KR20050113974A - A manufacture method high performance composite membranes with multi-active layers for gasoline retrievals - Google Patents
A manufacture method high performance composite membranes with multi-active layers for gasoline retrievals Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 47
- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 10
- 238000000034 method Methods 0.000 title abstract description 22
- 229920000642 polymer Polymers 0.000 claims abstract description 48
- 238000000926 separation method Methods 0.000 claims abstract description 24
- 229920002647 polyamide Polymers 0.000 claims abstract description 10
- 239000004677 Nylon Substances 0.000 claims abstract description 9
- 239000004952 Polyamide Substances 0.000 claims abstract description 9
- 229920001778 nylon Polymers 0.000 claims abstract description 9
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 9
- 239000010703 silicon Substances 0.000 claims abstract description 9
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 18
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 18
- -1 polydimethylsiloxane Polymers 0.000 claims description 8
- 239000004642 Polyimide Substances 0.000 claims description 7
- 229920001721 polyimide Polymers 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 239000004745 nonwoven fabric Substances 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 9
- 239000010410 layer Substances 0.000 description 63
- 230000008569 process Effects 0.000 description 13
- 239000012855 volatile organic compound Substances 0.000 description 10
- 238000011084 recovery Methods 0.000 description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 238000002834 transmittance Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 5
- 239000003960 organic solvent Substances 0.000 description 5
- 230000035699 permeability Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000008096 xylene Substances 0.000 description 3
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- JHWNWJKBPDFINM-UHFFFAOYSA-N Laurolactam Chemical compound O=C1CCCCCCCCCCCN1 JHWNWJKBPDFINM-UHFFFAOYSA-N 0.000 description 1
- 229920000571 Nylon 11 Polymers 0.000 description 1
- 229920000299 Nylon 12 Polymers 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 229920000305 Nylon 6,10 Polymers 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- DALDUXIBIKGWTK-UHFFFAOYSA-N benzene;toluene Chemical compound C1=CC=CC=C1.CC1=CC=CC=C1 DALDUXIBIKGWTK-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- YAIDLYRPOFNPHB-UHFFFAOYSA-N heptane;hexane;pentane Chemical compound CCCCC.CCCCCC.CCCCCCC YAIDLYRPOFNPHB-UHFFFAOYSA-N 0.000 description 1
- 229920000140 heteropolymer Polymers 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 229920005573 silicon-containing polymer Polymers 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
Classifications
-
- 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
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/62—Polycondensates having nitrogen-containing heterocyclic rings in the main chain
- B01D71/64—Polyimides; Polyamide-imides; Polyester-imides; Polyamide acids or similar polyimide precursors
-
- 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
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
- B01D71/72—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of the groups B01D71/46 - B01D71/70 and B01D71/701 - B01D71/702
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
본 발명은 가솔린 분리용 고효율 다중활성층 복합막 및 이의 제조방법에 관한 것으로서, 더욱 상세하게는 다공성 고분자 지지체상에, 나일론계, 실리콘계 및 폴리아마이드계 중에서 선택된 고분자층이 적층되어 다중활성층이 형성되어 있고, 상기 다중활성층을 형성하는 각 활성층에 함유되는 고분자는 서로 다른 다중활성층 복합막으로, 방향족 탄화수소의 선택성 및 내화학성과 같은 안정성이 월등하게 향상된 가솔린 분리용 고효율 다중활성층 복합막 및 이의 제조방법에 관한 것이다.The present invention relates to a high-efficiency multi-active layer composite membrane for gasoline separation and a method for manufacturing the same. More particularly, a polymer layer selected from nylon, silicon and polyamide is stacked on a porous polymer support to form a multi-active layer. , The polymer contained in each of the active layer forming the multi-active layer is a different multi-active layer composite membrane, a highly efficient multi-active layer composite membrane for gasoline separation with improved stability, such as selectivity and chemical resistance of aromatic hydrocarbons and a method for producing the same will be.
Description
본 발명은 가솔린 분리용 고효율 다중활성층 복합막 및 이의 제조방법에 관한 것으로서, 더욱 상세하게는 다공성 고분자 지지체상에, 나일론계, 실리콘계 및 폴리아마이드계 중에서 선택된 고분자층이 적층되어 다중활성층이 형성되어 있고, 상기 다중활성층을 형성하는 각 활성층에 함유되는 고분자는 서로 다른 다중활성층 복합막으로, 방향족 탄화수소의 선택성 및 내화학성과 같은 안정성이 월등하게 향상된 가솔린 분리용 고효율 다중활성층 복합막 및 이의 제조방법에 관한 것이다.The present invention relates to a high-efficiency multi-active layer composite membrane for gasoline separation and a method for manufacturing the same. More particularly, a polymer layer selected from nylon, silicon and polyamide is stacked on a porous polymer support to form a multi-active layer. , The polymer contained in each of the active layer forming the multi-active layer is a different multi-active layer composite membrane, a highly efficient multi-active layer composite membrane for gasoline separation with improved stability, such as selectivity and chemical resistance of aromatic hydrocarbons and a method for producing the same will be.
저유소 및 주유소에서 주유시 방출되는 휘발유는 일반적인 휘발성유기화합물(VOCs)들과 달리 소각 등과 같은 휘발성유기화합물질(VOCs) 방지설비 공정을 적용시키는데 있어 제약이 많으며, 특히 가솔린 회수를 위해서는 극히 몇몇 제한된 공정만이 도입 가능한 것으로 알려져 있다. Gasoline released from gasoline at low and petrol stations is very limited in the application of volatile organic compounds (VOCs) prevention processes, such as incineration, unlike conventional volatile organic compounds (VOCs). It is known that only can be introduced.
도입 가능한 공정중 분리막법은 저유소 및 주유소와 같은 규모에 적용이 가능하며 기존의 흡착 및 냉각공정들에 비해 에너지 소비가 낮으며, 또한 운전 안정성과 분리효율이 우수하고 다양한 농도에서 적용이 가능하다는 장점을 갖고 있다. 이에 90년대 초부터 이러한 분리막법을 이용한 가솔린 분리회수공정의 연구가 본격적으로 시작되었다. In-process separation membrane method can be applied to the same scale as low oil and gas station, has lower energy consumption than conventional adsorption and cooling processes, and also has excellent operational stability and separation efficiency and can be applied at various concentrations. Have Therefore, from the early 90's, the study of gasoline separation recovery process using this membrane method began in earnest.
분리막법을 이용하여 대기중의 휘발성유기화합물(VOCs)을 분리하는 증기투과(Vapor permeation)공정은 기존의 다른 분리공정기술에 비해 비교적 짧은 연구역사를 갖고 있다. 분리막을 이용한 기체/증기의 분리기술은 그 분리공정과 투과대상, 분리막소재의 선택기준, 투과메카니즘 등이 기체분리(gas separation) 및 투과증발(pervaoration)과 유사하여 분류가 아주 모호하나 투과증발(pervaoration)을 연구하던 그룹과 기체분리(gas separation)분야를 연구했던 그룹들에 의해 시작되었다는 이유로 일반적으로 증기투과법(Vapor permeation)으로 정의되어지고 있다. 또한, 증기투과법(Vapor permeation)은 기체분리, 투과증발, 역삼투법 및 한외여과법 등과 같이 이미 많은 연구와 상용화가 이루어진 기존의 다른 분리막 분야에 비해 아직 연구결과 및 실제 응용된 예가 적다고 할 수 있다. The vapor permeation process, which separates volatile organic compounds (VOCs) from the atmosphere using the membrane method, has a relatively short history of research compared to other separation process technologies. Gas / vapor separation technology using separation membrane is very ambiguous because the separation process, permeation target, selection criteria of membrane material and permeation mechanism are similar to gas separation and pervaoration, but permeation ( It is generally defined as vapor permeation because it was initiated by a group studying pervaoration and a group studying gas separation. In addition, the vapor permeation (Vapor permeation) is still less research results and practical applications compared to other existing membrane fields that have already been studied and commercialized, such as gas separation, permeation evaporation, reverse osmosis and ultrafiltration.
분리막법을 이용한 가솔린 증기혼합물의 분리회수 공정기술은 현재 미국의 MTR사와 일본의 Nitto Denko사(MTR과 기술제휴), 독일의 GKSS사 등에서 파일럿(Pilot) 규모의 장치가 개발되어 주로 각국 정부의 환경 정책적인 지원 하에 석유화학공장과 자동차 주유저장소 등에서 수 백개가 시험 가동되고 있다. 이와 같은 시스템들은 주로 염소계 및 탄화수소계 휘발성유기화합물(VOCs)들에 대해 70 ∼ 90% 분리회수가 가능하나 막소재로 널리 사용되어지고 있는 유기 실리콘계 고분자가 방향족 탄화수소에 대하여 화학적 안정성 등의 문제점을 갖고 있는 것으로 알려져 있다. 따라서, 방향족 탄화수소에 대한 상기 문제점을 개선한 고효율의 복합막의 개발이 절실히 요구되고 있는 실정이다.Separation recovery process technology of gasoline steam mixtures using the membrane method is currently developed by pilot-scale devices such as MTR in USA, Nitto Denko in Japan (technical partnership with MTR) and GKSS in Germany. With policy support, hundreds are being piloted at petrochemical plants and car service depots. Such systems are capable of 70-90% separation recovery for chlorine and hydrocarbon-based volatile organic compounds (VOCs), but organic silicone polymers, which are widely used as membrane materials, have problems such as chemical stability against aromatic hydrocarbons. It is known. Therefore, there is an urgent need for the development of a highly efficient composite membrane that improves the above problems with aromatic hydrocarbons.
본 발명은 종래의 가솔린 분리용 분리막이 방향족 탄화수소에 대한 분리회수율 저하의 문제를 개선하기 위하여 연구 노력한 결과, 다공성 고분자 지지체상에 나일론계, 실리콘계 및 폴리아마이드계 중에서 선택된 1종 이상의 고분자가 함유된 활성층용액을 도포하여 활성층을 형성하고, 상기 활성층 표면에, 형성된 활성층의 고분자와 다른 이종의 고분자 활성층용액을 재코팅하여 다중의 활성층이 적층된 복합막이 방향족 탄화수소의 선택성 및 내화학성과 같은 안정성을 월등하게 향상시킨다는 것을 알게되어 본 발명을 완성하게 되었다. According to the present invention, a conventional gasoline separation membrane has been studied to improve the problem of lowering the recovery rate of aromatic hydrocarbons. As a result, an active layer containing at least one polymer selected from nylon, silicon, and polyamide on a porous polymer support Applying a solution to form an active layer, and re-coating a polymer of the formed active layer and a heterogeneous polymer active layer solution on the surface of the active layer, a composite membrane in which multiple active layers are laminated has excellent stability such as selectivity and chemical resistance of aromatic hydrocarbons. It has been found that the present invention can be improved to complete the present invention.
따라서, 본 발명은 방향족 탄화수소에 대한 선택성 및 내화학성이 향상되어 고효율로 가솔린의 분리가 용이한 다중활성층 복합막 및 이의 제조방법을 제공하는데 그 목적이 있다. Accordingly, an object of the present invention is to provide a multi-active layer composite membrane having a high efficiency and easy separation of gasoline with high selectivity and chemical resistance to aromatic hydrocarbons, and a method of manufacturing the same.
본 발명은 다공성 고분자 지지체상에, 나일론계, 실리콘계 및 폴리아마이드계 중에서 선택된 고분자층이 적층된 다중활성층이 형성되어 있고, 상기 다중활성층을 형성하는 각 활성층에 함유되는 고분자는 서로 다른 고분자인 가솔린 분리용 다중활성층 복합막에 그 특징이 있다.According to the present invention, a multi-active layer in which a polymer layer selected from nylon, silicon and polyamide is stacked is formed on a porous polymer support, and the polymer contained in each active layer forming the multi-active layer is a different polymer from gasoline. The multi-active layer composite membrane has the characteristics.
이와 같은 본 발명을 더욱 상세하게 설명하면 다음과 같다.The present invention will be described in more detail as follows.
본 발명은 다공성 고분자 지지체 위에, 특정의 고분자 활성층이 적어도 2층 이상 적층되어 방향족 탄화수소에 대한 내화학성과 선택성이 월등하게 향상된 가솔린 분리용 다중활성층 복합막에 관한 것이다. 종래에 가솔린 분리용으로 사용된 복합막은 다공성 지지체 위에 폴리디메틸실록산(PDMS)이 코팅되어 활성층이 형성된 것이 일반적이나, 이는 방향족 탄화수소에 대한 내화학성의 부족으로 선택성의 저하 즉, 분리효율이 저하되었다. 그러나, 본 발명은 종래와 같이 다공성 지지체 위에 특정의 고분자 활성층이 적어도 2종 이상 적층된 복합막으로, 단순히 기존의 복합막에 방향족 탄화수소계에 대해 선택성을 보이는 고분자를 코팅시켜 적층시킨 것이 아니라 상기 방향족 탄화수소계 화합물에 선택성을 보이는 고분자를 선택 사용하고, 각 활성층은 서로 다른 이종의 고분자를 사용하며, 방향족 탄화수소계에 대해 내화학성을 갖는 기술구성상의 특징이 있으며, 이는 가솔린을 분리 회수하는 복합막으로서는 신규한 것이다. The present invention relates to a multi-active layer composite membrane for gasoline separation in which at least two layers of a specific polymer active layer are laminated on a porous polymer support, thereby improving chemical resistance and selectivity to aromatic hydrocarbons. Conventionally, a composite membrane used for gasoline separation is generally formed with an active layer formed by coating polydimethylsiloxane (PDMS) on a porous support, but this is due to a lack of chemical resistance to aromatic hydrocarbons, resulting in lower selectivity, that is, separation efficiency. However, the present invention is a composite membrane in which at least two or more specific polymer active layers are laminated on a porous support as in the prior art. Selected polymers that show selectivity to hydrocarbon compounds, each active layer uses different heterogeneous polymers, and have a characteristic feature of the technical configuration having chemical resistance to aromatic hydrocarbons, which is a composite membrane for separating and recovering gasoline. It is new.
본 발명에 따른 다중활성층 복합막을 그 제조방법에 따라 보다 구체적으로 설명하면 다음과 같다.Referring to the multi-active layer composite film according to the present invention in more detail according to the manufacturing method as follows.
먼저, 통상적인 상전이 공정으로 다공성 지지체의 제조가 가능한 고분자 용액을 제조하여 부직포 위에 도포하고, 상전이 공정을 이용하여 다공성 고분자 지지체를 제조한다. 이후에 상기 제조된 다공성 고분자 지지체를 상온에서 순수에 12 ∼ 24 시간 방치한 후, 55 ∼ 65 ℃의 열수에서 7 ∼ 10 시간동안 열수처리하여 분리막 내부에 잔존하는 유기용매를 추출하여 상온에서 건조한다.First, a polymer solution capable of preparing a porous support by a conventional phase change process is prepared, and then coated on a nonwoven fabric, and a porous polymer support is prepared by using a phase change process. Thereafter, the prepared porous polymer support is left in pure water at room temperature for 12 to 24 hours, and then hydrothermally treated for 7 to 10 hours in hot water at 55 to 65 ° C. to extract the organic solvent remaining in the separator and dried at room temperature. .
상기 고분자 용액 제조에 사용되는 고분자는 상전이 공정이 가능한 것으로 본 발명에서는 특별히 제약하지는 않으나, 폴리설폰계, 폴리이미드계 및 폴리플루오르계 중에서 선택된 고분자로 예를 들면 폴리이서설폰(PES), 폴리설폰(PSf), 폴리비닐리덴플로라이드(PVDF), 폴리이서이미드(PEI) 및 폴리아크릴로나이트릴(PAN)를 사용하는 것이 좋다. 상기 지지체를 제조하는 상전이 공정으로는 예를 들면 건식, 습식 및 건·습식 공정을 사용할 수 있으며, 본 발명에서는 습식공정을 이용하는 것이 좋다.The polymer used to prepare the polymer solution may be a phase-transfer process, and is not particularly limited in the present invention. For example, polyisulfone (PES), polysulfone (polysulfone, polyimide, and polyfluorine) PSf), polyvinylidene fluoride (PVDF), polyimide (PEI) and polyacrylonitrile (PAN) are preferably used. As a phase-transfer process of manufacturing the support, for example, a dry, wet and dry / wet process can be used, and in the present invention, it is preferable to use a wet process.
상기 고분자는 통상적으로 사용되는 유기용매 예를 들면 N-메틸-2-피롤리돈, 테트라하이드로퓨란, 노르말헥산, 메탄올, 에탄올, 부탄올에 용해시켜 지지체 용액을 제조하며, 이때 고분자는 10 ∼ 20 중량% 사용하는 것이 바람직하다. 상기 고분자 사용량이 10 중량% 미만이면 지지체 표면의 기공율이 높아지는 반면, 기공크기가 과대하게 커져 활성층 형성에 부적합한 기공 크기를 갖고 20 중량%를 초과하는 경우에는 지지체의 표면 기공율과 함께 기공 크기 역시 감소하여 투과율이 감소하는 문제가 발생한다.The polymer is dissolved in a conventionally used organic solvent such as N-methyl-2-pyrrolidone, tetrahydrofuran, normal hexane, methanol, ethanol, butanol to prepare a support solution, wherein the polymer is 10 to 20 weight It is preferable to use%. When the amount of the polymer used is less than 10% by weight, the porosity of the surface of the support is increased, while the pore size is excessively large, which has an unsuitable pore size for forming an active layer, and when it exceeds 20% by weight, the pore size is also reduced along with the surface porosity of the support. The problem of decreasing the transmittance arises.
이외에, 본 발명의 목적을 벗어나지 않는 범위내에서 지지체의 다양한 기능성을 부여하기 위해 통상적으로 사용되는 기공형성제로 감마부티로락톤(GBL) 및 폴리에틸렌 글라이콜(PEG) 등의 여러 첨가제를 첨가하는 것도 가능하다. In addition, it is also possible to add various additives such as gamma butyrolactone (GBL) and polyethylene glycol (PEG) as pore forming agents that are commonly used to impart various functionalities of the support without departing from the object of the present invention. It is possible.
다음으로, 상기 다공성 고분자 지지체 표면을 특정의 고분자가 함유된 활성층용액을 사용하여 도포하여 활성층을 형성한다.Next, the surface of the porous polymer support is applied using an active layer solution containing a specific polymer to form an active layer.
상기 활성층 형성에 사용되는 고분자는 나일론계, 실리콘계 및 폴리아마이드계 중에서 선택된 1종 이상의 것으로, 구체적으로 나일론 6, 나일론 66, 나일론 610, 나일론 11, 나일론 12, 폴리디메틸실록산(PDMS), 폴리아마이드(PA) 및 폴리이서블록아마이드(PEBA)등을 사용할 수 있다. 이러한 고분자는 통상적인 유기용매에 용해시켜 용액상으로 사용하며, 5 ∼ 30 중량%를 유기용매에 함유시켜 사용하는 것이 좋다. 상기 고분자 사용량이 5 중량% 미만이면 활성층의 두께가 얇아져 기체의 투과도는 증가할 수 있으나 제조 공정상 결함이 발생할 수 있으며 그로 인해 선택도가 감소할 수 있고, 30 중량%를 초과하는 경우에는 활성층의 두께가 비 이상적으로 증가하여 투과도가 감소되는 문제가 있다.The polymer used to form the active layer is one or more selected from nylon, silicon and polyamide, specifically, nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, polydimethylsiloxane (PDMS), polyamide ( PA) and polyisoblockamide (PEBA) and the like can be used. Such a polymer is dissolved in a conventional organic solvent and used as a solution phase, and 5 to 30% by weight of the organic solvent is preferably used. When the amount of the polymer used is less than 5% by weight, the thickness of the active layer may be reduced, so that the permeability of the gas may be increased, but defects may occur in the manufacturing process, and thus the selectivity may be reduced, and when the amount of the active layer exceeds 30% by weight, There is a problem in that the transmittance is decreased due to the non-ideal increase in the thickness.
또한, 다공성 지지체 위에 코팅하여 활성층이 형성된 후에 120 ∼ 140 ℃에서 2 ∼ 4 시간동안 통상적인 방법으로 경화시켜 활성층을 적층시켰다.In addition, after coating on the porous support to form an active layer, the active layer was laminated by curing in a conventional manner at 120 to 140 ℃ for 2 to 4 hours.
다음으로, 상기 다공성 지지체 위에 1층의 활성층을 적층시킨 후, 나일론계, 실리콘계 및 폴리아마이드계 중에서 선택된 고분자로, 상기 1층에 적층된 활성층과 다른 이종의 고분자를 코팅시킨 후, 건조하여 다중활성층 복합막을 제조한다. Next, after laminating one layer of the active layer on the porous support, a polymer selected from nylon, silicon, and polyamide-based, the active layer laminated on the first layer and other heteropolymers are coated, then dried to a multi-active layer A composite membrane is prepared.
상기 고분자도 앞에서 형성한 활성층 고분자와 동일한 양을 사용하여 코팅한 후, 상온에서 건조한다.The polymer is also coated using the same amount as the active layer polymer formed above, and then dried at room temperature.
이외에, 각각 다른 고분자가 함유된 활성층을 적층하여 2 ∼ 3층의 다중활성층 복합막을 제조할 수 있으며, 보다 바람직하기로는 공정의 복잡성 및 투과도 측면에서 다중활성층을 2층 정도로 적층하는 것이 좋다. In addition, two to three layers of a multi-active layer composite membrane may be prepared by stacking active layers containing different polymers, and more preferably, stacking two or more multi-active layers in terms of complexity and permeability of the process.
다음 도 1은 본 발명에 따라 제조된 다중활성층 복합막의 한 예로, 지지체로 제막성과 기계적 물성이 우수한 폴리이서이미드(PEI)을 사용하고, 투과도와 파라핀계 탄화수소에 대하여 선택도가 우수한 폴리디메틸실록산(PDMS)의 첫 번째 활성층과 방향족 탄화수소에 대해 화학적으로 안정하고 선택성이 우수한 폴리이서블록아마이드(PEBA)를 두 번째 활성층이 순차적으로 적층된 다중활성층 복합막의 단면을 나타낸 것이다.1 is an example of a multi-active layer composite membrane prepared according to the present invention, using a polyimide (PEI) having excellent film forming properties and mechanical properties as a support, and polydimethylsiloxane (excellent selectivity for permeability and paraffinic hydrocarbons ( The polyactive block amide (PEBA), which is chemically stable and highly selective for the first active layer and aromatic hydrocarbon of PDMS), shows a cross-section of a multi-active layer composite membrane in which a second active layer is sequentially stacked.
상기와 같이 본 발명에 따라 제조된 다중활성층 복합막은 방향족 탄화수소에 대하여 내화학성과 선택도가 매우 우수하여 가솔린 증기투과공정에 적용할 경우 분리회수 효율을 극대화시키고 분리막의 수명을 향상시킬 수 있다. As described above, the multi-active layer composite membrane prepared according to the present invention has excellent chemical resistance and selectivity to aromatic hydrocarbons, and when applied to a gasoline vapor permeation process, maximizes the separation recovery efficiency and improves the life of the membrane.
이하, 본 발명을 실시예에 의거하여 상세히 설명하면 다음과 같은 바, 본 발명이 실시 예에 의해 한정되는 것은 아니다.Hereinafter, the present invention will be described in detail with reference to Examples, as follows, but the present invention is not limited by the Examples.
실시예 1 : PEI/PDMS/PEBA의 다중활성층 복합막Example 1 Multi-Active Layer Composite Membrane of PEI / PDMS / PEBA
폴리이서이미드(PEI) 15 중량%를 n-메틸-2-플로리던(NMP) 55 중량%에 기공 형성제인 감마부티로락톤(GBL) 30 중량%를 첨가하여 도포용액을 제조한 다음, 용액 내의 기포를 제거하기 위하여 24시간 동안 상온에서 방치시켰다. 제조된 도포용액을 부직포 위에 일정 두께로 도포한 후 상전이 공정인 습식 공정을 통하여 지지체를 제조하였으며, 이때 비용매로는 순수를 사용하였다. 제조된 분리막을 상온에서 순수한 물속에 24시간 동안 보관시킨 다음, 60 ℃의 열수를 이용하여 9시간 동안 열수처리하여 지지체 내부에 잔존하고 있는 유기용매를 추출하였으며 상온에서 건조하였다.A coating solution was prepared by adding 15% by weight of polyimide (PEI) to 55% by weight of n-methyl-2-flolidone (NMP) and 30% by weight of gamma butyrolactone (GBL) as a pore former, and then It was left at room temperature for 24 hours to remove bubbles. After applying the prepared coating solution on a non-woven fabric to a predetermined thickness through a wet process, a phase transition process, a support was prepared, where pure water was used as a non-solvent. The prepared membrane was stored in pure water at room temperature for 24 hours, and then heat-treated with hot water at 60 ° C. for 9 hours to extract the organic solvent remaining in the support and dried at room temperature.
또한, 폴리디메틸실록산(PDMS) 10 중량%를 노르말헥산(n-Hexane) 90 중량%로 용해시켜 제1활성층 용액을 제조한 다음, 용액내의 기포를 제거한 후 상기에서 제조한 지지체 위에 도포하고, 상온에서 건조한 후 130 ℃온도에서 3시간 동안 경화시켜 제1활성층을 형성하였다.In addition, 10% by weight of polydimethylsiloxane (PDMS) was dissolved in 90% by weight of normal hexane (n-Hexane) to prepare a first active layer solution, and then the air bubbles were removed from the solution and then applied to the support prepared above, room temperature After drying at 130 ℃ to cure for 3 hours at 130 ℃ to form a first active layer.
그 다음, 폴리이서블록아마이드(PEBA) 20 중량%를 부탄올(Butanol) 80 중량%로 용해시켜 제조한 제2활성층 용액을, 상기에서 제조한 PDMS-PEI 복합막 위에 도포한 후 상온에서 건조하여 PEI/PDMS/PEBA 다중활성층 복합막을 제조하였다.Next, a second active layer solution prepared by dissolving 20% by weight of polyaceblockamide (PEBA) in 80% by weight of butanol was applied onto the PDMS-PEI composite membrane prepared above, followed by drying at room temperature, followed by PEI. / PDMS / PEBA multi-active layer composite membrane was prepared.
비교예 1: PDMS/PEI 단일층 복합막Comparative Example 1: PDMS / PEI Single Layer Composite Membrane
상기 실시예 1과 동일한 방법으로 수행하여, 종래의 PDMS-PEI 복합막으로 폴리디메틸실록산(PDMS) 10 중량%를 노르말헥산(n-Hexane) 90 중량%로 용해시켜 제조한 활성층 용액을 PEI 지지체 위에 도포하여 단일층 복합막을 제조하였다.The active layer solution prepared by dissolving 10% by weight of polydimethylsiloxane (PDMS) in 90% by weight of normal hexane (n-Hexane) with a conventional PDMS-PEI composite membrane was carried out in the same manner as in Example 1, on the PEI support. It was applied to prepare a single layer composite membrane.
비교예 2: PDMS/PEBA 단일층 복합막Comparative Example 2: PDMS / PEBA Monolayer Composite Membrane
상기 실시예 1과 동일한 방법으로 수행하여, 종래의 PEBA-PEI 복합막으로 PEBA 20 중량%를 부탄올(Butanol) 80 중량%로 용해시켜 제조한 활성층 용액을 PEI 지지체위에 도포하여 단일층 복합막을 제조하였다.In the same manner as in Example 1, the active layer solution prepared by dissolving 20% by weight of PEBA to 80% by weight of butanol in a conventional PEBA-PEI composite membrane was applied on a PEI support to prepare a single layer composite membrane. .
실험예 1Experimental Example 1
상기 실시예 1 및 비교예 1 ∼ 2에서 제조된 복합막의 투과특성을 다음과 같은 방법으로 측정하였으며, 그 결과를 다음 표 1에 나타내었다.The transmission characteristics of the composite membranes prepared in Example 1 and Comparative Examples 1 and 2 were measured by the following method, and the results are shown in Table 1 below.
[물성 측정 방법] [Measurement Method]
- 투과특성 : 제조된 복합막을 면적이 12.52 cm2 인 평막 모듈을 제작하여 증기투과 장치를 이용하여 방향족 탄화수소인 벤젠, 톨루엔, 자일렌 등에 대하여 투과도와 선택도를 측정하였다.-Permeation characteristics: The composite membrane of 12.52 cm 2 area was fabricated and the permeability and selectivity of aromatic hydrocarbons such as benzene, toluene and xylene were measured using a vapor permeation apparatus.
* 투과도(GPU)의 단위 : 10-6 ㎤/㎠·sec·cmHg* Unit of transmittance (GPU): 10 -6 cm 3 / cm 2 · sec · cmHg
* 선택도 : 질소에 대한 투과성분의 %비* Selectivity:% ratio of permeation component to nitrogen
상기 표 1에 나타낸 결과에서 보이는 바와 같이, 본 발명에 따라 다중활성층이 형성된 복합막이 종래의 상업화되어 있는 비교예보다 각 휘발성 유기화합물에 대한 투과도는 동일 수준을 보이지만, 벤젠, 톨루엔, 자일렌의 선택도는 윌등하게 향상되는 경향을 나타내었다.As shown in the results shown in Table 1, the composite membrane formed with the multi-active layer according to the present invention shows the same level of permeability for each volatile organic compound than the conventional commercialized comparative example, but the selection of benzene, toluene and xylene Figures showed a tendency to improve significantly.
상기한 바와 같이, 본 발명에 따라 다공성 고분자 지지체 위에 2층 이상의 활성층이 적층되어 형성된 다중활성층 복합막은 방향족 탄화수소에 대하여 안정적이고 선택성이 우수하여 휘발성 유기화합물의 분리회수 및 제거공정 특히 가솔린의 분리 회수공정에 유용하게 사용될 수 있다.As described above, the multi-active layer composite membrane formed by stacking two or more active layers on a porous polymer support according to the present invention is stable and selective for aromatic hydrocarbons, so that the recovery and removal of volatile organic compounds, in particular, the recovery and recovery of gasoline It can be usefully used.
도 1은 본 발명의 실시예 1에 따라 제조된 다중활성층 복합막의 단면도를 나타낸 것으로, 1 is a cross-sectional view of a multi-active layer composite film prepared according to Example 1 of the present invention.
부직포, 폴리이서이미드(PEI) 지지체, 폴리디메틸실록산(PDMS) 활성층 및 폴리이서블록아마이드(PEBA) 활성층이 순차적으로 적층된 다중활성층 복합막을 나타낸 것이다.It shows a multi-active layer composite film in which a nonwoven fabric, a polyimide (PEI) support, a polydimethylsiloxane (PDMS) active layer, and a polyisoblockamide (PEBA) active layer are sequentially stacked.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2009076025A1 (en) * | 2007-12-12 | 2009-06-18 | Uop Llc | Molecular sieve/polymer mixed matrix membranes |
| WO2009158157A2 (en) * | 2008-06-25 | 2009-12-30 | Uop Llc | Mixed matrix membranes containing ion-exchanged molecular sieves |
| CN102451621A (en) * | 2010-10-27 | 2012-05-16 | 中国科学院大连化学物理研究所 | Polyether-b-polyamide multilayer composite film and preparation method thereof |
| US8226862B2 (en) | 2007-12-12 | 2012-07-24 | Uop Llc | Molecular sieve/polymer asymmetric flat sheet mixed matrix membranes |
| CN106256417A (en) * | 2015-06-18 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of preparation method of high-performance organic gas separation film |
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| KR101035717B1 (en) * | 2007-10-01 | 2011-05-19 | 한국화학연구원 | A preparation of asymmetric porous PEBA membrane for composite membrane |
| KR101927722B1 (en) | 2017-08-18 | 2018-12-11 | 더블유스코프코리아 주식회사 | A vapor permeable membrane and a method for manufacturing the same |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009076025A1 (en) * | 2007-12-12 | 2009-06-18 | Uop Llc | Molecular sieve/polymer mixed matrix membranes |
| US8226862B2 (en) | 2007-12-12 | 2012-07-24 | Uop Llc | Molecular sieve/polymer asymmetric flat sheet mixed matrix membranes |
| WO2009158157A2 (en) * | 2008-06-25 | 2009-12-30 | Uop Llc | Mixed matrix membranes containing ion-exchanged molecular sieves |
| WO2009158157A3 (en) * | 2008-06-25 | 2010-04-29 | Uop Llc | Mixed matrix membranes containing ion-exchanged molecular sieves |
| CN102451621A (en) * | 2010-10-27 | 2012-05-16 | 中国科学院大连化学物理研究所 | Polyether-b-polyamide multilayer composite film and preparation method thereof |
| CN106256417A (en) * | 2015-06-18 | 2016-12-28 | 中国石油化工股份有限公司 | A kind of preparation method of high-performance organic gas separation film |
| CN115608177A (en) * | 2022-10-17 | 2023-01-17 | 南京工业大学 | Polyether block polyamide/polydimethylsiloxane composite gas separation membrane, preparation method and application |
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