| Popis: |
The marine black shale formations on the Upper Yangtze Platform (UYP), South China are exploration targets for shale gas. Here, we report on the methane sorption capacity of thermally overmature samples from the Lower Silurian and Lower Cambrian black shale intervals in the UYP (UYP-samples). Two immature shale samples from the Middle Cambrian formation in the Georgina Basin, North Australia (AU samples) were also tested to investigate the effect of thermal maturity on sorption isotherms. Excess sorption isotherms were performed over a pressure range of 0–25 MPa at 46 °C. The effects of TOC content, thermal maturity, clay minerals, moisture content, pore properties, particle size, temperature, and pressure on methane sorption capacity were analysed. In addition, thermovaporisation gas chromatography (Tvap-GC) was used to measure the residual gas that is stored in the samples under atmospheric pressure and temperature conditions. The results indicate that the maximum methane excess sorption of the Lower Silurian samples is between 0.045 and 0.064 mmol/g rock and that of Lower Cambrian samples is between 0.036 and 0.210 mmol/g rock. The Langmuir sorption capacity of the Lower Silurian samples ranges from 0.096 to 0.115 mmol/g rock, whereas that of the Lower Cambrian shale ranges from 0.077 to 0.310 mmol/g rock. These results are close to the sorption capacities of the Barnett (U.S.), Devonian–Mississippian (Western Canada), and Alum (Southern Scandinavia) shale samples. The shape of the sorption isotherms and methane sorption capacity vary from sample to sample. Under the measured pressure range, the isotherms of the selected immature AU Cambrian samples increase monotonously with pressure, whereas the overmature UYP samples exhibit maxima. The methane sorption capacity of the measured samples positively correlates with TOC content and exhibits a distinct linear relation. The TOC-normalised sorption capacity shows a positive correlation with thermal maturity; however, the corresponding pressure of maximum excess sorption and Langmuir pressure decrease substantially with increasing thermal maturity. The clay minerals show a positive effect on the TOC-normalised sorption capacity. The sorption capacity of clay minerals, however, should have been reduced by the moisture content. The two Lower Cambrian samples that have similar maturities were measured for porosity and pore-size distribution. The sample with a high TOC content shows a high total cumulative pore volume, surface area, total porosity and thus a higher sorption capacity than the sample with less TOC. In addition, larger-sized particles show slightly less sorption capacity than smaller-sized particles. The Tvap-GC results show that the residual gas content of core samples is evidently higher than that of the outcrop samples, which implies a remarkably negative effect of the weathering process. |
