Dense film membranes of the copolyimide 6FDA-DAM:DABA (3:2) are studied for simultaneous removal of CO2 and H2S from sour natural gas streams. Pure and mixed gas permeation as well as pure gas sorption data are reported at 35°C and pressures up to 62bar. The H2S partial pressures used are representative of highly aggressive field operations. Penetrant-induced plasticization effects are evident at feed pressures below 1bar in pure H2S feeds; sub-Tg thermal annealing is used to effectively mitigate this effect, and these annealed films are used throughout the study. Surprisingly, H2S/CH4 selectivity nearly doubles for mixed gas testing in comparison to the pure component ideal selectivity values and approaches the level of a state-of-the-art glassy polymer, cellulose acetate (CA), at H2S partial pressures above 2bar. Furthermore, permeation experiments using a 9.95% H2S, 19.9% CO2, 70.15% CH4 mixture at low feed pressures give CO2/CH4 selectivity of up to 49-over 30% greater than the pure component selectivity for 6FDA-DAM:DABA (3:2). The overall sour gas separation performance of this polyimide is comparable to high-performance rubbery polymer membranes, which have been reported for only moderate H2S partial pressure feeds, and is superior to that for CA based on a practical combined acid gas separation efficiency metric that we introduce. Finally, methods for continued development of the current polyimide membrane material for aggressive sour gas separations are presented. © 2012 Elsevier B.V.

A fluorinated, 6FDA based polyamide-imide is investigated for the purification of CH 4 from CO 2 and H 2S containing gas streams. Dense polymer films were thermally annealed and showed that increased annealing temperatures at constant annealing time caused transport behavior that does not resemble physical aging. Free volume increased after annealing at 200°C for 24h relative to annealing at 150°C for the same time. CO 2 and CH 4 permeabilities and diffusivities did not decrease as a result of the higher annealing temperature, and in fact, were shown to increase slightly. A change to the intrinsic microstructure that cannot be described by simple, densification based physical aging is hypothesized to be the reason for this trend. Furthermore, annealing increased CO 2 induced plasticization resistance and a temperature of 200°C was shown to have the greatest effect on plasticization suppression. Annealing at 200°C for 24h suppressed pure gas CO 2 plasticization up to 450psia. Fluorescence spectroscopy revealed increased intramolecular charge transfer, which is presumably due to increased electron conjugation over the N-phenyl bond. Additionally, intermolecular charge transfer increased with thermal annealing, as inferred from fluorescence intensity measurements and XRD patterns. 50/50 CO 2/CH 4 mixed gas permeation measurements reveal stable separation performance up to 1000psia. Ternary mixed gas feeds containing toluene/CO 2/CH 4 and H 2S/CO 2/CH 4 show antiplasticization, but more importantly, selectivity losses due to plasticization did not occur up to 900psia of total feed pressure. These results show that the polyamide-imide family represents a promising class of separation materials for aggressive acid gas purifications. © 2012 Elsevier B.V.

We report significantly enhanced propylene/propane (C 3H 6/C 3H 8) selectivity in mixed matrix membranes fabricated using 6FDA-DAM polyimide and a zeolitic imidazolate framework (ZIF-8). Equilibrium isotherms and sorption kinetics of C 3H 6 and C 3H 8 at 35°C were studied on a 200nm commercially available ZIF-8 sample produced by BASF. Mixed matrix dense films were formed with 6FDA-DAM and 200nm BASF ZIF-8 particles. SEM imaging showed generally good adhesion between the ZIF-8 and 6FDA-DAM without the need for surface-treating ZIF-8. Pure gas permeation showed significantly enhanced mixed matrix ZIF-8/6FDA-DAM membrane C 3H 6/C 3H 8 separation performance over the pure 6FDA-DAM membrane performance. A C 3H 6 permeability of 56.2Barrer and C 3H 6/C 3H 8 ideal selectivity of 31.0 was found in ZIF-8/6FDA-DAM mixed matrix membrane with 48.0wt% ZIF-8 loading, which are 258% and 150% higher than the pure 6FDA-DAM membrane, respectively for permeability and selectivity. Permeation properties of C 3H 6 and C 3H 8 in ZIF-8 were back-calculated by the Maxwell model for composite permeability using pure gas permeation data, leading to a C 3H 6 permeability of 277Barrer and C 3H 6/C 3H 8 selectivity of 122. Mixed gas permeation also verified that selectivity enhancements were achievable in mixed gas environment by ZIF-8. © 2011 Elsevier B.V.