Two swollen polyamide thin-film composite membranes were tested for effective CO2/CH4 separation. It was found that the water wettability has a key role for the separation of binary mixture representing a raw biogas, i.e. containing CO2 and CH4. The transport properties were analyzed by means of a mathematical model simulating gas permeation. A new modification of the mass transport coefficient model provided the concentration profiles of individual components on both sides of the membrane (inaccessible in experiments). Furthermore, the model enabled the evaluation of the mass transport coefficients of the gases in the mixture under varying stream flow rates and arrangements with respect to the membrane separation cell size. Therefore, the possibility of scale-up was discussed for both membranes and flow cell arrangement. Although the mathematical model was developed for a flat sheet membrane configuration, the results can be applied for a real spiral wound module with a wider surface.