Carbon molecular sieve membranes for nitrogen/methane separation

Nitrogen-selective Carbon Molecular Sieve (CMS) membranes were developed for nitrogen/methane separation. Effects of pyrolysis conditions including pyrolysis temperature protocol and pyrolysis atmosphere were studied for Matrimid® and 6FDA:BPDA-DAM precursors. It was revealed that high pyrolysis temperature is essential to achieve attractive nitrogen/methane selectivity due to the subtle size difference between the two gas penetrants. Detailed study on one of the best performing CMS membranes showed that diffusion selection, more specifically, the entropic factor responsible for diffusion selection provides a significant contribution to the high selectivity. The effect of precursor was studied by considering nine carefully selected polymers. The structures and properties of these polymer precursors were compared and correlated with the separation performance of resulting CMS membranes. The translation of intrinsic CMS transport properties into the hollow fiber morphology was also explored. Substructure collapse and asymmetry lost during pyrolysis were observed, which resulted in significant increases of separation layer thickness and decreases in permeance. Vinyltrimethoxy silane (VTMS)-treatment was applied to polymer hollow fiber before pyrolysis to overcome the problem of substructure collapse. The effects of VTMS-treatment on both the substructure and skin layer are discussed.Ph.D