Thermodynamics of methane adsorption on carbon adsorbent prepared from mineral coal

Methane adsorption on a recuperated activated carbon, AR-V, was studied over the temperature range of 213–393 K and at pressures up to 10 MPa from the perspective of its potential application for adsorption-based storage and separation technologies. The porous structure, phase and chemical compositions of AR-V were examined by nitrogen adsorption at 77 K, x-ray diffraction, and scanning electron microscopy. The amount of adsorbed methane increased with pressure up to 6.3 mmol/g at 243 K and fell dramatically to ~ 1 mmol/g with a temperature rise to 393 K. The molar differential isosteric heat of methane adsorption on AR-V was evaluated from the linear isosteres within the studied P,T-range; the effects from the non-ideality of a gaseous phase and the AR-V non-inertness were considered. The maximal summarized contribution from the AR-V thermal expansion and directly measured adsorption-induced deformation to the molar differential isosteric heat of methane adsorption turned out to be less than that from the gas compressibility. The initial drastic changes in the thermodynamic state functions of the adsorption system were attributed to the binding methane molecules with non-uniformly distributed high-energy adsorption sites. When methane molecules occupied all high-energy adsorption sites, the subsequent variations in the thermodynamic functions were governed by the intensifying attractive forces between methane molecules upon methane adsorption resulting in the formation of adsorption clusters. The temperature dependence of the isosteric heat capacity of the methane/AR-V system varied during adsorption; its value exceeded 2–3 times the isochoric heat capacity of the equilibrium methane gaseous phase.