Breakthrough analysis of the CO 2 /CH 4 separation on electrospun carbon nanofibers

The removal of the main impurity CO 2 is a crucial step in biogas upgrading. In this work, the separation of CO 2 from CH 4 on electrospun polyacrylonitrile-based carbon nanofibers (CNFs) is investigated using breakthrough experiments. The CNFs are prepared at various carbonization temperatures ranging from 600 to 900 °C and feature a tailorable pore size that decreases at higher carbonization temperatures. The adsorption properties of the different CNFs are studied measuring pure component isotherms as well as column breakthrough experiments. Adsorption kinetics are discussed using a linear driving force approach to model the breakthrough experiment and obtain the adsorption rate constant. Moreover, different approaches to determine the selectivity of the competitive CO 2 /CH 4 adsorption are applied and discussed in detail. The results clearly prove that a size exclusion effect governs the adsorption selectivity on the CNFs. While CH 4 cannot adsorb in the pores of CNFs prepared at 800 °C or above, the smaller CO 2 is only excluded from the pores of CNFs prepared at 900 °C. For CNFs carbonized in the range from 600 to 750 °C, values of the CO 2 /CH 4 selectivity of 11–14 are obtained. On the CNFs prepared at 800 °C the CH 4 adsorption is severely hindered, leading to a reduced adsorbed amount of CH 4 and consequently to an improved CO 2 /CH 4 selectivity of 40. Furthermore, owing to the shrinking pores, the adsorption rates of CH 4 and CO 2 decrease with higher carbonization temperature.