(672b) Highly Cross-Linked Polymers for Membrane H2/CO2 Separation at Elevated Temperatures

Authors: 
Omidvar, M., University at Buffalo, The State University of New York
Swihart, M. T., University at Buffalo, The State University of New York
Lin, H., University at Buffalo, The State University of New York
Highly Cross-linked Polymers for Membrane H2/CO2 Separation at Elevated Temperatures

Maryam Omidvar, Mark Swihart, and Haiqing Lin

 

Department of Chemical and Biological Engineering

University at Buffalo, The State University of New York)

 

Membrane technology has attracted significant interest for pre-combustion H2 purification and CO2 capture. The key to the success of this technology is membrane materials with high H2 permeability and H2/CO2 selectivity at elevated temperatures of syngas processing (>100 °C). Polyimides such as P84 have been explored for H2/CO2 separation due to their strong size-sieving ability and resulting high H2/CO2 diffusivity selectivity. In this study, we demonstrate that these polymers can be cross-linked chemically to further improve H2/CO2 selectivity. We systematically evaluate the effect of cross-linking P84 using amines such as propane diamines, butane diamines and p-xylene diamine on the H2/CO2 separation properties. The cross-linking can significantly increase H2/CO2 selectivity while retaining moderate H2 permeability. For example, cross-linking of P84 with butane diamine with 42% conversion increases H2/CO2 selectivity from 2.4 to 8.0, while decreasing H2 permeability from 40 to 24 Barrers at 100 oC. The combination of 24 Barrers for H2 permeability and 8.0 for H2/CO2 selectivity is very close to the Robeson’s upper bound for H2/CO2 separation, demonstrating the potential of this approach for membrane development. These cross-linked polymers are thoroughly evaluated using FTIR, DSC, TGA, WAXD, and XPS. The effect of cross-linking degree on the physical properties will be discussed, including glass transition temperature, fractional free volume and pure- and mixed-gas H2/CO2 separation properties at various temperatures. This presentation will also discuss the fundamental structure/property relationship in these highly cross-linked polymers with promising H2/CO2 separation properties.