KR20150036857A - Hollow fiber membrane composition and hollow fiber membrane using same - Google Patents
Hollow fiber membrane composition and hollow fiber membrane using same Download PDFInfo
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- KR20150036857A KR20150036857A KR20130115809A KR20130115809A KR20150036857A KR 20150036857 A KR20150036857 A KR 20150036857A KR 20130115809 A KR20130115809 A KR 20130115809A KR 20130115809 A KR20130115809 A KR 20130115809A KR 20150036857 A KR20150036857 A KR 20150036857A
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- hollow fiber
- fiber membrane
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- polyvinylidene fluoride
- dimethylacetamide
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- 239000012528 membrane Substances 0.000 title claims abstract description 82
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 65
- 239000000203 mixture Substances 0.000 title claims abstract description 25
- 239000002033 PVDF binder Substances 0.000 claims abstract description 50
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 50
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 25
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 25
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000654 additive Substances 0.000 claims abstract description 13
- 230000000996 additive effect Effects 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 19
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 11
- 239000003966 growth inhibitor Substances 0.000 claims description 7
- 235000005074 zinc chloride Nutrition 0.000 claims description 6
- 239000011592 zinc chloride Substances 0.000 claims description 6
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 20
- 239000000126 substance Substances 0.000 abstract description 8
- 239000002351 wastewater Substances 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000008569 process Effects 0.000 description 13
- 238000000926 separation method Methods 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- 238000011109 contamination Methods 0.000 description 4
- 239000010408 film Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000011001 backwashing Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 238000009285 membrane fouling Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/02—Hydrophilization
-
- 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
- B01D2323/18—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
- B01D2323/2185—Polyethylene glycol
-
- 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
- B01D2325/02—Details relating to pores or porosity of the membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/0283—Pore size
- B01D2325/02833—Pore size more than 10 and up to 100 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/34—Molecular weight or degree of polymerisation
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
본 발명은 중공사막 조성물 및 이를 이용한 중공사막에 관한 것으로서, 특히 폴리불화비닐리덴, 중공사막의 친수성을 부여하는 첨가제, 용매제를 포함하는 중공사막 조성물 및 이를 이용한 중공사막에 관한 것이다.The present invention relates to a hollow fiber membrane composition and a hollow fiber membrane using the same, and more particularly, to a hollow fiber membrane composition comprising polyvinylidene fluoride, an additive for imparting hydrophilicity to the hollow fiber membrane, a solvent agent, and a hollow fiber membrane using the same.
일반적으로 효과적인 물질의 분리를 위한 방법으로서, 증류, 추출, 흡수, 흡착 또는 재결정 등의 다양한 분리 공정이 이용되어 왔다. 그러나, 위와 같은 재래식 분리 공정은 다량의 에너지 소비 및 공간 이용의 비효율성 등과 같은 문제점을 가지고 있다.In general, as a method for effectively separating substances, various separation processes such as distillation, extraction, absorption, adsorption or recrystallization have been used. However, such conventional separation processes have problems such as a large amount of energy consumption and inefficiency of space utilization.
이에 따라 전술한 재래식 분리 공정을 대체하기 위한 에너지 절약형 분리 공정으로서 막분리의 중요성이 대두되고 있다. 막분리는 두 개의 상(phase)의 사이에 존재하는 선택적 장벽(selective barrier)으로 정의될 수 있는데, 특히 공업 및 농업 폐수, 음용수의 공급이나 독성 산업 폐기물의 처리 등을 포함하여, 환경 오염의 심각성이 전세계적으로 대두되면서 고분자 막분리에 대한 중요성은 더욱 커지고 있다.Accordingly, the importance of membrane separation as an energy-saving separation process for replacing the conventional separation process has arisen. Membrane separation can be defined as a selective barrier between two phases, in particular the severity of environmental pollution, including industrial and agricultural wastewater, the supply of drinking water and the treatment of toxic industrial wastes Is emerging worldwide, the importance of separating polymer membranes is increasing.
이와 더불어 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, 무방류 시스템 개발과 관련된 청정생산공정 등 그 응용범위가 점차 확대되어 가고 있으며 21세기에 주목받게 될 핵심기술의 하나로서 자리잡고 있다.In addition, the membrane separation technology is a highly separation technology that can almost completely separate the substances to be treated in the treated water according to the pore size of the membrane and the membrane surface charge. As a result, the production of high quality drinking water and industrial water , The advanced treatment and reuse of wastewater, and the clean production process related to the development of the zero-discharge system, and it is becoming one of the core technologies that will be noticed in the 21st century.
종래의 수처리막은 오염된 원수로부터 정제된 생산수를 얻는 동안 파울링이라 불리는 막오염 현상을 불가피하게 경험하게 된다. 이러한 막오염 현상은 대개 원수속의 오염원이 막표면에 불가피하게 경험하게 된다. Conventional water treatment membranes inevitably experience film fouling, called fouling, while obtaining purified water from contaminated raw water. Such membrane contamination usually results in contamination of the source water inevitably on the membrane surface.
이러한 막오염 현상은 대개 원수속의 오염원이 막표면에 흡착하여 발생하는 것으로 알려져 있으며, 이러한 막 표면의 오염은 여과시 작용하는 압력을 상승시키고 생산수량을 점차 감소시켜 막여과 공정에 심각한 악영향을 주게 된다. Such membrane fouling is generally known to occur by adsorbing contaminants in the raw water on the membrane surface, and contamination of the membrane surface increases the pressure acting on the filtration and gradually decreases the production yield, thereby seriously affecting the membrane filtration process .
이러한 공정 중 막오염 현상을 방지하기 위해 통상의 수처리 운전은 역세공정을 삽입하여 막표면에 흡착된 오염물을 제거하게 되는데 이때 역세공정은 산, 염기성 물질을 포함한 수용액을 막여과 방향과 반대방향으로 공급하고 산, 염기성 물질에 의해 비대칭성의 막 표면과 외표 부분에 핑거 구조에 의해 불안정한 지지 형태를 보이고, 더불어 불규칙한 외표면과 거칠 스크래치 등에 의해 파울링 현상에 취약한 문제점을 내포하고 있는 실정이다.In order to prevent membrane contamination during this process, the normal water treatment operation inserts a backwash process to remove contaminants adsorbed on the membrane surface. In this case, the backwash process is performed by supplying an aqueous solution containing an acidic or basic substance in a direction opposite to the membrane filtration direction In addition, unstable support structures due to the finger structure are present on the asymmetric membrane surface and the outer surface of the asymmetric membrane due to acid and basic substances, and the membrane is vulnerable to fouling by irregular outer surfaces and rough scratches.
이에 따라 수처리 분야에서는 기계적 강도가 우수하면서도, 기공크기가 작고 투과유량이 높으며 막오염 저항성이 높은 분리막을 경제적으로 제조하는 방법에 대한 요구가 증가하고 있다.Accordingly, there is an increasing demand for a method for economically producing a membrane having a high mechanical strength, a small pore size, a high permeation flow rate, and high membrane fouling resistance in the water treatment field.
본 발명은 상기와 같은 종래 기술의 문제점을 해결하기 위하여 발명된 것으로서, 중공사막의 원료가 되는 폴리불화비닐리덴에 중공사막의 친수성을 부여하도록 폴리에틸렌글리콜을 첨가제로 사용하고 디메틸아세트아미드를 용매제로 사용되는 중공사막 조성물로 하여금 내화학성 및 내구성이 향상되어 정수 및 오폐수 공정에 유용하게 사용될 수 있는 중공사막을 제조할 수 있는 중공사막 조성물 및 이를 이용한 중공사막을 제공하는 것에 목적이 있다.Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made in order to solve the problems of the prior art as described above, and it is an object of the present invention to provide a hollow fiber membrane in which polyethyleneglycol is used as an additive, Which can improve the chemical resistance and durability of the hollow fiber membrane composition and can be usefully used in water purification and wastewater treatment, and a hollow fiber membrane using the hollow fiber membrane composition.
상기와 같은 목적을 실현하기 위하여 본 발명은, 폴리불화비닐리덴(PVDF, Polyvinylidenefluoride); 첨가제로 사용되는 폴리에틸렌글리콜(PEG, Poly ethylene glycol); 용매로 사용되는 디메틸아세트아미드(DMAC);가 포함되어 이루어짐을 특징으로 하는 중공사막 조성물을 제공한다.In order to achieve the above-mentioned object, the present invention provides a polyvinylidene fluoride (PVDF); Polyethylene glycol (PEG) used as an additive; And dimethylacetamide (DMAC) used as a solvent. The present invention also provides a hollow fiber membrane composition comprising the same.
또한 상기 중공사막 조성물은 폴리불화비닐리덴(PVDF, Polyvinylidenefluoride) 18 ~ 30중량%, 폴리에틸렌글리콜(PEG, Poly ethylene glycol)은 10 ~ 16중량%, 디메틸아세트아미드(DMAC)는 58 ~ 68중량%로 이루어짐을 특징으로 한다.The hollow fiber membrane composition may further contain 18 to 30% by weight of polyvinylidene fluoride (PVDF), 10 to 16% by weight of polyethylene glycol (PEG), and 58 to 68% by weight of dimethylacetamide (DMAC) .
또한 상기 중공사막 조성물은 분자량 300,000 ~ 600,000인 폴리불화비닐리덴(PVDF, Polyvinylidenefluoride)이 22 ~ 30중량%, 폴리에틸렌글리콜(PEG, Poly ethylene glycol)은 10 ~ 12중량%, 디메틸아세트아미드(DMAC)는 58 ~ 66중량%로 이루어짐을 특징으로 한다.The hollow fiber membrane composition may further contain 22 to 30% by weight of polyvinylidene fluoride (PVDF) having a molecular weight of 300,000 to 600,000, 10 to 12% by weight of polyethylene glycol (PEG) and dimethylacetamide (DMAC) 58 to 66% by weight.
또한 상기 폴리불화비닐리덴(PVDF, Polyvinylidenefluoride) 100중량부를 기준으로 기공 형성제인 염화리튬(LiCl) 0.5 ~ 15 중량부가 혼합됨을 특징으로 한다.Also, 0.5 to 15 parts by weight of lithium chloride (LiCl) as a pore forming agent is mixed based on 100 parts by weight of the polyvinylidene fluoride (PVDF).
또한 상기 폴리불화비닐리덴(PVDF, Polyvinylidenefluoride) 100중량부를 기준으로 기공성장 억제제인 염화아연(Zinc Chloride) 0.5 ~ 15 중량부가 혼합됨을 특징으로 한다.Also, 0.5 to 15 parts by weight of zinc chloride (Zinc Chloride) as a pore growth inhibitor is mixed based on 100 parts by weight of the polyvinylidene fluoride (PVDF).
그리고 상기 중공사막의 조성물을 이용하여 표면 스킨층의 기공크기가 0.01 ~ 0.05㎛이고, 기공율이 70% ~ 95%로 이루어짐을 특징으로 하는 중공사막을 제공한다.Also, the present invention provides a hollow fiber membrane using the hollow fiber membrane composition, wherein the surface skin layer has a pore size of 0.01 to 0.05 μm and a porosity of 70% to 95%.
전술한 바와 같이 본 발명에 따르면, 중공사막의 원료가 되는 폴리불화비닐리덴에 중공사막의 친수성을 부여하도록 폴리에틸렌글리콜을 첨가제로 사용하고 디메틸아세트아미드를 용매제로 사용되는 중공사막 조성물로 하여금 내화학성 및 내구성이 향상되어 정수 및 오폐수 공정에 유용하게 사용될 수 있는 중공사막을 제조할 수 있는 효과가 있다.As described above, according to the present invention, polyethylene glycol is used as an additive to impart hydrophilicity of hollow fiber membranes to polyvinylidene fluoride which is a raw material of hollow fiber membranes, and a hollow fiber membrane composition using dimethylacetamide as a solvent, The durability is improved and a hollow fiber membrane which can be usefully used in purification of water and wastewater can be produced.
또한 본 발명에 따른 조성물의 중량비율에 의해 제조되는 중공사막은 생산효율을 높이면서도 양질의 중공사막을 제조할 수 있게 되는 효과가 있다.Also, the hollow fiber membrane produced by the weight ratio of the composition according to the present invention can produce a high quality hollow fiber membrane while improving the production efficiency.
또한 분자량이 300,000 ~ 600,000로 이루어지는 고분자량 폴리불화비닐리덴에 특정한 중량비율로 첨가제 및 용매제를 조성물로 사용함으로서 인장강도가 일반적인 기준치를 초과하는 고강도의 중공사막을 제조할 수 있게 되어 기계적 강도의 향상으로 파울링 제어에 효과적이면서도 우수한 역세성능 및 여과 성능을 구비하여 수질 처리 능력의 안정성을 높일 수 있는 중공사막을 제공할 수 있는 효과가 있다.Further, by using additive agent and solvent agent as a composition in a specific weight ratio to high molecular weight polyvinylidene fluoride having a molecular weight of 300,000 to 600,000, it is possible to produce a high strength hollow fiber membrane having a tensile strength exceeding a general reference value, It is possible to provide a hollow fiber membrane which is effective for fouling control and which has excellent backwashing performance and filtration performance and can enhance the stability of the water quality treatment capability.
또한 폴리불화비닐리덴에 기공 형성제 및 기공성장 억제제를 특정하게 한정된 범위로 사용함으로서 용매와 상호작용을 통하여 중공사막의 기공율을 높이고 표면 스킨층의 기공크기를 미세하게 하는 중공사막을 제공하는 효과가 있다.Further, by using the pore-forming agent and the pore growth inhibitor in a specific limited range, it is possible to increase the porosity of the hollow fiber membrane and to make the pore size of the surface skin layer fine by interacting with the solvent by providing polyvinylidene fluoride have.
또한 중공사막은 기공율 70% ~ 95%를 갖도록 하며, 표면 스킨층의 기공크기가 0.01 ~ 0.05 ㎛로 유지되도록 제조됨으로서 안정적인 수처리공정이 가능하게 됨으로써 수처리 생산비용 및 유지비용을 절감할 수 있고, 날로 엄격해지고 있는 고도정수처리, 용수처리공정을 포함한 차세대 고효율 분리공정산업에 유용하게 활용되는 효과가 있다.In addition, the hollow fiber membrane has a porosity of 70% to 95% and a pore size of the surface skin layer is maintained in a range of 0.01 to 0.05 탆, thereby making it possible to perform a stable water treatment process, thereby reducing water treatment production cost and maintenance cost, It is effective for the next generation high-efficiency separation process industry including advanced water treatment and water treatment process which is becoming severe.
이하 본 발명의 실시를 위한 구체적인 내용을 더욱 상세하게 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명은 폴리불화비닐리덴(PVDF, Polyvinylidenefluoride 이하, 폴리불화비닐리덴)과, 첨가제로 사용되는 폴리에틸렌글리콜(PEG, Poly ethylene glycol, 이하 폴리에틸렌글리콜)과, 용매로 사용되는 디메틸아세트아미드(DMAC)가 포함되어 이루어진다.The present invention relates to a process for producing polyvinylidene fluoride (PVDF), polyvinylidene fluoride (hereinafter referred to as polyvinylidene fluoride), polyethyleneglycol (PEG) used as an additive and dimethylacetamide (DMAC) .
여기서 상기 폴리불화비닐리덴은 내화학성 및 강도가 높으면서도 가공성이 좋아 얇은 막으로 가공이 용이하여 중공사막으로의 재료로서 탁월한 기능을 가지고 있다.The polyvinylidene fluoride is excellent in chemical resistance and strength, and is easy to process into a thin film because of its good processability, and thus has excellent functions as a material for a hollow fiber membrane.
그리고 첨가제로 사용되는 폴리에틸렌글리콜은 폴리불화비닐리덴을 조성물로 이루어지는 중공사막의 친수성을 부여하도록 사용되며, 후술되는 디메틸아세트아미드와 혼합될 경우 온도 및 점도변화와 더불어 성형 과정의 용이성에 지대한 영향을 끼치도록 상전이를 야기시켜 중공사막 표면의 공극크기와 공극률을 증가시키고 투과유량을 높이는 역할을 하여 고강도 고투과수율을 얻는데 큰 역할을 담당하게 된다.Polyethylene glycol used as an additive is used to impart hydrophilicity to the hollow fiber membrane composed of polyvinylidene fluoride. When mixed with dimethylacetamide described later, it has a great influence on the ease of molding process in addition to temperature and viscosity changes. Phase transition to increase the pore size and porosity on the surface of the hollow fiber membrane and to increase the permeation flow rate, thereby playing a large role in obtaining high strength and high permeation yield.
또한 용매로 사용되는 디메틸아세트아미드는 폴리불화비닐리덴계 수지를 용해시키기 위해 당 분야에서 일반적으로 사용되고 있다.Also, dimethylacetamide used as a solvent is generally used in the art to dissolve a polyvinylidene fluoride resin.
한편, 상기 중공사막 조성물은 폴리불화비닐리덴 18 ~ 30중량%, 폴리에틸렌글리콜 10 ~ 16중량%, 디메틸아세트아미드 58 ~ 68중량%로 이루어짐이 바람직하다.Meanwhile, the hollow fiber membrane composition preferably comprises 18 to 30% by weight of polyvinylidene fluoride, 10 to 16% by weight of polyethylene glycol, and 58 to 68% by weight of dimethylacetamide.
중공사막 조성물을 상기의 범위로 한정하는 것은 폴리불화비닐리덴이 18중량% 미만이면 점도가 너무 낮아 중공사막으로서의 필요한 강도에 도달되지 못하면서 중공사막 형태를 얻지 못하고, 설사 중공사막 형태를 갖추더라도 기공크기가 조절범위 이상으로 커지는 문제가 있고, 30중량%를 초과하면 점도가 너무 높아 방사가 용이하지 않을 수 있고, 설사 방사온도를 높이더라도 열분해현상에 의해 원하는 기계적물성의 중공사막을 얻을 수 없어 기공율이 낮아지는 문제가 있다. If the content of the polyvinylidene fluoride is less than 18% by weight, the hollow fiber membrane composition can not be obtained while the required strength as the hollow fiber membrane can not be attained and the pore size The hollow fiber membrane having a desired mechanical property can not be obtained due to thermal decomposition even if the spinning temperature is increased. As a result, the porosity There is a problem of lowering.
또한 첨가제로 사용되는 폴리에틸렌글리콜이 10중량% 미만이면 기공율이 나빠져서 표면의 기공 형성이 미비하게 되어 투과유량이 크게 향상되지 않는 문제가 있을 수 있고, 16중량%를 초과하면 표면 기공이 너무 커서 중공사막 강도가 약하게 됨과 동시에 고분자 용액을 제조하는 데 있어서 방사온도를 150℃ 이상의 고온으로 높혀야 함으로서 효율성 및 생산성이 저하되는 문제가 있다.If the amount of polyethylene glycol used as an additive is less than 10% by weight, porosity may be poor and pore formation on the surface may be insufficient. In this case, there may be a problem that the permeation flow rate is not greatly improved. When the content exceeds 16% by weight, There is a problem that efficiency and productivity are lowered because the strength is weakened and the spinning temperature must be raised to a high temperature of 150 ° C or higher in producing the polymer solution.
그리고 용매로 사용되는 디메틸아세트아미드가 58중량% 미만이면 고분자 용액 점도가 너무 높아서 방사온도를 고온으로 올려야 하기 때문에 방사가 어렵고 68중량%를 초과하는 경우에는 용매의 중량비율이 폴리불화비닐리덴의 중량비율 보다 현저하게 높아져 효율이 떨어지며 폴리불화비닐리덴의 중량비율이 떨어져 최종적으로 제조되는 중공사막의 강도가 너무 약하여 중공사막으로서의 기능을 수행하지 못하는 문제가 있다.If the amount of dimethylacetamide used as a solvent is less than 58% by weight, the viscosity of the polymer solution is too high to raise the spinning temperature to a high temperature. If the amount exceeds 88% by weight, the weight ratio of the solvent to the polyvinylidene fluoride The efficiency is lowered and the weight ratio of polyvinylidene fluoride is lowered so that the strength of the hollow fiber membrane to be finally produced is too weak to perform the function as a hollow fiber membrane.
따라서 본 발명에 따른 조성물의 중량비율에 의해 제조되는 중공사막은 생산효율을 높이면서도 양질의 중공사막을 제조할 수 있게 되는 효과를 가지게 되는 것이다.Therefore, the hollow fiber membrane produced by the weight ratio of the composition according to the present invention has the effect of producing a high quality hollow fiber membrane while increasing the production efficiency.
여기서 고강도로 유지되는 중공사막을 제조하기 위해 폴리불화비닐리덴의 중량 평균분자량을 300,000 ~ 600,000의 범위인 것을 사용한다.The polyvinylidene fluoride having a weight average molecular weight in the range of 300,000 to 600,000 is used for producing a hollow fiber membrane maintained at high strength.
이는 상기의 분자량 범위 내에 폴리불화비닐리덴을 사용하여야만 중공사막의 고강도를 유지할 수 있으면서도 성형온도 또한 적당한 온도로 요구되어 대량생산이 편리해지기 때문이다.This is because polyvinylidene fluoride should be used within the above-mentioned molecular weight range so that the high strength of the hollow fiber membrane can be maintained, and the molding temperature is also required to be a suitable temperature, thereby facilitating mass production.
상기 폴리불화비닐리덴의 중량 평균분자량이 100,000 ~ 300,000 미만의 범위와 300 ,000 ~ 600,000의 범위인 것을 각각 대비하여 첨가물과 용매의 조성물을 범위 또한 다양하게 함유되어 이루어져 제조된 중공사막에 대한 기공막의 형태 및 인장강도를 비교한 데이터를 아래 [표 1]에서 나타내었다.Wherein the polyvinylidene fluoride has a weight average molecular weight in the range of 100,000 to less than 300,000 and a molecular weight in the range of 300,000 to 600,000, The data comparing the shape and tensile strength are shown in Table 1 below.
sample
sample
(molecular weight)Polyvinylidene fluoride
(molecular weight)
(wt%)Polyvinylidene fluoride
(wt%)
Result
Result
(wt%)Polyethylene glycol
(wt%)
(wt%)Dimethylacetamide
(wt%)
100,000 ~ 300,000 미만
100,000 ~ 300,000
58 ~ 66
58 ~ 66
기공막 형성 O
인장강도 55 ~101.8kgf/cm2
Porous film formation O
Tensile Strength 55 to 101.8 kgf / cm 2
300,000 ~ 600,000
300,000 ~ 600,000
No Spinning
인장강도 110. 2kgf/cm2 Porous film formation O
Tensile strength 110. 2 kgf / cm 2
상기 [표 1]에서 나타난 바와 같이 폴리불화비닐리덴의 중량 평균분자량이 100,000 ~ 300,000 미만의 범위일 때에는 중공사막의 기공막은 안전하게 형성되었으나 중공사막의 인장강도가 일반적인 기준치인 100kgf/cm2에 도달하지 못하는 경우가 있었다.As shown in Table 1, when the weight average molecular weight of the polyvinylidene fluoride was in the range of 100,000 to less than 300,000, the pore film of the hollow fiber membrane was safely formed, but the tensile strength of the hollow fiber membrane did not reach a general reference value of 100 kgf / cm 2 I could not.
또한 폴리불화비닐리덴의 중량 평균분자량이 300,000 ~ 600,000인 경우에도 첨가제인 폴리에틸렌글리콜의 함유량이 12중량%를 초과할 때에는 방적(Spinning)이 이루어지지 않아 중공사막의 형태로 성형되지 못하였다.In addition, even when the weight average molecular weight of the polyvinylidene fluoride is 300,000 to 600,000, when the content of polyethylene glycol as an additive exceeds 12% by weight, spinning can not be performed and molding can not be performed in the form of a hollow fiber membrane.
하지만 분자량 300,000 ~ 600,000인 폴리불화비닐리덴이 22 ~ 30중량%, 폴리에틸렌글리콜은 10 ~ 12중량%, 디메틸아세트아미드는 58 ~ 66중량%로 이루어지는 조성물은 중공사막의 기공막의 형성은 물론 중공사막의 인장강도가 일반적인 기준치를 초과하는 110. 2kgf/cm2에 도달하여 고강도의 중공사막을 제조할 수 있게 되어 기계적 강도의 향상으로 파울링 제어에 효과적이면서도 우수한 역세성능 및 여과 성능을 구비하여 수질 처리 능력의 안정성을 높일 수 있는 중공사막을 제공할 수 있는 효과를 가지게 되는 것이다.However, a composition comprising 22 to 30 wt% of polyvinylidene fluoride having a molecular weight of 300,000 to 600,000, 10 to 12 wt% of polyethylene glycol, and 58 to 66 wt% of dimethylacetamide is not limited to the formation of the porous membrane of the hollow fiber membrane, It is possible to produce a high strength hollow fiber membrane with a tensile strength exceeding a general reference value of 110. 2 kgf / cm 2 , thereby improving the mechanical strength and effective in fouling control, and having excellent backwashing performance and filtration ability, It is possible to provide a hollow fiber membrane capable of improving the stability of the hollow fiber membrane.
한편, 상기 폴리불화비닐리덴은 소수성이 매우 강한 물질이므로 상전이 공정 중 응고제와 용매의 상호교환이 원활하게 일어나지 않아 기공형성이 잘 되지 않을 수 있으며, 이러한 문제점을 해결하기 위해 상기 조성물의 범위를 한정하여 사용되나, 이와 더불어 본 발명에서는 기공 형성제로 염화리튬(LiCl)을 사용할 수 있다.On the other hand, since the polyvinylidene fluoride is a very strong hydrophobic substance, the coagulation agent and the solvent are not exchanged smoothly during the phase transition process, and pore formation may not be performed well. In order to solve this problem, In addition, lithium chloride (LiCl) may be used as a pore-forming agent in the present invention.
상기 기공 형성제는 중공사막 조성물 중 폴리불화비닐리덴 100중량부를 기준으로 0.5 ~ 15 중량부가 혼합하는 것이 바람직하며, 이는 기공 형성제의 함유량이 0.5중량부 미만이면 기공 형성제의 효능이 미비하게 되어 기공크기가 커지지 않고 투과유량이 증가하지 않는 문제가 발생되고, 기공 형성제의 함유량이 15중량부를 초과하게 되면 중공막사의 강도가 약해지는 문제가 발생되기 때문이다.It is preferable that 0.5 to 15 parts by weight of the pore-forming agent is mixed with 100 parts by weight of polyvinylidene fluoride in the hollow fiber membrane composition. If the content of the pore-forming agent is less than 0.5 part by weight, the effect of the pore- The pore size is not increased and the permeation flow rate is not increased. When the content of the pore-forming agent is more than 15 parts by weight, the strength of the hollow bar yarn becomes weak.
그리고 본 발명에서 기공율 변화에 관계없이 기공크기를 일정범위 내에서 조절하는 역할을 하는 기공성장 억제제를 사용할 수 있으며, 상기 기공성장 억제제는 염화아연(Zinc Chloride)을 사용할 수 있다.In the present invention, a pore growth inhibitor which plays a role of controlling the pore size within a certain range irrespective of the porosity change may be used. The pore growth inhibitor may be zinc chloride (Zinc Chloride).
상기 기공성장 억제제는 중공사막 조성물 중 폴리불화비닐리덴 100중량부를 기준으로 0.5 ~ 15 중량부가 혼합하는 것이 바람직하다.The pore growth inhibitor is preferably used in an amount of 0.5 to 15 parts by weight based on 100 parts by weight of polyvinylidene fluoride in the hollow fiber membrane composition.
여기서 기공성장 억제제를 폴리불화비닐리덴 100중량부를 기준으로 0.5 ~ 15 중량부로 한정하는 것은 기공 형성제와 동일하게 한정된 범위로 한정하여 기공 형성제와 기공성장 억제제를 함께 사용함으로서 용매와 상호작용을 통하여 중공사막의 기공율을 높이고 표면 스킨층의 기공크기를 미세하게 하는 중공사막을 제공하는 효과를 가지게 되는 것이다.Herein, the pore growth inhibitor is limited to 0.5 to 15 parts by weight based on 100 parts by weight of polyvinylidene fluoride, and is limited to the same limited range as that of the pore-forming agent. By using the pore-forming agent together with the pore- It is possible to provide a hollow fiber membrane that increases the porosity of the hollow fiber membrane and makes the pore size of the surface skin layer fine.
한편, 상기에서 언급된 조성물에 의해 제조되는 중공사막은 기공율 70% ~ 95%를 갖도록 하며, 표면 스킨층의 기공크기가 0.01 ~ 0.05 ㎛로 유지되도록 제조된다. 따라서 본 발명에 따른 안정적인 수처리공정이 가능하게 됨으로써 수처리 생산비용 및 유지비용을 절감할 수 있고, 날로 엄격해지고 있는 고도정수처리, 용수처리공정을 포함한 차세대 고효율 분리공정산업에 유용하게 활용되는 효과를 가지게 되는 것이다.Meanwhile, the hollow fiber membrane produced by the above-mentioned composition has a porosity of 70% to 95%, and the pore size of the surface skin layer is maintained to be 0.01 to 0.05 탆. Therefore, the stable water treatment process according to the present invention can be performed, thereby reducing water treatment production cost and maintenance cost, and has an effect of being usefully utilized in the next generation high efficiency separation process industry including advanced water treatment process and water treatment process .
Claims (6)
가 포함되어 이루어짐을 특징으로 하는 중공사막 조성물.Polyvinylidene fluoride (PVDF); Polyethylene glycol (PEG) used as an additive; Dimethylacetamide (DMAC) used as a solvent;
Wherein the hollow fiber membrane composition comprises a hollow fiber membrane.
상기 폴리불화비닐리덴(PVDF, Polyvinylidenefluoride)은 18 ~ 30중량%, 폴리에틸렌글리콜(PEG, Poly ethylene glycol)은 10 ~ 16중량%, 디메틸아세트아미드(DMAC)는 58 ~ 68중량%로 이루어짐을 특징으로 하는 중공사막 조성물.The method according to claim 1,
The polyvinylidene fluoride (PVDF) is 18 to 30% by weight, the polyethylene glycol (PEG) is 10 to 16% by weight, and the dimethylacetamide (DMAC) is 58 to 68% by weight. Lt; / RTI >
분자량 300,000 ~ 600,000인 폴리불화비닐리덴(PVDF, Polyvinylidenefluoride)이 22 ~ 30중량%, 폴리에틸렌글리콜(PEG, Poly ethylene glycol)은 10 ~ 12중량%, 디메틸아세트아미드(DMAC)는 58 ~ 66중량%로 이루어짐을 특징으로 하는 중공사막 조성물.The method according to claim 1,
22 to 30% by weight of polyvinylidene fluoride (PVDF) having a molecular weight of 300,000 to 600,000, 10 to 12% by weight of polyethylene glycol (PEG) and 58 to 66% by weight of dimethylacetamide (DMAC) Wherein the hollow fiber membrane composition is a hollow fiber membrane.
상기 폴리불화비닐리덴(PVDF, Polyvinylidenefluoride) 100중량부를 기준으로 기공 형성제인 염화리튬(LiCl) 0.5 ~ 15 중량부가 혼합됨을 특징으로 하는 중공사막 조성물.4. The method according to any one of claims 1 to 3,
0.5 to 15 parts by weight of lithium chloride (LiCl) as a pore forming agent is mixed with 100 parts by weight of the polyvinylidene fluoride (PVDF).
상기 폴리불화비닐리덴(PVDF, Polyvinylidenefluoride) 100중량부를 기준으로 기공성장 억제제인 염화아연(Zinc Chloride) 0.5 ~ 15 중량부가 혼합됨을 특징으로 하는 중공사막 조성물.4. The method according to any one of claims 1 to 3,
0.5 to 15 parts by weight of zinc chloride (Zinc Chloride) as a pore growth inhibitor is mixed based on 100 parts by weight of the polyvinylidene fluoride (PVDF).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107866153A (en) * | 2016-09-27 | 2018-04-03 | 乐天化学株式会社 | Film and water purification installation prepared by film composition, the method for preparing the film, the film composition |
| CN108939931A (en) * | 2018-08-21 | 2018-12-07 | 烯膜科技（深圳）有限公司 | A kind of preparation method of hollow-fibre membrane |
| KR101942807B1 (en) * | 2018-04-13 | 2019-04-17 | (주)신우엔지니어링 | Polymer resin composition for making porous hollow fiber membrane |
| CN114471190A (en) * | 2020-10-28 | 2022-05-13 | 南京工大膜应用技术研究所有限公司 | Preparation method of modified polyvinylidene fluoride film applied to agricultural chemical wastewater |
-
2013
- 2013-09-30 KR KR20130115809A patent/KR20150036857A/en not_active Application Discontinuation
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107866153A (en) * | 2016-09-27 | 2018-04-03 | 乐天化学株式会社 | Film and water purification installation prepared by film composition, the method for preparing the film, the film composition |
| KR101942807B1 (en) * | 2018-04-13 | 2019-04-17 | (주)신우엔지니어링 | Polymer resin composition for making porous hollow fiber membrane |
| CN108939931A (en) * | 2018-08-21 | 2018-12-07 | 烯膜科技（深圳）有限公司 | A kind of preparation method of hollow-fibre membrane |
| CN114471190A (en) * | 2020-10-28 | 2022-05-13 | 南京工大膜应用技术研究所有限公司 | Preparation method of modified polyvinylidene fluoride film applied to agricultural chemical wastewater |
| CN114471190B (en) * | 2020-10-28 | 2023-10-20 | 南京工大膜应用技术研究所有限公司 | Preparation method of modified polyvinylidene fluoride membrane applied to agrochemical wastewater |
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