KR20030076013A - Nanofiltration composite membrane and the process for the preparing the same - Google Patents
Nanofiltration composite membrane and the process for the preparing the same Download PDFInfo
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- KR20030076013A KR20030076013A KR1020020015639A KR20020015639A KR20030076013A KR 20030076013 A KR20030076013 A KR 20030076013A KR 1020020015639 A KR1020020015639 A KR 1020020015639A KR 20020015639 A KR20020015639 A KR 20020015639A KR 20030076013 A KR20030076013 A KR 20030076013A
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- 239000012528 membrane Substances 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 14
- 230000008569 process Effects 0.000 title description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 18
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000004952 Polyamide Substances 0.000 claims abstract description 14
- GLUUGHFHXGJENI-UHFFFAOYSA-N diethylenediamine Natural products C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229920002647 polyamide Polymers 0.000 claims abstract description 14
- 150000001412 amines Chemical class 0.000 claims abstract description 12
- 239000000243 solution Substances 0.000 claims abstract description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 8
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 6
- 150000004820 halides Chemical class 0.000 claims abstract description 6
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000003960 organic solvent Substances 0.000 claims abstract description 5
- -1 polyoxyethylene p-tert octylphenyl ether Polymers 0.000 claims abstract description 5
- 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 claims abstract description 4
- 239000001488 sodium phosphate Substances 0.000 claims abstract description 4
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims abstract description 4
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims abstract description 4
- 235000019801 trisodium phosphate Nutrition 0.000 claims abstract description 4
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 125000004193 piperazinyl group Chemical group 0.000 claims abstract 2
- 238000007654 immersion Methods 0.000 claims description 3
- 239000002516 radical scavenger Substances 0.000 claims description 2
- 230000035699 permeability Effects 0.000 abstract description 11
- 239000004094 surface-active agent Substances 0.000 abstract description 5
- 238000007598 dipping method Methods 0.000 abstract 3
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 230000000379 polymerizing effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 6
- 239000013504 Triton X-100 Substances 0.000 description 5
- 229920004890 Triton X-100 Polymers 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000001223 reverse osmosis Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000011148 porous material 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
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229940018564 m-phenylenediamine Drugs 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000600 sorbitol Substances 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- BOSAWIQFTJIYIS-UHFFFAOYSA-N 1,1,1-trichloro-2,2,2-trifluoroethane Chemical compound FC(F)(F)C(Cl)(Cl)Cl BOSAWIQFTJIYIS-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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229920003235 aromatic polyamide Polymers 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000005470 impregnation Methods 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
- 229920002113 octoxynol Polymers 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
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- 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
- B01D61/027—Nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0095—Drying
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/1213—Laminated layers
-
- 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
-
- 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
- B01D2323/15—Use of additives
- B01D2323/216—Surfactants
-
- 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
Abstract
Description
본 발명은 계면중합법으로 나노필트레이션 복합막을 제조하는 방법에 관한 것으로, 보다 상세하게는 나노필트레이션 복합막 제조시 계면활성제를 첨가하여 투과 성능이 뛰어난 나노필트레이션 복합막을 제조하는 방법에 관한 것이다. 또한 이러한 방법으로 제조한 나노필트레이션 복합막에 관한 것이다.The present invention relates to a method for producing a nanofiltration composite membrane by the interfacial polymerization method, and more particularly to a method for producing a nanofiltration composite membrane having excellent permeability by the addition of a surfactant in the production of nanofiltration composite membrane. . In addition, the present invention relates to a nanofiltration composite membrane prepared by such a method.
물에 용해되어 있는 저분자량 유기물, 2가 이상의 금속염 등은 나노필트레이션 복합막을 사용하여 효과적으로 제거할 수 있다. 나노필트레이션 복합막은 역삼투 막으로부터 파생된 막으로, 분자량이 200 내지 1000인 유기물, 2가 이상의 금속염 및 저분자량 유기물을 제거하는 데 주로 사용되고 있으며, 투수량이 역삼투 막에 비해 5 내지 10배 정도 크기 때문에, 수처리 비용과 설비비를 크게 절약할 수 있는 이점이 있다. 나노필트레이션 복합막이 주로 사용되고 있는 분야로는 정수 시스템, 염색 폐수 속에 함유된 염료의 재활용, 경수(硬水)의 연수화(軟水化), 공업용수의 제조 등을 들 수 있다.Low molecular weight organic substances, divalent or more metal salts, and the like dissolved in water can be effectively removed using nanofiltration membranes. Nanofiltration composite membrane is a membrane derived from reverse osmosis membrane, and is mainly used to remove organic material of 200 to 1000 molecular weight, divalent or higher metal salt, and low molecular weight organic substance, and the permeability is about 5 to 10 times that of reverse osmosis membrane. Because of its size, there is an advantage that can greatly reduce the cost of water treatment and equipment. Nanofiltration composite membranes are mainly used in water purification systems, recycling of dyes contained in dyeing wastewater, softening soft water, and production of industrial water.
나노필트레이션 복합막의 용도를 확대하기 위해서는 다음과 같은 몇 가지 조건을 만족시켜야 한다. 즉, 투수성, 내구성, 내압축성이 뛰어나야 하고, pH와 온도 및 세균의 공격 및 염소와 같은 산화성 물질에 대한 내구성이 뛰어나아야 한다. 대부분의 상업용 막들은 위의 대부분의 조건을 만족시키지만, 가장 개선해야 할 점은 투수성 향상에 있다. 투수성을 향상시키면, 공정의 설비비, 운전 비용 등이 절감되어 나노필트레이션 복합막의 사용이 보다 증대될 것이다.In order to expand the use of the nanofiltration composite membrane, several conditions must be satisfied. That is, it must be excellent in permeability, durability and compression resistance, and should be excellent in pH and temperature, bacterial attack and resistance to oxidizing substances such as chlorine. Most commercial membranes satisfy most of the above conditions, but the most important improvement is in improving permeability. Improving the water permeability will reduce the process cost, operating cost, etc. of the process will further increase the use of nanofiltration composite membrane.
방향족 폴리아미드 복합막의 제조방법에 관한 사사키(Sasaki) 등의 미국 특허 제4,758,343호에서는, 지지체용 평막형 한외여과막을 피페라진 1 내지 4중량%, 1,3-비스-(4-피페리딜)프로판 0.05 내지 0.5중량부[피페라진 1중량부를 기준으로 함], 나트륨 도데실 설페이트, 트리나트륨 포스페이트 및 소르비톨 0 내지 1.0%를 함유하는 수용액에 함침시키고, 함침 용액으로부터 꺼내어 표면수를 고무 롤러로 제거한 다음, 70℃에서 1분 동안 건조시키고, 이소프탈로일 클로라이드 또는 트리메조일 클로라이드를 함유하는 트리클로로트리플루오로에탄(FREON) 용액에 약 10초 동안 함침시킨 다음, 100℃의 공기 속에서 건조시켜 복합막을 제조하고 있다. 소르비톨의 농도가 0%에서 1.0%로 높아짐에 따라 플럭스[flux(15기압, 25℃, 염화나트륨 0.15중량% 함유)]는 1.7에서 2.4로 높아졌지만, 염 배제율(salt rejection)은 큰 변화가 없었다. 그러나 투수성을 보다 향상시켜야만 나노필트레이션 복합막에 의한 수처리시 처리 비용이 감소되어 나노필트레이션 복합막의 사용이 확대될 것이다.In US Patent No. 4,758,343 to Sasaki et al. Concerning a method for producing an aromatic polyamide composite membrane, 1 to 4% by weight of piperazine, 1,3-bis- (4-piperidyl) Impregnated in an aqueous solution containing 0.05 to 0.5 parts by weight of propane (based on 1 part by weight of piperazine), sodium dodecyl sulfate, trisodium phosphate and sorbitol, taken out of the impregnation solution, and the surface water was removed with a rubber roller. Next, the mixture was dried at 70 ° C. for 1 minute, immersed in a trichlorotrifluoroethane (FREON) solution containing isophthaloyl chloride or trimesoyl chloride for about 10 seconds, and then dried in air at 100 ° C. The membrane is manufactured. As the sorbitol concentration increased from 0% to 1.0%, the flux (15 atm, 25 ° C, containing 0.15% by weight of sodium chloride) increased from 1.7 to 2.4, but the salt rejection did not change significantly. . However, the permeability should be further improved to reduce the treatment cost during water treatment by the nanofiltration composite membrane, thereby expanding the use of the nanofiltration composite membrane.
본 발명은 수처리에 적합한 폴리아미드 고분자 복합막의 제조방법에 관한 것이다.The present invention relates to a method for producing a polyamide polymer composite membrane suitable for water treatment.
즉, 본 발명은That is, the present invention
지지체용 한외여과막을 아민 및 비이온성 계면활성제 함유 수용액에 침지시켜서 폴리아미드를 형성하는 단계,Immersing the ultrafiltration membrane for the support in an aqueous solution containing an amine and a nonionic surfactant to form a polyamide,
침지 용액으로부터 한외여과막을 꺼내어 폴리아실 할라이드가 용해되어 있는 유기 용매에 침지시키는 단계 및Removing the ultrafiltration membrane from the immersion solution and immersing it in an organic solvent in which the polyacyl halide is dissolved; and
계면중합시켜 폴리아미드를 형성시키고, 건조시키는 단계를 포함하여, 폴리아미드 나노필트레이션 복합막을 제조하는 방법에 관한 것이다.It relates to a method for producing a polyamide nanofiltration composite membrane, including the step of interfacial polymerization to form a polyamide, and drying.
나노필트레이션 복합막과 같은 복합막의 제조에서는 지지체용 한외여과막이 필요하다. 한외여과막의 기공 크기가 너무 작은 경우에는 투수성이 저하되는 반면, 이의 기공 크기가 너무 큰 경우에는 복합막의 제조가 이루어지지 않는다. 따라서 기공의 크기가 2 내지 5㎚이고 분획 분자량(molecular weight cut-off, MWCO)이 5,000 내지 100,000인 지지체용 한외여과막(ultrafiltration membrane)이 가장 적합하다.In the production of a composite membrane such as a nanofiltration composite membrane, an ultrafiltration membrane for a support is required. If the pore size of the ultrafiltration membrane is too small, the permeability is lowered, whereas if the pore size is too large, the composite membrane is not produced. Therefore, an ultrafiltration membrane for a support having a pore size of 2 to 5 nm and a molecular weight cut-off (MWCO) of 5,000 to 100,000 is most suitable.
이러한 한외여과막 위에 계면중합에 의해 폴리아미드가 피복되는데, 이때 사용되는 아민으로서는 m-페닐렌 디아민(m-phenylene diamine), p-페닐렌 디아민(p-phenylenediamine) 또는 피페라진 등이 사용되고 있는데, 이들 중에서 피페라진은 보통 저압용 역삼투 막 또는 나노필트레이션 복합막에 주로 사용되고 있으며, 역삼투 막에는 m-페닐렌 디아민이 가장 적합하며, 이의 사용량은 0.01 내지 3중량%가 적합하다. 0.01중량% 미만이면 활성층이 잘 형성되지 않고, 3중량%을 초과하면 활성층이 두꺼워져 투수량이 감소하는 문제점이 있다.Polyamide is coated on the ultrafiltration membrane by interfacial polymerization, and m-phenylene diamine, p-phenylenediamine, or piperazine is used as the amine used. Among the piperazine is usually mainly used for low pressure reverse osmosis membrane or nanofiltration composite membrane, m-phenylene diamine is most suitable for reverse osmosis membrane, the amount of use is preferably 0.01 to 3% by weight. If it is less than 0.01% by weight, the active layer is not well formed, and if it exceeds 3% by weight, the active layer becomes thick and there is a problem in that the amount of permeation decreases.
복합막의 투수성을 향상시키기 위해 아민 용액에 첨가되는 계면활성제는 비이온성 계면활성제인데, 예를 들면, 폴리옥시에틸렌 알킬 아민(polyoxyethylene alkyl amine), 코코아민 옥사이드[cocoamine oxide(상품명: Barlox 120)], 폴리옥시에틸렌소르비탄 모노올레에이트[polyoxyethylenesorbitane monooleate{상품명: Tween 80(더 다우 케미칼 캄파니 제품)}], 폴리옥시에틸렌 p-3급 옥틸페닐 에테르[polyoxyethylene p-tert octylphenyl ether(상품명: Triton X-100)] 등을 들 수 있다. 이들 중에서 본 발명의 방법에서 사용해본 결과, 트리톤(Triton) X-100이 가장 우수한 효과를 나타내었다. 계면활성제의 투입량은 0.01 내지 1중량%가 적합하다. 0.01중량% 미만이면 투수성 향상 효과가 미미하고, 1중량%초과하면 더 이상 투수성이 향상되지 않는다. 계면반응 도중에 발생하는 염산을 제거하기 위해, 산 제거제로서 수산화나트륨 또는 트리나트륨 포스페이트가 사용되며, 이의 첨가량은 0.01 내지 5중량%가 적합하다. 0.01중량%미만이면 산제거속도가 감소하여 반응속도가 늦여지고, 5중량%초과하면 산제거속도가 더 이상 빨라지지 않는다.Surfactants added to the amine solution to improve the permeability of the composite membrane is a nonionic surfactant, for example, polyoxyethylene alkyl amine, cocoamine oxide (trade name: Barlox 120) , Polyoxyethylenesorbitane monooleate {trade name: Tween 80 (product of The Dow Chemical Company)], polyoxyethylene p-tert octylphenyl ether (brand name: Triton X -100)]. Among them, Triton X-100 showed the most excellent effect when used in the method of the present invention. The amount of the surfactant added is preferably 0.01 to 1% by weight. If less than 0.01% by weight The water permeability improvement effect is insignificant, and when it exceeds 1 weight%, water permeability will not improve anymore. In order to remove hydrochloric acid generated during the interfacial reaction, sodium hydroxide or trisodium phosphate is used as the acid remover, and an amount thereof is preferably 0.01 to 5% by weight. If the amount is less than 0.01% by weight, the rate of acid removal is reduced to slow the reaction rate. If it exceeds 5% by weight, the rate of acid removal is no longer faster.
피페라진, 폴리비닐 알콜 및 수산화나트륨을 증류수에 용해시켜 아민 수용액을 제조한다. 폴리아미드의 제조시 사용되는 산(acid)인 폴리아실 할라이드로는 트리메조일 클로라이드(trimesoyl chloride), 이소프탈로일클로라이드(isophthaloyl chloride) 등을 예로 들 수 있으며, 이들 중에서 이소프탈로일 클로라이드를 사용하는 경우, 코팅층의 가교도가 낮아져서 염 배제율이 낮아지는 단점이 있으므로, 트리메조일 클로라이드를 사용하는 것이 바람직하며, 이의 사용량은 0.01 내지 3중량%이다. 0.01중량%미만이면 반응속도가 늦어 활성층형성이 잘 되지 않고, 3중량%초과하면 더 이상 반응속도는 빨라지지 않는 문제점이 있다. 트리메조일 클로라이드를 헥산에 용해시켜 아민 용액을 제조한다.Aqueous amine solution is prepared by dissolving piperazine, polyvinyl alcohol and sodium hydroxide in distilled water. Examples of polyacyl halides, which are acids used in the preparation of polyamides, include trimesoyl chloride and isophthaloyl chloride. Among them, isophthaloyl chloride is used. In this case, since the crosslinking degree of the coating layer is lowered and the salt rejection rate is lowered, it is preferable to use trimezoyl chloride, the amount of which is used is 0.01 to 3% by weight. If the amount is less than 0.01% by weight, the reaction rate is slow and the active layer is not formed well. Trimezoyl chloride is dissolved in hexane to prepare an amine solution.
나노필트레이션 복합막은 한외여과막을 아민 수용액에 1 내지 20분 동안 침지시키고, 침지 용액으로부터 꺼내어 표면수를 고무 롤러로 제거한 다음, 위의 유기 용액에 1 내지 1000초 동안 침지시키고, 꺼내어 공기 속에서 건조시키거나, 50 내지 150℃에서 20분 내지 60시간 동안 건조시켜 제조한다.The nanofiltration composite membrane was immersed in an amine aqueous solution for 1 to 20 minutes, removed from the immersion solution to remove the surface water with a rubber roller, then immersed in the organic solution for 1 to 1000 seconds, taken out and dried in air Or dried at 50 to 150 ° C. for 20 minutes to 60 hours.
이하에서 본 발명을 실시예에 의거하여 보다 상세하게 설명하고자 하며, 단 이들 실시예는 본 발명을 제한하거나 한정하는 것으로 간주되어서는 안된다.Hereinafter, the present invention will be described in more detail with reference to examples, provided that these examples should not be considered as limiting or limiting the present invention.
실시예 1Example 1
16중량% 폴리설폰 수지가 용해되어 있는 N-메틸피롤리돈(N-methylpyrrolidone, NMP) 용액을 유리판 위에 캐스팅(casting)하고, 유리판을 물에 침지, 응고시켜 지지체용 한외여과막을 제조하였다. 이렇게 하여 제조된 한외여과막의 분획 분자량(MWCO)은 35,000이었다. 이러한 지지체용 한외역과막을 피페라진 1중량%, 트리톤 X-100 0.5중량% 및 반응 도중에 발생하는 염산 제거용 산 제거제로서의 수산화나트륨 0.5중량%를 함유하는 수용액에 침지시키고, 침지 용액으로부터꺼내어 표면수를 고무 롤러로 제거한 다음, 트리메조일 클로라이드를 0.2중량% 함유하는 헥산 용액에 일정 시간 동안 침지시키고, 꺼내어 100℃에서 10분 동안 건조시킨다.An N-methylpyrrolidone (NMP) solution in which 16 wt% polysulfone resin was dissolved was cast on a glass plate, and the glass plate was immersed in water and coagulated to prepare an ultrafiltration membrane for a support. The fractional molecular weight (MWCO) of the ultrafiltration membrane thus prepared was 35,000. The ultrafiltration membrane for this support was immersed in an aqueous solution containing 1% by weight of piperazine, 0.5% by weight of Triton X-100 and 0.5% by weight of sodium hydroxide as an acid scavenger for removing hydrochloric acid generated during the reaction. After removal with a rubber roller, it was immersed in a hexane solution containing 0.2% by weight of trimezoyl chloride for a certain time, taken out and dried at 100 ° C for 10 minutes.
투수 실험은 0.3%의 Na2SO4을 함유하는 수용액을 200psi의 압력하에서 24시간 동안 실시하였다. 막의 염 배제율은 97.7%였고, 플럭스는 3.8ton/㎡·day였다.Permeation experiments were carried out for 24 hours in an aqueous solution containing 0.3% Na 2 SO 4 at a pressure of 200 psi. The salt rejection rate of the membrane was 97.7%, and the flux was 3.8 tons / m 2 · day.
실시예 2 내지 4Examples 2-4
트리톤 X-100의 농도를 0.2중량%에서 1.0%까지 변화시켜 나노필트레이션 복합막을 제조하였다. 나머지 제조 조건은 실시예 1에서 적용한 제조 조건과 동일하였다.The nanofiltration composite membrane was prepared by changing the concentration of Triton X-100 from 0.2% by weight to 1.0%. The remaining manufacturing conditions were the same as the manufacturing conditions applied in Example 1.
실시예 2 내지 4,비교예1의 실험 결과는 다음 표 1에 기재되어 있다.The experimental results of Examples 2 to 4 and Comparative Example 1 are shown in Table 1 below.
비교예 1Comparative Example 1
트리톤 X-100을 첨가하지 않고 실시예 1에서 적용한 과정과 동일하게 하여 실험하였다.The experiment was conducted in the same manner as in Example 1 without adding Triton X-100.
나노필트레이션 복합막의 제조시 계면활성제를 투입하여 막의 투과 성능을 향상시킴으로써, 나노필트레이션 복합막을 수처리, 초순수 제조 및 폐수처리 등에 적용하는 경우, 처리공정의 효율성을 높이고 처리비용을 감소시킬 수 있다.In the preparation of the nanofiltration composite membrane, by adding a surfactant to improve the permeation performance of the membrane, when the nanofiltration composite membrane is applied to water treatment, ultrapure water production, and wastewater treatment, the efficiency of the treatment process and the treatment cost can be reduced.
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| CN110773001A (en) * | 2019-10-29 | 2020-02-11 | 南京大学 | Nanofiltration composite membrane, preparation method and application |
| CN111097294A (en) * | 2019-08-20 | 2020-05-05 | 宁波水艺膜科技发展有限公司 | Preparation method of nanofiltration membrane for reclaimed water treatment |
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| JP2001038175A (en) * | 1999-05-27 | 2001-02-13 | Toyobo Co Ltd | Composite semipermeable membrane |
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| CN102580556A (en) * | 2012-03-06 | 2012-07-18 | 北京科泰兴达高新技术有限公司 | Antipollution flat membrane and method for producing same |
| CN102580556B (en) * | 2012-03-06 | 2015-04-29 | 北京科泰兴达高新技术有限公司 | Antipollution flat membrane and method for producing same |
| KR20170030931A (en) * | 2015-09-10 | 2017-03-20 | 주식회사 엘지화학 | Composition for interfacial polymerizing polyamide, method for preparing reverse osmosis membrane using the same, and reverse osmosis membrane and water treatment module comprising the compound |
| CN109647201A (en) * | 2018-12-21 | 2019-04-19 | 天津膜天膜科技股份有限公司 | The method of ultrasonic wave added interfacial polymerization continuous production External Pressure Type hollow fiber nanofiltration membrane |
| CN109647202A (en) * | 2018-12-21 | 2019-04-19 | 天津膜天膜科技股份有限公司 | The method of high concentration proton absorbent continuous production External Pressure Type hollow fiber nanofiltration membrane |
| CN111097294A (en) * | 2019-08-20 | 2020-05-05 | 宁波水艺膜科技发展有限公司 | Preparation method of nanofiltration membrane for reclaimed water treatment |
| CN111097294B (en) * | 2019-08-20 | 2022-02-18 | 宁波水艺膜科技发展有限公司 | Preparation method of nanofiltration membrane for reclaimed water treatment |
| CN110773001A (en) * | 2019-10-29 | 2020-02-11 | 南京大学 | Nanofiltration composite membrane, preparation method and application |
| CN113786738A (en) * | 2021-08-26 | 2021-12-14 | 同济大学 | Method for recycling scrapped low-pressure membrane based on interface wettability regulation and control and polyamide nanofiltration membrane prepared by method |
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