The hybrid membrane/distillation process has been suggested as an alternative to the conventional energy-intensive olefin/paraffin separation technology. In this study, bulky ethyl substituent-containing polyimides were synthesized from various aromatic dianhydrides and 4,4'-methylenebis (2,6-diethylaniline) by azeotropic imidization, and its gas tranport properties were investigated. Ethyl groups were placed ortho to the imide nitrogen, which hinders backbone rotation, chain packing, and flexibility. The synthesized polyimides exhibited a good thermal stability with high glass transition temperatures (268-285 ℃). The prepared polyimide membranes exhibited high propylene/propane selectivity and lied near to the upper bound line.

Plasticization is one of the biggest challenges in gas separation polymeric membranes. Mixed matrix membrane (MMM) comprising inorganic nanofiller is the most promising solution for anti-plasticization, however, it requires large amount of nanofillers to achieve desired performance. We adopted 2-D nanocomposite of zeolitic imidazolate framework (ZIF) attached on graphene oxide to effectively prevent plasticization of polyimide membrane under mixed gas condition. ZIF nanofillers, known as suitable additive for olefin/paraffin separation membranes, were grown on graphene oxide 2-D nanotemplates to maximize encounter frequency between gas permeant and nanofillers even in lower concentrations. The prepared MMMs successfully showed an improved mixed gas selectivity compapred to pristine membrane, indicating better anti-plasticization effect.

본 총설은 분리막기술이 적용된 수소생산에 대한 개론으로, 특히, 암모니아를 수소운반체로 이용하는 수소생산에 대한 연구결과를 중점적으로 서술하였다. 암모니아를 수소운반체로 적용한 수소생산은 추가적인 탄소생성이 없다는 점 외에 여러 측면에 있어 이점이 있다. 많은 연구들이 고순도 수소 분리 및 생산을 위한 분리막 개발을 위해 진행되고 있으며, 이들 중 팔라듐을 기본으로 한 분리막(예를 들어, 다공성 세라믹 또는 다공성 금속 지지체와 팔라듐 합금의 얇은 선택층으로 이루어진 분리막)에 대한 연구가 활발하다. 반면에, 효율적인 암모니아 분해를 위해서는 주로 루테늄 촉매가 적용되고 있으며, 루테늄과 지지체 및 촉진제로 이루어진 루테늄에 기반을 둔 촉매에 대한 연구발표가 다수 존재한다. 수소생산을 위한 분리막 반응기 형태로는 충전층, 유동층, 그리고 마이크로반응기 등이 있으며, 이들의 최적화 및 원활한 물질전달 연구는 현재진행형 이다. 또한, 높은 암모니아 분해율, 고순도 수소생산 및 높은 수소생산율을 얻기 위해 분리막과 촉매의 다양한 조합에 대한 연구 및 분리막과 촉매의 역할을 동시에 구현할 수 있는 분리막에 대한 연구가 발표되고 있다.

Poly(imide siloxane)(Si-PI)와 polyvinylpyrrolidone (PVP)를 혼합한 고분자를 사용하여 실리카가 함유된 탄소 분리막을 제조하였다. 고분자 혼합물의 열분해에 의해 제조 된 다공성 탄소 구조의 특성은 두 고분자의 미세 상 분리 거동과 관련이 있다. Si-PI와 PVP의 고분자 혼합물의 유리 전이 온도(Tg)는 시차 주사 열량계를 사용하여 단일 Tg로 관찰되었다. 또 한 C-SiO2 막의 질소 흡착 등온선을 조사하여 다공성 탄소 구조의 특성을 규명했다. Si-PI/PVP로부터 유도 된 C-SiO2 막은 IV형 등온선을 나타내었고 중간기공의 탄소 구조와 관련된 히스테리시스 루프를 가지고 있었다. 분자 여과 확인을 위해서, Si-PI/PVP의 비율과 열분해 온도 및 등온 시간과 같은 열분해 조건을 다르게 하여 C-SiO2 막을 제조하였다. 결과적으로, 120 분 간의 등온 시간 동안 550°C에서 Si-PI/PVP의 열분해에 의해 제조된 C-SiO2 막의 투과도는 820 Barrer (1 × 10-10 cm3 (STP) cm/cm2⋅s⋅cmHg)이었으며, O2/N2 선택도는 14이었다.

Among the fuel cell electrolyte candidates in the intermediate temperature range, glass materials show stable physical properties and are also expected to have higher ion conductivity than crystalline materials. In particular, phosphate glass has a high mobility of protons since such a structure maintains a hydrogen bond network that leads to high proton conductivity. Recently, defects like volatilization of phosphorus and destruction of the bonding structure have remarkably improved with introduction of cations, such as Zr4+ and Nb5+, into phosphate. In particular, niobium has proton conductivity on the surface because of higher surface acidity. It can also retain phosphorus content during heat treatment and improve chemical stability by bonding with phosphorus. In this study, we fabricate niobium phosphate glass thin films through sol-gel processing, and we report the chemical stability and electrical properties. The existence of the hydroxyl group in the phosphate is confirmed and found to be preserved at the intermediate temperature region of 150-450 oC.

Current petrochemical product mainly comes from light olefin, such as ethylene and propylene. these olefins can be obtained as mixture form of olefin/paraffin, which is co-product of naphtha cracking process. However, the mixture of light olefin and paraffin is considerably difficult to separate because they have similar physicochemical properties such as density, boiling point, and molecular weight. Cryogenic distillation is currently utilized, but still suffered from high operating cost. Membrane separation with polyimide-based material is a promising alternative due to its lower energy cost and modular operation. Here, we synthesized composite membrane with metal-organic framework (MOF) based on polyimide exhibiting high permeability and selectivity in propylene/propane separation, as well as simple preparation and high stability.

Separation of propylene and propane is one of the most important processes in the petrochemical industry due to the large demand of propylene as a feedstock for organic chemicals. It is now carried out with cryogenic distillation, which consumes a lot of energy due to a small differences in relative volatility of propylene and propane. The incorporation of a highly selective membranes has the potential to reduce the energy demands for the process. Polyimides, especially the 6FDA-based polyimide membranes offer excellent C3H6/C3H8 separation properties, chemical, thermal and mechanical stability. In this study, we synthesized polyimides from 6FDA and sterically hindered diamines containing ortho ethyl substituents. Characterization and gas permeation properties of propylene and propane were investigated.

Polyamide (PA) thin-film composite (TFC) membranes consisting of m-phenylenediamine (MPD) and trimesoylchloride (TMC)　monomers have been widely used in desalination process for decades. Still, a rational design of PA TFC membranes by tailoring monomer species and concentration could further reduce the energy consumption in desalination process. In this study, we prepared PA TFC membranes using mixed amine monomer depends on the number of -NH₂group and investigated the desalination performance of prepared membranes. The crosslinking between amine and acyl chloride group was confirmed by infrared spectroscopy regardless of amine species. Surface morphologies which were characterized using scanning electron microscopy (SEM) and atomic force microscopy (AFM) showed increased surface roughness.

Zeolitic imidazolate framework-8 (ZIF-8) has drawn attention as a nanofiller for thin-film nanocomposite (TFN) reverse osmosis (RO) membranes to improve desalination performance due to their high porosity and high surface area. Although a few studies on ZIF-8 embedded TFNs have been reported, size effects of ZIF-8 particles on TFNs have not yet been studied. In this work, TFNs incorporated with different sizes of ZIF-8 (small, middle, large) were prepared and the ZIF-8 particles were characterized using electron microscopy and XRD. All of TFNs incorporated with ZIF-8 showed a higher water permeance without losing NaCl rejection compared to the bare RO membranes. Remarkably, TFNs with middle size of ZIF-8 represented the highest water permeance, which is attributed to the highest volume fraction of ZIF-8 filler in polyamide matrix.

Recently, Graphene Oxide (GO) has extensively studied as a membrane material due to its 2D structure and high CO2 sorption property, however, GO membrane still has challenging issues; low gas permeability to apply to practical system and low stability under dry condition. In this study, we introduced GO as a nanofiller in CO2-philic polymer matrix because GO has molecular sieving property and 2D structure. First, we mixed two kinds of PEO-containing polymers by controlling the ratio of free volume in polymer networks to increase the permeability, and then, we added GO in the mixed polymer matrix for improving the CO2/N2 selectivity. Finally, we fabricated GO-incorporated mixed matrix membranes with high CO2/N2 separation performance beyond the upper bound. High long-term stability and high CO2/N2 selectivity were also achieved in mixed gas system.

Separation of light olefin and paraffin element is one of the most crucial issuses in petrochemical industry due to its profitable potential as precursor of petrochemical products, but facing technical predicament from similar physicochemical properties of two components. Membrane technology is considered as a good alternative for current cryogenic separation, however, current olefin/paraffin separation membranes are suffered from generally low permeability and selectivity, as well as its durability problem. Here, we have synthesized mixed matrix composite membrane using polyimide-based ZIF-8/graphene oxide 2-D nanocomposite, presenting high propylene/ propane separation performance and long-term stability.

원자 수준의 두께를 가지는 그래핀 단일층이 흑연으로부터 박리되어 구현된 이래로, 그래핀은 2차원 소재의 활용 가능성을 연 물질로서 각광받고 있으며, 그래핀 고유의 뛰어난 물리적 특성으로 인하여 활발히 연구되고 있다. 특히 분리막 분야는 그래핀과 산화 그래핀이 활용 가능한 가장 중요한 분야 중의 하나로서, 최근의 다양한 시뮬레이션 연구를 통하여 그 가능성이 입증되고 있다. 그래핀과 산화 그래핀은 원자 수준의 얇은 두께, 뛰어난 기계적 강도, 높은 수준의 내화학성, 기공 생성이 가능한 2차원 구조 또는 기체 확산 유로 생성이 가능한 적층 구조 등 분리막 소재로서 매우 유리한 특성들을 보유하 고 있음이 밝혀졌다. 본 총설에서는 그래핀과 산화 그래핀의 고유 특성을 기반으로 기체 분리막 분야로의 응용 가능성과 현 재까지의 개발 현황 및 향후 전망에 대하여 논하고자 한다.

For possibility of specific gas sieve and adsorption, metal organic framework has attracted expectation in the gas separation field. But, this enhances gas transport performance only at high loading. So we designed effective composite growing MOF on porous 2D template to improve membrane at low concentration. The mixed matrix membranes showed improved CO2 permeability drastically by improved CO2/N2 diffusion selectivity and showed anti-plasticization effect.

‘Upper bound’ is very well known notion in membrane field, which explains the trade-off relationship between permeability and selectivity in gas pairs. Many researches have worked on overcoming the current limitation in order to develop cost-effective and energy-efficient membrane system. Thus, understanding the intrinsic material properties (permeation, diffusivity and solubility) are prerequisite to set the strategy how to get over the upper bound. In this study, we introduced Quartz crystal microbalance to measure diffusion coefficient and compare the results to apparent diffusivity value obtained from the high-vauum time lag method. We consider the quartz type, temperature and pressure effect on diffusion coefficient and also characterize defect density of deposited film.

Recently, a few-layered graphene oxide (GO), which high CO2/N2 selective characters in the humidified feed, has been extensively investigated as a membrane material for gas and liquid separation. Although GO membrane is considered as one of promising membranes, it has a limitation to apply for practical application because of low CO2 permeance and low stability under dry condition. As such, in this study, we fabricated CO2-philic polymers and GO composite membranes by using GO as a filler for high CO2/N2 selectivity. We used two kinds of PEO-containing polymers to increase CO2 permeability by controlling the ratio of free volume in polymer networks. High CO2 permeability (~850barrer) and high CO2/N2 selectivity (~55) were achieved in CO2-philic composite membranes.

Graphene-based derivatives such as graphene oxide(GO) have great potential as membrane material due to their controllable d-spacing, extremely large surface area and tunability of multifunctional groups. GO, highly oxidized graphene, has especially good affinity to CO2 arose from its oxide functional groups(e.g. carboxylic acid, hydroxyl groups) on 2-D nanosheet plane. Here, we synthesized GO/polymer composite materials and fabricated large-area thin film composite(TFC) membrane for CO2 separation using polymeric porous support. Further, we have produced flat-sheet membrane modules with the TFC membranes and tested the performance of the module under CO2/N2 mixed gas and flue gas conditions. The membrane module exhibited high CO2 separation performance as 74% of purity and 22% of recovery under flue gas condition including CO2, O2 and N2.

Thin-film nanocomposite (TFN) reverse osmosis (RO) membranes have drawn keen attention to overcome the limitations in polymeric desalination membranes. However, preparation of TFN-RO membranes using conventional protocol involves problems such as a waste of expensive nanomaterials and inaccurate control of loading amount. In this work, we suggest a new protocol of TFN-RO membranes through pre-adsorption of carbon nanotubes (CNTs) on the support layer using spray coating. SEM images of spray coated supports showed well-dispersed adsorption of CNTs compared with those using conventional method. RO performances of TFN membranes using spray coating were comparable to conventionally prepared membranes. Thus, this new protocol is useful to prepare TFN membranes in terms of cost-efficiency.

Owing to high energy efficiency and superior efficacy, membrane-based desalination processes have gained widespread implementation in a wide variety of water treatment applications. Tremendous research efforts on new membrane materials have been made to improve the separation performance of the state-of-the-art thin-film composite (TFC) membranes, particularly polyamide TFC membranes, hoping to overcome the permeability-selectivity trade-off relations. Currently, many nanomaterials such as zeolites, metal-organic frameworks (MOFs), graphene oxide (GO), and carbon nanotubes (CNTs) have been explored to enhance the separation performance of existing polymeric membranes, but it has been argued that the positive transformation of nanomaterials-embedded TFC membranes hold promising potential to realize the sustainable development of current desalination membranes. Here we have tried to discuss some misconceptions and challenging items delaying industrial-scale implementation of nanomaterialsembedded desalination membranes.

그래핀 기반 소재는 높은 가공성과 초박성으로 인하여 분리막 소재로서 각광받고 있다. 본 연구에서는, 스핀 코팅 법을 이용하여 제조된 산화그래핀 분리막의 기체 투과 거동을 평가하였다. 산화그래핀 분리막의 구조는 산화그래핀의 크기와 산화그래핀 용액의 pH 조절을 통하여 조절될 수 있다. 산화그래핀의 크기가 작을수록 굴곡률이 작아짐에 따라 분리막의 기 체 투과도 및 선택도가 증가하는 경향을 보인다. 또한 산화그래핀에서의 기체 투과 거동은 적층된 산화그래핀 사이의 채널 크기에 따라 영향을 받는다. 특히 산화그래핀 분리막의 좁은 기공과 이산화탄소 선택적인 산화그래핀 자체의 특성으로 인하 여 산화그래핀 분리막은 이산화탄소에 대한 높은 투과도 및 선택성을 가지며, 이는 이산화탄소 포집에 적합한 특성을 가진다. 이러한 산화그래핀 분리막의 특이한 기체 투과 거동은 흡착-촉진 확산 거동(표면 확산 기작)으로 설명될 수 있다. 본 연구를 통하여 이산화탄소 선택성 분리막 소재 설계와 슬릿 형태의 기공과 적층 구조를 가진 분리막을 통한 기체 투과 거동 연구가 활발히 이루어질 것으로 기대한다.