WO2012102678A1 - A forward osmosis membrane - Google Patents
A forward osmosis membrane Download PDFInfo
- Publication number
- WO2012102678A1 WO2012102678A1 PCT/SG2012/000021 SG2012000021W WO2012102678A1 WO 2012102678 A1 WO2012102678 A1 WO 2012102678A1 SG 2012000021 W SG2012000021 W SG 2012000021W WO 2012102678 A1 WO2012102678 A1 WO 2012102678A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- osmosis membrane
- forward osmosis
- support layer
- porous support
- thin film
- Prior art date
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 100
- 238000009292 forward osmosis Methods 0.000 title claims abstract description 86
- 239000010409 thin film Substances 0.000 claims abstract description 76
- 239000002086 nanomaterial Substances 0.000 claims abstract description 71
- 239000010410 layer Substances 0.000 claims description 132
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- 238000000034 method Methods 0.000 claims description 40
- 239000004744 fabric Substances 0.000 claims description 37
- 229920000642 polymer Polymers 0.000 claims description 32
- 239000012510 hollow fiber Substances 0.000 claims description 27
- 229920002492 poly(sulfone) Polymers 0.000 claims description 21
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 17
- 238000005266 casting Methods 0.000 claims description 16
- 239000002105 nanoparticle Substances 0.000 claims description 16
- 238000011282 treatment Methods 0.000 claims description 15
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 14
- -1 aluminum ion Chemical class 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 238000012695 Interfacial polymerization Methods 0.000 claims description 13
- 238000011065 in-situ storage Methods 0.000 claims description 13
- 239000002243 precursor Substances 0.000 claims description 13
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- 150000003839 salts Chemical class 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
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- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 8
- 229920002678 cellulose Polymers 0.000 claims description 8
- 239000001913 cellulose Substances 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 8
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- 229920002554 vinyl polymer Polymers 0.000 claims description 7
- 229920002284 Cellulose triacetate Polymers 0.000 claims description 6
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 6
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 6
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- 239000011148 porous material Substances 0.000 claims description 6
- JCVQKRGIASEUKR-UHFFFAOYSA-N triethoxy(phenyl)silane Chemical compound CCO[Si](OCC)(OCC)C1=CC=CC=C1 JCVQKRGIASEUKR-UHFFFAOYSA-N 0.000 claims description 6
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical class [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical class [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
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- SLYCYWCVSGPDFR-UHFFFAOYSA-N octadecyltrimethoxysilane Chemical compound CCCCCCCCCCCCCCCCCC[Si](OC)(OC)OC SLYCYWCVSGPDFR-UHFFFAOYSA-N 0.000 claims description 4
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- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical compound C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 claims description 2
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
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- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
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- 229910052712 strontium Inorganic materials 0.000 claims description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000243 solution Substances 0.000 description 53
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- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 13
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- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 7
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
- B01D69/1251—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction by interfacial polymerisation
-
- 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
-
- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/14—Dynamic membranes
- B01D69/141—Heterogeneous membranes, e.g. containing dispersed material; Mixed matrix membranes
- B01D69/148—Organic/inorganic mixed matrix membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/28—Pore treatments
- B01D2323/283—Reducing the pores
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/34—Use of radiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/20—Specific permeability or cut-off range
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/28—Degradation or stability over time
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- 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
Definitions
- the invention relates to a forward osmosis membrane for forward osmosis applications, such as sea and brackish water desalination, wastewater reclamation, methane and hydrogen gas production, food and pharmaceutical processing, power generation, and their combinations thereof.
- the forward osmosis process has shown great potential for seawater desalination, wastewater reclamation and power generation.
- the key obstacle for widely applying the forward osmosis process is the lack of an ideal forward osmosis membrane, which should have high permeate flux and high salt rejection rate.
- a known forward osmosis membrane made of cellulose obtains a water permeate flux that is lower than expected, and its salt rejection rate is also quite low.
- the low permeate flux is mainly attributed to the thick selective layer of this known forward osmosis membrane which make it difficult for osmosis of water therethrough.
- the low salt rejection rate is mainly attributed to the relatively porous selective layer of this known forward osmosis membrane, which makes it easy for salts to diffuse through.
- Conventional reverse osmosis ( O) membranes are typically prepared by coating a porous polysulfone support layer with a polyamide thin film; therefore they are called thin film composite membranes.
- the water permeate flux and salt rejection rate of conventional thin film composite RO membranes are reasonable high under high operation pressure. These are attributed to the thin polyamide selective layer.
- the thin polyamide selective layer can maintain the high salt rejection rate, but has a low water permeate flux because the polysulfone support layer is dense and relatively hydrophobic, making it difficult for water to pass through, because of a phenomenon known as internal concentration polarization.
- the forward osmosis membrane is a thin film nanocomposite forward osmosis membrane comprising a porous support layer and a thin film polymerized on the porous support layer. Nanomaterials are dispersed in the porous support layer or the thin film, or both.
- the thin film nanocomposite forward osmosis membrane is semi-permeable, being substantially permeable to water and substantially impermeable to impurities.
- the thin film nanocomposite forward osmosis membrane may be in flat sheet or hollow fiber form. Where the forward osmosis membranes have a flat sheet form, the flat sheet membranes can be used in spiral wound elements with high membrane packing density.
- the forward osmosis membrane of the present invention finds uses in a variety of applications including forward osmosis-based wastewater reclamation, seawater and brackish water desalination, bioenergy production, food and pharmaceutical processing, power generation, and their combinations thereof.
- the nanomaterials are preformed, that is, the porous support layer is made by phase inversion in the presence of nanomaterials, and/or the thin film is made by interfacial polymerization in the presence of nanomaterials.
- the nanomaterials are in situ formed, that is, the porous support layer is made by phase inversion in the presence of the precursors (such as metal alkoxide) for nanomaterials, and/or the thin film is formed by interfacial polymerization in the presence of the precursors for nanomaterials.
- the precursors such as metal alkoxide
- the forward osmosis membrane can further include a hydrophilic layer on top of the thin film to further decrease membrane fouling. .
- Post-treatments for the interfaciai-polymerized thin film may be conducted to enhance water permeability, solute rejection, or fouling resistance of a formed membrane.
- the porous support layer may be subjected to a post-treatment process to reduce pore size of the porous support layers.
- a forward osmosis membrane comprising a porous support layer, a thin film formed on one side of the porous support layer, and nanomaterials dispersed in at least one of the porous support layer and the thin film.
- the forward osmosis membrane may comprise a form selected from the group consisting of: flat sheet, hollow fiber and tubular.
- the forward osmosis membrane may be in hollow fiber form and the thin film may be polymerized on an internal surface of the hollow fiber.
- the forward osmosis membrane may be in hollow fiber form and the thin film may be polymerized on an external surface of the hollow fiber.
- the thickness of the forward osmosis membrane may be between 20 ⁇ and 400 ⁇ .
- the forward osmosis membrane may further comprise a porous smooth layer formed on a side of the porous support layer opposite the side of the porous support layer on which the thin film is polymerized.
- the forward osmosis membrane may further comprise a hydrophilic polymeric layer on top of the thin film.
- a matrix material for the hydrophilic polymeric layer may comprise at least one of: polyvinyl alcohol, polyvinyl pyrrole, polyvinyl pyrrolidone, polyethylene glycol, saponified polyethylene- vinyl acetate copolymer, triethylene glycol, and diethylene glycol. Nanomaterials may be dispersed in the hydrophilic layer.
- the thin film may be configured to be permeable to water and relatively impermeable to impurities.
- the thin film may be configured to be relatively impermeable to impurities comprising at least one of: dissolved, dispersed, or suspended solids; monovalent, divalent, trivalent ions of sodium, potassium, magnesium, calcium, iron, aluminum ion, silicate, dissolved organics, and nonionized dissolved solids with a molecular weight of greater than about 200 Daitons.
- the thickness of the thin film may be between 30 nm and 3 ⁇ .
- a matrix material for the thin film may comprise at least one of: polyamide, aromatic polyamide, polypiperazine polyamide, polybenzimidazole, polyether, polyester, polyether-urea, polyvinyl alcohol, polyvinyl pyrrole, polyvinyl pyrrolidone, polyethylene glycol, saponified polyethylene-vinyl acetate copolymer, triethylene glycol, diethylene glycol, and a copolymer thereof.
- the porous support layer may comprise a polymeric fabric selected from the group consisting of: a woven polymeric fabric screen and a non-woven polymeric fabric mesh.
- the thickness of the polymeric fabric may be between 1 ⁇ and 200 ⁇
- a material of the polymeric fabric may comprise at least one of: a hydrophilic polymer, a hydrophobic polymer, polyester, polypropylene, acrylics, cotton, cellulose, and nylon.
- a surface of the polymeric fabric may be modified by treatment with at least one of: plasma, UV light, and a solvent.
- the thickness of the porous support layer may be between 10 ⁇ and 100 ⁇ .
- a matrix material for the porous support layer may comprise at least one of: a natural polymer or a synthetic polymers, polysulfone, polyethersulfone, sulfonated polysulfone, poly(ether sulfone ketone), poly(ether ethyl ketone), poly(phthalazinone ether sulfone ketone), polyacrylonitrile, polypropylene, cellulose acetate, cellulose diacetate, cellulose triacetate, polyvinyl alcohol, polyvinyl pyrrole, polyvinyl pyrrolidone, polyethylene glycol, saponified polyethylene-vinyl acetate copolymer, triethylene glycol, diethylene glycol, polyaniline, and Pluronic F127.
- a natural polymer or a synthetic polymers polysulfone, polyethersulfone, sulfonated polysulfone, poly(ether sulfone ketone), poly(ether ethyl ketone),
- a surface of the porous support layer may be modified by treatment with at least one of: plasma, UV light, and a solvent. Sizes of the nanomaterials may be in the range of less than 500 nm.
- the nanomaterials may be in the form of at least one of: nanoparticles, nanofiber, nanowire. nanotube, and nanospheres.
- the nanomaterials may be at least one of: inorganics and organics.
- the nanomaterials may be inorganics and comprise at least one of: salts of silver, gold, zinc, copper, sodium, titanium, silicon, aluminum, zirconium, indium, tin, magnesium, calcium, their oxide, and their alloy.
- the nanomaterials may be inorganics and may comprise at least one of: mesoporous materialss of the oxide of aluminum, titania, silicon, magnesium, strontium, beryllium, mesoporous molecular sieve, aluminosilicate, aluminophopsphate, and zeolite.
- the nanomaterials may be organics and may comprise at least one of: dendrimers, graphite, graphene, carbon nanotubes, and fullerene.
- a weight percentage of the nanomaterials by weight of the matrix polymer in at least one of the porous support layer and the thin film may range from 0.01 to 20 wt %.
- the nanomaterials may be surface modified nanomaterials.
- a forward osmosis membrane comprising a porous support layer, a thin film formed on one side of the porous support layer, and nanomaterials dispersed in at least one of the porous support layer and the thin film
- the method comprising forming the porous support layer by phase inversion of a polymer solution; forming the thin film by interfacial polymerization of monomers in a liquid on the porous support layer; and dispersing the nanomaterials in at least one of the porous support layer and the thin film.
- Forming the porous support layer may comprise casting the porous support layer on a rotating drum.
- Casting the porous support layer on the rotating drum may comprise casting the polymer solution directly on a surface of the rotating drum while pulling a polymeric fabric into the polymer solution, thereby embedding the polymeric fabric in the polymer solution, wherein the polymeric fabric may be one selected from the group consisting of: a woven polymeric fabric screen and a non-woven polymeric fabric mesh.
- casting the porous support layer on the rotating drum may comprise casting the polymer solution on a polymeric fabric laid on a surface of the rotating drum, wherein the polymeric fabric may be one selected from the group consisting of: a woven polymeric fabric screen and a non-woven polymeric fabric mesh.
- the method may further comprise modifying a surface of the polymeric fabric by treatment with at least one of: plasma, UV light, and a solvent.
- the method may further comprise modifying a surface of the porous support layer by treatment with at least one of: plasma, UV light, and a solvent.
- Dispersing the nanomaterials in the porous support layer may comprise providing preformed nanomaterials in the polymer solution for the phase inversion.
- dispersing the nanomaterials in the porous support layer may comprise providing nanomaterial precursors in the polymer solution and in-situ forming the nanomaterials by chemical reactions during the phase inversion.
- Dispersing the nanomaterials in the thin film may comprise providing preformed nanomaterials in the liquid.
- dispersing the nanomaterials in the thin film may comprise providing nanomaterial precursors in the liquid and in-situ forming the nanomaterials by chemical reactions during the interfacial polymerization.
- the nanomaterial precursors may comprise at least one of: a metal alkoxide, titanium tetra isopropoxide (TTIP), Tetrabutyl titanate (TnBT), tetraethyl orthosilicate (TEOS), bis (triethoxy silyl) ethane (BTESE), phenyltriethoxysilane (PhTES), methyltriethoxysilane ( eTES), octyltriethoxysilane (OcTES), and octadecyltrimethoxysilane (OdTMS).
- TTIP titanium tetra isopropoxide
- TnBT Tetrabutyl titanate
- TEOS tetraethyl orthosilicate
- BTESE bis (triethoxy silyl) ethane
- PhTES phenyltriethoxysilane
- eTES methyltriethoxysilane
- OcTES oct
- the method may further comprise forming a porous smooth layer formed on a side of the porous support layer opposite the side of the porous support layer on which the thin film may be polymerized.
- the method may further comprise forming a hydrophilic polymeric layer on top of the thin film.
- the method may further comprise dispersing the nanomaterials in the hydrophilic polymeric layer.
- the method may further comprise subjecting the porous support layer to a post-treatment process to reduce pore size.
- FIG. 1 is a schematic cross-sectional diagram of an exemplary forward osmosis membrane in flat sheet form
- FIG. 2. is a schematic cross-sectional diagram of an exemplary forward osmosis membrane in hollow fiber form.
- FIG. 3. is a schematic cross-sectional diagram of another exemplary forward osmosis membrane in hollow fiber form.
- Exemplary forward osmosis membranes 1 0, 20, 30 will be described with reference to FIGS. 1 to 3 below. Exemplary methods of forming the forward osmosis membrane will be described in Examples 1 to 8 below.
- the forward osmosis membrane 10, 20, 30 is a thin film nanocomposite forward osmosis membrane and comprises a porous support layer 1 10, 210, 310, a thin film 120, 220, 320 formed on one side of the porous support layer 1 10, 210, 310 and nanomaterials 130, 230, 330 dispersed in at least one of the porous support layer 1 10, 210, 310 and the thin film 120, 220, 320.
- the nanomaterials 130, 230, 330 may be dispersed in only the porous support layer 210, 310 as shown in FIGS. 2 and 3, or in only the thin film, or in both the porous support layer 1 10 and the thin film 120 as shown in FIG. 1.
- the forward osmosis membrane may be in the form of a flat sheet 10, or in hollow fiber form 20, 30.
- the forward osmosis membrane may also be tubular.
- the porous support layer 1 10, 210, 310 is generally formed by phase inversion of a polymer solution. This normally comprising the following steps: first, a solution of polymer and additives is prepared in an appropriate solvent or system of solvents and the porous support layer is then obtained by casting or spinning the polymer solution. Second, volatile components of the solvent are partially vaporized at room temperature, and then the liquid film is immersed in a water bath or water/sol vents bath, giving rise to the phase inversion, which leaves the porous support layer in the form of a water-swollen gel of the polymer.
- the porous support layer, prepared by the phase inversion method normally consist of a dense top layer 1 1 1 and a porous bottom layer 1 12 comprising a plurality of pores 1 13.
- polymer solution casting is used wherein a polymer solution comprising polymers (5 to 20 wt%) and solvents (80 to 95 wt%). and nanomaterials (0 to 20 wt%) is stirred continuously until the solution become homogenous. Then the polymer solution may be cast on a glass plate using a casting knife. The cast film is then immersed in a coagulation bath to complete the phase inversion. The membrane of porous support layer 1 10 can then be post-treated in a hot water bath.
- a porous support layer 210,3 10 having a hollow fiber form may be prepared by dry-wet spinning, in which the polymer solution same as that used for preparing a flat sheet is flowed through a ring nozzle of a spinneret while a bore fluid is flowed through an inner tube of the spinneret. Flow rates of the polymer solution and the bore solution are controlled by syringe pumps.
- a hollow fiber is produced and the resulting fiber is then passed through a controlled environment air gap before entering a coagulation bath.
- the hollow fiber filament is passed through a series of rollers in the coagulation bath. Subsequently, the hollow fiber is then passed through a washing bath.
- the fully formed hollow fiber can be continuously collected on a wind- up drum.
- the porous support layer 1 10, 210, 3 10 can be subjected to a post-treatment process to reduce the pore size of the porous support layer 1 10, 210. 310.
- the porous support layer 1 10, 210, 310 is immersed in a water bath at room temperature.
- the water bath containing the porous support layer 1 10, 210, 310 is then gradually heated from ambient temperature to a temperature in the range of 60 to 95 °C, in about 20 to 30 minutes.
- the final temperature is kept constant for about 10 minutes.
- the water bath together with the membranes or porous support layer 1 10, 210, 310 is cooled drastically to below 60 °C by pouring cold water directly into the bath to freeze the porous structure.
- the thin film 120, 220, 320 is general ly formed by interfacial polymerization of monomers in a polar or non-polar liquid on the porous support layer 1 10, 210, 310.
- the interfacial polymerization normally comprises the following steps: first, an aqueous solution of a first monomer and additives are allowed to cover the top of the porous support layer for some time. Then, an organic solution of a second monomer and additives are allowed to cover the top of the porous support layer for interfacial polymerization.
- the first monomer can be a polynucleophilic monomer, such as diaminobenzene, m-phenylenediamine, piperazine or piperazine derivative.
- the second monomer can be a polyelectrophilic monomer, such as a trimesoyl halide or a trimesoyl chloride.
- the polar liquid can be water.
- the non-polar liquid can be a linear hydrocarbon, a branched hydrocarbon, a cyclic hydrocarbon, naptha, heavy naptha, paraffin, isoparaffin, hexane, or their combinations thereof.
- the nanomaterials 130, 230, 330 may be either preformed or formed in-situ.
- the preformed nanomaterials are provided in the polymer solution for the phase inversion.
- preformed nanomaterials can be provided in the liquid of polymerization of the monomers for dispersal in the thin film.
- nanomaterial precursors can be provided in the polymer solution and in-situ forming the nanomaterials in the porous support layer by chemical reactions.
- nanomaterial precursors can be provided in the liquid of polymerization of the monomers and in-situ forming the nanomaterials in the thin film by chemical reactions during the interfacial polymerization.
- a forward osmosis membrane can be immersed in an acidic and/or basic solution to remove residual, unreacted acid chlorides and diamines which can improve the flux of the formed forward osmosis membrane.
- heat treatment, or curing can also be applied to promote contact between the polyamide film and polysulfone support or to promote cross-linking within the formed polyamide film.
- a forward osmosis membrane can be exposed to an oxidant such as chlorine, for example, sodium hypochlorite.
- Post-chlorination of a fully aromatic polyamide thin film forms chloramines as free chlorine reacts with pendant amine functional groups within the polyamide film.
- This can increase the negative charge density, by neutralizing positively-charged pendant amine groups, and the result is a more hydrophilic, negatively charged forward osmosis membrane with higher flux, salt rejection, and fouling resistance.
- the membranes can further include a hydrophilic layer on top of the thin film to further decrease the membrane fouling.
- a hydrophilic and smooth membrane surface can be accomplished by applying an additional coating layer comprised of a water-soluble polymer such as polyvinyl alcohol (PVA), polyvinyl pyrrole (PVP), or polyethylene glycol (PEG) on the surface of a polyamide film.
- PVA polyvinyl alcohol
- PVP polyvinyl pyrrole
- PEG polyethylene glycol
- the forward osmosis membrane may further comprise a porous smooth layer formed on a side of the porous support layer opposite the side of the porous support layer on which the thin film is polymerized.
- the porous smooth layer has pore sizes the same as that of microfiltration or ultrafiltration membranes. In this way, forming a "double-skinned" forward osmosis membrane is formed to decrease membrane fouling and internal concentration polarization in the porous support layer.
- Example 1 Fabrication of a flat sheet porous support layer dispersed with nanomaterials by phase inversion using preformed nanoparticles
- the porous support layer is prepared by dissolving 9 g polysulfone (PSf) beads in 96 mL of ⁇ , ⁇ -dimethylformamide (DMF) containing 0.5 % PVP and 0.3% Pluronic F127 in a glass bottle. 0.3 g nanoparticles (Degussa P25 Ti0 2 nanoparticles) are dispersed in the DMF before its addition to the PSf polymer. The solution is then agitated ultrasonically for 24 hours until complete dissolution, forming the cast solution which is then set aside for 2 days to eliminate air bubbles. The cast solution is then spread over a non-woven polyester (PET) fabric that is attached to a glass plate and wetted by the solvent of DMF.
- PPT non-woven polyester
- the glass plate is immediately immersed in tap water at room temperature to induce phase inversion. After 30 minutes, the non-woven PET fabric supported PSf nanocomposite porous support layer is removed from the water bath and separated from the glass plate. The porous support layer dispersed with nanocomposites is washed thoroughly with tap water and stored at 5° C.
- Example 2 Fabrication of a flat sheet porous support layer dispersed with nanomaterials by phase inversion with in-situ formed nanoparticles
- the porous support layer is prepared by dissolving 9 g polysulfone (PSf) beads in a mixed solvents of 80 mL of N-methyl pyrrolidone (NMP) and 80 mL of N,N-dimethylformamide (DMF) containing 0.5 % PVP in a glass bottle.
- NMP N-methyl pyrrolidone
- DMF N,N-dimethylformamide
- 3.5 ml of tetraetnoxysilane and 0.1 ml of hydrochloric acid precursors for S1O2 nanoparticie
- the solution is then agitated ultrasonically for 24 hours until complete dissolution, forming the cast solution which is then set aside for 2 days to eliminate air bubbles.
- the cast solution is then spread over a woven polyester (PET) fabric screen that is attached to a glass plate and wetted by the solvents of DMF and NMP.
- PET woven polyester
- the glass plate is immediately immersed in tap water at room temperature to induce phase inversion.
- the woven PET fabric screen supported PSf nanocomposite porous support layer is removed from the water bath and separated from the glass plate.
- the porous support layer dispersed with nanomaterials is washed thoroughly with tap water and stored at 5° C.
- Example 3 Fabrication of a flat sheet porous support layer of cellulose dispersed with nanomaterials by phase inversion with in-situ formed nanoparticles
- the cellulose porous support layer is prepared from cellulose triacetate using the phase inversion technique.
- the casting solution is prepared by dissolving 15 g cellulose triacetate (CA) (Mw 30,000 g mol "1 , 39.8 wt % acetyl content) in 86 ml acetone/forrnamide (2: 1 ) mixture in a glass bottle.
- CA cellulose triacetate
- Example 4 Fabrication of a hollow fiber porous support layer dispersed with nanomaterials using preformed nanoparticles
- Fabrication of the hollow fiber porous support layer is based on the dry-wet spinning technique.
- a homogenous dope solution is prepared in the same way as the cast solution in Example 1.
- the dope solution is prepared by dissolving 9 g polysulfone (PSf) beads in 96 mL of N,N- dimethylformamide (DMF) containing 0.5 % PVP in a glass bottle.
- 0.3 g nanoparticles (Degussa P25 Ti0 2 nanoparticles) are dispersed in the DMF before its addition to the PSf polymer.
- the solution is then agitated ultrasonically for 24 hours until complete dissolution, forming the dope solution which is then set aside for 2 days to eliminate air bubbles.
- the dope is extruded through a hollow fiber spinneret.
- Flow rates of the bore and dope solutions are controlled by syringe pumps.
- Both the bore liquid and the external coagulant are pure water, and the external coagulant temperature is controlled at 80°C.
- the air gap which is the distance between the tip of spinneret and the surface of the external coagulant is kept 10 cm.
- the resulting hollow fiber porous support layer dispersed with nanomaterials is wound up with a roller at a free falling velocity and rinsed with water to remove residual solvents.
- the hollw fiber is then annealed in a hot water bath at 80°C.
- Example 5 Fabrication of a hollow fiber porous support layer dispersed with nanomaterials with in-situ formed nanoparticles
- a homogenous dope solution is prepared in the same way as the cast solution in Example 1.
- the dope solution is prepared by dissolving 9 g polysulfone (PSf) beads in 96 mL of M,N- dimethylformamide (DMF) containing 0.5 % PVP in a glass bottle.
- PSf polysulfone
- DMF M,N- dimethylformamide
- 3.5 ml of tetraethoxysilane and 0.1 ml of hydrochloric acid (precursors for S1O2 nanoparticle) are dispersed in the DMF before its addition to the PSf polymer.
- the solution is then agitated ultrasonically for 24 hours until complete dissolution, forming the dope solution. Afterward, the dope is extruded through a hollow fiber spinneret.
- Flow rates of the bore and dope solutions are controlled by syringe pumps. Both the bore liquid and the external coagulant are pure water, and the external coagulant temperature is controlled at 80°C.
- the air gap which is the distance between the tip of spinneret and the surface of the external coagulant is kept 10 cm.
- the resulting hollow fiber porous support layer dispersed with nanomaterials is wound up with a roller at a free falling velocity and rinsed with water to remove residual solvents.
- the hollw fiber is then annealed in a hot water bath at 80°C.
- Example 6 Fabrication of a thin film dispersed with nanomaterials by interfacial polymerization using preformed nanoparticles
- a porous support layer formed by any of the methods described in Examples 1 to 6 above is immersed in an aqueous solution of 3 wt% m-phenylenediamine (MPD) which contains other additives like triethyl amine (TEA), 10-champhor sulfonic acid (CSA), sodium lauryl sulfate (SLS), and isopropanol for 25 seconds. Excess MPD solution is removed from the surface of the porous support layer using an air knife.
- MPD m-phenylenediamine
- the aqueous MPD saturated porous support layer is then immersed in 0.15 wt% trimesoyl chloride (TMC) solution in isoparaffin at 30 °C for 60 seconds to form the thin film, where 0.1 wt of zeolite nanoparticles are suspended in the isoparaffin solution.
- TMC trimesoyl chloride
- the resulting membrane is cured in deionized water at 50 °C for 20 min, then rinsed with a 200 ppm NaOCl aqueous solution for 120 s, followed by rinsing for 60 s with a lOOOppm NaHSC aqueous solution, before a final heat curing step at 90 °C for 60 s.
- Example 7 Fabrication of thin film dispersed with nanomaterials bv interfacial polymerization with in-situ formed nanoparticles
- a porous support layer formed by any of the methods described in Examples 1 to 6 above is immersed in an aqueous solution of 3 wt% m-phenylenediamine (MPD) which contains other additives like triethyl amine (TEA), 10-champhor sulfonic acid (CSA), sodium lauryl sulfate (SLS), and isopropanol for 25 seconds. Excess MPD solution is removed from the surface of the porous support layer using an air knife.
- MPD m-phenylenediamine
- the aqueous MPD saturated porous support layer is then immersed in 0.15 wt% trimesoyl chloride (TMC) solution in isoparaffin containing phenyl triethoxy silane (PhTES) at 3wt% concentrations for 60 seconds to form the thin film.
- TMC trimesoyl chloride
- PhTES phenyl triethoxy silane
- the resulting membrane is cured in deionized water at 50 °C for 20 min, then rinsed with a 200 ppm NaOCl aqueous solution for 120 s, followed by rinsing for 30 s with a l OOOppm NaHS0 3 aqueous solution, before a final heat curing step at 90 °C for 60 s.
- the final forward osmosis membrane formed is rinsed thoroughly with deionized water and stored in deionized water at 4 °C.
- the thin film nanocomposite forward osmosis membrane is immersed in 50 wt% glycerol solution for another 24 h and then dried in air at room temperature.
- Example 8 Fabrication of polyamide thin film by interfacial polymerization on top of a cellulose porous support layer
- the cellulose porous support layer formed by the method described in Example 3 above is immersed in an aqueous solution of 3 wt% m-phenylenediamine (MPD) which contains other additives like triethyl amine (TEA), 10-champhor sulfonic acid (CSA), sodium lauryl sulfate (SLS), and isopropanol for 25 seconds.
- MPD 3 wt% m-phenylenediamine
- CSA 10-champhor sulfonic acid
- SLS sodium lauryl sulfate
- isopropanol 25 seconds.
- Excess MPD solution is removed from the surface of the porous support layer using an air knife.
- the aqueous MPD saturated porous support layer is then immersed in 0.15 wt% trimesoyl chloride (TMC) solution in isoparaffin at 30° C for 60 seconds to get thin film.
- TMC trimesoyl chloride
- the resulting membrane is cured in deionized water at 50 °C for 20 min, then rinsed with a 200 ppm NaOCl aqueous solution for 120 s, followed by rinsing for 60 s with a l OOOppm " NaHS0 3 aqueous solution, before a final heat curing step at 90 °C for 60 s.
- the final thin film nanocomposite forward osmosis membrane formed is rinsed thoroughly with deionized water and stored in deionized water at 4 °C.
- the thin film 220, 320 may be formed on either an external surface of the porous support layer 210 as shown in F1G.2, or an internal surface of the porous support layer 31 0 as shown in FIG.3.
Abstract
A forward osmosis membrane comprising a porous support layer, a thin film formed on one side of the porous support layer, and nanomaterials dispersed in at least one of the porous support layer and the thin film.
Description
A FORWARD OSMOSIS MEMBRANE
Field of the Invention
The invention relates to a forward osmosis membrane for forward osmosis applications, such as sea and brackish water desalination, wastewater reclamation, methane and hydrogen gas production, food and pharmaceutical processing, power generation, and their combinations thereof.
Background
Water shortage is an urgent problem for many parts of the world. Currently, pressure-driven membranes, such as, reverse osmosis or nanofiltration membranes, are heavily used in the water industry. However, these pressure-driven membranes are not environmental friendly because of their high energy consumption and severe membrane fouling problems. Processes using forward osmosis membranes utilizes a natural osmosis phenomenon for the extraction or transfer of water from a low solute concentration feed solution to a high solute concentration draw solution across a semipermeable membrane. After the water has naturally moved into the draw solution without intensive energy input, the diluted draw solution can then be concentrated to produce high quality water, while the concentrated draw solution can be reused. This process can be operated with very low energy consumption because the osmotic pressure difference between the feed and the draw solution is the only driving force for water production. Also, forward osmosis membranes experience less membrane fouling problems.
The forward osmosis process has shown great potential for seawater desalination, wastewater reclamation and power generation. However, the key obstacle for widely applying the forward osmosis process is the lack of an ideal forward osmosis membrane, which should have high permeate flux and high salt rejection rate. Currently, a known forward osmosis membrane made
of cellulose obtains a water permeate flux that is lower than expected, and its salt rejection rate is also quite low. The low permeate flux is mainly attributed to the thick selective layer of this known forward osmosis membrane which make it difficult for osmosis of water therethrough. The low salt rejection rate is mainly attributed to the relatively porous selective layer of this known forward osmosis membrane, which makes it easy for salts to diffuse through.
Conventional reverse osmosis ( O) membranes are typically prepared by coating a porous polysulfone support layer with a polyamide thin film; therefore they are called thin film composite membranes. The water permeate flux and salt rejection rate of conventional thin film composite RO membranes are reasonable high under high operation pressure. These are attributed to the thin polyamide selective layer. When tested in the forward osmosis process, the thin polyamide selective layer can maintain the high salt rejection rate, but has a low water permeate flux because the polysulfone support layer is dense and relatively hydrophobic, making it difficult for water to pass through, because of a phenomenon known as internal concentration polarization.
Therefore, there remains a need for methods and compositions to fabricate forward osmosis membranes having improved water permeability, salt rejection, and fouling resistance. Summary of the Invention
The forward osmosis membrane is a thin film nanocomposite forward osmosis membrane comprising a porous support layer and a thin film polymerized on the porous support layer. Nanomaterials are dispersed in the porous support layer or the thin film, or both. The thin film nanocomposite forward osmosis membrane is semi-permeable, being substantially permeable to water and substantially impermeable to impurities. The thin film nanocomposite forward osmosis membrane may be in flat sheet or hollow fiber form. Where the forward osmosis
membranes have a flat sheet form, the flat sheet membranes can be used in spiral wound elements with high membrane packing density.
With the adding of nanomaterials in the porous support layers or the thin films, many advantages, such as higher water permeate flux, less membrane fouling and higher mechanical strength, can be achieved compared with membranes without the adding of nanomaterials. High impurities rejection rate can be maintained for the thin film nanocomposite forward osmosis membrane. The forward osmosis membrane of the present invention finds uses in a variety of applications including forward osmosis-based wastewater reclamation, seawater and brackish water desalination, bioenergy production, food and pharmaceutical processing, power generation, and their combinations thereof. In some examples, the nanomaterials are preformed, that is, the porous support layer is made by phase inversion in the presence of nanomaterials, and/or the thin film is made by interfacial polymerization in the presence of nanomaterials.
In other examples, the nanomaterials are in situ formed, that is, the porous support layer is made by phase inversion in the presence of the precursors (such as metal alkoxide) for nanomaterials, and/or the thin film is formed by interfacial polymerization in the presence of the precursors for nanomaterials.
The forward osmosis membrane can further include a hydrophilic layer on top of the thin film to further decrease membrane fouling.
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Post-treatments for the interfaciai-polymerized thin film may be conducted to enhance water permeability, solute rejection, or fouling resistance of a formed membrane.
Optionally, the porous support layer may be subjected to a post-treatment process to reduce pore size of the porous support layers.
According to a first exemplary aspect, there is provided a forward osmosis membrane comprising a porous support layer, a thin film formed on one side of the porous support layer, and nanomaterials dispersed in at least one of the porous support layer and the thin film.
The forward osmosis membrane may comprise a form selected from the group consisting of: flat sheet, hollow fiber and tubular.
The forward osmosis membrane may be in hollow fiber form and the thin film may be polymerized on an internal surface of the hollow fiber.
Alternatively, the forward osmosis membrane may be in hollow fiber form and the thin film may be polymerized on an external surface of the hollow fiber. The thickness of the forward osmosis membrane may be between 20 μπι and 400 μηι.
The forward osmosis membrane may further comprise a porous smooth layer formed on a side of the porous support layer opposite the side of the porous support layer on which the thin film is polymerized.
The forward osmosis membrane may further comprise a hydrophilic polymeric layer on top of the thin film.
A matrix material for the hydrophilic polymeric layer may comprise at least one of: polyvinyl alcohol, polyvinyl pyrrole, polyvinyl pyrrolidone, polyethylene glycol, saponified polyethylene- vinyl acetate copolymer, triethylene glycol, and diethylene glycol. Nanomaterials may be dispersed in the hydrophilic layer.
The thin film may be configured to be permeable to water and relatively impermeable to impurities. The thin film may be configured to be relatively impermeable to impurities comprising at least one of: dissolved, dispersed, or suspended solids; monovalent, divalent, trivalent ions of sodium, potassium, magnesium, calcium, iron, aluminum ion, silicate, dissolved organics, and nonionized dissolved solids with a molecular weight of greater than about 200 Daitons. The thickness of the thin film may be between 30 nm and 3 μπ\.
A matrix material for the thin film may comprise at least one of: polyamide, aromatic polyamide, polypiperazine polyamide, polybenzimidazole, polyether, polyester, polyether-urea, polyvinyl alcohol, polyvinyl pyrrole, polyvinyl pyrrolidone, polyethylene glycol, saponified polyethylene-vinyl acetate copolymer, triethylene glycol, diethylene glycol, and a copolymer thereof.
The porous support layer may comprise a polymeric fabric selected from the group consisting of: a woven polymeric fabric screen and a non-woven polymeric fabric mesh.
The thickness of the polymeric fabric may be between 1 μιη and 200 μηι
A material of the polymeric fabric may comprise at least one of: a hydrophilic polymer, a hydrophobic polymer, polyester, polypropylene, acrylics, cotton, cellulose, and nylon.
A surface of the polymeric fabric may be modified by treatment with at least one of: plasma, UV light, and a solvent.
The thickness of the porous support layer may be between 10 μπι and 100 μηα.
A matrix material for the porous support layer may comprise at least one of: a natural polymer or a synthetic polymers, polysulfone, polyethersulfone, sulfonated polysulfone, poly(ether sulfone ketone), poly(ether ethyl ketone), poly(phthalazinone ether sulfone ketone), polyacrylonitrile, polypropylene, cellulose acetate, cellulose diacetate, cellulose triacetate, polyvinyl alcohol, polyvinyl pyrrole, polyvinyl pyrrolidone, polyethylene glycol, saponified polyethylene-vinyl acetate copolymer, triethylene glycol, diethylene glycol, polyaniline, and Pluronic F127.
A surface of the porous support layer may be modified by treatment with at least one of: plasma, UV light, and a solvent. Sizes of the nanomaterials may be in the range of less than 500 nm.
The nanomaterials may be in the form of at least one of: nanoparticles, nanofiber, nanowire. nanotube, and nanospheres. The nanomaterials may be at least one of: inorganics and organics.
The nanomaterials may be inorganics and comprise at least one of: salts of silver, gold, zinc,
copper, sodium, titanium, silicon, aluminum, zirconium, indium, tin, magnesium, calcium, their oxide, and their alloy.
The nanomaterials may be inorganics and may comprise at least one of: mesoporous materialss of the oxide of aluminum, titania, silicon, magnesium, strontium, beryllium, mesoporous molecular sieve, aluminosilicate, aluminophopsphate, and zeolite.
The nanomaterials may be organics and may comprise at least one of: dendrimers, graphite, graphene, carbon nanotubes, and fullerene.
A weight percentage of the nanomaterials by weight of the matrix polymer in at least one of the porous support layer and the thin film may range from 0.01 to 20 wt %.
The nanomaterials may be surface modified nanomaterials.
According to a second exemplary aspect, there is provided a method of forming a forward osmosis membrane comprising a porous support layer, a thin film formed on one side of the porous support layer, and nanomaterials dispersed in at least one of the porous support layer and the thin film, the method comprising forming the porous support layer by phase inversion of a polymer solution; forming the thin film by interfacial polymerization of monomers in a liquid on the porous support layer; and dispersing the nanomaterials in at least one of the porous support layer and the thin film.
Forming the porous support layer may comprise casting the porous support layer on a rotating drum.
Casting the porous support layer on the rotating drum may comprise casting the polymer
solution directly on a surface of the rotating drum while pulling a polymeric fabric into the polymer solution, thereby embedding the polymeric fabric in the polymer solution, wherein the polymeric fabric may be one selected from the group consisting of: a woven polymeric fabric screen and a non-woven polymeric fabric mesh.
Alternatively, casting the porous support layer on the rotating drum may comprise casting the polymer solution on a polymeric fabric laid on a surface of the rotating drum, wherein the polymeric fabric may be one selected from the group consisting of: a woven polymeric fabric screen and a non-woven polymeric fabric mesh.
The method may further comprise modifying a surface of the polymeric fabric by treatment with at least one of: plasma, UV light, and a solvent.
The method may further comprise modifying a surface of the porous support layer by treatment with at least one of: plasma, UV light, and a solvent.
Dispersing the nanomaterials in the porous support layer may comprise providing preformed nanomaterials in the polymer solution for the phase inversion. Alternatively, dispersing the nanomaterials in the porous support layer may comprise providing nanomaterial precursors in the polymer solution and in-situ forming the nanomaterials by chemical reactions during the phase inversion.
Dispersing the nanomaterials in the thin film may comprise providing preformed nanomaterials in the liquid.
Alternatively, dispersing the nanomaterials in the thin film may comprise providing
nanomaterial precursors in the liquid and in-situ forming the nanomaterials by chemical reactions during the interfacial polymerization.
The nanomaterial precursors may comprise at least one of: a metal alkoxide, titanium tetra isopropoxide (TTIP), Tetrabutyl titanate (TnBT), tetraethyl orthosilicate (TEOS), bis (triethoxy silyl) ethane (BTESE), phenyltriethoxysilane (PhTES), methyltriethoxysilane ( eTES), octyltriethoxysilane (OcTES), and octadecyltrimethoxysilane (OdTMS).
The method may further comprise forming a porous smooth layer formed on a side of the porous support layer opposite the side of the porous support layer on which the thin film may be polymerized.
The method may further comprise forming a hydrophilic polymeric layer on top of the thin film. The method may further comprise dispersing the nanomaterials in the hydrophilic polymeric layer.
The method may further comprise subjecting the porous support layer to a post-treatment process to reduce pore size.
Brief Description of the Drawings
In order that the invention may be fully understood and readily put into practical effect there shall now be described by way of non-limitative example only exemplary embodiments of the present invention, the description being with reference to the accompanying illustrative drawings.
In the drawings:
FIG. 1 is a schematic cross-sectional diagram of an exemplary forward osmosis membrane in flat sheet form;
FIG. 2. is a schematic cross-sectional diagram of an exemplary forward osmosis membrane in hollow fiber form; and
FIG. 3. is a schematic cross-sectional diagram of another exemplary forward osmosis membrane in hollow fiber form.
Detailed Description of the Exemplary Embodiments
Exemplary forward osmosis membranes 1 0, 20, 30 will be described with reference to FIGS. 1 to 3 below. Exemplary methods of forming the forward osmosis membrane will be described in Examples 1 to 8 below.
The forward osmosis membrane 10, 20, 30 is a thin film nanocomposite forward osmosis membrane and comprises a porous support layer 1 10, 210, 310, a thin film 120, 220, 320 formed on one side of the porous support layer 1 10, 210, 310 and nanomaterials 130, 230, 330 dispersed in at least one of the porous support layer 1 10, 210, 310 and the thin film 120, 220, 320. Thus, the nanomaterials 130, 230, 330 may be dispersed in only the porous support layer 210, 310 as shown in FIGS. 2 and 3, or in only the thin film, or in both the porous support layer 1 10 and the thin film 120 as shown in FIG. 1. The forward osmosis membrane may be in the form of a flat sheet 10, or in hollow fiber form 20, 30. The forward osmosis membrane may also be tubular.
The porous support layer 1 10, 210, 310 is generally formed by phase inversion of a polymer solution. This normally comprising the following steps: first, a solution of polymer and additives is prepared in an appropriate solvent or system of solvents and the porous support layer is then obtained by casting or spinning the polymer solution. Second, volatile components
of the solvent are partially vaporized at room temperature, and then the liquid film is immersed in a water bath or water/sol vents bath, giving rise to the phase inversion, which leaves the porous support layer in the form of a water-swollen gel of the polymer. The porous support layer, prepared by the phase inversion method, normally consist of a dense top layer 1 1 1 and a porous bottom layer 1 12 comprising a plurality of pores 1 13.
When preparing a porous support layer having a form of a flat sheet 1 10 as shown in FIG. 1 , polymer solution casting is used wherein a polymer solution comprising polymers (5 to 20 wt%) and solvents (80 to 95 wt%). and nanomaterials (0 to 20 wt%) is stirred continuously until the solution become homogenous. Then the polymer solution may be cast on a glass plate using a casting knife. The cast film is then immersed in a coagulation bath to complete the phase inversion. The membrane of porous support layer 1 10 can then be post-treated in a hot water bath. A porous support layer 210,3 10 having a hollow fiber form may be prepared by dry-wet spinning, in which the polymer solution same as that used for preparing a flat sheet is flowed through a ring nozzle of a spinneret while a bore fluid is flowed through an inner tube of the spinneret. Flow rates of the polymer solution and the bore solution are controlled by syringe pumps. A hollow fiber is produced and the resulting fiber is then passed through a controlled environment air gap before entering a coagulation bath. The hollow fiber filament is passed through a series of rollers in the coagulation bath. Subsequently, the hollow fiber is then passed through a washing bath. The fully formed hollow fiber can be continuously collected on a wind- up drum. Optionally, the porous support layer 1 10, 210, 3 10 can be subjected to a post-treatment process to reduce the pore size of the porous support layer 1 10, 210. 310. In the post-treatment process, the porous support layer 1 10, 210, 310 is immersed in a water bath at room temperature. The
water bath containing the porous support layer 1 10, 210, 310 is then gradually heated from ambient temperature to a temperature in the range of 60 to 95 °C, in about 20 to 30 minutes. The final temperature is kept constant for about 10 minutes. Subsequently, the water bath together with the membranes or porous support layer 1 10, 210, 310 is cooled drastically to below 60 °C by pouring cold water directly into the bath to freeze the porous structure.
The thin film 120, 220, 320 is general ly formed by interfacial polymerization of monomers in a polar or non-polar liquid on the porous support layer 1 10, 210, 310. The interfacial polymerization normally comprises the following steps: first, an aqueous solution of a first monomer and additives are allowed to cover the top of the porous support layer for some time. Then, an organic solution of a second monomer and additives are allowed to cover the top of the porous support layer for interfacial polymerization. The first monomer can be a polynucleophilic monomer, such as diaminobenzene, m-phenylenediamine, piperazine or piperazine derivative. The second monomer can be a polyelectrophilic monomer, such as a trimesoyl halide or a trimesoyl chloride. The polar liquid can be water. The non-polar liquid can be a linear hydrocarbon, a branched hydrocarbon, a cyclic hydrocarbon, naptha, heavy naptha, paraffin, isoparaffin, hexane, or their combinations thereof.
The nanomaterials 130, 230, 330 may be either preformed or formed in-situ. For example, when using preformed nanomaterials and dispersing them in the porous support layer, the preformed nanomaterials are provided in the polymer solution for the phase inversion. Similarly, preformed nanomaterials can be provided in the liquid of polymerization of the monomers for dispersal in the thin film. When forming the nanomaterials in-situ, for the porous support layer, this comprises providing nanomaterial precursors in the polymer solution and in-situ forming the nanomaterials in the porous support layer by chemical reactions. Similarly, for the thin film, nanomaterial precursors can be provided in the liquid of polymerization of the monomers and in-situ forming the nanomaterials in the thin film by chemical reactions during the interfacial
polymerization.
Various post-treatments can be employed to enhance water permeability, solute rejection, or fouling resistance of a formed forward osmosis membrane. For example, a forward osmosis membrane can be immersed in an acidic and/or basic solution to remove residual, unreacted acid chlorides and diamines which can improve the flux of the formed forward osmosis membrane. Additionally, heat treatment, or curing, can also be applied to promote contact between the polyamide film and polysulfone support or to promote cross-linking within the formed polyamide film. Finally, a forward osmosis membrane can be exposed to an oxidant such as chlorine, for example, sodium hypochlorite. Post-chlorination of a fully aromatic polyamide thin film forms chloramines as free chlorine reacts with pendant amine functional groups within the polyamide film. This can increase the negative charge density, by neutralizing positively-charged pendant amine groups, and the result is a more hydrophilic, negatively charged forward osmosis membrane with higher flux, salt rejection, and fouling resistance. In some examples, the membranes can further include a hydrophilic layer on top of the thin film to further decrease the membrane fouling. A hydrophilic and smooth membrane surface can be accomplished by applying an additional coating layer comprised of a water-soluble polymer such as polyvinyl alcohol (PVA), polyvinyl pyrrole (PVP), or polyethylene glycol (PEG) on the surface of a polyamide film.
The forward osmosis membrane may further comprise a porous smooth layer formed on a side of the porous support layer opposite the side of the porous support layer on which the thin film is polymerized. The porous smooth layer has pore sizes the same as that of microfiltration or ultrafiltration membranes. In this way, forming a "double-skinned" forward osmosis membrane is formed to decrease membrane fouling and internal concentration polarization in the porous support layer.
The present invention can be understood more readily with reference to the following examples.
Example 1 : Fabrication of a flat sheet porous support layer dispersed with nanomaterials by phase inversion using preformed nanoparticles
The porous support layer is prepared by dissolving 9 g polysulfone (PSf) beads in 96 mL of Ν,Ν-dimethylformamide (DMF) containing 0.5 % PVP and 0.3% Pluronic F127 in a glass bottle. 0.3 g nanoparticles (Degussa P25 Ti02 nanoparticles) are dispersed in the DMF before its addition to the PSf polymer. The solution is then agitated ultrasonically for 24 hours until complete dissolution, forming the cast solution which is then set aside for 2 days to eliminate air bubbles. The cast solution is then spread over a non-woven polyester (PET) fabric that is attached to a glass plate and wetted by the solvent of DMF. The glass plate is immediately immersed in tap water at room temperature to induce phase inversion. After 30 minutes, the non-woven PET fabric supported PSf nanocomposite porous support layer is removed from the water bath and separated from the glass plate. The porous support layer dispersed with nanocomposites is washed thoroughly with tap water and stored at 5° C.
Example 2: Fabrication of a flat sheet porous support layer dispersed with nanomaterials by phase inversion with in-situ formed nanoparticles
The porous support layer is prepared by dissolving 9 g polysulfone (PSf) beads in a mixed solvents of 80 mL of N-methyl pyrrolidone (NMP) and 80 mL of N,N-dimethylformamide (DMF) containing 0.5 % PVP in a glass bottle. 3.5 ml of tetraetnoxysilane and 0.1 ml of hydrochloric acid (precursors for S1O2 nanoparticie) are dispersed in the solvents of NMP and DMF before its addition to the PSf polymer. The solution is then agitated ultrasonically for 24 hours until complete dissolution, forming the cast solution which is then set aside for 2 days to eliminate air bubbles. The cast solution is then spread over a woven polyester (PET) fabric
screen that is attached to a glass plate and wetted by the solvents of DMF and NMP. The glass plate is immediately immersed in tap water at room temperature to induce phase inversion. After 30 minutes the woven PET fabric screen supported PSf nanocomposite porous support layer is removed from the water bath and separated from the glass plate. The porous support layer dispersed with nanomaterials is washed thoroughly with tap water and stored at 5° C.
Example 3: Fabrication of a flat sheet porous support layer of cellulose dispersed with nanomaterials by phase inversion with in-situ formed nanoparticles The cellulose porous support layer is prepared from cellulose triacetate using the phase inversion technique. The casting solution is prepared by dissolving 15 g cellulose triacetate (CA) (Mw 30,000 g mol"1, 39.8 wt % acetyl content) in 86 ml acetone/forrnamide (2: 1 ) mixture in a glass bottle. 3.5 ml of tetraethoxysilane and 0.1 ml of hydrochloric acid (precursors for Si02 nanoparticle) is dispersed in the acetone/formamide (2:1 ) mixture. The casting solution of 15 wt % CA is then spread over a commercial woven polyester fabric screen taped to a glass plate with the help of a casting blade. The glass plate is immediately immersed in distilled water at 4 °C to induce phase-inversion. After 30 min of gelation, the woven fabric reinforced cellulose acetate film is removed from the water bath and separated from the glass plate and wetted by the solvent of acetone. Finally, the resultant cellulose porous support layer dispersed with nanomaterials was annealed for 10 min in a water bath at the desired temperature at 60 °C, and stored in de-ionized water at 5 °C.
Example 4: Fabrication of a hollow fiber porous support layer dispersed with nanomaterials using preformed nanoparticles
Fabrication of the hollow fiber porous support layer is based on the dry-wet spinning technique. A homogenous dope solution is prepared in the same way as the cast solution in Example 1. The
dope solution is prepared by dissolving 9 g polysulfone (PSf) beads in 96 mL of N,N- dimethylformamide (DMF) containing 0.5 % PVP in a glass bottle. 0.3 g nanoparticles (Degussa P25 Ti02 nanoparticles) are dispersed in the DMF before its addition to the PSf polymer. The solution is then agitated ultrasonically for 24 hours until complete dissolution, forming the dope solution which is then set aside for 2 days to eliminate air bubbles. Afterward, the dope is extruded through a hollow fiber spinneret. Flow rates of the bore and dope solutions are controlled by syringe pumps. Both the bore liquid and the external coagulant are pure water, and the external coagulant temperature is controlled at 80°C. The air gap which is the distance between the tip of spinneret and the surface of the external coagulant is kept 10 cm. After coagulation in iced water, the resulting hollow fiber porous support layer dispersed with nanomaterials is wound up with a roller at a free falling velocity and rinsed with water to remove residual solvents. The hollw fiber is then annealed in a hot water bath at 80°C.
Example 5: Fabrication of a hollow fiber porous support layer dispersed with nanomaterials with in-situ formed nanoparticles
A homogenous dope solution is prepared in the same way as the cast solution in Example 1. The dope solution is prepared by dissolving 9 g polysulfone (PSf) beads in 96 mL of M,N- dimethylformamide (DMF) containing 0.5 % PVP in a glass bottle. 3.5 ml of tetraethoxysilane and 0.1 ml of hydrochloric acid (precursors for S1O2 nanoparticle) are dispersed in the DMF before its addition to the PSf polymer. The solution is then agitated ultrasonically for 24 hours until complete dissolution, forming the dope solution. Afterward, the dope is extruded through a hollow fiber spinneret. Flow rates of the bore and dope solutions are controlled by syringe pumps. Both the bore liquid and the external coagulant are pure water, and the external coagulant temperature is controlled at 80°C. The air gap which is the distance between the tip of spinneret and the surface of the external coagulant is kept 10 cm. After coagulation in iced water, the resulting hollow fiber porous support layer dispersed with nanomaterials is wound up
with a roller at a free falling velocity and rinsed with water to remove residual solvents. The hollw fiber is then annealed in a hot water bath at 80°C.
Example 6: Fabrication of a thin film dispersed with nanomaterials by interfacial polymerization using preformed nanoparticles
A porous support layer formed by any of the methods described in Examples 1 to 6 above is immersed in an aqueous solution of 3 wt% m-phenylenediamine (MPD) which contains other additives like triethyl amine (TEA), 10-champhor sulfonic acid (CSA), sodium lauryl sulfate (SLS), and isopropanol for 25 seconds. Excess MPD solution is removed from the surface of the porous support layer using an air knife. The aqueous MPD saturated porous support layer is then immersed in 0.15 wt% trimesoyl chloride (TMC) solution in isoparaffin at 30 °C for 60 seconds to form the thin film, where 0.1 wt of zeolite nanoparticles are suspended in the isoparaffin solution. The resulting membrane is cured in deionized water at 50 °C for 20 min, then rinsed with a 200 ppm NaOCl aqueous solution for 120 s, followed by rinsing for 60 s with a lOOOppm NaHSC aqueous solution, before a final heat curing step at 90 °C for 60 s. The final thin film nanocomposite forward osmosis membrane formed are rinsed thoroughly with deionized water and stored in deionized water at 4 °C. Example 7: Fabrication of thin film dispersed with nanomaterials bv interfacial polymerization with in-situ formed nanoparticles
A porous support layer formed by any of the methods described in Examples 1 to 6 above is immersed in an aqueous solution of 3 wt% m-phenylenediamine (MPD) which contains other additives like triethyl amine (TEA), 10-champhor sulfonic acid (CSA), sodium lauryl sulfate (SLS), and isopropanol for 25 seconds. Excess MPD solution is removed from the surface of the porous support layer using an air knife. The aqueous MPD saturated porous support layer is
then immersed in 0.15 wt% trimesoyl chloride (TMC) solution in isoparaffin containing phenyl triethoxy silane (PhTES) at 3wt% concentrations for 60 seconds to form the thin film. The resulting membrane is cured in deionized water at 50 °C for 20 min, then rinsed with a 200 ppm NaOCl aqueous solution for 120 s, followed by rinsing for 30 s with a l OOOppm NaHS03 aqueous solution, before a final heat curing step at 90 °C for 60 s. The final forward osmosis membrane formed is rinsed thoroughly with deionized water and stored in deionized water at 4 °C.
Finally, the thin film nanocomposite forward osmosis membrane is immersed in 50 wt% glycerol solution for another 24 h and then dried in air at room temperature.
Example 8: Fabrication of polyamide thin film by interfacial polymerization on top of a cellulose porous support layer
The cellulose porous support layer formed by the method described in Example 3 above is immersed in an aqueous solution of 3 wt% m-phenylenediamine (MPD) which contains other additives like triethyl amine (TEA), 10-champhor sulfonic acid (CSA), sodium lauryl sulfate (SLS), and isopropanol for 25 seconds. Excess MPD solution is removed from the surface of the porous support layer using an air knife. The aqueous MPD saturated porous support layer is then immersed in 0.15 wt% trimesoyl chloride (TMC) solution in isoparaffin at 30° C for 60 seconds to get thin film. The resulting membrane is cured in deionized water at 50 °C for 20 min, then rinsed with a 200 ppm NaOCl aqueous solution for 120 s, followed by rinsing for 60 s with a l OOOppm "NaHS03 aqueous solution, before a final heat curing step at 90 °C for 60 s. The final thin film nanocomposite forward osmosis membrane formed is rinsed thoroughly with deionized water and stored in deionized water at 4 °C.
In the case of hollow fiber forward osmosis membranes 20. 30, the thin film 220, 320 may be formed on either an external surface of the porous support layer 210 as shown in F1G.2, or an
internal surface of the porous support layer 31 0 as shown in FIG.3.
Whilst there has been described in the foregoing description exemplar}' embodiments of the present invention, it will be understood by those skilled in the technology concerned that many variations in details of design, construction and/or operation may be made without departing from the present invention.
Claims
1. A forward osmosis membrane comprising:
a porous support layer;
a thin film formed on one side of the porous support layer; and
nanomaterials dispersed in at least one of the porous support layer and the thin film.
2. The forward osmosis membrane of claim 1 , wherein the forward osmosis membrane comprises a form selected from the group consisting of: flat sheet, hollow fiber and tubular.
3. The forward osmosis membrane of claim 2, wherein the forward osmosis membrane is in hollow fiber form and the thin film is polymerized on an internal surface of the hollow fiber.
4. The forward osmosis membrane of claim 2, wherein the forward osmosis membrane is in hollow fiber form and the thin film is polymerized on an external surface of the hollow fiber.
5. The forward osmosis membrane of any preceding claim, wherein the thickness of the forward osmosis membrane is between 20 μτη and 400 μπ .
6. The forward osmosis membrane of any preceding claim, further comprising a porous smooth layer formed on a side of the porous support layer opposite the side of the porous support layer on which the thin film is polymerized.
7. The forward osmosis membrane of any preceding claim, further comprising a hydrophilic polymeric layer on top of the thin film.
8. The forward osmosis membrane of claim 7, wherein a matrix material for the hydrophilic polymeric layer comprises at least one of: polyvinyl alcohol, polyvinyl pyrrole, polyvinyl pyrrolidone, polyethylene glycol, saponified polyethylene-vinyl acetate copolymer, triethylene glycol, and diethylene glycol.
9. The forward osmosis membrane of claim 7 or 8, wherein the nanomaterials are dispersed in the hydrophilic layer.
10. The forward osmosis membrane of any preceding claim, wherein the thin film is configured to be permeable to water and relatively impermeable to impurities.
1 1 . The forward osmosis membrane of claim 10, wherein the thin film is configured to be relatively impermeable to impurities comprising at least one of: dissolved, dispersed, or suspended solids; monovalent, divalent, trivalent ions of sodium, potassium, magnesium, calcium, iron, aluminum ion, silicate, dissolved organics, and nonionized dissolved solids with a molecular weight of greater than about 200 Daltons.
12. The forward osmosis membrane of any preceding claim, wherein the thickness of the thin film is between 30 nm and 3 μιη.
13. The forward osmosis membrane of any preceding claim, wherein a matrix material for the thin film comprises at least one of: polyamide, aromatic polyamide, polypiperazine polyamide, polybenzimidazole, polyether, polyester, polyether-urea, polyvinyl alcohol, polyvinyl pyrrole, polyvinyl pyrrolidone, polyethylene glycol, saponified polyethylene- vinyl acetate copolymer, triethylene glycol, diethylene glycol, and a copolymer thereof.
14. The forward osmosis membrane of any preceding claim, wherein the porous support layer comprises a polymeric fabric selected from the group consisting of: a woven polymeric fabric screen and a non-woven polymeric fabric mesh.
15. The forward osmosis membrane of claim 14, wherein the thickness of the polymeric fabric is between 1 μιη and 200 μπι
16. The forward osmosis membrane of claim 14 or 15, wherein a material of the polymeric fabric comprises at least one of: a hydrophilic polymer, a hydrophobic polymer, polyester, polypropylene, acrylics, cotton, cellulose, and nylon.
1 7. The forward osmosis membrane of any one of claims 14 to 16, wherein a surface of the polymeric fabric is modified by treatment with at least one of: plasma, UV light, and a solvent.
18. The forward osmosis membrane of any preceding claim, wherein the thickness of the porous support layer is between 10 μτη and 100 μηι.
19. The forward osmosis membrane of any preceding claim, wherein a matrix material for the porous support layer comprises at least one of: a natural polymer or a synthetic polymers, polysulfone, polyethersulfone, sulfonated polysulfone, poly(ether sulfone ketone), poly(ether ethyl ketone), poly(phthalazinone ether sulfone ketone), polyacrylonitrile, polypropylene, cellulose acetate, cellulose diacetate, cellulose triacetate, polyvinyl alcohol, polyvinyl pyrrole, polyvinyl pyrrolidone, polyethylene glycol, saponified polyethylene- vinyl acetate copolymer, triethylene glycol, diethylene glycol, polyaniline, and Pluronic
F127.
20. The forward osmosis membrane of any preceding claim, wherein a surface of the porous support layer is modified by treatment with at least one of: plasma. UV light, and a solvent.
21. The forward osmosis membrane of any preceding claim, wherein sizes of the nanomaterials are in the range of less than 500 nm.
22. The forward osmosis membrane of any preceding claim, wherein the nanomaterials are in the form of at least one of: nanoparticles, nanofiber, nanowire, nanotube, and nanospheres.
23. The forward osmosis membrane of any preceding claim, wherein the nanomaterials are at least one of: inorganics and organics.
24. The forward osmosis membrane of claim 23, wherein the nanomaterials are inorganics and comprise at least one of: salts of silver, gold, zinc, copper, sodium, titanium, silicon, aluminum, zirconium, indium, tin, magnesium, calcium, their oxide, and their alloy.
The forward osmosis membrane of claim 23, wherein the nanomaterials are inorganics and comprise at least one of: mesoporous materialss of the oxide of aluminum, titania, silicon, magnesium, strontium, beryllium, mesoporous molecular sieve, aluminosilicate, aluminophopsphate, and zeolite.
26. The forward osmosis membrane of claim 23, wherein the nanomaterials are organics and comprise at least one of: dendrimers, graphite, graphene, carbon nanotubes, and fullerene.
27. The forward osmosis membrane of any preceding claim, wherein a weight percentage of the nanomaterials by weight of the matrix polymer in at least one of the porous support layer and the thin film ranges from 0.01 to 20 wt %.
28. The forward osmosis membrane of any preceding claim, wherein the nanomateriais are surface modified nanomateriais.
29. A method of forming a forward osmosis membrane comprising a porous support layer, a thin film formed on one side of the porous support layer, and nanomateriais dispersed in at least one of the porous support layer and the thin film, the method comprising:
forming the porous support layer by phase inversion of a polymer solution;
forming the thin film by interfacial polymerization of monomers in a liquid on the porous support layer; and
dispersing the nanomateriais in at least one of the porous support layer and the thin film.
30. The method of claim 29. wherein forming the porous support layer comprises casting the porous support layer on a rotating drum.
31. The method of claim 30, wherein casting the porous support layer on the rotating drum comprises casting the polymer solution directly on a surface of the rotating drum while pulling a polymeric fabric into the polymer solution, thereby embedding the polymeric fabric in the polymer solution, wherein the polymeric fabric is one selected from the group consisting of: a woven polymeric fabric screen and a non-woven polymeric fabric mesh.
32. The method of claim 30, wherein casting the porous support layer on the rotating drum comprises casting the polymer solution on a polymeric fabric laid on a surface of the rotating drum, wherein the polymeric fabric is one selected from the group consisting of: a woven polymeric fabric screen and a non-woven polymeric fabric mesh.
33. The method of any one of claims 31 or 32, further comprising modifying a surface of the polymeric fabric by treatment with at least one of: plasma, UV light, and a solvent.
34. The method of any one of claims 29 to 33, further comprising modifying a surface of the porous support layer by treatment with at least one of: plasma, UV light, and a solvent.
35. The method of any one of claims 29 to 34, wherein dispersing the nanomateriais in the porous support layer comprises providing preformed nanomateriais in the polymer solution for the phase inversion.
36. The method of any one of claims 29 to 34, wherein dispersing the nanomateriais in the porous support layer comprises providing nanomaterial precursors in the polymer solution and in-situ forming the nanomateriais by chemical reactions during the phase inversion.
37. The method of any one of claims 29 to 36, wherein dispersing the nanomateriais in the thin film comprises providing preformed nanomateriais in the liquid.
38. The method of any one of claims 29 to 36, wherein dispersing the nanomateriais in the thin film comprises providing nanomaterial precursors in the liquid and in-situ forming the nanomateriais by chemical reactions during the interfacial polymerization.
39. The method of any one of claims 36 and 38, wherein the nanomaterial precursors comprise at least one of: a metal alkoxide, titanium tetra isopropoxide (TTIP), Tetrabutyl titanate (TnBT), tetraethyl orthosilicate (TEOS), bis (triethoxy silyl) ethane (BTESE), phenyltriethoxysilane (PhTES), methyltriethoxysilane (MeTES), octyltriethoxysilane
(OcTES), and octadecyltrimethoxysilane (OdTMS).
40. The method of any one of claims 29 to 39, further comprising forming a porous smooth layer formed on a side of the porous support layer opposite the side of the porous support layer on which the thin film is polymerized.
41. The method of any one of claims 29 to 40, further comprising forming a hydrophilic polymeric layer on top of the thin film.
42. The method of any one of claims 29 to 41 , further comprising dispersing the nanomaterials in the hydrophilic polymeric layer.
43. The method of any one of claims 29 to 42, further comprising subjecting the porous support layer to a post-treatment process to reduce pore size.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| SG201100519 | 2011-01-24 | ||
| SG201100519-6 | 2011-01-24 |
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| WO2012102678A1 true WO2012102678A1 (en) | 2012-08-02 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/SG2012/000021 WO2012102678A1 (en) | 2011-01-24 | 2012-01-25 | A forward osmosis membrane |
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| CN113019150A (en) * | 2019-12-25 | 2021-06-25 | 戴念华 | Forward osmosis membrane with high chemical resistance |
| CN113856492A (en) * | 2021-10-26 | 2021-12-31 | 泰州九润环保科技有限公司 | Polyamide reverse osmosis membrane with porous support layer doped with molecular sieve |
| WO2023035555A1 (en) * | 2021-09-09 | 2023-03-16 | 北京宝盛通国际电气工程技术有限公司 | Forward osmosis membrane and preparation method therefor |
| CN117085524A (en) * | 2023-10-07 | 2023-11-21 | 安庆市长三角未来产业研究院 | High-flux nanofiltration membrane with non-woven fabric as supporting layer and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060226067A1 (en) * | 2005-04-07 | 2006-10-12 | Hydration Technologies Inc. | Asymmetric forward osmosis membranes |
| US20080149561A1 (en) * | 2006-12-05 | 2008-06-26 | Benjamin Chu | Articles Comprising a Fibrous Support |
| US20080237126A1 (en) * | 2006-10-27 | 2008-10-02 | Hoek Eric M V | Micro-and nanocomposite support structures for reverse osmosis thin film membranes |
| WO2008137082A1 (en) * | 2007-05-02 | 2008-11-13 | Yale University | Method for designing membranes for osmotically driven membrane processes |
| US20090272692A1 (en) * | 2008-05-05 | 2009-11-05 | Nanoh20 Inc. | Thin film membranes with additives for forward and pressure retarded osmosis |
| WO2011008549A2 (en) * | 2009-06-29 | 2011-01-20 | NanoH2O Inc. | Improved hybrid tfc ro membranes with nitrogen additives |
| WO2011069050A1 (en) * | 2009-12-03 | 2011-06-09 | Yale University | High flux thin-film composite forward osmosis and pressure-retarded osmosis membranes |
| WO2011133116A1 (en) * | 2010-04-22 | 2011-10-27 | Nanyang Technological University | Method of preparing a nanocomposite membrane and nanocomposite membranes prepared thereof |
| WO2012047282A2 (en) * | 2010-09-30 | 2012-04-12 | Porifera Inc. | Thin film composite membranes for forward osmosis, and their preparation methods |
-
2012
- 2012-01-25 WO PCT/SG2012/000021 patent/WO2012102678A1/en active Application Filing
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060226067A1 (en) * | 2005-04-07 | 2006-10-12 | Hydration Technologies Inc. | Asymmetric forward osmosis membranes |
| US20080237126A1 (en) * | 2006-10-27 | 2008-10-02 | Hoek Eric M V | Micro-and nanocomposite support structures for reverse osmosis thin film membranes |
| US20080149561A1 (en) * | 2006-12-05 | 2008-06-26 | Benjamin Chu | Articles Comprising a Fibrous Support |
| WO2008137082A1 (en) * | 2007-05-02 | 2008-11-13 | Yale University | Method for designing membranes for osmotically driven membrane processes |
| US20090272692A1 (en) * | 2008-05-05 | 2009-11-05 | Nanoh20 Inc. | Thin film membranes with additives for forward and pressure retarded osmosis |
| WO2011008549A2 (en) * | 2009-06-29 | 2011-01-20 | NanoH2O Inc. | Improved hybrid tfc ro membranes with nitrogen additives |
| WO2011069050A1 (en) * | 2009-12-03 | 2011-06-09 | Yale University | High flux thin-film composite forward osmosis and pressure-retarded osmosis membranes |
| WO2011133116A1 (en) * | 2010-04-22 | 2011-10-27 | Nanyang Technological University | Method of preparing a nanocomposite membrane and nanocomposite membranes prepared thereof |
| WO2012047282A2 (en) * | 2010-09-30 | 2012-04-12 | Porifera Inc. | Thin film composite membranes for forward osmosis, and their preparation methods |
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