Abstract

The effect on the gas transport properties of Matrimid®5218 of blending with the polymer of intrinsic microporosity PIM-EA(H2)-TB was studied by pure and mixed gas permeation measurements. Membranes of the two neat polymers and their 50/50 wt % blend were prepared by solution casting from a dilute solution in dichloromethane. The pure gas permeability and diffusion coefficients of H2, He, O2, N2, CO2 and CH4 were determined by the time lag method in a traditional fixed volume gas permeation setup. Mixed gas permeability measurements with a 35/65 vol % CO2/CH4 mixture and a 15/85 vol % CO2/N2 mixture were performed on a novel variable volume setup with on-line mass spectrometric analysis of the permeate composition, with the unique feature that it is also able to determine the mixed gas diffusion coefficients. It was found that the permeability of Matrimid increased approximately 20-fold with the addition of 50 wt % PIM-EA(H2)-TB. Mixed gas permeation measurements showed a slightly stronger pressure dependence for selectivity of separation of the CO2/CH4 mixture as compared to the CO2/N2 mixture, particularly for both the blended membrane and the pure PIM. The mixed gas selectivity was slightly higher than for pure gases, and although N2 and CH4 diffusion coefficients strongly increase in the presence of CO2, their solubility is dramatically reduced as a result of competitive sorption. A full analysis is provided of the difference between the pure and mixed gas transport parameters of PIM-EA(H2)-TB, Matrimid®5218 and their 50:50 wt % blend, including unique mixed gas diffusion coefficients.

Highlights

  • Significant progress has been made in the development of new polymers for the fabrication of gas separation membranes

  • While the CO2 and CH4 permeability of polysulfone/Matrimid® 5218 blend membranes increase with the polyimide content, there is an optimum in the CO2 /CH4 mixed gas selectivity ('30) for the blend with 20% of Matrimid [18]

  • The membrane performance for two relevant industrial separations was investigated via mixed gas permeability measurements on the pristine Matrimid® 5218, polymers of intrinsic microporosity (PIMs)-EA(H2 )-Tröger’s Base (TB) and on the

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Summary

Introduction

Significant progress has been made in the development of new polymers for the fabrication of gas separation membranes. While the CO2 and CH4 permeability of polysulfone/Matrimid® 5218 blend membranes increase with the polyimide content, there is an optimum in the CO2 /CH4 mixed gas selectivity ('30) for the blend with 20% of Matrimid [18] With their unique properties, starting with PIM-1 [19] that defined the 2008 Robeson upper bound [2], numerous new PIMs with a wide range of different chemical structures [6,20,21,22,23,24,25,26,27,28] and increasingly efficient gas separation performance, have moved the Robeson upper bounds further for several gas pairs [3]. Single gas permeation tests were gas permeation setup with the unique possibility to determine the mixed gas diffusion coefficients carried out at 25 °C and at a feed pressure of 1 bar, using a fixed-volume pressure increase instrument will provide unprecedented information on the coupling effect between CO2 and CH4 or CO2 and N2 during permeation of the respective mixtures in the neat polymers and the blend

Materials
Membranes Characterization
Discussion
Mixed Gas Permeability
REVIEW
Mixed Gas Diffusion and Solubility
Robeson Plots and Comparison with Literature Blend-Data
Conclusions
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