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Mineral dissolution significantly impacts many geological systems. Carbon released by diagenesis, carbon sequestration, and acid injection are examples where geochemical reactions, fluid flow, and solute transport are strongly coupled. The complexity in these systems involves interplay between various mechanisms that operate at timescales ranging from microseconds to years. Current experimental techniques characterize dissolution processes using static images that are acquired with long measurement times and/or low spatial resolution. These limitations prevent direct observation of how dissolution reactions progress within an intact rock with spatially heterogeneous mineralogy and morphology. We utilize microfluidic cells embedded with thin rock samples to visualize dissolution with significant temporal resolution (100 ms) in a large observation window (3 × 3 mm). We injected acidic fluid into eight shale samples ranging from 8 to 86 wt % carbonate. The pre- and postreaction microstructures are characterized at the scale of pores (0.1 to 1 µm) and fractures (1 to 1,000 µm). We observe that nonreactive particle exposure, fracture morphology, and loss of rock strength are strongly dependent on both the relative volume of reactive grains and their distribution. Time-resolved images of the rock unveil the spatiotemporal dynamics of dissolution, including two-phase flow effects in real time and illustrate the changes in the fracture interface across the range of compositions. Moreover, the dynamical data provide an approach for characterizing reactivity parameters of natural heterogeneous samples when porous media effects are not negligible. The platform and workflow provide real-time characterization of geochemical reactions and inform various subsurface engineering processes.
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Hydraulic fracturing of unconventional oil/gas shales has changed the energy landscape of the U.S. Recovery of hydrocarbons from tight, hydraulically fractured shales is a highly inefficient process, with estimated recoveries of <25% for natural gas and <5% for oil. This review focuses on the complex chemical interactions of additives in hydraulic fracturing fluid (HFF) with minerals and organic matter in oil/gas shales. These interactions are intended to increase hydrocarbon recovery by increasing porosities and permeabilities of tight shales. However, fluid-shale interactions result in the dissolution of shale minerals and the release and transport of chemical components. They also result in mineral precipitation in the shale matrix, which can reduce permeability, porosity, and hydrocarbon recovery. Competition between mineral dissolution and mineral precipitation processes influences the amounts of oil and gas recovered. We review the temporal/spatial origins and distribution of unconventional oil/gas shales from mudstones and shales, followed by discussion of their global and U.S. distributions and compositional differences from different U.S. sedimentary basins. We discuss the major types of chemical additives in HFF with their intended purposes, including drilling muds. Fracture distribution, porosity, permeability, and the identity and molecular-level speciation of minerals and organic matter in oil/gas shales throughout the hydraulic fracturing process are discussed. Also discussed are analysis methods used in characterizing oil/gas shales before and after hydraulic fracturing, including permeametry and porosimetry measurements, X-ray diffraction/Rietveld refinement, X-ray computed tomography, scanning/transmission electron microscopy, and laboratory- and synchrotron-based imaging/spectroscopic methods. Reactive transport and spatial scaling are discussed in some detail in order to relate fundamental molecular-scale processes to fluid transport. Our review concludes with a discussion of potential environmental impacts of hydraulic fracturing and important knowledge gaps that must be bridged to achieve improved mechanistic understanding of fluid transport in oil/gas shales.
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Fraturamento Hidráulico , Minerais/química , Gás Natural , Campos de Petróleo e Gás , Águas Residuárias/químicaRESUMO
Despite the advantageous resolution of electron tomography (ET), reconstruction of three-dimensional (3D) images from multiple two-dimensional (2D) projections presents several challenges, including small signal-to-noise ratios, and a limited projection range. This study evaluates the capabilities of ET for thin sections of shale, a complex nanoporous medium. A numerical phantom with 1.24 nm pixel size is constructed based on the tomographic reconstruction of a Barnett shale. A dataset of 2D projection images is numerically generated from the 3D phantom and studied over a range of conditions. First, common reconstruction techniques are used to reconstruct the shale structure. The reconstruction uncertainty is quantified by comparing overall values of storage and transport metrics, as well as the misclassification of pore voxels compared to the phantom. We then select the most robust reconstruction technique and we vary the acquisition conditions to quantify the effect of artifacts. We find a strong agreement for large pores over the different acquisition workflows, while a wider variability exists for nanometer-scale features. The limited projection range and reconstruction are identified as the main experimental bottlenecks, thereby suggesting that sample thinning, advanced holders, and advanced reconstruction algorithms offer opportunities for improvement.
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HYPOTHESIS: The dynamics of gas-liquid interfaces differs between aqueous surfactant and nanoparticle mixtures in rectangular cross-section capillaries. EXPERIMENTS: We designed and fabricated a new microfluidic device with a meter-long channel and a noncircular cross section (35 µm by 100 µm by 1 m) to study the flow behavior of long bubbles in capillaries wetted by water as well as surfactant and nanoparticle solutions. Flow in the novel symmetric loop device maintains essentially straight and inertialess conditions over a wide range of flow rates. FINDINGS: The pressure-drop versus velocity relationship of long bubbles in capillaries with noncircular cross sections has been studied theoretically but not extensively validated. The measured pressure drop (normalized with respect to interfacial properties) experienced by bubbles varies as Ca2/3 over the range 10-7Assuntos
Capilares
, Tensoativos
, Água
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Deep subsurface stimulation processes often promote fluid-rock interactions that can lead to the formation of small colloidal particles that are suspected to migrate through the rock matrix, partially or fully clog pores and microfractures, and promote the mobilization of contaminants. Thus, the goal of this work is to understand the geochemical changes of the host rock in response to reservoir stimulation that promote the formation and migration of colloids. Two different carbonate-rich shales were exposed to different solution pHs (pH = 2 and 7). Iron and other mineral transformations at the shale-fluid interface were first characterized by synchrotron-based XRF mapping. Then, colloids that were able to migrate from the shale into the bulk fluid were characterized by synchrotron-based extended X-ray absorption structure (EXAFS), scanning electron microscopy (SEM), and single-particle inductively coupled plasma time-of-flight mass spectrometry (sp-icpTOF-MS). When exposed to the pH = 2 solution, extensive mineral dissolution and secondary precipitation was observed; iron-(oxyhydr)oxide colloids colocated with silicates were observed by SEM at the fluid-shale interfaces, and the mobilization of chromium and nickel with these iron colloids into the bulk fluid was detected by sp-icpTOF-MS. Iron EXAFS spectra of the solution at the shale-fluid interface suggests the rapid (within minutes) formation of ferrihydrite-like nanoparticles. Thus, we demonstrate that the pH neutralization promotes the mobilization of existing silicate minerals and the rapid formation of new iron colloids. These Fe colloids have the potential to migrate through the shale matrix and mobilize other heavy metals (such as Cr and Ni, in this study) and impacting groundwater quality, as well produced waters from these hydraulic fracturing operations.
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Characterization of microscopic details of the fabric of mudstones and shales (i.e., structure and composition) is important to understand their storage and transport properties. Current characterization methods struggle to probe reliably multiple scales of interest (e.g., pore and fracture) and measure properties at the finest resolution under representative in situ conditions. Micro X-ray fluorescence (µXRF) is a high-performance imaging technique that produces elemental images at sub-10 µm spatial resolution and could offer insight into a diversity of shale properties, such as mineral composition, porosity, and in situ pressure gradients. This study designed and carried out a porosity mapping protocol using model and real-rock microfluidic devices and contrast fluids. Etched silicon micromodels with real-rock pore network patterns served as ideal models to establish a proof of concept. Measurements were performed on a novel µXRF microscope not powered by synchrotron radiation. We registered the µXRF datasets with the binary rock masks used for micromodel fabrication and applied segmentation algorithms to compare porosities. We assessed expected advantages and limitations through a sensitivity analysis and beam study. µXRF is an important new imaging technique for microfluidic applications.
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We designed and fabricated a new microfluidic device to better enable study of foam microstructure and rheology in planar fractures. The design phase included stress-strain finite element analysis to enhance the pressure tolerance of the device. The optimized design is a 2 cm wide by 7.75 cm long rough fracture that includes 25 posts to anchor the glass cover plate. The posts simulate asperities and provide structural support during bonding of a glass cover plate to the device. Importantly, the new design illustrates improved ability to sustain large differential pressure compared to previous designs in the literature. The rheometer permits study of the relationship among foam bubble morphology, pressure drop, and flow rates. Our findings validated the previous, sparse microvisual studies mentioned in the literature and confirmed that small quality foam, ranging from 20 to 50% gas by volume, contains dispersed bubbles separated by liquid lenses. In this range, the distribution of bubble sizes was roughly 80-90% small uniform bubbles and only 10-20% of larger and more elongated bubbles. Additionally, our studies reveal that foam apparent viscosity is a strong function of foam quality, velocity, and texture (i.e., bubble size). Apparent viscosity of foam ranged from 100 to 600 cP for the conditions studied. High quality foams in fractures are independent of gas flow rates but very sensitive to liquid flow rates. On the other hand, low quality foams are sensitive to gas flow rates but independent of liquid flow rates.
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Viscosidade , ReologiaRESUMO
Image-based characterization offers a powerful approach to studying geological porous media at the nanoscale and images are critical to understanding reactive transport mechanisms in reservoirs relevant to energy and sustainability technologies such as carbon sequestration, subsurface hydrogen storage, and natural gas recovery. Nanoimaging presents a trade off, however, between higher-contrast sample-destructive and lower-contrast sample-preserving imaging modalities. Furthermore, high-contrast imaging modalities often acquire only 2D images, while 3D volumes are needed to characterize fully a source rock sample. In this work, we present deep learning image translation models to predict high-contrast focused ion beam-scanning electron microscopy (FIB-SEM) image volumes from transmission X-ray microscopy (TXM) images when only 2D paired training data is available. We introduce a regularization method for improving 3D volume generation from 2D-to-2D deep learning image models and apply this approach to translate 3D TXM volumes to FIB-SEM fidelity. We then segment a predicted FIB-SEM volume into a flow simulation domain and calculate the sample apparent permeability using a lattice Boltzmann method (LBM) technique. Results show that our image translation approach produces simulation domains suitable for flow visualization and allows for accurate characterization of petrophysical properties from non-destructive imaging data.
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HYPOTHESIS: The effects of mutual transfer of momentum between two immiscible flowing fluids in porous media are not well understood nor predictable yet. From considerations at the pore-scale, it should be possible to determine whether and to what extent interfacial viscous coupling effects are significant. EXPERIMENTS: We visualize the velocity distributions inside immobile globules of wetting phase (water) while a non-wetting phase (oil) is injected. We investigate viscous coupling effects and their relationship with the viscosity ratio and the capillary number. FINDINGS: Four regimes of viscous dissipation are identified: (i) a regime for which the fluid-fluid interface acts as a solid wall; (ii) a regime where the wetting phase is dragged in the direction of the imposed flow; (iii) and (iv) two regimes for which the trapped globule of water shows a recirculating motion due to the shear stress at the oil/water interface. We demonstrate the significant role of the lubricating effect and of the topology of the pore space on the magnitude of viscous dissipation. Importantly, for a viscosity ratio close to one and low capillary number, we demonstrate that viscous coupling effects should be incorporated into the existing Darcy's law formulation for two-phase flow in porous media.
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A primary question investigated in this study is the influence of brine chemistry on the behavior of short-range non-DLVO (e.g., hydration, discrete ion charge effects, and so on) forces at calcite surfaces. Specifically, how do wetting films containing Na+ differ from those containing Mg2+? Force-distance spectroscopy as measured by atomic force microscopy is used to probe short-range non-DLVO forces in various single-salt and multiple-salt electrolyte solutions. Experimental results reveal that, in single-component solutions, a greater concentration of Na+ ions decreases the decay length of short-range repulsion while a greater concentration of Mg2+ ions increases decay length. These results imply that Na+ ions reduce the affinity of calcite surfaces for water whereas Mg2+ ions make calcite more hydrophilic. Importantly, the relationship between the behavior of non-DLVO forces at small separations and concentrations of ions is not monotonic in multiple-component brines. Our observations support the hypothesis that Na+ ions disturb the interfacial water structure of calcite while Mg2+ ions are arranged farther away from the surface. Results obtained here may have implications for the design of so-called low salinity waterfloods where the composition of brines used for crude oil recovery is manipulated to increase oil recovery.
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A conventional high-pressure/high-temperature experimental apparatus for combined geomechanical and flow-through testing of rocks is not X-ray compatible. Additionally, current X-ray transparent systems for computed tomography (CT) of cm-sized samples are limited to design temperatures below 180 °C. We describe a novel, high-temperature (>400 °C), high-pressure (>2000 psi/>13.8 MPa confining, >10 000 psi/>68.9 MPa vertical load) triaxial core holder suitable for X-ray CT scanning. The new triaxial system permits time-lapse imaging to capture the role of effective stress on fluid distribution and porous medium mechanics. System capabilities are demonstrated using ultimate compressive strength (UCS) tests of Castlegate sandstone. In this case, flooding the porous medium with a radio-opaque gas such as krypton before and after the UCS test improves the discrimination of rock features such as fractures. The results of high-temperature tests are also presented. A Uintah Basin sample of immature oil shale is heated from room temperature to 459 °C under uniaxial compression. The sample contains kerogen that pyrolyzes as temperature rises, releasing hydrocarbons. Imaging reveals the formation of stress bands as well as the evolution and connectivity of the fracture network within the sample as a function of time.
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Dissolution of carbonate minerals in porous media is important to many instances of subsurface flow, including geological carbon dioxide (CO2) sequestration, karst formation, and crude-oil reservoir stimulation and acidizing. Of particular interest, geological CO2 storage in deep carbonate reservoirs presents a significant long-term opportunity to mitigate atmospheric carbon emissions. The reactivity of carbonate reservoirs, however, may negatively impact storage formation integrity and hence jeopardize sequestered CO2 storage security. In this work, we develop a novel biogenically calcite-functionalized microvisual device to study the fundamental pore-scale reactive transport dynamics in carbonate formations. Importantly, we discover a new microscale mechanism that dictates the overall behavior of the reactive transport phenomenon, where the reaction product, CO2, due to carbonate rock dissolution forms a separate, protective phase that engulfs the carbonate rock grain and reduces further dissolution. The presence of the separate, protective CO2 phase determines overall dissolution patterns in the storage reservoir and leads to formation of preferential leakage paths. We scale these results using nondimensional numbers to demonstrate their influence on industrial CO2 storage security, safety, and capacity.
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A well-characterized set of large-scale laboratory experiments is presented, illustrating forced imbibition displacements in the presence of irreducible wetting phase saturation in a cylindrical, homogeneous Berea sandstone rock. Experiments are designed to operate in the regime of compact microscopic flows and large-scale viscous instability. The distribution of fluid phases during the flow process is visualized by high-resolution computed tomography imaging. Linear stability analysis and high-accuracy numerical simulations are employed to analyze the ability of macroscopic continuum equations to provide a consistent approximation of the displacement process. The validity of the equilibrium relative permeability functions, which form the basis for the continuum model, is fundamentally related to the stability of the displacement process. It is shown that not only is the stable flow regime modeled accurately by existing continuum models, but the onset of instability as well as the initial unstable modes are also determined with reasonable accuracy for unstable flows. However, the continuum model is found to be deficient in the case of fully developed unstable flows.
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Silicon-based microfluidic devices, so-called micromodels in this application, are particularly useful laboratory tools for the direct visualization of fluid flow revealing pore-scale mechanisms controlling flow and transport phenomena in natural porous media. Current microfluidic devices with uniform etched depths, however, are limited when representing complex geometries such as the multiple-scale pore sizes common in carbonate rocks. In this study, we successfully developed optimized sequential photolithography to etch micropores (1.5 to 21 µm width) less deeply than the depth of wider macropores (>21 µm width) to improve the structural realism of an existing single-depth micromodel with a carbonate-derived pore structure. Surface profilimetry illustrates the configuration of the dual-depth dual-porosity micromodel and is used to estimate the corresponding pore volume change for the dual-depth micromodel compared to the equivalent uniform- or single-depth model. The flow characteristics of the dual-depth dual-porosity micromodel were characterized using micro-particle image velocimetry (µ-PIV), relative permeability measurements, and pore-scale observations during imbibition and drainage processes. The µ-PIV technique provides insights into the fluid dynamics within microfluidic channels and relevant fluid velocities controlled predominantly by changes in etching depth. In addition, the reduction of end-point relative permeability for both oil and water in the new dual-depth dual-porosity micromodel compared to the equivalent single-depth micromodel implies more realistic capillary forces occurring in the new dual-depth micromodel. Throughout the imbibition and drainage experiments, the flow behaviors of single- and dual-depth micromodels are further differentiated using direct visualization of the trapped non-wetting phase and the preferential mobilization of the wetting phase in the dual-depth micromodel. The visual observations agree with the relative permeability results. These findings indicate that dual-porosity and dual-depth micromodels have enhanced physical realism that is pertinent to oil recovery processes in complex porous media.
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We present an experimental protocol for fast determination of hydrate stability in porous media for a range of pressure and temperature (P, T) conditions. Using a lab-on-a-chip approach, we gain direct optical access to dynamic pore-scale hydrate formation and dissociation events to study the hydrate phase equilibria in sediments. Optical pore-scale observations of phase behavior reproduce the theoretical hydrate stability line with methane gas and distilled water, and demonstrate the accuracy of the new method. The procedure is applicable for any kind of hydrate transitions in sediments, and may be used to map gas hydrate stability zones in nature.
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When a wetting liquid is displaced by air in a capillary tube, a wetting film develops between the tube wall and the air that is responsible for the snap-off mechanism of the gas phase. By dissolving a dye in the wetting phase it is possible to relate a measure of the absorbance in the capillary to the thickness of liquid films. These data could be used to compare with cutting edge numerical simulations of the dynamics of snap-off for which experimental and numerical data are lacking. Drainage experiments in constricted capillary tubes were performed where a dyed wetting liquid is displaced by air for varying flow rates. We developed an optical method to measure liquid film thicknesses that range from 3 to 1000µm. The optical measures are validated by comparison with both theory and direct numerical simulations. In a constricted capillary tube we observed, both experimentally and numerically, a phenomenon of snap-off coalescence events in the vicinity of the constriction that bring new insights into our understanding and modeling of two-phase flows. In addition, the good agreement between experiments and numerical simulations gives confidence to use the numerical method for more complex geometries in the future.
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The impact of injection brine salinity and ionic composition on oil recovery has been an active area of research for the past 25years. Evidence from laboratory studies and field tests suggests that implementing certain modifications to the ionic composition of the injection brine leads to greater oil recovery. The role of salinity modification is attributed to its ability to shift wettability of a rock surface toward water wetness. The amount of trapped oil released depends on the nature of rock, oil, and brine surface interactions. Reservoir rocks exhibit different affinities to fluids. Carbonates show stronger adsorption of oil films as opposed to the strongly water-wet and mixed-wet sandstones. The concentration of divalent ions and total salinity of the injection brine are other important factors to consider. Accordingly, this paper provides a review of laboratory and field studies of the role of brine composition on oil recovery from carbonaceous rock as well as rationalization of results using DLVO (Derjaguin, Landau, Verwey and Overbeek) theory of surface forces. DLVO evaluates the contribution of each component of the oil/brine/rock system to the wettability. Measuring zeta potential of each pair of surfaces by a charged particle suspension method is used to estimate double layer forces, disjoining pressure, and contact-angle. We demonstrate the applicability of the DLVO approach by showing a comprehensive experimental study that investigates the effect of divalent ions in carbonates, and uses disjoining pressure results to rationalize observations from core flooding and direct contact-angle measurements.
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The stability of foam in porous media is extremely important for realizing the advantages of foamed gas on gas mobility reduction. Foam texture (i.e., bubbles per volume of gas) achieved is dictated by foam generation and coalescence processes occurring at the pore-level. For foam injection to be widely applied during gas injection projects, we need to understand these pore-scale events that lead to foam stability/instability so that they are modeled accurately. Foam flow has been studied for decades, but most efforts focused on studying foam generation and coalescence in the absence of oil. Here, the extensive existing literature is reviewed and analyzed to identify open questions. Then, we use etched-silicon micromodels to observe foam generation and coalescence processes at the pore-level. Special emphasis is placed on foam coalescence in the presence of oil. For the first time, lamella pinch-off as described by Myers and Radke [40] is observed in porous media and documented. Additionally, a new mechanism coined "hindered generation" is found. Hindered generation refers to the role oil plays in preventing the successful formation of a lamella following snap-off near a pore throat.
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Sandstone formations are ubiquitous in both aquifers and petroleum reservoirs, of which clay is a major constituent. The release of clay particles from pore surfaces as a result of reduced injection fluid salinity can greatly modify the recovery of hydrocarbons from subsurface formations by shifting the wettability properties of the rock. In this paper we demonstrate a microfluidic approach whereby kaolinite is deposited into a two-dimensional microfluidic network (micromodel) to enable direct pore-scale, real-time visualization of fluid-solid interactions with representative pore-geometry and realistic surface interactions between the reservoir fluids and the formation rock. Structural characterization of deposited kaolinite particles agrees well with natural modes of occurrence in Berea sandstones; hence, the clay deposition method developed in this work is validated. Specifically, more than 90% of the deposited clay particles formed pore-lining structures and the remainder formed pore bridging structures. Further, regions of highly concentrated clay deposition likely leading to so-called Dalmatian wetting properties were found throughout the micromodel. Two post-deposition treatments are described whereby clay is adhered to the silicon surface reversibly and irreversibly resulting in microfluidic systems that are amenable to studies on (i) the fundamental mechanisms governing the increased oil recovery during low salinity waterfloods and (ii) the effect of a mixed-wet surface on oil recovery, respectively. The reversibly functionalized platform is used to determine the conditions at which stably adhered clay particles detach. Specifically, injection brine salinity below 6000 ppm of NaCl induced kaolinite particle release from the silicon surface. Furthermore, when applied to an aged system with crude oil, the low salinity waterflood recovered an additional 14% of the original oil in place compared to waterflooding with the formation brine.
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In a conventional ramped temperature oxidation kinetics cell experiment, an electrical furnace is used to ramp temperature at a prescribed rate. Thus, the heating rate of a kinetics cell experiment is limited by furnace performance to heating rates of about 0.5-3 °C/min. A new reactor has been designed to overcome this limit. It uses an induction heating method to ramp temperature. Induction heating is fast and easily controlled. The new reactor covers heating rates from 1 to 30 °C/min. This is the first time that the oxidation profiles of a crude oil are available over such a wide range of heating rate. The results from an induction reactor and a conventional kinetics cell at roughly 2 °C/min are compared to illustrate consistency between the two reactors. The results at low heating rate are the same as the conventional kinetics cell. As presented in the paper, the new reactor couples well with the isoconversional method for interpretation of reaction kinetics.