The carbon dioxide, methane and nitrogen high-pressure sorption properties of South African bituminous coals

In this paper, we report the CO2, CH4 and N-2 sorption isotherms of four dry South African bituminous coals at pressures up to 16 MPa at 55 degrees C. The sorption capacities of the samples with respect to the adsorbate gases decreased in the order: CO2 > CH4 approximate to N-2 by weight, and CO2 > CH4 > N-2 by volume. A new model, based on a hybrid Dubinin-Radushkevich and Henry law approach (DR-HH) provided substantially better fits to the sorption isotherm data than the previously used modified DR (M-DR) model. Obtained uncertainty metrics show that the DR-HH model generally returned lower error sum of squares (ESS) and root mean square (RMS) residuals, and higher quality of fit (QOF) compared to the M-DR model. The net heat of sorption, beta E-s, of the samples for the three adsorbate gases were generally low (8.5-12.8 kJ/mol), but comparable to previous determinations of other coals, indicating that physisorption was the dominating sorption mechanism. The sorption capacities of the samples were found to be rank-dependent as they decreased with increasing vitrinite reflectance and elemental carbon content. The micropore properties of the samples as measured by both CO2 low-pressure gas adsorption (LPGA) and small angle X-ray scattering (SAXS), impacted the sorption properties of the sample more than both the mesopore and macropore properties determined from N-2 LPGA, SAXS, and mercury intrusion porosimetry. The sorption capacities of the samples were found to increase with increasing lithotypes abundance, suggesting that lithotype bandings enhances either the fluid transport processes or the micropore properties of the coal matrix. In addition, it has been demonstrated that critical properties of the adsorbate gases influenced their sorption properties.