Development of CO₂ Molecular Gate Membrane Module Systems for Pre-Combustion CO₂ Capture

Research and development of novel CO₂-selective membranes, called molecular gate membranes (MGMs), has been conducted. Unlike conventional CO₂-selective membranes, MGMs show exceptionally high CO₂ separation over H₂. The membranes and the membrane modules were developed for CO₂ separation at low energy consumption and low cost in pre-combustion processes such as integrated gasification combined cycle (IGCC) and hydrogen production. To date, two candidate membrane materials-poly(ethylene glycol) (PEG)-based and poly(vinyl alcohol) (PVA)-based membranes-have been used. As for PEG-based membrane materials, the effect of operating conditions, such as relative humidity in feed gas and sweep gas and operating pressure, on CO₂ separation performance were investigated. Both CO₂ permeance and selectivity increased with increasing relative humidity on both the feed and permeate sides. The CO₂ permeance increased from the 10^-12 to the 10^-11 order, while the selectivity increased from 2.8 to 25. In addition, it was found that the water vapor permeates from the high to the low relative humidity side with a permeance typically on the order of 10^-8 m³(STP)m^-2·s^-1·Pa^-1, regardless of the total pressure difference between the feed side and the permeate side. This finding is important in the design of membrane systems. However, we found that PVA-based membranes exhibited superior thin-film coating ability and higher separation performance compared with PEG-based membranes. As for PVA-based materials, membranes that showed high CO₂ separation performance under high-pressure conditions of 2.4 MPa (the supposed pressure in the IGCC process) were successfully prepared. In addition, the technology to prepare MGMs with a large membrane area was developed by a continuous membrane-forming method, and the membrane elements (diameter: 10-20 cm; length: 20-60 cm) were also fabricated. Pre-combustion CO₂ capture tests of the membrane elements were conducted using coal-derived gasification gas, and it was confirmed that the membrane elements were durable against the real gas, which contained components such as H₂S (on the order of 100 ppm) and CO (32.4%).