Antiplasticization and plasticization of Matrimid® asymmetric hollow fiber membranes—Part A. Experimental

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.