Membrane gas separation

Gas mixtures can be effectively separated by synthetic membranes made from polymers such as polyamide or cellulose acetate, or from ceramic materials.

While polymeric membranes are economical and technologically useful, they are bounded by their performance, known as the Robeson limit (permeability must be sacrificed for selectivity and vice versa). This limit affects polymeric membrane use for CO₂ separation from flue gas streams, since mass transport becomes limiting and CO2 separation becomes very expensive due to low permeabilities. Membrane materials have expanded into the realm of silica, zeolites, metal-organic frameworks, and perovskites due to their strong thermal and chemical resistance as well as high tunability (ability to be modified and functionalized), leading to increased permeability and selectivity. Membranes can be used for separating gas mixtures where they act as a permeable barrier through which different compounds move across at different rates or not move at all. The membranes can be nanoporous, polymer, etc. and the gas molecules penetrate according to their size, diffusivity, or solubility.

There are 3 main diffusion mechanisms, the first (b), Knudsen diffusion holds at very low pressures where lighter molecules can move across a membrane faster than heavy ones, in a material with reasonably large pores. The second (c), molecular sieving, is the case where the pores of the membrane are too small to let one component pass, a process which is typically not practical in gas applications, as the molecules are too small to design relevant pores. In these cases the movement of molecules is best described by pressure-driven convective flow through capillaries, which is quantified by Darcy’s Law. However, the more general model in gas applications is the solution-diffusion (d) where particles are first dissolved onto the membrane and then diffuse through it both at different rates. This model is employed when the pores in the polymer membrane appear and disappear faster relative to the movement of the particles.

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