Impact of experimental parameters for manometric equipment on CO2 isotherms measured: Comment on “Inter-laboratory comparison II: CO2 isotherms measured on moisture-equilibrated Argonne premium coals at 55°C and up to 15 MPa” by Goodman et al. (2007)

Modelling the sorption properties of coals for carbon dioxide under supercritical conditions is necessary for accurate prediction of the sequestering ability of coals in seams. We present recent data for sorption curves of three dry Argonne Premium coals, for carbon dioxide, methane and nitrogen at two different temperatures at pressures up to 15 MPa. The sorption capacity of coals tends to decrease with increasing temperature. An investigation into literature values for sorption of nitrogen and methane by charcoal also show sorption capacities that decrease dramatically with increasing temperature. This is inconsistent with expectations from Langmuir models of coal sorption, which predict a sorption capacity that is independent of temperature. We have successfully fitted the isotherms using a modified Dubinin–Radushkevich equation that uses gas density rather than pressure. A simple pore-filling model that assumes there is a maximum pore width that can be filled in supercritical conditions and that this maximum pore width decreases with increasing temperature, can explain this temperature dependence of sorption capacity. It can also explain why different supercritical gases give apparently different surface sorption capacities on the same material. The calculated heat of sorption for these gases on these coals is similar to those found for these gases on activated carbon.