CMS membranes from PBI/PI blends: Temperature effect on gas transport and separation performance

This study reports pure gas permeability and diffusion coefficients for carbon molecular sieve membranes (CMSM) derived from dense membranes based on blends of a rigid polyimide PI DPPD-IMM (PI) and polybenzimidazole (PBI), PI/PBI, at different concentrations. The permeability, diffusion and selectivity for PI/PBI blend CMS membranes was systematically tested as a function of concentration and temperature. CMS membrane derived from pure PI DPPD-IMM membrane (PI100-600) exhibited the highest permeability coefficients (P-He = 960 Barrer, P-CO2 = 503 Barrer) and the highest separation factors (alpha(O2/N2) = 8.3 and alpha(CO)(2/CH4) = 56.5). Increasing PI concentration in the membranes blend precursors shows a positive effect on CMS membranes permeability, diffusion coefficients and selectivity. These results are attributed to an increase in micropores dimension that was reflected by the emergence of a d-spacing shift from 5.9 angstrom to 7.1 angstrom. It was also found that large concentrations of PBI (>50 wt%) in the precursor showed a negative effect on permeability and also in gas pair selectivity for carbon membranes which was attributed to carbazole-type strands densification of the structure. As PI concentration increases in PI/PBI CMS membranes, they present higher entropic selectivity and low energetic selectivity leading to the best permeability/selectivity relationship surpassing 2008 Robeson's upper bound for O-2/N-2 and CO2/CH4 gas pairs.