Air separation by single wall carbon nanotubes: thermodynamics and adsorptive selectivity.

Separation of a nitrogen-oxygen mixture (air) by single wall carbon nanotubes has been studied using grand canonical Monte Carlo simulations at a range of nanotube diameters, temperatures, and pressures. It is demonstrated that depending on these operating parameters, the extent of adsorptive selectivity can vary significantly. Detailed calculations are also presented for the adsorption isotherms, energies, and isosteric heats of pure nitrogen, oxygen, and their mixture at 100 K in a carbon nanotube of 12.53-A diameter. In single-component simulations, it is found that near saturation loading nitrogen forms only an annular layer close to the nanotube wall, while smaller-sized oxygen also occupies the region near the center of the nanotube. In mixture adsorption, the energetically favored nitrogen is preferentially adsorbed at low loadings. However, at high loadings oxygen replaces nitrogen due to the dominant entropic effects, and therefore a high selectivity towards oxygen is observed close to the saturation loading. The effect of the entropic change on mixture adsorption is evident from the calculated isosteric heats of adsorption. The mixture isotherms obtained from simulations are found to be in good agreement with the predictions based only on the pure component simulation results.