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WO2010144057A1 - Membranes à deux couches sélectives - Google Patents

Membranes à deux couches sélectives Download PDF

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Publication number
WO2010144057A1
WO2010144057A1 PCT/SG2010/000219 SG2010000219W WO2010144057A1 WO 2010144057 A1 WO2010144057 A1 WO 2010144057A1 SG 2010000219 W SG2010000219 W SG 2010000219W WO 2010144057 A1 WO2010144057 A1 WO 2010144057A1
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WIPO (PCT)
Prior art keywords
layer
polymer
cellulose
membrane
polymeric membrane
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Ceased
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PCT/SG2010/000219
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English (en)
Inventor
Kaiyu Wang
Tai-Shung Neal Chung
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National University of Singapore
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National University of Singapore
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Publication of WO2010144057A1 publication Critical patent/WO2010144057A1/fr
Anticipated expiration legal-status Critical
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Classifications

    • 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
    • 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
    • B01D61/002—Forward osmosis or direct osmosis
    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1216—Three or more layers
    • 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
    • B01D69/12—Composite membranes; Ultra-thin membranes
    • B01D69/1218—Layers having the same chemical composition, but different properties, e.g. pore size, molecular weight or porosity
    • 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
    • B01D2325/022—Asymmetric membranes
    • B01D2325/0233—Asymmetric membranes with clearly distinguishable layers
    • 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
    • B01D2325/0283—Pore size
    • B01D2325/02831—Pore size less than 1 nm
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2325/00—Details relating to properties of membranes
    • B01D2325/04—Characteristic thickness
    • 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
    • C02F1/445—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by forward osmosis
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/08—Seawater, e.g. for desalination
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A20/00—Water conservation; Efficient water supply; Efficient water use
    • Y02A20/124—Water desalination
    • Y02A20/131—Reverse-osmosis

Definitions

  • F Forward osmosis
  • this invention relates to a polymeric membrane.
  • the membrane includes a porous supporting layer having a first surface and a second surface opposed to the first surface, a first skin layer over the first surface of the supporting layer, and a second skin layer over the second surface of the supporting layer.
  • the supporting layer formed of a first polymer, has a first pore size and a first porosity.
  • the first skin layer, formed of a second polymer has a second pore size and a second porosity.
  • the second skin layer formed of a third polymer, has a third pore size and a third porosity. Both the second and third pore sizes are smaller than the first pore size and both the second and third porosities are smaller than the first porosity.
  • pore size refers to an average diameter of the pores or voids in different layers of the polymeric membrane and the term “porosity” refers to the volume ratio of the pores.
  • the pore size corresponds to the size of the largest molecule mat can permeate each individual layer of the membrane while the porosity corresponds to the density of each individual layer.
  • Embodiments of the membrane described above may include one or more of the following features.
  • the first skin layer is in contact with the first surface of the supporting layer.
  • the second skin layer is in contact with the second surface of the supporting layer.
  • the porous supporting layer has a thickness between 10 ⁇ m and 200 ⁇ m.
  • Each of the first skin layer and the second skin layer independently, has a thickness between 0.01 ⁇ m and 10 ⁇ m.
  • the first pore size is between 10 nm and 1000 nm.
  • Each of the second pore size and the third pore size independently, is between 0.1 nm and 0.5 nm (e.g., 0.2-0.5 nm).
  • the first porosity is between 30% and 90%. Both the second porosity and third porosity are less than 1%.
  • Two of the first, second, and third polymers are the same.
  • the first, second, and third polymers are the same.
  • Each of the first, second, and third polymers is a hydrophilic polymer such as cellulosic polymer (e.g., cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose dibutyrate, cellulose tributyrate, and a combination thereof), polyacrylonitrile, polyvinyl alcohol, polyamide, polyamide-imide, sulphonated polyethersulphone, sulphonated polysulphone, polybenzimidazole (PBI), and a combination thereof.
  • the membrane is in the form of a flat sheet or a hollow fiber.
  • the term "combination" refers to a polymer blend or a copolymer of the aforementioned polymers.
  • the invention in another aspect, relates to a method (e.g., a non-solvent induced phase inversion process) for producing a polymeric membrane.
  • the method includes mixing a polymer, a solvent, and a pore-forming additive to form a polymer solution; disposing the polymeric solution onto a surface of a substrate; immersing the substrate in a coagulation bath (e.g., a water coagulant bath), whereby the polymer solution coagulates to form on the substrate a polymeric film that includes a first surface layer in contact with the substrate, a second surface layer opposed to the first surface layer, and a porous middle layer between the first and second surface layers, the porous middle layer having a larger pore size and a higher porosity than both the first and the second surface layers; separating the polymeric film from the substrate; and heat-annealing the polymeric film in a water bath at 40 0 C- 120 0 C (e.g., 50-90 0 C).
  • non-solvent induced phase inversion refers to a process in which a polymer in a casting solution containing the polymer and a solvent (e.g., a ketone) is induced by a non-solvent (e.g., water) to precipitate out from the solution to form a film having a structure different from that of the polymer in the solution (i.e., polymer undergoing phase inversion).
  • a solvent e.g., a ketone
  • coagulation bath refers to a bath containing a suitable coagulant to cause a liquid or sol to coagulate.
  • Suitable coagulant for a cellulosic polymer solution include but are not limited to pure water, organic solvent miscible with water, an aqueous solution containing salts, or a combination thereof.
  • Different coagulants may be chosen for different polymer solutions.
  • the coagulants can be alcohol such as methanol, ethanol, and isopropanol.
  • water bath refers to a bath containing a heating medium having at least 50% of water by volume. The maximum heating temperature of the water bath can be controlled by selecting the composition of the heating medium. For example, when a mixture of water and a high boiling point organic solvent is used as the heating medium, the temperature of the water bath can reach beyond 100 0 C at room atmosphere.
  • Embodiments of the method described above may include one or more of the following features.
  • the polymer solution contains 10% to 35% (e.g., 18-35%) by weight of the polymer.
  • the polymer used is cellulosic polymer such as cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose dibutyrate, cellulose tributyrate, and a combination thereof.
  • the substrate can be formed of silica, alumina, mica, other metal oxides, or polymer.
  • the surface of the substrate upon which the polymer solution is disposed is a hydrophilic surface.
  • the substrate can either be a flat plate (e.g., a glass slide) or a rotating drum (e.g., that described in WO 2006/110497).
  • the solvent used is selected from the group consisting of N, N-dimethylacetamide(DMAc), dimethyl sulfoxide (DMSO), dimethyl formamide (DMF), N-methyl-pyrrolidone (NMP), acetone, 1,4- dioxane, methyl ethyl ketone, and a combination thereof.
  • the pore-forming additive is selected from the group consisting of an alcohol (e.g., methanol, ethanol, propanol, and butanols), Methylene glycol , diethylene glycol, ethylene glycol, glycerol, ketone, an organic acid, polyethylene glycol, polyvinylpyrrolidone, formamide and a combination thereof.
  • the solvent and the pore-forming additive can be the same or different.
  • the coagulation bath may have a temperature between 0 0 C and 80 0 C (e.g., between 20 0 C and 60 0 C).
  • the porous middle layer of the polymeric film is in contact with both the first and second surface layers of the film.
  • the temperature of heat-annealing the polymeric film in a water bath can be controlled at 40 0 C- 120 0 C (e.g., 50-90 0 C).
  • the time of heat-annealing the polymeric film can be controlled between 5 min and 60 min.
  • the porous middle layer of the polymeric film still has a pore size of 10-1000 nm and a porosity of 30%-90% while each of the first and second surface layers, independently, has a pore size of 0.1-0.5 nm (e.g., 0.2-0.5 nm) and a porosity of less than 1%.
  • this invention relates to a method for extracting water from a saline solution through a forward osmosis process.
  • the method includes contacting a first saline solution with the first skin layer of the polymeric membrane described above and contacting a second saline solution with the second skin layer of the membrane to allow one of the first and second saline solutions to extract water from the other through a forward osmosis process.
  • the first and second saline solutions are separated by the membrane, the first saline solution has a first water content, and the second saline solution has a second water content different from the first water content or the two solutions have different osmotic pressures.
  • the membranes described herein include one or more of the following.
  • the membranes are suitable for use in the forward osmosis (FO) process, which requires less energy than the RO process for water treatment.
  • FO forward osmosis
  • FO offers the advantages of high rejection of a wide range of contaminants and lower membrane-fouling propensities than traditional pressure-driven membrane processes.
  • Membrane fouling can be significantly reduced, as the effect of internal concentration polarization has been eliminated by the two selective layers that prevent contact between the feed/draw solution and the middle porous supporting layer of the membrane.
  • Figure 1 illustrates the transport mechanism of an asymmetric membrane used in a pressure-retarded osmosis (PRO) process (left panel) and in a forward osmosis (FO) process (right panel), hi PRO mode, the draw solution is placed against the dense selective layer of the asymmetric membrane, while in FO mode, the feed is placed against the dense selective layer.
  • Figure 2 illustrates a cross section of a common composite reverse osmosis
  • Figures 3(a)-(e) are scanning electron microscopy (SEM) images that show the cross section and surface morphologies of a double selective-layer membrane made by the method described herein.
  • Figure 4 illustrates the transport mechanism of the double-selective layer membrane shown in Figure 2 in the top mode (left) or bottom mode (right), hi the top mode, the draw solution is placed against the thicker dense selective layer of the membrane, while in the bottom mode, the feed is placed against the thicker dense selective layer.
  • FIG 5 is a schematic of a forward osmosis testing set-up.
  • Figures 6 A and 6B demonstrate the effect of draw solution (MgCl 2 , 22 ⁇ 0.5 0 C) concentration on (6A) water permeation flux and (6B) salt leakage of the double selective-layer membrane shown in Figures 3(a)-(e). Pure water was used as the feed, hi the top mode, the draw solution was placed against the thicker selective layer of the membrane, while in the bottom mode, the feed was placed against the thicker selective layer. ⁇ o,b'- osmotic pressure of bulk draw solution.
  • Figure 7 demonstrate the effect of draw solution (MgCl 2 , 22 ⁇ 0.5 0 C) concentration on water permeation flux of the double selective-layer membrane shown in Figures 3(a)-(e).
  • draw solution MgCl 2 , 22 ⁇ 0.5 0 C
  • 3.5 wt% NaCl solution was used as the feed.
  • the draw solution was placed against the thicker selective layer of the membrane, while in the bottom mode, the feed was placed against the thicker selective layer.
  • ⁇ ,b osmotic pressure of bulk draw solution
  • ⁇ F ,b osmotic pressure of bulk feed solution.
  • Figure 8 shows the fouling test results with the two membranes in the top mode.
  • This invention is based in part on the unexpected discovery that the membranes having double selective layers described herein have very high water flux and a salt rejection of more than 99.5% during forward osmosis separation.
  • membranes having double selective layers described herein have very high water flux and a salt rejection of more than 99.5% during forward osmosis separation.
  • almost all membranes used in the FO process are asymmetric, i.e., having only one selective layer and a porous supporting layer.
  • the cross section of an asymmetric membrane is illustrated in Figure 2, left panel.
  • the double selective- layer membrane (as shown in Figure 2, right panel) described herein does not suffer from the influence of internal concentration polarization (ICP) in the FO process.
  • the double selective layers ensure the rejections of ions, sugar and other dissolved solutes, but let water transport freely, which results in the elimination of ICP through preventing the contact between the feed or draw solution and the porous support layer as the concentration gradient in the middle porous layer is prevented to be established.
  • ECP exterior concentration polarization
  • ICP interior concentration polarization
  • the additional selective layer of the membrane described herein induces extra water transport resistance and subsequently decreases the water permeation flux.
  • the double selective-layer membranes have comparable or greater water flux than those asymmetric membranes in the FO process. More specifically, the membrane described herein can achieve a water flux as high as 48.0 LMH (i.e., L/(m 2 -h)) without elevated operation temperatures and the salt leakage less than 10.0 GMH (i.e., g/(m 2 -h)) in the FO process.
  • the two selective layers of the membrane described herein have a much smaller pore size and porosity that the porous supporting layer.
  • the supporting layer has a pore size of 10-1000 nm and a porosity of 30-90% while the selective layers have a pore size of 0.2-0.5 nm and a porosity less than 1%.
  • the two selective layers one may have a slightly greater or smaller pore size/porosity than the other.
  • the two selective layers of the membrane described herein are formed of the same polymer, e.g., cellulosic polymer.
  • the supporting porous middle layer can also be formed of the same polymer as the selective layer.
  • a double selective-layer membrane formed via the phase inversion process described herein has all three layers formed of the same polymer.
  • the two selective layers are formed of different polymers. This can be achieved by coating an asymmetric membrane on the side of its porous layer with a polymer different from that constitutes the selective layer. Alternatively, this can be achieved by subjecting a double selective-layer membrane formed via the method described herein to a surface treatment process that results in different chemical compositions for the two selective layers.
  • polymers in one of the two selective layers are branched or cross-linked while those in the other selective layer are not.
  • Membranes of other layer configurations such as that having two selective layers formed of the same polymer but a porous supporting layer formed of a different polymer, are also contemplated and can be produced by, e.g., coating, surface treatment, or combination thereof.
  • the polymers constituting the selective layers and the porous supporting layer are hydrophilic.
  • hydrophilic polymer include cellulosic polymer (e.g., cellulose acetate, cellulose diacetate, cellulose triacetate, cellulose propionate, cellulose butyrate, cellulose acetate propionate, cellulose dibutyrate, cellulose tributyrate, and a combination thereof), polyacrylonitrile, polyvinyl alcohol, polyamide, polyaniide-imide, sulphonated polyethersulphone, sulphonated polysulphone, polybenzimidazole (PBI), and a combination thereof.
  • PBI polybenzimidazole
  • the process includes, among others, coagulating a polymer solution in a coagulation bath (e.g., a water bath) to form upon a substrate a polymer film that has two dense surface layers sandwiching a porous layer.
  • a coagulation bath e.g., a water bath
  • the formation of the two dense surface layers depends on many parameters such as temperature of the coagulation bath, coagulant, dope components of the polymer solution, and substrate chemistry.
  • the coagulant water is the generally used coagulant.
  • a substrate having a hydrophilic surface appears to promote forming two dense layers.
  • Example 1 Fabrication of a double selective-layer membrane using cellulose acetate A homogeneous polymer solution was prepared by dissolving cellulose acetate (CA, 22.5 wt%) in a mixture of N-methyl-pyrrolidone (72.5 wt%) and acetone (5 wt%). Next, the polymeric solution was coated onto a surface of the horizontal glass plate to form a uniform polymer layer by a casting knife with a gap of 50 mm. The coated plate was then immersed into the water coagulant bath (25°C) to allow CA to precipitate and a membrane was formed on top of the plate.
  • CA cellulose acetate
  • N-methyl-pyrrolidone 72.5 wt%)
  • acetone 5 wt%
  • the membrane was separated from the plate and rinsed with water to get rid of residual solvent before it was heat annealed in a hot water bath at 85 o C for l5 min.
  • the membrane as obtained was examined with SEM. As shown in Figure 3, the membrane produced has two dense surface layers and a porous middle layer.
  • Example 2 Water and salt transport characterization Water flux of the membrane made in Example 1 in the FO process was determined by measuring the volume change of the feed solution over a selected period, using a setup as shown in Figure 5.
  • the setup includes a crossflow cell of a plate and frame design with a rectangular channel on each side of the membrane.
  • the flow velocity during the testing was set at 6.4 cm/s for both feed and draw solutions, which concurrently flew through the cell channels.
  • the temperatures of the feed and draw solutions were maintained at 22 ⁇ 0.5 0 C.
  • the pressures at two channel inlets were kept at 1.0 psi.
  • the draw solutions used were MgCl 2 solutions with different concentrations.
  • the salt leakage was calculated by measuring the conductivity in the feed solution at the end of experiment.
  • the water permeation flux (Jv) is calculated from the feed volume change.
  • ⁇ F(L) is the permeation water collected over a predetermined time At (h) in FO process duration and A is the effective membrane surface area (m 2 ).
  • the salt concentration in the feed water was determined from the conductivity measurement using a calibration curve for the single salt solution.
  • the salt leakage, i.e., salt back-flowing from the draw solution to the feed, J s in g/(m 2 -h) (abbreviated as gMH), is thereafter determined from the increase of the feed conductivity: J s A(C t Vdl(AAi) (2) where Q and V t are the salt concentration and the volume of the feed at the end of FO tests, respectively.
  • Example 1 For sea water desalination, its water flux was assessed in a manner similar to that described in Example 2 except that 3.5 wt% NaCl instead of pure water was used. As shown in Figure 7, the water permeation flux was close to that shown in Figure 6A. Again, the water flux in the bottom mode was observed to be higher than that in the top mode.
  • Example 4 Fabrication and characterization of a double selective-layer membrane using cellulose triacetate
  • a homogeneous polymer solution was prepared by dissolving the cellulose triacetate (CTA, 20.0 wt%) in N-methyl-pyrrolidone (80.0 wt%). Then, a membrane was prepared in a manner similar to that described in Example 1 except that the membrane was thermal annealed in hot water at 9O 0 C for 15 min. The membrane formed had two dense surface layers and a porous middle layer.
  • the membrane was then characterized in a manner similar to that described in Example 2.
  • the water flux of the membrane reached 42.2 LMH in the bottom mode, which was much higher than that in the top mode, i.e., 30.2 LMH, when using 5.0 M MgCl 2 as the draw solution.
  • Example 5 Membrane fouling test Two CA membranes were produced using different coagulants: pure water and
  • NMP/water in a volume ratio of 90/10 The membrane formed with water coagulant had double selective layers while the other membrane formed with NMP/water coagulant had a single selective layer.
  • a colloidal solution of aluminum oxide nanoparticles whose actual size is around 200 nm was employed as the feed. Water flux was normalized to the initial value when the feed was DI water. As illustrated in Figure 8, the single- selective-layer membrane showed more serious fouling. Its water flux dropped to about 70 percent of its initial value after several hours.
  • the double selective-layer membrane showed only a slight decrease (less than 10 percent) in water flux, hi addition, after washing the two membranes with DI water for 1 h, the water flux of the double selective-layer membrane almost went back to the initial value, while the water flux of the single dense-layer membrane only reached 80 percent of the initial value.

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

Abstract

L'invention porte sur une membrane polymère, qui comprend une couche support poreuse ayant une première surface et une deuxième surface opposée à la première surface, une première couche formant peau sur la première surface de la couche support, et une deuxième couche formant peau sur la deuxième surface de la couche support. La couche support formée d'un premier polymère a une première dimension de pore et une première porosité. La première couche formant peau, formée d'un deuxième polymère, a une deuxième dimension de pore et une deuxième porosité. La deuxième couche formant peau, formée d'un troisième polymère, a une troisième dimension de pore et une troisième porosité. La deuxième et la troisième dimension de pore sont toutes les deux inférieures à la première dimension de pore, et la deuxième et la troisième porosité sont toutes les deux inférieures à la première porosité. La membrane polymère peut être utilisée en tant que membrane d'osmose directe.
PCT/SG2010/000219 2009-06-10 2010-06-10 Membranes à deux couches sélectives Ceased WO2010144057A1 (fr)

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Cited By (26)

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WO2012102680A1 (fr) * 2011-01-25 2012-08-02 Nanyang Technological University Membrane d'osmose directe et procédé de fabrication d'une membrane d'osmose directe
WO2012112123A1 (fr) * 2011-02-14 2012-08-23 National University Of Singapore Membrane d'osmose directe et procédé de fabrication
CN103055713A (zh) * 2012-12-28 2013-04-24 中国海洋大学 一种双皮层正渗透膜及其制备方法
WO2013118859A1 (fr) * 2012-02-09 2013-08-15 東洋紡株式会社 Membrane semi-perméable à fibres creuses, son procédé de fabrication, module et procédé de traitement de l'eau
KR20140040065A (ko) * 2010-09-30 2014-04-02 포리페라 인코포레이티드 정삼투용 박막 복합 멤브레인 및 이의 제조 방법
AU2013200495B2 (en) * 2012-02-01 2014-07-10 Pall Corporation Asymmetric membranes
US8960448B2 (en) 2011-09-22 2015-02-24 National University Of Singapore Thin film composite osmosis membranes
US9216391B2 (en) 2011-03-25 2015-12-22 Porifera, Inc. Membranes having aligned 1-D nanoparticles in a matrix layer for improved fluid separation
US9227360B2 (en) 2011-10-17 2016-01-05 Porifera, Inc. Preparation of aligned nanotube membranes for water and gas separation applications
WO2016077560A1 (fr) * 2014-11-12 2016-05-19 The Trustees Of Dartmouth College Matériau piézo-électrique poreux à surface dense, et procédés et dispositifs associés
CN105636676A (zh) * 2013-10-11 2016-06-01 三菱丽阳株式会社 中空多孔膜
US9636635B2 (en) 2012-12-21 2017-05-02 Porifera, Inc. Separation systems, elements, and methods for separation utilizing stacked membranes and spacers
US9861937B2 (en) 2013-03-15 2018-01-09 Porifera, Inc. Advancements in osmotically driven membrane systems including low pressure control
CN108126537A (zh) * 2018-03-20 2018-06-08 延怀军 一种废水脱盐用聚酰胺复合正渗透膜
CN108187506A (zh) * 2018-03-20 2018-06-22 延怀军 一种废水脱盐用正渗透膜
CN108339403A (zh) * 2018-04-16 2018-07-31 延怀军 一种水处理用聚酰胺正渗透膜
CN108339402A (zh) * 2018-03-20 2018-07-31 延怀军 一种废水脱盐用正渗透膜的制备方法
CN108392991A (zh) * 2018-04-16 2018-08-14 延怀军 一种废水脱盐用聚酰胺复合正渗透膜
US10252222B2 (en) 2012-02-24 2019-04-09 Toyobo Co., Ltd. Hollow fiber type semipermeable membrane, method for manufacturing the same, module, and water treatment method
US10259723B2 (en) 2010-05-21 2019-04-16 Znano Llc Self-assembled surfactant structures
US10384169B2 (en) 2014-10-31 2019-08-20 Porifera, Inc. Supported carbon nanotube membranes and their preparation methods
US10589231B2 (en) 2010-05-21 2020-03-17 Znano Llc Self-assembled surfactant structures
WO2021067058A1 (fr) * 2019-10-01 2021-04-08 Entegris, Inc. Membranes à formation de particules réduite
US11541352B2 (en) 2016-12-23 2023-01-03 Porifera, Inc. Removing components of alcoholic solutions via forward osmosis and related systems
US11571660B2 (en) 2015-06-24 2023-02-07 Porifera, Inc. Methods of dewatering of alcoholic solutions via forward osmosis and related systems
US12384699B2 (en) 2010-05-21 2025-08-12 Crosstek Holding Company Llc Self-assembled surfactant structures

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0913186A1 (fr) * 1997-02-07 1999-05-06 Asahi Kasei Kogyo Kabushiki Kaisha Membrane a fibres creuses et procede de fabrication
WO2001034372A1 (fr) * 1999-11-05 2001-05-17 Baxter International Inc. Procede de fabrication d'une membrane semi-permeable anisotrope
WO2001097957A1 (fr) * 2000-06-23 2001-12-27 Lg Chemical Co. Ltd. Membrane composite a composants multiples et procede permettant de la produire
WO2002015299A1 (fr) * 2000-08-12 2002-02-21 Lg Chemical Co., Ltd. Film composite a multicomposants et son procede de preparation
US6413070B1 (en) * 1997-04-11 2002-07-02 Cuno Incorporated System for manufacturing reinforced three-zone microporous membrane
US20040154978A1 (en) * 2000-08-07 2004-08-12 Richard Sale Pre-metered, unsupported multilayer microporous membrane
US20040222148A1 (en) * 2003-05-05 2004-11-11 Youxin Yuan Preparation of porous poly(aryl ether) articles and use thereof
US20060226067A1 (en) * 2005-04-07 2006-10-12 Hydration Technologies Inc. Asymmetric forward osmosis membranes
WO2007128488A1 (fr) * 2006-05-06 2007-11-15 Membrana Gmbh Membrane d'ultrafiltration
EP2022555A1 (fr) * 2006-04-26 2009-02-11 Toyo Boseki Kabushiki Kaisha Membrane a fibres creuses poreuses polymeriques

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0913186A1 (fr) * 1997-02-07 1999-05-06 Asahi Kasei Kogyo Kabushiki Kaisha Membrane a fibres creuses et procede de fabrication
US6413070B1 (en) * 1997-04-11 2002-07-02 Cuno Incorporated System for manufacturing reinforced three-zone microporous membrane
WO2001034372A1 (fr) * 1999-11-05 2001-05-17 Baxter International Inc. Procede de fabrication d'une membrane semi-permeable anisotrope
WO2001097957A1 (fr) * 2000-06-23 2001-12-27 Lg Chemical Co. Ltd. Membrane composite a composants multiples et procede permettant de la produire
US20040154978A1 (en) * 2000-08-07 2004-08-12 Richard Sale Pre-metered, unsupported multilayer microporous membrane
WO2002015299A1 (fr) * 2000-08-12 2002-02-21 Lg Chemical Co., Ltd. Film composite a multicomposants et son procede de preparation
US20040222148A1 (en) * 2003-05-05 2004-11-11 Youxin Yuan Preparation of porous poly(aryl ether) articles and use thereof
US20060226067A1 (en) * 2005-04-07 2006-10-12 Hydration Technologies Inc. Asymmetric forward osmosis membranes
EP2022555A1 (fr) * 2006-04-26 2009-02-11 Toyo Boseki Kabushiki Kaisha Membrane a fibres creuses poreuses polymeriques
WO2007128488A1 (fr) * 2006-05-06 2007-11-15 Membrana Gmbh Membrane d'ultrafiltration

Cited By (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11401179B2 (en) 2010-05-21 2022-08-02 Diamond Gold Investors, Llc Self-assembled surfactant structures
US10259723B2 (en) 2010-05-21 2019-04-16 Znano Llc Self-assembled surfactant structures
US12384699B2 (en) 2010-05-21 2025-08-12 Crosstek Holding Company Llc Self-assembled surfactant structures
US10589231B2 (en) 2010-05-21 2020-03-17 Znano Llc Self-assembled surfactant structures
AU2011312881B2 (en) * 2010-09-30 2015-07-16 Porifera, Inc. Thin film composite membranes for forward osmosis, and their preparation methods
EP2621615A4 (fr) * 2010-09-30 2015-06-17 Porifera Inc Membranes composites à film mince pour l'osmose directe et leurs procédés de préparation
KR20140040065A (ko) * 2010-09-30 2014-04-02 포리페라 인코포레이티드 정삼투용 박막 복합 멤브레인 및 이의 제조 방법
KR101892108B1 (ko) 2010-09-30 2018-08-27 포리페라 인코포레이티드 정삼투용 박막 복합 멤브레인 및 이의 제조 방법
US12048897B2 (en) 2011-01-25 2024-07-30 Nanyang Technological University Forward osmosis membrane and method of forming a forward osmosis membrane
WO2012102680A1 (fr) * 2011-01-25 2012-08-02 Nanyang Technological University Membrane d'osmose directe et procédé de fabrication d'une membrane d'osmose directe
WO2012112123A1 (fr) * 2011-02-14 2012-08-23 National University Of Singapore Membrane d'osmose directe et procédé de fabrication
US9216391B2 (en) 2011-03-25 2015-12-22 Porifera, Inc. Membranes having aligned 1-D nanoparticles in a matrix layer for improved fluid separation
US8960448B2 (en) 2011-09-22 2015-02-24 National University Of Singapore Thin film composite osmosis membranes
US9227360B2 (en) 2011-10-17 2016-01-05 Porifera, Inc. Preparation of aligned nanotube membranes for water and gas separation applications
US9005496B2 (en) 2012-02-01 2015-04-14 Pall Corporation Asymmetric membranes
AU2013200495B2 (en) * 2012-02-01 2014-07-10 Pall Corporation Asymmetric membranes
US9415347B2 (en) 2012-02-01 2016-08-16 Pall Corporation Asymmetric membranes
JP5418739B1 (ja) * 2012-02-09 2014-02-19 東洋紡株式会社 中空糸型半透膜及びその製造方法及びモジュール及び水処理方法
WO2013118859A1 (fr) * 2012-02-09 2013-08-15 東洋紡株式会社 Membrane semi-perméable à fibres creuses, son procédé de fabrication, module et procédé de traitement de l'eau
US10369530B2 (en) 2012-02-09 2019-08-06 Toyobo Co., Ltd. Hollow fiber semipermeable membrane, method for manufacturing same, module, and water treatment method
US10252222B2 (en) 2012-02-24 2019-04-09 Toyobo Co., Ltd. Hollow fiber type semipermeable membrane, method for manufacturing the same, module, and water treatment method
US10464023B2 (en) 2012-12-21 2019-11-05 Porifera, Inc. Separation systems, elements, and methods for separation utilizing stacked membranes and spacers
US11090611B2 (en) 2012-12-21 2021-08-17 Porifera, Inc. Separation systems, elements, and methods for separation utilizing stacked membranes and spacers
US11759751B2 (en) 2012-12-21 2023-09-19 Porifera, Inc. Separation systems, elements, and methods for separation utilizing stacked membranes and spacers
US9636635B2 (en) 2012-12-21 2017-05-02 Porifera, Inc. Separation systems, elements, and methods for separation utilizing stacked membranes and spacers
CN103055713A (zh) * 2012-12-28 2013-04-24 中国海洋大学 一种双皮层正渗透膜及其制备方法
US12005396B2 (en) 2013-03-15 2024-06-11 Porifera, Inc. Advancements in osmotically driven membrane systems including multi-stage purification
US9861937B2 (en) 2013-03-15 2018-01-09 Porifera, Inc. Advancements in osmotically driven membrane systems including low pressure control
US10500544B2 (en) 2013-03-15 2019-12-10 Porifera, Inc. Advancements in osmotically driven membrane systems including multi-stage purification
CN105636676B (zh) * 2013-10-11 2018-05-22 三菱化学株式会社 中空多孔膜
CN105636676A (zh) * 2013-10-11 2016-06-01 三菱丽阳株式会社 中空多孔膜
US10384169B2 (en) 2014-10-31 2019-08-20 Porifera, Inc. Supported carbon nanotube membranes and their preparation methods
WO2016077560A1 (fr) * 2014-11-12 2016-05-19 The Trustees Of Dartmouth College Matériau piézo-électrique poreux à surface dense, et procédés et dispositifs associés
US10147870B2 (en) 2014-11-12 2018-12-04 The Trustees Of Dartmouth College Porous piezoelectric material with dense surface, and associated methods and devices
US11571660B2 (en) 2015-06-24 2023-02-07 Porifera, Inc. Methods of dewatering of alcoholic solutions via forward osmosis and related systems
US11541352B2 (en) 2016-12-23 2023-01-03 Porifera, Inc. Removing components of alcoholic solutions via forward osmosis and related systems
US12390767B2 (en) 2016-12-23 2025-08-19 Porifera, Inc. Removing components of alcoholic solutions via forward osmosis and related systems
CN108339402A (zh) * 2018-03-20 2018-07-31 延怀军 一种废水脱盐用正渗透膜的制备方法
CN108126537A (zh) * 2018-03-20 2018-06-08 延怀军 一种废水脱盐用聚酰胺复合正渗透膜
CN108187506A (zh) * 2018-03-20 2018-06-22 延怀军 一种废水脱盐用正渗透膜
CN108339403A (zh) * 2018-04-16 2018-07-31 延怀军 一种水处理用聚酰胺正渗透膜
CN108392991A (zh) * 2018-04-16 2018-08-14 延怀军 一种废水脱盐用聚酰胺复合正渗透膜
WO2021067058A1 (fr) * 2019-10-01 2021-04-08 Entegris, Inc. Membranes à formation de particules réduite

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