KR100480989B1 - Manufacturing method of reverse osmosis membrane with high flux and high exclusion ratio of salts - Google Patents
Manufacturing method of reverse osmosis membrane with high flux and high exclusion ratio of salts Download PDFInfo
- Publication number
- KR100480989B1 KR100480989B1 KR10-1998-0045898A KR19980045898A KR100480989B1 KR 100480989 B1 KR100480989 B1 KR 100480989B1 KR 19980045898 A KR19980045898 A KR 19980045898A KR 100480989 B1 KR100480989 B1 KR 100480989B1
- Authority
- KR
- South Korea
- Prior art keywords
- reverse osmosis
- porous support
- halide
- polyamine
- solution
- Prior art date
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- 239000012528 membrane Substances 0.000 title claims abstract description 43
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 28
- 150000003839 salts Chemical class 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 230000007717 exclusion Effects 0.000 title 1
- 230000004907 flux Effects 0.000 title 1
- 239000000243 solution Substances 0.000 claims abstract description 36
- 229920000768 polyamine Polymers 0.000 claims abstract description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 27
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 23
- 150000004820 halides Chemical class 0.000 claims abstract description 22
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000007864 aqueous solution Substances 0.000 claims abstract description 19
- 239000000654 additive Substances 0.000 claims abstract description 15
- -1 polysulfonyl Polymers 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 12
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 11
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 7
- 229920001228 polyisocyanate Polymers 0.000 claims abstract description 7
- 239000005056 polyisocyanate Substances 0.000 claims abstract description 7
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 6
- 239000003960 organic solvent Substances 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 10
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 abstract description 5
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000523 sample Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 15
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 12
- 229920002492 poly(sulfone) Polymers 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000010410 layer Substances 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- 238000012695 Interfacial polymerization Methods 0.000 description 4
- 150000001412 amines Chemical class 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000013535 sea water Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000011247 coating layer Substances 0.000 description 3
- 238000010612 desalination reaction Methods 0.000 description 3
- 230000029142 excretion Effects 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 150000001266 acyl halides Chemical group 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- YMHQVDAATAEZLO-UHFFFAOYSA-N cyclohexane-1,1-diamine Chemical compound NC1(N)CCCCC1 YMHQVDAATAEZLO-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 2
- AJDIZQLSFPQPEY-UHFFFAOYSA-N 1,1,2-Trichlorotrifluoroethane Chemical compound FC(F)(Cl)C(F)(Cl)Cl AJDIZQLSFPQPEY-UHFFFAOYSA-N 0.000 description 1
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 description 1
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 1
- HHSBHVJQXZLIRW-UHFFFAOYSA-N 3-n,3-n-dimethylbenzene-1,3-diamine Chemical compound CN(C)C1=CC=CC(N)=C1 HHSBHVJQXZLIRW-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical class OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- GKXVJHDEWHKBFH-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC=C1CN GKXVJHDEWHKBFH-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011033 desalting Methods 0.000 description 1
- 125000003963 dichloro group Chemical group Cl* 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 210000002615 epidermis Anatomy 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- RTWNYYOXLSILQN-UHFFFAOYSA-N methanediamine Chemical compound NCN RTWNYYOXLSILQN-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000012454 non-polar solvent Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003495 polar organic solvent Substances 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 150000003141 primary amines Chemical group 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000005270 trialkylamine group Chemical group 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Classifications
-
- 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
- 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
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/44—Polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of groups B01D71/26-B01D71/42
-
- 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
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/60—Polyamines
-
- 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
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
본 발명은 고유량 및 고염배제율을 가지는 역삼투 복합막의 제조방법에 관한 것으로서, 특히 다공성 지지체에 함침된 수용액 층의 폴리아민과 폴리아실할라이드, 폴리술포닐할라이드 또는 폴리이소시아네이트를 함유하는 유기용액을 반응시킴으로써 생성되는 반응생성물에 의하여 향상된 유량 및 염배제율을 가진 역삼투 복합막을 만들 수 있도록 하는 것을 목적으로 한다. The present invention relates to a method for producing a reverse osmosis composite membrane having a high flow rate and a high salt rejection, and in particular, reacts an organic solution containing polyamine and polyacyl halide, polysulfonyl halide or polyisocyanate in an aqueous solution layer impregnated with a porous support. It is an object to make a reverse osmosis composite membrane having an improved flow rate and salt rejection rate by the reaction product produced by the.
본 발명에 따른 역삼투 복합막의 제조방법은, 폴리아민 수용액에 다공성 지지체를 탐침하여 과잉의 용액을 제거하는 단계와; 상기 다공성 지지체에 함유된 폴리아민 수용액을, 폴리아실할라이드, 폴리술포닐할라이드 또는 폴리이소시아네이트를 함유하는 유기용액과 접촉시켜 반응시킴으로써 다공성 지지체 표면에 반응생성물을 코팅하는 단계를 포함하여 이루어지는데, 이때 폴리아실할라이드의 경우는 탄화수소를 사용한 트리메조일클로라이드, 이소프탈로일클로라이드, 테레프탈로일클로라이드 또는 이들을 혼합한 것 중에서 선택되며, 상기 유기용액에는 사염화탄소, 클로로포름, 디클로로메탄 혹은 그 혼합물을 포함하는 군에서 선택된 어느 하나의 첨가제가 첨가되는 것을 특징으로 한 것이다. Method for producing a reverse osmosis composite membrane according to the present invention comprises the steps of removing the excess solution by probe the porous support in a polyamine aqueous solution; Coating the reaction product on the surface of the porous support by reacting the aqueous polyamine solution contained in the porous support with an organic solution containing polyacyl halide, polysulfonyl halide or polyisocyanate, wherein the polyacyl The halide is selected from trimethoyl chloride, isophthaloyl chloride, terephthaloyl chloride or a mixture thereof using a hydrocarbon, and the organic solution is selected from the group comprising carbon tetrachloride, chloroform, dichloromethane or mixtures thereof. It is characterized in that one additive is added.
Description
본 발명은 고유량 및 고염배제율을 가지는 역삼투 복합막의 제조방법에 관한 것으로서, 특히 다공성 지지체에 함침되는 수용액 층의 폴리아민과 유기용액을 반응시킴으로써 생성되는 반응생성물에 의하여 향상된 유량 및 염배제율을 가진 역삼투 복합막을 만들 수 있는 고유량 및 고염배제율을 가지는 역삼투 복합막의 제조방법에 관한 것이다. The present invention relates to a method for producing a reverse osmosis composite membrane having a high flow rate and a high salt rejection, and in particular, improved flow rate and salt rejection rate by a reaction product produced by reacting an organic solution with a polyamine in an aqueous solution layer impregnated with a porous support. The present invention relates to a method for producing a reverse osmosis composite membrane having a high flow rate and a high salt excretion ratio capable of making a reverse osmosis composite membrane.
해리된 물질은 정밀여과막, 한외여과막, 역삼투막과 같은 선택성을 가지는 막에 의하여 용매로부터 분리될 수 있다. 역삼투막은 분자 수준의 물질을 분리하고, 기수 혹은 해수에서 염을 제거하여 가정용 및 건축용 용수 뿐만 아니라 예컨대 화학공정에 사용되는 용수와 같은 산업용 용수를 공급하는데 경제적이다. The dissociated material can be separated from the solvent by a membrane having a selectivity such as a microfiltration membrane, an ultrafiltration membrane, a reverse osmosis membrane. Reverse osmosis membranes are economical for separating molecular material and removing salts from brackish or seawater to supply industrial and industrial water, as well as water for use in chemical processes, for example.
탈염화에서 중요한 인자는 막의 염배제율과 유량이며, 막공정의 경제성을 고려할 때 해수에서는 800psi 압력에서 10gallon/ft2-day(gfd) 이상, 기수에서는 220psi에서 15gfd 이상의 유량을 나타내어야 한다. 탈염화에 사용되는 알려진 반투과 역삼투막은 폴리아미드막의 여러 형태이며, 특히 가교방향족 폴리아미드 막은 미국 특허 제3,904,519호, 제3996,318호 및 제4,277,344호에 개시되어 있다. Important desalination factors are membrane removal rates and flow rates, and considering the economics of the membrane process, the flow rate should be at least 10 gallon / ft2-day (gfd) at 800 psi in seawater and at least 15 gfd at 220 psi in brackish water. Known semipermeable reverse osmosis membranes used for desalting are several forms of polyamide membranes, in particular crosslinked aromatic polyamide membranes are disclosed in US Pat. Nos. 3,904,519, 3996,318 and 4,277,344.
이 중 미국 특허 제4,277,344호에 따르면, 해수담수화 조건(1,000psi)에서 염배제율 99.5%, 유량은 35gfd의 막을 제조할 수 있다고 언급되어 있다. 이러한 역삼투막은 두 개의 1급 아민 치환체를 함유하는 방향족 폴리아민과 세 개 이상의 아실할라이드 관능기를 가지는 방향족의 아실할라이드를 미세 다공성 폴리술폰 지지체 상에서 계면중합함으로써 얻어진다. 특히 물에 녹인 메타페닐렌디아민(MPD)을 프레온(듀퐁사, trichorotrifluoroethane, Freon TF)에 녹인 트리메조일클로라이드(TMC)와 반응시켰을 때 그 성능이 아주 우수하다고 개시되어 있다. According to US Pat. No. 4,277,344, it is mentioned that a salt removal rate of 99.5% and a flow rate of 35 gfd can be produced under seawater desalination conditions (1,000 psi). Such reverse osmosis membranes are obtained by interfacial polymerization of aromatic polyamines containing two primary amine substituents and aromatic acyl halides having three or more acyl halide functional groups on the microporous polysulfone support. In particular, it is disclosed that the performance is excellent when the metaphenylenediamine (MPD) dissolved in water is reacted with trimesoyl chloride (TMC) dissolved in Freon (DuPont, trichorotrifluoroethane, Freon TF).
프레온은 그 비휘발성 때문에 계면중합반응에 있어 아주 훌륭한 용매로 사용되어 왔으나, 1990년 이후 프레온의 오존층 파괴 문제로 인하여 사용에 제약이 가해지고, 2002년에는 모든 프레온의 생산이 금지됨에 따라 새로운 유기용매로의 대체가 요구되고 있다. Freon has been used as a very good solvent for interfacial polymerization because of its non-volatility, but since 1990 it has been restricted in use due to the ozone layer destruction problem, and in 2002 all new freon production was banned. Substitution is required.
이와 같은 요구에 부응하여 헥산을 대체용매로 사용하는 방법이 제안되었으나, 이 방법에 따르면 헥산의 휘발성에 의하여 생겨날 수 있는 화재 위험성 때문에 헥산보다 고온의 비등점을 갖는 용매의 경우 계면중합 이후 건조시간이 길어지거나, 고온의 건조조건이 요구되는 문제가 있다. 이러한 제조조건의 변화는 막의 투과성을 저하시키는 요인으로 작용하고, 따라서 건조과정동안 막의 물성 저하를 방지하기 위하여 첨가제를 투입하거나 후처리 공법에 관한 연구가 시도되었다. In order to meet these demands, a method of using hexane as a replacement solvent has been proposed.However, according to this method, a solvent having a boiling point higher than hexane has a long drying time after interfacial polymerization because of the risk of fire caused by volatility of hexane. Or a high temperature drying condition is required. This change in manufacturing conditions acts as a factor to reduce the permeability of the membrane, and therefore, in order to prevent the degradation of the properties of the membrane during the drying process, an additive or a study on the post treatment method has been attempted.
한편, 미국 특허 제4,872,984호에 따르면, 탄소수 8∼12개의 탄화수소 용매에 해리된 아실할라이드와 계면중합하는 아민수용액층에 아민염을 첨가하여 계면중합시킨 후 막을 70℃∼100℃ 범위에서 건조하면 아민염의 작용으로 기수조건은 220psi 압력하에서 20gfd 이상의 유량을 나타낸다고 개시되어 있다. On the other hand, according to U.S. Patent No. 4,872,984, an amine salt is added to an amine aqueous solution layer interfacially polymerized with an acyl halide dissociated in a hydrocarbon solvent having 8 to 12 carbon atoms, followed by interfacial polymerization to dry the membrane in a range of 70 ° C to 100 ° C. Under the action of the salt, the brackish condition is said to exhibit a flow rate of 20 gfd or more under 220 psi pressure.
또한, 미국 특허 제4,950,404호 및 동 제4,983,291호에 따르면, 아민 용액내에 비극성 및 극성 용매를 첨가하는 막 제조법과, 산으로 후처리 하는 방법이 개시되어 있다. 이 방법들 역시 막 제조후 100℃로 승온처리함으로써 유량의 감소를 막는다. In addition, U.S. Patent Nos. 4,950,404 and 4,983,291 disclose membrane preparation methods for adding nonpolar and polar solvents in amine solutions and post-treatment with acids. These methods also prevent the decrease in flow rate by heating up to 100 ° C. after membrane preparation.
또한, 미국 특허 제5,576,057호에는 미국 특허 제4,872,984호와 유사한 아민 용액에 10∼50중량%의 알콜을 첨가함으로써 담수화 공정조건에서 유량을 24gfd로 개선하는 방법이 개시되어 있다. U.S. Patent No. 5,576,057 also discloses a method for improving the flow rate to 24 gfd in desalination process by adding 10-50 wt% alcohol to an amine solution similar to U.S. Patent No. 4,872,984.
또한, 미국 특허 제5,614,099호에는, 상기 특허와 유사한 방법으로, 첨가제로 알콜, 에테르, 에틸렌글리콜 유도체, 케톤 및 황을 함유하는 다양한 유기용매를 사용하는 방법이 개시되어 있다. 예컨대 아민염을 함유하는 아민용액에 20중량% 알콜을 첨가함으로써 기수 처리조건에서 40gfd를 상회하는 유량을 나타낸다고 개시되어 있다. 그러나, 실제 이러한 조건으로 시험한 결과 상기 유량과 같은 성능을 재현할 수 없었다. 상기 실시예에 의하여 제조된 막의 향상된 유량은 표피층의 조도(roughness)의 증가에 기인한 것으로 설명하고 있다. U. S. Patent No. 5,614, 099 also discloses a method using a variety of organic solvents containing alcohols, ethers, ethylene glycol derivatives, ketones and sulfur as additives in a manner similar to the above patents. For example, it is disclosed that by adding 20% by weight alcohol to the amine solution containing the amine salt, the flow rate exceeds 40 gfd under the water treatment conditions. However, in fact, the test under these conditions could not reproduce the same performance as the flow rate. The improved flow rate of the membrane produced by this example is explained by the increase in the roughness of the epidermal layer.
위의 실시예, 즉 10∼20중량% 알콜과 6중량% 아민염을 첨가하여 120℃에서 건조하는 공법으로 제조된 역삼투막 복합막은 고유량을 나타내었으나 위의 공법보다 더욱 경제적인 공법이 개발이 요구된다. The reverse osmosis membrane composite membrane prepared by the above embodiment, that is, a method of drying at 120 ° C. by adding 10-20% by weight of alcohol and 6% by weight of an amine salt, exhibited a high flow rate, but a more economical method than the above method requires development. do.
따라서, 본 발명은 고유량 및 고염배제율을 가지는 역삼투 복합막을 효과적으로 얻을 수 있는 역삼투 복합막의 제조방법의 제공을 목적으로 한다. Accordingly, an object of the present invention is to provide a method for producing a reverse osmosis composite membrane which can effectively obtain a reverse osmosis composite membrane having a high flow rate and a high salt excretion rate.
상기 목적을 달성하기 위하여, 본 발명에 따른 역삼투 복합막의 제조방법은, 폴리아민 수용액에 다공성 지지체를 탐침하여 과잉의 용액을 제거하는 단계와; 상기 다공성 지지체에 함유된 폴리아민 수용액을, 폴리아실할라이드, 폴리술포닐할라이드 또는 폴리이소시아네이트를 함유하는 유기용액과 접촉시켜 반응시킴으로써 다공성 지지체 표면에 반응생성물을 코팅하는 단계를 포함하는데, 이때 상기 유기용액에 사염화탄소 등의 첨가제를 첨가하는 것을 특징으로 한다. In order to achieve the above object, the method for producing a reverse osmosis composite membrane according to the present invention comprises the steps of removing the excess solution by probing a porous support in a polyamine aqueous solution; Coating the reaction product on the surface of the porous support by reacting the aqueous polyamine solution contained in the porous support with an organic solution containing polyacyl halide, polysulfonyl halide or polyisocyanate. It is characterized by adding an additive such as carbon tetrachloride.
이와 같이 제조되는 역삼투 복합막은 폴리아실할라이드, 폴리술포닐할라이드 또는 폴리이소시아네이트와 폴리아민과의 반응에 의하여 생성되는 반응생성물이 다공성 지지체에 코팅됨으로써 기수, 해수처리에 유용하다. The reverse osmosis composite membrane prepared as described above is useful for brackish water and seawater treatment by coating a porous support with a reaction product produced by the reaction of polyacyl halide, polysulfonyl halide or polyisocyanate with polyamine.
또한, 본 발명에 따른 역삼투 복합막의 제조방법은, 다공성 지지체를 폴리아민 수용액에 탐침한 후 과잉의 수용액을 제거하는 단계와; 상기 다공성 지지체에 함유된 폴리아민 수용액을, 용매로서 탄화수소를 사용한 트리메조일클로라이드, 이소프탈로일클로라이드, 테레프탈로일클로라이드 또는 이들을 혼합한 것을 함유함과 아울러 첨가제가 첨가된 유기용액과 접촉시켜 다공성 지지체 표면에 반응생성물을 코팅하는 단계를 포함하여 이루어질 수 있다. 예컨대 다공성 폴리술폰 지지체를 메타페닐렌디아민 수용액를 탐침한 후 과잉을 용액을 제거하고, 첨가제로 사염화탄소, 클로로포름, 디클로로메탄 혹은 그 혼합물을 함유하는 높은 비등점의 트리메조일클로라이드 유기용액에 상기 다공성 폴리술폰 지지체를 접촉시켜 다공성 폴리술폰 지지체 표면에 반응에 의하여 생성물이 코팅되고 이와 같이 코팅된 반응생성물은 상온에서 40℃까지 어느 적정온도에서 건조된 후 알칼리 수용액에 수세함으로써 고염배제율과 고유량을 가지는 역삼투 복합막이 제조될 수 있다. In addition, the method for producing a reverse osmosis composite membrane according to the present invention comprises the steps of: removing the excess aqueous solution after the porous support is probed in a polyamine aqueous solution; The polyamine aqueous solution contained in the porous support contains a trimezoyl chloride, isophthaloyl chloride, terephthaloyl chloride or a mixture thereof using a hydrocarbon as a solvent, and is in contact with an organic solution to which an additive is added to the surface of the porous support. It may comprise the step of coating a reaction product. For example, the porous polysulfone support is probed with an aqueous solution of metaphenylenediamine, and the excess solution is removed, and the porous polysulfone support is contained in a high boiling point trimezoyl chloride organic solution containing carbon tetrachloride, chloroform, dichloromethane or a mixture thereof as an additive. The product is coated by the reaction on the surface of the porous polysulfone support by contact with and the coated reaction product is dried at an appropriate temperature from room temperature to 40 ° C. and then washed with an aqueous alkali solution to reverse osmosis having high salt rejection rate and high flow rate. Composite membranes can be prepared.
즉, 극성 유기용매와 사염화탄소, 클로로포름, 디클로로메탄 또는 그 혼합물이 조합된 첨가제에 의하여 수용액 층의 폴리아민에 대한 용해성 향상 및 유기용액의 비중 증가로 인하여 고유량 및 고염배제율을 나타내는 것이다. In other words, the additives in which the polar organic solvent and carbon tetrachloride, chloroform, dichloromethane, or mixtures thereof are combined to show high flow rates and high salt rejection rates due to the improved solubility in the polyamine of the aqueous solution layer and an increase in the specific gravity of the organic solution.
본 발명의 다른 특징 및 이점들은 다음의 상세한 설명으로 더욱 명백해질 것이다. Other features and advantages of the present invention will become more apparent from the following detailed description.
본 발명에 따른 제조방법에 의하여 역삼투 복합막을 만들기 위하여 폴리아민 수용액을 미세 다공성 지지체에 코팅한다. The polyamine aqueous solution is coated on the microporous support to make a reverse osmosis composite membrane by the manufacturing method according to the present invention.
다음에 롤, 스펀지 또는 에어 나이프를 이용하여 다공성 지지체로부터 과잉의 용액을 제거한다. The excess solution is then removed from the porous support using a roll, sponge or air knife.
다음에, 사염화탄소, 클로로포름, 디클로로메탄 또는 그 혼합물을 함유한 폴리아실할라이드, 폴리술포닐할라이드 또는 폴리이소시아네이트를 다공성 지지체에 탐침된 폴리아민과 접촉,반응시켜 반응생성물을 다공성 지지체에 코팅함으로써 역삼투 복합막을 제조한다. Next, a polyosyl halide, polysulfonyl halide or polyisocyanate containing carbon tetrachloride, chloroform, dichloromethane or mixtures thereof is contacted with a polyamine probed on the porous support to react the reaction product with the porous support to form a reverse osmosis composite membrane. Manufacture.
코팅층을 형성하기 위하여 폴리아민과 반응되는 반응물로는 상기한 것들 중에서 폴리아실할라이드를 사용하는 것이 가장 바람직하다. 폴리아민과 폴리아실할라이드가 반응하면 폴리아미드가 생성되어 다공성 지지체에 흡착된다. As the reactants to be reacted with the polyamine to form the coating layer, it is most preferable to use polyacyl halides among those mentioned above. When the polyamine and polyacyl halide react, polyamide is produced and adsorbed to the porous support.
다음에 다공성 지지체에 코팅된 반응생성물을 상온에서 40℃까지 어느 적정온도에서 건조한 후 알칼리 수용액에 수세함으로써 고유량 및 고염배제율 특성을 가지는 역삼투 복합막을 만든다. Next, the reaction product coated on the porous support is dried at an appropriate temperature from room temperature to 40 ° C., and then washed with an aqueous alkali solution to prepare a reverse osmosis composite membrane having high flow rate and high salt rejection characteristics.
본 발명에 사용되는 다공성 지지체로는 기공 크기가 1∼500nm인 것이 사용되는 것이 바람직하다. 다공성 지지체의 기공의 크기가 500nm 이상이면 코팅층이 기공 사이로 스며 들어 균일한 구조가 형성되기 어렵다. 본 발명에서 유용한 미세 다공성 지지체로 사용되는 고분자로는 폴리술폰, 폴리에테르술폰. 폴리아미드, 폴리프로필렌, 폴리비닐이덴플로라이드와 같은 여러 할로겐화 고분자가 사용될 수 있다. As the porous support used in the present invention, one having a pore size of 1 to 500 nm is preferably used. If the size of the pores of the porous support is 500nm or more, the coating layer penetrates between the pores, making it difficult to form a uniform structure. The polymer used as the microporous support useful in the present invention is polysulfone, polyethersulfone. Various halogenated polymers can be used such as polyamide, polypropylene, polyvinylidene fluoride.
이와 같은 다공성 지지체에 폴리아민 수용액을 탐침하는 방법으로는 연속공정 또는 핸드코팅 등의 방법이 사용될 수 있다. As a method of probing an aqueous polyamine solution on such a porous support, a method such as a continuous process or a hand coating may be used.
폴리아민은 1,3-프로판디아민, N-알킬 또는 아릴 치환체를 가지고 있거나 없는 이성질체와 같은 알칸디아민, 사이클로헥산디아민, 피페라진과 그 알킬 유도체인 파라페닐렌 디아민과 그 유도체와 같은 사이클로헥산디아민, 피페라진과 알킬 유도체와 같은 사이클릭폴리아민, 메타페닐렌디아민, 파라페닐렌디아민과 메틸기, 에틸기, 메톡기, 에톡기와 같은 알콕시기, 하이드록시알킬기, 하이드록시기 또는 할로겐 원자 등으로 치환된 유도체와 같은 방향족 폴리아민이다. 폴리아민은 또한 N,N-디메틸-1,3-페닐렌디아민, 자이릴렌디아민, 벤지딘과 그 유도체 또는 조합이다. 본 발명에 있어서 바람직하게 적용되는 폴리아민은 방향족 1급 디아민이며, 그 중에서 페닐렌디아민이 더욱 바람직하다. 폴리아민 수용액은 폴리아민의 함량이 0.1∼20중량%이며, 바람직하게는 0.5∼8중량%가 사용된다. 폴리아민 수용액의 pH는 7∼13의 영역을 가진다. pH는 0.001∼5중량%의 산 받게를 첨가함으로써 조절될 수 있다. 이러한 산 주게의 예로서는 하이드록사이드, 카르복실레이트, 카보네이트, 보레이트, 알킬금속의 포스포레이트, 트리알킬아민이다. Polyamines include alkanediamines, such as isomers with or without 1,3-propanediamine, N-alkyl or aryl substituents, cyclohexanediamine, piperazine and cyclophenyldiamine such as its alkyl derivatives, and cyclohexanediamines and derivatives thereof. Cyclic polyamines such as azine and alkyl derivatives, metaphenylenediamines, paraphenylenediamines and derivatives substituted with alkoxy, hydroxyalkyl, hydroxy or halogen atoms such as methyl, ethyl, methoxy and ethoxy groups Aromatic polyamines. Polyamines are also N, N-dimethyl-1,3-phenylenediamine, xylylenediamine, benzidine and derivatives or combinations thereof. The polyamine which is preferably applied in the present invention is an aromatic primary diamine, of which phenylenediamine is more preferable. The polyamine aqueous solution has a polyamine content of 0.1 to 20% by weight, preferably 0.5 to 8% by weight. The pH of the polyamine aqueous solution has a range of 7-13. The pH can be adjusted by adding 0.001-5% by weight of acid acceptor. Examples of such acid donors are hydroxides, carboxylates, carbonates, borates, phosphorates of alkyl metals, trialkylamines.
폴리아민 수용액으로 코팅된 다공성 지지체로부터 그 표면의 과잉용액을 제거한 후 디핑 또는 스프레이와 같은 방법에 의하여 폴리아실할라이드 유기용액과 5초∼10분, 바람직하게는 20초∼4분간 접촉시킨다. The excess solution on the surface is removed from the porous support coated with the polyamine aqueous solution and then contacted with the polyacyl halide organic solution for 5 seconds to 10 minutes, preferably 20 seconds to 4 minutes by a method such as dipping or spraying.
폴리아실할라이드는 트리메조일클로라이드, 이소프탈로일클로라이드, 테레프탈로일클로라이드, 또는 이소프탈로일클로라이드와 트리카르복실클로라이드가 조합된 것이다. 폴리아실할라이드 유기용액에 함유된 방향족 폴리아실할라이드는 트리메조일클로라이드 또는 트리메조일클로라이드와 이소프탈로일클로라이드의 조합, 트리메조일클로라이드와 테레프탈로일클로라이드의 조합으로서 그 함량은 0.005중량%이며, 바람직하게는 0.01∼0.5중량%이다.Polyacyl halides are trimezoyl chloride, isophthaloyl chloride, terephthaloyl chloride, or a combination of isophthaloyl chloride and tricarboxy chloride. The aromatic polyacyl halides contained in the polyacyl halide organic solution are trimezoyl chloride or a combination of trimezoyl chloride and isophthaloyl chloride, a combination of trimezoyl chloride and terephthaloyl chloride, and its content is 0.005% by weight. Preferably it is 0.01 to 0.5 weight%.
본 발명에 있어서 적용되는 유기용매는 프레온류와 헥산, 사이클로헥산, 헵탄, 탄소수가 8～12인 알칸과 같이 물과 섞이지 않는 액체이다. 폴리아민 용액이 사염화탄소, 클로로포름, 디클로로메탄 또는 그 혼합물을 함유한 폴리아실의 유기용매와 반응하여 제조된 막은 탄산용액에서 1～30분간 수세후, 기수조건에서 염배제율이 97%에서 98～99.3%로 증가하는 효과를 나타낸다. 폴리아실 유기용매에 첨가되는 사염화탄소, 클로로포름, 디클로로메탄 또는 그 혼합물의 함량은 0.01～0.5중량%이며, 바람직하게는 0.05～0.3중량%이다. The organic solvents applied in the present invention are liquids which are not mixed with water such as freons, hexane, cyclohexane, heptane and alkanes having 8 to 12 carbon atoms. Membranes prepared by reacting polyamine solution with organic solvents of polyacyl containing carbon tetrachloride, chloroform, dichloromethane or mixtures thereof were washed with carbonic acid solution for 1 to 30 minutes, and salt rejection ratio was 98% to 99.9% at 97%. To increase the effect. The content of carbon tetrachloride, chloroform, dichloromethane or a mixture thereof added to the polyacyl organic solvent is 0.01 to 0.5% by weight, preferably 0.05 to 0.3% by weight.
또한, 본 발명에 따르면, 다공성 폴리술폰 지지체를 2중량% 메타페닐렌디아민 용액에 1분간 코팅한 후, 1분간 0.05∼0.2%의 사염화탄소, 클로로포름, 디클로로메탄과 탄화수소의 0.1중량% 트리메조일클로라이드 용액에 디핑하여 코팅되는 코팅층을 1분간 상온∼40℃에서 건조하고 탄산칼슘 수용액에서 1∼30분간 수세하여 기수조건(220psi)에서 유량이 18∼22gfd이고 염배제율이 97∼99.3%인 특성을 나타내었다. According to the present invention, the porous polysulfone support is coated with 2% by weight metaphenylenediamine solution for 1 minute, and then 0.1% by weight of trimezoyl chloride of 0.05 to 0.2% carbon tetrachloride, chloroform, dichloromethane and hydrocarbon for 1 minute. The coating layer dipped into the solution was dried for 1 minute at room temperature to 40 ° C., washed with calcium carbonate solution for 1 to 30 minutes, and the flow rate was 18 to 22 gfd and the salt rejection ratio was 97 to 99.3% under radiated conditions (220 psi). Indicated.
<실시예 1-9><Example 1-9>
부직포 위에 캐스팅된 140㎛ 두께의 다공성 폴리술폰 지지체를 2중량% 메타페닐렌디아민 용액에 40초간 담구고, 지지체로부터 과잉의 메타페닐렌디아민 용액을 제거한 후 용매로 탄화수소를 사용하고 첨가제로 0.05% 사염화탄소를 포함하는 0.1중량% 트리메조일클로라이드 용액에 1분간 침적한 다음, 공기중에 건조하여 0.2중량% 탄산칼슘 수용액에 상온에서 30분간 수세하여 실시예 1의 역삼투 복합막을 제조함과 아울러 다음의 표 1과 같이 첨가제를 달리하여 실시예 2 내지 실시예 9의 역삼투 복합막을 제조하고, 제조된 역삼투 복합막에 대하여 225psi에서 2000ppm 염화나트륨 수용액을 이용하여 유량 및 염배제율을 측정한 결과를 다음의 표 1에 나타내었다. A 140 μm-thick porous polysulfone support cast on a nonwoven fabric was immersed in 2 wt% metaphenylenediamine solution for 40 seconds, and the excess metaphenylenediamine solution was removed from the support, followed by using hydrocarbon as a solvent and 0.05% carbon tetrachloride as an additive. It was immersed in a 0.1% by weight trimezoyl chloride solution containing for 1 minute, and then dried in air and washed with 0.2% by weight aqueous calcium carbonate solution at room temperature for 30 minutes to prepare a reverse osmosis composite membrane of Example 1 and the following Table 1 The reverse osmosis composite membranes of Examples 2 to 9 were prepared by varying the additives, and the flow rate and salt excretion rate were measured using a 2000 ppm sodium chloride aqueous solution at 225 psi with respect to the prepared reverse osmosis composite membrane. 1 is shown.
<비교예>Comparative Example
첨가제를 사용하지 않은 것 이외에는 전술한 실시예와 같은 방법으로 역삼투 복합막을 제조하여 상기한 바와 같은 방법으로 그 성능을 측정한 결과를 다음의 표 1에 나타내었다. 단 비교예에서는 첨가제를 사용하지 않았다. Except not using an additive, the reverse osmosis composite membrane was manufactured by the same method as in the above-described example, and the results of the measurement by the method as described above are shown in Table 1 below. In the comparative example, no additive was used.
상기 표 1에서 알 수 있듯이, 사염화탄소 및 클로로포름의 경우 첨가량이 0.1중량% 이하일 때 첨가제를 사용하지 않았을 때보다 고유량 및 고염배제율의 특성을 나타내고, 디클로로메탄의 경우 첨가량이 많을수록 첨가제를 사용하지 않았을 때보다 고유량의 특성을 나타냄을 알 수 있다. As can be seen from Table 1, the carbon tetrachloride and chloroform when the addition amount is 0.1% by weight or less shows the characteristics of the high flow rate and high salt removal rate than when the additive is not used, the more addition amount in the case of dichloromethane did not use the additive It can be seen that the characteristics of the high flow rate than when.
상기한 바와 같이 본 발명에 의하면, 다공성 지지체에 함침되는 폴리아민 수액을 폴리아실할라이드, 폴리술포닐할라이드 또는 폴리이소시아네이트를 함유하는 유기용액과 접촉시켜 반응시키거나 상기 유기용액에 첨가제로서 사염화탄소, 클로로포름, 디클로로메탄 또는 그 혼합물을 첨가하여 다공성 지지체에 함침된 수용액 층의 폴리아민과 반응시킴으로써 생성되는 반응생성물에 의하여 다공성 지지체를 코팅함으로써 우수한 유량 특성 및 염배제율을 특성을 가진 역삼투 복합막을 제조할 수 있다. As described above, according to the present invention, the polyamine sap impregnated in the porous support is brought into contact with an organic solution containing polyacyl halide, polysulfonyl halide or polyisocyanate, or reacted with carbon tetrachloride, chloroform, dichloro as an additive to the organic solution. The reverse osmosis composite membrane having excellent flow rate and salt rejection properties can be prepared by coating the porous support with a reaction product produced by adding methane or a mixture thereof and reacting with the polyamine of the aqueous layer impregnated with the porous support.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2012161483A3 (en) * | 2011-05-20 | 2013-01-17 | 주식회사 엘지화학 | Method for preparing a reverse osmosis membrane, and reverse osmosis membrane prepared thereby |
| KR20160121987A (en) | 2015-04-13 | 2016-10-21 | 엘지전자 주식회사 | Monomer Limited Interfacial Polymerization Method and Separation Membrane Prepared by the Same |
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|---|---|---|---|---|
| US4277344A (en) * | 1979-02-22 | 1981-07-07 | Filmtec Corporation | Interfacially synthesized reverse osmosis membrane |
| US4900443A (en) * | 1980-03-14 | 1990-02-13 | Memtec North America Corporation | Porous aramid membranes and emulsions useful for the casting thereof |
| US5271843A (en) * | 1991-09-09 | 1993-12-21 | Allied-Signal Inc. | Chlorine-tolerant, thin-film composite membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4277344A (en) * | 1979-02-22 | 1981-07-07 | Filmtec Corporation | Interfacially synthesized reverse osmosis membrane |
| US4900443A (en) * | 1980-03-14 | 1990-02-13 | Memtec North America Corporation | Porous aramid membranes and emulsions useful for the casting thereof |
| US5271843A (en) * | 1991-09-09 | 1993-12-21 | Allied-Signal Inc. | Chlorine-tolerant, thin-film composite membrane |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012161483A3 (en) * | 2011-05-20 | 2013-01-17 | 주식회사 엘지화학 | Method for preparing a reverse osmosis membrane, and reverse osmosis membrane prepared thereby |
| KR20160121987A (en) | 2015-04-13 | 2016-10-21 | 엘지전자 주식회사 | Monomer Limited Interfacial Polymerization Method and Separation Membrane Prepared by the Same |
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