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The effect of humidity on the CO_2/N_2 separation performance of copolymers based on hard polyimide segments and soft polyether chains:Experimental and modeling

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Green Energy & Environment 2016年第3期1卷 201-210页

作者： Luca Olivieri Alberto Tena Maria Grazia De Angelis Antonio Hernández Giménez Angel E.Lozano Giulio Cesare Sarti Dipartimento di Ingegneria Civile Chimica Ambientale e dei Materiali Alma Mater Studiorum-Università di Bologna SMAP UA UVA-CSIC Universidad de Valladolid Facultad de Ciencias Real de Burgos s/n Helmholtz-Zentrum Geesthacht Institute of Polymer Research Instituto de Ciencia y Tecnología de Polímeros CSIC

In this work, we studied two copolymers formed by segments of a rubbery polyether（PPO or PEO） and of a glassy polyimide（BPDA-ODA or BKDA-ODA） suitable for gas separation and CO2 capture. Firstly, we assessed the absorption of water vapor in the materials, as a function of relative humidity（R.H.）, finding that the humidity uptake of the copolymers lies between that of the corresponding pure homopolymers ***, we studied the effect of humidity on CO2 and N2 permeability, as well as on CO2/N2 selectivity, up to R.H. of 75%. The permeability decreases with increasing humidity, while the ideal selectivity remains approximately constant in the entire range of water activity investigated. The humidity-induced decrease of permeability in the copolymers is much smaller than the one observed in polyimides such as Matrimid? confirming the positive effect of the polyether phase on the membrane ***, we modeled the humidity-induced decrease of gas solubility, diffusivity and, consequently, permeability, using a suitable approach that considers the free volume theory for diffusion and LF model for solubility. Such model allows estimating the extent of competition that the gases undergo with water during sorption in the membranes, as a function of the relative humidity, as well as the expected reduction of free volume by means of water molecules occupation and consequent reduction of diffusivity.

关键词： CO2 capture Humid gas permeation transport properties in polymeric membranes Water vapor sorption Modeling

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