KR20110066683A - Manufacturing method for polyamide-based reverse osmosis membrane and polyamide-based reverse osmosis membrane manufactured thereby - Google Patents
Manufacturing method for polyamide-based reverse osmosis membrane and polyamide-based reverse osmosis membrane manufactured thereby Download PDFInfo
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- KR20110066683A KR20110066683A KR1020090123430A KR20090123430A KR20110066683A KR 20110066683 A KR20110066683 A KR 20110066683A KR 1020090123430 A KR1020090123430 A KR 1020090123430A KR 20090123430 A KR20090123430 A KR 20090123430A KR 20110066683 A KR20110066683 A KR 20110066683A
- Authority
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- South Korea
- Prior art keywords
- reverse osmosis
- osmosis membrane
- polyamide reverse
- polyamide
- acid
- Prior art date
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- 239000012528 membrane Substances 0.000 title claims abstract description 87
- 229920002647 polyamide Polymers 0.000 title claims abstract description 83
- 238000001223 reverse osmosis Methods 0.000 title claims abstract description 80
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 24
- 239000004952 Polyamide Substances 0.000 claims abstract description 81
- 238000000034 method Methods 0.000 claims abstract description 37
- 150000003839 salts Chemical class 0.000 claims abstract description 29
- 150000001412 amines Chemical class 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000008569 process Effects 0.000 claims abstract description 21
- 239000012266 salt solution Substances 0.000 claims abstract description 18
- 150000007524 organic acids Chemical class 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims abstract description 11
- 239000012153 distilled water Substances 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 8
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims abstract description 6
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940098779 methanesulfonic acid Drugs 0.000 claims abstract description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- 238000012695 Interfacial polymerization Methods 0.000 claims description 9
- 229920002492 poly(sulfone) Polymers 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 3
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 3
- 238000007598 dipping method Methods 0.000 claims description 3
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 claims description 3
- DAZXVJBJRMWXJP-UHFFFAOYSA-N n,n-dimethylethylamine Chemical compound CCN(C)C DAZXVJBJRMWXJP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004745 nonwoven fabric Substances 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920006393 polyether sulfone Polymers 0.000 claims description 3
- 229920001721 polyimide Polymers 0.000 claims description 3
- 229920006380 polyphenylene oxide Polymers 0.000 claims description 3
- ZVYSGOITVWNULH-UHFFFAOYSA-N 1-methylpiperidine Chemical compound CN1CCCCC1.CN1CCCCC1 ZVYSGOITVWNULH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 2
- 239000004697 Polyetherimide Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- GNVRJGIVDSQCOP-UHFFFAOYSA-N n-ethyl-n-methylethanamine Chemical compound CCN(C)CC GNVRJGIVDSQCOP-UHFFFAOYSA-N 0.000 claims description 2
- 229920002530 polyetherether ketone Polymers 0.000 claims description 2
- 229920001601 polyetherimide Polymers 0.000 claims description 2
- 229920000306 polymethylpentene Polymers 0.000 claims description 2
- 239000011116 polymethylpentene Substances 0.000 claims description 2
- -1 polypropylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims 1
- 238000005266 casting Methods 0.000 claims 1
- 239000002861 polymer material Substances 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 abstract description 10
- 238000000926 separation method Methods 0.000 abstract 7
- 239000000243 solution Substances 0.000 description 22
- 239000010410 layer Substances 0.000 description 11
- 239000010409 thin film Substances 0.000 description 9
- 230000029142 excretion Effects 0.000 description 7
- 150000001266 acyl halides Chemical class 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 4
- 239000012267 brine Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000010612 desalination reaction Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- 230000003204 osmotic effect Effects 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- RPHKINMPYFJSCF-UHFFFAOYSA-N benzene-1,3,5-triamine Chemical compound NC1=CC(N)=CC(N)=C1 RPHKINMPYFJSCF-UHFFFAOYSA-N 0.000 description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical compound C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 230000007717 exclusion Effects 0.000 description 2
- 125000005843 halogen group Chemical group 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- 229920000728 polyester Polymers 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-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
- MGLZGLAFFOMWPB-UHFFFAOYSA-N 2-chloro-1,4-phenylenediamine Chemical compound NC1=CC=C(N)C(Cl)=C1 MGLZGLAFFOMWPB-UHFFFAOYSA-N 0.000 description 1
- ZWUBBMDHSZDNTA-UHFFFAOYSA-N 4-Chloro-meta-phenylenediamine Chemical compound NC1=CC=C(Cl)C(N)=C1 ZWUBBMDHSZDNTA-UHFFFAOYSA-N 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- XVTUIWSJGAKEHZ-UHFFFAOYSA-N C1(=CC(=CC=C1)N)N.ClC=1C=C(C=C(C1)N)N Chemical compound C1(=CC(=CC=C1)N)N.ClC=1C=C(C=C(C1)N)N XVTUIWSJGAKEHZ-UHFFFAOYSA-N 0.000 description 1
- JQRGJKGJUJLSDS-UHFFFAOYSA-N CN(C)CCO.CN(C)CCO Chemical compound CN(C)CCO.CN(C)CCO JQRGJKGJUJLSDS-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- SXEHKFHPFVVDIR-UHFFFAOYSA-N [4-(4-hydrazinylphenyl)phenyl]hydrazine Chemical compound C1=CC(NN)=CC=C1C1=CC=C(NN)C=C1 SXEHKFHPFVVDIR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 235000013405 beer Nutrition 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
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002301 cellulose acetate Polymers 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 210000002615 epidermis Anatomy 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 230000008570 general process Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- NTNWKDHZTDQSST-UHFFFAOYSA-N naphthalene-1,2-diamine Chemical group C1=CC=CC2=C(N)C(N)=CC=C21 NTNWKDHZTDQSST-UHFFFAOYSA-N 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 150000003461 sulfonyl halides Chemical class 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
- 235000015192 vegetable juice Nutrition 0.000 description 1
Classifications
-
- 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
-
- 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
- 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
- B01D67/0013—Casting processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
-
- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/107—Organic support material
- B01D69/1071—Woven, non-woven or net mesh
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1216—Three or more layers
-
- 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
-
- 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
Abstract
Description
본 발명은 폴리아마이드 역삼투 분리막의 후처리 공정 및 그에 의해 제조된 폴리아마이드 역삼투 분리막에 관한 것으로, 보다 상세하게는 높은 염배제율을 지니면서도 유량(flux)이 증가한 폴리아마이드 역삼투 분리막의 제조방법에 관한 것이다.The present invention relates to a post-treatment process of a polyamide reverse osmosis membrane and a polyamide reverse osmosis membrane produced by the same, and more particularly, to a polyamide reverse osmosis membrane having a high salt rejection rate and increased flux. It is about a method.
삼투현상이란 반투과성막으로 격리된 두 용액 사이에서 용매가 용질의 농도가 낮은 용액에서 높은 용액 쪽으로 분리막을 통과하여 이동하는 현상을 말하며 이때 용매의 이동으로 용질의 농도가 높은 용액 측에 작용하는 압력을 삼투압(osmotic pressure)이라고 한다. 그런데 역으로 삼투압보다 높은 외부압력을 걸어주면 용매는 용질의 농도가 낮은 용액 쪽으로 이동하게 되는데 이 현상을 역삼투(reverse osmosis)라고 하며, 역삼투 원리를 이용하여 압력구배를 구동력으로 해 서 반투과성막을 통해 각종 염이나 유기물질을 분리해 낼 수 있다. 즉, 역삼투막을 사용하여 염수로부터 물은 통과하나, 염과 기타 용해된 이온 또는 분자들은 통과하지 못하도록 가압하여 분리해 낼 수 있다. Osmotic phenomenon is a phenomenon in which a solvent moves from a solution having a low solute concentration to a high solution between two solutions separated by a semi-permeable membrane. It is called osmotic pressure. On the contrary, if the external pressure is applied higher than the osmotic pressure, the solvent moves toward the solution of low solute concentration. This phenomenon is called reverse osmosis. Through this, various salts and organic substances can be separated. That is, reverse osmosis membranes can be used to separate the water from the brine by pressurizing it to prevent passage of the salt and other dissolved ions or molecules.
역삼투 공정의 사용목적은 크게 정화된 물의 제조와 원수에 녹아있는 용질의 농축으로 크게 나뉘는데, 전자는 해수 및 염수의 담수화, 반도체 산업용 초순수 제조, 각종 산업용 폐수의 처리 등이 이에 속하며, 후자에는 과일과 야채 주스의 농축, 저알콜 맥주와 와인의 제조 등이 포함된다. The purpose of the reverse osmosis process is largely divided into the production of purified water and the concentration of solutes dissolved in raw water. The former includes the desalination of seawater and brine, the manufacture of ultrapure water for semiconductor industry, and the treatment of various industrial wastewater. And vegetable juice concentrates, low-alcohol beer and wine production.
이러한 역삼투 공정을 이용한 물의 담수화 가능성은 1953년 레이드(Reid)에 의해 처음으로 제시되었고, 1964년 로브(Lobe)와 수리라잔(Sourirajan)이 셀룰로우즈 아세테이트(cellulose acetate)로서 조밀한 표피층과 그 밑에 다공성의 지지체로 구성된 상업적 잠재력을 가진 일체형 비대칭막을 제조하였으며, 그 후 셀룰로우즈막의 단점을 보완하기 위해 폴리아마이드계(polyamide), 폴리우레탄계(polyurethane), 방향족 폴리술폰계(polysulfone), 방향족 폴리아마이드계 등을 대상으로 연구가 활발히 진행되어 왔다.The possibility of desalination of water using this reverse osmosis process was first presented by Reid in 1953, and in 1964 by Lobe and Sourirajan as cellulose acetate, A monolithic asymmetric membrane with a commercial potential consisting of a porous support underneath was prepared, and then polyamide, polyurethane, aromatic polysulfone, and aromatics were used to compensate for the shortcomings of the cellulose membrane. Research has been actively conducted on polyamides and the like.
이러한 역삼투막은 내부 구조에 따라 일체형의 비대칭막과 박막형 복합막으로 양분되는데, 비대칭막은 염배제층과 그 아래 다공성 지지체가 동일 물질로 이루어져 있고 제조가 쉽고 가격이 저렴한 반면 염배제율이나 투과량이 낮은 단점이 있다. 근래에 들어서 표피층과 지지층이 서로 다른 물질로 이루어진 복합(thin film composite) 구조의 막이 개발되고 있는데, 이러한 복합막은 최적의 활성층 소재를 선택할 수 있어 막의 전체적인 성능을 향상시킬 수 있을 뿐 아니라, 활성층에 가교 를 부여할 수 있기 때문에 보다 높은 내화학성을 얻을 수 있는 장점을 가지고 있다. The reverse osmosis membrane is divided into a monolithic asymmetric membrane and a thin film composite membrane according to the internal structure. The asymmetric membrane is composed of the same material as the salt excretion layer and the porous support under it, and is easy to manufacture and inexpensive, but has a low salt excretion rate and a low permeability. There is this. In recent years, thin film composite membranes have been developed in which the epidermal layer and the support layer are different from each other. Such composite membranes can select the optimal active layer material to improve the overall performance of the membrane as well as to crosslink the active layer. Since it can be given to have a high chemical resistance can be obtained.
이러한 역삼투 분리막이 상업적으로 이용되어 대량으로 탈염화하기 위해서는 염제거율이 높아야 하며, 비교적 낮은 압력에서도 막을 통해서 상대적으로 과량의 물을 통과시킬 수 있는 투과유량 특성이 우수해야 한다. 따라서, 높은 염배제율을 지니면서도 고유량의 특성을 갖는 역삼투분리막을 제조하기 위한 보다 경제적인 공법의 개발이 요구되고 있다.In order to desalize a large amount of the reverse osmosis membrane commercially used, the salt removal rate must be high, and the permeate flow rate characteristic of allowing excess water to pass through the membrane at a relatively low pressure must be excellent. Therefore, there is a demand for the development of a more economical process for producing a reverse osmosis membrane having a high salt rejection rate and high flow characteristics.
본 발명이 해결하고자 하는 하나의 과제는 높은 염배제율과 고유량 특성을 부여하기 위한 후처리 공정을 추가로 포함하는 폴리아마이드 역삼투 분리막의 제조방법을 제공하는 것이다.One problem to be solved by the present invention is to provide a method for producing a polyamide reverse osmosis membrane further comprising a post-treatment step for imparting high salt rejection rate and high flow rate characteristics.
본 발명이 해결하고자 하는 다른 과제는 상기 방법으로 제조된 폴리아마이드 역삼투 분리막을 제공하는 것이다.Another object of the present invention is to provide a polyamide reverse osmosis membrane prepared by the above method.
상기 과제를 달성하기 위한 본 발명의 하나의 양상은 계면중합에 의해 폴리아마이드 역삼투 분리막을 제조하는 방법에 있어서, 상기 방법이 폴리아마이드 역삼투 분리막을 제조한 후 후처리 공정으로 하기의 단계를 추가로 포함하는 폴리아마이드 역삼투 분리막의 제조방법에 관한 것이다.One aspect of the present invention for achieving the above object is a method for producing a polyamide reverse osmosis membrane by interfacial polymerization, the method is to produce a polyamide reverse osmosis membrane after the addition of the following steps to the post-treatment process It relates to a method for producing a polyamide reverse osmosis membrane comprising a.
(i) 유기산 및 아민을 포함하는 유기염 용액에 상기 제조된 폴리아마이드 역삼투 분리막을 침지시키는 단계; 및(i) immersing the prepared polyamide reverse osmosis membrane in an organic salt solution containing an organic acid and an amine; And
(ii) 상기 폴리아마이드 역삼투 분리막을 증류수로 세척하는 단계.(ii) washing the polyamide reverse osmosis membrane with distilled water.
상기 유기염 용액은 유기염을 2 내지 10 중량% 포함할 수 있으며, 이에 제한되는 것은 아니다. The organic salt solution may include 2 to 10% by weight of organic salt, but is not limited thereto.
상기 (i) 침지 단계는 10 분 내지 1 시간 동안 수행될 수 있다.The (i) immersion step may be performed for 10 minutes to 1 hour.
상기 과제를 달성하기 위한 본 발명의 다른 양상은 상기 제조방법에 의해 제 조된 폴리아마이드 역삼투 분리막에 관한 것으로, 상기 폴리아마이드 역삼투 분리막은 다공성 지지체; 및 상기 다공성 지지체의 적어도 일측면에 형성된 폴리아마이드 활성층을 포함한다.Another aspect of the present invention for achieving the above object relates to a polyamide reverse osmosis membrane prepared by the manufacturing method, the polyamide reverse osmosis membrane is a porous support; And a polyamide active layer formed on at least one side of the porous support.
본 발명의 구현예들에 의하면, 높은 염배제율을 지니면서도 고유량의 특성을 가지는 폴리아마이드 역삼투 분리막을 제공할 수 있는바, 해수 및 염수의 담수화, 반도체 산업용 초순수 제조 및 각종 산업용 폐수의 처리에 유용하게 사용할 수 있다.According to the embodiments of the present invention, it is possible to provide a polyamide reverse osmosis membrane having a high salt rejection rate and high flow rate characteristics. The desalination of seawater and brine, the manufacture of ultrapure water for the semiconductor industry, and the treatment of various industrial wastewater This can be useful for.
이하, 본 발명의 구현예들에 대하여 보다 상세하게 설명하기로 한다.Hereinafter, embodiments of the present invention will be described in more detail.
본 발명에서는 폴리아마이드 역삼투 분리막을 제조함에 있어서, 보다 향상된 염배제율과 고유량 특성을 부여하기 위하여 폴리아마이드 역삼투 분리막의 제조방법 상 후처리 공정을 제공한다. In the present invention, in the preparation of the polyamide reverse osmosis membrane, in order to give more improved salt rejection rate and high flow rate characteristics, a post-treatment process is provided according to the method of manufacturing the polyamide reverse osmosis membrane.
본 발명의 일구현예에 따른 하나의 양상은 계면중합에 의해 폴리아마이드 역삼투 분리막을 제조하는 방법에 있어서, 상기 방법이 폴리아마이드 역삼투 분리막을 제조한 후 후처리 공정으로 하기의 단계를 추가로 포함하는 폴리아마이드 역삼투 분리막의 제조방법에 관계한다. One aspect according to an embodiment of the present invention is a method for producing a polyamide reverse osmosis membrane by interfacial polymerization, wherein the method further comprises the following steps as a post-treatment process after preparing a polyamide reverse osmosis membrane; It relates to a method for producing a polyamide reverse osmosis membrane comprising.
(i) 유기산 및 아민을 포함하는 유기염 용액에 상기 제조된 폴리아마이드 역 삼투 분리막을 침지시키는 단계; 및(i) immersing the prepared polyamide reverse osmosis membrane in an organic salt solution comprising an organic acid and an amine; And
(ii) 상기 폴리아마이드 역삼투 분리막을 증류수로 세척하는 단계.(ii) washing the polyamide reverse osmosis membrane with distilled water.
일반적으로 폴리아마이드계 역삼투 분리막은 미세다공성 지지체를 다관능성 아민 수용액으로 코팅한 후, 이어서 다관능성 아실할라이드 등을 포함하는 유기용액을 접촉시켜 폴리아마이드를 계면중합시키고 건조한 후 염기성 수용액 및/또는 증류수에서 세척하여 제조할 수 있으나, 이렇게 제조된 역삼투 분리막은 염배제율이 낮고 유량이 적은 것이 문제로 지적되어 왔다.In general, a polyamide reverse osmosis membrane is coated with a microporous support with an aqueous polyfunctional amine solution, and then contacted with an organic solution including a polyfunctional acyl halide, followed by interfacial polymerization of the polyamide and drying, followed by basic aqueous solution and / or distilled water. It can be prepared by washing in, but the reverse osmosis membrane thus prepared has been pointed out as a problem of low salt excretion rate and low flow rate.
따라서, 본 발명자는 상기 문제를 해결하고 염배제율이 높으면서도 고유량의 특성을 가진 폴리아마이드계 역삼투 분리막을 제공하기 위하여 일반적인 폴리아마이드계 역삼투 분리막의 제조공정에 추가로 후처리 공정을 도입하였다.Therefore, the present inventors have introduced a post-treatment process in addition to the general manufacturing process of the polyamide reverse osmosis membrane in order to solve the above problems and to provide a polyamide reverse osmosis membrane having high salt rejection rate and high flow rate characteristics. It was.
구체적으로 본 발명의 구현예들에 의한 후처리 공정은 다음과 같다.Specifically, the aftertreatment process according to the embodiments of the present invention is as follows.
본 발명에 의한 후처리 공정은 계면중합에 의해 제조된 폴리아마이드 역삼투 분리막을 유기산 및 아민을 포함하는 유기염 용액에 침지하여 후처리하고 증류수로 세척함에 의해 수행될 수 있다. The post-treatment process according to the present invention may be carried out by immersing the polyamide reverse osmosis membrane prepared by interfacial polymerization in an organic salt solution containing an organic acid and an amine, followed by post-treatment and washing with distilled water.
본 발명의 구현예들에서 사용가능한 유기산으로는 캠포술폰산(camphorsulfonic acid, CSA), 염산(hydrochloric acid), 초산(acetic acid), 메탄술폰산(methanesulfonic acid) 또는 트리플루오로아세트산(trifluoroacetic acid) 등을 들 수 있으나, 이에 제한되는 것은 아니다.Organic acids usable in embodiments of the present invention include camphorsulfonic acid (CSA), hydrochloric acid, acetic acid, methanesulfonic acid or trifluoroacetic acid, and the like. But it is not limited thereto.
또한, 본 발명의 구현예들에서 사용가능한 아민으로는 트리에틸아 민(triethylamine, TEA), 트리메틸아민(trimethylamine), 트리프로필아민(tripropylamine), 디프로필아민(dipropylamine), 1-메틸피페리딘(1-methylpiperidine), N,N-디에틸메틸아민(N,N-diethylmethylamine), N,N-디메틸에틸아민(N,N-dimethylethylamine), N,N-디메틸에탄올아민(N,N-dimethylethanolamine) 또는 N,N-디메틸-4-아미노-피리딘(N,N-dimethyl-4-amino-pyridine) 등을 들 수 있으나, 이에 제한되는 것은 아니다.In addition, amines usable in the embodiments of the present invention include triethylamine (TEA), trimethylamine, tripropylamine, tripropylamine, dipropylamine, 1-methylpiperidine (1-methylpiperidine), N, N-diethylmethylamine, N, N-dimethylethylamine, N, N-dimethylethanolamine (N, N-dimethylethanolamine ) Or N, N-dimethyl-4-amino-pyridine and the like, but is not limited thereto.
상기 유기염 용액은 유기염을 2 내지 10 중량% 포함할 수 있으며 이에 제한되는 것은 아니다.The organic salt solution may include 2 to 10% by weight of organic salt, but is not limited thereto.
이때 상기 유기염 용액에의 침지 단계는 10 분 내지 1 시간 동안 상기 유기산과 상기 아민을 포함하는 유기염 수용액에 상기 폴리아마이드 활성층이 형성된 폴리아마이드 역삼투 분리막을 침지하여 수행될 수 있다.In this case, the immersion in the organic salt solution may be performed by immersing the polyamide reverse osmosis membrane in which the polyamide active layer is formed in an aqueous organic salt solution including the organic acid and the amine for 10 minutes to 1 hour.
침지 단계에 이어지는 세척 단계는 일반적인 공정에 따라 증류수로 약 30분 가량 세척함에 의해 수행될 수 있다. The washing step following the dipping step may be performed by washing for about 30 minutes with distilled water according to a general process.
본 발명의 구현예들에 의한 폴리아마이드 역삼투 분리막의 후처리 공정은 통상적인 계면중합에 의한 폴리아마이드 역삼투 분리막의 제조방법에 모두 적용가능하다.The post-treatment process of the polyamide reverse osmosis membrane according to the embodiments of the present invention is applicable to all methods of preparing a polyamide reverse osmosis membrane by conventional interfacial polymerization.
그 중 일례를 들어 설명하자면, 본 발명의 구현예들에 의한 후처리 공정을 포함하는 폴리아마이드 역삼투 분리막의 제조방법은 하기와 같다.For example, a method of manufacturing a polyamide reverse osmosis membrane comprising a post-treatment process according to embodiments of the present invention is as follows.
구체적으로, 폴리술폰 등의 고분자 지지체가 코팅된 미세다공성 지지체에 다관능성 아민 수용액을 코팅한 후, 과잉의 용액을 제거하여 제 1 박막을 형성한다. 이어서, 상기 제 1 박막이 형성된 미세다공성 지지체를 다관능성 아실할라이드 등을 포함하는 지방족 탄화수소계 유기용액과 접촉시킨다. 이때, 계면중합에 따른 다관능성 아민과 다관능성 아실할라이드의 반응에 의해 폴리아마이드가 생성되어 미세다공성 지지체에 흡착되어 제 2 박막인 폴리아마이드 활성층을 형성한다. 그 후 상기 수득된 박막을 건조한 후, 염기성 수용액과 증류수에서 세척하면 1차로 폴리아마이드 역삼투 분리막이 제조된다.Specifically, after coating a polyfunctional aqueous solution on a microporous support coated with a polymer support such as polysulfone, the excess solution is removed to form a first thin film. Subsequently, the microporous support on which the first thin film is formed is contacted with an aliphatic hydrocarbon-based organic solution containing a polyfunctional acyl halide or the like. At this time, the polyamide is generated by the reaction of the polyfunctional amine and the polyfunctional acyl halide due to the interfacial polymerization, and is adsorbed onto the microporous support to form the polyamide active layer as the second thin film. Thereafter, the obtained thin film is dried and then washed in a basic aqueous solution and distilled water to prepare a polyamide reverse osmosis membrane.
이렇게 제조된 폴리아마이드 역삼투 분리막의 염배제율과 유량을 향상시키기 위해서 후처리 공정을 이어서 수행한다. 즉, 전 단계에서 제조된 폴리아마이드 역삼투 분리막을 유기산과 아민의 유기염을 2 내지 10중량% 포함하는 수용액에서 10분 내지 1 시간 동안 침지하여 후처리한 뒤, 이를 증류수로 약 30분 가량 세척함으로써 고유량과 고염제거율의 특징을 갖는 성능이 향상된 폴리아마이드 역삼투 분리막을 제조할 수 있다.In order to improve the salt rejection rate and the flow rate of the polyamide reverse osmosis membrane thus prepared is followed by a post-treatment process. That is, the polyamide reverse osmosis membrane prepared in the previous step was immersed for 10 minutes to 1 hour in an aqueous solution containing 2 to 10% by weight of organic salts of organic acids and amines, followed by washing for about 30 minutes with distilled water. By doing so, it is possible to manufacture a polyamide reverse osmosis membrane having improved performance having characteristics of high flow rate and high salt removal rate.
본 발명의 구현예들에서 사용가능한 미세다공성 지지체는 폴리에스테르 등의 부직포 상에 고분자 지지체가 캐스팅된 것을 사용할 수 있는데, 이러한 고분자로는 폴리술폰(polysulfone), 폴리에테르술폰(polyethersulfone), 폴리카보네이트(polycarbonate), 폴리페닐렌옥사이드(polyphenylene oxide), 폴리이미드(polyimide), 폴리에테르이미드(polyetherimide), 폴리에테르에테르케톤(polyetheretherketone), 폴리프로필렌(polypropylene), 폴리메틸펜텐(polymethylpentene), 폴리메틸클로라이드(polymethyl chloride), 및 폴리비닐리덴플로오라이드(polyvinylidenefluoride)로 이루어진 군에서 선택될 수 있으나, 반 드시 이들로 제한되는 것은 아니다.The microporous support that can be used in the embodiments of the present invention may be a polymer support cast on a nonwoven fabric such as polyester, such polymers, such as polysulfone, polyethersulfone, polycarbonate ( polycarbonate, polyphenylene oxide, polyimide, polyetherimide, polyetheretherketone, polypropylene, polymethylpentene, polymethylchloride polymethyl chloride), and polyvinylidene fluoride, but are not necessarily limited thereto.
상기 미세다공성 지지체의 기공 크기는 1 내지 500nm 인 것이 바람직하며, 기공 크기가 500nm 이상일 경우에는 코팅층이 기공 사이로 스며들어 균일한 구조를 형성하기 어렵다. The pore size of the microporous support is preferably 1 to 500 nm, and when the pore size is 500 nm or more, it is difficult to form a uniform structure by the coating layer penetrating between the pores.
상기 제조방법에 있어서, 미세다공성 지지체에 다관능성 아민 수용액을 코팅하는 방법으로는 습식 코팅법으로 다관능성 아민 수용액에 침지하는 딥 코팅, 스핀 코팅, 스프레이 코팅 등 공지된 바의 방법이 가능하며, 연속공정 또는 핸디코팅 등을 이용할 수 있으며, 코팅 공정은 30초 내지 10분간 수행될 수 있다. 상기 다관능성 아민은 탄소수 1 내지 6의 알킬기, 탄소수 1 내지 6의 알콕시기, 하이드록시알킬기, 하이드록시기 또는 할로겐 원자 등으로 치환된 방향족 다관능성 아민, 또는 벤지딘, 디아미노벤지딘 또는 알킬 또는 할로겐 원자 등으로 치환된 벤지딘 유도체와 나프탈렌다이아민과 같은 다관능성 아민일 수 있다. 상기 다관능성 아민의 보다 구체적인 예로는 o-페닐렌디아민(o-phenylenediamine), m-페닐렌디아민(m-phenylenediamine), p-페닐렌디아민(p-phenylenediamine), 1,3,5-벤젠트리아민(1,3,5-benzenetriamine), 4-클로로-1,3-페닐렌디아민(4-chloro-1,3-phenylenediamine), 5-클로로-1,3-페닐렌디아민(5-chloro-1,3-phenylenediamine) 또는 3-클로로-1,4-페닐렌디아민(3-chloro-1,4-phenylenediamine) 등을 들 수 있으나, 반드시 이들로 제한되는 것은 아니다.In the above production method, as a method of coating the polyfunctional amine aqueous solution on the microporous support, a known method such as dip coating, spin coating, spray coating, etc., immersed in the aqueous polyfunctional amine solution by a wet coating method is possible, and continuous Process or hand coating may be used, the coating process may be performed for 30 seconds to 10 minutes. The polyfunctional amine is an aromatic polyfunctional amine substituted with an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyalkyl group, a hydroxy group or a halogen atom, or a benzidine, diaminobenzidine or an alkyl or halogen atom. And a polyfunctional amine such as a benzidine derivative substituted with naphthalenediamine and the like. More specific examples of the polyfunctional amine include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 1,3,5-benzenetri Amine (1,3,5-benzenetriamine), 4-chloro-1,3-phenylenediamine, 5-chloro-1,3-phenylenediamine 1,3-phenylenediamine) or 3-chloro-1,4-phenylenediamine, and the like, but are not necessarily limited thereto.
이 때, 상기 다관능성 아민 수용액의 다관능성 아민은 0.1 내지 20중량% 포함되는 것이 바람직하며, 더욱 바람직하게는 1.0 내지 10중량%, 가장 바람직하게는 1.5 내지 4중량%가 사용될 수 있다. At this time, the polyfunctional amine of the aqueous polyfunctional amine solution is preferably included 0.1 to 20% by weight, more preferably 1.0 to 10% by weight, most preferably 1.5 to 4% by weight may be used.
또한, 본 발명의 다른 구현예에 따르면, 다관능성 아민 수용액은 첨가제로서 소듐 라우릴 설페이트(sodium lauryl sulfate), 소듐 도데실벤젠술포네이트(sodium dodecylbenzenesulfonate), 캠포술폰산 (camphorsulfonic acid)을 추가로 포함할 수 있다. 또한, 다관능성 아민 수용액은 산수용체(acid acceptor)로서, 소듐아세테이트, 소듐바이카보네이트 또는 트리에틸아민 등을 추가로 포함할 수도 있다. According to another embodiment of the present invention, the aqueous polyfunctional amine solution may further include sodium lauryl sulfate, sodium dodecylbenzenesulfonate, and camphorsulfonic acid as additives. Can be. The aqueous polyfunctional amine solution may further include sodium acetate, sodium bicarbonate, triethylamine, or the like as an acid acceptor.
미세다공성 지지체에 다관능성 아민 수용액을 코팅한 후, 표면의 과잉의 용액을 롤을 이용한 압착기, 에어나이프 또는 스펀지 등을 이용하여 제거하여 제 1 박막을 형성한다.After coating the multifunctional amine aqueous solution on the microporous support, the excess solution on the surface is removed using a press using a roll, an air knife or a sponge to form a first thin film.
이어서, 상기 다관능성 아민 수용액으로 코팅된 미세다공성 지지체의 적어도 일측면에 폴리아마이드 활성층을 형성하는 단계는 상기 제 1 박막이 형성된 미세다공성 지지체와 다관능성 아실할라이드, 다관능성 술포닐할라이드 또는 다관능성 이소시아네이트를 포함하는 지방족 탄화수소계 유기용액을 접촉함으로써 수행되며, 상기 접촉은 디핑(dipping) 또는 스프레이 방법에 의해 수행될 수 있으나, 반드시 이들로 제한되는 것은 아니다. 계면중합 단계는 5초 내지 10분 동안 수행될 수 있으며, 보다 바람직하게는 20초 내지 4분 동안 수행될 수 있다.Subsequently, the step of forming the polyamide active layer on at least one side of the microporous support coated with the aqueous polyfunctional amine solution may include the microporous support on which the first thin film is formed and the polyfunctional acyl halide, polyfunctional sulfonyl halide or polyfunctional isocyanate. It is carried out by contacting an aliphatic hydrocarbon-based organic solution comprising a, the contact may be carried out by a dipping or spray method, but is not necessarily limited thereto. The interfacial polymerization step may be performed for 5 seconds to 10 minutes, more preferably 20 seconds to 4 minutes.
이때, 상기 지방족 탄화수소계 유기용액은 트리메조일클로라이드, 이소프탈로일클로라이드 및 테레프탈로일클로라이드로 이루어진 군에서 선택되는 1종 이상의 다관능성 아실할라이드 0.01 내지 1 중량%를 포함할 수 있다. In this case, the aliphatic hydrocarbon-based organic solution may include 0.01 to 1% by weight of at least one polyfunctional acyl halide selected from the group consisting of trimezoyl chloride, isophthaloyl chloride and terephthaloyl chloride.
또한, 이때 사용되는 지방족 탄화수소 용매는 계면 중합반응에 참가하지 않 아야 하고 아실할라이드와 화학적 결합이 없어야 하며 다공성 지지층에 손상을 입혀서는 안 되는 조건을 만족시켜야 한다. In addition, the aliphatic hydrocarbon solvents used should not participate in interfacial polymerization, must be free of chemical bonds with acyl halides and must not damage the porous support layer.
폴리아마이드 활성층으로 된 제 2 박막이 형성된 미세다공성 지지체를 건조한 후, 세척함으로써 후처리 공정 이전의 폴리아마이드 역삼투 분리막을 수득할 수 있다. 건조와 세척단계는 특별히 제한되지 아니하고, 당해 기술 분야에서 통상적으로 사용하는 것을 적용할 수 있으나, 일례를 들어 설명하면, 상온에서 건조할 수 있고, 용매가 어느 정도 증발되었다고 여겨지면, 30 내지 120℃의 상태로 30초 내지 10분간 완전 건조시킨 후, 이러한 박막을 다시 상온으로 식힌 다음 20 내지 80℃의 탄산나트륨 수용액에서 30분 내지 1시간 동안 세정한 후 순수에 넣어서 보관하면 1차로 폴리아마이드 역삼투 분리막을 제조할 수 있다.The polyamide reverse osmosis membrane before the post-treatment process may be obtained by drying and then washing the microporous support on which the second thin film of the polyamide active layer is formed. The drying and washing steps are not particularly limited, and may be those conventionally used in the art, but, for example, may be dried at room temperature, and if the solvent is evaporated to some extent, 30 to 120 ° C. After completely drying for 30 seconds to 10 minutes in the state of, the film is cooled again to room temperature, and then washed for 30 minutes to 1 hour in an aqueous sodium carbonate solution at 20 to 80 ℃ and then stored in pure water, polyamide reverse osmosis membrane first Can be prepared.
본 발명의 또 다른 양상은 상기 제조방법에 따라 제조된 폴리아마이드 역삼투 분리막에 관계한다. 본 발명의 구현예들에 의한 폴리아마이드 역삼투 분리막은 다공성 지지체; 및 상기 다공성 지지체의 적어도 일측면에 형성된 폴리아마이드 활성층을 포함한다. 상기 폴리아마이드 역삼투 분리막은 높은 염배제율을 지니면서도 고유량의 특성을 가지므로 해수 및 염수의 담수화, 반도체 산업용 초순수 제조 및 각종 산업용 폐수의 처리에 유용하게 사용될 수 있다.Another aspect of the invention relates to a polyamide reverse osmosis membrane prepared according to the above method. Polyamide reverse osmosis membrane according to embodiments of the present invention is a porous support; And a polyamide active layer formed on at least one side of the porous support. Since the polyamide reverse osmosis membrane has a high salt rejection rate and has a high flow rate characteristic, the polyamide reverse osmosis membrane may be usefully used for desalination of seawater and brine, preparation of ultrapure water for semiconductor industry, and treatment of various industrial wastewater.
이하, 본 발명의 이해를 돕기 위하여 하기의 실시예를 통하여 본 발명을 더욱 상세히 설명하지만, 본 발명에 따른 실시예들을 다양하게 변형될 수 있으며, 본 발명의 범위가 하기의 실시예에 한정되는 것으로 해석되어서는 아니된다.Hereinafter, the present invention will be described in more detail with reference to the following examples in order to help understand the present invention, but various modifications may be made to the embodiments according to the present invention, and the scope of the present invention is limited to the following examples. It should not be interpreted.
제조예 1Preparation Example 1
폴리에스테르 부직포 상에 디메틸포름아미드(dimethylformamide) 82중량%와 폴리술폰 18중량%를 포함하는 용액을 160㎛ 두께로 캐스팅하고, 이를 즉시 25℃의 증류수 응고액에 침지하여 고형화시킨 후, 부직포를 보강하는 폴리술폰 미세다공성 기질을 충분히 수세하여 기질 중의 잔류 용매를 물과 치환한 후 순수에 보관하였다.A solution containing 82 wt% of dimethylformamide and 18 wt% of polysulfone was cast on a polyester nonwoven fabric to a thickness of 160 μm, immediately immersed in a distilled water coagulation solution at 25 ° C., and solidified, and then reinforced. The polysulfone microporous substrate was washed with water sufficiently and the residual solvent in the substrate was replaced with water and then stored in pure water.
상기와 같이 얻은 폴리술폰 미세다공성 지지체를 메타페닐렌디아민 2중량%, 벤조산 1.5중량%, 소듐 라우릴 설페이트(Sodium Lauryl Sulfate, SLS) 0.2 중량%, 캠포술폰산(camphorsulfonic acid) 2.2 중량%, 트리에틸아민 4.4 중량% 및 잔량으로서 물을 포함하는 다관능성 아민 수용액에 2분간 침지시킨 후 표면의 물기를 제거하였다. 상기 다관능성 아민 수용액이 코팅된 미세다공성 지지체를 트리메조일클로라이드 0.1중량%를 아이오파(IsoPar, EXXON 사) 용매에 용해시킨 유기용액에 1분간 함침시킨 후, 공기 중에서 건조하고 탄산나트륨 0.2중량%를 포함하는 수용액 상에서 30분간 수세한 후 상온에서 순수로 다시 세정하여 1차로 폴리아마이드 역삼투 분리막을 제조하였다. The polysulfone microporous support obtained as above was 2% by weight of metaphenylenediamine, 1.5% by weight of benzoic acid, 0.2% by weight of sodium lauryl sulfate (SLS), 2.2% by weight of camphorsulfonic acid, triethyl After immersion for 2 minutes in an aqueous polyfunctional amine solution containing 4.4% by weight of amine and water as a balance, the surface was dried. The microporous support coated with the polyfunctional amine aqueous solution was impregnated with an organic solution in which 0.1% by weight of trimezoyl chloride was dissolved in IoPar (EXOON) solvent for 1 minute, dried in air and 0.2% by weight of sodium carbonate. After washing for 30 minutes on an aqueous solution containing, washed again with pure water at room temperature to prepare a polyamide reverse osmosis membrane first.
실시예 1Example 1
상기 제조예 1에서 1차로 제조된 폴리아마이드 역삼투 분리막을 캠포술폰산 4.4 중량% 및 트리에틸아민 2.2 중량%를 포함하는 유기염 용액에 1 시간 동안 침지시킨 후 상온에서 순수로 다시 세정하는 후처리 공정을 실시하여 폴리아마이드 역삼투 분리막을 제조하였다.A post-treatment step of immersing the polyamide reverse osmosis membrane prepared in Preparation Example 1 in an organic salt solution containing 4.4% by weight of camphorsulfonic acid and 2.2% by weight of triethylamine for 1 hour and then washed again with pure water at room temperature. To perform a polyamide reverse osmosis membrane was prepared.
실시예 2Example 2
상기 실시예 1에서 유기염 용액으로 캠포술폰산 2.2 중량% 및 트리에틸아민 1.1 중량%를 포함하는 것을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 폴리아마이드 역삼투 분리막을 제조하였다.A polyamide reverse osmosis membrane was prepared in the same manner as in Example 1, except that 2.2 wt% of camphorsulfonic acid and 1.1 wt% of triethylamine were used as the organic salt solution.
실시예 3Example 3
상기 실시예 1에서 유기염 용액으로 캠포술폰산 6.6 중량% 및 트리에틸아민 3.3 중량%를 포함하는 것을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 폴리아마이드 역삼투 분리막을 제조하였다.A polyamide reverse osmosis membrane was prepared in the same manner as in Example 1, except that 6.6% by weight of camphorsulfonic acid and 3.3% by weight of triethylamine were used as the organic salt solution.
실시예 4Example 4
상기 실시예 1에서 유기염 용액으로 캠포술폰산 6 중량% 및 N,N-디메틸에틸아민 4 중량%를 포함하는 것을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 폴리아마이드 역삼투 분리막을 제조하였다.A polyamide reverse osmosis membrane was manufactured in the same manner as in Example 1, except that 6 wt% of camphorsulfonic acid and 4 wt% of N, N-dimethylethylamine were used as the organic salt solution in Example 1.
실시예 5Example 5
상기 실시예 1에서 유기염 용액으로 0.1 N 염산 1 중량% 및 트리에틸아민 4 중량%를 포함하는 것을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 폴리아마이드 역삼투 분리막을 제조하였다. A polyamide reverse osmosis membrane was prepared in the same manner as in Example 1, except that 1 wt% of 0.1 N hydrochloric acid and 4 wt% of triethylamine were used as the organic salt solution in Example 1.
비교예 1Comparative Example 1
상기 실시예 1에서 유기염 용액으로 캠포술폰산 8 중량% 및 트리에틸아민 4 중량%를 포함하는 것을 사용한 것을 제외하고는 실시예 1과 동일한 방법으로 폴리아마이드 역삼투 분리막을 제조하였다.A polyamide reverse osmosis membrane was prepared in the same manner as in Example 1, except that 8 wt% of camphorsulfonic acid and 4 wt% of triethylamine were used as the organic salt solution.
비교예 2Comparative Example 2
제조예 1에서 1차로 제조된 폴리아마이드 역삼투 분리막을 실시예 1 내지 5에서 실시한 후처리 공정을 실시하지 아니하고 특성을 평가하였다.The polyamide reverse osmosis membrane prepared primarily in Preparation Example 1 was evaluated without performing the post-treatment process performed in Examples 1 to 5.
<역삼투 분리막의 물성 평가 방법><Method for evaluating the properties of reverse osmosis membrane>
상기 실시예 1 내지 5 및 비교예 1 내지 2에서 제조된 폴리아마이드 역삼투 분리막의 물성을 하기와 같은 방법으로 측정하여 하기 표 1에 나타내었다.The physical properties of the polyamide reverse osmosis membranes prepared in Examples 1 to 5 and Comparative Examples 1 to 2 were measured in the same manner as shown in Table 1 below.
실험예 1 - 유랑 평가Experimental Example 1 Evaluation of the Drift
유량은 25℃, 800 psi 조건 하에서 40분 동안 폴리아마이드 역삼투 분리막을 통해서 35,000ppm 의 NaCl 수용액을 통과시킨 후, 투과유량을 측정하였다.The flow rate was passed through a 35,000 ppm NaCl aqueous solution through a polyamide reverse osmosis membrane for 40 minutes at 25 ℃, 800 psi conditions, and then the permeate flow rate was measured.
실험예 2 - 염배제율 평가Experimental Example 2-Evaluation of salt excretion rate
염배제율은 아래의 식에 의하여 계산하였다.Salt exclusion rate was calculated by the following equation.
상기 식에서, R은 염배제율, C f 는 공급수중의 용질의 농도이며, C p 는 투과수중의 용질 농도이다.Where R is the salt excretion rate, C f is the concentration of the solute in the feed water, and C p is the concentration of the solute in the permeate.
상기 표 1에서 확인할 수 있는 바와 같이, 특정 함량의 유기산과 아민을 포함하는 유기염 수용액을 사용하여 후처리한 경우(실시예 1 내지 실시예 5)에는 99% 이상의 높은 염배제율을 유지하면서도 고유량 특성을 지닌 폴리아마이드 역삼투 분리막을 수득할 수 있으나, 그러한 후처리 공정을 실시하지 아니하고 제조된 폴리아마이드 역삼투 분리막의 경우(비교예 2)에는 염배제율 및 유량 측면 모두에 있어서, 저조한 성능을 보임을 확인할 수 있으며, 유기염의 함량이 12중량%인 용액을 사용한 경우(비교예 1)의 경우에는 유량은 좋아졌으나, 오히려 염배제율이 후처리 공정을 실시하기 전보다 저하됨을 확인할 수 있다.As can be seen in Table 1, in the case of post-treatment using an aqueous organic salt solution containing a specific content of an organic acid and an amine (Examples 1 to 5), while maintaining a high salt exclusion rate of 99% or more Polyamide reverse osmosis membranes having flow characteristics can be obtained, but in the case of polyamide reverse osmosis membranes prepared without performing such a post-treatment process (Comparative Example 2), poor performance in terms of both salt rejection and flow rate In the case of using a solution having an organic salt content of 12% by weight (Comparative Example 1), the flow rate was improved, but it can be confirmed that the salt excretion rate is lower than before the post-treatment process.
즉, 상기 실시예 및 비교예에 대한 실험예의 결과로부터, 본 발명과 같은 후처리 공정을 실시하여 제조된 폴리아마이드 역삼투 분리막은 높은 염배제율을 유지하면서도 고유량의 특성을 달성할 수 있음을 확인할 수 있다.That is, from the results of the experimental examples for the above Examples and Comparative Examples, the polyamide reverse osmosis membrane prepared by performing the post-treatment process as described in the present invention can achieve the characteristics of high flow rate while maintaining a high salt excretion rate You can check it.
이상에서 본 발명의 바람직한 실시예를 참고로 본 발명에 대해서 상세하게 설명하였으나, 이들은 단지 예시적인 것에 불과하며, 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자라면 이로부터 다양한 변형 및 균등한 다른 실시예가 가능하다는 점을 이해할 것이다. 따라서, 본 발명의 진정한 기술적 보호 범위는 첨부된 특허청구범위의 기술적 사상에 의하여 정해져야 할 것이다.Although the present invention has been described in detail with reference to preferred embodiments of the present invention, these are merely exemplary, and those skilled in the art to which the present invention pertains have various modifications and equivalents therefrom. It will be appreciated that embodiments are possible. Therefore, the true technical protection scope of the present invention will be defined by the technical spirit of the appended claims.
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| KR20120027748A (en) * | 2010-09-13 | 2012-03-22 | 주식회사 효성 | Method for manufacturing polyamide-based reverse osmosis membrane having antifouling property |
| WO2013176524A1 (en) * | 2012-05-24 | 2013-11-28 | 주식회사 엘지화학 | Reverse osmosis membrane |
| KR101453794B1 (en) * | 2012-11-23 | 2014-10-23 | 도레이케미칼 주식회사 | High boron rejection polyamide composite membrane and manufacturing method thereof |
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| KR100905901B1 (en) | 2006-09-07 | 2009-07-02 | 웅진코웨이주식회사 | Amine aqueous solution for forming an active layer of polyamide reverse osmosis composite membrane, polyamide reverse osmosis composite membrane prepared thereby, and preparation method thereof |
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| KR20120027748A (en) * | 2010-09-13 | 2012-03-22 | 주식회사 효성 | Method for manufacturing polyamide-based reverse osmosis membrane having antifouling property |
| WO2013176524A1 (en) * | 2012-05-24 | 2013-11-28 | 주식회사 엘지화학 | Reverse osmosis membrane |
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| KR101453794B1 (en) * | 2012-11-23 | 2014-10-23 | 도레이케미칼 주식회사 | High boron rejection polyamide composite membrane and manufacturing method thereof |
| CN104548945A (en) * | 2013-10-23 | 2015-04-29 | 中国石油化工股份有限公司 | After-treatment method for increasing flux of ultra-filtration membrane |
| US10668694B2 (en) | 2014-03-12 | 2020-06-02 | Iucf-Hyu (Industry-University Cooperation Foundation Hanyang University) | Composite film including a graphene oxide coating layer, a porous polymer support including the same and a method for preparing the same |
| KR20150108631A (en) * | 2014-03-18 | 2015-09-30 | 한양대학교 산학협력단 | Sparator membrane comprising graphene oxide coating layer having improved stability and preparation method thereof |
| CN111437732A (en) * | 2020-04-07 | 2020-07-24 | 蓝星（杭州）膜工业有限公司 | Preparation method of high-selectivity high-flux nanofiltration membrane |
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