KR20190103668A - A method for preparing membrane having nano-sized pore with good chemical resistance - Google Patents
A method for preparing membrane having nano-sized pore with good chemical resistance Download PDFInfo
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- KR20190103668A KR20190103668A KR1020180024365A KR20180024365A KR20190103668A KR 20190103668 A KR20190103668 A KR 20190103668A KR 1020180024365 A KR1020180024365 A KR 1020180024365A KR 20180024365 A KR20180024365 A KR 20180024365A KR 20190103668 A KR20190103668 A KR 20190103668A
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- South Korea
- Prior art keywords
- nylon
- water
- membrane
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- 239000012528 membrane Substances 0.000 title claims abstract description 59
- 239000011148 porous material Substances 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000000126 substance Substances 0.000 title abstract description 16
- 239000002105 nanoparticle Substances 0.000 title 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 70
- 238000004519 manufacturing process Methods 0.000 claims abstract description 16
- 239000004065 semiconductor Substances 0.000 claims abstract description 6
- 229920001778 nylon Polymers 0.000 claims description 92
- 239000004677 Nylon Substances 0.000 claims description 89
- 239000004952 Polyamide Substances 0.000 claims description 36
- 229920002647 polyamide Polymers 0.000 claims description 36
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 32
- 229920000098 polyolefin Polymers 0.000 claims description 27
- 239000002904 solvent Substances 0.000 claims description 17
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 16
- 235000019253 formic acid Nutrition 0.000 claims description 16
- 229920003189 Nylon 4,6 Polymers 0.000 claims description 14
- 150000001412 amines Chemical class 0.000 claims description 14
- 150000001266 acyl halides Chemical class 0.000 claims description 10
- -1 polyethylene Polymers 0.000 claims description 10
- 150000003839 salts Chemical class 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 5
- 229920000573 polyethylene Polymers 0.000 claims description 5
- 229920002292 Nylon 6 Polymers 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 4
- 239000012498 ultrapure water Substances 0.000 claims description 4
- 238000004065 wastewater treatment Methods 0.000 claims description 4
- 229920002302 Nylon 6,6 Polymers 0.000 claims description 3
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000013535 sea water Substances 0.000 claims description 3
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 claims description 2
- 229920000571 Nylon 11 Polymers 0.000 claims description 2
- 229920000299 Nylon 12 Polymers 0.000 claims description 2
- 229920000305 Nylon 6,10 Polymers 0.000 claims description 2
- 238000010612 desalination reaction Methods 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 239000012466 permeate Substances 0.000 abstract description 8
- 239000010410 layer Substances 0.000 description 65
- 239000000243 solution Substances 0.000 description 32
- 230000000052 comparative effect Effects 0.000 description 14
- 229920000642 polymer Polymers 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- 238000012695 Interfacial polymerization Methods 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 3
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 3
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920002492 poly(sulfone) Polymers 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical group NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- ZWUBBMDHSZDNTA-UHFFFAOYSA-N 4-Chloro-meta-phenylenediamine Chemical compound NC1=CC=C(Cl)C(N)=C1 ZWUBBMDHSZDNTA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 150000004985 diamines Chemical class 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 229920001059 synthetic polymer Polymers 0.000 description 2
- XBTRYWRVOBZSGM-UHFFFAOYSA-N (4-methylphenyl)methanediamine Chemical compound CC1=CC=C(C(N)N)C=C1 XBTRYWRVOBZSGM-UHFFFAOYSA-N 0.000 description 1
- CBCKQZAAMUWICA-UHFFFAOYSA-N 1,4-phenylenediamine Chemical compound NC1=CC=C(N)C=C1 CBCKQZAAMUWICA-UHFFFAOYSA-N 0.000 description 1
- BAHPQISAXRFLCL-UHFFFAOYSA-N 2,4-Diaminoanisole Chemical compound COC1=CC=C(N)C=C1N BAHPQISAXRFLCL-UHFFFAOYSA-N 0.000 description 1
- VPMMJSPGZSFEAH-UHFFFAOYSA-N 2,4-diaminophenol;hydrochloride Chemical compound [Cl-].NC1=CC=C(O)C([NH3+])=C1 VPMMJSPGZSFEAH-UHFFFAOYSA-N 0.000 description 1
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical compound CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- UENRXLSRMCSUSN-UHFFFAOYSA-N 3,5-diaminobenzoic acid Chemical compound NC1=CC(N)=CC(C(O)=O)=C1 UENRXLSRMCSUSN-UHFFFAOYSA-N 0.000 description 1
- 239000004953 Aliphatic polyamide Substances 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229920001007 Nylon 4 Polymers 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 229920003231 aliphatic polyamide Polymers 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- JSYBAZQQYCNZJE-UHFFFAOYSA-N benzene-1,2,4-triamine Chemical compound NC1=CC=C(N)C(N)=C1 JSYBAZQQYCNZJE-UHFFFAOYSA-N 0.000 description 1
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1213—Laminated layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- 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
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- 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
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
- B01D69/105—Support pretreatment
-
- 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
- B01D69/106—Membranes in the pores of a support, e.g. polymerized in the pores or voids
-
- 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
-
- 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
- B01D71/26—Polyalkenes
-
- 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
- B01D71/26—Polyalkenes
- B01D71/261—Polyethylene
-
- 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
- B01D71/26—Polyalkenes
- B01D71/262—Polypropylene
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F5/00—Softening water; Preventing scale; Adding scale preventatives or scale removers to water, e.g. adding sequestering agents
- C02F5/08—Treatment of water with complexing chemicals or other solubilising agents for softening, scale prevention or scale removal, e.g. adding sequestering agents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/0283—Pore size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/20—Specific permeability or cut-off range
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/02—Non-contaminated water, e.g. for industrial water supply
- C02F2103/04—Non-contaminated water, e.g. for industrial water supply for obtaining ultra-pure water
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/32—Nature of the water, waste water, sewage or sludge to be treated from the food or foodstuff industry, e.g. brewery waste waters
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/346—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from semiconductor processing, e.g. waste water from polishing of wafers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Nanotechnology (AREA)
- Environmental & Geological Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
본 발명은 내화학성이 우수한 수처리용 멤브레인의 제조방법; 및 상기 방법으로 제조된 멤브레인에 관한 것이다.The present invention is a method for producing a membrane for water treatment excellent in chemical resistance; And to a membrane prepared by the above method.
내화학성이 높은 멤브레인은 대부분 기공 크기가 크고 나노급 불순물을 제거하기는 매우 어려워 상용화되어 있는 경우가 드물다. 일반적으로 상용화되어 있는 고내화학성 소재는 나일론, 폴리올레핀 및 폴리테트라플루오르에틸렌 등이 있으며, 필터로 제조할 경우 대부분 기공 크기가 100nm 이상인 것으로 보고되어 왔다. 또한, 일부 나일론 및 폴리에틸렌필터가 상용화되고 있지만 20-50nm 정도의 기공 크기를 가지며, 그 이하의 기공 크기를 형성하는 제조방법은 알려져 있지 않다. Most chemically resistant membranes are rarely commercialized because they have large pore sizes and are very difficult to remove nanoscale impurities. In general, commercially available high chemical resistance materials include nylon, polyolefin and polytetrafluoroethylene, and most of them have been reported to have a pore size of 100 nm or more when manufactured with a filter. In addition, although some nylon and polyethylene filters are commercially available, a production method having a pore size of about 20-50 nm and a pore size of less than that is not known.
현재는 나일론 계열 또는 폴리올레핀 계열과 같이 화학적 내구성이 우수한 고분자 계열의 멤브레인이 사용되고 있지만 아직까지 정제 순도가 높지 않은 것으로 알려져 있다. 폴리올레핀 멤브레인을 이용하는 경우, 불순물 중 금속 입자는 멤브레인의 기공 크기에 의해서 제거할 수가 있지만 유기물 응집 입자는 기공 크기뿐만 아니라 멤브레인 전체에서 입자와의 접촉 과정에서 흡착에 의해 제거되어야 하는데 폴리올레핀 자체의 극성기가 없어서 흡착에 의한 메커니즘으로 분리가 불가능한 단점이 있다. 나일론 멤브레인의 경우는 일반적으로 증기유도 상분리법(vapor-induced phase separation, VIPS)에 의해서 만들어지는데, 이와 같이 제조된 나일론 멤브레인은 나노급 기공을 갖도록 제조하기가 어려운 것으로 알려져 있다. 또한, 상기 나일론 멤브레인은 폴리올레핀 멤브레인에 비해서 극성기는 높지만 불순물과 단면에서의 접촉시간이 짧아서 유기물 응집 입자의 제거가 용이하지 않다는 한계가 있다.Currently, polymer membranes having excellent chemical durability, such as nylon or polyolefin series, are used. However, it is known that the purification purity is not high. In the case of using a polyolefin membrane, the metal particles in the impurities can be removed by the pore size of the membrane, but the organic aggregated particles must be removed by adsorption in contact with the particles not only in the pore size but also throughout the membrane. There is a disadvantage that the separation by the mechanism by adsorption is impossible. Nylon membranes are generally made by vapor-induced phase separation (VIPS), which is known to be difficult to fabricate with nano-grade pores. In addition, the nylon membrane has a higher polarity than the polyolefin membrane, but has a limitation in that the contact time between the impurities and the cross-section is short and thus it is not easy to remove the organic aggregated particles.
상기와 같은 배경 하에, 본 발명자들은 나일론 소재를 이용하여 작은 기공 크기에 비해 수투과유량이 높게 유지되는 나노급 멤브레인을 제조하고자 연구하였다. Under the above background, the present inventors have studied to prepare a nano-grade membrane using a nylon material in which the water permeation flow rate is kept high compared to a small pore size.
본 발명의 목적은 다공성 폴리올레핀 지지체에 나일론층 및 폴리아미드층을 형성하는 단계를 포함하는, 수처리용 나노 멤브레인의 제조방법을 제공하는 것이다. An object of the present invention is to provide a method for producing a nano-membrane for water treatment, comprising the step of forming a nylon layer and a polyamide layer on a porous polyolefin support.
본 발명의 다른 목적은 상기 제조방법으로 제조한 수처리용 나노 멤브레인을 제공하는 것이다. Another object of the present invention to provide a water treatment nano-membrane prepared by the above production method.
본 발명의 또 다른 목적은 상기 멤브레인을 포함하는 수처리용 장치; 및 수처리된 물의 제조방법을 제공하는 것이다. Still another object of the present invention is to provide a water treatment apparatus including the membrane; And it provides a method for producing water treated water.
본 발명의 제1양태는 제1 기공을 갖는 다공성 폴리올레핀 지지체에 나일론 함유 용액을 도포하는 제1단계; 상기 지지체를 비용매에 침지하여 나일론 함유 용액을 고형화함으로써, 지지체의 표면 또는 단면에 존재하는 기공을 채우는 나일론층을 형성하는 제2단계; 및 상기 나일론층이 형성된 지지체를 다관능성 아민 함유 용액에 침지한 후 다관능성 아실 할라이드 함유 용액에 침지하여 폴리아미드층을 형성하는 제3단계;를 포함하고, 수투과유량은 15kgf/㎠에서 70 내지 120L/㎡hr이고 염 제거율은 95% 이상이며, 표면에 상기 제1 기공보다 작은 크기의 제2 기공을 갖는 수처리용 멤브레인의 제조방법을 제공한다.A first aspect of the invention is a first step of applying a nylon containing solution to a porous polyolefin support having a first pore; Immersing the support in a non-solvent to solidify the nylon-containing solution to form a nylon layer filling the pores present on the surface or cross section of the support; And a third step of immersing the support on which the nylon layer is formed in a polyfunctional amine containing solution and then immersing in a polyfunctional acyl halide containing solution to form a polyamide layer. The water permeation flow rate is 70 to 15 kgf / cm 2. Provided is a method for producing a membrane for water treatment having 120 L / m 2 hr and a salt removal rate of 95% or more and having a second pore of a smaller size than the first pore on the surface.
본 발명의 제2양태는 제1 기공을 갖는 다공성 폴리올레핀 지지층; 지지층의 외면에 구비되어 지지층의 표면 또는 단면에 존재하는 공극을 채우는 나일론층; 및 지지층 및 나일론층을 덮도록 구비된 폴리아미드층;을 포함하고, 수투과유량은 15kgf/㎠에서 70 내지 120L/㎡hr이고 염 제거율은 95% 이상이고, 표면에 상기 제1 기공보다 작은 크기의 제2 기공을 갖는 수처리용 멤브레인을 제공한다.A second aspect of the invention provides a porous polyolefin support layer having a first pore; A nylon layer provided on an outer surface of the support layer to fill voids present on the surface or cross section of the support layer; And a polyamide layer provided to cover the support layer and the nylon layer; wherein the water permeation flow rate is 70 to 120 L / m 2 hr at 15 kgf / cm 2 and the salt removal rate is 95% or more and is smaller than the first pore on the surface. Provided is a membrane for water treatment having second pores.
본 발명의 제3양태는 제2양태에 따른 수처리용 멤브레인을 포함하는 수처리용 장치를 제공한다.A third aspect of the invention provides an apparatus for water treatment comprising the membrane for water treatment according to the second aspect.
본 발명의 제4양태는 제2양태에 따른 수처리용 멤브레인을 이용하여 수처리하는 단계를 포함하는, 수처리된 물의 제조방법을 제공한다.A fourth aspect of the invention provides a process for the preparation of water treated water, comprising the step of water treatment using the membrane for water treatment according to the second aspect.
이하 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
본 발명자들은 나일론 소재를 이용하여 나노급으로 작은 크기의 기공을 함유하는 폴리아미드 복합 멤브레인을 제조하기 위해 연구한 결과, 다공성 폴리올레핀 지지체에 나일론층과 폴리아미드층을 차례로 형성함으로써, 고형화된 나일론 용액과 폴리아미드가 지지체의 거대한 기공에 함유되어 기공의 부피를 감소시키면서 적어도 일부를 노출시킴으로써, 다공성 폴리올레핀 지지체의 기공에 비하여 작은 크기의 기공을 함유하면서도 투과유량과 염 제거율이 우수하고, 또한 내화학성이 뛰어나 유기 용매 등 화학물질에 의한 손상에 강한 멤브레인을 제조할 수 있음을 확인하였다. The inventors of the present invention have studied to prepare a polyamide composite membrane containing pores of small size at a nanoscale using a nylon material. As a result, a nylon layer and a polyamide layer are sequentially formed on a porous polyolefin support, thereby solidifying a nylon solution and The polyamide is contained in the large pores of the support to expose at least a portion of the pores to reduce the volume of the pores, so that the polyamide contains pores of a smaller size than the pores of the porous polyolefin support, and has excellent permeation flow rate and salt removal rate and excellent chemical resistance. It was confirmed that membranes resistant to damage by chemicals such as organic solvents can be prepared.
폴리에틸렌, 폴리프로필렌과 같은 폴리올레핀 계열의 멤브레인은 화학적 내구성이 우수하나 거대 기공 크기로 인해 정제순도가 높지 않은 문제점이 있다. 반면, 본 발명의 제조방법에서는, 폴리올레핀 지지체를 사용하여 강한 내구성과 내화학성을 확보함과 동시에, 나일론 용액 도포 후 이를 고형화하고 폴리아미드층을 추가로 형성함으로써, 지지체의 표면 또는 단면에 존재하는 거대 기공에 고형화된 나일론과 폴리아미드를 균일하게 채워 다공성 폴리올레핀 지지체의 제1 기공보다 작은 크기의 제2 기공을 갖는 멤브레인을 제조한 특징이 있다. 본 발명의 제조방법에 의할 경우, 나노 수준의 작은 기공을 함유하고, 수처리시 투과유량과 내화학성이 우수하면서도 폴리올레핀 지지체의 강한 내구성 또한 보유하는 멤브레인을 제조할 수 있으며, 이는 본 발명자들에 의해 최초로 규명되었다. Polyolefin-based membranes such as polyethylene and polypropylene have excellent chemical durability but have a problem in that the purification purity is not high due to the large pore size. On the other hand, in the production method of the present invention, by using a polyolefin support to secure a strong durability and chemical resistance, at the same time to solidify it after application of nylon solution and to further form a polyamide layer, the presence on the surface or cross section of the support The pores are uniformly filled with nylon and polyamide solidified to prepare a membrane having second pores of a smaller size than the first pores of the porous polyolefin support. According to the production method of the present invention, it is possible to produce a membrane containing nano-level small pores, excellent in permeation flow rate and chemical resistance during water treatment, but also retaining the strong durability of the polyolefin support. First identified.
본 발명의 제조방법은 제1 기공을 갖는 다공성 폴리올레핀 지지체에 나일론 함유 용액을 도포하는 제1단계를 포함한다. 상기 나일론 함유 용액은 나일론을 용매에 용해시켜 얻은 고분자 용액을 의미한다. The manufacturing method of the present invention includes a first step of applying a nylon-containing solution to a porous polyolefin support having a first pore. The nylon-containing solution means a polymer solution obtained by dissolving nylon in a solvent.
본 발명에서 나일론은 지방족 폴리아미드 계열의 합성 고분자 화합물을 총칭한다. 폴리아미드는 그 주쇄를 이루는 구조단위가 아미드 결합에 의해 연결된 합성고분자를 말하며, 아미드 결합으로 연결된 구조단위가 주로 지방족 단량체로 이루어진 폴리아미드를 나일론이라고 하고, 아미드 결합 중 최소한 85% 이상이 직접 방향족 고리와 연결된 폴리아미드를 아라미드라고 한다. 나일론은 나일론 m,n 및 나일론 m으로 분류할 수 있고, 상기 나일론 m,n은 디카복실산(dicarboxylic acid) 및 디아민(diamine)이 반응하여 아미드 결합을 형성하는 경우로 디아민에 포함된 탄소의 수를 m, 디카르복시산에 포함된 탄소의 수를 n으로 나타낸다. 또한, 아미드 결합은 아민기와 카복실기를 동시에 갖는 단량체로부터도 형성될 수 있으며 이 때 단량체에 포함된 탄소의 수를 m이라고 하면 이러한 폴리아미드는 나일론 m이라고 명명한다. 예컨대, 나일론 4,6은 하기의 구조를 갖는 화합물이다. In the present invention, nylon refers to synthetic polymer compounds of the aliphatic polyamide family. Polyamide refers to synthetic polymers in which the structural units constituting the main chain are linked by amide bonds. Polyamides composed mainly of aliphatic monomers linked by amide bonds are called nylon, and at least 85% of the amide bonds are directly aromatic rings. The polyamide connected with is called aramid. Nylon can be classified into nylon m, n and nylon m, and the nylon m, n is a case in which dicarboxylic acid and diamine react to form an amide bond, and the number of carbon contained in the diamine is determined. m and the number of carbon contained in dicarboxylic acid are represented by n. Also, the amide bond may be formed from a monomer having an amine group and a carboxyl group at the same time. When the number of carbons contained in the monomer is m, such polyamide is called nylon m. For example, nylon 4,6 is a compound having the following structure.
[나일론 4,6][Nylon 4,6]
본 발명에서, 나일론은 나일론 4,6, 나일론 6, 나일론 6,6, 나일론 6,9, 나일론 6,10, 나일론 6,12, 나일론 11, 나일론 12, 또는 이들의 혼합물일 수 있고, 구체적으로, 나일론 4,6일 수 있다. 특히, 본 발명에 따라 수투과유량은 15kgf/㎠에서 70 내지 120L/㎡hr이고, 염 제거율은 95% 이상인 멤브레인을 제조하기 위해서는, 나일론 4,6 또는 이를 포함하는 나일론 혼합물을 사용할 수 있다. 나일론 4,6은 나일론 6 또는 나일론 6,6 등의 다른 나일론 고분자들보다 극성이 더 높고, 본 발명의 제조방법에서 코팅층 형성에 이용되어 나노급 기공을 함유하는 멤브레인으로 제조될 수 있다. In the present invention, nylon may be nylon 4,6, nylon 6, nylon 6,6, nylon 6,9, nylon 6,10, nylon 6,12, nylon 11, nylon 12, or mixtures thereof, and specifically It can be 4,6 nylon. In particular, according to the present invention, in order to prepare a membrane having a water permeation flow rate of 70 to 120 L / m 2 hr at 15 kgf / cm 2 and a salt removal rate of 95% or more, nylon 4,6 or a nylon mixture including the same may be used. Nylon 4,6 has a higher polarity than other nylon polymers such as nylon 6 or nylon 6,6, and can be used to form a coating layer in the manufacturing method of the present invention to form a membrane containing nano-grade pores.
본 발명에서, 나일론 4,6을 다른 나일론 고분자와 혼합하여 사용할 경우, 최종 생성되는 멤브레인의 평균 기공 크기 및 수투과유량 측면을 고려하여 나일론 혼합물의 비율을 조절할 수 있으며, 구체적으로 나일론 4,6을 주성분으로 하고 혼합되는 다른 나일론 고분자는 나일론 4,6에 비해 적은 양으로 사용할 수 있다. In the present invention, when nylon 4,6 is used in combination with other nylon polymers, the ratio of the nylon mixture can be adjusted in consideration of the average pore size and water permeation flow rate of the resulting membrane, specifically, nylon 4,6 Other nylon polymers that are blended and blended can be used in smaller amounts compared to nylon 4,6.
본 발명에서 용매(solvent)는 약 60℃ 이하에서 나일론을 용해시킬 수 있는 용매를 의미한다. 본 발명에서, 용매는 나일론의 종류에 따라 해당 분야에서 일반적으로 사용 가능한 것으로 알려져 있는 것을 적절하게 선택하여 사용할 수 있다. 구체적으로, 나일론을 용해시켜 고분자 용액을 얻기 위한 용매로 포름산, 또는 포름산과 물의 혼합용매를 사용할 수 있다. 즉, 상기 제1단계의 용매는 99% 이상의 시약 등급의 포름산, 또는 물이 함유된 희석된 포름산을 사용하는 것이 가능하지만, 이에 제한되지 않는다. 포름산 외에, 아세트산과 같은 유기산을 포름산과 혼합하여 용매로 사용할 수 있고, 구체적으로 수투과유량은 15kgf/㎠에서 70 내지 120L/㎡hr이고, 염 제거율은 95% 이상인 본 발명의 멤브레인 제조를 위해 다른 유기산과 혼합하지 않고 포름산을 단독으로 사용할 수 있다. In the present invention, a solvent means a solvent capable of dissolving nylon at about 60 ° C. or less. In the present invention, the solvent may be appropriately selected from those known to be generally usable in the art according to the type of nylon. Specifically, formic acid or a mixed solvent of formic acid and water may be used as a solvent for dissolving nylon to obtain a polymer solution. That is, the solvent of the first step may be, but is not limited to, using formic acid of 99% or more reagent grade, or diluted formic acid containing water. In addition to formic acid, an organic acid such as acetic acid may be mixed with formic acid and used as a solvent. Specifically, the water flux is 70 to 120 L / m 2 hr at 15 kgf / cm 2, and the salt removal rate is 95% or more. Formic acid can be used alone without mixing with an organic acid.
고분자 용액 중 나일론과 포름산의 혼합 비율은 1 : 4 내지 1 : 12, 1 : 6 내지 1 : 12, 1 : 8 내지 1 : 12, 또는 1 : 9일 수 있으나, 이에 제한되는 것은 아니다. The mixing ratio of nylon and formic acid in the polymer solution may be 1: 4 to 1:12, 1: 6 to 1:12, 1: 8 to 1:12, or 1: 9, but is not limited thereto.
나일론과 포름산의 혼합 비율이 1 : 4 미만일 경우 나일론 농도가 높아서 계면중합할 경우에 지지층의 저항이 너무 커서 투과유량이 크게 감소하며, 1 : 12 초과일 경우 나일론 농도가 너무 낮아서 멤브레인 형성이 어렵고, 폴리아미드 계면중합층이 잘 형성되지 않는 문제가 있다.When the mixing ratio of nylon and formic acid is less than 1: 4, the nylon concentration is high, so that the permeation flow rate is large because the resistance of the support layer is too large in the case of interfacial polymerization. There is a problem that the polyamide interfacial polymerization layer is hardly formed.
상기 용매에 나일론을 용해하여 본 발명의 고분자 용액으로 사용하며, 고분자 용액 중 나일론의 농도는 5 내지 20중량%, 5 내지 17중량%, 5 내지 15중량%, 5 내지 12중량%, 또는 10중량%일 수 있으나, 이에 제한되는 것은 아니다. Nylon is dissolved in the solvent to be used as the polymer solution of the present invention, and the concentration of nylon in the polymer solution is 5 to 20% by weight, 5 to 17% by weight, 5 to 15% by weight, 5 to 12% by weight, or 10% by weight. %, But is not limited thereto.
본 발명의 다공성 폴리올레핀 지지체는 폴리에틸렌, 폴리프로필렌, 또는 이들의 조합으로 이루어질 수 있으나, 이에 제한되는 것은 아니다. 상기 지지층은 당업계에 공지된 상업화된 다공성 지지체를 구입하여 사용할 수 있다. 상기 지지체는 다공성 고분자 필름의 형태로 성형이 가능한 것을 사용하며, 특히 본 발명에서는 목적하는 내화학성과 투과유량을 나타내는 수처리용 멤브레인의 제조를 위해 나일론 등과 같은 고분자 용액으로 코팅 처리하여도 손상을 받지 않는 폴리올레핀계 지지체를 사용하였다.The porous polyolefin support of the present invention may be made of polyethylene, polypropylene, or a combination thereof, but is not limited thereto. The support layer may be purchased by using a commercially available porous support known in the art. The support may be molded in the form of a porous polymer film, and in particular, the present invention is not damaged even when coated with a polymer solution such as nylon in order to prepare a membrane for water treatment having a desired chemical resistance and permeate flow rate. Polyolefin-based support was used.
또한, 본 발명의 제조방법에서 고분자 용액에 나일론을 용해시키기 위해 포름산 용매를 사용하는데, 폴리올레핀은 포름산에 안정한 특성을 가지므로 강한 내구성을 가지는 멤브레인을 제조할 수 있다. 본 발명의 다공성 폴리올레핀 지지체는 소수성으로 0.02㎛ 이상 거대한 크기의 제1기공을 포함할 수 있다. 따라서 나노급 불순물은 제거하기가 어려운 문제점이 있다. In addition, the formic acid solvent is used to dissolve the nylon in the polymer solution in the production method of the present invention, since the polyolefin has a stable property in formic acid, it is possible to produce a membrane having a strong durability. The porous polyolefin support of the present invention may include hydrophobic first pores having a large size of 0.02 μm or more. Therefore, there is a problem that is difficult to remove nano-grade impurities.
본 발명의 제조방법은 상기 지지체를 비용매에 침지하여 나일론 함유 용액을 고형화함으로써, 지지체의 표면 또는 단면에 존재하는 기공을 채우는 나일론층을 형성하는 제2단계를 포함한다. The manufacturing method of the present invention includes a second step of forming a nylon layer filling the pores present on the surface or cross section of the support by solidifying the nylon-containing solution by immersing the support in a non-solvent.
본 발명에서 비용매(non-solvent)는 고분자의 융점 또는 액체의 비점까지 고분자를 용해시키거나 팽윤시키지 못하는 용매로서, 나일론의 비용매로 물, 알콜, 에테르, 헥산 등을 포함하며, 구체적으로 물을 사용할 수 있다. 상기 비용매는 나일론 함유 용액 중에 포함된 나일론의 고형화를 유도할 수 있고, 고형화된 나일론은 지지체의 표면 상에서 기공을 채우거나, 지지체의 표면에서 불연속적인 층을 구비할 수 있다. In the present invention, non-solvent is a solvent that does not dissolve or swell the polymer to the melting point of the polymer or the boiling point of the liquid, and includes non-solvent of nylon as water, alcohol, ether, hexane, and the like. Can be used. The nonsolvent may lead to solidification of the nylon contained in the nylon containing solution, and the solidified nylon may fill pores on the surface of the support, or may have a discontinuous layer at the surface of the support.
예컨대, 상기 고형화된 나일론은 지지체의 기공 내에 구비되어 거대 기공의 부피를 감소시키면서, 지지체 표면의 적어도 일부를 노출시키도록 구비될 수 있다. 또한, 상기 나일론 함유 용액으로 상기 지지체 내부로 함침되어 지지체의 표면 및 단면 내에 고정되도록 구비될 수 있다. 따라서, 멤브레인을 사용하는 과정에서 상기 나일론층이 유실되지 않고, 상기 지지체의 표면 및 단면 상의 기공을 안정적으로 감소시킬 수 있으므로 상기 멤브레인의 투과유량 및 염 제거율이 향상될 수 있다.For example, the solidified nylon may be provided in the pores of the support to expose at least a portion of the support surface while reducing the volume of the macropores. In addition, the nylon-containing solution may be impregnated into the support to be fixed in the surface and the cross section of the support. Therefore, the nylon layer is not lost in the process of using the membrane, and since the pores on the surface and the cross section of the support can be stably reduced, the permeation flow rate and the salt removal rate of the membrane can be improved.
본 발명의 제조방법은 상기 나일론층이 형성된 지지체를 다관능성 아민 함유 용액에 침지한 후 다관능성 아실 할라이드 함유 용액에 침지하여 폴리아미드층을 형성하는 제3단계를 포함한다. 상기 제3단계는 다관능성 아민과 다관능성 아실 할라이드가 중합반응하여 폴리아미드를 형성하는 단계일 수 있다. The production method of the present invention includes a third step of forming a polyamide layer by immersing the support on which the nylon layer is formed in a solution containing polyfunctional amine and then immersing in a solution containing polyfunctional acyl halide. The third step may be a step in which the polyfunctional amine and the polyfunctional acyl halide are polymerized to form a polyamide.
상기 다관능성 아민은 메타페닐렌디아민, 파라페닐렌디아민, 1,3,6-벤젠트리아민, 4-클로로-1,3-페닐렌디아민, 6-클로로-1,3-페닐렌디아민, 3-클로로-1,4-페닐렌 디아민, 3,5-디아미노 벤조산, 2,4-디아미노톨루엔, 2,4-디아미노아니솔, 아미돌 및 크실렌디아민으로 이루어진 군에서 선택된 1종 이상일 수 있고, 구체적으로 메타페닐렌디아민일 수 있으나, 이에 제한되는 것은 아니다. 상기 다관능성 아실 할라이드는 2 내지 3개의 카복실산 할라이드를 갖는 방향족 화합물로서, 예컨대 트리메조일클로라이드, 이소프탈로일클로라이드 또는 테레프탈로일클로라이드일 수 있고, 구체적으로 트리메조일클로라이드일 수 있으나, 이에 제한되는 것은 아니다. The polyfunctional amine is metaphenylenediamine, paraphenylenediamine, 1,3,6-benzenetriamine, 4-chloro-1,3-phenylenediamine, 6-chloro-1,3-phenylenediamine, 3 At least one member selected from the group consisting of -chloro-1,4-phenylene diamine, 3,5-diamino benzoic acid, 2,4-diaminotoluene, 2,4-diaminoanisole, amidol and xylenediamine And, specifically, may be metaphenylenediamine, but is not limited thereto. The polyfunctional acyl halide is an aromatic compound having 2 to 3 carboxylic acid halides, for example, may be trimezoyl chloride, isophthaloyl chloride or terephthaloyl chloride, and specifically may be trimezoyl chloride, but is not limited thereto. It is not.
상기 제3단계는 나일론층이 형성된 지지체를 다관능성 아민 함유 용액과 다관능성 아실 할라이드 함유 용액에 각각 30초 내지 5분, 30초 내지 3분, 30초 내지 2분, 또는 1분 동안 침지시키는 것일 수 있다. The third step is to immerse the support on which the nylon layer is formed in the solution containing the polyfunctional amine and the polyfunctional acyl halide for 30 seconds to 5 minutes, 30 seconds to 3 minutes, 30 seconds to 2 minutes, or 1 minute, respectively. Can be.
상기 다관능성 아민 함유 용액 중 다관능성 아민의 함량은 0.1 중량% 내지 5중량%일 수 있고, 구체적으로, 0.5 내지 5 중량%, 1 내지 4중량%, 1 내지 2중량%, 또는 1.5중량%일 수 있으나, 이에 제한되는 것은 아니다.The content of the polyfunctional amine in the polyfunctional amine-containing solution may be 0.1% by weight to 5% by weight, specifically, 0.5 to 5% by weight, 1 to 4% by weight, 1 to 2% by weight, or 1.5% by weight. May be, but is not limited thereto.
또한, 다관능성 아실 할라이드 함유 용액 중 다관능성 아실 할라이드의 함량은 0.005 중량% 내지 1 중량%일 수 있고, 구체적으로, 0.01 내지 0.5 중량%, 0.01 내지 0.25 중량%, 0.01 내지 0.1 중량%, 0.01 내지 0.05중량%, 0.01 내지 0.02중량%, 또는 0.005중량%일 수 있으나, 이에 제한되는 것은 아니다. In addition, the content of the multifunctional acyl halide in the polyfunctional acyl halide-containing solution may be 0.005% by weight to 1% by weight, specifically, 0.01 to 0.5% by weight, 0.01 to 0.25% by weight, 0.01 to 0.1% by weight, 0.01 to 0.01%. 0.05 wt%, 0.01 to 0.02 wt%, or 0.005 wt%, but is not limited thereto.
상기 제3단계는 나일론층이 형성된 지지체를 다관능성 아민 함유 용액에 침지한 후 표면에 잔류하는 과잉의 수용액을 제거하는 단계를 추가로 수행할 수 있다. 과잉의 아민 함유 수용액이 존재하는 경우 아민 함유 수용액이 불균일하게 분포할 수 있으며, 그 결과 이후의 계면 중합에 의해 불균일한 폴리아미드 활성층이 형성될 수 있다. 과잉의 수용액 제거는 특별히 제한되지는 않으나, 예를 들면, 압착 롤, 스펀지, 에어나이프, 질소 가스 블로잉, 자연건조 등을 이용하여 행할 수 있다.The third step may further be performed to remove the excess aqueous solution remaining on the surface after immersing the support on which the nylon layer is formed in the polyfunctional amine-containing solution. If an excess amine-containing aqueous solution is present, the amine-containing aqueous solution may be unevenly distributed, and as a result, a non-uniform polyamide active layer may be formed by subsequent interfacial polymerization. Excess aqueous solution removal is not particularly limited, but may be performed using, for example, a pressing roll, a sponge, an air knife, a nitrogen gas blowing, or natural drying.
상기 폴리아미드층은 폴리아미드 함유 용액이 폴리올레핀 지지층 표면 및 나일론층 외면에 구비되어 코팅되는 것으로서, 상기 지지층 및 나일론층을 전체적으로 덮으면서도 일부를 노출시켜 표면에 제1 기공보다 작은 크기의 제2 기공을 갖도록 구비될 수 있다. The polyamide layer is a polyamide-containing solution is coated on the surface of the polyolefin support layer and the outer surface of the nylon layer, and is partially coated while covering the support layer and nylon layer as a whole to expose a second pore having a smaller size than the first pore on the surface. It may be provided to have.
또한, 상기 폴리아미드는 다관능성 아민 용액과 다관능성 아실 할라이드 용액을 접촉시켜 계면 중합을 통해 형성한 것일 수 있다. 상기 다관능성 아민은 나일론층과의 친화력이 우수하여 나일론층에 쉽게 흡착되며, 따라서 나일론층 위에 형성된 폴리아미드층과 나일론층과의 높은 접착력으로 인해 멤브레인의 염 제거율이 높아지고, 얇은 두께의 폴리아미드층을 형성하여 투과유량을 높이는 특징이 있다.In addition, the polyamide may be formed through interfacial polymerization by contacting a polyfunctional amine solution with a polyfunctional acyl halide solution. The polyfunctional amine has an excellent affinity with the nylon layer and is easily adsorbed to the nylon layer. Therefore, the salt removal rate of the membrane is increased due to the high adhesion between the polyamide layer and the nylon layer formed on the nylon layer, and a thin polyamide layer It is characterized by increasing the transmission flow rate.
본 발명의 수처리용 멤브레인은 제1 기공을 갖는 다공성 폴리올레핀 지지층; 지지층의 외면에 구비되어 지지층의 표면 또는 단면에 존재하는 기공을 채우는 나일론층; 및 지지층 및 나일론층을 덮도록 구비된 폴리아미드층;을 포함하고, 수투과유량은 15kgf/㎠에서 70 내지 120L/㎡hr이고 염 제거율은 95% 이상이고, 표면에 상기 제1 기공보다 작은 크기의 제2 기공을 갖는 것일 수 있다. The membrane for water treatment of the present invention comprises a porous polyolefin support layer having first pores; A nylon layer provided on an outer surface of the support layer to fill pores existing on the surface or cross section of the support layer; And a polyamide layer provided to cover the support layer and the nylon layer; wherein the water permeation flow rate is 70 to 120 L / m 2 hr at 15 kgf / cm 2 and the salt removal rate is 95% or more and is smaller than the first pore on the surface. It may have a second pore of.
또한, 상기 수처리용 멤브레인은 상기 설명한 제조방법으로 제조된 것일 수 있다. 상기 수처리용 멤브레인은 수증기에 노출된 표면의 기공이 이의 하부 표면의 기공에 비해서 더욱 작은 비대칭 다공성 형태를 가질 수 있다. 구체적으로, 폴리올레핀 지지체의 제1 기공의 크기가 거대하더라도, 나일론층과 폴리아미드층이 차례로 제1 기공을 적절히 메우고 일부를 노출시킴으로써, 표면에 상기 제1 기공보다 작은 크기의 제2 기공을 갖는 형태의 멤브레인일 수 있다. In addition, the membrane for water treatment may be prepared by the above-described manufacturing method. The membrane for water treatment may have a less asymmetric porous form in which the pores of the surface exposed to water vapor are smaller than the pores of its lower surface. Specifically, even if the size of the first pores of the polyolefin support is large, the nylon layer and the polyamide layer in turn have the second pores of a smaller size than the first pores on the surface by appropriately filling the first pores and exposing a portion It may be a membrane of.
또한, 본 발명은 상기 수처리용 멤브레인을 포함하는 수처리용 장치를 제공한다. 예컨대 반도체 공정의 폐수처리 장치, 반도체 공정의 초순수 정제 장치, 정수기, 해수담수화 공정의 전처리 장치, 연수기, 정수처리 장치, 폐수 처리 장치 또는 식품 정제장치 등일 수 있다.The present invention also provides an apparatus for water treatment comprising the membrane for water treatment. For example, the wastewater treatment apparatus of a semiconductor process, the ultrapure water purification apparatus of a semiconductor process, a water purifier, the pretreatment apparatus of a seawater desalination process, a water softener, a water purification apparatus, a wastewater treatment apparatus, or a food purification apparatus may be sufficient.
또한, 본 발명은 상기 수처리용 멤브레인을 이용하여 수처리하는 단계를 포함하는, 수처리된 물의 제조방법을 제공한다. 상기 수처리에 사용되는 물은 초순수, 폐수 또는 해수 등일 수 있다.In addition, the present invention provides a method of producing water-treated water comprising the step of water treatment using the membrane for water treatment. The water used for the water treatment may be ultrapure water, wastewater or seawater.
본 발명에서, 상기 수처리된 물은 초순수, 정제수 또는 음용수 등일 수 있다.In the present invention, the water treated water may be ultrapure water, purified water or drinking water.
본 발명에서, 상기 수처리는 정밀여과, 한외여과, 나노여과, 역삼투 또는 이들의 조합 공정일 수 있다.In the present invention, the water treatment may be a microfiltration, ultrafiltration, nanofiltration, reverse osmosis or a combination thereof.
본 발명에 따라 제조된 수처리용 멤브레인은 나노급 기공 구조를 가지며 내화학성과 투과유량이 우수하여, 반도체 공정의 수처리 장치를 포함한 다양한 수처리 장치에 사용할 수 있다.The membrane for water treatment prepared according to the present invention has a nano-grade pore structure and excellent chemical resistance and permeation flow rate, and thus can be used in various water treatment apparatuses including water treatment apparatuses of semiconductor processes.
이하, 실시예를 통해 본 발명의 구성 및 효과를 보다 더 구체적으로 설명하고자 하나, 이들 실시예는 본 발명의 예시적인 기재일 뿐 본 발명의 범위가 이들 실시예에만 한정되는 것은 아니다.Hereinafter, the configuration and effects of the present invention will be described in more detail with reference to examples, but these examples are merely illustrative of the present invention, and the scope of the present invention is not limited only to these examples.
실시예Example 1: 나일론층을 포함하는 폴리아미드 1: polyamide with nylon layer 멤브레인Membrane 제조 Produce
나일론 4,6 10중량%를 포름산 90중량%에 용해시킨 고분자 용액을 제조하고, 폴리에틸렌 다공성 필름(평균 기공 크기 0.05㎛, W-Scope)에 100㎛ 두께로 균일하게 도포한 후 물에 침지하여 나일론 용액을 고형화한 후, 용매를 제거하여 나일론층을 형성하였다. 피페라진 2중량%, 트리메틸아민 1중량%를 포함하는 수용액에 1분 동안 침지한 후, 표면에 과량의 용액을 롤러를 이용하여 압착한 후, 트리메조일클로라이드 0.1중량%, isol-C 99.9부피%에 1분 동안 침지하고 상온에서 4분 동안 건조하였다. A polymer solution prepared by dissolving 10% by weight of nylon 4,6 in 90% by weight of formic acid was prepared, uniformly applied to a polyethylene porous film (average pore size 0.05 μm, W-Scope) at a thickness of 100 μm, and then immersed in water to give a nylon solution. After solidifying the solution, the solvent was removed to form a nylon layer. After immersion in an aqueous solution containing 2% by weight of piperazine and 1% by weight of trimethylamine for 1 minute, the excess solution was pressed onto the surface using a roller, and then 0.1% by weight of trimezoyl chloride and 99.9% by volume of isol-C It was immersed in% for 1 minute and dried at room temperature for 4 minutes.
실시예Example 2: 나일론층을 포함하는 폴리아미드 2: polyamide with nylon layer 멤브레인Membrane 제조 Produce
나일론 4,6 15중량%와 포름산 85중량%를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 제조하였다. Except for using 15% by weight of nylon 4,6 and 85% by weight of formic acid was prepared in the same manner as in Example 1.
실시예Example 3: 나일론층을 포함하는 폴리아미드 3: polyamide with nylon layer 멤브레인Membrane 제조 Produce
피페라진 1중량%, 트리메틸아민 0.5중량%, 트리메조일클로라이드 0.05중량%를 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 제조하였다.Except for using 1% by weight of piperazine, 0.5% by weight of trimethylamine, 0.05% by weight of trimezoyl chloride was prepared in the same manner as in Example 1.
비교예Comparative example 1: 나일론층이 없는 폴리아미드 1: polyamide without nylon layer 멤브레인Membrane 제조 Produce
나일론층을 형성하지 않은 것을 제외하고는 실시예 1과 동일한 방법으로 제조하였다.It was prepared in the same manner as in Example 1 except that the nylon layer was not formed.
비교예Comparative example 2: 2: EVOH층을EVOH layer 포함하는 폴리아미드 Polyamide containing 멤브레인Membrane 제조 Produce
나일론 4,6을 EVOH로 대체한 것을 제외하고는 실시예 1과 동일한 방법으로 제조하였다. It was prepared in the same manner as in Example 1 except for replacing nylon 4,6 with EVOH.
비교예Comparative example 3: 폴리술폰층을 포함하는 폴리아미드 3: polyamide comprising polysulfone layer 멤브레인Membrane 제조 Produce
나일론 4,6을 폴리술폰으로 대체한 것을 제외하고는 실시예 1과 동일한 방법으로 제조하였다. It was prepared in the same manner as in Example 1 except that nylon 4,6 was replaced with polysulfone.
실험예Experimental Example 1: One: 수처리용For water treatment 멤브레인의Membrane 투과유량 및 기공 크기 분석 Permeate Flow and Pore Size Analysis
상기 실시예 및 비교예에서 제조된 멤브레인의 투과유량 및 MgSO4 제거율은 15kgf/㎠에서 측정하였고, MgSO4 제거율은 전도도 측정기를 사용하였다. 피드용액은 MgSO4 0.2중량% 수용액을 사용하였다.Flux MgSO 4 and removal of the membrane prepared in Example and Comparative Example was measured at 15kgf / ㎠, MgSO 4 removal rate was used as a conductivity meter. As a feed solution, 0.2 wt% aqueous solution of MgSO 4 was used.
또한, MgSO4 제거율은 다음 식을 이용하여 계산하였으며, 그 결과를 하기 표 1에 나타내었다.In addition, MgSO 4 removal rate was calculated using the following equation, the results are shown in Table 1 below.
R(%) = (Cf - Cp) × 100 / CfR (%) = (Cf-Cp) × 100 / Cf
(R은 제거율, Cf는 원액의 농도, Cp는 투과액의 농도를 나타냄)(R is the removal rate, Cf is the concentration of stock solution, Cp is the concentration of permeate)
상기 표 1에서 알 수 있듯이, 나일론층을 형성하지 않은 비교예 1, 나일론이 아닌 다른 종류의 고분자층을 형성한 비교예 2,3에 비하여, 나일론 4,6층과 폴리아미드층을 형성한 실시예 1 내지 3의 경우 투과유량과 MgSO4 제거율이 모두 높게 나타남을 확인하였다. As can be seen from Table 1, compared to Comparative Example 1, which does not form a nylon layer, Comparative Examples 2, 3 in which a polymer layer of a different type is formed, the nylon 4,6 layer and the polyamide layer are formed. In Examples 1 to 3, it was confirmed that both the permeate flow rate and the MgSO 4 removal rate were high.
특히, 실시예 1과 2를 비교하였을 때, 나일론 농도가 나일론 함유 용액의 10중량%를 초과할 경우(실시예 2) 투과유량이 감소하는 것을 확인하였으며, 폴리아미드 농도를 절반으로 사용한 실시예 3의 경우, 실시예 1에 비하여 투과유량이 더욱 증가함을 알 수 있었다. In particular, when comparing the Examples 1 and 2, it was confirmed that when the nylon concentration exceeds 10% by weight of the nylon-containing solution (Example 2), the permeate flow rate is reduced, Example 3 using the polyamide concentration in half In the case of, it was found that the permeation flow rate was further increased compared to Example 1.
실험예Experimental Example 2: 2: 수처리용For water treatment 멤브레인의Membrane 내화학성 평가 Chemical resistance evaluation
상기 실시예 및 비교예에서 제조된 멤브레인의 내화학성 평가를 위하여 50% NMP (N-methyl-2-pyrrolidone) 수용액에 멤브레인을 24시간 침지한 후, 실험예 1과 같은 방법으로 평가를 진행하였다. In order to evaluate the chemical resistance of the membranes prepared in Examples and Comparative Examples, the membrane was immersed in 50% NMP (N-methyl-2-pyrrolidone) aqueous solution for 24 hours, and then evaluated in the same manner as in Experimental Example 1.
상기 표 1을 통해, 나일론 4,6층과 폴리아미드층을 형성한 실시예 1 내지 3의 멤브레인은 유기 용매에 대한 내화학성을 가지지만, 나일론이 아닌 다른 종류의 고분자층을 형성한 비교예 2,3의 경우, 투과유량이 급격히 증가하고 MgSO4 제거율은 감소하여 다공성 폴리올레핀 지지층의 특성을 나타냈으며, 상기 결과를 통해 각각 EVOH층과 폴리술폰층이 손상되어 다공성 폴리올레핀 지지층이 노출되었음을 알 수 있었다. Through Table 1, the membranes of Examples 1 to 3 in which the nylon 4 and 6 layers and the polyamide layer were formed had chemical resistance to organic solvents, but Comparative Example 2 in which a polymer layer of a type other than nylon was formed In the case of, 3, the permeation flow rate increased rapidly and the MgSO 4 removal rate decreased, indicating the characteristics of the porous polyolefin support layer. From the above results, it was found that the EVOH layer and the polysulfone layer were damaged and the porous polyolefin support layer was exposed.
이상의 설명으로부터, 본 발명이 속하는 기술분야의 당업자는 본 발명이 그 기술적 사상이나 필수적 특징을 변경하지 않고서 다른 구체적인 형태로 실시될 수 있다는 것을 이해할 수 있을 것이다. 이와 관련하여, 이상에서 기술한 실시예들은 모든 면에서 예시적인 것이며 한정적인 것이 아닌 것으로 이해해야만 한다. 본 발명의 범위는 상기 상세한 설명보다는 후술하는 특허 청구범위의 의미 및 범위 그리고 그 등가 개념으로부터 도출되는 모든 변경 또는 변형된 형태가 본 발명의 범위에 포함되는 것으로 해석되어야 한다.From the above description, those skilled in the art will appreciate that the present invention can be implemented in other specific forms without changing the technical spirit or essential features. In this regard, it should be understood that the embodiments described above are exemplary in all respects and not limiting. The scope of the present invention should be construed that all changes or modifications derived from the meaning and scope of the following claims and equivalent concepts rather than the detailed description are included in the scope of the present invention.
Claims (13)
상기 지지체를 비용매에 침지하여 나일론 함유 용액을 고형화함으로써, 지지체의 표면 또는 단면에 존재하는 기공을 채우는 나일론층을 형성하는 제2단계; 및
상기 나일론층이 형성된 지지체를 다관능성 아민 함유 용액에 침지한 후 다관능성 아실 할라이드 함유 용액에 침지하여 폴리아미드층을 형성하는 제3단계;를 포함하고,
수투과유량은 15kgf/㎠에서 70 내지 120L/㎡hr이고 염 제거율은 95% 이상이며, 표면에 상기 제1 기공보다 작은 크기의 제2 기공을 갖는 수처리용 멤브레인의 제조방법.
A first step of applying a nylon-containing solution to a porous polyolefin support having first pores;
Immersing the support in a non-solvent to solidify the nylon-containing solution to form a nylon layer filling the pores present on the surface or cross section of the support; And
And immersing the support on which the nylon layer is formed in a solution containing polyfunctional amine and then immersing in a solution containing polyfunctional acyl halide to form a polyamide layer.
The water permeation flow rate is 70 to 120L / ㎡hr at 15kgf / ㎠ and the salt removal rate is 95% or more, the method of producing a membrane for water treatment having a second pore size smaller than the first pore on the surface.
The method of claim 1, wherein the nylon is selected from the group consisting of nylon 4,6, nylon 6, nylon 6,6, nylon 6,9, nylon 6,10, nylon 6,12, nylon 11, and nylon 12. , Manufacturing method.
The method of claim 1, wherein the nylon is 5 to 20 weight percent based on the total weight of the nylon containing solution.
The method of claim 1, wherein the solvent of the nylon containing solution is formic acid or a mixture of formic acid and water.
The method of claim 5, wherein the mixing ratio of nylon and formic acid is 1: 4 to 1: 12.
The method of claim 1, wherein the porous polyolefin support consists of polyethylene, polypropylene, or a combination thereof.
The method of claim 1, wherein the pore size of the porous polyolefin support is at least 0.02 μm.
The process according to claim 1, wherein the polyamide is produced by a polymerization reaction of a polyfunctional amine and a polyfunctional acyl halide.
수투과유량은 15kgf/㎠에서 70 내지 120L/㎡hr이고 염 제거율은 95% 이상이고, 표면에 상기 제1 기공보다 작은 크기의 제2 기공을 갖는 수처리용 멤브레인.
A porous polyolefin support layer having first pores; A nylon layer provided on an outer surface of the support layer to fill voids present on the surface or cross section of the support layer; And a polyamide layer provided to cover the support layer and the nylon layer.
Water permeation flow rate is 70 to 120L / ㎡hr at 15kgf / ㎠ and salt removal rate is 95% or more, the membrane for water treatment having a second pore size smaller than the first pore on the surface.
10. The membrane according to claim 9, wherein the membrane for water treatment is prepared by the method of any one of claims 1 to 8.
A water treatment device comprising the water treatment membrane of claim 9.
The apparatus according to claim 11, which is a wastewater treatment apparatus of a semiconductor process, an ultrapure water purification apparatus of a semiconductor process, a water purifier, a pretreatment apparatus of a seawater desalination process, a water softener, a water purification apparatus, a wastewater treatment apparatus, or a food purification apparatus.
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| KR102035271B1 (en) | 2019-10-22 |
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