Gas Sorption, Diffusion and Permeation in a Polymer of Intrinsic Microporosity (PIM-7)

  • Nasser Y. Alaslai

Student thesis: Master's Thesis


The entire world including Saudi Arabia is dependent on natural gas to provide new energy supplies for the future. Conventional ways for gas separation are expensive, and, hence, it is very important to reduce the cost and lower the energy consumption. Membrane technology is a relatively new separation process for natural gas purification with large growth potential, specifically for off-shore applications. The economics of any membrane separation process depend primarily on the intrinsic gas permeation properties of the membrane materials. All current commercial membranes for natural gas separation are made from polymers, which have several drawbacks, including low permeability, moderate selectivity, and poor stability in acid gas and hydrocarbon environments. The recent development of polymeric materials called “polymers of intrinsic microporosity” (PIMs) provide a new class of high-performance membrane materials that are anticipated to be used in natural gas separation processes including, but not limited to, acid gas removal and separation of hydrocarbons from methane. PIM-7 is an excellent example of a material from the PIMs series for gas separation. It was selected for this work since it has not been extensively tested for its gas permeation properties to date. Specifically, sorption and mixed-gas permeation data were not available for PIM-7 prior to this work. Sorption isotherms of N2, O2, CH4, CO2, C2H6, C3H8 and n-C4H10 were determined over a range of pressures at 35 oC for PIM-7 using a custom-designed dual-volume pressure decay system. Condensable hydrocarbon gases, such as C3H8 and n-C4H10, show significantly higher solubility than the other less condensable gas of the test series due to their high affinity to the polymer matrix. Dual-mode sorption model parameters were determined from the sorption isotherms. Henry’s law solubility, Langmuir capacity constant and the affinity constant increased with gas condensability. Permeability coefficients of He, H2, N2, O2, CH4, CO2, C2H6, C3H8 and n-C4H10 were measured at 35 oC and 2 atm feed pressure using a home-made constant-volume/variable pressure pure-gas permeation system. Hydrocarbon-induced plasticization of PIM-7 was confirmed by measuring the permeability coefficients of C3H8 and n-C4H10 as function of pressure at 35 oC. Diffusion coefficients were calculated from the permeability and solubility data at 2 atm for all penetrants tested and as function of pressure for C3H8 and n-C4H10; the values for C3 and C4 increased significantly with pressure because of plasticization. Physical aging was studied by measuring the permeability coefficients of a number of gases in fresh and aged films. Mixed-gas permeation tests were performed for a feed mixture of 2 vol% n-butane and 98 vol% methane. Based on BET surface area measurements using N2 as a probe molecule, PIM-7 is a microporous polymer (S = 690 m2/g) and it was expected to exhibit selectivity for n-butane over methane, as previously observed for other microporous polymers, such as PIM-1 and PTMSP. Surprisingly, PIM-7 is more permeable to methane than n-butane and exhibits a mixed-gas methane/n-butane selectivity of up to 2.3. This result indicates that the micropore size in PIM-7 is smaller than that in other PIMs materials. Consequently, PIM-7 is not a suitable candidate membrane material for separation of higher hydrocarbons from methane.
Date of AwardMay 8 2013
Original languageEnglish (US)
Awarding Institution
  • Physical Science and Engineering
SupervisorIngo Pinnau (Supervisor)


  • Natural Gas
  • Gas Separation
  • Permeation
  • Sorption
  • PIM-7
  • PIMs
  • Mixed Gas

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