DK201900343A1 - Forward osmosis membrane obtained by using sulfonated polysulfone (sPSf) polymer and production method thereof - Google Patents
Forward osmosis membrane obtained by using sulfonated polysulfone (sPSf) polymer and production method thereof Download PDFInfo
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- DK201900343A1 DK201900343A1 DKPA201900343A DKPA201900343A DK201900343A1 DK 201900343 A1 DK201900343 A1 DK 201900343A1 DK PA201900343 A DKPA201900343 A DK PA201900343A DK PA201900343 A DKPA201900343 A DK PA201900343A DK 201900343 A1 DK201900343 A1 DK 201900343A1
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- polysulfone
- spsf
- forward osmosis
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- osmosis membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 166
- 229920002492 poly(sulfone) Polymers 0.000 title claims abstract description 124
- 229920000642 polymer Polymers 0.000 title claims abstract description 106
- 238000009292 forward osmosis Methods 0.000 title claims abstract description 86
- 238000004519 manufacturing process Methods 0.000 title abstract description 20
- 239000002121 nanofiber Substances 0.000 claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
- 239000004952 Polyamide Substances 0.000 claims abstract description 28
- 229920002647 polyamide Polymers 0.000 claims abstract description 28
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 230000035699 permeability Effects 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 65
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 54
- 230000004907 flux Effects 0.000 claims description 28
- 239000002904 solvent Substances 0.000 claims description 27
- 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 claims description 25
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 24
- 230000008569 process Effects 0.000 claims description 21
- 238000006277 sulfonation reaction Methods 0.000 claims description 21
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 20
- 238000006243 chemical reaction Methods 0.000 claims description 20
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 19
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 19
- QWQONZVLXJGXHV-UHFFFAOYSA-N [chlorosulfonyloxy(dimethyl)silyl]methane Chemical compound C[Si](C)(C)OS(Cl)(=O)=O QWQONZVLXJGXHV-UHFFFAOYSA-N 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000012153 distilled water Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 13
- 238000012695 Interfacial polymerization Methods 0.000 claims description 10
- 238000001523 electrospinning Methods 0.000 claims description 9
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 238000007865 diluting Methods 0.000 claims description 3
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- 239000012429 reaction media Substances 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000012467 final product Substances 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims 3
- XTHPWXDJESJLNJ-UHFFFAOYSA-M chlorosulfate Chemical compound [O-]S(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-M 0.000 claims 1
- 238000007791 dehumidification Methods 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 21
- 239000010409 thin film Substances 0.000 abstract description 9
- 230000006872 improvement Effects 0.000 abstract description 6
- 229920000728 polyester Polymers 0.000 abstract description 3
- 239000010410 layer Substances 0.000 description 56
- 239000000243 solution Substances 0.000 description 54
- 239000013535 sea water Substances 0.000 description 11
- 239000012510 hollow fiber Substances 0.000 description 9
- 238000012512 characterization method Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000012527 feed solution Substances 0.000 description 5
- 239000010408 film Substances 0.000 description 4
- 229920001477 hydrophilic polymer Polymers 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000010612 desalination reaction Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 125000001174 sulfone group Chemical group 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- -1 aromatic acid halide Chemical class 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000004185 ester group Chemical group 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000009477 glass transition Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 125000000542 sulfonic acid group Chemical group 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- CNPVJWYWYZMPDS-UHFFFAOYSA-N 2-methyldecane Chemical compound CCCCCCCCC(C)C CNPVJWYWYZMPDS-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- 229920002284 Cellulose triacetate Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 208000029422 Hypernatremia Diseases 0.000 description 1
- 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 1
- 230000004913 activation Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 238000012668 chain scission Methods 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000010797 grey water Substances 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000011426 transformation method Methods 0.000 description 1
- 239000005051 trimethylchlorosilane Substances 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 235000020681 well water Nutrition 0.000 description 1
- 239000002349 well water Substances 0.000 description 1
- 238000009736 wetting Methods 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
-
- 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
- B01D61/0021—Forward osmosis or direct osmosis comprising multiple forward osmosis steps
-
- 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
-
- 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
- B01D71/56—Polyamides, e.g. polyester-amides
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
DESCRIPTIONDESCRIPTION
FORWARD OSMOSIS MEMBRANE OBTAINED BY USINGFORWARD OSMOSIS MEMBRANE OBTAINED BY USING
SULFONATED POLYSULFONE (sPSf) POLYMER AND PRODUCTION METHOD THEREOFSULFONATED POLYSULPHONE (sPSf) POLYMER AND PRODUCTION METHOD THEREOF
Field of the InventionField of the Invention
The present invention relates to producing a forward osmosis membrane by forming a nanofiber support membrane layer on a polyester nonwoven material using sulfonated polysulfone (sPSf) polymer, and by coating this sulfonated polysulfone nanofiber support membrane layer with a thin film composite of polyamide.The present invention relates to producing a forward osmosis membrane by forming a nanofiber support membrane layer on a polyester nonwoven material using sulfonated polysulfone (sPSf) polymer, and by coating this sulfonated polysulfone nanofiber support membrane layer with a thin film composite of polyamide.
Background of the InventionBackground of the Invention
Osmosis can be explained as movement/passage of solvents from a lower solute concentration to a higher solution concentration through a semi-permeable membrane without consuming energy. Although osmosis is a frequently encountered process in the nature, the most important part thereof is that it does not need any external driving power for passage of the solvent. Osmosis frequently takes place with water, which is the most common solvent in nature, and it can be expressed that, particularly in cells, when the cell is present in a solution with a higher concentration (e.g. sea water) than its own internal concentration, it will get more concentrated as the water therein will move out through the cell membrane. In other words, it can be said that it is diffusion of water from a less salty medium to a more salty medium without consuming energy.Osmosis can be explained as movement / passage of solvents from a lower solute concentration to a higher solution concentration through a semi-permeable membrane without consuming energy. Although osmosis is a frequently encountered process in nature, the most important part of it is that it does not need any external driving power for the passage of the solvent. Osmosis frequently takes place with water, which is the most common solvent in nature, and it can be expressed that, particularly in cells, when the cell is present in a solution with a higher concentration (eg sea water) than its own internal concentration, it will get more concentrated as the water therein will move out through the cell membrane. In other words, it can be said that it is diffusion of water from a less salty medium to a more salty medium without consuming energy.
This concept in nature can be used for controlled water filtration and this filtration process is called “forward osmosis process”. In this process, a forward osmosis (FO) membrane is used as the semi-permeable membrane, a draw solution containing a high salt concentration is used as the higher concentration medium and feed water is used as the lower concentration medium. The feed water may be water such as waste water, greywater, sea water or well water. Concentrated solutions of various salts such as chloride and sulfate salts can be used as the draw solution. The forward osmosis membrane serves here as a semi-permeable membrane and allows passage of the water while rejecting passage of the minerals and particles.This concept in nature can be used for controlled water filtration and this filtration process is called “forward osmosis process”. In this process, a forward osmosis (FO) membrane is used as the semi-permeable membrane, a draw solution containing a high salt concentration is used as the higher concentration medium and feed water is used as the lower concentration medium. The feed water may be water such as waste water, greywater, sea water or well water. Concentrated solutions of various salts such as chloride and sulfate salts can be used as the draw solution. The forward osmosis membrane serves here as a semi-permeable membrane and allows passage of the water while rejecting passage of the minerals and particles.
There are two basic characterization parameters for FO membranes. These are; the water flux (Jw) denoting the amount of water passing through a unit area and the reverse salt flux (Js/Jw) denoting the amount of salt in a unit weight which diffuses back from the draw solution to the feed solution per the amount of the water in a unit volume passing through the membrane. Here, Js denotes the amount of salt diffusing from the draw solution to the feed water. Reverse salt flux unit is given as g/L. In other words, it is the amount of salt in grams lost from the draw solution per a liter of the obtained product water. The higher the water flux and the lower the reverse salt flux of the FO membranes are, the better their performance will be.There are two basic characterization parameters for FO membranes. These are; the water flux (Jw) denoting the amount of water passing through a unit area and the reverse salt flux (Js / Jw) denoting the amount of salt in a unit weight which diffuses back from the draw solution to the feed solution per the amount of the water in a unit volume passing through the membrane. Here, Js denotes the amount of salt diffusing from the draw solution to the feed water. Reverse salt flux unit is given as g / L. In other words, it is the amount of salt in grams lost from the draw solution per liter of the obtained product water. The higher the water flux and the lower the reverse salt flux of the FO membranes are, the better their performance will be.
It is observed that the state-of-the-art membranes are either produced in a polymer-dense structure by using polymers such as cellulose triacetate or by applying a thin layer of dense polymer coating on a microporous support membrane. Phase transformation method is widely used to form this polymer dense structure or microporous support layer in the membranes.It is observed that the state-of-the-art membranes are either produced in a polymer-dense structure by using polymers such as cellulose triacetate or by applying a thin layer of dense polymer coating on a microporous support membrane. Phase transformation method is widely used to form this polymer dense structure or microporous support layer in the membranes.
It is known that in the recent years, as an alternative to these microporous support membranes, forward osmosis membranes are produced by forming a thin film composite by interfacial polymerization of aromatic acid halide with aromatic amine on a nanofiber support membrane. (Wang et al. (2005), US20130105395 A1)It is known that in recent years, as an alternative to these microporous support membranes, forward osmosis membranes are produced by forming a thin film composite by interfacial polymerization of aromatic acid halide with aromatic amine on a nanofiber support membrane. (Wang et al. (2005), US20130105395 A1)
There are two basic characterization parameters for FO membranes. These are; the water flux (Jw) denoting the amount of water passing through a unit area and the reverse salt flux (Js/Jw) denoting the amount of salt in a unit weight which diffuses back from the draw solution to the feed solution per the amount of the water in a unit volume passing through the membrane. Here, Js denotes the amount of salt diffusing from the draw solution to the feed water. Reverse salt flux unit is given as g/L. In other words, it is the amount of salt in grams lost from the draw solution per a liter of the obtained product water. The higher the water flux and the lower the reverse salt flux of the FO membranes are, the better their performance will be. In the prior art, an excess amount of reverse salt flux was observed in forward osmosis membranes and therefore water flux could not be increased to high levels.There are two basic characterization parameters for FO membranes. These are; the water flux (Jw) denoting the amount of water passing through a unit area and the reverse salt flux (Js / Jw) denoting the amount of salt in a unit weight which diffuses back from the draw solution to the feed solution per the amount of the water in a unit volume passing through the membrane. Here, Js denotes the amount of salt diffusing from the draw solution to the feed water. Reverse salt flux unit is given as g / L. In other words, it is the amount of salt in grams lost from the draw solution per liter of the obtained product water. The higher the water flux and the lower the reverse salt flux of the FO membranes are, the better their performance will be. In the prior art, an excess amount of reverse salt flux was observed in forward osmosis membranes and therefore water flux could not be increased to high levels.
Korean patent document no. KR20130078827, an application known in the art, discloses a hollow fiber type forward osmosis membrane and a method of manufacturing the same. This method of manufacturing the forward osmosis membrane comprises the steps of forming hollow fiber by simultaneously spinning a doping solution containing 0.5-5% by weight of sulfonated polysulfone-based polymer and a hollow fiber forming core solution to polymer, exposing the resultant product to the air, impregnating the product into a coagulating bath, and drying the product; and forming a polyamide layer on the hollow fiber by impregnating the hollow fiber in an aqueous solution containing multifunctional or alkylated aliphatic amine, washing the excessive amount of the aqueous solution, processing the hollow fiber with an organic solution containing multifunctional acid in order to generate interfacial polymerization between the compounds. The prepared hollow fiber is immersed in an aqueous solution containing phenylenediamine (MPD), and compression is applied to the surface layers in order to remove the excess amount of water. The hollow fiber is immersed in an organic solvent containing trimesoyl chloride (TMC) in order to form a polyamide layer. In order to form hollow membranes, spinning is performed on the polymer dope solution and a hollow-forming core solution for containing the sulfonated polysulfone-based polymer 0.5 to 5% by weight. The core solution includes a mixture of organic polar solvent (solvent A) and water (solvent B) with a mixing ratio of 4:6 to 9:1. One of the said organic polar solvents is dimethylacetamide (DMAc). Cross-sectional thicknesses of the hollow fibers are 30 to 250 micrometers.Korean patent document no. KR20130078827, an application known in the art, discloses a hollow fiber type forward osmosis membrane and a method of manufacturing the same. This method of manufacturing the forward osmosis membrane comprises the steps of forming hollow fiber by simultaneously spinning a doping solution containing 0.5-5% by weight of sulfonated polysulfone-based polymer and a hollow fiber forming core solution to polymer, exposing the resultant product to the air, impregnating the product into a coagulating bath, and drying the product; and forming a polyamide layer on the hollow fiber by impregnating the hollow fiber in an aqueous solution containing multifunctional or alkylated aliphatic amine, washing the excessive amount of the aqueous solution, processing the hollow fiber with an organic solution containing multifunctional acid in order to generate interfacial polymerization between the compounds. The prepared hollow fiber is immersed in an aqueous solution containing phenylenediamine (MPD), and compression is applied to the surface layers in order to remove the excess amount of water. The hollow fiber is immersed in an organic solvent containing trimesoyl chloride (TMC) in order to form a polyamide layer. In order to form hollow membranes, spinning is performed on the polymer dope solution and a hollow-forming core solution for containing the sulfonated polysulfone-based polymer 0.5 to 5% by weight. The core solution includes a mixture of organic polar solvent (solvent A) and water (solvent B) with a mixing ratio of 4: 6 to 9: 1. One of the said organic polar solvents is dimethylacetamide (DMAc). Cross-sectional thicknesses of the hollow fibers are 30 to 250 micrometers.
Korean patent document no KR20030088090, an application known in the art, discloses a method for producing sulfonated polysulfone for cation exchange membranes. This method comprises the steps of (a) causing reaction between chlorosulfonic acid and trimethylchlorosilane, (b) dissolving polysulfone in a solvent, (c) adding triethylamine to the polysulfone solution, and (d) mixing the complex sulfonation agent of the step (a) and the polysulfone of the step (c) to cause reaction therebetween.Korean patent document no KR20030088090, an application known in the art, discloses a method for producing sulfonated polysulfone for cation exchange membranes. This method comprises the steps of (a) causing reaction between chlorosulfonic acid and trimethylchlorosilane, (b) dissolving polysulfone in a solvent, (c) adding triethylamine to the polysulfone solution, and (d) mixing the complex sulfonation agent of the step (a ) and the polysulfone of the step (c) to cause reaction therebetween.
United States patent document no. US2013026091, an application known in the art, discloses a method for improving the performance of forward osmosis membrane. The document describes thin film composite (TFC) membranes for use in forward osmosis (FO) and pressure reduced osmosis (PRO) processes. This membrane is comprised of two layers: a composite layer combining a backing layer and a porous, polymer-based support into a single layer, and a rejection layer disposed on top of the composite layer. The rejection layer is formed from a thin coating of a hydrophilic polymer. The composite layer's surface may be coated with a pre-formed polymer or a polymer may be formed via in situ polymerization. One of the polymers which may be used is sulfonated polysulfone. Alternatively, a polymer such as polyamide may be polymerized in situ on the composite layer to form the rejection layer. For the in situ polymerization of polyamide, the composite layer is first soaked in an aqueous solution of m-phenylenediamine (m-PDA). Excess m-PDA is removed with a roller or an air knife. Subsequently, a solution of trimesoyl chloride (TMC) in an organic fluid, such as hexane or Isopar G, is applied to the top surface of the processed composite layer. Thus, interfacial polymerization occurs to yield a thin polyamide rejection layer on the composite layer. Thickness of this coating layer can be 1 micron or less (e.g., 0.2 micron).United States patent document no. US2013026091, an application known in the art, discloses a method for improving the performance of forward osmosis membrane. The document describes thin film composite (TFC) membranes for use in forward osmosis (FO) and pressure reduced osmosis (PRO) processes. This membrane is comprised of two layers: a composite layer combining a backing layer and a porous, polymer-based support into a single layer, and a rejection layer disposed on top of the composite layer. The rejection layer is formed from a thin coating of a hydrophilic polymer. The composite layer's surface may be coated with a pre-formed polymer or a polymer may be formed via in situ polymerization. One of the polymers which may be used is sulfonated polysulfone. Alternatively, a polymer such as polyamide may be polymerized in situ on the composite layer to form the rejection layer. For the in situ polymerization of polyamide, the composite layer is first soaked in an aqueous solution of m-phenylenediamine (m-PDA). Excess m-PDA is removed with a roller or an air knife. Subsequently, a solution of trimesoyl chloride (TMC) in an organic fluid, such as hexane or Isopar G, is applied to the top surface of the processed composite layer. Thus, interfacial polymerization occurs to yield a thin polyamide rejection layer on the composite layer. Thickness of this coating layer can be 1 micron or less (e.g., 0.2 micron).
Chinese patent document no. CN103977718, an application known in the art, discloses a high-water-flux forward-osmosis composite membrane and a production method thereof. This forward-osmosis composite membrane is a polysulfone-sulfonated polysulfone-inorganic filler blended/polyamide composite membrane. The method of producing this composite membrane comprises the steps of: blending a polymer with a modifier to form film casting liquid; performing non-solvent coagulating bath with water; preparing a polysulfone ultrafiltration membrane, airing the polysulfone membrane to dry the surface thereof, and growing a polyamide active layer by performing interfacial polymerization. One of the monomers used for forming polyamide layer is m-phenylenediamine (MPD). Additionally, the reaction oil phase contains trimesoyl chloride dissolved in hexane.Chinese patent document no. CN103977718, an application known in the art, discloses a high-water-flux forward-osmosis composite membrane and a production method thereof. This forward-osmosis composite membrane is a polysulfone-sulfonated polysulfone-inorganic filler blended / polyamide composite membrane. The method of producing this composite membrane comprises the steps of: blending a polymer with a modifier to form film casting liquid; performing non-solvent coagulating bath with water; preparing a polysulfone ultrafiltration membrane, airing the polysulfone membrane to dry the surface thereof, and growing a polyamide active layer by performing interfacial polymerization. One of the monomers used for forming polyamide layer is m-phenylenediamine (MPD). Additionally, the reaction oil phase contains trimesoyl chloride dissolved in hexane.
Chinese patent document no. CN102665882, an application known in the art, discloses a forward osmosis membrane of high flux for desalinating seawater and a method for manufacturing the same. This membrane is comprised of a nonwoven fabric layer, a hydrophilic polymer support layer, and a polyamide layer. The said hydrophilic polymer support layer includes 0.1 to 10% by weight of sulfonated polysulfone-based polymer. The polyamide layer is formed on the surface of the hydrophilic polymer support layer. During formation of the polyamide layer, polymerization reaction takes place between its components. The aqueous solution includes 2% by weight of phenylenediamine (MPD), 0.1% by weight of trimesoyl chloride (TMC) in organic solution (dissolved in ISOPAR agent).Chinese patent document no. CN102665882, an application known in the art, discloses a forward osmosis membrane of high flux for desalinating seawater and a method for manufacturing the same. This membrane is comprised of a nonwoven fabric layer, a hydrophilic polymer support layer, and a polyamide layer. The said hydrophilic polymer support layer includes 0.1 to 10% by weight of sulfonated polysulfone-based polymer. The polyamide layer is formed on the surface of the hydrophilic polymer support layer. During formation of the polyamide layer, polymerization reaction takes place between its components. The aqueous solution includes 2% by weight of phenylenediamine (MPD), 0.1% by weight of trimesoyl chloride (TMC) in organic solution (dissolved in ISOPAR agent).
Summary of the InventionSummary of the Invention
The objective of the present invention is to realize a forward osmosis membrane production method by using sulfonated polysulfone (sPSf) polymer, which enables performance improvements in parameters such as water permeability and reverse salt passage in production of thin film composite forward osmosis membranes.The objective of the present invention is to realize a forward osmosis membrane production method by using sulfonated polysulfone (sPSf) polymer, which enables performance improvements in parameters such as water permeability and reverse salt passage in production of thin film composite forward osmosis membranes.
Another objective of the present invention is to realize a forward osmosis membrane production method by using sulfonated polysulfone (sPSf) polymer, which enables to obtain forward osmosis membranes developed to be used in water and waste water treatment (e.g. desalination of sea water) and mining.Another objective of the present invention is to realize a forward osmosis membrane production method by using sulfonated polysulfone (sPSf) polymer, which enables to obtain forward osmosis membranes developed to be used in water and waste water treatment (eg desalination of sea water) and mining .
Another objective of the present invention is to realize a forward osmosis membrane production method by using sulfonated polysulfone (sPSf) polymer, which enables to obtain forward osmosis membranes developed to be used in energy sectors for energy production by means of pressure-retarded osmosis technology.Another objective of the present invention is to realize a forward osmosis membrane production method by using sulfonated polysulfone (sPSf) polymer, which enables to obtain forward osmosis membranes developed to be used in energy sectors for energy production by means of pressure-retarded osmosis technology.
Detailed Description of the InventionDetailed Description of the Invention
The method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer of the present invention, which enables to prevent problems of reverse salt flux and low water permeability observed in forward osmosis membranes, comprises the steps of - sulfonating the polysulfone polymer; o introducing the polysulfone (PSf) into the reaction vessel, o adding a solvent onto the polysulfone, o placing the mixture in a water bath and stirring, o obtaining the polysulfone solution, o passing inert gas over the solution after it becomes homogeneous, o diluting trimethylsilyl chlorosulfonate reagent solution with dichloromethane at a ratio of 1:1 by volume, o adding the resulting trimethylsilyl chlorosulfonate reagent solution into the previously obtained polysulfone solution, o proceeding until the reaction is completed, o adding the mixture obtained as a result of the reaction dropwise into alcohol thereby precipitating the polysulfone samples, o filtering the mixture, o washing the separated solid samples with alcohol and then drying, - producing nanofiber support membrane layer with sulfonated polysulfone; o allowing the sulfonated polysulfone to dry in a vacuum oven, o mixing the dehumidified polymer solution with dimethylacetamide (DMAc) solvent, o forming the nanofibers by means of electrospinning method; placing the polymer solution onto the collection layer via a nozzle, applying voltage on the nozzle tip, o applying heat treatment to improve mechanical strength of the produced nanofibers, o nanofibers accumulating on the collection layer in bulk forming the nanofiber support membrane layer structure, - allowing the nanofibers to rest in distilled water in order to increase wettability thereof, - coating the produced nanofiber support membrane layer surface with a thin polyamide film, o passing nitrogen gas through the distilled water in order to remove the oxygen dissolved therein, o adding MPD (m-phenylenediamine), pH adjusting agent (camphor sulfonic acid (CSA)), acid removal agent (triethylamine (TEA)) and surfactant (sodium dodecyl sulfate (SDS)) into distilled water and stirring to form the primary solution, o adding TMC (trimesoyl chloride) into hexane to form the secondary solution, o immersing the nanofiber support membrane layer first into the primary solution and then into the secondary solution, o forming the coating by means of the interfacial polymerization performed on the membrane surface, o subjecting the coating to heat treatment, - obtaining the forward osmosis membrane which is the final product.The method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer of the present invention, which enables to prevent problems of reverse salt flux and low water permeability observed in forward osmosis membranes, comprises the steps of - sulfonating the polysulfone polymer; o introducing the polysulfone (PSf) into the reaction vessel, o adding a solvent onto the polysulfone, o placing the mixture in a water bath and stirring, o obtaining the polysulfone solution, o passing inert gas over the solution after it becomes homogeneous, o diluting trimethylsilyl chlorosulfonate reagent solution with dichloromethane at a ratio of 1: 1 by volume, o adding the resulting trimethylsilyl chlorosulfonate reagent solution into the previously obtained polysulfone solution, o proceeding until the reaction is completed, o adding the mixture obtained as a result of the reaction dropwise into alcohol thereby precipitating the polysulfone samples, o filtering the mixture, o washing the separated solid samples with alcohol and then drying, - producing nanofiber support membrane layer with sulfonated polysulfone; o allowing the sulfonated polysulfone to dry in a vacuum oven, o mixing the dehumidified polymer solution with dimethylacetamide (DMAc) solvent, o forming the nanofibers by means of electrospinning method; placing the polymer solution onto the collection layer via a nozzle, applying voltage on the nozzle tip, o applying heat treatment to improve mechanical strength of the produced nanofibers, o nanofibers accumulating on the collection layer in bulk forming the nanofiber support membrane layer structure, - allowing the nanofibers to rest in distilled water in order to increase wettability thereof, - coating the produced nanofiber support membrane layer surface with a thin polyamide film, o passing nitrogen gas through the distilled water in order to remove the oxygen dissolved therein, o adding MPD (m-phenylenediamine), pH adjusting agent (camphor sulfonic acid (CSA)), acid removal agent (triethylamine (TEA)) and surfactant (sodium dodecyl sulfate (SDS)) into distilled water and stirring to form the primary solution, o adding TMC (trimesoyl chloride) into hexane to form the secondary solution, o immersing the nanofiber support membrane layer first into the primary solution and then into the secondary solution, o forming the coating by means of the interfacial polymerization performed on the membrane surface, o subjecting the coating to heat treatment, - obtaining the forward osmosis membrane which is the final product.
Within the scope of the invention, first of all sulfonation of the commercial polysulfone polymer is performed. Trimethylsilyl chlorosulfonate is used in sulfonation of commercial polysulfone samples. Sulfonation reactions performed by using trimethylsilyl chlorosulfonate take place in two steps: 1. In the first step, the isopropyl group (CH3-C-CH3) increases activation of the aromatic ring and as a result of this, substitution takes place in the aromatic ring in the dihydroxyl compound. In this first stage the ligated group is not sulfonic acid group but trimethylsilyl ester of sulfonic acid. Since the ester group does not cause an important change in the polarity of the polymer, it does not significantly change dissolution properties of the polymer. Therefore, no precipitation takes place in the reaction medium. Thus, undesired side reactions are prevented; equal ratio of sulfonation is enabled to occur in polymer chains; and furthermore, trimethylsilyl chlorosulfonate does not cause chain scissions due to its low reactivity compared to the other sulfonation agents. 2. In the second step, these ester groups are hydrolyzed and transformed into sulfonic acid groups.Within the scope of the invention, first of all sulfonation of the commercial polysulfone polymer is performed. Trimethylsilyl chlorosulfonate is used in sulfonation of commercial polysulfone samples. Sulfonation reactions performed by using trimethylsilyl chlorosulfonate take place in two steps: 1. In the first step, the isopropyl group (CH3-C-CH3) increases activation of the aromatic ring and as a result of this, substitution takes place in the aromatic ring in the dihydroxyl compound. In this first stage the ligated group is not sulfonic acid group but trimethylsilyl ester of sulfonic acid. Since the ester group does not cause an important change in the polarity of the polymer, it does not significantly change dissolution properties of the polymer. Therefore, no precipitation takes place in the reaction medium. Thus, undesired side reactions are prevented; equal ratio of sulfonation is enabled to occur in polymer chains; and furthermore, trimethylsilyl chlorosulfonate does not cause chain scissions due to its low reactivity compared to the other sulfonation agents. 2. In the second step, these ester groups are hydrolyzed and transformed into sulfonic acid groups.
In order to reach the desired degree of sulfonation, assays are conducted by taking necessary starting amounts from trimethylsilyl chlorosulfonate taking into consideration the number of the repeating units of the commercially available polysulfone homopolymer. In order to perform the reactions in a controlled medium, temperature of the reaction medium is aimed to be kept fixed at (4065°C) 15-40°C above the room temperature (25°C). For this purpose, solvents having relatively low boiling point within the range of 40-65 °C are preferred in the reactions. Accordingly, a solvent selected from the group comprising dichloromethane (DCM), chloroform, polysulfone or mixtures thereof is used. Thus, commercially available polysulfone samples are enabled to have a desired degree of sulfonation such that they will not yield undesirable side reactions.In order to reach the desired degree of sulfonation, assays are conducted by taking necessary starting amounts from trimethylsilyl chlorosulfonate taking into consideration the number of the repeating units of the commercially available polysulfone homopolymer. In order to perform the reactions in a controlled medium, temperature of the reaction medium is aimed to be kept fixed at (4065 ° C) 15-40 ° C above the room temperature (25 ° C). For this purpose, solvents having relatively low boiling point within the range of 40-65 ° C are preferred in the reactions. Accordingly, a solvent selected from the group comprising dichloromethane (DCM), chloroform, polysulfone or mixtures thereof is used. Thus, commercially available polysulfone samples are enabled to have a desired degree of sulfonation such that they will not yield undesirable side reactions.
Since sulfonated polymers having 40% sulfonation degree are used within the scope of the present invention, the commercial polysulfones are sulfonated such that their sulfonation degree is 40%. As an example to this sulfonation process, 40% sulfonation of 100 grams of the polysulfone sample can be described as follows. As the ratio of sulfonated polymer increases, the sizes of the vessels and materials that are used will also vary. - A solvent is added onto a polysulfone (PSf) sample (680 mL (900 gr) dichloromethane (DCM) is added onto 100 g polysulfone (PSf) sample) which is introduced into a 3 neck reaction vessel of 2L that is preferably made of glass such that polysulfone:solvent ratio will be 1:9 by mass (w/w), - then, the reaction vessel is placed into a water bath of 35°C and is kept there for a period of 12 to 24 hours and stirred in order for the polysulfone to be completely dissolved, - after the solution becomes completely homogenous, argon gas at fixed temperature (35°C) is passed over it, - in order to achieve a sulfonation degree of 40%, trimethylsilyl chlorosulfonate (TMSCS) is diluted with dichloromethane (DCM) such that trimethylsilyl chlorosulfonate (TMSCS):dichloromethane (DCM) ratio will be 2:1 by volume (v/v) (18.2 g trimethylsilyl chlorosulfonate is diluted with 10 mL DCM), - the resulting trimethylsilyl chlorosulfonate solution is added dropwise to the homogenous polysulfone solution which is obtained previously by the help of a dropping funnel, - the reaction is continued for 72-96 hours in order to obtain high yield, - sulfonation degree can be defined as the number of the repeating units in a polymer chain containing sulfone group. Dissolution characteristics of polymers may vary significantly depending on the increase of the sulfonation degree; for example, a polymer, which in the beginning can easily dissolve in a solvent, may hardly or do not at all dissolve in this solvent due to the sulfone groups included in its structure. Similarly, as the number of sulfone groups in a polymer chain increases, a solvent, which is non-solvent for it in the beginning, may start to dissolve this polymer. Therefore, this situation should be taken into consideration during purification of the sulfonated polymers from the solution via precipitation, and different non-solvent solvent types should be found and applied. The solution obtained at the end of this process is added dropwise under high stirring into an alcohol (selected from a group consisting of methanol, ethanol, isopropyl alcohol or mixtures thereof) suitable to the sulfonation degree and having a volume of 10-15 times more than the volume of the solution, and the sulfonated polysulfone samples are precipitated, - the solid polymer samples which are filtered through a filter paper or a Gooch crucible under vacuum are washed by a suitable alcohol and then dried in an oven at 55°C for 48 hours.Since sulfonated polymers having 40% sulfonation degree are used within the scope of the present invention, the commercial polysulfones are sulfonated such that their sulfonation degree is 40%. As an example to this sulfonation process, 40% sulfonation of 100 grams of the polysulfone sample can be described as follows. As the ratio of sulfonated polymer increases, the sizes of the vessels and materials that are used will also vary. - A solvent is added onto a polysulfone (PSf) sample (680 mL (900 gr) dichloromethane (DCM) is added onto 100 g polysulfone (PSf) sample) which is introduced into a 3 neck reaction vessel of 2L that is preferably made of glass such that polysulfone: solvent ratio will be 1: 9 by mass (w / w), - then, the reaction vessel is placed into a water bath of 35 ° C and is kept there for a period of 12 to 24 hours and stirred in order for the polysulfone to be completely dissolved, - after the solution becomes completely homogenous, argon gas at fixed temperature (35 ° C) is passed over it, - in order to achieve a sulfonation degree of 40%, trimethylsilyl chlorosulfonate (TMSCS) is diluted with dichloromethane (DCM) such that trimethylsilyl chlorosulfonate (TMSCS): dichloromethane (DCM) ratio will be 2: 1 by volume (v / v) (18.2 g trimethylsilyl chlorosulfonate is diluted with 10 mL DCM), - the resulting trimethylsilyl chlorosulfonate solution is added dropwise to the homogenous polysulfone solution which is obtained previously by the help of a dropping funnel, - the reaction is continued for 72-96 hours in order to obtain high yield, - sulfonation degree can be defined as the number of the repeating units in a polymer chain containing sulfone group. Dissolution characteristics of polymers may vary significantly depending on the increase of the sulfonation degree; for example, a polymer, which in the beginning can easily dissolve in a solvent, may hardly or do not at all dissolve in this solvent due to the sulfone groups included in its structure. Similarly, as the number of sulfone groups in a polymer chain increases, a solvent, which is non-solvent for it in the beginning, may start to dissolve this polymer. Therefore, this situation should be taken into consideration during purification of the sulfonated polymers from the solution via precipitation, and different non-solvent solvent types should be found and applied. The solution obtained at the end of this process is added dropwise under high stirring into an alcohol (selected from a group consisting of methanol, ethanol, isopropyl alcohol or mixtures thereof) suitable to the sulfonation degree and having a volume of 10-15 times more than the volume of the solution, and the sulfonated polysulfone samples are precipitated, - the solid polymer samples which are filtered through a filter paper or a Gooch crucible under vacuum are washed by a suitable alcohol and then dried in an oven at 55 ° C for 48 hours.
The stage of sulfonation of the polysulfone polymer is followed by the stage of production of the nanofiber support membrane layer by using this polymer. Sulfonated polymer having 40% sulfonation degree is allowed to rest in a vacuum oven overnight at 60-80°C for the last time before proceeding with the other membrane production steps. The solution containing 30% by weight of polymer after the polymer is dehumidified as above is mixed with DMAc solvent at 3040°C for 24-48 hours to be prepared. Electrospinning method is used in the scope of the invention in order to produce a nanofiber. The produced nanofibers are collected on a PET nonwoven support layer which is used as a membrane base. In the electrospinning process, the process conditions are arranged as follows: polymer feed rate: 4 ml/min, applied voltage: 27 kV, distance between the nozzle tip and the collection layer: 19 cm, and ambient temperature 25°C. However, electrospinning conditions may vary according to the machinery that is used and the process medium. In order to improve mechanical strength of the produced nanofibers, heat treatment is applied by allowing them to rest at a temperature of 180-190 °C for 3 hours. Heat post treatment is based on hardening and mechanically improving the polymers by subjecting them to a temperature near or above the glass transition temperature. These nanofibers are allowed to rest for 3 hours at a temperature near glass transition temperature of polysulfone polymer and heat post treatment is applied.The stage of sulfonation of the polysulfone polymer is followed by the stage of production of the nanofiber support membrane layer by using this polymer. Sulfonated polymer having 40% sulfonation degree is allowed to rest in a vacuum oven overnight at 60-80 ° C for the last time before proceeding with the other membrane production steps. The solution containing 30% by weight of polymer after the polymer is dehumidified as above is mixed with DMAc solvent at 3040 ° C for 24-48 hours to be prepared. Electrospinning method is used in the scope of the invention in order to produce a nanofiber. The produced nanofibers are collected on a PET nonwoven support layer which is used as a membrane base. In the electrospinning process, the process conditions are arranged as follows: polymer feed rate: 4 ml / min, applied voltage: 27 kV, distance between the nozzle tip and the collection layer: 19 cm, and ambient temperature 25 ° C. However, electrospinning conditions may vary according to the machinery that is used and the process medium. In order to improve mechanical strength of the produced nanofibers, heat treatment is applied by allowing them to rest at a temperature of 180-190 ° C for 3 hours. Heat post treatment is based on hardening and mechanically improving the polymers by subjecting them to a temperature near or above the glass transition temperature. These nanofibers are allowed to rest for 3 hours at a temperature near glass transition temperature of polysulfone polymer and heat post treatment is applied.
The characterization information related to this nanofiber formed by sulfonated polysulfone is provided in Table 1. Average diameter of the fibers is about 247 nm. Average pore diameter of the resulting nanofiber structure is measured as 1.562 μm. Bubble point flow rate is determined as 0.091 l/min. 67% porosity value of the obtained nanofiber support membrane is found to be high and favorable. Water permeability depending on high porosity is measured as 8820 l/m2.h.bar. Normally, sulfonation process favorably decreases contact angle values of the polysulfone polymer. However, this improvement is not exactly observed in the nanofiber structures due to the air bag effect. Hydrophilicity of the membranes is determined by the method of contact angle measurement. In this measurement method, one distilled water drop is dropped on the membranes, and the angle remaining between this water drop and the membrane surface is measured. The smaller this angle is, the more hydrophilic the membrane is. It is observed in the experimental studies conducted that while the contact angle of nanofibers produced with unsulfonated polymers is found to be around 122°, contact angles of the nanofibers produced with sulfonated polymers is found to be around 117°. An improvement of 5° is observed in the contact angles. Zeta potential value of the nanofiber support membrane layer is found to be lower than the value (pH 7.58.4) -50 mV. This result is favorable in terms of both hydrophilicity and fouling resistance of the membrane.The characterization information related to this nanofiber formed by sulfonated polysulfone is provided in Table 1. Average diameter of the fibers is about 247 nm. Average pore diameter of the resulting nanofiber structure is measured as 1,562 μm. Bubble point flow rate is determined as 0.091 l / min. 67% porosity value of the obtained nanofiber support membrane is found to be high and favorable. Water permeability depending on high porosity is measured as 8820 l / m2.h.bar. Normally, sulfonation process favorably decreases contact angle values of the polysulfone polymer. However, this improvement is not exactly observed in the nanofiber structures due to the air bag effect. Hydrophilicity of the membranes is determined by the method of contact angle measurement. In this measurement method, one distilled water drop is dropped on the membranes, and the angle remaining between this water drop and the membrane surface is measured. The smaller this angle is, the more hydrophilic the membrane is. It is observed in the experimental studies conducted that while the contact angle of nanofibers produced with unsulfonated polymers is found to be around 122 °, contact angles of the nanofibers produced with sulfonated polymers is found to be around 117 °. An improvement of 5 ° is observed in the contact angles. Zeta potential value of the nanofiber support membrane layer is found to be lower than the value (pH 7.58.4) -50 mV. This result is favorable in terms of both hydrophilicity and fouling resistance of the membrane.
Table 1 shows the data regarding the characterization of the nanofiber support membrane layer produced with sulfonated polysulfone.Table 1 shows the data regarding the characterization of the nanofiber support membrane layer produced with sulfonated polysulfone.
There are a total of three layers in the forward osmosis membranes of the present invention; namely PET nonwoven support layer, nanofiber support membrane layer produced on the former, and a rejection layer, i.e. active layer, produced on the membrane layer. After the nanofiber support membrane layer is produced with sulfonated polysulfone, it is proceeded with the process of thin film composite coating. Prior to this process, the sPSf nanofiber support membrane layer is kept in distilled water for 12-36 hours, preferably 24 hours, for a better wettability. Before preparation of the MPD solution (m-phenylenediamine), nitrogen gas is passed through the distilled water and the dissolved oxygen in the distilled water is removed from the medium. Following this process, MPD and the other auxiliary chemicals are added into the distilled water thereby producing theThere are a total of three layers in the forward osmosis membranes of the present invention; namely PET nonwoven support layer, nanofiber support membrane layer produced on the former, and a rejection layer, i.e. active layer, produced on the membrane layer. After the nanofiber support membrane layer is produced with sulfonated polysulfone, it is proceeded with the process of thin film composite coating. Prior to this process, the sPSf nanofiber support membrane layer is kept in distilled water for 12-36 hours, preferably 24 hours, for a better wettability. Before preparation of the MPD solution (m-phenylenediamine), nitrogen gas is passed through the distilled water and the dissolved oxygen in the distilled water is removed from the medium. Following this process, MPD and the other auxiliary chemicals are added into the distilled water thereby producing the
primary solution. TMC (trimesoyl chloride) is added into hexane and thereby the secondary solution is formed (Table 2). Firstly, the sPSf nanofiber support membrane layer is immersed in MPD solution and it is allowed to rest for 1 to 10 minutes, preferably 5 minutes, to enable a thorough wetting, and then excess MPD solution is removed by using a silicone or rubber roller. Subsequent to this process, sPSf membranes saturated with MPD are immersed in TMC solution for 0.5 - 3 minutes, preferably 2 minutes. Here, only the surface part of the membrane is reacted with TMC solution. Thus, a polyamide film layer is produced by interfacial polymerization on the surface of the sulfonated polysulfone (sPSf) nanofiber support membrane layer which is immersed in TMC solution after MPD solution. Following this interfacial polymerization process, the membrane is dried and subjected to heat treatment in an oven at 60-80 °C, preferably 70°C, for 5 to 10 minutes, preferably 7.5 minutes. Subsequent to all of the processes, the membrane is stored in distilled water until the characterization tests are conducted. As a result of the characterization tests, thickness of the produced active layer (polyamide film) is found to be 900-930 nanometers.primary solution. TMC (trimesoyl chloride) is added into hexane and thereby the secondary solution is formed (Table 2). Firstly, the sPSf nanofiber support membrane layer is immersed in MPD solution and it is allowed to rest for 1 to 10 minutes, preferably 5 minutes, to enable a thorough wetting, and then excess MPD solution is removed by using a silicone or rubber roller. Subsequent to this process, sPSf membranes saturated with MPD are immersed in TMC solution for 0.5 - 3 minutes, preferably 2 minutes. Here, only the surface part of the membrane is reacted with TMC solution. Thus, a polyamide film layer is produced by interfacial polymerization on the surface of the sulfonated polysulfone (sPSf) nanofiber support membrane layer which is immersed in TMC solution after MPD solution. Following this interfacial polymerization process, the membrane is dried and subjected to heat treatment in an oven at 60-80 ° C, preferably 70 ° C, for 5 to 10 minutes, preferably 7.5 minutes. Subsequent to all of the processes, the membrane is stored in distilled water until the characterization tests are conducted. As a result of the characterization tests, thickness of the produced active layer (polyamide film) is found to be 900-930 nanometers.
Table 2 shows the data regarding the characterization of the solutions used for producing active layer.Table 2 shows the data regarding the characterization of the solutions used for producing active layer.
* 0.1 gram TMC is dissolved in 1 L hexane.* 0.1 gram TMC is dissolved in 1 L hexane.
Water permeability and reverse salt flux performances of the forward osmosis membranes produced within the scope of the invention obtained by using 1 MWater permeability and reverse salt flux performances of the forward osmosis membranes produced within the scope of the invention obtained by using 1 M
draw solution are given in Table 3 in comparison to some of the best performance values given in the literature. As seen in Table 3, the membrane in this study has (65.7/313) L/m2 h water flux values in (FO/PRO) operation modes. In addition to these high water flux values, the produced membranes have shown very low reverse salt flux of 2.5/5.3 g/m2 h particularly in PRO mode. As it can also be seen in Table 3, performance values of the forward osmosis membranes of the present invention have been found to be better than those of all of the other membranes given in the comparison. It is seen that the membrane of the invention, due to its high salt retention, has the lowest reverse salt flux value among the other membranes. By using the advantage of these high performance properties, operating costs may be substantially reduced in forward osmosis processes. Additionally, this membrane, by means of its high water flux, has a great potential and advantages both in desalination of sea water and energy production via osmosis.draw solution are given in Table 3 in comparison to some of the best performance values given in the literature. As seen in Table 3, the membrane in this study has (65.7 / 313) L / m2 h water flux values in (FO / PRO) operation modes. In addition to these high water flux values, the produced membranes have shown very low reverse salt flux of 2.5 / 5.3 g / m2 h particularly in PRO mode. As it can also be seen in Table 3, performance values of the forward osmosis membranes of the present invention have been found to be better than those of all of the other membranes given in the comparison. It is seen that the membrane of the invention, due to its high salt retention, has the lowest reverse salt flux value among the other membranes. By using the advantage of these high performance properties, operating costs may be substantially reduced in forward osmosis processes. Additionally, this membrane, by means of its high water flux, has a great potential and advantages both in desalination of sea water and energy production via osmosis.
Table 3 is a representation of the performance comparisons regarding various membranes in the experimental studies conducted within the scope of the invention.Table 3 is a representation of the performance comparisons regarding various membranes in the experimental studies conducted within the scope of the invention.
After detection of forward osmosis performances of the membranes by widespread methods in the experimental studies conducted within the scope of the invention, performances thereof with real sea water were desired to be detected. To this end, sea water (15.77 mS/cm) was collected from the Bosphorus on February 2015, and it was used as feed solution. 2 M NaCl solution was used as the draw solution. The sea water, before being used, was subjected to microfiltration process in order to get rid of the suspended substances which may interfere and have negative impacts. Water flux was measured for both FO mode and PRO mode such that flow directions of the draw and feed solutions were opposite to each other. The system was operated for an average of 3 hours and average water flux value was derived.After detection of forward osmosis performances of the membranes by widespread methods in the experimental studies conducted within the scope of the invention, performances thereof with real sea water were desired to be detected. To this end, sea water (15.77 mS / cm) was collected from the Bosphorus on February 2015, and it was used as feed solution. 2 M NaCl solution was used as the draw solution. The sea water, before being used, was subjected to microfiltration process in order to get rid of the suspended substances which may interfere and have negative impacts. Water flux was measured for both FO mode and PRO mode such that flow directions of the draw and feed solutions were opposite to each other. The system was operated for an average of 3 hours and average water flux value was derived.
As can be seen in Table 4, the membrane of the present invention showed high water flux values for FO and PRO modes which are 15.11 and 49.44 LMH respectively. When sea water was used instead of distilled water, water fluxAs can be seen in Table 4, the membrane of the present invention showed high water flux values for FO and PRO modes which are 15.11 and 49.44 LMH respectively. When sea water was used instead of distilled water, water flux
values significantly decreased, because the osmotic pressure difference between the draw solution and the feed solution on both sides of the membrane decreased.values significantly decreased, because the osmotic pressure difference between the draw solution and the feed solution on both sides of the membrane decreased.
Table 4 is a representation of PRO and FO performances of TFC-FO membranes for sea water having reverse flow direction.Table 4 is a representation of PRO and FO performances of TFC-FO membranes for sea water having reverse flow direction.
The forward osmosis membrane production method of the present invention is realized for solving the problem of reverse salt flux and low water permeability typically observed in forward osmosis membranes. These two basic parameters, which constitute the biggest obstacle for widespread use of the forward osmosis membranes, are optimized thanks to the present invention.The forward osmosis membrane production method of the present invention is realized for solving the problem of reverse salt flux and low water permeability typically observed in forward osmosis membranes. These two basic parameters, which constitute the biggest obstacle for widespread use of the forward osmosis membranes, are optimized thanks to the present invention.
The present invention enables performance improvement in parameters such as water permeability and reverse salt passage in production of thin film composite forward osmosis membranes. The present invention is based on producing a forward osmosis membrane by forming a nanofiber support membrane layer on a polyester nonwoven material specifically using sulfonated polysulfone (sPSf) polymer, and by coating this sulfonated polysulfone nanofiber support membrane layer with a thin film composite of polyamide; and the performance improvements of this membrane structure. Sulfonation process is carried out by using trimethyl sulfonate. Electrospinning method is used for obtaining nanofibers from sulfonated polymers. In order to produce thin composite polyamide film coating, the nanofiber support membrane layer is first immersed in an aqueousThe present invention enables performance improvement in parameters such as water permeability and reverse salt passage in production of thin film composite forward osmosis membranes. The present invention is based on producing a forward osmosis membrane by forming a nanofiber support membrane layer on a polyester nonwoven material specifically using sulfonated polysulfone (sPSf) polymer, and by coating this sulfonated polysulfone nanofiber support membrane layer with a thin film composite of polyamide; and the performance improvements of this membrane structure. Sulfonation process is carried out by using trimethyl sulfonate. Electrospinning method is used for obtaining nanofibers from sulfonated polymers. In order to produce thin composite polyamide film coating, the nanofiber support membrane layer is first immersed in an aqueous
solution of MPD (m-phenylenediamine) solution, and then is processed with TMC (trimesoyl chloride) dissolved in hexane. Thus, polymerization process is performed on the membrane surface. sPSf nanofiber support membrane layers have a wide variety of areas of use such as water and waste water treatment, mining, and energy sectors including petroleum and natural gas. On the other hand, the forward osmosis membrane structure obtained in the scope of the present invention is designed particularly for desalination of sea water. Additionally, it is also suitable for energy production via pressure-retarded osmosis technology.solution of MPD (m-phenylenediamine) solution, and then is processed with TMC (trimesoyl chloride) dissolved in hexane. Thus, polymerization process is performed on the membrane surface. sPSf nanofiber support membrane layers have a wide variety of areas of use such as water and waste water treatment, mining, and energy sectors including petroleum and natural gas. On the other hand, the forward osmosis membrane structure obtained in the scope of the present invention is designed particularly for desalination of sea water. Additionally, it is also suitable for energy production via pressure-retarded osmosis technology.
The forward osmosis membrane of the present invention can be easily applied and can be used for providing water and treating waste water for both residential areas and the industry. Thus waste water is not only treated but it can also be recovered and used as a product.The forward osmosis membrane of the present invention can be easily applied and can be used for providing water and treating waste water for both residential areas and the industry. Thus waste water is not only treated but it can also be recovered and used as a product.
Claims (35)
- DK 2019 00343 A11. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer, which enables to prevent the problems of reverse salt flux and low water permeability observed in forward osmosis membranes, and is characterized by the steps of- sulfonating the polysulfone polymer;o introducing the polysulfone (PSf) into a reaction vessel, o adding a solvent onto the polysulfone, o placing the mixture in a water bath and stirring, o obtaining the polysulfone solution, o passing inert gas over the solution after it becomes homogeneous, o diluting trimethyl chlorosulfonate solution with dichloromethane, o adding the resulting trimethylsilyl chlorosulfonate solution into the previously obtained polysulfone solution, o proceeding until the reaction is completed, o adding the mixture obtained as a result of the reaction dropwise into alcohol thereby precipitating the polysulfone samples, o filtering the mixture, o washing the separated solid samples with alcohol and then drying,- producing nanofiber support membrane layer with sulfonated polysulfone;o allowing the sulfonated polysulfone to dry in a vacuum oven, o mixing the dehumidified polymer solution with dimethylacetamide (DMAc) solvent, o forming the nanofibers by means of electrospinning method;placing the polymer solution onto the collection layer via a nozzle, applying voltage on the nozzle tip, o applying heat treatment to improve mechanical strength of the produced nanofibers,DK 2019 00343 A1 o nanofibers accumulating on the collection layer in bulk forming the nanofiber support membrane layer structure,- allowing the nanofibers to rest in distilled water in order to increase wettability thereof,- coating the produced nanofiber support membrane layer surface with a thin polyamide film;o passing nitrogen gas through the distilled water in order to remove the oxygen dissolved therein, o adding MPD (m-phenylenediamine), pH adjusting agent, acid removal agent and a surfactant into distilled water and stirring to form the primary solution, o adding TMC (trimesoyl chloride) into hexane to form the secondary solution, o immersing the nanofiber support membrane layer first into the primary solution and then into the secondary solution, o forming the coating by means of the interfacial polymerization performed on the membrane surface, o subjecting the coating to heat treatment,- obtaining the forward osmosis membrane which is the final product.
- 2. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 1, characterized in that temperature of the reaction medium is kept fixed at (40-65°C) 15-40°C above the room temperature (25°C) in the step of sulfonating the polysulfone polymer.
- 3. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 1, characterized in that a solvent having a low boiling point within the range of 40-65°C is used in the step of sulfonating the polysulfone polymer.DK 2019 00343 A1
- 4. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 1 and 3, characterized in that a solvent selected from a group comprising dichloromethane (DCM), chloroform, polysulfone or mixtures thereof is used in the step of sulfonating the polysulfone polymer.
- 5. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 1, 3 or 4, characterized in that a solvent is added onto the polysulfone (PSf) sample which is located in a reaction vessel such that polysulfone:solvent ratio will be 1:9 by mass (w/w) in the step of sulfonating the polysulfone polymer.
- 6. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 1, characterized in that the glass reaction vessel is placed into a water bath of 35°C and is kept in the water bath for a period of 12 to 24 hours in order for the polysulfone to be completely dissolved in the step of sulfonating the polysulfone polymer.
- 7. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 1, characterized in that, after the solution becomes completely homogenous, argon gas at fixed temperature (35°C) is passed over it, in the step of sulfonating the polysulfone polymer.
- 8. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 1, characterized in that, in order to achieve a sulfonation degree of 40%, trimethylsilyl chlorosulfonate (TMSCS) is diluted with dichloromethane (DCM) such that trimethylsilyl chlorosulfonate (TMSCS):dichloromethane (DCM)DK 2019 00343 A1 ratio will be 2:1 by volume (v/v), in the step of sulfonating the polysulfone polymer.
- 9. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 1, characterized in that the trimethylsilyl chlorosulfonate solution obtained by diluting with DCM is added dropwise to the homogenous polysulfone solution, which is obtained previously, by the help of a dropping funnel, in the step of sulfonating the polysulfone polymer.
- 10. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 1, characterized in that the reaction is performed for a period of 72 - 96 hours in order to obtain high yield in the step of sulfonating the polysulfone polymer.
- 11. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 1, characterized in that, in the step of sulfonating the polysulfone polymer, the solution obtained as a result of the reaction is added dropwise under high stirring into an alcohol which has a volume of 10-15 times more than the volume of the solution and is selected from a group consisting of methanol, ethanol, isopropyl alcohol and mixtures thereof.
- 12. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 1, characterized in that, in the step of sulfonating the polysulfone polymer, the precipitates occurring after addition of the reaction solution into alcohol are filtered off from the mixture by the help of a filter paper.
- 13. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 1, characterized in that,DK 2019 00343 A1 in the step of sulfonating the polysulfone polymer, the precipitates occurring after addition of the reaction solution into alcohol are filtered off from the mixture by the help of a Gooch crucible under vacuum.
- 14. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 10, characterized in that, after filtration of the precipitates, washing the solid polymer samples with alcohol and drying in an oven at 55°C for 48 hours.
- 15. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 1, characterized in that, in the step of producing nanofiber support membrane layer with sulfonated polysulfone, the sulfonated polysulfone is allowed to rest in a vacuum oven overnight at 70°C for complete dehumidification thereof.
- 16. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 1, characterized in that, in the step of producing nanofiber support membrane layer with sulfonated polysulfone, a solution containing 30% by weight of polymer is prepared by stirring with DMAc solvent at 30-40°C for 24-48 hours.
- 17. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 1, characterized in that, in the step of forming the nanofibers by means of the electrospinning method, the support base on which the produced nanofibers are collected and which is used as a membrane base is selected from PET nonwoven material.
- 18. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 1, characterized in thatDK 2019 00343 A1 electrospinning technique is used in the stage of producing the nanofiber support membrane layer.
- 19. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 1, characterized in that, in the step of forming the nanofibers by means of the electrospinning method, the process conditions are selected as follows: polymer feed rate: 4 ml/min, applied voltage: 27 kV, distance between the nozzle tip and the collection layer: 19 cm, ambient temperature 25°C.
- 20. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 1, characterized in that, in the step of producing nanofiber support membrane layer with sulfonated polysulfone, heat post treatment is applied to the produced nanofibers by allowing them to rest at a temperature of 180-190°C for 3 hours in order to improve mechanical strength thereof.
- 21. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 1, characterized in that, in the step of coating the produced nanofiber support membrane layer surface with a thin polyamide film, the produced sulfonated polysulfone (sPSf) nanofiber support membrane layer is kept within MPD (mphenylenediamine) solution for 1-10 minutes.
- 22. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 21, characterized in that, in the step of coating the produced nanofiber support membrane layer surface with a thin polyamide film, the sulfonated polysulfone (sPSf) nanofiber support membrane layer taken out of MPD (mphenylenediamine) solution is kept in TMC (trimesoyl chloride) solution for 0.5 - 3 minutes.DK 2019 00343 A1
- 23. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 22, characterized in that, in the step of coating the produced nanofiber support membrane layer surface with a thin polyamide film, a polyamide film layer is produced by interfacial polymerization on the surface of the sulfonated polysulfone (sPSf) nanofiber support membrane layer which is immersed in TMC solution after MPD solution.
- 24. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 23, characterized in that, in the step of coating the produced nanofiber support membrane layer surface with a thin polyamide film, following the interfacial polymerization process, the membrane is dried and subjected to heat treatment in an oven at 60-80°C, preferably at 70°C, for 5 to 10 minutes, preferably 7.5 minutes.
- 25. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 1, characterized in that, in the step of preparing the primary solution, camphor sulfonic acid (CSA) is used as the pH adjusting agent.
- 26. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 1, characterized in that, in the step of preparing the primary solution, triethylamine (TEA) is used as the acid removal agent.
- 27. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 1, characterized in that, in the step of preparing the primary solution, sodium dodecyl sulfate (SDS) is used as the surfactant.DK 2019 00343 A1
- 28. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 1, characterized in that, in the step of coating the produced nanofiber support membrane layer surface with a thin polyamide film, the MPD solution used for forming a polyamide film as the active layer includes by weight of 2% MPD (mphenylenediamine), 2% triethylamine (TEA), 4% camphor sulfonic acid (CSA), 0.1% sodium dodecyl sulfate (SDS) with the rest being distilled water.
- 29. A method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to Claim 1, characterized in that, in the step of coating the produced nanofiber support membrane layer surface with a thin polyamide film, the TMC solution used for forming a polyamide film as the active layer includes 0.1% w/v TMC (0.1 grams of TMC in 1 liter hexane).
- 30. A forward osmosis membrane, which is produced by the method of producing forward osmosis membrane by using sulfonated polysulfone (sPSf) polymer according to any one of the preceding claims, and which is obtained by using sulfonated polysulfone (sPSf) polymer having 65.7/313 L/m2 h water flux values in forward osmosis (FO) and pressure-retarded osmosis (PRO) operation modes, and 2.5/5.3 g/m2 h reverse salt flux in PRO mode.
- 31. A forward osmosis membrane obtained by using sulfonated polysulfone (sPSf) polymer according to Claim 30, characterized by the active layer having an average thickness of 930 nanometers.DK 2019 00343 A1
- 32. A forward osmosis membrane obtained by using sulfonated polysulfone (sPSf) polymer according to Claim 30, characterized by the nanofibers having an average diameter of 247 nm.
- 33. A forward osmosis membrane obtained by using sulfonated polysulfone (sPSf) polymer according to Claim 30, characterized by the nanofiber support membrane layer having an average pore diameter of 1.562 pm.
- 34. A forward osmosis membrane obtained by using sulfonated polysulfone (sPSf) polymer according to Claim 30, characterized by the nanofiber support membrane layer having a porosity value of 67%.
- 35. A forward osmosis membrane obtained by using sulfonated polysulfone (sPSf) polymer according to Claim 30, characterized by the nanofiber support membrane layer having a water permeability of 8820 l/m2.h.bar.
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| TR2016/12129A TR201612129A2 (en) | 2016-08-26 | 2016-08-26 | ADVANCED OSMOS MEMBRANE OBTAINED BY USING SULPHONED POLYSULPHONE (sPSf) POLYMER AND THEIR PRODUCTION METHOD |
| TR2016/12129 | 2016-08-26 | ||
| PCT/TR2017/050334 WO2018063122A2 (en) | 2016-08-26 | 2017-07-24 | Forward osmosis membrane obtained by using sulfonated polysulfone (spsf) polymer and production method thereof |
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| CN113262643B (en) * | 2021-04-02 | 2022-05-03 | 蓝星（杭州）膜工业有限公司 | High-flux polyamide composite membrane and preparation method and application thereof |
| CN114307646A (en) * | 2021-12-31 | 2022-04-12 | 北京建筑大学 | Preparation method of high-water-flux composite forward osmosis membrane beneficial to permeation of driving agent |
| CN114392656B (en) * | 2022-02-28 | 2023-07-21 | 启成（江苏）净化科技有限公司 | Preparation method of multi-scale nanofiber reverse osmosis membrane |
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| WO2008137082A1 (en) * | 2007-05-02 | 2008-11-13 | Yale University | Method for designing membranes for osmotically driven membrane processes |
| WO2011060202A1 (en) | 2009-11-11 | 2011-05-19 | The Regents Of The University Of California | Nanostructured membranes for engineered osmosis applications |
| JP5596784B2 (en) | 2010-04-30 | 2014-09-24 | ウンジン ケミカル カンパニー，リミテッド | Forward osmosis membrane for seawater fresh water and method for producing the same |
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| KR101391653B1 (en) | 2011-12-30 | 2014-05-07 | 도레이케미칼 주식회사 | Hollow fiber type forward osmosis membrane and manufacturing method thereof |
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