The objective of this study was to correlate shale hydrous pyrolysis with thermal maturity measurements based on solid bitumen reflectance (BRo) at the U.S. Geological Survey (USGS) and Raman microscopy (RM) at WellDog. In semi-blind Phase I, BRo values of the initial set of 8 samples were withheld prior to RM analysis. As reported previously, a strong correlation was observed between BRo and Raman parameters. For Phase-II, BRo values for the second set of 8 samples were shared before RM. Observations from Phase-II are reported here as well as the ability of RM to correctly order the semi-blind Phase I samples.
Immature shale samples from the Bakken (Phase-I) and Duvernay (Phase-II) formations were subjected to hydrous pyrolysis for 72 hours at temperatures from 280°C to 360°C. Rock residues from both series were mounted and polished (ASTM D2797) for analysis of BRo (ASTM D7708) and confocal laser-scanning Raman microscopy. For RM, multiple hyperspectral maps were collected from each sample, resulting in tens of thousands of spectra per sample. Map areas were ~5,000 μm2, with a spectrum collected from every square micrometer. The organic carbon G- (Graphitic-) and D- (Disordered) bands in each Raman spectrum were fit algorithmically to a multi-peak model, yielding a number of diagnostic parameters that correlate with changes occurring in samples as a result of thermal maturation and pyrolysis.
Parameters extracted from analysis of Raman spectra were plotted against the previously determined BRo values to determine which Raman parameters best correlate with thermal maturity. Plotting two of the sample-averaged anonymized spectral parameters versus BRo in the Bakken series indicated an exponential trend with strong correlations (R2>0.8) as reported at URTeC in 2017 (MS-2671253). Similar strong relationships occurred in the Duvernay samples with respect to increasing maturity when using Partial Least-Squares analysis.
Quantifying thermal maturity is crucial for properly evaluating an unconventional resource. However, the most widely used methods – vitrinite reflectance and programmed pyrolysis – may be inadequate for shales. Reflectance of solid bitumen has wider applicability in shales, because of greater abundance than vitrinite. But additional techniques that can accurately and objectively characterize the thermal maturity of shale samples are still needed.