Separation characteristics and dynamic behavior of two binary mixtures, CO2/CH4 (50:50, vol%) and CH4/N-2 (50:50, vol%), on methyltriethoxysilane templated silica (MTES) membrane were studied experimentally and theoretically. The permeation of the binary mixtures was compared with that of pure CO2, CH4, and N-2 at 323-473 K and 300-600 kPa. The permeation flux of pure CO2, which has the strong adsorption affinity, was much higher than that of CH4. However, the permeation flux of the CO2/CH4 mixture was hindered by CH4 with large kinetic diameter. Although the permeation flux of pure N-2 was higher than that of pure CH4, the permeation flux of CH4 in the CH4/N-2 mixture was greater than that of N-2 owing to the disturbance of N-2 permeation by CH4 and the relatively weak adsorption affinity of N-2. Because the molecular interactions, adsorption affinity, and kinetic diameter and structure of each component contributed to the separation, compared to the separation factors, the permselectivity was overestimated in the CO2/CH4 mixture, but somewhat underestimated in the CH4/N-2 mixture. Due to its kinetic effects, the diffusion mechanism of CH4 needs to be investigated thoroughly in pore-controlled silica-based membranes. The transient permeation and separation behaviors of the binary mixtures on MTES membranes were successfully predicted by the generalized Maxwell-Stefan model, which incorporated the dusty gas model and Langmuir isotherm model. (C) 2017 Elsevier B.V. All rights reserved.