KR100418269B1 - Hollow fiber surface modificating method by using plasma in atmosphere - Google Patents
Hollow fiber surface modificating method by using plasma in atmosphere Download PDFInfo
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- KR100418269B1 KR100418269B1 KR10-2000-0074045A KR20000074045A KR100418269B1 KR 100418269 B1 KR100418269 B1 KR 100418269B1 KR 20000074045 A KR20000074045 A KR 20000074045A KR 100418269 B1 KR100418269 B1 KR 100418269B1
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- Prior art keywords
- hollow fiber
- plasma
- atmospheric pressure
- reaction chamber
- surface modification
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- 239000012510 hollow fiber Substances 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000009987 spinning Methods 0.000 claims abstract description 10
- 239000012528 membrane Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 8
- 238000012986 modification Methods 0.000 claims abstract description 8
- -1 polyethylene Polymers 0.000 claims abstract description 7
- 239000004698 Polyethylene Substances 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims abstract description 6
- 229920000573 polyethylene Polymers 0.000 claims abstract description 6
- 239000012495 reaction gas Substances 0.000 claims abstract description 6
- 238000004804 winding Methods 0.000 claims abstract description 6
- 229910052786 argon Inorganic materials 0.000 claims abstract description 5
- 238000002844 melting Methods 0.000 claims abstract description 5
- 230000008018 melting Effects 0.000 claims abstract description 5
- 239000000843 powder Substances 0.000 claims abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 239000001301 oxygen Substances 0.000 claims abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 4
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000002715 modification method Methods 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 239000002351 wastewater Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000010865 sewage Substances 0.000 abstract description 4
- 244000144972 livestock Species 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 239000004753 textile Substances 0.000 abstract description 3
- 238000009628 steelmaking Methods 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 150000003839 salts Chemical class 0.000 description 7
- 239000000356 contaminant Substances 0.000 description 5
- 229910001385 heavy metal Inorganic materials 0.000 description 5
- 229920003002 synthetic resin Polymers 0.000 description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- 239000002952 polymeric resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- 239000000945 filler Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229920002492 poly(sulfone) Polymers 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- 239000004695 Polyether sulfone Substances 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
-
- 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
- B01D67/002—Organic membrane manufacture from melts
-
- 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
-
- 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
- B01D71/26—Polyalkenes
- B01D71/261—Polyethylene
-
- 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
- B01D2323/02—Hydrophilization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/06—Surface irregularities
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
본 발명은 대규모의 하수처리장, 섬유제조분야, 제철분야, 축산 폐수 등의 하수처리시설 및 반도체, PCB 라인 등에서 발생하는 폐수를 처리하여 재활용할 수 있도록 정화시키는 대기압 플라즈마를 이용한 중공사 분리막 표면개질방법에 관한 것이다.The present invention is a method for surface modification of hollow fiber membranes using atmospheric pressure plasma to purify and recycle wastewater from large-scale sewage treatment plants, textile manufacturing, steelmaking, livestock wastewater, and semiconductors and PCB lines. It is about.
본 발명은 분말형태의 폴리에틸렌을 200~300℃에서 용융시킨 후 방사기를 통해 방사하는 단계와; 상기 단계를 통해 방사된 중공사를 반응실로 유입시키는 단계와; 아르곤, 산소, 수소, 질소 중에서 선택된 어느 하나 혹은 이들의 혼합으로 이루어진 반응가스를 반응실에 공급하여 이들 반응가스의 분위기하에서 플라즈마발생기로부터 10KV의 전위차를 이용하여 대기압하 플라즈마를 발생시키고, 그 플라즈마를 중공사 표면에 형성된 분리막에 가하여 미세한 요철을 형성하는 표면개질단계와; 상기 단계에서 표면개질된 중공사를 인출하여 희석된 아크릴닉엑시드에 접촉시켜 친수화된 표면조직을 갖도록 냉각시키는 단계와; 냉각된 중공사를 권취하는 단계를 포함하여 구성된다.The present invention comprises the steps of melting the polyethylene in powder form at 200 ~ 300 ℃ and spinning through a spinning machine; Introducing the hollow fiber radiated through the step into the reaction chamber; Supplying a reaction gas consisting of argon, oxygen, hydrogen, nitrogen or any one of them, or a mixture thereof, to the reaction chamber to generate a plasma under atmospheric pressure using a potential difference of 10 KV from the plasma generator in the atmosphere of these reaction gases, A surface modification step of forming fine unevenness by adding to the separator formed on the surface of the hollow fiber; Extracting the surface-modified hollow fiber in the step and contacting the diluted acrylic acid to cool to have a hydrophilized surface tissue; Winding the cooled hollow fiber.
이러한 본 발명은 대기압 플라즈마를 이용하여 중공사의 표면을 개질시킴으로써 중공사 표면의 활성 및 표면에너지를 증대시켜 친수화를 촉진하게 되어 저렴하면서도 반영구적인 필터를 제조할 수 있는 효과를 제공한다.The present invention improves the activity and surface energy of the hollow fiber surface by modifying the surface of the hollow fiber by using an atmospheric pressure plasma to promote hydrophilicity, thereby providing the effect of producing a cheap and semi-permanent filter.
Description
본 발명은 대규모의 하수처리장, 섬유제조분야, 제철분야, 축산 폐수 등의 하수처리시설 및 반도체, PCB 라인 등에서 발생하는 폐수를 처리하여 재활용할 수 있도록 정화시키는 대기압 플라즈마를 이용한 중공사 분리막 표면개질방법에 관한 것이다.The present invention is a method for surface modification of hollow fiber membranes using atmospheric pressure plasma to purify and recycle wastewater from large-scale sewage treatment plants, textile manufacturing, steelmaking, livestock wastewater, and semiconductors and PCB lines. It is about.
통상, 물과 물속에 녹아 있는 염분이나 미립자, 분자상태의 물질들을 걸러주는 분야에 고분자 수지를 필터로 사용하고 있다.In general, polymer resins are used as filters to filter salts, particles, and molecular substances dissolved in water and water.
이러한 필터를 멤브레인(MEMBRANE)이라고 하는데 걸러주는 오염물의 종류에 따라 마이크로필터(MF), 울트라필터(UF), 나노필터(NF) 등으로 대별된다.Such a filter is called a membrane (MEMBRANE) and is classified into a micro filter (MF), an ultra filter (UF), a nano filter (NF), and the like depending on the type of contaminant to be filtered.
마이크로필터는 물과 염분 그리고 중금속은 통과시키고 미립자는 통과시키지 않아 이들의 분리에 사용되고, 울트라필터는 물과 염분만 통과시키며, 나노필터는 염분, 미립자, 거대분자는 표면에서 차단하고 물만 미세기공으로 흘러들어가게 한다.The microfilter is used for separation of water, salt and heavy metals, but not fine particles. Ultrafilters pass only water and salts. Nanofilters block salts, particles, and macromolecules from the surface, and only water flows into the micropores. Let go.
이러한 필터는 폴리술펀(POLYSULFONE)이나 폴리에테르술펀(POLYETERSULFONE) 수지에 미세기공을 형성하고, 이 미세기공을 통해 물은 흘러가고 나머지 오염물은 미세기공 외곽에서 차단되도록 하여 물과 오염물을 분리할 수 있도록 한 것이다.These filters form micropores in POLYSULFONE or POLYETERSULFONE resin, through which the water flows and the remaining contaminants are blocked outside the micropores so that water and contaminants can be separated. It is.
이때, 미세기공 안으로 물이 흘러들어가기 위해서는 고분자수지가 물과 친화력이 있는 친수성이어야만 물과 오염물을 용이하게 분리할 수 있다.In this case, in order for water to flow into the micropores, the polymer resin must be hydrophilic with affinity with water so that water and contaminants can be easily separated.
이와 같이, 고분자수지에 친수성을 부여하기 위해 글리세린 용액으로 수지의 표면에 얇은 막을 형성하고 있으나, 글리세린과 고분자수지의 결합력이 약하여 수지 표면에 형성된 막이 쉽게 제거되고 이로 인해 필터의 여과능력이 현저히 저하되는 문제가 유발되었다.As such, although a thin film is formed on the surface of the resin with a glycerin solution in order to impart hydrophilicity to the polymer resin, the film formed on the surface of the resin is easily removed due to the weak bonding force between the glycerin and the polymer resin, and thus the filtration capacity of the filter is significantly reduced. The problem was caused.
따라서, 필터를 일정시간 동안 사용한 후에는 새것으로 반드시 교체하여야 하는 단점이 있었고, 더구나 폴리술펀이나 폴리에테르술펀 수지는 원재료비가 고가이고 산 용액이나 알칼리용액에 대해 매우 취약하다는 단점도 있었다.Therefore, after using the filter for a certain time, there was a disadvantage that it must be replaced with a new one. Moreover, polysulfone or polyethersulfone resin had a disadvantage in that the raw material cost was high and it was very vulnerable to an acid solution or an alkaline solution.
본 발명은 상술한 바와 같은 종래 기술이 갖는 제반 문제점을 감안하여 이를 해결하고자 창출한 것으로, 분리막의 재료비가 저렴하면서도 반영구적으로 필터 성능을 유지할 수 있고, 대규모적인 물이 필요한 섬유산업, 전자산업, 반도체산업, 제철산업, 축산처리시설, 하수처리장 등에서 고효율의 필터기능을 갖고 장기간동안 사용될 수 있도록 대기압 플라즈마를 이용한 중공사 분리막 표면개질방법을 제공함에 그 목적이 있다.The present invention has been made in view of the above-mentioned problems of the prior art, and has been created to solve the problem. The material cost of the separator can be maintained semi-permanently while maintaining the filter performance, and the textile industry, the electronic industry, and the semiconductor requiring large-scale water The purpose of the present invention is to provide a method for surface modification of hollow fiber membranes using atmospheric plasma so that it can be used for a long time with high efficiency filter function in industry, steel industry, livestock treatment facility, sewage treatment plant.
본 발명의 상기한 목적은 분말형태의 폴리에틸렌을 200~300℃에서 용융시킨 후 방사기를 통해 방사하는 단계와; 상기 단계를 통해 방사된 중공사를 반응실로 유입시키는 단계와 ; 아르곤, 산소, 수소, 질소 중에서 선택된 어느 하나 혹은 이들의 혼합으로 이루어진 반응가스를 반응실에 공급하여 이들 반응가스의 분위기하에서 플라즈마발생기로부터 10KV의 전위차를 이용하여 대기압하 플라즈마를 발생시키고, 그 플라즈마를 중공사 표면에 형성된 분리막에 가하여 미세한 요철을 형성하는 표면개질단계와; 상기 단계에서 표면개질된 중공사를 인출하여 희석된 아크릴닉엑시드에 접촉시켜 친수화된 표면조직을 갖도록 냉각시키는 단계와; 냉각된 중공사를 권취하는 단계를 포함하여 구성되는 것을 특징으로 하는 대기압 플라즈마를 이용한 중공사 분리막 표면개질방법을 제공함에 의해 달성된다.The above object of the present invention comprises the steps of melting the polyethylene in powder form at 200 ~ 300 ℃ and then spinning through a spinning machine; Introducing the hollow fiber radiated through the step into the reaction chamber; Supplying a reaction gas consisting of argon, oxygen, hydrogen, nitrogen or any one of them, or a mixture thereof, to the reaction chamber to generate a plasma under atmospheric pressure using a potential difference of 10 KV from the plasma generator in the atmosphere of these reaction gases, A surface modification step of forming fine unevenness by adding to the separator formed on the surface of the hollow fiber; Extracting the surface-modified hollow fiber in the step and contacting the diluted acrylic acid to cool to have a hydrophilized surface tissue; It is achieved by providing a hollow fiber membrane surface modification method using an atmospheric plasma, characterized in that it comprises the step of winding the cooled hollow fiber.
도 1은 본 발명에 따른 중공사 표면개질 과정을 보인 개략적인 공정도,1 is a schematic process chart showing a hollow fiber surface modification process according to the present invention,
도 2는 본 발명에 따른 표면개질된 중공사로 이루어진 필터 내부구조도,Figure 2 is a filter internal structure consisting of surface modified hollow fiber according to the present invention,
도 3은 본 발명에 따른 중공사의 사용상태 예시도.Figure 3 is an illustration of the state of use of hollow yarn according to the present invention.
* 도면의 주요 부분에 대한 부호의 설명 *Explanation of symbols on the main parts of the drawings
1 : 용융기, 2 : 방사기,1: melter, 2: spinner,
3 : 반응실, 4 : 플라즈마발생기,3: reaction chamber, 4: plasma generator,
5 : 냉각기, 6 : 권취기.5: cooler, 6: winder.
이하에서는, 첨부도면을 참조하여 본 발명을 상세히 설명한다.Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.
도 1은 본 발명의 중공사 분리막 표면개질방법을 실현하기 위한 장치의 개략적인 구성도이고, 도 2는 도 1 장치에 의해 생산된 중공사를 스택(STACKS)하여 하나의 필터를 형성하고 그 사용예를 도시한 예시도이다.1 is a schematic configuration diagram of an apparatus for realizing the hollow fiber membrane surface modification method of the present invention, Figure 2 is a stack of hollow fiber produced by the apparatus of Figure 1 (STACKS) to form a filter and use thereof An illustration showing an example.
도 1 내지 도 2에 따르면, 용융기(1)가 구비되고 상기 용융기(1)의 출측에는 방사기(2)가 설치된다.1 to 2, a melter 1 is provided, and a radiator 2 is installed at the exit side of the melter 1.
용융기(1)는 200~300℃의 고온과 고압을 이용하여 분말상태의 폴리에틸렌을용융시킨 후 상기 방사기(2)를 통해 방사하여 가운데 구멍이 있는 중공사 섬유상태로 만들게 된다.The melter 1 melts polyethylene in a powder state by using a high temperature and a high pressure of 200 to 300 ° C., and then spins it through the spinning machine 2 to form a hollow fiber with a central hole.
방사기(2)의 출측에는 밀폐된 반응실(3)이 구비되고, 상기 반응실(3)의 일측 상단 및 하단에는 반응가스를 공급시킬 수 있는 가스입구 및 가스출구가 형성된다.The exit side of the radiator 2 is provided with a sealed reaction chamber 3, and gas inlets and gas outlets for supplying reaction gas are formed at upper and lower ends of one side of the reaction chamber 3.
상기 반응실(3)의 일측에는 이와 연통되고 고도로 이온화된 플라즈마를 생성하는 플라즈마발생기(4)가 설치된다.One side of the reaction chamber (3) is provided with a plasma generator (4) for communicating with and generating a highly ionized plasma.
반응실(3)의 직하방에는 방사된 중공사를 냉각시키기 위한 냉각기(5)가 구비되고, 상기 냉각기(5)를 빠져나온 중공사를 권취하기 위한 권취기(6)가 그 인접측에 구비된다.Directly below the reaction chamber 3 is provided with a cooler 5 for cooling the radiated hollow fiber, and a winder 6 for winding up the hollow fiber exiting the cooler 5 is provided on the adjacent side. do.
도 2에서와 같이, 방사된 다수의 중공사(12)를 다발(STACKS) 형태로 묶고 그 사이에는 충전재(14)를 부가함으로써 필터(10)를 형성하고, 필터(10)는 폐수의 입구와 출구 사이에 위치하여 폐수에 함유된 이물과 물 간을 분리하게 된다.As shown in FIG. 2, the plurality of spun hollow fibers 12 are bundled in the form of a bundle and a filler 14 is added therebetween to form a filter 10, and the filter 10 forms an inlet of the wastewater. It is located between the outlets to separate the foreign matter and water contained in the wastewater.
상기 충전재(14)는 엑폭시와 같은 것이 바람직하다.The filler 14 is preferably the same as epoxy.
도 3은 이러한 필터의 기능을 모식적으로 도시한 것으로, 멤브레인을 형성한 중공사(12)의 다발로 된 필터에 염분, 중금속, 미립자를 함유한 폐수가 유입되면 물은 중공사(12)를 관통하여 흐르게 되고 염분, 중금속 및 미립자는 걸러지게 된다.FIG. 3 schematically illustrates the function of such a filter. When wastewater containing salt, heavy metals, and fine particles flows into the bundled filter of the hollow fiber 12 having the membrane formed thereon, the water is removed from the hollow fiber 12. It penetrates through, and salts, heavy metals, and particulates are filtered out.
이와 같이 형성되는 필터의 중공사 표면개질방법을 살펴보면 다음과 같다.Looking at the hollow fiber surface modification method of the filter formed as described above are as follows.
먼저, 분말형태의 폴리에틸렌을 용융기(1) 내에서 방사하기에 적당한 온도와 압력으로 용융시켜 방사기(2)를 통해 방사하는 단계를 수행한다.First, the polyethylene in powder form is melted at a temperature and pressure suitable for spinning in the melter 1, and then spun through the spinner 2.
이때, 용융온도는 상술한 바와 같이 200~300℃가 적당하다.At this time, the melting temperature is appropriately 200 ~ 300 ℃ as described above.
상기 온도범위를 벗어나게 되면 방사작업이 용이치 않고 방사가 안되거나 방사중 중공사가 끊어지기 때문에 상기 용융온도로 용융함이 바람직하다.If it is out of the temperature range it is preferable to melt at the melting temperature because the spinning operation is not easy and spinning is not or the hollow fiber during the spinning is broken.
방사기(2)를 통해 방사된 중공사는 반응실(3)로 안내되고, 동시에 상기 반응실(3)에는 플라즈마발생기(4)로부터 발생된 대기압 플라즈마가 공급는 단계를 수행한다.The hollow yarns radiated through the radiator 2 are guided to the reaction chamber 3, and at the same time, the atmospheric pressure plasma generated from the plasma generator 4 is supplied to the reaction chamber 3.
이때, 미량의 반응가스, 이를테면 아르곤, 산소, 수소, 질소 중에서 선택된 어느 하나 혹은 그들이 혼합되어 이루어진 반응가스를 상기 반응실(3)로 공급한다.At this time, a small amount of reaction gas, such as argon, oxygen, hydrogen, nitrogen, any one selected from or a mixture of them is supplied to the reaction chamber (3).
이는 상기 플라즈마발생기(4)에 인가된 고전압에 의해 생성된 플라즈마를 안정화시키기 위한 것이다.This is to stabilize the plasma generated by the high voltage applied to the plasma generator 4.
상기 단계에서 플라즈마에 의해 표면개질되는 중공사는 그 표면에 미세한 요철이 형성되면서 활성이 높아지게 되고 동시에 표면에너지가 증대되게 된다.In this step, the hollow fiber surface-modified by plasma increases activity while fine concavities and convexities are formed on the surface thereof, and at the same time, surface energy is increased.
이와 같은 현상은 지속적으로 유지되지 않기 때문에 이를 지속화시키기 위해 상기 반응실(3)를 거쳐 인출된 중공사는 냉각기(5)로 안내되어 냉각되는 단계를 수행하게 된다.Since such a phenomenon is not continuously maintained, the hollow fiber drawn out through the reaction chamber 3 is guided to the cooler 5 to cool it.
상기 냉각기(5)에서는 친수화된 중공사의 표면을 고착시켜 활성과 표면에너지가 높은 상태를 지속적으로 유지할 수 있도록 하여 준다.The cooler (5) is to maintain the state of high activity and surface energy by fixing the surface of the hydrophilized hollow yarn.
이를 위해, 상기 냉각기(5) 내부에는 희석된 아크릴닉엑시드를 공급하여 친수화된 중공사 표면을 고착시키게 된다.To this end, the cooler 5 is supplied with diluted acrylnic acid to fix the hydrophilized hollow fiber surface.
고착이 완료되면 권취기(6)를 통해 코일형태로 권취되는 단계를 수행한다.When the fixing is completed, the coil winding is performed through the winder 6.
상기 단계에서는 권취시 도시하지 않았으나 과다한 장력이 걸리게 되면 중공사가 쉽게 끊어지므로 주의를 요하여 권취하여야 한다.Although not shown at the time of winding in the above step, the hollow yarn is easily broken when excessive tension is applied, so it must be wound with caution.
이를 위해, 장력조절수단을 상기 권취기에 부설할 수 있다.To this end, tension adjusting means can be attached to the winder.
이와 같은 단계가 완료되면 적정 개수 및 폭과 두께로 상기 중공사를 잘라내어 충전재로 적당히 몰딩하여 필터를 형성하게 된다.When such a step is completed, the hollow fiber is cut out to an appropriate number, width, and thickness to form a filter by appropriately molding the filler.
[실시예]EXAMPLE
이하에서는, 본 발명의 실시예에 대하여 설명한다.Hereinafter, embodiments of the present invention will be described.
본 실시예에서는 피처리물을 폴리에틸렌으로 하였고, 대기압에서 10KV 전위차를 이용해 플라즈마를 발생시킨 후 상기 피처리물을 반응실로 유입시켰다.In the present embodiment, the workpiece was made of polyethylene, and plasma was generated using a 10 KV potential difference at atmospheric pressure, and then the workpiece was introduced into the reaction chamber.
그리고, 반응가스로는 아르곤 가스를 100sccm 사용하였고, 아크릴닉엑시드 10%를 솔벤트에 희석하여 냉각기에서 50m/min 속도로 냉각한 후 권취하였다.In addition, 100 sccm of argon gas was used as a reaction gas, and 10% of acrylnic acid was diluted in a solvent, cooled at a rate of 50 m / min in a cooler, and then wound up.
이렇게 하여 제조된 중공사와 기존 방식에 의한 중공사를 투수계수, 인장강도, 미세기공의 크기 면에서 비교하여 하기한 표 1에 나타내었다. The hollow fiber prepared in this way and the hollow fiber by the conventional method is shown in Table 1 below by comparing the coefficient of permeability, tensile strength, size of micropores.
상기 표 1에서와 같이, 본 발명에 따른 발명재는 기존재에 비해 단위 시간당 통과되는 투수계수가 2배 이상 향상되었고, 인장강도 역시 60%이상 증대되었으며, 특히 미세기공에 있어서도 나노단위의 미세분자를 걸러내기에 충분한 결과를 나타내었다.As shown in Table 1, the inventive material according to the present invention has improved the permeability coefficient per unit time more than two times compared to the existing material, the tensile strength is also increased by more than 60%, especially in the fine pores of nano units Sufficient results were shown.
또한, 본 발명에 따른 필터를 제조한 뒤 도 2와 같은 구조를 통해 오수를 직접 흘려보내 중금속 및 오염물을 분석한 결과 출수된 물에서는 0.1㎛ 크기 이상의 염분 및 중금속, 미립자 등이 완벽하게 걸러지는 것을 확인하였다.In addition, after manufacturing the filter according to the present invention by direct flow of sewage through the structure as shown in Figure 2 to analyze the heavy metals and contaminants as a result of the water is filtered out of the salt and heavy metals, fine particles, such as 0.1㎛ size or more perfectly Confirmed.
이상에서 상세히 설명한 바와 같이, 본 발명은 대기압 플라즈마를 이용하여 중공사의 표면을 개질시킴으로써 중공사 표면의 활성 및 표면에너지를 증대시켜 친수화를 촉진하게 되어 저렴하면서도 반영구적인 필터를 제조할 수 있게 됨은 물론 각종 정수기용필터, 대규모 수처리시스템, 오폐수정화시스템, 염색분야, 생체적 합성수지 흡수성이 높은 부직포의 개발 등에 매우 융용하게 활용될 수 있는 장점을 제공한다.As described in detail above, the present invention is to improve the activity and surface energy of the hollow fiber surface by modifying the surface of the hollow fiber using an atmospheric pressure plasma to promote hydrophilicity, as well as to be able to manufacture a cheap but semi-permanent filter Various water purifier filters, large-scale water treatment system, waste water purification system, dyeing field, the development of non-woven fabrics with high absorption of biological synthetic resins provides the advantage that can be very widely used.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| KR101403277B1 (en) * | 2012-06-30 | 2014-06-02 | 도레이케미칼 주식회사 | Hollow fiber type forward osmosis membrane and manufacturing method thereof |
| KR20140077001A (en) * | 2012-12-13 | 2014-06-23 | 엘지전자 주식회사 | Method of Introducing Functionalities on Surface of Hollow Fiber Membrane By Electro-spraying When Preparing the Membrane |
| KR101496376B1 (en) * | 2012-06-30 | 2015-02-27 | 도레이케미칼 주식회사 | Hollow fiber type nanofiltration membrane and manufacturing method thereof |
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| CN105032720B (en) * | 2015-06-12 | 2017-07-28 | 浙江理工大学 | To the atmospheric plasma application system and method for olefin-based film hydrophilic modifying |
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| JPS588517A (en) * | 1981-07-08 | 1983-01-18 | Sumitomo Electric Ind Ltd | Preparation of composite film with selective permeability for gas |
| US4824444A (en) * | 1986-04-11 | 1989-04-25 | Applied Membrane Technology, Inc. | Gas permselective composite membrane prepared by plasma polymerization coating techniques |
| JPH051166A (en) * | 1991-06-26 | 1993-01-08 | Ishikawajima Harima Heavy Ind Co Ltd | Production of fluororesin porous film |
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| KR101403277B1 (en) * | 2012-06-30 | 2014-06-02 | 도레이케미칼 주식회사 | Hollow fiber type forward osmosis membrane and manufacturing method thereof |
| KR101496376B1 (en) * | 2012-06-30 | 2015-02-27 | 도레이케미칼 주식회사 | Hollow fiber type nanofiltration membrane and manufacturing method thereof |
| KR20140077001A (en) * | 2012-12-13 | 2014-06-23 | 엘지전자 주식회사 | Method of Introducing Functionalities on Surface of Hollow Fiber Membrane By Electro-spraying When Preparing the Membrane |
| KR101968308B1 (en) | 2012-12-13 | 2019-04-11 | 주식회사 엘지화학 | Method of Introducing Functionalities on Surface of Hollow Fiber Membrane By Electro-spraying When Preparing the Membrane |
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