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Tristan G. A. Youngs

Publications and source records attributed to Tristan G. A. Youngs.

5 recordsLinked to original sources

Neutron scattering reveals fractionation of natural gas mixtures in unconventional petroleum reservoir pores: Perspectives on energy resource recovery and storage

In unconventional petroleum reservoirs hydrocarbon fluids are hosted by both mineral and organic matter pores. These pores can have diameters that range from microns to less than a single nanometer and, for unconventional reservoirs, there is evidence that small pores ( <20 nm diameter) may constitute a large proportion of the available space. Understanding subsurface volumes and how fluids behave in them can be helpful for predicting hydrocarbon production and storage in the subsurface. One area with knowledge gaps regarding hydrocarbon behavior in small pores is the possibility for mixtures to fractionate (i.e., unmix) based on pore size or pore type. Mixture fractionation as a function of pore size could impact recovery of hydrocarbons, drive compositional shifts during production, and limit fluid storage within candidate reservoirs. To investigate natural gas fractionation in small geologic pores, we applied total neutron scattering to probe methane-ethane mixtures at reservoir pressures (up to ≈30 MPa) and temperature (60°C) within a sample from the Upper Cretaceous Niobrara Formation. Neutron scattering data reveal only minor fractionation occurs between methane and ethane in 20-nm diameter sample mesopores. Increased fractionation is observed for sample micropores, with up to 72% (±1% at 1-sigma) methane found in 2 nm diameter pores following injection of a 50%-50% methane-ethane mixture. These data provide rarely available direct experimental observations of hydrocarbon mixture behavior under nanoconfinement in a sample from an important unconventional petroleum reservoir. Our results are discussed in the context of evaluating hydrocarbon resources in unconventional reservoir meso- and micropores, reconciling observed gas composition changes during production, and more broadly, understanding subsurface pore volumes within an energy storage framework.

Fuel↗

Methane pore accessibility, densification, and accommodation by organic matter in the Niobrara Formation at wet-gas thermal maturity conditions

Petroleum within unconventional source-rock reservoirs is hosted in organic matter and mineral pore space as well as in voids and microfractures. Recent work has shown that for source-rock reservoirs in the dry gas window, significant portions of methane (CH 4 ), the main component of petroleum at elevated maturities, can be stored within fine (<5 nm) organic matter porosity. However, within reservoirs at lower thermal maturities (e.g., peak oil or wet-gas conditions), the distribution and behavior of CH 4 and the higher alkanes that comprise gas condensates across pore sizes is unclear, especially for pores with diameters <50 nm. Understanding CH 4 distribution within these settings provides insight for petroleum generation, movement, and recoverability, ultimately enabling increased accuracy of estimated ultimate recovery. Here wide Q-range total neutron scattering was used to evaluate perdeuterated methane (CD 4 ) behavior at reservoir pressures (200–750 bar) and temperature (60 °C) in a sample at the late oil/wet gas thermal maturity stage from the Late Cretaceous Niobrara Formation, an active petroleum producing formation within the Denver-Julesburg Basin, U.S. Neutron scattering data show that mesopores within the Niobrara Formation sample exhibit mass fractal scattering, similar to previously measured U.S. marine shale samples. In the presence of CD 4 , scattering intensities between Q = 0.02–0.1 Å −1 (corresponding to nominal pore diameters from 25 to 5 nm, respectively) decrease with increased pressure up to 750 bar where at least 80% of all pores with ~25 nm diameters are CD 4 accessible. In contrast, between Q = 0.1–1 Å −1 (corresponding to nominal pore diameters from 5 to 0.5 nm, respectively), scattering intensity initially increased at the lowest CD 4 pressure tested (200 bar) before decreasing with increasing pressure. These signal fluctuations with CD 4 pressure are interpreted to arise from the creation of pores with diameters <5 nm, likely through deformation of solid bitumen by supercritical CD 4 , and/or the incorporation of CD 4 within sample organic matter. This new porosity represents an increase of at least ~8% in available pore volume within the sample, although the majority of these pores do not persist following removal of CD 4 . Additionally, there is strong evidence for densification of CD 4 within the sample indicated by a shift in the CD 4 intermolecular scattering peak to higher Q-values compared to bulk CD 4 . These results provide insight into fluid properties within source-rock reservoirs at late oil/wet gas thermal maturities, especially as they relate to organic porosity interconnectivity, and are discussed with perspective toward pressure management of gas condensate wells.

Colorado, Kansas, Nebraska, Wyoming↗

Exploring methane behavior in Marcellus Shale micropores via contrast matching neutron scattering

Petroleum in shale reservoirs is hosted in organic matter and mineral pores as well as in natural fractures and voids. For thermally mature plays, e.g., the Marcellus Shale, methane and other light alkane gases are thought to be primarily contained in organic matter pores with radii ≦50 nm. Thus, in order to understand natural gas occurrence, transport, storage, and recoverability within unconventional reservoirs at the dry-gas stage of thermal maturity, it is critical to characterize the associated organic matter porosity across length scales from 50 nm down to the angstrom level. We utilized wide Q-range neutron total scattering to characterize deuterated methane (CD 4 ) adsorption at 60ºC up to the zero average contrast (ZAC) pressure (~60 MPa) within two mineralogically different samples collected from the same producing interval from the Middle Devonian Marcellus Shale. The neutron scattering approach used here provides structural information from the inter-atomic regime up to a nominal pore radius of ~12.5 nm and, by reaching the CD 4 ZAC pressure (~60 MPa), it is possible to examine the distribution of open versus closed pores within this pore size range in the samples. Our results indicate that ~10% of the largest pores measured are closed to CD 4 for a quartz-rich sample whereas up to 25% of pores with a nominal radius of ~12.5 nm are inaccessible within a sample with an equivalent proportion of quartz, carbonate, and clay. As pore size decreases, accessibility also decreases; all pores with radii ~0.5 nm are effectively closed to CD 4 in both samples. Additionally, up to ~4.5× more CD 4 is adsorbed within the quartz-rich sample at 60 MPa and we see no evidence for densification of CD 4 within the shale pores. These findings suggest that, for shale samples within the dry-gas window, (i) nanometer-scale porosity is primarily located within organic matter, (ii) the amount of available nano-porosity can vary widely over meter scales, and (iii) mineralogy plays a secondary role in dictating methane behavior within these systems.

West Virginia↗

Impacts of mineralogical variation on CO2 behavior in small pores from producing intervals of the Marcellus Shale: Results from neutron scattering

The Near and InterMediate Range Order Diffractometer (NIMROD) was used to examine the potential impact of shale mineralogy on CO 2 behavior within micropores. Two samples with varying mineral compositions were obtained from producing intervals in the dry gas window in the Middle Devonian Marcellus Shale. One of the samples contained relatively high amounts of quartz and clay and low carbonate, the other contained relatively equal amounts of quartz, carbonate, and clay. The samples were probed with CO 2 at subcritical pressures (20–50 bar) and temperature (22 °C) and characterized over a neutron scattering vector ( Q ) range of 0.02 < Q < 50 Å –1 . This Q range provides information from the atomistic length-scale up to pore radii of 10 nm. Mineralogy variations between the samples did not affect scattering ratios over the entire Q range accessible with the NIMROD. Q values for the minimum scattering ratios of both samples at similar pressures are remarkably similar, particularly for Q < ∼0.09 Å –1 , and maximum scattering ratios are similar in both samples suggesting that mineral pores are so uncommon in the pore sizes examined that they cannot be resolved due to the overwhelming amounts of organic pores in these samples. Overall, these findings suggest that mineralogical variations have little effect on CO 2 behavior within organic matter-hosted shale micropores at high thermal maturities and they lend support to the assertion that CO 2 cannot be stored in the vast surface areas of micropores in organic material in shale formations. In addition, CO 2 enhanced oil recovery (EOR) is unlikely to displace petroleum from some of the smaller mesopores (2.5 to ∼3.5 nm) and all of the micropores because they are effectively closed to CO 2 . amples were probed with CO2 at subcritical pressures (20 50 bar) and temperature (22 oC) and characterized over a neutron scattering vector (Q) range of 0.02 < Q < 50 -1. This Q range provides information on nominal pore size radii of around 10 0.5 nm. Mineralogy variations between the samples did not affect scattering ratios over the entire Q range accessible with the NIMROD. Q values for the minimum scattering ratios of both samples at similar pressures are statistically indistinguishable and maximum scattering ratios are similar in both samples suggesting that mineral pores are either absent or are so uncommon that they cannot be resolved due to the overwhelming amounts of organic pores in these samples. Overall, these findings suggest that mineralogical variations have little effect on CO2 behavior within organic matter-hosted shale micropores at high thermal maturities and they lend support to the assertion that CO2 cannot be stored in the vast surface areas of micropores (<2.5 nm) in shale formations. In addition, CO2 enhanced oil recovery (EOR) is unlikely to displace petroleum from some of the smaller mesopores (2.5 10 nm) and all of the micropores because they are effectively closed to CO2.

Energy & Fuels↗

Neutron scattering measurements of carbon dioxide adsorption in pores within the Marcellus Shale: Implications for sequestration

Shale is an increasingly viable source of natural gas and a potential candidate for geologic CO 2 sequestration. Understanding the gas adsorption behavior on shale is necessary for the design of optimal gas recovery and sequestration projects. In the present study neutron diffraction and small-angle neutron scattering measurements of adsorbed CO 2 in Marcellus Shale samples were conducted on the Near and InterMediate Range Order Diffractometer (NIMROD) at the ISIS Pulsed Neutron and Muon Source, STFC Rutherford Appleton Laboratory along an adsorption isotherm of 22 °C and pressures of 25 and 40 bar. Additional measurements were conducted at approximately 22 and 60 °C at the same pressures on the General-Purpose Small-Angle Neutron Scattering (GP-SANS) instrument at Oak Ridge National Laboratory. The structures investigated (pores) for CO 2 adsorption range in size from Å level to ∼50 nm. The results indicate that, using the conditions investigated densification or condensation effects occurred in all accessible pores. The data suggest that at 22 °C the CO 2 has liquid-like properties when confined in pores of around 1 nm radius at pressures as low as 25 bar. Many of the 2.5 nm pores, 70% of 2 nm pores, most of the <1 nm pores, and all pores <0.25 nm, are inaccessible or closed to CO 2 , suggesting that despite the vast numbers of micropores in shale, the micropores will be unavailable for storage for geologic CO 2 sequestration.

Environmental Science & Technology↗