KR101833882B1 - Method for separation of fluorinated gas using multi-stage gas separation process comprising high-selectivity hollow fiber membrane modules - Google Patents
Method for separation of fluorinated gas using multi-stage gas separation process comprising high-selectivity hollow fiber membrane modules Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 54
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 44
- 238000000926 separation method Methods 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims description 13
- 239000004952 Polyamide Substances 0.000 claims description 4
- 239000004642 Polyimide Substances 0.000 claims description 4
- 229920002647 polyamide Polymers 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 239000004697 Polyetherimide Substances 0.000 claims description 3
- 229920002301 cellulose acetate Polymers 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 229920000515 polycarbonate Polymers 0.000 claims description 3
- 239000004417 polycarbonate Substances 0.000 claims description 3
- 229920001601 polyetherimide Polymers 0.000 claims description 3
- 239000004962 Polyamide-imide Substances 0.000 claims description 2
- 229920002312 polyamide-imide Polymers 0.000 claims description 2
- 239000007789 gas Substances 0.000 abstract description 155
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 15
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000011084 recovery Methods 0.000 description 15
- 229910018503 SF6 Inorganic materials 0.000 description 12
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 description 12
- 229960000909 sulfur hexafluoride Drugs 0.000 description 12
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 229910052731 fluorine Inorganic materials 0.000 description 6
- 239000011737 fluorine Substances 0.000 description 6
- 239000012466 permeate Substances 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 2
- 238000011020 pilot scale process Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002747 voluntary effect Effects 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/68—Halogens or halogen compounds
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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- B01D53/228—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by diffusion characterised by specific membranes
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
본 발명은 I) 불화가스를 함유하는 혼합기체를 압축하여 중공사막 모듈을 포함하는 제1단 기체분리부로 공급하는 단계; II) 상기 제1단 기체분리부에서 제1 농축기체 및 제1 투과기체로 분리하는 단계; 및 III) 상기 제1 농축기체를 중공사막 모듈을 포함하는 제2단 기체분리부로 공급하여 제2 농축기체 및 제2 투과기체로 분리하는 단계;를 포함하는 불화가스 회수방법을 제공한다.
본 발명에 따르면, 불화가스에 대한 질소의 선택도가 높은 중공사막 모듈을 포함하는 2단계 이상의 다단 기체분리공정을 이용하여 불화가스를 함유하는 혼합기체로부터 불화가스를 고효율로 회수 및 피드의 불화가스 농도 대비 5% 이내로 분리하여 배출할 수 있으며, 또한 다단 기체분리부의 스테이지 컷을 조절함으로써 투과기체 쪽으로 배출되는 가스의 양을 크게 높일 수 있다.The present invention relates to a method for producing a hollow fiber membrane module, comprising the steps of: I) compressing a mixed gas containing a fluorinated gas and supplying the compressed gas to a first stage gas separation unit including a hollow fiber membrane module; II) separating the first concentrated gas and the first permeated gas in the first-stage gas separation unit; And III) supplying the first concentrated gas to the second stage gas separator including the hollow fiber membrane module, and separating the second concentrated gas and the second permeated gas.
According to the present invention, it is possible to recover fluorinated gas with high efficiency from a mixed gas containing fluorinated gas by using a multistage gas separation process of two or more stages including a hollow fiber membrane module having high selectivity of nitrogen with respect to fluorinated gas, And the amount of gas discharged toward the permeable gas can be greatly increased by controlling the stage cut of the multi-stage gas separation unit.
Description
본 발명은 고선택도의 중공사막 모듈을 포함하는 다단 기체분리공정을 이용한 불화가스 분리방법에 관한 것으로, 보다 상세하게는 불화가스에 대한 질소의 선택도가 높은 중공사막 모듈을 포함하는 2단계 이상의 다단 기체분리공정을 이용하여 불화가스를 고효율로 회수 및 분리하는 방법에 관한 것이다.The present invention relates to a method for separating fluorinated gas using a multistage gas separation process including a hollow fiber membrane module having a high selectivity, and more particularly, to a method for separating fluorinated gas using a multistage gas separation process including a hollow fiber membrane module having a high selectivity, And a method for recovering and separating fluorinated gas with high efficiency using a multi-stage gas separation process.
현재 미국은 교토의정서에서 탈퇴하였지만 지구 온난화 방지를 위한 연구 및 기술 개발을 위하여 2002년 2월에 에너지부(Department of Energy)의 주도로 여러 정부기관이 참여하는 미국기후변화 기술프로그램(U.S. Climate Change Technology Program)을 수립하여 불화가스의 배출저감 및 재사용에 관한 연구와 투자를 이끌어 왔다. 또한 미국 환경보호국은 산업계와 협조하여 육불화황(SF6)을 포함한 지구온난화 가스감축을 위한 자발적인 프로그램을 성공적으로 진행시켜 오고 있다. 최근 미국기후변화 기술프로그램은 극저온 포집(Cryogenic Capture)과 막분리(Membrane Separation) 기술이 육불화황의 회수와 재사용에 있어 전통적인 가압스윙흡착(Pressure Swing Adsorption) 기술에 비하여 효과적이라고 결론을 내린바 있다.Currently, the United States has withdrawn from the Kyoto Protocol, but in February 2002, the US Department of Energy led the US Climate Change Technology Program Program) has been established and has led research and investment on emission reduction and reuse of fluorocarbons. In addition, the US Environmental Protection Agency has been working with industry to successfully implement voluntary programs to reduce global warming gases, including sulfur hexafluoride (SF 6 ). Recent US climate change technology programs have concluded that cryogenic capture and membrane separation techniques are more effective than conventional pressure swing adsorption techniques in the recovery and reuse of sulfur hexafluoride.
프랑스의 에어 리퀴드사는 2003년에 파워(power) IC 제조공장에 분리막을 이용한 육불화황의 회수 및 재사용 시스템을 파일롯 스케일로 설치하였는데, 공정에서 발생되는 가스는 60%의 육불화황과 40%의 공기로 구성된 가스로 압축한 후, 두 개의 분리막 시스템에 투입하여 처리한 결과 89%의 육불화황 회수율과 99% 이상의 순도를 나타냈다.
In 2003, Air Liquide in France installed a filtration system of sulfur hexafluoride on a pilot scale at a power IC manufacturing plant in a pilot scale. The gas produced in the process was 60% sulfur hexafluoride and 40% air , And then treated with two membrane systems to obtain 89% of sulfur hexafluoride recovery and 99% or more purity.
이러한 육불화황과 같은 불화가스를 분리하기 위한 종래기술로서 폴리이미드막, 탄소막 또는 제올라이트 막 중에서 선택된 어느 하나의 기체분리막을 이용하여 육뷸화황을 함유하는 혼합기체로부터 육불화황을 선택적으로 분리 및 회수하는 방법이 알려져 있으나, 기체분리막을 투과하는 가스 중에 육불화황이 혼입되어 육불화황의 회수 손실이 발생하므로 육불화황을 고효율로 분리 및 회수하는 것이 어려운 문제점이 있다(특허문헌 1, 2).
As a conventional technique for separating fluorinated gas such as sulfur hexafluoride, sulfur hexafluoride is selectively separated and recovered from a mixed gas containing a bentonite sulfur by using a gas separation membrane selected from a polyimide membrane, a carbon membrane or a zeolite membrane However, there is a problem in that it is difficult to separate and recover sulfur hexafluoride with high efficiency because sulfur hexafluoride is mixed in the gas permeating through the gas separation membrane and recovery loss of sulfur hexafluoride occurs (
또한, 다단의 기체분리막을 이용하는 방법도 공지되어 있으나, 제1단의 기체분리막의 투과 기체로서 희석제 가스에 동반하여 불화가스가 유출되므로 역시 회수 손실이 발생하는 단점이 있어 육불화황 가스를 고농도 및 고효율로 분리 회수하는 것이 곤란하다(특허문헌 3, 4).
In addition, although a method using a multi-stage gas separation membrane is known, there is a disadvantage in that recovery gas is generated because the fluorinated gas flows out along with the diluent gas as a permeation gas of the gas separation membrane in the first stage. It is difficult to separate and recover them with high efficiency (Patent Documents 3 and 4).
따라서 본 발명에서는 불화가스에 대한 질소의 선택도가 높은 중공사막 모듈을 포함하는 2단계 이상의 다단 기체분리공정을 이용하면 다양한 선택도에 따라 불화가스를 고효율로 회수 및 분리할 수 있음에 착안하여 본 발명을 완성하였다.Therefore, in the present invention, it is possible to collect and separate fluorinated gas with high efficiency according to various degrees of selectivity by using a multi-stage gas separation process of two or more stages including a hollow fiber membrane module having high selectivity of nitrogen to fluorinated gas. Thereby completing the invention.
본 발명은 상기와 같은 문제점을 감안하여 안출된 것으로, 본 발명의 목적은 불화가스에 대한 질소의 선택도가 높은 중공사막 모듈을 포함하는 2단계 이상의 다단 기체분리공정을 이용하여 불화가스를 함유하는 혼합기체로부터 불화가스를 고효율로 회수 및 피드의 불화가스 농도 대비 5% 이내로 분리하는 방법을 제공하고자 하는 것이다.SUMMARY OF THE INVENTION The present invention has been made in view of the above problems, and it is an object of the present invention to provide a hollow fiber membrane module having a high selectivity for nitrogen with respect to fluorine gas, And to provide a method for separating fluorinated gas from the mixed gas at a high efficiency and within 5% of the fluorinated gas concentration of the feed.
상기한 바와 같은 목적을 달성하기 위한 본 발명은 I) 불화가스를 함유하는 혼합기체를 압축하여 중공사막 모듈을 포함하는 제1단 기체분리부로 공급하는 단계; II) 상기 제1단 기체분리부에서 제1 농축기체 및 제1 투과기체로 분리하는 단계; 및 III) 상기 제1 농축기체를 중공사막 모듈을 포함하는 제2단 기체분리부로 공급하여 제2 농축기체 및 제2 투과기체로 분리하는 단계;를 포함하는 불화가스 회수방법을 제공한다.According to an aspect of the present invention, there is provided a method for producing a hollow fiber membrane module, including: (I) compressing a gas mixture containing fluorinated gas and supplying the compressed gas to a first stage gas separation unit including a hollow fiber membrane module; II) separating the first concentrated gas and the first permeated gas in the first-stage gas separation unit; And III) supplying the first concentrated gas to the second stage gas separator including the hollow fiber membrane module, and separating the second concentrated gas and the second permeated gas.
상기 불화가스를 함유하는 혼합기체는 SF6, NF3, BF3, SiF4, CF4, C2F4, C2F6, C3F8, C4F10 또는 CHF3 가스에 N2 가스가 혼합된 것을 특징으로 한다.Mixed gas containing the fluoride gas is SF 6, NF 3, BF 3 , SiF 4, CF 4, C 2 F 4, C 2 F 6, C 3 F 8, C 4 F 10 , or N 2 in the CHF 3 gas Gas is mixed.
상기 불화가스를 함유하는 혼합기체는 N2/SF6인 것을 특징으로 한다.And the mixed gas containing the fluorinated gas is N 2 / SF 6 .
상기 중공사막의 소재는 폴리술폰, 폴리이미드, 폴리에테르이미드, 폴리아미드, 폴리아미드이미드, 폴리카보네이트 및 셀룰로오스 아세테이트로 이루어진 군으로부터 선택된 어느 하나의 것을 특징으로 한다. The material of the hollow fiber membrane is any one selected from the group consisting of polysulfone, polyimide, polyetherimide, polyamide, polyamideimide, polycarbonate, and cellulose acetate.
상기 중공사막은 외경 300~400㎛, 내경 150~250㎛인 것을 특징으로 한다.Wherein the hollow fiber membrane has an outer diameter of 300 to 400 mu m and an inner diameter of 150 to 250 mu m.
상기 중공사막 모듈은 N2/SF6의 선택도가 50~150인 것을 특징으로 한다.The hollow fiber membrane module is characterized in that the selectivity of N 2 / SF 6 is 50 to 150.
상기 제1단 기체분리부 및 제2단 기체분리부의 총 스테이지 컷은 0.12~0.51인 것을 특징으로 한다.And the total stage cut of the first stage gas separation unit and the second stage gas separation unit is 0.12 to 0.51.
본 발명에 따르면, 불화가스에 대한 질소의 선택도가 높은 중공사막 모듈을 포함하는 2단계 이상의 다단 기체분리공정을 이용하여 불화가스를 함유하는 혼합기체로부터 불화가스를 고효율로 회수 및 피드의 불화가스 농도 대비 5% 이내로 분리하여 배출할 수 있으며, 또한 다단 기체분리부의 스테이지 컷을 조절함으로써 투과기체 쪽으로 배출되는 가스의 양을 크게 높일 수 있다.According to the present invention, it is possible to recover fluorinated gas with high efficiency from a mixed gas containing fluorinated gas by using a multistage gas separation process of two or more stages including a hollow fiber membrane module having high selectivity of nitrogen with respect to fluorinated gas, And the amount of gas discharged toward the permeable gas can be greatly increased by controlling the stage cut of the multi-stage gas separation unit.
도 1은 본 발명에 따른 2단 기체분리공정을 이용한 불화가스를 함유하는 혼합기체의 분리공정도.
도 2는 본 발명에 따른 중공사막의 단면을 촬영한 주사전자현미경(SEM) 이미지.
도 3은 실험예 1 내지 4의 스테이지 컷에 따른 SF6 회수율을 나타낸 그래프.
도 4는 실시예 및 실험예 3의 스테이지 컷에 따른 N2/SF6 혼합기체의 처리량(공급유량)을 나타낸 그래프.BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a process for separating a mixed gas containing fluorine gas using a two-stage gas separation process according to the present invention. FIG.
2 is a scanning electron microscope (SEM) image of a section of a hollow fiber membrane according to the present invention.
3 is a graph showing SF 6 recovery rates according to the stage cuts of Experimental Examples 1 to 4;
4 is a graph showing the relationship between N 2 / SF 6 A graph showing the throughput (supply flow rate) of the mixed gas.
이하에서는 본 발명에 따른 고선택도의 중공사막 모듈을 포함하는 다단 기체분리공정을 이용한 불화가스 분리방법에 관하여 상세히 설명하기로 한다.
Hereinafter, the fluorine gas separation method using the multi-stage gas separation process including the high selectivity hollow fiber membrane module according to the present invention will be described in detail.
본 발명은 I) 불화가스를 함유하는 혼합기체를 압축하여 중공사막 모듈을 포함하는 제1단 기체분리부로 공급하는 단계; II) 상기 제1단 기체분리부에서 제1 농축기체 및 제1 투과기체로 분리하는 단계; 및 III) 상기 제1 농축기체를 중공사막 모듈을 포함하는 제2단 기체분리부로 공급하여 제2 농축기체 및 제2 투과기체로 분리하는 단계;를 포함하는 불화가스 회수방법을 제공한다. 도 1에 본 발명에 따른 2단 기체분리공정을 이용한 불화가스를 함유하는 혼합기체의 분리공정도를 나타내었다.
The present invention relates to a method for producing a hollow fiber membrane module, comprising the steps of: I) compressing a mixed gas containing a fluorinated gas and supplying the compressed gas to a first stage gas separation unit including a hollow fiber membrane module; II) separating the first concentrated gas and the first permeated gas in the first-stage gas separation unit; And III) supplying the first concentrated gas to the second stage gas separator including the hollow fiber membrane module, and separating the second concentrated gas and the second permeated gas. FIG. 1 shows a process of separating a mixed gas containing fluorine gas using a two-stage gas separation process according to the present invention.
본 발명에서 불화가스라고 하는 것은 불소원자를 포함하는 기체로 정의할 수 있고, 주로 반도체 공정에 사용되고 배출되는 SF6, NF3, BF3, SiF4, CF4, C2F4, C2F6, C3F8, C4F10 또는 CHF3 가스 등을 말하며 그 중에서도 육불화황(SF6)을 그 대표적인 예로 들 수 있다. 또한, 이러한 반도체 공정에서는 상기 불화가스에 희석제 가스로서 N2(질소) 가스를 포함하여 혼합기체 형태로 배출되므로, 상기 I) 단계에서 불화가스를 함유하는 혼합기체는 SF6, NF3, BF3, SiF4, CF4, C2F4, C2F6, C3F8, C4F10 또는 CHF3 가스에 N2 가스가 혼합된 것일 수 있다. 바람직하게는, 상기 불화가스를 함유하는 혼합기체는 N2/SF6인 것일 수 있다.
In the present invention, fluorinated gas can be defined as a gas containing fluorine atoms, and SF 6 , NF 3 , BF 3 , SiF 4 , CF 4 , C 2 F 4 , and C 2 F 6 , C 3 F 8 , C 4 F 10 or CHF 3 gas, among which sulfur hexafluoride (SF 6 ) is a typical example. In this semiconductor process, N 2 (nitrogen) gas is supplied as a diluent gas to the fluorinated gas and discharged in the form of a mixed gas. In the step I), the mixed gas containing fluorine gas is SF 6 , NF 3 , BF 3 , SiF 4 , CF 4 , C 2 F 4 , C 2 F 6 , C 3 F 8 , C 4 F 10 or CHF 3 gas mixed with N 2 gas. Preferably, the mixed gas containing the fluorinated gas may be N 2 / SF 6 .
또한, 상기 제1단 기체분리부 및 제2단 기체분리부에서는 중공사막 모듈에 의하여 기체분리가 수행되는바, 상기 중공사막의 소재는 폴리술폰, 폴리이미드, 폴리에테르이미드, 폴리아미드, 폴리아미드이미드, 폴리카보네이트 및 셀룰로오스 아세테이트로 이루어진 군으로부터 선택된 어느 하나의 것일 수 있다.The gas separation is performed by the hollow fiber membrane module in the first and second gas separators. The material of the hollow fiber membrane may be polysulfone, polyimide, polyetherimide, polyamide, polyamide, Amide, polycarbonate, and cellulose acetate.
아울러 상기 중공사막은 외경 300~400㎛, 내경 150~250㎛인 것이 불화가스에 대한 질소의 선택도를 높일 수 있어 바람직하다.The hollow fiber membrane preferably has an outer diameter of 300 to 400 탆 and an inner diameter of 150 to 250 탆, because the selectivity of nitrogen to fluorine gas can be increased.
상기 중공사막 모듈은 통상의 방법에 따라 기체 선택투과성의 상기 중공사막을 기체공급구, 투과기체 배출구, 비투과기체 배출구가 구비된 용기 내에 중공사막의 기체공급 측과 기체투과 측의 공간이 이격되도록 장착한 것으로서, 특히 상기 중공사막 모듈을 제1단 기체분리부 및 제2단 기체분리부에 채용하는 경우에 N2/SF6의 선택도는 50~150인 것이 바람직하다. N2/SF6의 선택도가 50 미만이면 배출가스의 농도를 도입 가스 대비 5% 이내로 유지하기가 어렵고, 또한 스테이지 컷 0.4 이상에서 95% 이상의 회수율을 얻기가 어렵다. 아울러 N2/SF6의 선택도가 150을 초과하는 중공사막 모듈은 현실적으로 제조하기 어려운 단점이 있다.
In the hollow fiber membrane module, the gas-permeable hollow fiber membrane is mounted in a vessel provided with a gas feed port, a permeate gas outlet port, and a non-permeate gas outlet port so that the gas supply side and the gas permeation side space of the hollow fiber membrane are spaced apart from each other In particular, when the hollow fiber membrane module is employed in the first stage gas separator and the second stage gas separator, the selectivity of N 2 / SF 6 is preferably 50 to 150. When the selectivity of N 2 / SF 6 is less than 50, it is difficult to keep the concentration of the exhaust gas within 5% of the introduced gas, and it is difficult to obtain a recovery rate of 95% or more at the stage cut of 0.4 or more. In addition, the hollow fiber membrane module having a selectivity of N 2 / SF 6 exceeding 150 has a disadvantage that it is difficult to produce the hollow fiber membrane module in reality.
또한, 본 발명에 따른 다단 기체분리공정에서 스테이지 컷(stage cut)이라는 것은 제1단 기체분리부 및 제2단 기체분리부에 공급되는 각 유량대비 각 투과기체 유량의 비율을 의미하는 것으로서, 상기 제1단 기체분리부 및 제2단 기체분리부의 총 스테이지 컷은 0.12~0.51인 것이 바람직하다. 상기 총 스테이지 컷이 0.12 미만이면 도입가스 대비 배출가스의 양이 적어 잔류 불화가스의 농도를 농축하기 어렵고, 그 총 스테이지 컷이 0.51을 초과하면, 잔류 불화가스의 농도를 농축하기 쉬운 반면 회수율 95% 이상을 달성하기 어렵다는 단점이 있다. The stage cut in the multi-stage gas separation process according to the present invention means the ratio of the flow rate of each permeate gas to each flow rate supplied to the first stage gas separation unit and the second stage gas separation unit. The total stage cut of the first stage gas separation unit and the second stage gas separation unit is preferably 0.12 to 0.51. If the total stage cut is less than 0.12, it is difficult to concentrate the concentration of the residual fluorinated gas because the amount of the exhaust gas is smaller than the introduction gas. If the total stage cut exceeds 0.51, the concentration of the residual fluorinated gas is easily concentrated, It is difficult to achieve the above.
이하 구체적인 실시예를 상세히 설명한다.
Hereinafter, specific examples will be described in detail.
(중공사막 모듈 제작 및 단일 기체 투과도 테스트)(Hollow fiber membrane module fabrication and single gas permeability test)
폴리술폰을 소재로 하여 통상의 방법에 따라 중공사막을 제조하되, 중공사막의 외경은 400㎛, 내경은 250㎛, 유효 막면적은 1.24m2로 조절하였으며, 중공사막 모듈은 직경 1.5inch, 길이 12inch로 제작하였다. 도 2의 중공사막 단면을 촬영한 주사전자현미경 이미지로부터 결함 없는 균일한 중공사막이 제조되었음을 확인할 수 있다. 아울러 네 종류의 중공사막 모듈을 이용하여 공급압력 0.5Mpa에서 육불화황(SF6) 가스 및 질소(N2) 가스 각각의 투과도를 측정함으로써 N2/SF6의 선택도가 51.31, 61.38, 81.55 및 108.44임을 확인하였다.
The hollow fiber membrane was adjusted to have an outer diameter of 400 m, an inner diameter of 250 m, and an effective membrane area of 1.24 m < 2 >. The hollow fiber membrane module had a diameter of 1.5 inches, 12 inch. From the scanning electron microscope image of the cross section of the hollow fiber membrane of FIG. 2, it can be seen that a defect-free uniform hollow fiber membrane was produced. In addition, four types of sulfur hexafluoride in the supply pressure 0.5Mpa, using a hollow fiber membrane module (SF 6) gas and nitrogen (N 2) by measuring the gas permeance of each of N 2 / SF 6 selectivity of 51.31, 61.38, 81.55 of And 108.44, respectively.
(( 실험예Experimental Example 1 내지 4) 1 to 4)
상기 N2/SF6의 선택도가 각각 51.31, 61.38, 81.55 및 108.44인 네 종류의 중공사막 모듈을 이용하여 N2 : SF6=50 : 50인 혼합기체를 대상으로 1단 분리공정을 수행하였으며, 그 상세한 실험결과를 표 1 내지 4에 각각 나타내었다.
The selection of the N 2 / SF 6 also respectively 51.31, 61.38, using the 81.55 and 108.44 in four types of the hollow fiber membrane module N 2: SF 6 = 50: target 50 in the mixed gas was carried out for one-stage separation process , And detailed experimental results thereof are shown in Tables 1 to 4, respectively.
또한, 도 3에는 상기 실험예 1 내지 4의 스테이지 컷에 따른 SF6 회수율을 그래프로 나타내었는바, 상기 표 1 내지 4 및 도 3으로부터 스테이지 컷이 약 0.1~0.5에서는 SF6 회수율이 약 95% 이상의 결과를 보였으며, N2/SF6의 선택도가 높을수록 동일한 스테이지 컷에서 더 높은 SF6 회수율을 나타냄을 확인할 수 있다.
3, the recovery rate of SF 6 according to the stage cuts of Experimental Examples 1 to 4 is graphically shown. As shown in Tables 1 to 4 and FIG. 3, when the stage cut is about 0.1 to 0.5, the SF 6 recovery rate is about 95% The results show that the higher the selectivity of N 2 / SF 6, the higher the SF 6 recovery rate in the same stage cut.
(실시예)(Example)
상기 실험예 3에 따른 중공사막 모듈(N2/SF6의 선택도 81.55)을 이용하여 2단 분리공정을 수행하였으며, 그 상세한 수행결과를 표 5에 나타내었다.
A two-stage separation process was carried out using the hollow fiber membrane module (N 2 / SF 6 selectivity of 81.55) according to Experimental Example 3, and the detailed performance results are shown in Table 5.
또한, 도 4에는 상기 실시예 및 실험예 3의 스테이지 컷에 따른 N2/SF6 혼합기체의 처리량(공급기체 유량)을 나타내었는바, 상기 표 5 및 도 4로부터 동일한 선택도의 1단 분리공정과 비교하여 2단 분리공정이 SF6 회수율이 조금 더 높은 것을 확인할 수 있고, 스테이지 컷이 약 0.1에서의 처리량은 약 2배, 스테이지 컷이 약 0.5에서는 처리량이 약 4배로 현저하게 높아진 것을 확인할 수 있다.
4 is a graph showing the relationship between N 2 / SF 6 From Table 5 and FIG. 4, it can be seen that the SF 6 recovery rate is slightly higher in the two-stage separation process than in the one-stage separation process of the same selectivity, It can be seen that the throughput at the cut of about 0.1 was about twice that of the cut at about 0.1 and the throughput was about four times that of the stage cut of about 0.5.
따라서 본 발명에 따르면, 불화가스에 대한 질소의 선택도가 높은 중공사막 모듈을 포함하는 2단계 이상의 다단 기체분리공정을 이용하여 불화가스를 함유하는 혼합기체로부터 불화가스를 고효율로 회수 및 피드의 불화가스 농도 대비 5% 이내로 분리하여 배출할 수 있으며, 또한 다단 기체분리부의 스테이지 컷을 조절함으로써 투과기체 쪽으로 배출되는 가스의 양을 크게 높일 수 있다.Therefore, according to the present invention, it is possible to recover fluorinated gas from a mixed gas containing fluorinated gas with high efficiency by using a multistage gas separation process of two or more stages including a hollow fiber membrane module having high selectivity of nitrogen with respect to fluorinated gas, And the amount of gas discharged toward the permeable gas can be greatly increased by controlling the stage cut of the multi-stage gas separation unit.
Claims (7)
II) 상기 제1단 기체분리부에서 제1 농축기체 및 제1 투과기체로 분리하는 단계; 및
III) 상기 제1 농축기체를 중공사막 모듈을 포함하는 제2단 기체분리부로 공급하여 제2 농축기체 및 제2 투과기체로 분리하는 단계;를 포함하는 불화가스 회수방법으로서,
상기 불화가스를 함유하는 혼합기체는 N2/SF6이고,
상기 중공사막 모듈은 N2/SF6의 선택도가 50~150이며,
상기 제1단 기체분리부 및 제2단 기체분리부의 총 스테이지 컷은 0.12~0.51인 것을 특징으로 하는 불화가스 회수방법.I) compressing a mixed gas containing fluorinated gas and supplying the compressed gas to a first stage gas separation unit including a hollow fiber membrane module;
II) separating the first concentrated gas and the first permeated gas in the first-stage gas separation unit; And
III) supplying the first concentrated gas to a second stage gas separation unit including a hollow fiber membrane module, and separating the second concentrated gas into a second concentrated gas and a second permeated gas,
The mixed gas containing the fluorinated gas is N 2 / SF 6 ,
The hollow fiber membrane module has a selectivity of N 2 / SF 6 of 50 to 150,
Wherein the total stage cut of the first stage gas separation unit and the second stage gas separation unit is 0.12 to 0.51.
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