KR20130078824A - Hollow fiber membrane having high water permeability for water treatment and manufacturing method thereof - Google Patents
Hollow fiber membrane having high water permeability for water treatment and manufacturing method thereof Download PDFInfo
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- KR20130078824A KR20130078824A KR1020110147959A KR20110147959A KR20130078824A KR 20130078824 A KR20130078824 A KR 20130078824A KR 1020110147959 A KR1020110147959 A KR 1020110147959A KR 20110147959 A KR20110147959 A KR 20110147959A KR 20130078824 A KR20130078824 A KR 20130078824A
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- 239000012528 membrane Substances 0.000 title claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 230000035699 permeability Effects 0.000 title abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000000654 additive Substances 0.000 claims abstract description 13
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 239000000701 coagulant Substances 0.000 claims abstract description 10
- 230000000996 additive effect Effects 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims description 16
- 238000005345 coagulation Methods 0.000 claims description 14
- 230000015271 coagulation Effects 0.000 claims description 14
- 239000002033 PVDF binder Substances 0.000 claims description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 11
- 229920001577 copolymer Polymers 0.000 claims description 5
- HCDGVLDPFQMKDK-UHFFFAOYSA-N hexafluoropropylene Chemical group FC(F)=C(F)C(F)(F)F HCDGVLDPFQMKDK-UHFFFAOYSA-N 0.000 claims description 3
- 229920002959 polymer blend Polymers 0.000 claims description 3
- 229920000131 polyvinylidene Polymers 0.000 claims description 3
- IYMUEWIEVFJWMR-UHFFFAOYSA-N 1-chloro-1,2,2-trifluoroethene;hydrofluoride Chemical group F.FC(F)=C(F)Cl IYMUEWIEVFJWMR-UHFFFAOYSA-N 0.000 claims description 2
- HLKZFSVWBQSKKH-UHFFFAOYSA-N but-3-enoic acid;1-ethenylpyrrolidin-2-one Chemical compound OC(=O)CC=C.C=CN1CCCC1=O HLKZFSVWBQSKKH-UHFFFAOYSA-N 0.000 claims description 2
- 229920001519 homopolymer Polymers 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 14
- 238000007599 discharging Methods 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- 230000009977 dual effect Effects 0.000 abstract 4
- 239000000243 solution Substances 0.000 description 37
- 230000001112 coagulating effect Effects 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 229920001477 hydrophilic polymer Polymers 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000002952 polymeric resin Substances 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UUAGAQFQZIEFAH-UHFFFAOYSA-N chlorotrifluoroethylene Chemical group FC(F)=C(F)Cl UUAGAQFQZIEFAH-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0016—Coagulation
- B01D67/00165—Composition of the coagulation baths
-
- 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
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- 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
- B01D69/08—Hollow fibre membranes
- B01D69/087—Details relating to the spinning process
- B01D69/088—Co-extrusion; Co-spinning
-
- 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/08—Specific temperatures applied
-
- 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
- B01D2323/18—Pore-control agents or pore formers
-
- 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
- B01D2323/218—Additive materials
- B01D2323/2182—Organic additives
- B01D2323/21839—Polymeric additives
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/20—Specific permeability or cut-off range
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Dispersion Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
본 발명은 정수, 오폐수, 하수 등의 수처리공정에 사용하기 위한 목적으로 고투수도 및 내구성이 우수한 중공사막 및 이의 제조방법에 관한 것이다.The present invention relates to a hollow fiber membrane excellent in high water permeability and durability and a method for producing the same for use in water treatment processes such as purified water, waste water, sewage.
막분리 기술은 분리막의 세공크기와 막표면 전하에 따라 처리수중에 존재하는 처리대상물질을 거의 완벽하게 분리하여 제거할 수 있는 고도의 분리기술로서 수처리 분야에서 양질의 음용수 및 공업용수의 생산, 하폐수의 고도처리 및 재이용, 그리고 무방류 시스템 개발과 관련된 청정생산공정 등 그 응용범위가 점차 확대되어 가고 있으며 21세기에 주목받게 될 핵심기술의 하나로서 자리잡고 있다.Membrane separation technology is an advanced separation technology that can almost completely separate and remove the material to be treated in the treated water according to the pore size of the membrane and the surface charge of the membrane. Production of high-quality drinking water and industrial water in the field of water treatment and wastewater Its application range is gradually expanding, including advanced processing and reuse, and clean production processes related to the development of zero discharge systems. It is becoming one of the key technologies that will be noticed in the 21st century.
그러나 수처리막이 상업성을 갖기 위해선 무엇보다도 우수한 투수도와 강한 내구성을 가져야 하는데 그 이유는 투수도가 낮게되면 여과수 생산성에 문제가 되며 내구성이 약하게 되면 수처리막의 잦은 교체로 인해 경제성이 떨어지게 된다. 이에 종래의 수처리막은 다양한 첨가제 도입 혹은 표면개질을 통한 친수화에 의해 상기한 문제점을 회피, 개선하기 위해 노력해왔다. 그러나 일반적으로 많이 사용되는 친수성고분자인 폴리비닐피롤리돈, 폴리에틸렌글리콜과 같은 친수성 첨가제는 비록 친수성 향상에 의한 투수도를 증가시킬수는 있으나 내구성을 향상시키는 못하였다.However, in order for the water treatment membrane to have commerciality, it has to have excellent permeability and strong durability, among other things, because a low water permeability is a problem for the filtrate productivity, and if the durability is weak, economical efficiency decreases due to frequent replacement of the water treatment membrane. Accordingly, the conventional water treatment membranes have tried to avoid and improve the above problems by introducing various additives or hydrophilization through surface modification. However, hydrophilic additives such as polyvinylpyrrolidone and polyethylene glycol, which are commonly used hydrophilic polymers, can increase the water permeability due to the improvement of hydrophilicity, but have not improved the durability.
예를 들어, 대한민국 특허공개공보 제2005-0072311호, 제2004-0075003호, 제2002-0074465호 등에는 종래의 수처리용 분리막 제조시 친수화를 통한 투수도 향상을 위해 폴리비닐피롤리돈과 같은 친수성 고분자를 도입하는 기술이 개시되어 있다. 그러나 이들은 내구성이 약해지는 단점이 있다. 이러한 문제로 인해 정수, 오 폐수처리 등의 수처리 공정에 사용되는 수처리막의 경우 장기운전에 따라 막의 오염이 증가하고 이로 인해 투수도가 점차 감소하여 생산비용 및 유지비용 등이 증가하는 문제점이 종종 발생하고 있다.For example, the Republic of Korea Patent Publication No. 2005-0072311, 2004-0075003, 2002-0074465, etc., such as polyvinylpyrrolidone to improve the water permeability through hydrophilization in the conventional water treatment membrane manufacturing Techniques for introducing hydrophilic polymers are disclosed. However, they have a disadvantage of weak durability. Due to these problems, in case of water treatment membranes used for water treatment processes such as water purification and wastewater treatment, the contamination of the membranes increases with long-term operation, and as a result, water permeability gradually decreases, resulting in increased production and maintenance costs. have.
이러한 수처리막의 투수도 및 내구성 문제를 개선하기 위해 본 발명자들은 수없이 많은 노력을 시도한 결과,방사원액의 온도와 응고조의 온도차 조절을 통해 투수도 및 내구성이 월등히 개선됨을 발견하고 본 발명에 이르게 되었다.As a result of numerous efforts to improve the water permeability and durability of the water treatment membrane, the inventors have found that the water permeability and durability are greatly improved by adjusting the temperature difference between the spinning solution and the coagulation bath, and thus, the present invention has been achieved.
본 발명의 목적은 투수도와 내구성이 향상된 수처리용 중공사 막의 제조방법을 제공하는 것이다.An object of the present invention is to provide a method for producing a hollow fiber membrane for water treatment with improved water permeability and durability.
본 발명의 다른 목적은 상기 방법에 의하여 제조되는 수처리용 중공사 막을 제공하는 것이다.Another object of the present invention is to provide a hollow fiber membrane for water treatment prepared by the above method.
본 발명의 중공사막 제조방법은 고분자, 용매, 첨가제로 구성된 도프용액을 40 ℃ 내지 150 ℃ 이하의 온도로 유지하는 이중노즐의 외부관으로 이송한 후 이중노즐의 내부 및 외부로 내부응고제 및 도프용액을 동시에 각각 토출하여 중공형태를 형성한 후 일정조건의 응고액에 침전시켜 중공사막을 제조하는 단계; 및 형성된 중공사막으로부터 응고액을 이용하여 용매를 추출하는 세척 및 건조단계;를 포함한다.The hollow fiber membrane manufacturing method of the present invention transfers the dope solution composed of a polymer, a solvent, and an additive to an outer tube of a double nozzle which maintains the temperature of 40 ° C. to 150 ° C. or lower, and then internally and externally the coagulant and the dope solution into the double nozzle. Simultaneously discharging each of them to form a hollow shape and then precipitating it to a coagulating solution under a predetermined condition to produce a hollow fiber membrane; And a washing and drying step of extracting a solvent from the formed hollow fiber membrane using a coagulating solution.
상기 도프용액의 고분자로는 폴리비닐리덴풀루오라이드(PVDF) 단일중합체, 폴리비닐리덴헥사플루오르프로필렌 (PVDF-HFP)공중합체, 폴리비닐리덴풀루오라이드클로로트리플루오르에틸렌 (PVDF-TCFE) 공중합체 중 1종이상 선택된 것이다.Polymers of the dope solution include polyvinylidene fluoride (PVDF) homopolymer, polyvinylidene hexafluoropropylene (PVDF-HFP) copolymer, polyvinylidene fluoride chlorotrifluoroethylene (PVDF-TCFE) copolymer At least one of them is selected.
상기 첨가제는 폴리(비닐피롤리돈-비닐아세테이트) 및 폴리(비닐피롤리돈-비닐엑시드) 중 1종이상 선택된 것이다.The additive is at least one selected from poly (vinylpyrrolidone-vinylacetate) and poly (vinylpyrrolidone-vinylexide).
강기 지지체는 폴리에스터를 이용하여 제조된 것이다.The steel support is made using polyester.
상기 도프용액의 조성은 35 내지 90 중량 %의 용매 및 10 내지 65 중량%의 기공형성제/고분자 혼합물이고, 상기 혼합물에서 기공형성제/고분자의 중량비율은 1 내지 2 이하인 것이 바람직하다.The composition of the dope solution is 35 to 90% by weight of the solvent and 10 to 65% by weight of the pore-forming / polymer mixture, the weight ratio of the pore-forming agent / polymer in the mixture is preferably 1 to 2 or less.
상기 응고액으로 30 ℃ 내지 70 ℃ 이하의 온도로 물을 이용하여 용매를 추출하는 것이 바람직하다.It is preferable to extract the solvent using water at a temperature of 30 ° C to 70 ° C as the coagulation solution.
본 발명은 기존에 문제시 됐던 투수도 및 내구성을 동시에 개선시키기 위한 목적으로 본 발명의 방사원액과 응고조의 온도차 조절을 막제조에 도입하게 되면 향상된 투수도 및 내구성을 가진 분리막을 제공하게 되어 정수 및 오폐수 공정에 유용하게 사용될 수 있는 특징을 제공한다.The present invention is to provide a separation membrane having improved water permeability and durability when introducing the temperature difference control of the spinning stock solution and the coagulation bath of the present invention for the purpose of improving the water permeability and durability at the same time that was previously a problem. Provides features that can be useful in wastewater processes.
본 발명은 도프용액과 응고액의 온도차 조절을 통해 투수도 및 내구성을 개선시킬 수 있게 되어 날로 엄격해지고 있는 고도정수처리, 용수처리공정을 포함한 차세대 고효율 분리공정산업에 사용하기에 매우 적합하다.The present invention is able to improve the water permeability and durability through the temperature difference between the dope solution and the coagulation solution is very suitable for use in the next-generation high efficiency separation process industry, including advanced water treatment, water treatment process is becoming increasingly stringent.
본 발명은 The present invention
a) PVDF의 고분자, 용매 및 첨가제로 구성된 혼합물을 40 ℃ 내지 150 ℃ 이하의 온도에서 균일하게 용해하여 도프용액을 제조하고 a) preparing a dope solution by uniformly dissolving a mixture of PVDF polymer, solvent and additives at a temperature of 40 ℃ to 150 ℃
b) 상기 도프용액을 40 ℃ 내지 150 ℃ 이하의 온도로 유지하는 이중노즐의 외부관으로 이송한 후 일정조건하의 에어갭내에서 이중노즐의 내부 및 외부로 내부응고제 및 도프용액을 동시에 각각 토출하여 중공형태를 형성하고b) The dope solution is transferred to an outer tube of a double nozzle maintaining a temperature of 40 ° C. to 150 ° C. or lower, and then the internal coagulant and the dope solution are simultaneously discharged into and out of the double nozzle in an air gap under a predetermined condition. To form
c) 토출물을 10 ℃ 내지 100 ℃ 이하 온도의 응고액에 침전시켜 막성형을 유도하고c) the discharge is precipitated in a coagulation solution at a temperature of 10 ℃ to 100 ℃ or less to induce membrane formation
d) 상기 성형된 막을 세척, 건조하여 중공사막을 제조하는 공정으로 구성된다.
d) washing and drying the molded membrane to produce a hollow fiber membrane.
이하에서, 본 발명의 중공사막 제조방법 구체적으로 설명한다.Hereinafter, the hollow fiber membrane manufacturing method of the present invention will be described in detail.
(a) 도프용액의 제조공정(a) Manufacturing process of dope solution
상술한 바와 같이, 본 발명에서 도프용액은 폴리비닐리덴풀루오라이드계 수지, 용매 및 첨가제로 구성되고, 40 ℃ 내지 150 ℃ 이하의 온도에서 침전물이나 부유물의 형성없이 균일하게 혼합된 것을 가리킨다. 상기 고분자수지에서 폴리비닐리덴계 고분자는 폴리비닐리덴플루오라이드 (PVDF) 등과 같은 단일 중합체 또는 헥사플루오르프로필렌 (PVDF-HFP) 혹은클로로트리플루오르에틸렌 (PVDF-TCFE) 등을 포함하는 공중합체를 단독 혹은 혼합하여 사용 가능하다. As described above, in the present invention, the dope solution is composed of a polyvinylidene fluoride resin, a solvent, and an additive, and refers to a mixture uniformly without formation of precipitates or suspended solids at a temperature of 40 ° C. to 150 ° C. or less. In the polymer resin, the polyvinylidene-based polymer may be a single polymer such as polyvinylidene fluoride (PVDF) or a copolymer including hexafluoropropylene (PVDF-HFP) or chlorotrifluoroethylene (PVDF-TCFE) or the like. Can be mixed.
본 발명에서 사용되는 용매는 N-메틸피롤리돈, 디메틸아세트아미드, 디메틸설록사이드, 디메틸포름아마이드 등이 있으며, 이들은 단독 또는 1종 이상 혼합하여 사용 가능하다. The solvent used in the present invention includes N-methylpyrrolidone, dimethylacetamide, dimethyl sulfoxide, dimethylformamide, and the like, and these may be used alone or in combination of one or more thereof.
본 발명에서 사용되는 첨가제는 비닐피롤리돈계 수지, 글리콜류 화합물 등이 있으며, 이들은 단독 또는 1종 이상 혼합하여 사용가능하다.The additives used in the present invention include vinylpyrrolidone-based resins and glycol compounds, and these may be used alone or in combination of one or more thereof.
상기 도프용액에 있어서, 각 성분의 조성비는 전체 도프용액 조성물에 대하여 35 내지 90 중량%의 용매 및 10 내지 65 중량%의 첨가제와 고분자수지 혼합물을 포함하는 것이 바람직하며, 더욱 바람직하기로는 용매 60 내지 85 중량% 및 첨가제와 고분자 혼합물 15 내지 40 중량% 인 것이 좋다. 또한, 상기 혼합물에서 첨가제의 중량비율은 전체 도프용액 조성물에 대해 1 내지 20% 이하인 것이 바람직하다.
In the above dope solution, the composition ratio of each component is preferably 35 to 90% by weight of the solvent and 10 to 65% by weight of the additive and the polymer resin mixture with respect to the total dope solution composition, more preferably from 60 to 60 solvent. It is preferably 85% by weight and 15-40% by weight of the additive and polymer mixture. In addition, the weight ratio of the additive in the mixture is preferably 1 to 20% or less based on the total dope solution composition.
(b) 중공형성 공정(b) hollow forming process
본 발명의 중공형성 공정은 상기 도프용액을 40 ℃ 내지 150 ℃ 이하의 온도로 유지하는 이중노즐의 외부관으로 이송한 후 이중노즐의 내부 및 외부로 내부응고제 및 도프용액을 동시에 각각 토출하여 중공형태를 형성한다.In the hollow forming process of the present invention, the dope solution is transferred to an outer tube of a double nozzle maintaining the temperature of 40 ° C. to 150 ° C. or lower, and then the internal coagulant and the dope solution are simultaneously discharged into and out of the double nozzle. To form.
본 발명에서 사용된 내부응고제는 용매와 비용매의 혼합물로 용매의 중량비율이 10 내지 60 중량%인 것이 바람직하다.
The internal coagulant used in the present invention is a mixture of the solvent and the non-solvent, it is preferable that the weight ratio of the solvent is 10 to 60% by weight.
(c) 응고공정(c) solidification process
본 발명의 응고공정은 이중노즐을 통해 중공형태로 토출된 도프용액을 10 ℃ 내지 100 ℃ 이하의 온도로 유지되는 응고액에 토출시키거나 침전시켜 용매를 추출함으로써 중공사막을 제조하는 단계로 응고액으로서 물 또는 물과 용매의 혼합물이 바람직하다. 응고액의 온도는 도프용액의 온도에 따라 조절되며 도프용액과 응고액의 온도차를 20℃ 내지 60℃이하의 온도롤 유지 하는 것이 바람직하다. 도프용액과 응고액의 온도차가 20℃이하이면 중공형태가 유지되지 않는 문제가 있으며, 60℃이상이면 용매의추출에 많은 시간이 소요되어 투과도가 감소하고 강도가 낮아지는 단점이 있다.In the coagulation process of the present invention, the dope solution discharged in a hollow form through a double nozzle is discharged or precipitated into a coagulation solution maintained at a temperature of 10 ° C. to 100 ° C. or lower to extract a solvent to prepare a hollow fiber membrane. Preference is given to water or mixtures of water and solvents. The temperature of the coagulation solution is adjusted according to the temperature of the dope solution, it is preferable to maintain the temperature difference between the dope solution and the coagulation solution at a temperature of 20 ℃ to 60 ℃ or less. If the temperature difference between the dope solution and the coagulation solution is less than 20 ℃, there is a problem that the hollow form is not maintained, if more than 60 ℃ takes a lot of time to extract the solvent has a disadvantage that the permeability is reduced and the strength is lowered.
(d) 세척 및 건조공정(d) cleaning and drying process;
본 발명에서는 분리막내외에 잔존하는 용매를 제거하기 위해 세척과정을 더욱 포함한다. 세척액으로 물의 사용이 바람직하며, 세척시간은 특별히 한정되지는 않으나, 적어도 1일 이상, 3일 이하가 바람직하다. 본 발명은 제조된 중공사막을 글리세린 50 중량% 수용액에 침지후 대기중에서 건조하는 과정을 더욱 포함하며, 침지 및 건조기간은 특별히 한정하지 않으나, 1일 이하가 바람직하다.
The present invention further includes a washing process to remove the solvent remaining in the membrane. Water is preferably used as the washing liquid, and the washing time is not particularly limited, but at least one day or more and three days or less is preferable. The present invention further includes a step of drying the prepared hollow fiber membrane in a 50% by weight aqueous solution of glycerin and then drying in the air. The immersion and drying period are not particularly limited, but are preferably 1 day or less.
이하, 본 발명의 구성 및 작용을 다음의 실시예를 통해 설명한다. 그러나, 본 발명이 아래 실시예에 의해 한정되는 것은 아니다.
Hereinafter, the configuration and operation of the present invention will be described through the following examples. However, the present invention is not limited by the following examples.
[실시예] [Example]
(비교예)(Comparative Example)
상온의 응고조에 응고시킨 수처리막의 제조 The crude was water coagulation bath film solidification at room temperature
고분자 함량이 도프용액 전체의 22중량%가 되도록, N,N-디메틸아세트아마이드(DMAC)에 폴리비닐리덴플루오라이드 (Solvay, Mw: 304,000) 를 서서히 첨가한 후 이들을 혼합하여 120 ℃에서 균일한 도프용액을 제조하였다. 그런 다음, 제조된 균일한 도프용액속에 함유된 기포를 진공펌프를 이용하여 제거한 뒤, 기어펌프를 이용하여 도프용액을 내부직경이 0.7 mm, 외부직경이 1.3 mm이고 120 ℃로 유지되는 이중노즐로 이송시키고 내부응고제로 물/DMAc 혼합물(70중량%/30중량%)을 사용하여 중공사막을 제조하였다. 이어서, 상온(25℃)의 응고액(물)을 통과한 중공사막은 연속적으로 권취보빈을 통해 권취되고, 잔존하는 더 많은 유기용매를 제거하기 위해 물세척조내에서 48시간 동안 세척하였다. 완전 세척된 중공사막을 50 중량%의 글리세린 수용액에 24시간 침지후 상온에서 건조시켰으며 내부직경이 0.8mm이고 외부직경이 1.5mm인 중공사막 10가닥을 유효길이 10cm로 하여 막면적이 0.00471m2 인 막모듈을 제조하였다.Add polyvinylidene fluoride (Solvay, Mw: 304,000) slowly to N, N-dimethylacetamide (DMAC) so that the polymer content is 22% by weight of the entire dope solution, and then mix them to obtain a uniform dope at 120 ° C. The solution was prepared. Then, bubbles contained in the prepared uniform dope solution were removed using a vacuum pump, and then the dope solution was removed using a gear pump with a double nozzle having an internal diameter of 0.7 mm and an external diameter of 1.3 mm and maintained at 120 ° C. The hollow fiber membranes were prepared by transferring and using a water / DMAc mixture (70 wt% / 30 wt%) as the internal coagulant. Subsequently, the hollow fiber membrane which passed the coagulating liquid (water) of normal temperature (25 degreeC) was wound up continuously through a winding bobbin, and it wash | cleaned for 48 hours in the water washing tank to remove more organic solvent which remains. The completely washed hollow fiber membrane was immersed in 50% by weight aqueous solution of glycerin for 24 hours, and dried at room temperature. The membrane area was 0.00471 m2 with 10 strands of the hollow fiber membrane having an inner diameter of 0.8 mm and an outer diameter of 1.5 mm. Membrane modules were prepared.
상기 중공사막 및 모듈을 이용하여 수투과도, 인장강도 평가를 하기한 방법으로 측정하였고, 그 결과를 표 1에 나타내었다.
Using the hollow fiber membrane and the module, water permeability and tensile strength were measured by the following method, and the results are shown in Table 1 below.
(1) 순수투과도의 측정(1) Measurement of pure permeability
제조된 중공사막 모듈에 대해 상온의 순수를 1기압하에 dead-end방식으로 모듈의 한측면으로 공급하여 투과된 물의 양을 측정하였으며 이를 단위 시간, 단위 면적당 여과되는 투과량(L/m2·hr)로 환산하여 하기의 표1에 나타내었다.We measured the amount of water permeation was supplied to one side of the module to the dead-end method for pure water at room temperature under 1 atmosphere for the produced hollow fiber membrane module and a unit time, per unit area that is filtered transmission amount (L / m 2 · hr) It is shown in Table 1 below.
(2) 인장강도 측정(2) Measurement of tensile strength
제조된 중공사막을 인장시험기(LLOYD사)를 이용하여, 파지거리 300mm의 시료를 50mm/min 의 크로스헤드 속도로 5회 측정하여 평균값을 하기의 표1에 나타내었다.
Using a tensile tester (LLOYD Co., Ltd.) of the prepared hollow fiber membrane, a sample having a holding distance of 300 mm was measured five times at a crosshead speed of 50 mm / min and the average value is shown in Table 1 below.
(실시예1)(Example 1)
90℃의 응고액(물)을 사용하는 것을 제외하고는 상기 비교예와 동일하게 수행하여 중공사막을 제조하였다.A hollow fiber membrane was prepared in the same manner as in Comparative Example except that a coagulating solution (water) at 90 ° C. was used.
(실시예2)(Example 2)
80℃의 응고액(물)을 사용하는 것을 제외하고는 상기 비교예와 동일하게 수행하여 중공사막을 제조하였다.A hollow fiber membrane was prepared in the same manner as in Comparative Example except that a coagulating solution (water) at 80 ° C. was used.
(실시예3)(Example 3)
50℃의 응고액(물)을 사용하는 것을 제외하고는 상기 비교예와 동일하게 수행하여 중공사막을 제조하였다.A hollow fiber membrane was prepared in the same manner as in Comparative Example except that a coagulating solution (water) at 50 ° C. was used.
온도(℃)Dope solution
Temperature (℃)
온도(℃)Coagulant
Temperature (℃)
(℃)Temperature difference
(℃)
(ℓ/m2hr)Pitcher
(ℓ / m 2hr)
(MPa)The tensile strength
(MPa)
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