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At least 91 records · Page 5

Air quality impacts from the development of unconventional oil and gas well pads: Air toxics and other volatile organic compounds

Unconventional oil and natural gas development (UOGD) has expanded rapidly across the United States in recent decades and raised concerns about associated air quality impacts. While significant effort has been made to quantify methane emissions, relatively few observations have been made of Volatile Organic Compounds (VOCs), especially during drilling and completion of new wells. Extensive air monitoring during development of several large, multi-well pads in Broomfield, Colorado, in the Denver-Julesburg Basin, provides a novel opportunity to examine changes in local air toxics and other VOC concentrations during well drilling and completions and production. These operations offer an especially useful case to study as several management practices were implemented to reduce emissions (e.g., electrified, grid-powered drill rigs and closed loop fluid handling systems to reduce truck traffic and limit fluid handling on the pad). With simultaneous measurements of methane and 50 VOCs from October 2018 to December 2022 at as many as 19 sites near well pads, in adjacent neighborhoods, and at a more distant reference location, we identify impacts from each phase of well development and production. Use of weekly, time-integrated canisters, a Proton Transfer Reaction Mass Spectrometer (PTR-MS), continuous photoionization detectors (PID) to trigger canister collection upon detection of VOC-rich plumes, and an instrumented vehicle, provided a powerful suite of measurements to characterize both transient plumes and longer-term changes in air quality. Prior to the start of well development, VOC gradients were small across Broomfield. Once drilling commenced, concentrations of oil and gas (O&G) related VOCs, including alkanes and aromatics, increased around active well pads. Concentration increases were clearly apparent during certain operations, including drilling, coil tubing/millout operations, and production tubing installation. Emissions of C 8 –C 10 n-alkanes during drilling operations highlighted the importance of VOC emissions from synthetic drilling mud chosen to reduce odor impacts. More than 90 samples were collected of transient plumes. Using composition measurements, meteorological data, and information about well pad activities, these plumes were connected with specific UOGD operations including drilling, flowback, and production equipment maintenance. The chemical signatures of these plumes differed by operation type (e.g., C 8 –C 10 n-alkanes constituted a larger fraction of measured VOCs in drilling-related plumes). Concentrations of individual, oil and gas-related VOCs in these plumes were often several orders of magnitude higher than in background air, with maximum ethane and benzene concentrations of 79,600 and 819 ppbv, respectively. Because these plumes typically impact a monitoring site for just several minutes, they are easily missed by slower-responding instruments. Study measurements highlight future emission mitigation opportunities during UOGD operations, including better control of emissions from shakers that separate drill cuttings from drilling mud, production separator maintenance operations, and periodic emptying of sand cans during flowback operations.

54 ENVIRONMENTAL SCIENCES↗

Predicting the potential for mineral scale precipitation in unconventional reservoirs due to fluid-rock and fluid mixing geochemical reactions

Mineral precipitation within hydraulically fractured shale may affect fluid flow pathways and impact longterm hydrocarbon production. The ability to predict geochemical reactions that lead to problematic mineral precipitation will lead to active reservoir management strategies to improve overall production. Using the Marcellus Shale as a case study, a combination of laboratory experiments and reaction path modeling was applied to determine which reactions are likely to occur upon introduction of hydraulic fracturing fluid into the shale reservoir. Experimental results indicate that contact between fracturing fluid and shale will result in dissolution of primary minerals (quartz, feldspars, kaolinite, chlorite, pyrite) and secondary mineral precipitation over time periods of less than one week. Precipitation of barite, Fe-oxides, feldspars, amorphous silica and clay is likely to occur within the reservoir during shut in and early flowback due to mixing between fracturing fluid and reservoir brine as based on modeling saturation indices using experimental fluid data. Reaction path modeling of the experimental scenarios corroborates the specific dissolution and precipitation reactions observed experimentally. Comparison of the results to injected and produced waters from a Marcellus Shale well pad in Greene County, PA, USA, shows that the mineral reactions occur during the hydraulic fracturing, shut in, and early flowback periods. The results presented in this paper demonstrate the value in applying experimental approaches to identify mineral precipitation/dissolution reactions that may significantly impact reservoir performance. The good agreement between geochemical models and experimental results provides confidence that numerical models can be applied to screen the potential fluid-mineral and fluid-mixing reactions in unconventional reservoirs that result in undesired mineral scale precipitation.

58 GEOSCIENCES↗

Multi-Size Proppant Pumping Schedule of Hydraulic Fracturing: Application to a MP-PIC Model of Unconventional Reservoir for Enhanced Gas Production

Slickwater hydraulic fracturing is becoming a prevalent approach to economically recovering shale hydrocarbon. It is very important to understand the proppant’s transport behavior during slickwater hydraulic fracturing treatment for effective creation of a desired propped fracture geometry. The currently available models are either oversimplified or have been performed at limited length scales to avoid high computational requirements. Another limitation is that the currently available hydraulic fracturing simulators are developed using only single-sized proppant particles. Motivated by this, in this work, a computationally efficient, three-dimensional, multiphase particle-in-cell (MP-PIC) model was employed to simulate the multi-size proppant transport in a field-scale geometry using the Eulerian–Lagrangian framework. Instead of tracking each particle, groups of particles (called parcels) are tracked, which allows one to simulate the proppant transport in field-scale geometries at an affordable computational cost. Then, we found from our sensitivity study that pumping schedules significantly affect propped fracture surface area and average fracture conductivity, thereby influencing shale gas production. Motivated by these results, we propose an optimization framework using the MP-PIC model to design the multi-size proppant pumping schedule that maximizes shale gas production from unconventional reservoirs for given fracturing resources.

42 ENGINEERING↗

Structural Design and Aeromechanical Analysis of Unconventional Blades for Future Mars Rotorcraft

The structural design for rotor blades with thin, unconventional airfoils for Earth-based testing is obtained using three-Dimensional (3D) aeromechanical analysis. This analysis is in support of the NASA ROAMX project. The outer mold was provided by NASA, but the internal structural design was developed at the University of Maryland and is presented here, along with a thorough aeromechanical analysis. The main objectives are to verify the structural integrity of the design and understand the unique aeroelastic behavior of the non-conventional airfoils designed for low-Reynolds number and high-Mach number flow. Six different blade models are considered, with the pitch axis varied from quarter-chord to mid-chord to determine the effect of C.G. offset on natural frequencies, blade deformations, root loads, and 3D stresses. All six blade designs are first studied under rotation in pure vacuum, and significant reductions in root loads and 3D stresses are achieved by moving the pitch axis closer to mid-chord to reduce the C.G. offset. Based on the vacuum analysis, the blade design with the pitch axis at 40% chord is selected for aerodynamic analysis. The blade control load, airloads, deformations, and 3D stresses are studied for steady hover. Dynamic control load and dynamic 3D stresses are studied for unsteady hover achieved using cyclic. Significant elastic twist is observed due to the trapeze effect and propeller moment, affecting the spanwise distribution of aerodynamic loads on the blades. However, the effect of aerodynamic loads on 3D stresses and the blade control load is found to be minimum. The dynamic control load is found to increase significantly due to inertial coupling from the C.G. offset. The dynamic stresses also increase, although still have factors of safety greater than two for both tensile and compressive stress.

Structural Design↗

Structural Design and Aeromechanical Analysis of Unconventional Blades for Future Mars Rotorcraft

The structural design for rotor blades with thin, unconventional airfoils for Earth-based testing is obtained using three-Dimensional (3D) aeromechanical analysis in support of the NASA ROAMX project. The outer mold line was provided by NASA, but the internal structural design was developed at the University of Maryland and is presented here along with a thorough aeromechanical analysis. The main objectives are to verify the structural integrity of the design and understand the unique aeroelastic behavior of the non-conventional airfoils designed for low-Reynolds number and high subsonic Mach number. Four different blade models are considered, with the pitch axis varied from quarter-chord to mid-chord to determine the effect of C.G. offset on natural frequencies, blade deformations, root loads, and 3D stresses. First, torsional stability is calculated for each of the designs – especially important due to the low Lock number on Mars. All four blade designs are studied under rotation in vacuum, and significant reductions in root loads and 3D stresses are achieved by moving the pitch axis closer to mid-chord to reduce the C.G. offset. Based on the vacuum analysis, the blade design with the pitch axis at 40% chord is selected for aeromechanical analysis. The blade control load, airloads, deformations, and 3D stresses are studied for steady hover. Dynamic control load and dynamic 3D stresses are studied for unsteady hover achieved using cyclic. Significant elastic twist is observed due to the trapeze effect and propeller moment, affecting the spanwise distribution of aerodynamic loads on the blades. The dynamic control load is found to increase significantly due to inertial coupling from the C.G. offset. The dynamic stresses also increase, although still have factors of safety greater than two for both tensile and compressive stress.

Structural Design↗

Spin Frustration and Unconventional Surface Spin Canting State in Van der Waals Ferromagnet/Antiferromagnet Heterostructures

Atomically flat surfaces of van der Waals (vdW) materials pave an avenue for addressing a long-standing fundamental issue of how a compensated antiferromagnet (AFM) surface frustrates a ferromagnetic (FM) overlayer in FM/AFM heterostructures. We investigate Fe5GeTe2/NiPS3 vdW heterostructures by characterizing AFM and FM spins separately. We find that in-plane zig-zag AFM NiPS3 develops three equivalent AFM domains, which are robust against external magnetic field and magnetic coupling with Fe5GeTe2. Moreover, evidence is provided of in-plane-AFM-induced perpendicular magnetic anisotropy (PMA) in adjacent Fe5GeTe2, and an unconventional out-of-plane surface spin canting state with the Fe5GeTe2 spins spatially turn from out-of-plane direction near the interface to in-plane direction away from the interface in Fe5GeTe2/NiPS3. The out-of-plane surface spin canting is a unique property of spin frustration in vdW magnetic heterostructures.

Wang, Tianye↗

Unconventional Highly Active and Stable Oxygen Reduction Catalysts Informed by Computational Design Strategies

Abstract Discovering and engineering new materials with fast oxygen surface exchange kinetics and robust long‐term stability is essential for the large‐scale, economically viable commercialization of solid oxide fuel cell (SOFC) technology. The perovskite catalyst material BaFe 0.125 Co 0.125 Zr 0.75 O 3 (BFCZ75), predicted to be promising from recent density functional theory (DFT) calculations and unconventional due to its extremely high Zr content and low electronic conductivity, exhibits oxygen reduction reaction surface exchange rates on par with Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3 (BSCF) and excellent stability at typical operating temperatures. New composite electrodes are engineered by integrating BFCZ75 with commercial electrode materials La 1– x Sr x MnO 3 (LSM) and La 1– x Sr x Co y Fe 1– y O 3 (LSCF) and achieve high performance as measured by low area specific resistance (ASR) values, with the LSCF/BFCZ75 ASR values comparable to top performing noncomposite electrode materials such as SrCo 0.8 Sc 0.2 O 3– δ , BaNb 0.05 Fe 0.95 O 3– δ and BaCo 0.7 Fe 0.22 Y 0.08 O 3– δ . The use of BFCZ75 as a composite with LSCF achieving low ASR values shows that BFCZ75 is highly active and can easily integrate into existing SOFC material supply chains, lowering the barrier for potential commercial application of new electrode materials. Finally, these findings point to a broader unexplored class of perovskite materials with high fractions of redox inactive species (e.g., Zr, Nb, and Ta) that may unlock new pathways to realizing improved commercial SOFCs.

Jacobs, Ryan↗

Unconventional Pathway in the Gas‐Phase Synthesis of 9 H ‐Fluorene (C 13 H 10 ) via the Radical–Radical Reaction of Benzyl (C 7 H 7 ) with Phenyl (C 6 H 5 )

Abstract The simplest polycyclic aromatic hydrocarbon (PAH) carrying a five‐membered ring—9 H ‐fluorene (C 13 H 10 )—is produced isomer‐specifically in the gas phase by reacting benzyl (C 7 H 7 ⋅) with phenyl (C 6 H 5 ⋅) radicals in a pyrolytic reactor coupled with single photon ionization mass spectrometry. The unconventional mechanism of reaction is supported by theoretical calculations, which first produces diphenylmethane and unexpected 1‐(6‐methylenecyclohexa‐2,4‐dienyl)benzene intermediates (C 13 H 12 ) accessed via addition of the phenyl radical to the ortho position of the benzyl radical. These findings offer convincing evidence for molecular mass growth processes defying conventional wisdom that radical‐radical reactions are initiated through recombination at their radical centers. The structure of 9 H ‐fluorene acts as a molecular building block for complex curved nanostructures like fullerenes and nanobowls providing fundamental insights into the hydrocarbon evolution in high temperature settings.

He, Chao↗

Unconventional Pathway in the Gas-Phase Synthesis of 9 H -Fluorene (C 13 H 10 ) via the Radical–Radical Reaction of Benzyl (C 7 H 7 ) with Phenyl (C 6 H 5 )

The simplest polycyclic aromatic hydrocarbon (PAH) carrying a five-membered ring - 9H-fluorene (C 13 H 10 ) - is produced isomer-specifically in the gas phase by reacting benzyl (C 7 H 7 •) with phenyl (C 6 H 5 •) radicals in a pyrolytic reactor coupled with single photon ionization mass spectrometry. The unconventional mechanism of reaction is supported by theoretical calculations, which first produces diphenylmethane and unexpectedly 1-(6-methylenecyclohexa-2,4-dienyl)benzene intermediates (C 13 H 12 ) accessed via addition of the phenyl radical to the ortho position of the benzyl radical. These findings offer convincing evidence for molecular mass growth processes defying conventional wisdom that radical–radical reactions are initiated through recombination at their radical centers. Furthermore, the structure of 9H-fluorene acts as a molecular building block for complex curved nanostructures like fullerenes and nanobowls providing fundamental insights into the hydrocarbon evolution in high temperature settings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Unconventional Photoconversion from In‐Plane 2D Heterostructures of 2D Transition Metal Carbides/Semiconductors

2D transition metal carbides/nitrides (MXenes) are thought of promising photothermal materials due to their broadband localized surface plasma resonance (LSPR) and attractive electromagnetic interference (EMI) properties. However, the weak oxidation resistance and unclear photothermal mechanism of MXenes impede their photothermal modulations. Herein, the in‐plane 2D Ti 3 C 2 /TiO 2 heterostructures are fabricated by partial oxidation and an unconventional photothermal effect under near infrared irradiation, even if the oxidation compromises the EMI and LSPR capacities, is demonstrated. Such performance is ascribed to the faster transfer of photoexcited electrons across the seamless in‐plane Ti 3 C 2 /TiO 2 heterointerface than the reported out‐of‐plane one, and the 1–2 orders of magnitude faster relaxation processes of electrons than the ground bleaching in the Original MXene. These experimental results are well‐supported by theoretical calculations. The conceptual advances broaden the fundamental understanding of the photoconversion of MXenes, which would be extended into a variety of applications, such as biomedical therapy, photosynthesis, and photovoltaics.

Energy & Fuels↗

Intrinsic Bulk Quantum Oscillations in a Bulk Unconventional Insulator SmB 6

The finding of bulk quantum oscillations in the Kondo insulator SmB 6 proved a considerable surprise. Subsequent measurements of bulk quantum oscillations in other correlated insulators including YbB 12 lent support to our discovery of a class of bulk unconventional insulators that host bulk quantum oscillations. Here we perform a series of experiments to examine evidence for the intrinsic character of bulk quantum oscillations in floating zone-grown single crystals of SmB 6 that have been the subject of our quantum oscillation studies. We present results of thermodynamic, transport, and composition analysis experiments on pristine floating zone-grown single crystals of SmB 6 and compare quantum oscillations with metallic LaB 6 and elemental aluminum. These results establish the intrinsic origin of quantum oscillations from the insulating bulk of floating zone-grown SmB 6 . The similarity of the Fermi surface in insulating SmB 6 with the conduction-electron Fermi surface in metallic hexaborides is at the heart of a theoretical mystery.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

A Novel Zwitterionic Chromatography Approach to Separate Lithium from Unconventional Resources

Lithium (Li) is a key element for clean energy technologies, and, accordingly, the global lithium demand has been increasing rapidly. Therefore, to meet the Li demand and maintain supply chain stability, it is critical to develop efficient lithium extraction technologies that allow exploitation of unconventional lithium resources, such as geothermal brines and inland brine streams. However, the recovery of Li from these resources is challenging due to low Li concentration, low ratios of Li/Na, Li/Mg, or Li/Ca, and complex feed compositions. To address this, we introduced a new Direct Lithium Extraction (DLE) process using Zwitterionic Chromatography (ZIC) to separate Li from other salts. Since salts are partitioned on ZIC under water elution, no reagent chemicals are needed, and the Li separation is not limited by the adsorption capacity. We prepared 13 different zwitterionic (ZI) resins to investigate the salt retention on various ZI groups and then screened out promising sorbents for efficient Li separation. It was found that salt retention was synergistically affected by the pore size and ZI configurations. Using carboxybetaine (QAC3CA) sorbents, multicomponent separations showed that Li can be partitioned from divalent salts or Na with selectivities of 1.8 or 1.9, respectively. Although the selectivity is relatively low, in real brine tests, Li was separated from Ca and Mg with 79.2 % yield, showing the potential for a continuous process to achieve high productivity and high yield. Simulation studies suggest the salt elution mechanism is related to the hydration reaction energy and the effective hydrated radius of cations.

critical minerals↗

Impact of Acid–Base Stimulation Sequence on Mineral Stability for Tight/Impermeable Unconventional Carbonate-Rich Rocks: A Delaware Basin Case Study

We report mineral precipitation due to reactions with injected fluids during unconventional fracture stimulation is a well-recognized problem. The goal of this study is to evaluate secondary mineral precipitation and permeability attenuation under chemical injection scenarios specific to the Delaware basin. Whole cylindrical cores (2.54 cm diameter and 2.54 cm height) and ground shale (150–250 μm) from the carbonate-rich Bone Spring Formation, Delaware Basin TX (Leonardian), were reacted at 80 °C and 85 bar using a hydraulic fracturing fluid (HFF) recipe and an injection sequence typical of the Delaware Basin. The reacted shales and solutions were analyzed using a variety of laboratory- and synchrotron-based techniques to characterize both the chemical and spatial distributions of secondary mineral precipitation and identify changes in permeability and mineralogy. This carbonate-rich shale (>84% calcite) rapidly neutralized the acidic HFF. Synchrotron-based X-ray fluorescence mapping coupled with X-ray absorption spectroscopy (both bulk and micro) showed that most of the iron was in an oxidized form prior to exposure to HFF and that almost all iron(II) became fully oxidized after the reaction. Scanning electron microscopy images of the ground shale samples primarily identified iron(oxyhydr)oxide microcrystals on grain surfaces. A few small isolated iron-rich areas also contained sulfur, suggesting that some pyrite was preserved when isolated within a calcite crystal but that most was oxidized. The rapid neutralization of the acid spearhead in these carbonate-rich samples demonstrates that the acid spearhead is useful for initiating fractures in extremely calcite-rich rocks but does little to enhance rock permeability. This suggests that the impact of the acid spearhead is significantly smaller for carbonate-rich shales compared to clay-rich shales, which has broad implications for acidizing in carbonate-rich shale formations and iron transformations within these shales.

58 GEOSCIENCES↗

Experimental Investigation of Barium Sources and Fluid–Rock Interaction in Unconventional Marcellus Shale Wells Using Ba Isotopes

Produced waters from unconventional Marcellus Shale gas wells have anomalously high barium (Ba) concentrations and yield some of the isotopically heaviest Ba measured to date. Experiments were conducted to constrain the source of Ba in these fluids and the controls on barite (BaSO 4 ) precipitation and dissolution in oil and gas wells. Experiments simulating the acidizing stage evaluated the solubility of pure barite and drilling mud in 2 M HCl at 80 °C for periods of 2, 6, and 48 h and resulted in <0.01% barite dissolution with no appreciable change in δ 138 Ba ( 138 Ba/ 134 Ba normalized to NIST standard 3104a). Static autoclave experiments conducted at 66 °C and 20.7 MPa with combinations of ground Marcellus Shale solids and/or barite-bearing drilling mud with synthetic low-Ba fracturing fluid resulted in decreased Ba concentrations in the fluid, with the largest decrease in the shale-only run. Fluid δ 138 Ba values increased by about 0.5‰ as Ba concentrations decreased, consistent with closed-system Rayleigh fractionation. Flow-through experiments in Marcellus Shale core conducted for 28 days resulted in effluent Ba concentrations an order of magnitude lower than the influent, while sulfate concentrations increased over time. Effluent δ 138 Ba values increased over the first 12 days and plateaued at about 1‰ higher than the influent. Modeling suggests a combination of the release of labile shale Ba and barite precipitation. This work indicates that the processes of Ba release from fluid–shale interactions and barite precipitation in fractures and the well bore, while capable of producing high δ 138 Ba fluids, are unlikely to generate fluids with high-Ba concentrations and δ 138 Ba values like those in Marcellus-produced waters. As a result, we find that the release of sulfate from shale pyrite oxidation rapidly catalyzes barite precipitation and that dissolution of drilling mud barite or natural barite in the shale is unlikely to be the major source of Ba in Marcellus-produced waters.

54 ENVIRONMENTAL SCIENCES↗

Dissolving Nonionic Surfactants in CO 2 to Improve Oil Recovery in Unconventional Reservoirs via Wettability Alteration

CO 2 injection is a promising method for enhanced oil recovery (EOR) in unconventional shale reservoirs. Here, in this work, we postulate that CO 2 EOR may be improved by the dissolution of surfactants into CO 2 . Although CO 2 is a relatively good solvent for oil, we show that CO 2 and Eagle Ford oil are immiscible at compositions above 70 wt % CO 2 , even at pressures as high as 62 MPa. The presence of a CO 2 –oil interface at reservoir conditions indicates that the addition of a surfactant has the potential to improve oil recovery–via wettability alteration from oil-wet to CO 2 -wet, CO 2 –oil interfacial tension (IFT) reduction, or both. Three nonionic surfactants (branched tridecyl ethoxylate Indorama SURFONIC TDA-9, branched nonylphenol ethoxylate Indorama SURFONIC N-100, and linear dodecyl ethoxylate Indorama SURFONIC L12-6) were evaluated for CO 2 -solubility, shale wettability alteration, effect on CO 2 –oil IFT, ability to generate CO 2 –oil foams, and ability to increase oil extraction from Eagle Ford, Mancos, and Bakken shale cores. Each surfactant dissolved in CO 2 up to 1 wt % at pressures and temperatures commensurate with CO 2 EOR. CO 2 -dissolved surfactants did not significantly affect CO 2 –oil IFT or generate CO2–oil foams, but they did induce a dramatic change in the contact angle of an oil droplet on an oil-aged shale chip in CO 2 from strongly oil-wet (11°) toward intermediate CO 2 –oil wettability (82°) (at 80 °C, 27.6 MPa). The branched tridecyl ethoxylated surfactant, SURFONIC TDA-9, afforded the highest oil recovery in core soaking experiments–75%, compared to 71% by pure CO 2 . Analysis of oil extracts by gas chromatography revealed that heavier oil components were produced when the surfactant was added to CO 2 . These results indicate that CO 2 -dissolved surfactants may increase oil recovery from shale by wettability alteration from oil-wet toward CO 2 -wet.

04 OIL SHALES AND TAR SANDS↗

Chemical Speciation and Stability of Uranium in Unconventional Shales: Impact of Hydraulic Fracture Fluid

Uranium and other radionuclides are prominent in many unconventional oil/gas shales and is a potential contaminant in flowback/produced waters due to the large volumes/types of chemicals injected into the subsurface during stimulation. In this work, to understand the stability of U before and after stimulation, a geochemical study of U speciation was carried out on three shales (Marcellus, Green River, and Barnett). To do so, two types of samples for each shale were subjected to sequential chemical extractions: unreacted and shale-reacted with a synthetic hydraulic fracture fluid. Furthermore, a significant proportion of the total U (20–57%) was released from these three shales after reaction with fracture fluid, indicating that U is readily leachable. The total U released exceeds labile water-soluble and exchangeable fractions in unreacted samples, indicating that fluids leach more recalcitrant phases in the shale. Radiographic analysis of unreacted Marcellus shale thin sections shows U associated with detrital quartz and the clay matrix in the shale. Detrital zircon and TiO2 identified by an electron microprobe could account for the hot spots. This study shows that significant proportions of U in three shales are mobile upon stimulation. In addition, the extent of mobilization of U depends on the U species in these rocks.

58 GEOSCIENCES↗

Controls on Barite (BaSO 4 ) Precipitation in Unconventional Reservoirs

Barite (BaSO 4 ) precipitation is one of the most ubiquitous examples of secondary sulfate mineral scaling in shale oil and gas reservoirs. Often, a suite of chemical additives is used during fracturing operations to inhibit the accumulation of mineral scales, though their efficacy is widely varied and poorly understood. This study combines experimental data and multi-component numerical reactive transport modeling to offer a more comprehensive understanding of the geochemical behavior of barite accumulation in shale matrices under conditions typical of fracturing operations. A variety of additives and conditions are individually tested in batch reactor experiments to identify the factors controlling barite precipitation. Our experimental results demonstrate a pH dependence in the rate of barite precipitation, which we use to develop a predictive model including a pH-dependent term that satisfactorily reproduces our observations. Further, this model is then extended to consider the behavior of three major shale samples of highly variable mineralogy (Eagle Ford, Marcellus, and Barnett). This data-validated model offers a reliable tool to predict and ultimately mitigate against secondary mineral accumulation in unconventional shale reservoirs.

54 ENVIRONMENTAL SCIENCES↗