KR20150001369A - Hollow fiber membrane using porous support - Google Patents
Hollow fiber membrane using porous support Download PDFInfo
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- KR20150001369A KR20150001369A KR20130074497A KR20130074497A KR20150001369A KR 20150001369 A KR20150001369 A KR 20150001369A KR 20130074497 A KR20130074497 A KR 20130074497A KR 20130074497 A KR20130074497 A KR 20130074497A KR 20150001369 A KR20150001369 A KR 20150001369A
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- 239000012528 membrane Substances 0.000 title claims abstract description 32
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 21
- 239000002904 solvent Substances 0.000 claims abstract description 7
- 230000000149 penetrating effect Effects 0.000 claims abstract description 5
- 239000010410 layer Substances 0.000 claims description 20
- 239000011241 protective layer Substances 0.000 claims description 11
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 9
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 9
- 229920002614 Polyether block amide Polymers 0.000 claims description 6
- 239000004697 Polyetherimide Substances 0.000 claims description 6
- 229920002492 poly(sulfone) Polymers 0.000 claims description 6
- 229920001601 polyetherimide Polymers 0.000 claims description 6
- 235000013870 dimethyl polysiloxane Nutrition 0.000 claims 1
- CXQXSVUQTKDNFP-UHFFFAOYSA-N octamethyltrisiloxane Chemical compound C[Si](C)(C)O[Si](C)(C)O[Si](C)(C)C CXQXSVUQTKDNFP-UHFFFAOYSA-N 0.000 claims 1
- 238000004987 plasma desorption mass spectroscopy Methods 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 9
- 230000009467 reduction Effects 0.000 abstract description 2
- 230000035699 permeability Effects 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000004695 Polyether sulfone Substances 0.000 description 5
- 229920006393 polyether sulfone Polymers 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- -1 Polydimethylsiloxane Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000000386 microscopy Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
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- 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
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/24—Mechanical properties, e.g. strength
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
Description
본 발명은 다공성 지지체를 이용한 혼합가스 분리용 중공사막에 관한 것으로, 더욱 상세하게는 선택도 향상을 위한 코팅공정에서 발생되는 다공성 지지체의 손상 및 내압성 저하를 방지한 혼합가스 분리용 중공사막에 관한 것이다.
The present invention relates to a hollow fiber membrane for separating mixed gas using a porous support, and more particularly, to a hollow fiber membrane for separating a mixed gas, which prevents damages of a porous support and pressure resistance caused in a coating process for improving selectivity .
기존의 가스분리용 중공사막은 비대칭 구조를 갖도록 도프용액의 조성과 방사 조건을 설정하였다. 비대칭 구조 중공사막의 내측부는 다공성(porous) 구조로써 막의 물리적 강도와 투과도와 연관된다. 그리고 막의 외측부는 치밀한 선택층으로 구성되어 용해-확산 메커니즘에 의한 선택도에 영향을 미치게 된다.The composition of the dope solution and the spinning conditions were set so that the conventional hollow fiber membranes for gas separation had an asymmetric structure. Asymmetric structure The medial side of the hollow fiber membrane is a porous structure and is related to the physical strength and permeability of the membrane. And the outer side of the membrane is composed of a dense selective layer and affects the selectivity by the dissolution-diffusion mechanism.
기존의 복합막은 내측부인 다공성층과 외측부인 치밀층을 동시에 제조함으로써, 막의 중간에 미세기공구조를 형성하여 투과도에 영향을 미치게 된다.Conventional composite membranes simultaneously produce a porous layer as a medial portion and a dense layer as an outer portion, thereby forming a fine pore structure in the middle of the membrane, thereby affecting the permeability.
좀 더 상술하면 외측부의 선택층인 치밀층은 투과선택성이 우수한 고무상 고분자를 선택하여 다공성 지지체 외측부에 코팅하여 복합막을 제조한다. 이 때, 코팅 용액의 용매의 특성(휘발속도, solvent power)에 따라서 몇가지 문제점이 발생할 수 있다. 다공성 지지체의 기공 내부로 깊숙이 침투되어 건조구간에서 완전히 건조되지 못하는 경우가 발생할 수 있다. 이 결과, 다공성 지지체가 부분적으로 손상되어 누설(leak)가 발생하거나, 내압성이 저하되어 분리막으로의 기능을 수행할 수 없게 된다. 또, 코팅용액의 용매 종류에 따라 지지체 고분자에 영향을 주어 코팅 도중 끊어지거나 늘어나는 현상이 생기게 된다.
More specifically, the dense layer, which is a selective layer of the outer side, is selected as a rubber-like polymer having excellent permeation selectivity and coated on the outer side of the porous support to produce a composite membrane. At this time, some problems may occur depending on the characteristics of the solvent (volatilization rate, solvent power) of the coating solution. It may penetrate deeply into the pores of the porous support and may not be completely dried in the drying zone. As a result, the porous support is partially damaged to cause a leak, and the pressure resistance is lowered, so that the porous support can not function as a separation membrane. In addition, depending on the type of the solvent of the coating solution, the support polymer may be affected, resulting in breakage or stretching during coating.
상술한 문제점을 해결하기 위해 안출된 본 발명의 목적은, 선택도 향상을 위한 코팅공정에서 발생되는 다공성 지지체의 손상 및 내압성 저하를 방지한 혼합가스 분리용 중공사막을 제공하는 데에 있다.
It is an object of the present invention, which has been devised to solve the above-mentioned problems, to provide a hollow fiber membrane for separating mixed gases, which prevents damage to a porous support and deterioration of pressure resistance generated in a coating process for improving selectivity.
상기의 목적을 달성하기 위한 본 발명은, 중공의 관형태를 가지는 다공성 지지체; 상기 다공성 지지체의 외표면에 선택층의 용매가 지지체로 침투하는 것을 방지하도록 코팅되는 보호층; 및 상기 보호층의 외표면에 코팅되어 특정기체를 선택하여 투과시키는 선택층을 포함하는 다공성 지지체를 이용한 혼합가스 분리용 중공사막이다.According to an aspect of the present invention, there is provided a porous support having a hollow tube shape; A protective layer coated on the outer surface of the porous support to prevent the solvent of the selective layer from penetrating into the support; And a selective layer coated on the outer surface of the protective layer to selectively transmit a specific gas.
상기 다공성 지지체으로 ES, 폴리설폰(PSf), 폴리이서이미드(PEI) 중에서 선택되는 어느 하나를 사용하고, 상기 보호층으로 PDMS를 사용하며, 상기 선택층으로 PEBAX을 사용하는 것이 가능하다.
It is possible to use any one selected from ES, polysulfone (PSf) and polyetherimide (PEI) as the porous support, use PDMS as the protective layer, and use PEBAX as the selective layer.
본 발명을 통하여, 선택층을 코팅에도 불구하고 다공성 지지체의 손상 또는 변형을 방지하여, 특정 물질에 대한 투과성을 향상시키면서도 중공사막의 내압성을 유지하고 지지체의 손상이 없는 신뢰도 높은 중공사막을 제공할 수 있다.
Through the present invention, it is possible to prevent damage or deformation of the porous support in spite of the coating of the selective layer, and to provide a highly reliable hollow fiber membrane which maintains the pressure resistance of the hollow fiber membrane while improving the permeability to a specific substance, have.
도 1은 종래기술에 따른 선택층이 코팅된 다공성 중공사막의 확대사진이다.
도 2는 본 발명의 실시예에 따른 보호층을 가지는 다공성 중공사막의 확대사진이다.
도 3은 도 2의 중공사막에서 두께방향에 따른 산소, 황, 실리콘, 카본의 성분분석 그래프이다.1 is an enlarged photograph of a porous hollow fiber membrane coated with a selective layer according to the prior art.
2 is an enlarged view of a porous hollow fiber membrane having a protective layer according to an embodiment of the present invention.
FIG. 3 is a graph showing the compositional analysis of oxygen, sulfur, silicon, and carbon in the thickness direction of the hollow fiber membrane of FIG.
이하, 본 발명을 도면과 실시예를 통해 설명한다. 본 발명의 요지를 불필요하게 흐릴 수 있다고 판단되는 공지 기능 및 구성에 대한 상세한 설명은 생략한다.Best Mode for Carrying Out the Invention The present invention will be described below with reference to the drawings and embodiments. Detailed descriptions of well-known functions and constructions which are considered to be unnecessarily obscured by the gist of the present invention will be omitted.
본 발명에서는 투과성을 향상시키면서 대상 혼합물에 따라 선택층을 다양하게 제조할 수 있는 중공사막을 제시하고자 한다.The present invention proposes a hollow fiber membrane capable of variously manufacturing selective layers according to a target mixture while improving permeability.
본 발명에서는 MF막을 다공성 지지체로 사용함으로써 기공의 크기 및 기공율이 기존의 가스분리막보다 향상된 하부구조를 가질 수 있다. 이는 막의 투과도와 직접적으로 연관되며, 투과도 향상은 막면적의 감소와 연관되기 때문에 공정의 경제성이 크게 향상될 수 있다. 이러한 다공성 지지체로는 PES, 폴리설폰(PSf), 폴리이서이미드(PEI) 등의 공지의 다공성 지지체에서 선택하여 사용할 수 있다.In the present invention, by using the MF membrane as a porous support, the pore size and the porosity can be improved compared to the conventional gas separation membrane. This is directly related to the permeability of the membrane, and the increase in permeability is associated with a reduction in membrane area, which can greatly improve the economics of the process. Such a porous support may be selected from known porous supports such as PES, polysulfone (PSf), and polyetherimide (PEI).
본 발명에서는 종래기술의 문제점을 방지하기 위하여 다공성 지지체와 선택층 사이에 보호층을 코팅한다.In the present invention, a protective layer is coated between the porous support and the selective layer to prevent the problems of the prior art.
상기 보호층으로는 Polydimethylsiloxane(PDMS)을 이용할 수 있다. PDMS는 투과도가 우수한 고무상 고분자 물질로써 막의 투과도와 선택도에 영향을 미치지 않고, 선택층의 용매가 지지체로 침투하는 것을 방지할 수 있다.Polydimethylsiloxane (PDMS) may be used as the protective layer. PDMS is a rubbery polymer material having an excellent permeability and can prevent the solvent of the selective layer from penetrating into the support without affecting the permeability and selectivity of the membrane.
도 1은 본 발명에 따라 제작된 중공사막으로써, 다공성 지지체로 PES(polyethersulfone)를 사용하였다. 그리고, 상기 다공성 지지체의 상측으로 보호층인 PDMS를 1차로 코팅한 후 2차로 선택층인 PEBAX(폴리에테르블록아미드)를 2차로 코팅한 이중 코팅의 중공사막을 형성하였다. 도 1은 상기 중공사막의 SEM(Scanning Election Microscopy) 사진촬영 결과이다.FIG. 1 is a hollow fiber membrane manufactured according to the present invention, and PES (polyethersulfone) is used as a porous support. PDMS, which is a protective layer, was first coated on the porous support, and then a second coating of PEBAX (polyether block amide) was selectively coated on the porous support to form a double coated hollow fiber membrane. FIG. 1 is a SEM (Scanning Election Microscopy) photograph of the hollow fiber membrane.
그리고, 상기 보호층이 다공성 지지체와 선택층의 사이에 정확하게 위치하는 지를 확인하기 위하여 도 2와 같이 PEBAX 코팅층을 강제로 박리한 이후에 EDX((Energy Dispersive X-ray Spectroscopy)를 측정하였고, 측정된 결과는 도 2에서 SEM사진에 오버랩되도록 표시하였으며, 도 3에서 다시 그래프만 도시하였다.In order to confirm whether the protective layer is accurately positioned between the porous support and the selective layer, EDX ((Energy Dispersive X-ray Spectroscopy) was measured after the PEBAX coating layer was forcibly peeled as shown in FIG. 2, The results are shown in FIG. 2 so as to overlap with the SEM photograph, and only the graph is shown again in FIG.
도 3의 그래프는 PDMS 코팅층을 시작으로 중공사막의 두께방향을 가로축(㎛)으로 원소별 강도(intensity)를 측정하였으며, 보라색은 산소(Oxygen), 파란색은 카본(Carbon), 녹색은 황(Sulphur), 붉은색은 실리콘(Silicon)을 표시한다.The graph of FIG. 3 was obtained by measuring the intensity of each element in the thickness direction of the hollow fiber membrane along the horizontal axis (탆) starting from the PDMS coating layer. The violet was Oxygen, blue was Carbon, ), And red indicates silicon (Silicon).
이를 통해 PES층과 PEBAX층 사이에 붉은색 피크가 증가했다가 감소하는 것을 확인할 수 있다. 이는 PDMS에 포함된 실리콘 성분을 나타낸 것으로 PES 지지체 위에 PDMS층의 코팅을 확인할 수 있다. It can be seen that the red peak between the PES layer and the PEBAX layer increases and then decreases. This indicates the silicon component contained in the PDMS, and the coating of the PDMS layer can be confirmed on the PES support.
상기와 같이, 본 발명의 바람직한 실시예를 참조하여 설명하였지만 해당 기술 분야의 숙련된 당업자라면 하기의 특허청구범위에 기재된 본 발명의 사상 및 영역으로부터 벗어나지 않는 범위 내에서 본 발명을 다양하게 수정 및 변경시킬 수 있음을 이해할 수 있을 것이다.While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. It can be understood that
Claims (4)
상기 다공성 지지체의 외표면에 선택층의 용매가 지지체로 침투하는 것을 방지하도록 코팅되는 보호층; 및
상기 보호층의 외표면에 코팅되어 특정기체를 선택하여 투과시키는 선택층을 포함하는 다공성 지지체를 이용한 혼합가스 분리용 중공사막.
A porous support having a hollow tube shape;
A protective layer coated on the outer surface of the porous support to prevent the solvent of the selective layer from penetrating into the support; And
And a selective layer coated on the outer surface of the protective layer to selectively transmit a specific gas.
The hollow fiber membrane according to claim 1, wherein the porous support comprises any one selected from the group consisting of PES, polysulfone (PSf) and polyetherimide (PEI).
The hollow fiber membrane according to claim 1, wherein the protective layer is made of PDMS.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| KR20160093262A (en) * | 2015-01-29 | 2016-08-08 | 울산과학기술원 | artificial gill apparatus and the method of the same |
| KR20190070249A (en) * | 2017-12-12 | 2019-06-20 | 서강대학교산학협력단 | Hybrid polymeric hollow fiber membrane, carbon molecular sieve hollow fiber membrane, and processes for fabricating the same |
| US11135552B2 (en) | 2017-12-12 | 2021-10-05 | Sogang University Research & Business Development Foundation | Hybrid polymeric hollow fiber membrane, hybrid carbon molecular sieve hollow fiber membrane, and processes for preparing the same |
| WO2022050542A1 (en) * | 2020-09-07 | 2022-03-10 | 한양대학교 산학협력단 | Method for manufacturing ultra-thin polymer separation membrane by using low-temperature coating |
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2013
- 2013-06-27 KR KR20130074497A patent/KR20150001369A/en not_active Application Discontinuation
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20160093262A (en) * | 2015-01-29 | 2016-08-08 | 울산과학기술원 | artificial gill apparatus and the method of the same |
| KR20190070249A (en) * | 2017-12-12 | 2019-06-20 | 서강대학교산학협력단 | Hybrid polymeric hollow fiber membrane, carbon molecular sieve hollow fiber membrane, and processes for fabricating the same |
| US11135552B2 (en) | 2017-12-12 | 2021-10-05 | Sogang University Research & Business Development Foundation | Hybrid polymeric hollow fiber membrane, hybrid carbon molecular sieve hollow fiber membrane, and processes for preparing the same |
| WO2022050542A1 (en) * | 2020-09-07 | 2022-03-10 | 한양대학교 산학협력단 | Method for manufacturing ultra-thin polymer separation membrane by using low-temperature coating |
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