Enhanced plasticization resistance of hollow fiber membranes via metal ion coordination for advanced helium recovery

Plasticization can significantly impair the gas separation performance of gas separation membranes, especially for hollow fiber membranes (HFMs) with ultrathin skin layer. While conventional thermal crosslinking is an effective method to address this issue, it often leads to the transition layer collapse in HFMs, resulting in a significant decrease in gas permeance. Herein, we fabricate polyimide-cerium (PI–Ce) complex HFMs using a carboxylic group-containing 6FDA-mPDA_0.65-DABA_0.3-TFMB_0.05 copolyimide through metal ion coordination to achieve plasticization-resistance helium recovery from natural gas. We optimized dope compositions and spinning conditions to produce defect-free hollow fiber membranes with a skin layer as thin as 300 nm. The coordination between carboxyl groups and cerium ions was characterized using Fourier Transform Infrared Spectroscopy (FTIR) and Extended X-ray Absorption Fine Structure (EXAFS) spectroscopy. The polymer-metal coordinated membranes exhibited enhanced gas selectivities compared to the pristine HFMs due to the tailored microporosity achieved through polymer-metal coordination. Furthermore, the PI-Ce HFMs demonstrated only a 10.8 % decline in mixed-gas He/CH₄ selectivity, which is significantly lower than the 55.4 % decline observed in pristine HFMs when exposed to CO₂-containing feed pressures below 400 PSIA. Molecular dynamics simulations confirmed that coordination confined molecular chain swelling, thereby suppressing plasticization caused by CO₂. The exceptional plasticization resistance of the PI-Ce complex HFMs provides a novel strategy for recovering helium from aggressive natural gas environments.