20 여 가지의 형태의 제올라이트 중에서 8-membered ring (8 MR) 구조를 지닌 제올라이트를 다공성 지지층 위에 연속적인 분리막 형태로 제작하고자 한다. 이 때, 궁극적인 분리막의 사용처에 해당되는 배가스 및 바이오가스 조건에서 이산화탄소를 분리하는 데 적합하도록 설계한 제올라이트 분리막에 대해 기술하고자 한다. 특히, 10% 정도의 수분에 의한 악영향을 최소화할 수 있는 방법에 대해 발표하고자 한다.

분자체(molecular sieve)로 알려진 제올라이트 분리막 중에 8-membered ring(8 MR) 구조를 지닌 제올라이트를 다공성 지지층 위에 연속적인 분리막 형태로 제작하고자 한다. 8 MR 구조 중에서도 소수성을 띠는 제올라이트 기반으로 높은 이산화탄소 선택적인 분리 능력을 보이고자 한다. 특히, 이산화탄소를 분자 크기가 큰 질소나 메탄으로부터 분리하는 게 아니라, 도전적인 과제로서 수분이 존재하는 feed 조건에서 높은 이산화탄소 분리 능력을 지닐 수 있도록 분리막을 제작하고자 한다. 이번 발표에서는 최근에 얻은 제올라이트 분리막을 만드는 방법과 그 방법으로 제작한 제올라이트 분리막의 이산화탄소 분리능력에 대해 발표하고자 한다.

A ZIF-8 membrane was prepared via counter diffusion method. To control the diffusion rate, two supports with different pore structure were employed, conventional and modified α-Al2O3 disc; disc A and disc B. The ZIF-8 membranes are derived their name from the supports; ZIF-8-A and ZIF-8-B. While ZIF-8-A was grown at the surface of the disc A, ZIF-8-B was grown inside the disc B. At 200°C, ZIF-8-A and -B exhibited H2/CO2 separation factor (SF) of 6.69 and 8.21. In long-term thermal stability tests, both ZIF-8-A and -B were withstood their properties at 200 and 250°C for 72 h. At 300°C, SF of ZIF-8-A fell after ~2 h, however, that of ZIF-8-B dropped after ~10 h. To sum up these features, ZIF-8-B showed higher H2 selectivity and thermal stability than ZIF-8-A, since ZIF-8 membrane was synthesized inside of the support.

Defects of zeolite membranes often lower their separation performance. Thus, the investigation of the defects is highly critical in achieving high separation performance. While general characterization methods (e.g. scanning electron microscopy; SEM) that examine the membrane surface cannot detect defects, the FCOM measurement is able to identify the defective structure inside the zeolite membrane using dye molecules of appropriate size [1]. In this work, various dyeing conditions (times and concentrations) were applied to a MFI zeolite membrane in an attempt to investigate the defective structure. Furthermore, the quantitative analysis is practiced to measure the defects in numerical form.

An all-silica deca-dodecasil 3R (Si-DDR) zeolite with a pore size of 0.36*0.44 nm2 is highly desirable for membrane-based separation of CO2 from N2, which critical in the post-combustion carbon capture process, via molecular recognition of their slight size difference. For the first time, we acquired h0h-oriented, hydrophobic DDR zeolite films through epitaxial growth of a DDR seed layer with a structure directing agent of methyltropinium iodide. The degree of the out-of-plane orientation and inter-growth was increased with the secondary growth time, while reducing the defects that provide non-selective pathways. The resulting DDR membrane showed a CO2/N2 separation factor (SF) as high as 11.9 at 50°C under dry conditions. More desirably, it could achieve a much enhanced CO2/N2 SF of up to 15.9 at 50°C in the presence of H2O vapor.

분자체(molecular sieve)로 알려진 제올라이트 분리막 중에 8-membered ring (MR) 구조를 지닌 제올라이트를 연속적인 분리막 형태로 제작하고자 한다. 8 MR 구조 중에서도 DDR 유형의 제오라이트 기반으로 이산화탄소에 대해 분자체 역할을 할 수 있는 분리막으로 사용할 수 있음을 보이고자 한다. 단순히 이산화탄소를 다른 분자 크기가 큰 질소나 메탄으로부터 분리하는 게 아니라, 도전적인 과제로서 수분이 존재하는 feed 조건에서 높은 이산화탄소 분리 능력을 지닐 수 있도록 분리막을 제작하고자 한다. 이번 발표에서는 최근에 얻은 DDR 유형 제올라이트 분리막을 만드는 방법과 그 분리막의 이산화탄소 분리 능력에 대해 발표하고자 한다.

Defects of zeolite membranes often lower their separation performance. Thus, the investigation of the defects is highly critical in achieving high separation performance. While general characterization methods (e.g. scanning electron microscopy; SEM) that examine the membrane surface cannot detect defects, the FCOM measurement is able to identify the defective structure inside the zeolite membrane using dye molecules of appropriate size [1]. In this work, various dyeing conditions (times and concentrations) were applied to a MFI zeolite membrane in an attempt to investigate the defective structure. Furthermore, the quantitative analysis is practiced to measure the defects in numerical form.

A ZIF-8 membrane was prepared via counter diffusion method. To control the diffusion rate, two supports with different pore structure were employed, conventional and modified α-Al2O3 disc; disc A and disc B. The ZIF-8 membranes are derived their name from the supports; ZIF-8-A and ZIF-8-B. While ZIF-8-A was grown at the surface of the disc A, ZIF-8-B was grown inside the disc B. At 200 °C, ZIF-8-A and -B exhibited H2/CO2 separation factor (SF) of 6.69 and 8.21. In long-term thermal stability tests, both ZIF-8-A and -B were withstood their properties at 200 and 250 °C for 72 h. At 300 °C, SF of ZIF-8-A fell after ~2 h, however, that of ZIF-8-B dropped after ~10 h. To sum up these features, ZIF-8-B showed higher H2 selectivity and thermal stability than ZIF-8-A, since ZIF-8 membrane was synthesized inside of the support.

Membrane-based CO2 capture is an energy-saving way to separate CO2 from N2 in post-combustion. Chabazite (Si-CHA) zeolites with a pore size of 0.37 nm × 0.42 nm are expected to separate CO2 from larger N2 (0.364 nm) by recognizing minute size differences. The pore mouth size on the Si-CHA zeolites outer surface was reduced via the chemical vapor deposition (CVD) to increase the molecular sieving effect by disfavoring the penetration of N2. The CVD process was conducted on CHA membranes to improve their CO2/N2 separation performance. Compared to the intact CHA membranes, the CO2/N2 max separation factor for CVD-treated CHA membranes increased by ~2.5 fold under dry conditions and by ~6.4 fold under wet conditions. It is noteworthy that the membrane kept its separation performance without degradation in the presence of H2O.