is, when seven or more second hollows 200 are formed, it can be seen that the concave portion 111 is far from the first virtual circle 310. That is, the concave portion 111 is formed to be closer to the direction of the third virtual circle 350 while gradually moving away from the vicinity of the first virtual circle 310.
  • the porous hollow fiber membrane 10 according to the third exemplary embodiment of the present invention omits the same components as those of the first exemplary embodiment, and the radius a2 of the first virtual circle 310 is set to the first.
  • the case in which the virtual circle 330 is formed smaller than the radius b2 will be described in detail.
  • Filtration efficiency can be increased while reducing the diameter of the porous hollow fiber membrane 10.
  • the porous hollow fiber membrane 10 is formed to have a smaller radius a2 of the first virtual circle 310, and increases the radius b2 of the second virtual circle 330 of the porous hollow fiber membrane 10. That is, by increasing the radius b1 of the second hollow 200 of the surface outer diameter of the porous hollow fiber membrane 10, the filtration efficiency and the packing density may be increased (see FIG. 6 or 7).
  • Unevenness is formed on the outer circumferential surface of the porous hollow fiber membrane 10.
  • the bending of the unevenness 110 is formed corresponding to the number of the second hollow 200 is arranged. That is, the concave-convex 110 may be divided into the shape of the concave portion 111 and the convex portion 113 (see FIG. 6).
  • Concave-convex 110 is a convex portion 113 is formed in a portion formed by extending the second hollow 200 in the circumferential direction.
  • the concave-convex 110 includes a concave portion 111 at a portion connecting the second hollow 200 and the second hollow 200 in the circumferential direction.
  • the convex portion 113 of the concave-convex 110 is formed to contact the inner side of the third virtual circle 350, and the concave portion 111 of the concave-convex 110 is the second hollow 200 and the second hollow 200. It is formed between. That is, the recess 111 has a space close to the space between the second hollow 200 and the second hollow 200 is formed.
  • the recess 111 has a depth of “v” shape in the direction of the first hollow 100.
  • the porous hollow fiber membrane 10 is increased by one second hollow 200.
  • the recess 111 is formed one by one between the second hollow 200 and the second hollow 200, the recess 111 is formed to be far from the first hollow 100 direction. That is, when four or more second hollows 200 are formed, it can be seen that the concave portion 111 is far from the first virtual circle 310. That is, the concave portion 111 is formed to be closer to the direction of the third virtual circle 350 while gradually moving away from the vicinity of the first virtual circle 310.
  • polyvinylidene fluoride resin weight average molecular weight 300,000 to 320,000
  • silica 30% by weight of dioctylphthalate and dibutyl
  • a porous (multibore) nozzle with an outer diameter of the nozzle
  • Dioctyl phthalate was used at 30 ° C. as a hollow forming agent, passed through an 80 mm air chamber, and solidified in a 60 ° C. water bath, stretched 50% in a 60 ° C. water bath, and stabilized in a hot air at 120 ° C.
  • the winding speed was adjusted to 15 m / min to prepare a porous hollow fiber membrane having an outer circumferential surface as shown in FIG. 1 in the shape of a petal (outer diameter 4.2 ⁇ , inner diameter 0.8 ⁇ ).
  • a porous hollow fiber membrane having an outer circumferential surface as shown in FIG. 1 in the shape of a petal (outer diameter 4.2 ⁇ , inner diameter 0.8 ⁇ ).
  • a porous hollow fiber membrane having a circular outer circumferential surface was prepared in the same manner as in the above experimental example, except that the nozzle had a circular porous diameter (multibore) nozzle, and the water permeability and mechanical properties were evaluated through post-treatment. It was.
  • the porous hollow fiber membrane of the outer circumferential surface prepared from the experimental example according to an embodiment of the present invention is petal-shaped compared to the porous hollow fiber membrane of which the outer circumferential surface prepared from the comparative example is circular. It can be seen that the remarkably increased, which is due to the fact that the outer diameter of the nozzle is petal-shaped, heat transfer is uniformly made during the hollow fiber membrane formation process, the surface area is large.
  • the porous hollow fiber membrane having the outer circumferential surface prepared from the experimental example has a petal-shaped porous hollow fiber membrane having the circular outer circumferential surface prepared from the comparative example It can be confirmed that it is much superior to that, this is because the porous hollow fiber membrane having the outer circumferential surface is formed in the bone during the hollow fiber membrane formation process, the orientation is good during stretching, the strength is increased, the pores are uniformly formed and the longitudinal direction is increased. It is interpreted that the bone is formed and the elongation is improved.
  • porous hollow fiber membrane of the present invention by increasing the packing density and the specific surface area compared to the conventional single-hole or porous hollow fiber membrane, not only the filtration efficiency and permeation performance is improved, but also the membrane fouling prevention effect is excellent, and the fine filtration membrane, It can be applied to the separation process of ultrafiltration membrane, degassing membrane and permeation membrane.

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

Abstract

Un mode de réalisation de la présente invention concerne une membrane poreuse à fibres creuses comprenant un premier creux formé dans une partie centrale d'une section transversale horizontale de celle-ci et N (N étant un entier naturel égal ou supérieur à 3) seconds creux formés de manière à être agencés uniformément à équidistance de la partie centrale. N parties évidées permettant de raccorder d'un seul tenant les espaces entre les seconds creux sont formées sur la surface périphérique externe de la section transversale horizontale.
PCT/KR2016/009712 2015-08-31 2016-08-31 Membrane poreuse à fibres creuses WO2017039309A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
KR20150122268 2015-08-31
KR10-2015-0122268 2015-08-31
KR1020160110882A KR101848817B1 (ko) 2015-08-31 2016-08-30 다공형 중공사막
KR10-2016-0110882 2016-08-30

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WO2017039309A1 true WO2017039309A1 (fr) 2017-03-09

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030140790A1 (en) * 2002-01-29 2003-07-31 Attila Herczeg Convoluted surface hollow fiber membranes
JP2004042024A (ja) * 2002-05-16 2004-02-12 Nok Corp 溶融紡糸中空糸膜およびそれを用いたエアー抜き用カートリッジ
JP2012040464A (ja) * 2010-08-13 2012-03-01 Asahi Kasei Chemicals Corp 複合多孔性中空糸膜、膜モジュール、膜ろ過装置、水処理方法
JP2014240071A (ja) * 2010-04-16 2014-12-25 旭化成ケミカルズ株式会社 異形多孔性中空糸膜、異形多孔性中空糸膜の製造方法、異形多孔性中空糸膜を用いたモジュール、ろ過装置、及び水処理方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030140790A1 (en) * 2002-01-29 2003-07-31 Attila Herczeg Convoluted surface hollow fiber membranes
JP2004042024A (ja) * 2002-05-16 2004-02-12 Nok Corp 溶融紡糸中空糸膜およびそれを用いたエアー抜き用カートリッジ
JP2014240071A (ja) * 2010-04-16 2014-12-25 旭化成ケミカルズ株式会社 異形多孔性中空糸膜、異形多孔性中空糸膜の製造方法、異形多孔性中空糸膜を用いたモジュール、ろ過装置、及び水処理方法
JP2012040464A (ja) * 2010-08-13 2012-03-01 Asahi Kasei Chemicals Corp 複合多孔性中空糸膜、膜モジュール、膜ろ過装置、水処理方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
WANG, PENG ET AL.: "Design and Fabrication of Lotus-root-like Multi-bore Hollow Fiber Membrane for Direct Contact Membrane Distillation", JOURNAL OF MEMBRANE SCIENCE, vol. 421, 1 December 2012 (2012-12-01), pages 361 - 374, XP055200236 *

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