The effect of chemical treatment on adsorption of natural gas by multi-walled carbon nanotubes: Sorption equilibria and thermodynamic studies

Abstract

In this study, adsorption of methane as the main constituent of natural gas was firstly studied on the pristine multi-walled carbon nanotubes (MWCNTs) and then purification and chemical treatments of MWCNTs was performed to enhance the natural gas adsorption capacity. MWCNTs were chemically treated using different methods in this research. The results revealed that chemical treatment of the MWCNTs in presence of H2SO4/HNO3 acidic mixture in 3:1 volume ratio, enhanced considerably natural gas adsorption capacity (an optimal up to 45 mmol/g) at temperature of 298.15 K and the pressure of 50 bar compared to the pristine MWCNTs (about 27 mmol/g) at the same operating conditions. This effect can be attributed to the opening of the nanotubes caps with a major alteration in its structural properties due to chemical treatment. The experimental data of adsorption were almost equally well described by Langmuir, Freundlich and Sips equations to determine the model isotherms. The best fit was obtained by the Sips model isotherm with the r-squared value near to unity. Furthermore, using the experimental data obtained in different temperatures the isosteric heat of natural gas adsorption onto pristine MWCNTs was also calculated in the interested range of pressures and temperatures using the thermodynamic-based Clausius-Clapeyron equation from the Sips isotherm model. The results revealed an energetically heterogeneous surface of MWCNTs in natural gas adsorption. Also the natural gas adsorption process was kinetically studied through pseudo-second order and intra-particle diffusion models which indicated the intra-particular diffusion is rate limiting step in adsorption of methane on MWCNTs.