Quantitative characterization of methane adsorption in shale using low-field NMR

Quantification of methane content in shales is a critical parameter for estimation of their potential gas production capacity. Traditional gravimetric methods for estimation of this quantity are sensitive only to adsorbed methane and are difficult to apply either to intact shale rock cores or via field measurements. Here non-invasive low-field nuclear magnetic resonance (LF-NMR) is applied to quantify excess methane adsorption capacity in two intact shale rock plugs at pressures up to 150 bar; validation is provided against destructive gravimetric methods performed on fragments from the same shale rock plugs. The resultant NMR transverse relaxation time (T₂) distributions contain three distinct peaks (referred to as peaks P1 – P3) which are allocated to adsorbed methane in organic pores, methane constrained to inorganic pores and bulk methane located predominately in fractures, respectively. The area of peak P1 is observed to increase with pressure up to 100 bar, after which it reaches a plateau, whilst the area of peaks P2 and P3 both increase linearly with pressure up to 150 bar. The most accurate estimate of excess methane adsorption capacity is obtained via a combination of an overall system mass balance and the methane located in inorganic pores and fractures (peaks P2 and P3, respectively), where excellent agreement is produced with corresponding gravimetric measurements for both shale samples studied.