WO2013016574A1 - Method to improve forward osmosis membrane performance - Google Patents
Method to improve forward osmosis membrane performance Download PDFInfo
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- WO2013016574A1 WO2013016574A1 PCT/US2012/048398 US2012048398W WO2013016574A1 WO 2013016574 A1 WO2013016574 A1 WO 2013016574A1 US 2012048398 W US2012048398 W US 2012048398W WO 2013016574 A1 WO2013016574 A1 WO 2013016574A1
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- WIPO (PCT)
- Prior art keywords
- layer
- membrane
- composite
- rejection
- polymer
- Prior art date
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- 239000012528 membrane Substances 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 37
- 238000009292 forward osmosis Methods 0.000 title abstract description 27
- 239000002131 composite material Substances 0.000 claims abstract description 41
- 229920000642 polymer Polymers 0.000 claims abstract description 31
- 230000008569 process Effects 0.000 claims abstract description 24
- 239000010409 thin film Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims description 30
- 239000003795 chemical substances by application Substances 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 10
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 10
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 10
- 229920001477 hydrophilic polymer Polymers 0.000 claims description 9
- 229920002492 poly(sulfone) Polymers 0.000 claims description 8
- 239000011159 matrix material Substances 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 6
- 238000011282 treatment Methods 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 5
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 229920006393 polyether sulfone Polymers 0.000 claims description 5
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 4
- 239000002759 woven fabric Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 230000015271 coagulation Effects 0.000 claims description 3
- 238000005345 coagulation Methods 0.000 claims description 3
- 229920001690 polydopamine Polymers 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000012530 fluid Substances 0.000 claims description 2
- 238000012986 modification Methods 0.000 claims description 2
- 230000004048 modification Effects 0.000 claims description 2
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 238000005728 strengthening Methods 0.000 claims description 2
- 229920006132 styrene block copolymer Polymers 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000007669 thermal treatment Methods 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 230000000379 polymerizing effect Effects 0.000 claims 1
- 238000002791 soaking Methods 0.000 claims 1
- 239000010410 layer Substances 0.000 abstract description 86
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 37
- 230000004907 flux Effects 0.000 abstract description 20
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002356 single layer Substances 0.000 abstract description 3
- 238000004804 winding Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 16
- 238000001223 reverse osmosis Methods 0.000 description 9
- 239000004744 fabric Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 229920002284 Cellulose triacetate Polymers 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 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 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 239000002357 osmotic agent Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 239000004734 Polyphenylene sulfide Substances 0.000 description 4
- 238000010276 construction Methods 0.000 description 4
- 229920001577 copolymer Polymers 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 230000003204 osmotic effect Effects 0.000 description 4
- 229920000069 polyphenylene sulfide Polymers 0.000 description 4
- 238000012695 Interfacial polymerization Methods 0.000 description 3
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000000835 fiber Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000004310 lactic acid Substances 0.000 description 2
- 235000014655 lactic acid Nutrition 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000009790 rate-determining step (RDS) Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 239000003021 water soluble solvent Substances 0.000 description 2
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 description 1
- 229920002633 Kraton (polymer) Polymers 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 229910019093 NaOCl Inorganic materials 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- -1 organic acid salts Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- HFQQZARZPUDIFP-UHFFFAOYSA-M sodium;2-dodecylbenzenesulfonate Chemical compound [Na+].CCCCCCCCCCCCC1=CC=CC=C1S([O-])(=O)=O HFQQZARZPUDIFP-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- 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
- B01D61/0022—Apparatus therefor
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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
- B01D69/10—Supported membranes; Membrane supports
-
- 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
- B01D67/0013—Casting processes
-
- 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
- B01D67/0016—Coagulation
-
- 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
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
- B01D69/1071—Woven, non-woven or net mesh
-
- 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
- B01D69/1213—Laminated layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
- B01D69/12—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
- B01D71/381—Polyvinylalcohol
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
- B01D71/421—Polyacrylonitrile
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/02—Hydrophilization
-
- 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
-
- 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
-
- 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
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
Definitions
- the invention relates to thin-film composite membranes for osmosis processes for removing contaminants from water and concentrating and diluting liquids containing a significant amount of water.
- Thin film composite membranes were originally developed for the reverse osmosis (RO) industry.
- the basic construction of these types of membranes consists of three layers: 1) a backing material for strength, 2) a porous polymer-based support formed on top of the backing material, and 3) a rejection layer on top of the porous support.
- Water flux is the rate of flow of water across the membrane.
- the rejection layer is also knows as the selection layer.
- the three layer membranes typically have a thickness of about 180 microns or more.
- this construction works well because the water flux depends only on the rejection layer, not on the underlying porous support.
- this construction is not ideal as a forward osmosis (FO) membrane, because in FO processes the water flux is defined by both the rejection layer as well as the two underlying layers (the support and backing layers).
- FO forward osmosis
- CTA-based FO membranes are typically based on cellulose triacetate (CTA).
- CTA-based FO membranes are available with either woven or non- woven backing materials.
- the woven-backed membranes show a distinct advantage over the non- woven backing due to a reduced diffusional barrier to osmotic agent migration within the support layer as well as the overall thinness of the membrane that can be produced.
- CTA-based FO membranes have the drawbacks that they are highly sensitive to pH and are slow from a water flux standpoint. It has been reported that thin film composites (TFC) membranes yield higher water fluxes and better salt rejection properties compared to the cellulose triacetate (CTA) membranes.
- TFC thin film composites
- CTA cellulose triacetate
- TFC thin film composite
- the membrane is comprised of two layers: a composite layer combining a backing layer and a porous, polymer-based support layer into a single layer, and a rejection layer disposed on top of the composite layer.
- the membrane of the invention exhibits high water flux values for FO processes, is durable, may be readily manufactured using typical membrane manufacturing processes, such as spiral winding and plate and frame processes, and has sufficient mechanical stability to handle the final membrane product.
- Described herein is a method for increasing the water flux performance of forward osmosis (FO) membranes by incorporating an embedded support material into the thin film composite (TFC) structure in order to facilitate a reduced thickness of the porous support layer while providing sufficient mechanical stability required by the final membrane product.
- FO forward osmosis
- TFC thin film composite
- the first layer is comprised of a single layer composite support layer that combines a backing layer and a porous polymer-based support. More particularly, the first layer is comprised of a backing material and a porous polymer-based support combined into one, substantially inseparable matrix.
- substantially inseparable matrix means that the backing material is essentially embedded within a matrix of the porous polymer-based support material, so that during normal use, the two components cannot be readily separated from one another.
- the backing material is a woven or non-woven fabric material.
- the material is a woven fabric material.
- the material may be made of any material known to one of ordinary skill in the art for use in osmotic membranes, particularly RO and/or FO membranes.
- the fabric be thin and provide open passageways between the fibers of the fabric.
- the second layer of the TFC membrane structure is a rejection layer.
- the second layer is a very thin rejection layer which is deposited on the first layer.
- the very thin rejection layer deposited onto the composite layer is the portion of the membrane which allows the passage of water while blocking other species such as salts and organic matter.
- Materials for the second layer are those known to those of ordinary skill in the art for use in rejection layers of RO, FO and other osmotic membranes.
- Also described herein is a two-step process to form a two-layer, high water flux, mechanically robust membrane by embedding a support structure within the porous support material during the fabrication process, followed by the addition of a thin second layer which serves as the rejection layer.
- the process forms a high water flux and mechanically robust membrane wherein the composite first layer is produced by combining the backing material and the porous polymer-based support into one, inseparable matrix. Then, a very thin rejection layer is deposited onto the composite first layer. The result is the formation of a two-layered TFC membrane (a thin, mechanically robust membrane that yields high water flux values).
- the process produces a membrane that is relatively thinner as compared with prior art FO membranes. The overall thinner membrane will minimize internal concentration polarization (ICP) and ultimately produce a higher flux membrane.
- the porous composite support layer acts as a support for this rejection layer and is comprised of two elements, the backing and the porous polymeric material.
- the backing that is incorporated into the porous polymeric matrix is preferably woven, but may be non- woven.
- the woven backing is preferred over a non-woven backing material for two key reasons: the woven backing yields membranes with sufficient mechanical integrity required for standard membrane manufacturing practices, and the woven backing simultaneously minimizes water transport resistance due to the inherent large openings in the backing structure.
- the immersion precipitation process such as described in U.S. Patent No. 3, 133, 132, (which is hereby incorporated herein in its entirety), may be employed.
- a membrane polymeric material particularly a hydrophilic polymer (e.g., polysulfone (PS), polyethersulfone (PES), sulfonated polysulfone, sulfonated polyethersulfone and mixtures thereof) is dissolved in water-soluble solvent (e.g., a non-aqueous solvent, such as N- methylpyrrolidone and the like) system to form a viscous solution.
- water-soluble solvent e.g., a non-aqueous solvent, such as N- methylpyrrolidone and the like
- a thin layer of the viscous solution is metered onto a casting drum surface followed by embedding a highly porous fabric into the viscous solution.
- a highly porous fabric examples of such fabrics are described in U.S. Patent No. 3,133,132 (which is hereby incorporated by reference). That is, the solution may be cast onto a rotating drum and an open fabric may be pulled into the solution so that the fabric is embedded into the solution.
- the liquid pre-membrane composite may then be quickly immersed into a coagulation bath (e.g., water bath) to solidify the viscous polymer solution.
- a coagulation bath e.g., water bath
- the coagulation bath causes the membrane components to coagulate and form the appropriate membrane characteristics (e.g., porosity, hydrophilic nature, asymmetric nature, and the like).
- the water contact causes the polymer in solution to become unstable and a layer of dense polymer precipitates on the surface very quickly. This layer acts as an impediment to water penetration further into the solution so the polymer beneath the dense layer precipitates much more slowly and forms a loose, porous matrix around the embedded fabric.
- the membrane can be washed and heat treated, if needed.
- the immersion/precipitation process may form a porous composite support layer with either macro-, ultra-, or nano- filtration sized pores.
- the composite support layer has its porosity controlled by both casting parameters (time, temperature, standard techniques, and the like) and by the choices of formulation components (solvent, ratio of solids of polymeric material to solvent solution, and the like).
- the rejection layer is formed from a thin coating of a hydrophilic polymer.
- a hydrophilic polymer may be coated with a pre-formed polymer or a polymer may be formed via in situ polymerization.
- polymers which may be used are, polyvinyl alcohol (PVA), polyacrylonitrile, sulfonated polysulfone, sulfonated polyethersulfone, sulfonated polyetherketone, sulfonated polyetheretherketone, sulfonated polyimides, sulfonated styrenic block copolymer, such as those available from Kraton, and the like, as well as mixtures of the foregoing.
- PVA polyvinyl alcohol
- polyacrylonitrile sulfonated polysulfone
- sulfonated polyethersulfone sulfonated polyetherketone
- polyetheretherketone sulfonated polyetheretherketone
- sulfonated polyimides sulfonated styrenic block copolymer
- Forming the rejection layer using pre-formed polymer may be accomplished using a variety of means, for example an extrusion head process, a
- a polymer such as polyamide may be polymerized in situ on the composite support layer to form the rejection layer.
- the composite support layer is first soaked in an aqueous solution of m-phenylenediamine (m-PDA). Excess m-PDA is removed from the surface with a roller or an air knife and a solution of trimesoyl chloride (TMC) in an organic fluid, such as hexane or Isopar G, is applied to the top surface of the amine-soaked composite support layer. Interfacial polymerization occurs to yield a thin polyamide rejection layer on the composite support layer. Coatings of thicknesses one (1) micron or less (e.g., 0.2 micron) are readily achievable.
- the result is the formation of a two-layered TFC membrane. It is a thin, mechanically robust membrane that yields high water flux values in FO processes.
- a thinner membrane is favored.
- the more open the backing material (i.e., the more spaces between the fibers) used to produce the membrane the better the functionality of the membrane.
- some applications of the membranes of the invention may require a thicker rather than a thinner membrane. It is the thickness of the backing material used in the first layer that tends to determine how thick the membrane will be. Moreover, if the backing material itself has variations in thickness, these variations may be accommodated by making the remainder of the membrane thicker.
- the thickness of the membrane be less than about
- the thickness of the membrane will be about 100 microns. In one exemplary embodiment, the thickness of the membrane is about 120 microns. In two other embodiments, the respective thicknesses of the membranes are 80 and 100.
- additional components can be incorporated into the first layer.
- pore-forming agents e.g., agents to optimize the porosity of the support layer, such as polyethylene glycol, organic acids, organic acid salts, mineral salts, amides, polymers, and the like, such as maleic acid, citric acid, lactic acid, lithium chloride, lithium bromide, polymers such as polyvinylpyrrolidone (PVP), polyethersulfone (PES), polyphenylene sulfide (PPS) and co-polymers of the foregoing polymers), hydrophilizing agents (e.g., PVP, polydopamine, polyvinylpyrrolidone (PVP), and copolymers of polyvinylpyrollidone and the like) and strengthening agents (e.g., agents to improve pliability and
- the resulting two-layered TFC membrane can be further treated with a hydrophilizing agent to increase water wettability (to make the membrane more hydrophilic).
- a hydrophilizing agent to increase water wettability (to make the membrane more hydrophilic).
- the first layer i.e., the composite layer incorporating the polymer-based support
- the first layer may be coated with a hydrophilizing agent on the surface of the first layer opposite the rejection layer.
- hydrophilizing agents that may be used are polydopamine, polyvinylpyrrolidone (PVP), and co-polymers of polyvinylpyrollidone and the like.
- the two-layer membrane can be further subjected to thermal treatments, chemical treatments (e.g., NaOCl followed by NaHSO 3 ) and surface modifications, such as grafting polyethylene glycol, to improve anti-fouling properties, water flux, salt rejection, long-term performance, and the like.
- thermal treatments e.g., thermal treatments, chemical treatments (e.g., NaOCl followed by NaHSO 3 ) and surface modifications, such as grafting polyethylene glycol, to improve anti-fouling properties, water flux, salt rejection, long-term performance, and the like.
- chemical treatments e.g., NaOCl followed by NaHSO 3
- surface modifications such as grafting polyethylene glycol
- Microporous polysulfone substrates were prepared from a casting solution of the formulation given in Table 1.
- the woven backing for the support membrane is incorporated into a thin layer of this casting solution to lend strength for manufacturing and end-used durability.
- This composite structure was then immersed into water which served as the non-solvent and caused the membrane to form by precipitating the polymer.
- pore forming agents such as polyethylene glycol, maleic acid, citric acid, lactic acid, lithium chloride, lithium bromide, polymers such as PVP, polyethersulfone (PES) and polyphenylene sulfide (PPS) and copolymers of the foregoing polymers, surfactants such as SLS and SDBS, non-solvents such as water, methanol, ethanol, glycerol, acetone and solvents such as DMAc, DMF and DMSO.
- pore forming agents such as polyethylene glycol, maleic acid, citric acid, lactic acid, lithium chloride, lithium bromide
- polymers such as PVP, polyethersulfone (PES) and polyphenylene sulfide (PPS) and copolymers of the foregoing polymers
- surfactants such as SLS and SDBS
- non-solvents such as water, methanol, ethanol, glycerol, acetone and solvents
- a rejection layer comprising a thin film of polyamide (PA) was deposited onto the membranes using the formulations provided in Table 2, which also contains the process variables that were used in combination with these formulas.
- PA polyamide
- Implementations of a two-layered TFC membrane are particularly useful in FO water treatment applications. Such applications may include osmotic-driven water purification and filtration, desalination of sea water, purification of contaminated aqueous waste streams, membrane bioreactors, and the like. However, implementations are not limited to uses relating to FO applications. Rather, any description relating to FO applications is for the exemplary purposes of this disclosure, and implementations may also be used with similar results in a variety of other applications. For example, two-layered TFC membrane implementations may also be used for PRO systems. The difference is that PRO generates osmotic pressure to drive a turbine or other energy- generating device. All that would be needed is to switch to feeding fresh water (as opposed to osmotic agent) and the salt water feed can be fed to the outside instead of source water (for water treatment applications).
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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EP12817939.7A EP2736959A4 (en) | 2011-07-26 | 2012-07-26 | Method to improve forward osmosis membrane performance |
KR1020147004910A KR20140059785A (en) | 2011-07-26 | 2012-07-26 | Method to improve forward osmosis membrane performance |
AU2012286754A AU2012286754A1 (en) | 2011-07-26 | 2012-07-26 | Method to improve forward osmosis membrane performance |
JP2014523025A JP2014526964A (en) | 2011-07-26 | 2012-07-26 | Improving forward osmosis membrane performance |
CN201280035467.9A CN103687895A (en) | 2011-07-26 | 2012-07-26 | Method to improve forward osmosis membrane performance |
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US201161511877P | 2011-07-26 | 2011-07-26 | |
US61/511,877 | 2011-07-26 |
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WO2013016574A1 true WO2013016574A1 (en) | 2013-01-31 |
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PCT/US2012/048398 WO2013016574A1 (en) | 2011-07-26 | 2012-07-26 | Method to improve forward osmosis membrane performance |
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US (1) | US20130026091A1 (en) |
EP (1) | EP2736959A4 (en) |
JP (1) | JP2014526964A (en) |
KR (1) | KR20140059785A (en) |
CN (1) | CN103687895A (en) |
AU (1) | AU2012286754A1 (en) |
WO (1) | WO2013016574A1 (en) |
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JP2016514039A (en) * | 2013-02-25 | 2016-05-19 | アクアポリン アー/エス | System for water extraction |
EP4201508A1 (en) | 2021-12-21 | 2023-06-28 | Gambro Lundia AB | Membrane coated with polydopamine and chondroitin and process for producing same |
CN117181016A (en) * | 2023-11-07 | 2023-12-08 | 深圳逗点生物技术有限公司 | Preparation method of porous composite filter material and porous composite filter material thereof |
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WO2015013358A1 (en) * | 2013-07-24 | 2015-01-29 | Hydration Systems, Llc | Method to improve forward osmosis membrane performance |
KR20150086122A (en) * | 2014-01-17 | 2015-07-27 | 삼성전자주식회사 | Membrane module for forward osmosis |
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Also Published As
Publication number | Publication date |
---|---|
CN103687895A (en) | 2014-03-26 |
KR20140059785A (en) | 2014-05-16 |
EP2736959A1 (en) | 2014-06-04 |
EP2736959A4 (en) | 2015-06-17 |
US20130026091A1 (en) | 2013-01-31 |
JP2014526964A (en) | 2014-10-09 |
AU2012286754A1 (en) | 2014-02-13 |
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