Carbon dioxide and methane gas permeations in thermally annealed and chemically cross-linked commercial polyimide hollow fiber membrane

Two types of modifications were performed on a commercial polyimide (PI) hollow fiber membrane for carbon dioxide (CO2) and methane (CH4) gas permeations. Thermal annealing was conducted between 50- and 200 °C while chemical cross-linking was performed using 0.1- to 1.0 wt% of N, (1-Naphthyl) ethylene-diamine dihydrochloride (NED). Membrane characterization revealed densification of the thermally annealed PIs. But formation of macrovoids was observed in PIs annealed near its glass transition temperature (207 °C). Fourier transform infrared spectroscopy confirmed the successful cross-linking of NED with PI. Highest CO2 permeance was obtained from pristine PI (P/L=225 GPU) but it also had the lowest selectivity (α=72). The performances of thermally annealed (P/L=160–219 GPU, α=76–106), NED crosslinked (P/L=68–139 GPU, α=65–95) and thermally induced NED cross-linked (P/L=51-91 GPU, α=98–138) PIs varied according to modification conditions. Among the modified membranes, highest CO2 permeance was obtained from thermally annealed PI at 100 °C (P/L=211GPU, α=106) while thermally induced NED cross-linked PI (100 °C, 0.5 wt% NED) exhibited the highest selectivity (P/L=91, α=138). Both modified membranes are the best candidates for CO2/CH4 separation.