KR20010061106A - Preparation of Polyamide Nanofiltration Membrane with a Superior Chemical Resistance - Google Patents
Preparation of Polyamide Nanofiltration Membrane with a Superior Chemical Resistance Download PDFInfo
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- KR20010061106A KR20010061106A KR1019990063592A KR19990063592A KR20010061106A KR 20010061106 A KR20010061106 A KR 20010061106A KR 1019990063592 A KR1019990063592 A KR 1019990063592A KR 19990063592 A KR19990063592 A KR 19990063592A KR 20010061106 A KR20010061106 A KR 20010061106A
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- nanofiltration membrane
- aqueous solution
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- polyamide
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- 239000012528 membrane Substances 0.000 title claims abstract description 49
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 20
- 229920002647 polyamide Polymers 0.000 title claims abstract description 15
- 239000004952 Polyamide Substances 0.000 title claims abstract description 13
- 239000000126 substance Substances 0.000 title abstract description 5
- 238000002360 preparation method Methods 0.000 title description 2
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 150000001412 amines Chemical class 0.000 claims abstract description 13
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 10
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000001266 acyl halides Chemical class 0.000 claims abstract description 5
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 4
- 239000012074 organic phase Substances 0.000 claims abstract description 4
- 239000003960 organic solvent Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract 3
- 239000003795 chemical substances by application Substances 0.000 claims abstract 2
- 125000004193 piperazinyl group Chemical group 0.000 claims abstract 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims 1
- MMIBBBCIWMMQGZ-UHFFFAOYSA-N benzene-1,3-dicarbonyl fluoride Chemical compound FC(=O)C1=CC=CC(C(F)=O)=C1 MMIBBBCIWMMQGZ-UHFFFAOYSA-N 0.000 claims 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 10
- 239000000460 chlorine Substances 0.000 abstract description 10
- 229910052801 chlorine Inorganic materials 0.000 abstract description 10
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical group ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 abstract description 6
- 238000007598 dipping method Methods 0.000 abstract description 4
- 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 2
- 239000004642 Polyimide Substances 0.000 abstract 2
- 229920001721 polyimide Polymers 0.000 abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 235000019422 polyvinyl alcohol Nutrition 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 230000007717 exclusion Effects 0.000 description 5
- 230000004907 flux Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 3
- 238000001223 reverse osmosis Methods 0.000 description 3
- 239000002352 surface water Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000004760 aramid Substances 0.000 description 2
- 229920003235 aromatic polyamide Polymers 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-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
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- YYQRGCZGSFRBAM-UHFFFAOYSA-N Triclofos Chemical group OP(O)(=O)OCC(Cl)(Cl)Cl YYQRGCZGSFRBAM-UHFFFAOYSA-N 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 244000052616 bacterial pathogen Species 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 229940015043 glyoxal Drugs 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000008233 hard water Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002516 radical scavenger Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000005728 strengthening 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
- 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
- B01D61/027—Nanofiltration
-
- 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
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- 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
- B01D71/38—Polyalkenylalcohols; Polyalkenylesters; Polyalkenylethers; Polyalkenylaldehydes; Polyalkenylketones; Polyalkenylacetals; Polyalkenylketals
- B01D71/381—Polyvinylalcohol
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
-
- 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
- B01D2323/00—Details relating to membrane preparation
- B01D2323/219—Specific solvent system
-
- 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
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
본 발명은 나노필트레이션막의 제조방법에 관한 것으로, 보다 상세하게로는 내염소성, 내유기용매성이 우수한 폴리아미드계 나노필트레이션막의 제조방법에 관한 것이다.The present invention relates to a method for producing a nanofiltration membrane, and more particularly, to a method for producing a polyamide-based nanofiltration membrane excellent in chlorine resistance and organic solvent resistance.
물에 녹아 있는 저분자 유기물, 2가 이상의 금속염 등은 나노필트레이션막에 의해 효과적으로 제거될 수 있다. 나노필트레이션막은 역삼투막으로부터 파생된 막으로 분자량 200∼1000의 유기물과 2가이상의 금속염을 제거하는데 주로 사용되며 투수량이 역삼투막에 비해 5∼10배 정도 커 수처리 비용 및 설비비를 크게 절약 할 수 있다. 주로 사용되는 분야는 정수시스템, 염색폐수중의 염료재활용 경수의 연수화, 공업용수 제조 등이 있다. 나노필트레이션막의 용도를 확대하기 위해서는 다음과 같은 몇 가지 조건을 만족하여야 한다.Low molecular organics, divalent or more metal salts dissolved in water can be effectively removed by the nanofiltration film. Nanofiltration membranes are membranes derived from reverse osmosis membranes and are mainly used to remove organic matters with molecular weights of 200-1000 and divalent or higher metal salts. The main fields of use include water purification systems, softening of dye recycled hard water in dyeing wastewater, and manufacturing industrial water. In order to expand the use of the nanofiltration film, several conditions must be satisfied.
내구성, 내압축성이 뛰어나야 하고 또는 pH와 온도 및 세균의 공격 및 염소와 같은 산화성 물질에 대한 내구성이 뛰어나야 한다. 대부분의 상업용 막들은 위의 대부분의 조건을 만족하나 가장 취약한 부분이 내산화성이다. 수처리시 수중의세균을 제거하기 위해 염소를 많이 사용하는데 방향족 폴리아마이드의 내염소성이 약해 장기 사용할 때 막의 투과성능이 매우 떨어지는 현상이 일어난다.It must be durable, compressible or resistant to pH and temperature and bacterial attack and to oxidizing substances such as chlorine. Most commercial membranes meet most of the above conditions, but the most vulnerable is oxidation resistance. Chlorine is used a lot to remove germs in water during water treatment. The chlorine resistance of aromatic polyamides is weak so that the permeability of the membrane becomes very poor when used for a long time.
미국특허 제 3,951,815호에서 염소는 폴리아마이드의-CO-NH그룹중 H를 공격한다. 따라서 모든 종류의 폴리아마이드는 강약의 차이는 있지만 내염소성이 취약할 수 밖에 없다. 미국특허 제 4,277,344호는 방향족폴리아마이드 복합막 제조법에 대한 특허인데 제조법은 다음과 같다.In US Pat. No. 3,951,815 chlorine attacks H in the -CO-NH group of polyamides. Therefore, all kinds of polyamides have different strengths and weaknesses, but are inevitably weak in chlorine resistance. U.S. Patent No. 4,277,344 discloses an aromatic polyamide composite membrane manufacturing method, which is as follows.
20mm이하의 기공을 갖는 지지체용 평막형 한외여과막을 메타펜닐렌이아민이 1∼4w% 함유된 수용액에 함침시킨 다음 꺼내어 표면수를 제거하고 0.1w%의 트리메조일크로라이드가 함유된 트리크롤로트리플오로에탄(FREON)액에 약 10초간 함침시킨 후 꺼내어 공기 중에 건조시켜 복합막이 만들어진다. 이 특허에서는 막의 내 산화성을 강화시키기 위해 그리옥살과 트리에틸아민이 각각 2% 함유된 수용액에 10분간 담그었다.A flat membrane-type ultrafiltration membrane for a support having pores of 20 mm or less was impregnated in an aqueous solution containing 1 to 4 w% of metafenylene diamine, and then taken out to remove surface water and trichloryl containing 0.1 w% of trimezoyl chloride. It is impregnated with a low triple uroethane (FREON) solution for about 10 seconds, then taken out and dried in air to form a composite membrane. The patent immersed in an aqueous solution containing 2% of glyoxal and triethylamine for 10 minutes to enhance the oxidation resistance of the membrane.
다른 방법으로는 100ppm의 하이포클로라이드가 함유된 수용액에 1일간 담근 다음에 오븐에서 110℃로 건조하여 막의 내산화성을 향상시켰다. 즉 막을 미리 산화시킴으로서 실제 수처리 공정에서 사용할 때 막의 산화를 막는 방식이다. 그러나 위와 같은 방법으로 내산화성을 강화시키는 것은 한 단계의 제조공정이 추가되고 막이 산화된 상태로 제조되기 때문에 막의 내구성 등이 저하될 수 있는 등의 문제점을 안고 있다.Alternatively, it was immersed in an aqueous solution containing 100 ppm of hypochloride for 1 day and then dried at 110 ° C. in an oven to improve the oxidation resistance of the membrane. In other words, the membrane is oxidized in advance to prevent oxidation of the membrane when used in an actual water treatment process. However, strengthening the oxidation resistance in the above method has a problem that the durability of the membrane may be lowered because the manufacturing process of one step is added and the membrane is manufactured in an oxidized state.
본 발명은 상기한 바와 같은 문제점을 해결하기 위한 것으로, 내화학성이 향상된 폴리아미드계 나노필트레이션막의 제조방법을 제공하는 것을 목적으로 한다.The present invention is to solve the problems described above, and an object of the present invention is to provide a method for producing a polyamide-based nanofiltration membrane with improved chemical resistance.
본 발명의 제조방법은 폴리아마이드 나노필트레이션막을 제조하는 데 있어서 지지체용 한외여과막을 아민이 함유된 수용액에 담근 다음 아실할라이드가 녹아 있는 유기상 용매에 담그어 계면중합에 의하여 폴리아마이드를 제조하는 것으로 구성된다.In the preparation method of the polyamide nanofiltration membrane, the polyamide is prepared by dipping the ultrafiltration membrane for the support into an aqueous solution containing an amine and then dipping it in an organic solvent in which acyl halide is dissolved. .
이하, 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail.
나노필트레이션막과 같은 복합막제조시에는 지지체용 한외여과막이 필요하다. 한외여과막의 기공의 크기가 너무 적을 때는 투수성이 저하되며 너무 클때는 복합막 제조가 잘 되지 않는다. 따라서 기공의 크기는 10∼50mm, 분획분자량(molecular weight cut-off, MWCO)는 5,000∼100,000인 지지체용 한외여과막(ultrafiltration membrane)이 가장 적합하다.In manufacturing a composite membrane such as a nanofiltration membrane, an ultrafiltration membrane for a support is required. When the pore size of the ultrafiltration membrane is too small, the permeability is lowered, and when it is too large, the composite membrane is not well prepared. Therefore, an ultrafiltration membrane for a support having a pore size of 10 to 50 mm and a molecular weight cut-off (MWCO) of 5,000 to 100,000 is most suitable.
이 한외과막위에 계면중합에 의해 폴리아마이드가 코팅되는데 이때 사용되는 아민은 메타페닐렌디아민(m-phenylonediamine), 파라페닐렌디아민(p-phenylenediamine)또는 피페라진(piperazinc)등이 쓰이는데 이중 피페라진은 보통 저압용 역삼투막 또는 나노필트레이션막에 주로 쓰이고 역삼투막에는 메타페닐렌디아민이 가장 적합하며 그 양은 0.002∼3w%가 적합하다. 복합막의 내화학성을 향상시키고자 첨가되는 폴리비닐알콜(polyvinylalcohol)는 0.01∼5w%가 적합하며 이 범위를 초과할 경우에는 계면중합이 잘 일어나지 않는다.Polyamide is coated on the ultrafiltration membrane by interfacial polymerization. The amines used are m-phenylonediamine, paraphenylenediamine or piperazinc. It is usually used for low pressure reverse osmosis membrane or nanofiltration membrane, and metaphenylenediamine is most suitable for reverse osmosis membrane, and its amount is 0.002 ~ 3w%. Polyvinyl alcohol (polyvinylalcohol) is added to improve the chemical resistance of the composite membrane is 0.01 ~ 5w% is suitable, if it exceeds this range, the interfacial polymerization does not occur well.
계면반응 중 발생하는 염산을 제거하기 위해 산제거제로는 소디움하이드록사이드(sodium hydroxide)가 사용되며 함량은 0.01∼5w%가 적합하다. 위의 피페라진, 폴리비닐알콜 및 소디움하이드로옥사이드는 증류수에 용해시켜 아민수용액을 제조한다.In order to remove hydrochloric acid generated during the interfacial reaction, sodium hydroxide is used as an acid remover, and a content of 0.01 to 5 w% is suitable. The above piperazine, polyvinyl alcohol and sodium hydrooxide are dissolved in distilled water to prepare an amine solution.
폴리아마이드 제조시 사용되는 산(acid)은 트리메조일클로라이드 (trimesoylchloride, "TMC"), 이소프탈로일클로라이드(isophthaloylchloride)등의 폴리아실할라이드가 사용되며 이중 트리메조일클로라이드를 사용할 때 코팅층의 가교도 낮아 배제율이 낮아 지는 단점이 있어 TMC가 선호되며 그 양은 0.01∼3w%이다. 이 TMC를 헥산에 녹여 아민용액을 제조한다.Acid used in polyamide production is polyacyl halide such as trimesoylchloride (TMC) and isophthaloyl chloride, and the degree of crosslinking of the coating layer when double trimezoyl chloride is used. TMC is preferred because of the low exclusion rate, and the amount is 0.01 to 3w%. This TMC is dissolved in hexane to prepare an amine solution.
나노필트레이션막은 한외여과막을 아민수용액에 1∼20분간 담그고 꺼내어 표면수를 고무 롤러로 제거한 다음 위의 유기상용액에 1∼1000초간 담그고 꺼내어 공기중에 건조시키거나 50∼150℃에서 20∼60시간 건조시켜 제조한다.The nanofiltration membrane is immersed in an amine aqueous solution for 1 to 20 minutes and removed by removing the surface water with a rubber roller, then immersed in the above organic phase solution for 1 to 1000 seconds, and dried in air or dried for 20 to 60 hours at 50 to 150 ° C. To make it.
본 발명의 실시예는 아래와 같다.An embodiment of the present invention is as follows.
<실시예 1><Example 1>
16w%의 폴리설폰 레진이 녹아 있는 노말메틸피롤리돈(N-methylpyrrolido NMP)용액을 유리판위에 캐스팅한 다음에 이 유리판을 물에 담구어 응고시켜 지지 체용 한외여과막을 제조하였다. 이렇게 제조된 한외여과막의 표면 기공 크기는 5∼50mm로 평균 25mm였다. 이지지체용 한외여과막을 피페라진(Piperazine) 1w%, 분자량 50,000의 폴리비닐알콜(polyvinylalcohol. PVA)이 0.5w%, 반응 중 발생하는 염산을 제거하기 위해 산제거제로 소디움하이드록사이드(sodium hydroxide, NaOH) 0.5w%가 함유된 수용액에 담그고 꺼내어 표면수를 고무 roller로 제거한 다음에 트리메조일크로라이드(trimesoylchloride)가 0.2w% 함유된 헥산용액에 담그고 꺼내어 100℃에서 10분간 건조시켰다.An N-methylpyrrolido NMP solution containing 16w% of polysulfone resin was cast on a glass plate, and the glass plate was immersed in water to coagulate to prepare an ultrafiltration membrane for a support body. The surface pore size of the ultrafiltration membrane thus prepared was 5 to 50 mm with an average of 25 mm. The ultrafiltration membrane for this support was composed of 1% by weight of piperazine, 0.5% by weight of polyvinylalcohol (PVA) with a molecular weight of 50,000, and sodium hydroxide as an acid scavenger to remove hydrochloric acid generated during the reaction. NaOH) was immersed in an aqueous solution containing 0.5w% and taken out to remove the surface water with a rubber roller, and then immersed in a hexane solution containing 0.2w% of trimesoylchloride and dried for 10 minutes at 100 ℃.
투과실험은 0.3%의 Na2SO4이 함유된 수용액을 10atm의 압력하에서 24시간 동안 실시하였다. 막의 염배제율은 97.1%, 플럭스는 2.9ton/㎡day였다.Permeation experiments were carried out for 24 hours in an aqueous solution containing 0.3% Na 2 SO 4 at a pressure of 10atm. The salt rejection rate of the membrane was 97.1% and the flux was 2.9ton / m 2 day.
<실시예 2∼4><Examples 2-4>
피페라진의 농도만 제외하고 실시예 1과 같은 방법으로 실험을 실하였다. 실험결과는 표에 나타내었다.The experiment was carried out in the same manner as in Example 1 except for the concentration of piperazine. The experimental results are shown in the table.
<실시예 5∼7><Examples 5-7>
폴리비닐알콜의 농도만 제외하고 실시예 1과 같은 방법으로 실험하였다. 실험 결과는 표에 나타내었다.The experiment was conducted in the same manner as in Example 1 except for the concentration of polyvinyl alcohol. The experimental results are shown in the table.
<비교예 1∼4><Comparative Examples 1-4>
폴리비닐알콜을 넣지 않고 실시예 1∼4와 동일하게 실험하였다. 이렇게 제조된 막들의 투과실험 결과가 아래 표에 나타나 있다. 또한 실시예 1∼7 및 비교예 1∼4의 방법으로 제조된 나노필트레이션막을 하이포클로라이드(hypochloride) 100ppm 수용액에 24시간 담가두어 막의 내염소성 실험을 실시하였다.The experiment was carried out in the same manner as in Examples 1 to 4 without adding polyvinyl alcohol. The results of permeation experiments of the membranes thus prepared are shown in the table below. In addition, the nanofiltration membranes prepared by the methods of Examples 1 to 7 and Comparative Examples 1 to 4 were immersed in a 100 ppm aqueous solution of hypochloride for 24 hours to conduct chlorine resistance experiments.
( )안은 나노필트레이션막을 하이포클로라이드(hypochloride) 100ppm 수용액에 24시간 담근후의 투과특성, 적용압력 : 10atmIn (), permeation characteristics after soaking nanofiltration membrane in 100 ppm aqueous solution of hypochloride for 24 hours, application pressure: 10atm
이상의 실시예를 통하여 알 수 있는 바와 같이, 본 발명에 의하여 얻어진 나노필트레이션막은 내염소성이 우수하여 수처리시 살균과정에서 주입된 염소의 공격에 대한 내구성이 향상되었다.As can be seen through the above embodiment, the nanofiltration membrane obtained by the present invention has excellent chlorine resistance and improved durability against attack of chlorine injected during sterilization during water treatment.
Claims (6)
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