Next-generation carbon molecular sieve membranes derived from polyimides and polymers of intrinsic microporosity for key energy intensive gas separations and carbon capture

Abstract

Membrane gas separation possesses the advantages of energy-saving, simple operation, environmental friendliness, and economic efficiency than traditional separation processes. Carbon molecular sieve (CMS) membranes have attracted increasing interest due to their superior chemical resistance and thermal stability compared to polymer membranes, as well as the ability to overcome the limitations of the trade-off between permeability and selectivity commonly present in polymer membranes. Specifically, polyimides (PIs) and polymers of intrinsic microporosity (PIMs), hold the intrinsic advantages of designable structure, superior gas separation performances, as well as good thermal and mechanical strength, serves as excellent precursors for making CMS membranes. Although significant progress has been achieved in the study of PI- and PIM-derived CMS membranes in the past decades, there is still a lack of systematic research on their pyrolysis protocols. Herein, the current work reviewed the research progress of PI- and PIM-derived CMS membranes in the field of CO2 separation (CO2/CH4, CO2/N2 and CO2/H2) and olefin/paraffin separation, as well as the process simulation and tecno-economic analysis of the CMS membrane based gas separation processes. Particularly, the effect of pyrolysis protocols including pyrolysis temperature, ramping rate, pyrolysis atmosphere and soaking time on the pore structure and gas separation performance of PI- and PIM-derived CMS membranes were systematically summarized and discussed. In addition, similar to CMS made via other precursors, the PI and PIM precursors also play an important role in the final CMS membrane separation performance. Generally, CMS fabricated from PI and PIM precursors with higher free volume exhibited better gas separation performance. Overall, PIs and PIMs have been proven promising candidate precursors for CMS membrane fabrication. In addition, this review also offers perspectives and future research directions of next-generation PI- and PIM-derived CMS membranes for various gas separation applications.