The complex effects of highly sorbing feed gas contaminants such as toluene and n-heptane on performance of both annealed and non-annealed Matrimid® asymmetric fibers relevant to CO2/CH4 separation are reported. Membrane performance was quantified both during contaminant exposure and after removal of the contaminant from the feed stream. Exposure to either toluene or n-heptane during permeation reduces carbon dioxide permeance and the carbon dioxide/methane selectivity in non-annealed fibers. After exchange with a contaminant-free feed containing only CO2 and CH4 mixed gas, the carbon dioxide permeance and carbon dioxide/methane selectivity were affected, indicating a glassy state conditioning effect due to the prior contaminant exposure. Interestingly, the conditioning effect after simultaneous exposure to toluene and n-heptane (284 ppm toluene and 504 ppm n-heptane) was less than the conditioning observed for either toluene (293 ppm) or n-heptane (505 ppm) individually. Sub-Tg annealing reduced carbon dioxide permeance during actual contaminant exposure more severely than in non-annealed fibers. On the other hand, except for exposure to the highest n-heptane contaminant feed (2003 ppm), annealing significantly reduced the post-exposure conditioning observed in carbon dioxide permeance and carbon dioxide/methane selectivity. It appears that annealing allows the consolidation of segmental packing which stabilized the glassy matrix against swelling. At sufficiently high activities of even a relatively non-interacting penetrant like n-heptane, the annealing-induced stabilization can be reversed. © 2010 Elsevier B.V. All rights reserved.

A previous paper characterized effects of exposure of Matrimid® asymmetric fibers to either toluene or n-heptane or a combination of both contaminants during permeation. In all cases, reductions in the carbon dioxide permeance and the carbon dioxide/methane selectivity were observed for both annealed and non-annealed samples. In this paper, the respective potential impacts of competitive sorption, fiber compaction, and antiplasticization/plasticization on membrane performance during contaminant exposure are quantified and analyzed. The combined impact of competitive sorption and antiplasticization/plasticization are shown to account for the loss in membrane performance observed during exposure to highly sorbing feed stream contaminants. The dual mode transport model for penetrant mixtures was used to explain reduction in CO2 permeance due to competitive sorption effects, while free volume-based modeling explained decrease in CO2 permeance due to antiplasticization. Finally, the impact on CO2 permeance during exposure of the annealed Matrimid® fibers to contaminants is analyzed. The analysis is based on reduction in segmental mobility expected due to reduction of residual unrelaxed volume as compared to unanealed sample. © 2010.