본 실험에서는 Ti를 기반으로 한 평판 수소 분리막을 설계하여 제조하였다. 새로운 조성의 Ti를 베이스로 한 수소 분 리막을 찾기 위하여 여러 합금들의 물리화학적 특성과 수소투과도 사이의 상관관계에 대해 조사하였다. 이를 바탕으로 신조성의 합금막 2종(Ti14.2Zr66.4Ni12.6Cu6.8 (70 μm), Ti17.3Zr62.7Ni20 (80 μm))을 설계 및 제조하였다. 제조된 평판 수소 분리막은 300~500°C, 1~4 bar의 조건에서 혼합 가스(H2, N2), sweep 가스(Ar)를 이용하여 수소 투과 실험을 진행하였다. Ti14.2Zr66.4Ni12.6Cu6.8 합금 막은 500°C, 4bar에서 최대 16.35 mL/cm2min의 flux를 가지며, Ti17.3Zr62.7Ni20 합금막은 450°C, 4 bar에서 최대 10.28 mL/ cm2min의 flux를 가진다.

에너지 패러다임의 변화가 요구되는 현대에 수소는 매력적인 에너지원이다. 이러한 수소를 정제하는 기술 중에서 분리막을 이용한 기술은 저비용으로 고순도의 수소를 정제할 수 있는 기술로 주목받고 있다. 그러나 수소 분리 성능이 뛰어 난 팔라듐(Pd)은 가격이 매우 비싸 이를 대체한 소재가 필요하다. 본 연구에서는 수소 투과 성능은 좋으나 수소 취성에 약한 니오븀(Nb)과 수소 투과 성능은 떨어지나 내구성이 뛰어난 니켈(Ni)과 지르코늄(Zr)을 혼합한 합금으로 분리막을 제조하여 1~4 bar, 350~450 °C 조건에서 수소 투과 특성을 확인하였다. Pd를 코팅하지 않은 Ni48Nb32Zr20 분리막의 경우 최대 0.69 ml/cm2/min의 투과량을 보였으며, Pd가 코팅된 경우에는 최대 13.05 ml/cm2/min의 투과량을 보였다.

수소 동위 원소는 중성자 수에 따라 경수소, 중수소, 삼중수소로 분류될 수 있으며, 각 원소는 특정 분야에서 사용 되고 있다. 구체적으로, 중수소는 전자 산업, 원자력에너지 산업, 분석기술 산업, 의약품 산업, 그리고 통신 산업에서 관심을 받고 있다. 냉각 증류, 열 주기 흡수 공정, Girdler sulfide 공정, 그리고 수전해와 같은 기존의 방법들은 각각의 장단점을 가지 고 있지만, 공통적으로 막대한 에너지를 필요로 하는 공정에 기반한다는 문제점을 가지고 있다. 높은 에너지 효율을 보이는 기술을 기반으로 분리하는 공정의 개발이 요구되는 실정이다. 이런 맥락에서 막을 사용한 수소 동위 원소 분리 기술이 에너 지 소비를 줄이는 유망한 해결책 중 하나라 볼 수 있다. 이 총설에서는 분리막을 활용한 수소 동위원소 분리에 관한 선행 연 구와 그들의 작동 원리를 소개하고자 한다. 특히 최근 제시되고 있는, 그래핀 기반 전기적 펌핑을 통한 수소 동위원소 분리 기술에 대하여 다루고자 한다. 분리막을 활용한 수소 동위원소 분리에 대한 기술은 이제 개념이 제안되기 시작한 단계이며, 많은 부분에서 해결해야 할 난제가 있다. 그러나 이를 달성할 경우 경제적인 효과가 상당할 것으로 판단된다. 이를 위한 향후 연구 방향에 대해서 논하고자 한다.

본 실험에서는 α-Al2O3 지지체에 무전해도금을 이용하여 Pd-Ag-Cu 분리막을 제조하였다. Pd, Ag, Cu는 각각 무 전해도금을 통해 지지체 표면에 코팅하였고, 합금의 형성을 위해 무전해도금 중간에 H2, 500°C의 조건에서 18 h 동안 열처리 를 진행하였다. 이를 통해 제조된 Pd-Ag-Cu 분리막은 SEM을 통해 표면을 관찰하였으며, Pd 분리막의 두께는 7.82 μm, Pd-Ag-Cu 분리막의 두께는 3.54 μm로 측정되었다. EDS와 XRD 분석을 통해 Pd-Ag-Cu 합금이 Pd-78%, Ag-8.81%, Cu-13.19%의 조성으로 형성된 것을 확인하였다. 기체투과 실험은 H2 단일가스와 H2/N2 혼합가스에서 실험을 진행하였다. H2 단일가스에서 측정한 수소 분리막의 최대 H2 flux는 Pd 분리막의 경우 450°C, 4 bar에서 74.16 ml/cm2·min이고, Pd-Ag-Cu 분리막의 경우 450°C, 4 bar에서 113.64 ml/cm2·min인 것을 확인하였고, H2/N2 혼합가스에서 측정한 separation factor의 경우 450°C, 4 bar에서 각각 2437, 11032의 separation factor가 측정되었다.

본 연구에서는 중공사형 이산화탄소 분리막 모듈을 사용하여 수소개질기 배가스로부터 이산화탄소 포집을 목적 으로 한 분리막 공정 최적화 연구를 진행하였다. 랩스케일의 소형 분리막 모듈을 사용하여 혼합기체를 대상으로 이산화탄소 순도 90% 및 회수율 90%을 달성하는 2단 공정 조건을 도출하였다. 막 면적이 정해진 모듈의 분리막 공정에서는 스테이지-컷, 주입부 및 투과부 압력에 따라서 포집 순도 및 회수율이 모두 다르게 나타나기 때문에 운전 조건에 대한 최적화가 필수적이 다. 본 연구에서는 다양한 운전 조건에서 1단 분리막에서 보이는 공정 포집 효율의 한계를 확인하고, 높은 순도와 회수율을 동시에 달성하기 위한 2단 회수 공정을 최적화하였다.

The physicochemical similarities of hydrogen isotopes have made their separation a challenging task. Conventional methods such as cryogenic distillation, Girdler sulfide process, chromatography, and thermal cycling absorption have low separation factors and are energy-intensive. To overcome these limitations, research has focused on kinetic quantum sieving (KQS) and chemical affinity quantum sieving (CAQS) effects for selective separation of hydrogen isotopes. Porous materials such as metal-organic frameworks (MOF), covalent organic frameworks (COF), zeolites, carbon, and organic cages have been studied for hydrogen separation. In this study, we focus the enhancement for CAQS to provide the cations due to the chemical affinity between hydrogen isotope and unsaturated sites by cations in zeolite beads. Cation exchanged zeolite beads was synthesized with cobalt, copper, nickel, iron and silver in zeolite 4A beads. Synthesized cation exchanged zeolite was analyzed for the surface area and pore size in N2 and adsorption behaviors of hydrogen isotopes (D2/H2) for various cation exchanged zeolite beads using BET at 77 K. The study predicts the D2/H2 adsorption selectivity based on the results obtained with BET. These hydrogen isotope adsorption results will provide a foundation for future processes for tritium separation.

Tritium is radioactive isotope, emitting beta ray, released as tritiated water from nuclear power plants. Due to the danger of radioactive isotope, the appropriate separation of tritium is essentially carried out for environment and safety. Further, it is also promising material for energy production and research. The tritiated water can be treated by diverse techniques such as water distillation, cryogenic distillation, Girdler-sulfide process, and catalytic exchange. After treatment, it is more desirable to convert as gas phase for storage, comparing to liquid phase. However, achieving complete separation of hydrogen gases with very similar physical and chemical properties is significantly challenging. Thus, it is necessary to develop materials with effective separation properties in gas separation. In this presentation, we present hydrogen isotope separation in the gas phase using modified mesoporous silica. Mesoporous silica is a form of silica that is characterized by its mesoporous structure possessing pores that range from 2 to 50 nm in diameter. This material can be functionalized to selectively capture and separate molecules having specific size and affinity. Here, the silver and copper incorporated mesoporous silica was synthesized to tailor a chemical affinity quantum sieving effect, thereby providing separation efficiency in D2/H2. The adsorption quantities of H2 and D2 were determined by sorption study, and the textural properties of each mesoporous silica were analyzed using N2 physisorption. The selectivity (D2/H2) in diverse feed composition (1:1, 1:9, and 1:99 of D2/H2) was estimated by applying ideal adsorbed solution theory to predict the loading of the gas mixture on bare, Ag- and Cu-mesoporous silica based on their sorption study. Further, the performance of each mesoporous silica was evaluated in the breakthrough adsorption under 1:1 mixture of D2 and H2 at 77 K.

Pt/C catalysts were prepared using black carbon (CB), and evaluated for their potential application as a catalyst of liquid-phase catalystic exchange for tritium treatment. CB was treated with 10% H2O2 solution for 0 and 2 hours at 105°C, Ethylene glycol and 40wt% Pt were added to the dried treated sample to prepare a Pt/C catalyst. The physical and chemical properties of the prepared catalysts were evaluated by BET, XRD, elemental analysis (EA), and TEM analyses. As a result of BET analysis, the surface area of CB without 10% H2O2 was 237.2 m2·g-1, and after treatment with 10% H2O2, it decreased to 181.2 m2·g-1 for 2 hours. However, the internal surface area increased, indicating the possibility that more Pt could be distributed inside the CB treated with 10% H2O2. In the XRD analysis results, the presence of Pt was confirmed by observing the Pt peak in the prepared Pt/C catalyst, and it was also observed through TEM analysis that Pt was evenly distributed within the CB. The elemental analysis (EA) results showed that the ratio of S and N decreased and the ratio of O increased with increasing 10% H2O2 treatment time. The H2O2 treated carbon supported Pt catalysts and polytetrafluoroethylene were then loaded together on a foamed nickel carrier to obtain hydrophobic catalysts. Our hydrophobic Pt catalyst using H2O2 treated black carbon are expected to be usefully used in the tritium treatment system.

Hydrogen isotope separation involves the separation of hydrogen, deuterium, tritium, and their isotopologues. It is an essential technology for removing radioactive tritium contamination and for obtaining valuable hydrogen isotope resources. Among various hydrogen isotope separation technologies, water electrolysis technology exhibits a high separation factor. Consequently, the electrolysis of tritiated water is of paramount importance as a tritium enrichment method for treating tritium-contaminated water and for analyzing tritium in environmental samples. More recently, hydroelectrolysis technology, which utilizes proton exchange membranes (PEM) to reduce water inventory, has gained favor over traditional alkaline hydroelectrolysis. Nevertheless, it is crucial to decrease the hydrogen permeability of the PEM in order to mitigate the explosion risk associated with tritium hydrogen electrolysis devices. Additionally, efforts are needed to enhance the hydrogen isotope selectivity of the PEM and optimize the manufacturing process of the membrane-electrode assembly (MEA), thereby improving both hydrogen isotope separation performance and water electrolysis efficiency. In this presentation, we will delve into two key aspects. Firstly, we’ll explore the reduction of hydrogen permeability and the enhancement of the hydrogen isotope separation factor in PEM through the incorporation of 2D nanomaterial additives. Secondly, we’ll examine the influence of various MEAs preparation methods on electrolysis and isotope separation performances. Lastly, we will discuss the effectiveness of the developed system in separating deuterium and tritium.

The separation of hydrogen isotopes is a critical issue in various fields, such as deuterium or tritium production and the treatment of radioactively contaminated water. In this presentation, we describe the pervaporative separation of hydrogen isotopes using proton conductive membranes and underlying separation mechanism. We investigated the H/D separation factors of perfluorosulfonic acid (Nafion) and polybenzimidazole membranes using pervaporation, and found that both membranes exhibited similar separation factors of approximately 1.026. Water permeation flux through the membranes was highly dependent on their thickness and type, and increased with operation temperature. However, the effect of temperature on H/D separation factor was negligible. We also demonstrated the cascade separation of H/D, indicating the potential application of multi-stage operation. We found that surface transport mechanisms such as hydron hopping contributed the most to H/D separation during the pervaporation process of proton conductive membranes.

The physicochemical similarities of hydrogen isotopes have made their separation a challenging task. Conventional methods such as cryogenic distillation, Girdler sulfide process, chromatography, and thermal cycling absorption have low separation factors and are energy-intensive. To overcome these limitations, research has focused on kinetic quantum sieving (KQS) and chemical affinity quantum sieving (CAQS) effects for selective separation of hydrogen isotopes. Porous materials such as metal-organic frameworks (MOF), covalent organic frameworks (COF), zeolites, carbon, and organic cages have been studied for hydrogen separation. This study have the literature review for previous research on D2/H2 adsorption and analyzes the D2/H2 adsorption behaviors of hydrogen isotopes for various zeolite using BET at 77 K. The study predicts the D2/H2 adsorption selectivity based on the results obtained with BET. These hydrogen isotope adsorption fundamentals provide a foundation for future processes for tritium separation.

Water electrolysis is an efficient method to enrich heavy hydrogen isotopes (tritium and deuterium) in the aqueous phase. Although an alkaline water electrolyzer has been commercialized for mass production of hydrogen, such a method requires additional purification steps to remove electrolytes from the final concentrates. On the other hand, proton exchange membrane water electrolysis (PEMWE) does not require additional electrolyte treatment steps, and PEMWE is operated at higher current density compared to the alkaline water electrolysis. In this study, we investigated deuterium and tritium separation from light water by PEMWE. Separation behaviors at the anode and cathode were analyzed, and H/D and H/T separation factors were compared.

Hydrogen isotopes (H, D, T) separation technologies have received great interest for treatments of tritiated liquid waste produced in Fukushima. In addition, the separated deuterium and tritium can be utilized in various industries such as semiconductors and nuclear fusion as expensive and rare resources. However, separating hydrogen isotopes in gas and liquid forms still requires energyintensive processes. To improve efficiency and performance of hydrogen isotope separation, we are developing water electrolysis, cryosorption, distillation, isotope exchange, and hydrophobic catalyst technologies. Furthermore, an analytical method is studied to evaluate the separation of hydrogen isotopes. This presentation introduces the current status of hydrogen isotope research in this research group.