KR100350361B1 - Polymeric membrane composed of nanometer sized fiber and carbon membrane thereof - Google Patents
Polymeric membrane composed of nanometer sized fiber and carbon membrane thereof Download PDFInfo
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- KR100350361B1 KR100350361B1 KR1020000022079A KR20000022079A KR100350361B1 KR 100350361 B1 KR100350361 B1 KR 100350361B1 KR 1020000022079 A KR1020000022079 A KR 1020000022079A KR 20000022079 A KR20000022079 A KR 20000022079A KR 100350361 B1 KR100350361 B1 KR 100350361B1
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 26
- 239000000835 fiber Substances 0.000 title claims description 17
- 239000012528 membrane Substances 0.000 title abstract description 56
- 229920000642 polymer Polymers 0.000 claims abstract description 24
- 229920005597 polymer membrane Polymers 0.000 claims abstract description 12
- 238000001523 electrospinning Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000004642 Polyimide Substances 0.000 claims description 8
- 229920001721 polyimide Polymers 0.000 claims description 8
- 229920006254 polymer film Polymers 0.000 claims description 8
- -1 polyethylene Polymers 0.000 claims description 5
- 239000004743 Polypropylene Substances 0.000 claims description 3
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 230000009477 glass transition Effects 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 26
- 239000000126 substance Substances 0.000 abstract description 13
- 238000001179 sorption measurement Methods 0.000 abstract description 11
- 230000035699 permeability Effects 0.000 abstract description 9
- 238000003763 carbonization Methods 0.000 abstract description 6
- 239000007789 gas Substances 0.000 description 22
- 239000000243 solution Substances 0.000 description 14
- 238000004519 manufacturing process Methods 0.000 description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 7
- 239000004065 semiconductor Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 5
- 239000000428 dust Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 239000003365 glass fiber Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 238000005191 phase separation Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920005594 polymer fiber Polymers 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920001410 Microfiber Polymers 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000013566 allergen Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 150000002013 dioxins Chemical class 0.000 description 1
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000002657 fibrous material Substances 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007792 gaseous phase Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229940088597 hormone Drugs 0.000 description 1
- 239000005556 hormone Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 239000002759 woven fabric 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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
-
- 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
- B01D67/0039—Inorganic membrane manufacture
- B01D67/0067—Inorganic membrane manufacture by carbonisation or pyrolysis
-
- 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
- B01D69/108—Inorganic support material
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
- D01F9/14—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments
- D01F9/20—Carbon filaments; Apparatus specially adapted for the manufacture thereof by decomposition of organic filaments from polyaddition, polycondensation or polymerisation products
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/02—Types of fibres, filaments or particles, self-supporting or supported materials
- B01D2239/025—Types of fibres, filaments or particles, self-supporting or supported materials comprising nanofibres
-
- 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
- B01D2323/081—Heating
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/39—Electrospinning
-
- 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
Abstract
본 발명은 고분자를 일렉트로스피닝 (electrospinning)하여 압력의 큰 손실 없이 나노미터 크기의 입자를 제거할 수 있도록 제조한 고분자막, 및 이를 열적 탄화시켜 화학적 안정성이 높고 투과 및 흡착력이 우수하도록 제조한 탄소막에 관한 것이다.The present invention relates to a polymer membrane prepared by electrospinning the polymer to remove nanometer-sized particles without a large loss of pressure, and a carbon membrane prepared by thermal carbonization to have high chemical stability and excellent permeability and adsorption. will be.
Description
본 발명은 나노미터 직경의 섬유상 고분자로 이루어진 막, 이로부터 얻어진 탄소막, 및 이들의 제조 방법에 관한 것이다. 보다 구체적으로는, 고분자 용액을 일렉트로스피닝 (electrospinning)하여 제조한 나노미터 직경의 섬유상 고분자를 부직 형태로 포집함으로써 제조된 고분자막 및 이를 열적 탄화시켜 얻은, 화학적 안정성 및 투과성이 높은 탄소막에 관한 것이다.The present invention relates to a film made of nanometer diameter fibrous polymer, a carbon film obtained therefrom, and a method for producing the same. More specifically, the present invention relates to a polymer membrane prepared by collecting a nanometer diameter fibrous polymer prepared by electrospinning a polymer solution in a nonwoven form and a carbon membrane having high chemical stability and permeability obtained by thermal carbonization thereof.
산업화로 인한 대기오염이 증가함에 따라 대기중의 유해입자를 제거하고 청정환경을 조성하기 위해 입자제거용 필터는 산업체뿐 아니라 일반 가정용품에서도 그 수요가 매우 많아지고 있다. 일반적으로 사용되고 있는 필터로는 캐빈 (cabin)필터, 정전필터, 오존필터 등이 있다.As the air pollution increases due to industrialization, the filter for removing particles is very demanded not only in the industry but also in general household goods to remove harmful particles in the air and to create a clean environment. Commonly used filters include cabin filters, electrostatic filters, and ozone filters.
그 중 캐빈필터는 활성탄소 섬유와 섬유를 대전시켜 영구적인 정전기력을 갖게 제조한 것으로 주로 차량용으로 많이 사용되며, 정전필터는 영구적으로 정전기력을 갖는 폴리프로필렌 초극세 섬유층과 탈취층으로 이루어져 있어 담배연기를 비롯한 각종 악취가스의 제거에 우수한 성능을 나타낸다. 오존필터의 경우, 공기중에서 방전이나 광에너지에 의해 간단히 발생하는 오존은 살균 및 탈취기능이 있고 대기중에서 산소로 자연분해되며 열, 빛, 금속, 금속산화물이나 알카리용액 등에 접촉시 분해가 촉진된다. 그러나, 이런 오존을 사용한 오존 필터의 경우 고농도의 오존발생은 인체에 매우 유해하다는 단점을 갖고 있다.Among them, the cabin filter is manufactured to have permanent electrostatic force by charging activated carbon fiber and fiber, and is mainly used for vehicles. The electrostatic filter is composed of polypropylene ultra-fine fiber layer and deodorizing layer which have permanent electrostatic force. Excellent performance in removing various odor gases. In the case of the ozone filter, ozone, which is simply generated by discharge or light energy in the air, has sterilization and deodorization function, and is naturally decomposed into oxygen in the air, and decomposition is promoted upon contact with heat, light, metal, metal oxide or alkaline solution. However, in the case of the ozone filter using such ozone has a disadvantage that high concentration ozone generation is very harmful to the human body.
또한, 상기 필터들은 1 마이크로미터 이하의 미세먼지나 알레르기를 일으키는 물질들을 제거하기가 어렵다는 단점을 갖고 있다. 전기 집진방법은 공기중의 먼지 입자를 제거하는데 고전압을 사용하고, 사용 48시간 안에 그 효율이 80%에서 20%로 떨어져 주기적으로 청소를 해주고 있고, 오존의 발생이나 전하를 띈 입자들의 발생과 같은 부작용이 있기 때문에 병원 같이 공기의 질에 민감한 곳에서는 그 사용이 제한되고 있다. 따라서, 이를 극복하기 위해 고성능 에어(HEPA; High Efficiency Particulate Air) 필터나 초고성능 에어(ULPA; Ultra Low Penetration Air) 필터를 제조하여 공기 중 입자를 제거하는 데 사용하고 있다[미국 특허 제5,507,847호 참조]. HEPA 필터는 직경 0.3 내지 0.5 마이크론, 길이 2 내지 3 mm의 아주 가는 유리방적섬유를 수중에 분산시킨 후 고운 망 위에서 탈수하고 건조하여 종이형태로 만들어 사용한다. 그러나, 이와 같은 HEPA 필터를 제조하기 위해서는 극세유리섬유의 배합 및 일정한 공극을 유지하기 위한 분산이 중요하므로 제작 기술이 어렵고 비용이 많이 들어 판매가격이 매우 비싸다는 단점을 갖고 있다. 또한, HEPA 필터의 경우는 0.3 마이크로미터 입자를 99.97%이상 제거할 수 있고, ULPA 필터의 경우에는 0.1 마이크로미터 입자를 99.999%이상 제거할 수 있는 장점이 있지만, HEPA 필터나 ULPA 필터의 재질이 보로실리케이트(borosilicate) 유리섬유로 되어 있고 바인더 (binder)의 문제 등, 화학적 안정성면에 문제점이 있다. 이는 대부분의 용도에서는 큰 문제가 되지 않으나 입자를 극도로 적은 수로 한정해야 하는 경우에는 주요한 오염문제로 대두된다. 예를 들어, 반도체 습화공정 용도로 사용되는 플루오르화 수소산은 통상의 공기 여과재에 특히 공격적이다. 이 화학물질을 사용하는 청정 환경 내에서 공기가 재순환되는 경우, 다수의 필터제품은 조기 손상되어 오염 입자의 확산이 시작된다. 소량의 화학물질, 예를 들어 붕소나 인 등도 필터를 오염시킨다.In addition, the filters have a disadvantage that it is difficult to remove fine dust or allergens of less than 1 micrometer. Electric dust collection method uses high voltage to remove dust particles in the air, and the efficiency drops from 80% to 20% periodically within 48 hours of use, and cleans them periodically, such as the generation of ozone or charged particles. Because of its side effects, its use is restricted in places such as hospitals where air quality is sensitive. Therefore, in order to overcome this, a high efficiency air filter (HEPA) or ultra low performance air (ULPA) filter is manufactured and used to remove particles from the air (see US Patent No. 5,507,847). ]. HEPA filter is used to make very thin glass spun fiber of 0.3 to 0.5 micron diameter and 2 to 3 mm length in water, and then dehydrated on fine net and dried to form paper. However, in order to manufacture such a HEPA filter, it is important to mix the ultrafine glass fibers and to maintain a constant void, so that manufacturing technology is difficult and expensive, and the selling price is very expensive. In addition, the HEPA filter can remove more than 99.97% of 0.3 micrometer particles, the ULPA filter can remove more than 99.999% of particles, but the material of the HEPA filter or ULPA filter It is made of silicate (borosilicate) glass fiber and there is a problem in terms of chemical stability, such as the problem of the binder (binder). This is not a big problem for most applications, but it is a major contamination problem when it is necessary to limit the particles to an extremely small number. For example, hydrofluoric acid used for semiconductor wetting process applications is particularly aggressive with conventional air filter media. When air is recycled in a clean environment using this chemical, many filter products are prematurely damaged and diffusion of contaminating particles begins. Small amounts of chemicals, such as boron or phosphorus, also contaminate the filter.
통상적으로, 고분자막은 고분자를 적정 용매에 녹인 다음 상분리를 이용하여 제조하는데, 이렇게 얻어진 막은 표면이 조밀하며, 이로 인해 분리 선택도는 향상되나 비대칭 단일 막으로 제조되기 때문에 용도가 한정되고 투과도가 낮다는 단점을 갖는다. 또한 상분리를 이용해서 제조되는 막의 표면 공극률 (porosity)은 10% 이하로 상당히 낮다. 따라서 기체 투과도를 높이기 위해서는 새로운 방법으로 막을 제조하여야 할 필요성이 있다. 또한 일반적으로 사용하는 필터는 섬유를 가늘게 제조하여 부직 형태로 막을 제조하며, 이는 섬유의 직경이 마이크로미터 수준이므로 상분리를 이용하여 제조되는 막보다는 공극률이 월등히 높으나 나노미터 크기의 입자를 제거하기에는 공극의 크기가 커서 주로 큰 먼지 입자를 미리 제거해주는 전처리 필터로만 사용되고 있다. 따라서 기존의 고분자막을 사용하는 데 있어서 압력의 큰 손실없이 효율을 좋게 하기 위해서 섬유상으로 만들어 HEPA보다 좋은 성능의 막을 제조하는 것이 필요하다. 따라서 막 표면의 공극이 충분히 작고 균일하여야 하며, 표면적이 넓어 투과압력손실이 적어야 함과 동시에 실제 분리 수행시 적용되는 압력을 지탱할 충분한 기계적 강도를 갖는 막을 제조할 필요가 있다.Typically, polymer membranes are prepared by dissolving the polymer in a suitable solvent and then using phase separation, which has a dense surface, which improves segregation selectivity but results in limited use and low permeability because it is made of an asymmetric single membrane. Has disadvantages. In addition, the surface porosity of membranes prepared using phase separation is significantly lower, below 10%. Therefore, there is a need to manufacture membranes in a new way to increase gas permeability. In addition, the commonly used filter is made of thin fibers to produce a membrane in the form of a nonwoven, because the diameter of the fiber is a micrometer level, the porosity is much higher than the membrane produced by the phase separation, but to remove the nanometer-sized particles of the pore Due to its large size, it is mainly used as a pretreatment filter to remove large dust particles in advance. Therefore, it is necessary to manufacture a membrane having a better performance than HEPA in order to improve the efficiency without using a large loss of pressure in the existing polymer membrane. Therefore, it is necessary to prepare a membrane having a sufficiently small and uniform pore on the surface of the membrane, a large surface area, low permeation pressure loss, and sufficient mechanical strength to support the pressure applied during the actual separation.
본 발명자들은 종래의 입자제거 필터의 화학적 불안정성에 기인한 오염문제 및 높은 제조비용 문제 등을 동시에 개선하기 위해, 고분자 용액을 일렉트로스피닝시켜 제조한 나노미터 직경의 섬유상 고분자막 및 이를 열적 탄화시켜 제조한 탄소막을 사용함으로써 상기 문제점을 해결할 수 있음을 밝혀내었다.MEANS TO SOLVE THE PROBLEM The present inventors made the nanometer diameter fibrous polymer film | membrane manufactured by electrospinning a polymer solution, and the carbon film | membrane manufactured by thermal carbonization in order to simultaneously improve the contamination problem and the high manufacturing cost problem by chemical instability of the conventional particle removal filter. It has been found that the problem can be solved by using.
본 발명의 목적은 상술한 종래 필터의 단점들을 개선함으로써, 제조비용이 저렴하고 투과도가 높으면서 입자 여과 효율이 높고 나아가 열적, 화학적으로 안정한 고분자막을 제공하는 것이다.SUMMARY OF THE INVENTION An object of the present invention is to provide a polymer membrane which is low in manufacturing cost, high in permeability, high in particle filtration efficiency and further thermally and chemically stable by improving the disadvantages of the conventional filter described above.
본 발명의 또 다른 목적은 이렇게 제조된 고분자막을 열적 탄화시켜 화학적 안정성 및 투과성을 향상시키고 유기물 흡착성능이 있는 탄소막을 제공하는 것이다.Still another object of the present invention is to thermally carbonize the polymer membrane thus prepared, to improve chemical stability and permeability, and to provide a carbon membrane having organic material adsorption performance.
본 발명의 상기 목적 및 기타 다른 목적들은 후술하는 명세서로부터 확인할 수 있을 것이다.The above and other objects of the present invention will be apparent from the following specification.
본 발명은 일렉트로스피닝법을 통해 제조된 300 나노미터 이하의 섬유상 고분자로 이루어진 필터용 고분자막, 및 이렇게 제조된 고분자막을 열적 탄화시켜 제조된 탄소막에 관한 것이다.The present invention relates to a polymer film for filters consisting of 300 nanometer or less fibrous polymer prepared by the electrospinning method, and a carbon film produced by thermally carbonizing the polymer film thus prepared.
본 발명의 한 실시태양으로, 나노미터 직경의 섬유상 고분자를 일렉트로스피닝법을 통해 지지막 없이 바로 포집한 자립 (free standing) 형태로 제조하거나, 또는 와이어 스크린(wire screen)이나 탄소펠트상에 포집한 지지 형태로 제조함으로써 기계적 강도를 높일 수 있다.In one embodiment of the present invention, a nanometer diameter fibrous polymer is prepared in a free standing form directly collected without a supporting film by electrospinning, or collected on a wire screen or carbon felt. By manufacturing in the form of support, the mechanical strength can be increased.
또한, 본 발명은 지지막이 없는 자립형 고분자막 또는 탄소펠트나 와이어 스크린 막과 같은 지지막상에 포집한 지지형 고분자막을 열적 탄화시킴으로써 제조된 탄소막에 관한 것이다. 본 발명의 탄소막은 화학적 안정성, 투과성 및 흡착성이 현저히 높으며, 증가된 흡착성으로 인해 기체중의 입자 분리뿐 아니라 기체상 또는 액체상 유기물의 흡착이 가능하다.The present invention also relates to a carbon film produced by thermally carbonizing a self-supporting polymer film having no support film or a support polymer film collected on a support film such as carbon felt or wire screen film. The carbon membrane of the present invention has a markedly high chemical stability, permeability and adsorptivity, and the increased adsorption enables not only particle separation in gas but also adsorption of gaseous or liquid organic matter.
나노미터크기의 입자를 제거하기 위한 막을 제조하는데 있어서, 고분자 용액은 고분자를 용매에 녹이거나 용융을 통해 액체상을 형성하면 된다. 즉, 일렉트로스피닝 방법을 통해, 섬유상이 길고 나노미터크기로 제조될 수 있는 고분자는 모두 적용될 수 있다. 이러한 고분자로는 유리전이온도가 350 ℃ 이하인 폴리에틸렌, 폴리프로필렌, 폴리술폰, 폴리이미드, 폴리에테르술폰, 폴리아크릴나이트릴, 폴리비닐리덴플루오라이드 등의 범용 고분자 또는 탄화가 잘 되는 고분자를 들 수 있다. 특히, 폴리이미드는 내열성이 높고 화학적 안정성이 높아 고온에서 사용하는 기체 분리막 재료로 그 가능성이 높은 물질중의 하나이다. 따라서 본 발명에서는 폴리이미드를 주로 사용하여 막을 제조하였으나, 이는 본 발명을 보다 상세히 설명하기 위한 것이지 본 발명이 이에 국한하는 것은 아니다.In preparing a membrane for removing nanometer-sized particles, the polymer solution may be formed by dissolving the polymer in a solvent or forming a liquid phase through melting. That is, through the electrospinning method, any polymer having a long fiber phase and which can be manufactured in nanometer size can be applied. Such polymers include general-purpose polymers such as polyethylene, polypropylene, polysulfone, polyimide, polyether sulfone, polyacrylonitrile, polyvinylidene fluoride having a glass transition temperature of 350 ° C. or lower, or polymers having good carbonization. . In particular, polyimide is one of the materials having high potential as a gas separation membrane material used at high temperature due to its high heat resistance and high chemical stability. Therefore, in the present invention, the film was mainly manufactured using polyimide, but this is to explain the present invention in more detail, but the present invention is not limited thereto.
일렉트로스피닝법을 이용하여 제조된 고분자 섬유의 굵기는 사용한 전압, 사용한 고분자의 크기, 사용한 용매의 특성, 그리고 고분자 용액의 농도 등에 따라변한다. 이 방법의 장점은 기존의 마이크로미터 직경의 섬유제조 방법에 비해 나노미터 두께의 섬유를 제작할 수 있을뿐 아니라, 제조되는 형태는 섬유들이 순간 전하를 띄게되어 분산이 양호한 부직 형태이므로 한번에 원하는 막형태의 최종 생산물을 얻을 수 있는 장점이 있다. 이렇게 일렉트로스피닝 벙법으로부터 제조된 고분자막은 나노미터 직경의 섬유상으로 이루어져서 막의 공극이 작아 표면적이 매우 넓고 공극률이 상당히 높다. 따라서 0.3 마이크로미터 입자를 99.99% 이상의 효율로 제거할 수 있다. 하기 수학식 1의 투과율 (P)은 필터 상류측의 입자 농도에 대한 하류측의 입자 농도 비를 의미하고, 여과 효율은 하기 수학식 2로 나타낸다.The thickness of the polymer fibers produced using the electrospinning method varies depending on the voltage used, the size of the polymer used, the properties of the solvent used, and the concentration of the polymer solution. The advantage of this method is that it can produce nanometer-thick fibers as compared to the conventional micrometer-based fiber manufacturing method. It has the advantage of getting the final product. The polymer film produced from the electrospinning method is composed of nanometer-fiber fibers, so that the pores of the film are small, the surface area is very large, and the porosity is quite high. Thus 0.3 micrometer particles can be removed with an efficiency of at least 99.99%. The transmittance P of the following formula (1) means the ratio of the particle concentration on the downstream side to the particle concentration on the upstream side of the filter, and the filtration efficiency is represented by the following formula (2).
식 중, n은 필터 하류측의 입자 농도이고, n0는 필터 상류측의 입자 농도이다.In the formula, n is the particle concentration on the filter downstream side, and n 0 is the particle concentration on the filter upstream side.
활성탄소 섬유 혹은 섬유상 활성탄소는 유기섬유를 탄화시키고 산화성 가스로 활성화시켜 만드는데, 입상이나 분말 활성탄에 비하여 비표면적이 월등히 큰 것 외에도 여러가지 독특한 특성을 갖고 있다. 탄소섬유의 직경이 15 마이크로미터 정도의 일반적인 탄소섬유에 비하여 본 연구에서 얻어진 섬유의 직경은 나노미터 두께로 가늘어 섬유상에서 발달된 미세공들은 기상 및 액상 흡착에 있어서 대단히신속한 세공내 흡착을 보일뿐 아니라, 기본 형태가 섬유이므로 직포나 부직포, 종이 등의 형태를 가공하여 사용할 수 있고 취급이 용이하다. 그리고 낮은 온도에서 탈착이 용이하므로 재생성이 뛰어나다.Activated carbon fibers or fibrous activated carbons are made by carbonizing organic fibers and activating them with oxidizing gases. They have a number of unique properties other than granular or powdered activated carbons. Compared to the general carbon fiber having a diameter of 15 micrometers, the diameter of the fiber obtained in this study is thinner than nanometer, so that the micropores developed on the fiber show very fast pore adsorption in gaseous phase and liquid phase adsorption. Since the basic form is fiber, it can be used by processing the form of woven fabric, nonwoven fabric, paper and the like and is easy to handle. And since it is easy to detach at low temperature, it is excellent in regeneration.
근래에는 기체혼합물의 선택적 흡착 기능성을 갖는 흡착제의 개발에 관심이 고조되고 있다. 활성탄소 재료의 미세공 크기분포를 휠씬 키우면 촉매의 담체로 사용할 수가 있기 때문에 화학적, 열적 안정성이 좋은 탄소계 담체를 제조할 수 있다. 또한 활성탄소 섬유의 균일한 공극에 균일하게 금속을 침착시키면, 미세공의 구조적 전기적 특성을 마음대로 변화시켜 흡착제는 물론 연료전지의 분리전극, 리튬 이차전지의 음극활물질 등 다양한 분야에 응용할 수 있다.In recent years, there has been increasing interest in the development of adsorbents with selective adsorption functionality of gas mixtures. If the micropore size distribution of the activated carbon material is greatly increased, it can be used as a catalyst carrier, and thus a carbon-based carrier having good chemical and thermal stability can be prepared. In addition, when the metal is uniformly deposited in the uniform pores of the activated carbon fibers, the structural electrical properties of the micropores can be changed at will, and thus it can be applied to various fields such as adsorbents, separator electrodes of fuel cells, and negative electrode active materials of lithium secondary batteries.
생활폐수, 오물, 하수종말처리장, 공장폐수 등의 처리시설에 있는 탈취장치, 소각시설의 배출가스 처리장치, 일반 산업체에서 발생되는 유해가스 제거장치, 반도체 제조시설의 유해가스 흡착장치, 화학공장의 정밀 기기를 보호하기 위한 부식가스 제거장치, 군용 방독면, 산업근로자의 방독면, 사무 및 주거시설의 공기청정장치등에 사용하고 있는 활성탄소의 재료로 사용할 수 있다.Deodorizers in treatment facilities such as domestic wastewater, sewage, sewage treatment plant, factory wastewater, exhaust gas treatment device of incineration facility, harmful gas removal device from general industry, harmful gas adsorption device of semiconductor manufacturing facility, chemical plant It can be used as the material of activated carbon used in the corrosive gas removal device for protecting precision equipment, military gas mask, gas mask for industrial workers, and air cleaning device for office and residential facilities.
본 발명에 따라 제조한 고분자막 또는 열적 탄화시켜 얻은 탄소막은 나노미터 직경의 섬유상 형태의 제조원가가 저렴한 고분자로 제조되어 기체 투과도가 높을뿐 아니라, 미립자 분리에 높은 효율을 갖고 있으며, 화학적 열적으로 안정하여 열악한 환경에서도 사용할 수 있는 장점이 있고 활성탄소 막의 흡착 성능까지 이끌어 낼 수 있다.The polymer membrane prepared according to the present invention or the carbon membrane obtained by thermal carbonization is made of a polymer having low manufacturing cost in the form of nanometer diameter fibrous material, which has high gas permeability, high efficiency in particle separation, and is chemically thermally stable and poor. It has the advantage of being used in the environment and can lead to the adsorption performance of activated carbon membranes.
이렇게 제조된 탄소막은 압력손실이 적고, 고속으로 저농도의 유해물질을 제거하기에 적합하다. 최근 문제로 대두되고 있는 물 중의 극미량 농도의 환경 호르몬이나 물 속에 다이옥신류등의 제거에 적합한 능력이 기대된다. 또한, 섬유상 활성탄을 사용해 반도체 제조공정에 유해한 가스를 흡착할 수 있다. 또한, 본 발명에서 제조된 화학적으로 안정한 탄소막은, 반도체 공정에 일반적으로 사용되는 HEPA 필터가 유리섬유로 되어 있어 가격이 비쌀뿐 아니라 반도체 공정의 배출가스에 의한 화학적 부식등의 문제점이 있기 때문에, 이를 대체할 수 있을 것으로 기대된다. 암모니아등 알카리성 가스나 톨루엔이나 저분자 실록산 등 유기계 가스를 여과하거나, 반도체 공장의 배출가스로부터 불소가스등을 직접 재회수하는데 사용할 수 있다. 이들 불소가스는 고가이며 온실가스 규제의 표적이기도 하다. 현재로서 불소 가스들을 재회수하는 상업적인 공정은 없다. 그러나 CFC가스에 대해 시험한 결과 탄소막은 선택성이 약 1000으로 일반적인 고분자막의 선택도 50보다 휠씬 높고 회수능력도 6-8배 더 높은 것으로 나타났다. 따라서 수명이 긴 반도체 제조용 클린룸의 공기청정필터용 막으로의 사용이 기대된다.The carbon film thus prepared has a low pressure loss and is suitable for removing low concentrations of harmful substances at high speed. The ability to be suitable for the removal of extremely low concentrations of environmental hormones and dioxins in water is emerging as a problem recently. In addition, fibrous activated carbon can be used to adsorb gases harmful to semiconductor manufacturing processes. In addition, the chemically stable carbon film produced in the present invention, because the HEPA filter generally used in the semiconductor process is made of glass fiber, not only is expensive, but also has problems such as chemical corrosion caused by the exhaust gas of the semiconductor process. It is expected to be replaced. It can be used to filter alkaline gases such as ammonia, organic gases such as toluene and low molecular siloxane, or to directly recover fluorine gas from the exhaust gas of a semiconductor factory. These fluorine gases are expensive and are the target of greenhouse gas regulations. There is currently no commercial process to recover fluorine gases. However, tests on CFC gas showed that the carbon film had a selectivity of about 1000, which is much higher than that of a typical polymer membrane and was 6-8 times higher than that of a typical polymer membrane. Therefore, it is expected to be used as an air cleaning filter membrane of a clean room for semiconductor manufacturing with a long lifespan.
다음의 실시 예들은 본 발명을 보다 상세히 설명하기 위한 것이지 본 발명이 이에 국한하는 것은 아니다.The following examples are intended to illustrate the present invention in more detail, but the present invention is not limited thereto.
<실시예 1><Example 1>
상표명이 매트리미드 (Matrimid) 5218 (Ciba-Geigy사제)인 폴리이미드 15 g을 N-메틸-2-피롤리돈 (NMP) 85 g에 용해시켜 15 중량%의 고분자 용액 100 g을 제조하였다. 제조된 용액 10 g을 노즐 직경이 0.25 mm인 주사기 형의 제조용기에 담고, 30 cm 떨어진 표면에 전하를 띈 드럼을 이용해서 막을 제조하였다. 사용한 전압은 약 10 KV이었다. 얻어진 막을 드럼에서부터 조심스럽게 제거한 후 진공 오븐에서 하룻 동안 건조시켰다. 얻어진 막의 두께는 약 40 마이크로미터이었다. 얻어진 막의 평균 섬유 직경은 300 나노미터이었다. 실험실에서 제조한 성능평가장치로 막의 성능을 측정하였다. 정전기적으로 중성화된 입자를 막에 통과시키고 입자의 농도는 응축핵계수기(Ultrafine Condensation Particle Counter)로 측정하였다. 막에 통과하기 전의 압력과 통과한 압력을 각각 측정하여 압력손실을 측정하였다. 이 막은 면속도가 5.33 cm/sec일 때 막의 압력손실이 20 mmH2O이었고 압력강하율은 필터막의 면속도에 선형적으로 비례하였다. 0.3 마이크로미터에서 최소 여과 효율이 99.97%이었다.15 g of a polyimide under the trade name Matrimid 5218 (manufactured by Ciba-Geigy) was dissolved in 85 g of N-methyl-2-pyrrolidone (NMP) to prepare 100 g of a 15% by weight polymer solution. 10 g of the prepared solution was placed in a syringe-shaped container having a nozzle diameter of 0.25 mm, and a membrane was prepared by using a drum charged on a surface 30 cm apart. The voltage used was about 10 KV. The resulting membrane was carefully removed from the drum and then dried in a vacuum oven for one day. The thickness of the obtained film was about 40 micrometers. The average fiber diameter of the obtained membrane was 300 nanometers. The performance of the membrane was measured by a performance evaluation device manufactured in a laboratory. Electrostatically neutralized particles were passed through the membrane and the concentration of particles was measured with an Ultrafine Condensation Particle Counter. The pressure loss was measured by measuring the pressure before passing through the membrane and the pressure passing through, respectively. The membrane had a pressure drop of 20 mmH 2 O at a surface velocity of 5.33 cm / sec and the pressure drop rate was linearly proportional to the surface velocity of the filter membrane. The minimum filtration efficiency at 99 microns was 99.97%.
<실시예 2><Example 2>
폴리이미드 15 g을 디메틸아세트아미드 (DMAc) 85 g에 용해시켜 15 중량%의 고분자 용액 100 g을 제조하였다. 제조된 용액 10 g을 노즐 직경이 0.25 mm인 주사기 형의 제조용기에 담고, 30 cm 떨어진 표면에 전하를 띈 드럼을 이용해서 막을 제조하였다. 걸어준 전압은 약 10 KV이었다. 얻어진 막의 평균 섬유 직경은 200 나노미터이었다. 얻어진 막의 두께는 약 40 마이크로미터이었다. 얻어진 막을 드럼에서부터 조심스럽게 제거한 후 진공 오븐에서 하룻 동안 건조시켰다. 막은 면속도가 5.33 cm/sec일 때 압력손실이 19 mmH2O이었다. 0.25 마이크로미터에서 최소 여과 효율이 99.999%이었다.15 g of polyimide was dissolved in 85 g of dimethylacetamide (DMAc) to prepare 100 g of 15 wt% polymer solution. 10 g of the prepared solution was placed in a syringe-shaped container having a nozzle diameter of 0.25 mm, and a membrane was prepared by using a drum charged on a surface 30 cm apart. The voltage applied was about 10 KV. The average fiber diameter of the obtained membrane was 200 nanometers. The thickness of the obtained film was about 40 micrometers. The resulting membrane was carefully removed from the drum and then dried in a vacuum oven for one day. The membrane had a pressure loss of 19 mmH 2 O at a surface velocity of 5.33 cm / sec. The minimum filtration efficiency at 99 microns was 99.999%.
<실시예 3><Example 3>
폴리이미드 15 g을 9:1 중량비로 혼합한 감마 부티로락톤 (γ-BL)/NMP 85 g에 용해시켜 15 중량%의 고분자 용액 100 g을 제조하였다. 제조된 용액 10 g을 노즐 직경이 0.25 mm인 주사기 형의 제조용기에 담고, 30 cm 떨어진 표면에 전하를 띈 드럼을 이용해서 막을 제조하였다. 걸어준 전압은 약 20 KV이었다. 얻어진 막의 두께는 약 45 마이크로미터이었다. 얻어진 막을 드럼에서부터 조심스럽게 제거한 후 진공 오븐에서 하룻동안 건조시켰다. 막은 면속도가 5.33 cm/sec일 때 압력손실이 22 mmH2O이었다. 0.2 마이크로미터에서 최소 여과 효율이 99.999%이었다.15 g of polyimide was dissolved in 85 g of gamma butyrolactone (γ-BL) / NMP mixed in a 9: 1 weight ratio to prepare 100 g of a 15% by weight polymer solution. 10 g of the prepared solution was placed in a syringe-shaped container having a nozzle diameter of 0.25 mm, and a membrane was prepared by using a drum charged on a surface 30 cm apart. The voltage applied was about 20 KV. The thickness of the obtained film was about 45 micrometers. The resulting membrane was carefully removed from the drum and dried in a vacuum oven for one day. The membrane had a pressure loss of 22 mmH 2 O at a surface velocity of 5.33 cm / sec. The minimum filtration efficiency at 99 micron was 99.999%.
<실시예 4><Example 4>
폴리이미드 20 g을 NMP 80 g에 용해시켜 20 중량%의 고분자 용액 100 g을 제조하였다. 제조된 용액 10 g을 노즐 직경이 0.25 mm인 주사기 형의 제조용기에 담고, 30 cm 떨어진 표면에 전하를 띈 드럼을 이용해서 막을 제조하였다. 걸어준 전압은 약 10 KV이었다. 얻어진 막의 두께는 약 40 마이크로미터이었다. 얻어진 막을 드럼에서부터 조심스럽게 제거한 후 진공 오븐에서 하룻동안 건조시켰다. 막은 면속도가 5.33 cm/sec일 때 압력손실이 25 mmH2O이었고 압력 강하율은 필터의 면속도에 선형적으로 비례하였다. 0.1 마이크로미터에서 최소 여과 효율이 99.9999%이었다.20 g of polyimide was dissolved in 80 g of NMP to prepare 100 g of 20 wt% polymer solution. 10 g of the prepared solution was placed in a syringe-shaped container having a nozzle diameter of 0.25 mm, and a membrane was prepared by using a drum charged on a surface 30 cm apart. The voltage applied was about 10 KV. The thickness of the obtained film was about 40 micrometers. The resulting membrane was carefully removed from the drum and dried in a vacuum oven for one day. The membrane had a pressure loss of 25 mmH 2 O at a surface velocity of 5.33 cm / sec and the pressure drop rate was linearly proportional to the surface velocity of the filter. The minimum filtration efficiency at 99 microns was 99.9999%.
<실시예 5>Example 5
실시예 1에서 제조된 고분자 용액 10 g을 노즐 직경이 0.25 mm인 주사기 형의 제조용기에 담고, 30 cm 떨어진 표면에 전하를 띈 와이어 스크린 위에 포집하여막을 제조하였다. 걸어준 전압은 약 10 KV이었다. 얻어진 막을 진공 오븐에서 하룻동안 건조시켰다. 막은 면속도가 5.33 cm/sec일 때 압력손실이 18 mmH2O이었다. 0.25 마이크로미터에서 최소 여과 효율이 99.999%이었다.10 g of the polymer solution prepared in Example 1 was placed in a syringe-type container having a nozzle diameter of 0.25 mm, and the membrane was prepared by collecting a charge on a wire screen with a charge of 30 cm away. The voltage applied was about 10 KV. The resulting membrane was dried in a vacuum oven for one day. The membrane had a pressure loss of 18 mmH 2 O at a surface velocity of 5.33 cm / sec. The minimum filtration efficiency at 99 microns was 99.999%.
<실시예 6><Example 6>
실시예 1에서 제조된 고분자 용액 10 g을 노즐 직경이 0.25 mm인 주사기 형의 제조용기에 담고, 30 cm 떨어진 표면에 전하를 띈 드럼을 이용해서 탄소펠트 (CH900-15) 위에 포집하여 막을 제조하였다. 걸어준 전압은 약 20 KV이었다. 얻어진 막을 진공 오븐에서 하룻동안 건조시켰다. 막은 면속도가 5.33 cm/sec일 때 압력손실이 21 mmH2O이었다. 0.1 마이크로미터에서 최소 여과 효율이 99.999%이었다.10 g of the polymer solution prepared in Example 1 was placed in a syringe-shaped container having a nozzle diameter of 0.25 mm, and the membrane was collected on a carbon felt (CH900-15) using a drum charged on a surface 30 cm apart. . The voltage applied was about 20 KV. The resulting membrane was dried in a vacuum oven for one day. The membrane had a pressure loss of 21 mmH 2 O at a surface velocity of 5.33 cm / sec. The minimum filtration efficiency at 99 microns was 99.999%.
<실시예 7><Example 7>
실시예 1의 방법으로 제조된 막을 오븐 안에 넣고 진공상태에서 500 ℃까지 온도를 올리면서 열분해하여 탄소막을 제조하였다. 제조된 막은 약 95%의 탄소와 5%의 산소로 구성되었다. 막은 면속도가 5.33 cm/sec일 때 압력손실이 17 mmH2O이었다. 0.3 마이크로미터에서 최소 여과 효율이 99.99%이었다. 프로판, 프로필렌, 헥산, 데칸, 헥사데칸 등의 유기물 환경에서는 이러한 유기물을 흡착하여 투과도가 다소 감소하였다.The membrane prepared by the method of Example 1 was placed in an oven and pyrolyzed while raising the temperature to 500 ° C. in a vacuum to prepare a carbon membrane. The film produced consisted of about 95% carbon and 5% oxygen. The membrane had a pressure loss of 17 mmH 2 O at a surface velocity of 5.33 cm / sec. The minimum filtration efficiency at 9 microns was 99.99%. In organic environments such as propane, propylene, hexane, decane and hexadecane, the permeability was slightly reduced due to the adsorption of these organics.
<실시예 8><Example 8>
실시예 6에서 제조된 막을 오븐 안에 넣고 1000 ℃까지 온도를 올리면서 열분해하여 활성탄소막을 제조하였다. 20%의 중량손실이 있었고, 막은 면속도가 5cm/sec일 때 압력손실이 15 mmH2O이었다. 0.25 마이크로미터에서 최소 여과 효율이 99.99%이었다.The membrane prepared in Example 6 was placed in an oven and thermally decomposed while raising the temperature to 1000 ° C. to prepare an activated carbon membrane. There was a 20% weight loss, and the membrane had a pressure loss of 15 mmH 2 O at a surface velocity of 5 cm / sec. The minimum filtration efficiency at 9 micrometers was 99.99%.
본 발명에 따르면, 일렉트로스피닝 방법을 이용함으로써 양호하게 분산된 형태로 포집된 나노미터 두께의 섬유상 고분자막 및 이를 열적 탄화시켜 화학적, 열적으로 안정한 탄소막을 제조할 수 있다. 구성하는 고분자 섬유의 직경이 나노미터 크기이고, 막의 표면적은 기존의 막에 비하여 현저히 높아, 0.3 마이크로미터 입자를 99.99% 이상의 고효율로 제거할 수 있는 고효율 필터용 막으로 사용할 수 있다. 또한 탄화 조건을 적절히 조절하여 탄소막을 제조하면 화학적, 열적으로 안정할뿐 아니라 유기물 흡착성능이 있는 막 재료로 사용하기에 적합하다.According to the present invention, a nanometer-thick fibrous polymer film collected in a well-dispersed form by using an electrospinning method and thermally carbonized it can be produced a chemically and thermally stable carbon film. The diameter of the constituent polymer fibers is nanometers in size, and the surface area of the membrane is significantly higher than that of the conventional membrane, so that the membrane can be used as a highly efficient filter membrane capable of removing 0.3 micrometer particles with a high efficiency of 99.99% or more. In addition, when the carbon film is manufactured by appropriately controlling the carbonization conditions, the carbon film is not only chemically and thermally stable but also suitable for use as a membrane material having an organic material adsorption performance.
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| KR100549140B1 (en) * | 2002-03-26 | 2006-02-03 | 이 아이 듀폰 디 네모아 앤드 캄파니 | A electro-blown spinning process of preparing for the nanofiber web |
| KR100804991B1 (en) * | 2005-01-15 | 2008-02-20 | 주식회사 엘지화학 | Surface-treated current collector and lithium secondary battery using the same |
| KR20080039278A (en) * | 2006-10-30 | 2008-05-07 | 주식회사 엘지화학 | Filter matter for air cleaning, filter made of the same and method of making the same |
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