Diffusion of Alkane Mixtures in Zeolites:  Validating the Maxwell−Stefan Formulation Using MD Simulations

2005-04-07T00:00:00Z (GMT) by R. Krishna J. M. van Baten
Molecular dynamics (MD) simulations have been carried out for pure components, binary, ternary, and quaternary mixtures containing methane, ethane, propane, and n-butane in FAU zeolite at 300 K for a range of molecular loadings ϑ, approaching saturation limits. The n-dimensional matrix of Maxwell−Stefan (M−S) diffusivities [Δ], defined by (N) = −ρ[Δ][Γ](∇ϑ), was determined along with the self-diffusivities, Di,self. Additionally, configurational-bias Monte Carlo (CBMC) simulations were carried out to obtain the pure component sorption isotherms and the saturation capacities ϑi,sat. From the information on Δij, Di,self, and ϑi,sat, the various M−S diffusivities were determined:  (1) component Đi, reflecting the interactions of the species i with the zeolite, self-exchange Đii, and (2) binary exchange Đij. The obtained data underline the major advantage of the M−S formulation that at a given occupancy, θ = ϑii,sat within the zeolite, the Đi has nearly the same value for species i whether this species is present on its own or in a mixture with other species. The same advantage holds, too, for the self-exchange Đii; the value at a given occupancy, θ, is the same whether determined from pure component, binary, or ternary mixture data. For all binary and ternary mixtures studied, it was verified that the binary exchange coefficient Đij can be interpolated from the corresponding values of the self-exchange parameters Đii and Đjj using a generalization of the interpolation formula developed earlier (Skoulidas et al., Langmuir, 2003, 19, 7977). We also demonstrate that if the occupancy dependence of the pure component parameters Đi and Đii are modeled properly, this information is sufficient to provide very good estimates of the matrix [Δ] for mixtures with 2, 3, or 4 components over the entire range of loadings. Simulations of mixture diffusion of alkanes in MFI and LTA confirm that the above-mentioned advantages of the M−S formulation also hold for these zeolite topologies.