Summary The hydrocarbon (HC)-storage capacity of organic-rich shales depends on porosity and surface area, whereas pore-throat-size distribution and pore-throat-network connectivity control permeability. The pores within the organic matter (OM) of organic-rich shales develop during thermal maturation as different HC phases are generated and expelled from the OM. Organic-rich shales can potentially retain a large proportion of the HCs generated during the diagenesis process. Commercial HC production from liquid-rich shale reservoirs can be achieved using completion technologies such as multistage-fractured horizontal wells. However, the ability of industry to identify “sweet spots” along multistage-fractured horizontal wells for both primary and enhanced oil recovery (EOR) is still hampered by insufficient understanding of the effects of type/content of entrained HC/OM components on reservoir quality. The primary objectives of the current study are therefore to establish an integrated experimental workflow to investigate the effect of entrained HC/OM on storage and transport properties of the organic-rich shales, and to provide examples of that experimental workflow through analyzing a selected sample suite from a prolific shale-oil reservoir (the Duvernay Formation) in western Canada. To accomplish this goal, a comprehensive suite of petrophysical analyses is performed on a diverse sample suite from the Duvernay Formation that differs in OM content (2.8 to 5 wt%; n = 5), before and after sequential pyrolysis by a revised Rock-Eval analysis [extended-slow-heating (ESH) Rock-Eval analysis]. Using the ESH cycle, different HC/OM components can be distinguished more easily and reliably during the pyrolysis process: free light oil (S1ESH; up to 150°C), fluid-like HC residue (FHR) (S2a; 150 to 380°C), and solid bitumen/residual carbon (S2b; 380 to 650°C). The characterization techniques used at each stage are helium pycnometry (grain density, helium porosity); low-pressure gas [nitrogen (N2), carbon dioxide (CO2)] adsorption (LPA) [pore volume (PV), surface area, pore-size distribution (PSD) within micropores, mesopores, and smaller macropores]; crushed-rock gas [helium, CO2, N2] permeability; and rate-of-adsorption (ROA) analysis (CO2, N2). Scanning-electron-microscopy (SEM) analysis is further conducted to verify/support the petrophysical observations. Powder X-ray-diffraction (XRD) analyses were performed on all samples in the “as-received” state and after Stage S2b (thermal pyrolysis up to 650°C) to quantify variations in mineralogical compositions and their possible controls on the evolution of petrophysical properties (i.e., porosity/permeability). Organic petrography was conducted on selected samples to characterize the nature of OM. Compared with the “as-received” state, porosity, permeability, modal-pore-size distribution, and surface-area increase with sequential pyrolysis stages, associated with the expulsion and devolatilization of free light oil and FHR (S2a; up to 380°C). However, the change in petrophysical properties associated with the degradation of solid bitumen/residual carbon (S2b; up to 650°C) is variable and unpredictable. The observed reduction in porosity/permeability values after Stage S2b is likely attributed to the occlusion of PV with solid bitumen/residual carbon degradation (i.e., coking); sample swelling caused by water loss from the lattice structure of clay minerals (i.e., illite); and sample compaction as a result of OM removal from the rock matrix. Among various stages of the ESH Rock-Eval pyrolysis, the petrophysical properties that are measured after Stages S1ESH and S2a, as they are related to the expulsion of the lighter and heavier free-HC compounds from the rock matrix, are expected to be the most important for primary and EOR applications. Quantification of the evolution of reservoir quality with HC generation/expulsion has important implications for identifying petrophysical “sweet spots” within unconventional reservoirs, optimizing stimulation design, and targeting specific zones within the reservoir of interest with the OM content/type amenable to maximizing gas storage/transport during cyclic solvent injection for EOR applications. The integrated experimental workflow proposed herein could be of significant interest to the operators of organic-rich shale/mudstone plays (e.g., the Duvernay) as a screening tool for developing optimized stimulation treatments for improving primary and enhanced HC recovery.
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