촉진수송: 기본 개념 및 기체분리막 응용

박철훈,이재훈,박민수,김종학 한국막학회 2017 멤브레인 Vol.27 No.3

고분자 분리막은 가격이 저렴하고, 쉽게 제조가 가능하며, 투과도와 선택도가 우수하여 수처리 분야뿐만 아니라 기체분리에서도 중요한 역할을 한다. 하지만, 고분자 분리막은 일반적으로 투과도와 선택도의 역상관 관계를 나타내는 단점 이 있다; 즉, 투과도가 높으면 선택도가 낮고, 선택도가 높으면 투과도가 높다. 이러한 단점을 극복하기 위한 방안 중의 하나 가 촉진수송이다. 지난 수십 년간 촉진수송 이론은 촉진수송 분리막 제조에 있어 매우 중요하고 다양한 모델을 제시하는 데 에 핵심적인 역할을 하였다. 한편, 촉진수송에서 주된 역할을 하는 운반체의 특성, 매질의 유동성 및 고분자 복합체의 물리화 학적 성질 등을 이해하는 것은 중요하다. 운반체의 유동성에 따라 촉진수송 분리막의 종류를 3가지로 나눌 수 있다; 즉, 이동 상 운반체 분리막, 준이동상 운반체 분리막, 고정상 운반체 분리막. 또한 촉진 운반체가 특정물질과 상호작용하는 데에는 4가 지 종류의 가역반응으로 나눌 수 있다; 즉, 수소원자 전달 반응, 친핵성 첨가반응, 파이-착체 반응, 그리고 전기화학 반응. 이 러한 촉진수송 분리막은 이산화탄소, 산소, 올레핀(프로필렌, 에틸렌)의 투과도를 선택적으로 향상시키는 역할을 한다. 이와 같이 본 총설에서는 다양한 촉진수송 분리막에 관련된 주요 연구내용과 이러한 연구를 수행하는 대표적인 전략들을 소개하 고자 한다. Polymer membranes are cheap and easy in fabrication, and show a high permeability and selectivity, thus play pivotal roles in gas separation as well as water purification. However, polymer membranes typically exhibit the trade-off relation between permeability and selectivity; i.e. when the permeability is high, the selectivity is low and vice versa. Facilitated transport has been considered one of the solutions to address this issue. Over the last decades, facilitated transport concept had played an important role in preparing the membranes and providing ideal and various models for the transport. Understanding the nature of carrier, the mobility of matrix and the physico-chemical properties of polymer composites are crucial for facilitated transport. Depending on the mobility of carrier, facilitated transport membrane is classified into three; mobile carrier membrane, semi-mobile carrier membrane, fixed-site carrier membrane. Also, there are four types of reversible reaction between the carrier and the specific target; proton transfer reaction, nucleophilic addition reaction, p-complexation reaction and electrochemical reaction. The facilitated transport membranes have been applied in the separation of CO2, O2 and olefin (propylene or ethylene). In this review, major challenges surrounding facilitated transport membranes and the strategies to tackle these challenges are given in detail.

Silver Polymer Electrolyte Membranes for Facilitated Olefin Transport: Carrier Properties, Transport Mechanism and Separation Performance

김종학,강용수,원종옥 한국고분자학회 2004 Macromolecular Research Vol.12 No.2

Facilitated transport membranes for the separation of olefin/paraffin mixtures have long been of interest in separation membrane science because olefins, such as propylene and ethylene, which are important chemicals in petrochemical industries, are currently separated by energy-intensive cryogenic distillation pro¬cesses. Recently, solid polymer electrolyte membranes containing silver ions have demonstrated remarkable performance in the separation of olefin/paraffin mixtures in the solid state and, thus, they can be considered as alternatives to cryogenic distillation. Here, we review recent progress, and critical issues affecting in the use of facilitated olefin transport membranes; in particular, we provide a general overview with reference to carrier properties, transport mechanisms, and separation performance.

Cultural Measures to China-Mongolia border Logistics promotion and Transportation Facilitation

Li Ruifeng(리 루펑) 한국글로벌문화학회 2017 글로벌문화연구 Vol.8 No.2

최근 중국, 몽골 및 러시아의 경제 회랑의 건설에 따른 기반시설의 전진적 배치로, 중국과 몽골 사이 화물 수송량과 내용에 대한 몇 가지 새로운 변화가 있었다. 중국과 몽골 사이의 교통 협력은 많은 기술적 문화적 문제가 존재하는 한편, 양국간 경제 협력의 지속적인 발전에 따른 수요를 충족할 수 없다. 몽골과 중국의 물류 운송에 종사하는 기업은 몽골과 중국의 국경 물류 촉진에서 몽골이 가지고 있는 문화적 침식에 대한 우려 뿐만 아니라, 운송 관련 요구 사항을 포함한 진입 조건 강화 등으로 협력이 제한되고 있다. 중국과 몽골 사이의 물류운송을 촉진하기 위해 기업의 실제수요를 분석하고 교차 국경물류교통 촉진 상태 및 문화적 영향 요인의 평가를 통해 정책적 시사점을 도출하였다. 특히, 경제 정책, 국내 조정, 철도 및 도로, 항구 건설, 기업 협회 및 기업의 설립측면에서 제안한 내용은 국내와 국제적인 협력에서 기초적 역할을 할 것이다. With the construction and advancement of the Economic Corridor of China, Mongolia and Russia, there have been some new changes on the quantity and content of the cargo transportation between China and Mongolia. Transportation cooperation between China and Mongolia still exists many problems and can"t meet the demand of further development of bilateral economic cooperation. The enterprises engaged in logistics transport of Mongolia and China put forward higher requirements on Mongolian and China’s cross-border logistics transporting facilitation. This paper puts forward some measures and suggestions to further improve the logistics transporting facilitation between China and Mongolia in the light of the actual demand of enterprises through analyzing and evaluating the cross-border logistics transport facilitation status and impacting factors. Some proposals about coordination with the economical policies, domestic coordination, construction of the railway and road, port construction, clearance facilitation, industry associations and enterprises are put forward on the basis of domestic and international experience.

Modeling of Facilitated Transport in Solid Membranes Containing Various Fixed Site Carriers

Kim, Jung Yong,Hong, Seong Uk,Kim, Hak-Kil,Kang, Yong Soo 한국공업화학회 2002 Journal of Industrial and Engineering Chemistry Vol.8 No.3

The extended series resistor-capacitor (RC) circuit model was developed to account for the effects of various kinds of carriers incorporated in the solid membranes on a facilitated mass transport. The sensitivity analysis based on the arbitrarily chosen reference state shows the degree of sensitivity as follows: the extent of pressure fluctuation > the number of hypothetical layers > the ratio of the total carrier concentration to the solute solubility by Henry's law ?? the time scale ratio of diffusion to chemical reaction > the combining driving force for facilitated transport. Furthermore, the model can describe multiple diffusional pathways from 4 to infinity depending on the number of different types of carriers, which can occurs in a real system.

Silver Polymer Electrolyte Membranes for Facilitated Olefin Transport: Carrier Properties, Transport Mechanism and Separation Performance

Kim, Jong-Hak,Kang, Yong-Soo The Polymer Society of Korea 2004 Macromolecular Research Vol.12 No.2

Facilitated transport membranes for the separation of olefin/paraffin mixtures have long been of interest in separation membrane science because olefins, such as propylene and ethylene, which are important chemicals in petrochemical industries, are currently separated by energy-intensive cryogenic distillation processes. Recently, solid polymer electrolyte membranes containing silver ions have demonstrated remarkable performance in the separation of olefin/paraffin mixtures in the solid state and, thus, they can be considered as alternatives to cryogenic distillation. Here, we review recent progress, and critical issues affecting in the use of facilitated olefin transport membranes; in particular, we provide a general overview with reference to carrier properties, transport mechanisms, and separation performance.

Facilitated Transport Membranes Based on PVA-g-PAA Graft Copolymer

박민수,강미소,박보령,김정훈,김종학,Park, Min Su,Kang, Miso,Park, Bo Ryoung,Kim, Jeong-Hoon,Kim, Jong Hak The Membrane Society of Korea 2021 멤브레인 Vol.31 No.3

It is inevitable to generate incomplete combustion gases when mankind utilizes fossil fuels. From this point of view, gas separation process of combustion gas suggests the possibility of recycling CO gas. In this study, we fabricated a facilitated transport polymeric composite membrane for CO separation using AgBF₄ and HBF₄. The copolymer was synthesized via free-radical polymerization of poly(vinyl alcohol) (PVA) as a main chain and acrylic acid (AA) monomer as a side chain. The polymer synthesis was confirmed by FT-IR and the interactions of graft copolymer with AgBF₄, and HBF₄ were characterized by TEM. PVA-g-PAA graft copolymer membranes showed good channels for facilitated CO transport. In this perspective, we suggest the novel approach in CO separation membrane area via combination of grafting and facilitated transport. 화석 연료를 사용할 때, 불완전 연소는 필연적으로 발생하는 문제이다. 이러한 관점에서 연소 후 기체 분리는 불완전 연소 기체의 재활용 가능성을 시사한다. 이와 관련하여 본 연구에서는 일산화탄소 기체 분리용 촉진수송 고분자 분리막을 제조하였다. 이를 위해 poly(vinyl alcohol) (PVA) 주사슬 기반으로 acrylic acid (AA) 단량체를 자유 라디칼 중합법으로 PVA-g-PAA 공중합체를 제조하였다. 본 공중합체를 일산화탄소 활용에 적용하는 사례는 처음이며, 제조한 공중합체는 AgBF₄ 염과 HBF₄를 혼합하여 기체 분리막에 적용하였다. 공중합체 합성 결과는 FT-IR을 통해 분석하였으며, 공중합체와 AgBF₄, HBF₄의 상호작용은 TEM를 통해 분석하였다. 염의 첨가를 통해 일산화탄소 기체의 촉진수송 채널을 형성하였으며 이를 통해 일산화탄소 분리막 분야에 촉진수송 및 그래프팅 방법이라는 새로운 접근법을 제시하였다.

Modeling of Facilitated Transport in Solid Membranes Containing Various Fixed Site Carriers

강용수,홍성욱,김학길,김정용 한국공업화학회 2002 Journal of Industrial and Engineering Chemistry Vol.8 No.3

The extended series resistor-capacitor (RC) circuit model was developed to account for the effects of various kinds of carriers incorporated in the solid membranes on a facilitated mass transport. The sensitivity analysis based on the arbitrarily chosen reference state shows the degree of sensitivity as follows: the extent of pressure fluctuation > the number of hypothetical layers > the ratio of the total carrier concentration to the solute solubility by Henry`s law ?? the time scale ratio of diffusion to chemical reaction > the combining driving force for facilitated transport. Furthermore, the model can describe multiple diffusional pathways from 4 to infinity depending on the number of different types of carriers, which can occurs in a real system.

Role of p-Benzoquinone for Dispersion of Silver Nanoparticles in Silver-Polymer Nanocomposite Membranes

강상욱 한국고분자학회 2010 Macromolecular Research Vol.18 No.7

Solid state facilitated transport membranes with higher olefin selectivity were prepared using silver nanoparticles activated by electron acceptors, such as p-benzoquinone (pBQ) as olefin carriers and inert poly(ethyleneco-propylene) (EPR) polymer matrix. Here, the effect of pBQ in silver-polymer nanocomposite membranes on the dispersion of silver nanoparticles on the polymer matrix and the structural properties of the membranes were investigated and correlated with the facilitated olefin transport. Transmission electron microscopy (TEM) and photographs clearly showed that pBQ plays an effective role as a stabilizing agent, resulting in a good dispersion of the silver nanoparticles in the EPR matrix. The good dispersion by pBQ was attributed to the strong interaction between pBQ and silver nanoparticles, as confirmed by x-ray photoelectron spectroscopy (XPS). Differential scanning calorimetry (DSC) also showed that the increased propylene permeance by pBQ was not caused by the increased chain flexibility of the membranes but facilitated olefin transport due to a reversible interaction between the olefin and silver nanoparticles.

Highly CO₂ selective membranes by potassium cations as carriers for facilitated transport with Ag₂O particles and free ions in ionic liquid

Park, Young Sung,Kang, Yong Soo,Kang, Sang Wook Elsevier 2017 CHEMICAL ENGINEERING JOURNAL -LAUSANNE- Vol.320 No.-

<P><B>Abstract</B></P> <P>The highly selective composite membranes consisting of ionic liquid 1-butyl-3-methyl imidazolium tetrafluoroborate (BMIM<SUP>+</SUP>BF<SUB>4</SUB> <SUP>−</SUP>)/Ag<SUB>2</SUB>O/KF were prepared for CO<SUB>2</SUB> separation. When Ag<SUB>2</SUB>O and KF were incorporated into BMIM<SUP>+</SUP>BF<SUB>4</SUB> <SUP>−</SUP>, the ideal selectivities of CO<SUB>2</SUB>/N<SUB>2</SUB> and CO<SUB>2</SUB>/CH<SUB>4</SUB> reached 105 and 52, respectively, with a CO<SUB>2</SUB> gas permeance of 31 GPU. These enhanced separation performance were attributable to synergistic effect of (1) K<SUP>+</SUP> cations in KF as CO<SUB>2</SUB> carriers for facilitated transport and (2) the oxide layer of the well-dispersed Ag<SUB>2</SUB>O and free ions in ionic liquid for improvement in CO<SUB>2</SUB> solubility. The coordinative interactions in the BMIM<SUP>+</SUP>BF<SUB>4</SUB> <SUP>−</SUP>/Ag<SUB>2</SUB>O/KF membrane were characterized by TGA, XPS, and FT-Raman spectroscopy.</P> <P><B>Highlights</B></P> <P> <UL> <LI> CO<SUB>2</SUB> separation membranes consisting of ionic liquid BMIMBF<SUB>4</SUB>/Ag<SUB>2</SUB>O/KF composite. </LI> <LI> Potassium cations as CO<SUB>2</SUB> carriers for facilitated transport. </LI> <LI> Enhanced solubility of CO<SUB>2</SUB> molecules by both Ag<SUB>2</SUB>O particles and free ions in ionic liquid. </LI> </UL> </P>

Investigation of solid state facilitated transport hollow fiber membrane for olfin/paraffin gas separation

임주환,이민희,이충섭,고형철,하성용 한국공업화학회 2015 한국공업화학회 연구논문 초록집 Vol.2015 No.1

Development of olefin/paraffin separation has been performed in various industries and institution. Especially, huge amount of light olefins such as ethylene and propylene are produced in chemical and petroleum industry due to their diverse utilization as raw materials for many products. However, it is very difficult to separate olefin from paraffin because their physical and chemical properties are very similar like molecular sizes and boiling point. Distillation process used to separate mixture gas so far, but it needs large amount of capital cost and energy. For this reason, many technologies are being investigated. Facilitated transport membrane is in the limelight for the separation of olefin/ paraffin because of its simplicity and low energy consumption. Silver (I) ions is commonly used as a carrier for facilitated olefin transport. In this study, AgBF₄ solution was produced as electrolyte for the olefin separation.