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At least 73 records · Page 4

Modeling of multi-component precipitation and crystallization for zero-liquid-discharge desalination

This study proposes novel ZLD treatment trains that integrate multi-component chemical precipitation and multi-effect evaporative crystallization for efficient brine management. The methodology emphasizes sustainability by integrating CO₂ for chemical precipitation and reducing environmental impact, exemplified with two case studies: produced water that includes industrial waste heat utilization by adopting the emerging vacuum air-gapped membrane distillation (VAGMD) technology, and brackish groundwater that is abundant in sulphate which undergoes treatment by low-salt-rejection reverse osmosis (LSRRO) with interstage chemical precipitation. Here, this study is the first of its kind to simultaneously account for reducing risk of mineral scaling and effective recovery of valuable solids when incorporating VAGMD and LSRRO in ZLD treatment trains. Using Reaktoro and WaterTAP, both Python-based, open-source platforms, we model the recovery of high-purity magnesium, calcium, and sodium salts while optimizing energy consumption and operational efficiency in proposed ZLD pathways for case studies of produced water and brackish desalination brine management. Validation with experimental and reference data confirms the reliability of the models used. In both case studies, the optimized ZLD process achieves recovery rates of 97%, 99%, and 90% for Mg, Ca, and Na, with purities exceeding 99%, and brine volume reduced to less than 4% of the initial feed flow.

3D CT scans↗

On Caprock Seal Integrity of Tuscaloosa Mudstone at Cranfield, MS (USA), CO 2 Injection Site

Saline formations deep underground are among the most promising targets for large-scale geologic carbon storage. The caprock seal integrity evaluation is an important component of commercial-scale CO 2 sequestration projects. Measurements of the porosity and permeability of mudstone samples from the NETL-supported Cranfield Project were performed using a helium porosimeter and a core flow apparatus, before and after exposure in a CO 2 -saturated brine environment. The permeability of the core samples rapidly decreased with the increase in confining pressure and did not fully recover after decompression. On the other hand, exposure to CO 2 led to an increase in the permeability by at least an order of magnitude. The porosity changes after the exposure were not substantial. The post-exposure increase in permeability was subsequently offset by its rapid decrease during the higher-pressure confinement. Extrapolation of the observed permeability trends to in situ reservoir conditions suggests that Tuscaloosa mudstone can effectively serve as a natural seal.

58 GEOSCIENCES↗

Tracer Testing to Characterize Hydraulic Stimulation Experiments at the Raft River EGS Demonstration Site

A series of three tracer tests was conducted over a 3.5-year period as part of the Raft River EGS Demonstration Project in order to characterize the evolution of fluid flow processes resulting from the hydraulic stimulation of the target injection well RRG-9. Injectivity increased very little in RRG-9 as the result of hydraulic stimulation experiments over a 300-day period but increased significantly as brine was injected continuously over the subsequent three years. Here, the tracer tests revealed that fluid flow patterns evolved over time along the injection/production pathway with tracer breaking through progressively earlier and to more wells over the duration of the testing.

EGS↗

Coupled Transport, Reactivity, and Mechanics in Fractured Shale Caprocks

Abstract Shales are low‐permeability caprocks that confine fluid, such as CO 2 , nuclear waste, and hydrogen, in storage formations. Stress‐induced fractures in shale caprocks provide pathways for fluid to leak and potentially contaminate fresh water aquifers. Fractured shales are also increasingly considered as resources for CO 2 sequestration, enhanced geothermal, and unconventional energy recovery. Injecting reactive fluids into shales introduces chemical disequilibrium, causing an onset of a series of dissolution, precipitation, and fines mobilization mechanisms. The reactions have rapid kinetics and significant impact on porosity and permeability; consequently, flow and storage properties of caprocks. While previous research has explored the separate effects of these reactions, this study aims to uncover their simultaneous occurrence and collective influence. This study unveils these highly coupled transport and reactivity mechanisms by tracking and visualizing the reaction‐induced alterations in the matrix, microcracks, and fractures of shales over time. We conducted brine injection experiments sequentially at pH 4 and 2 in a naturally fractured Wolfcamp shale sample while simultaneously imaging the dynamic processes using X‐ray computed tomography (CT). CT images are validated by finer resolution images obtained using micro‐CT and scanning electron microscopy. We also tracked the sample permeability and fluid chemistry using brine permeability and inductively coupled plasma mass spectrometry, respectively. Findings show that fluid primarily flowed through fractures, dissolving reactive minerals and mobilizing fines on fracture surfaces. Dissolution of fracture asperities under confining stress resulted in the closing of fractures. Clogging in narrow fracture pathways, caused by fines accumulation, diverted fluid flow into matrix pores.

58 GEOSCIENCES↗

Potential Formation Damage: An Integrated Reservoir Characterization Study of the Naturally Fractured Carbonate Middle Duperow Formation at the Kevin Dome, Montana

In this study, we integrate geologic and engineering data of a naturally fractured carbonate reservoir at the Kevin Dome, Montana. Well test data are correlated with core description, geochemical and lithology study to determine the flow behavior and communication within the injection test interval and to the surrounding area. Based on a dual-continuum geologic model, numerical brine injection simulations are carried out to validate the interpretation results from our well test analytical models and forecast the probability of CO 2 injection success using current reservoir properties. As a result, our well test analytical models as well as lithology/core description suggest that fluid flow may be mainly restricted to the injection interval and the assumption of radial (horizontal) flow may be appropriate. The well test models also indicate that there is potentially formation damage with a positive skin factor although prior to brine injection well tests, well stimulation through acid treatment was performed. Our numerical simulation results appear to confirm this formation damage by showing additional pressure buildup in the injection data during later test periods. To explain this, acid may have dissolved dolomite then dolomite or calcite may have been formed again further into the matrix/fracture system. Another possible explanation is mechanical clogging of the fractures due to acid dissolving dolomite and dislodging fine grains. Our work also predicts that if no additional well stimulation is performed, the project will have a lower probability of successfully injecting 1 million tons of CO 2 into the Middle Duperow formation over 4 years.

42 ENGINEERING↗

Produced Water and Waste Heat-aided Blowdown Water Treatment: Using Chemical and Energy Synergisms for Value Creation

The project objective was to develop a cooling blowdown water (BDW) treatment process utilizing produced water (PW) and low-grade heat to maximize water reuse and saleable by-product generation while reducing chemical and energy footprints of the treatment. The proposed treatment process consists of mixing, softening, organics and suspended solids removal, reverse osmosis (RO), thermal desalination, and brine electrolysis. BDW samples collected from a local coal-fired power plant and PW samples from two shale gas production wells were used in this study. Each treatment unit was first designed and tested to quantify its treatment efficiency, and its chemical and energy requirements. In addition, a process model was developed and model simulations were conducted based on the experimental results and literature data to optimize the treatment process. A techno-economic analysis was conducted to quantify chemical and energy savings as well as production of 10-lb brine as a saleable product. With the field-collected BDW and PW samples, mixing experiments determined a volumetric mixing ratio 10:1 (BDW:PW) resulted in the best performance of multivalent ions removal and largest chemical savings for softening. Softening of the BDW/PW mixtures using alkaline chemicals (Na 2 CO 3 and NaOH) achieved 95%-100% removal of scaling-forming cations (Ca, Mg, Fe, Ba, Sr) and 60% of silicon, and 10% of total organic carbon (TOC). The mixing and softening treatments yielded an effluent with total dissolved solids (TDS) concentration of 23 g/L. Activated carbon (AC) filtration removed TOC to a low level (< 3 mg/L) and further removed remaining scale-forming divalent metals and silica from the softened water. The AC filtration resulted in a slight reduction of TDS from 23 g/L to 20 g/L, leaving behind only mostly monovalent ions (i.e., sodium and chloride) in the filtered water. These pretreatments yielded a feed water that met the criteria of the downstream reverse osmosis (RO) to prevent membrane fouling. A cross-flow RO system was used to further concentrate the TDS of the AC effluent. Various factors including TDS, pH, and applied pressure were examined and optimal conditions were determined for the co-treatment process. An integrated process consisting of mixing, softening, AC filtration and RO was used to treat a continuous flow (0.25 – 1.2 L/min, or 0.07 – 0.32 gpm) and successfully generated RO permeate as product water (TDS < 0.5 g/L) for reuse in cooling operation, and a concentrate (TDS ~ 45 g/L) to be further treated in a thermal desalination unit. These flow rates meet the FOA’s criterion of 0.01 – 1 gpm. Overall, the co-treatment of BDW/PW allowed shorter ramp-up time compared to treatment of BDW alone. It resulted in 40% and 55% savings of Na 2 CO 3(s) and NaOH, respectively, compared to treating the BDW and PW individually for the same level of softening. The co-treatment also resulted in a 29% energy saving compared to treatment of BDW only for the level of TDS concentration. A thermal desalination system was designed using CFD simulations and manufactured in the WVU Innovation Hub for further treatment of the RO concentrate to generate 10-lb brine. The system has a design flow rate of 2 gpm and has been successfully tested. A bench-scale brine electrolysis system was developed for on-site generation of chlorine/hypochlorite (Cl 2 /OCl - ) and caustic soda (NaOH) as useful chemicals for the co-treatment process. Using salt solutions (0.5 M and 1 M), the system achieved faradaic efficiencies of 93%-97% and 70%-77% for caustic soda and chlorine/hypochlorite generation, respectively. An economic analysis showed that the electricity costs for on-site generation of these chemicals were significantly lower than the chemical prices offered by suppliers. An industrial-scale process model consisting of mixing, softening, AC filtration, RO, thermal desalination, and brine electrolysis was developed using the Aspen Plus V9 in conjunction with Aspen Custom Modeler V9. The model serves as a solvable Aspen Plus model and as basis to form the costing infrastructure. In addition, techno-economic analysis considering capital, operating, and transportation costs was conducted. An optimization solution showed that produced water for mixing is still advantageous in low quantities. The optimum solution approaches a leveled cost of water (LCW) of 2 $/m 3 which becomes cost competitive with nominal water treatment prices.

20 FOSSIL-FUELED POWER PLANTS↗

DECOVALEX-2023: Task E Final Report

This is the Task E final report for DECOVALEX-2023. Task E is focused on understanding thermal, two-phase hydrological, and mechanical (TH2M) processes, especially related to predicting brine migration in the excavation damaged zone around a heated excavation in salt. Salt is attractive as a disposal medium for radioactive waste because it is self-healing and is essentially impermeable and essentially non-porous in the far field (away from excavations). Investigation of the short-term (days to years) near-field (centimeters to tens of meters) behavior of salt is important for radioactive waste disposal because this early period strongly controls the amount of brine in a salt repository. Brine leads to corrosion of waste forms and waste packages, and possible dissolution of radionuclides with brine transport being a potential transport vector to the accessible environment. The main test case used in Task E is the ongoing Brine Availability Test in Salt (BATS) heater test located underground at the Waste Isolation Pilot Plant (WIPP) near Carlsbad, New Mexico, USA. The Task was divided into a series of Steps. Step 0 was an introduction to processes in salt, that included matching historical unheated brine inflow data from boreholes at WIPP and matching temperature observations during BATS heater test 1a. Step 1 included validation of models against a thermo-poroelastic analytical solution relevant to heated boreholes in salt, and two-phase flow around an excavation in salt. Step 2 required all the individual components covered in steps 0 and 1 to come together to match observed brine inflow behavior during the BATS 1a heater test. There were a range of approaches from the teams, from mechanistic to prescriptive. Given the uncertainties in the problem, some teams used one- or two-dimensional models of the processes, while other teams included more geometrical complexity in three-dimensional models. The key learning points from Task E have been: • Heat conduction through salt typically requires non-linear thermal conductivity (as a function of temperature), but most models do a good job matching observations, given appropriate adjustments to the applied power and some thermocouple locations. • Thermal pressurization requires coupled thermal-hydrological-mechanical (THM) responses that consider the thermal expansion of the fluid and solid phases. • Initialization of two-phase flow models around a borehole or excavation in salt are more realistically represented as “wetting up”, rather than “drying down” (i.e., the initial state after excavation is mostly dry, rather than mostly wet). • The BATS 1a heater test includes a significant release of brine after the end of heating, which requires a large increase in permeability to recreate. Task E has been a great learning experience for all the teams involved, and feedback from the modeling teams has led to changes in the design of follow-on BATS experiments, which are now ongoing underground at WIPP. There was a balance throughout the task between freedom to model phenomena how each team saw fit, and prescriptiveness in problem design to bring the modeling teams closer together to allow attribution of smaller differences between models to different modeling choices. The modeling approaches seem to go through two phases: an early phase of discovery or testing, and a later phase of refinement and improvement. In future modeling efforts, different field data could be used (e.g., BATS 2) and more time should be included in the processes for teams to make multiple model refinement or even significant changes to their conceptual model or setup, based on lessons learned from the modeling exercise.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Two-Phase Flow Mechanisms Controlling CO2 Intrusion into Shaly Caprock

Abstract Geologic carbon storage in deep saline aquifers has emerged as a promising technique to mitigate climate change. CO 2 is buoyant at the storage conditions and tends to float over the resident brine jeopardizing long-term containment goals. Therefore, the caprock sealing capacity is of great importance and requires detailed assessment. We perform supercritical CO 2 injection experiments on shaly caprock samples (intact caprock and fault zone) under representative subsurface conditions. We numerically simulate the experiments, satisfactorily reproducing the observed evolution trends. Simulation results highlight the dynamics of CO 2 flow through the specimens with implications to CO 2 leakage risk assessment in field practices. The large injection-induced overpressure drives CO 2 in free phase into the caprock specimens. However, the relative permeability increase following the drainage path is insufficient to provoke an effective advancement of the free-phase CO 2 . As a result, the bulk CO 2 front becomes almost immobile. This implies that the caprock sealing capacity is unlikely to be compromised by a rapid capillary breakthrough and the injected CO 2 does not penetrate deep into the caprock. In the long term, the intrinsically slow molecular diffusion appears to dominate the migration of CO 2 dissolved into brine. Nonetheless, the inherently tortuous nature of shaly caprock further holds back the diffusive flow, favoring safe underground storage of CO 2 over geological time scales.

58 GEOSCIENCES↗

Ion Exchange Processes for CO 2 Mineralization Using Industrial Waste Streams: Pilot Plant Demonstration and Life Cycle Assessment

Abstract An attractive technique for removing CO 2 from the environment is sequestration within stable carbonate solids (e. g., calcite). However, continuous addition of alkalinity is required to achieve favorable conditions for carbonate precipitation (pH>8) from aqueous streams containing dissolved CO 2 (pH<4.5) and Ca 2+ ions. In this study, a pH‐swing process using ion exchange was demonstrated to process 300 L of produced water brine per day for CO 2 mineralization. Proton titration capacities were quantified for aqueous streams in equilibrium with gas streams at various concentrations of CO 2 (pCO 2 =0.03–0.20 atm) and at various flow rates (0.5–2.0 L min −1 ). Energy intensities for the process were determined to be between 30 and 65 kWh per tonne of CO 2 sequestered depending on the composition of the brine stream. A life cycle assessment was performed to analyze the net carbon emissions of the technology which indicated a net CO 2 reduction for pCO 2 ≥0.12 atm (−0.06–−0.39 kg CO 2 e per kg precipitated CaCO 3 ) utilizing calcium‐rich brines. The results from this study indicate the ion exchange process can be used as a scalable method to provide alkalinity necessary for the capture and storage of CO 2 in Ca‐rich waste streams.

Chemistry↗

PREPARATION OF CLAY-COATED GLASS SURFACES FOR MICROFLUIDICS-BASED STUDY ON CLAY-FLUID INTERACTIONS

Unique characteristics of clay, even though make any clay abundant shales a good source of adsorbed gas, make them equally difficult to produce. The clay-water interaction can cause significant swelling and fines migration in the shale formation, both of which can significantly impair the overall hydrocarbon recovery from shale. Geomaterial micromodels, developed by functionalizing traditional glass or PDMS surface with geomaterials (e.g., calcite, quartz, clay) can represent the physico-chemical properties of the natural porous media and have been used during the last few years to understand and evaluate the solid-fluid physicochemical interactions. This study focuses on developing a clay-coated geomaterial surface and investigates the effect of base fluid's salinity on clay adsorption to the glass surface. Glass capillary tubes and straight channel borosilicate glass micromodels are coated with Illite clay minerals to represent the pore-scale clay chemistry of Caney Shale, a Mississippian unconventional play in Southern Oklahoma, USA. 10 wt.% of Illite clay slurries made with brines of four different salinities are used to coat the glass-capillary tubes to understand the effect of salinity in clay adsorption on the glass surface and overall coating quality. To achieve a stable coating and evaluate the impact of heat treatment on coating's stability, straight channel glass flow cells coated with Illite clay are heat-treated at low (25 °C) and high temperature (125 °C). Dynamic flooding tests were carried out with brines on the coated surface to evaluate the stability of the coating. The experiments' outcome indicated a strong relationship between the brine's salinity and the adsorption of clay particles on the glass surface. An increase in brine concentration resulted in improved adsorption of clay particles on the glass surface. Experiments involving heat treating the glass surface following the coating demonstrated significant improvement in the stability of the coating.

02 PETROLEUM↗

Pool boiling on metal-foam enhanced tube bundle: heat transfer characteristics and flow visualization

A flooded evaporator configuration is common in large central air conditioning or process cooling systems. It is basically a shell and tube heat exchanger, in which a secondary fluid (brine or water) circulates inside the tube bundle and is cooled by the vaporization of the refrigerant on the outside surface of the tubes. The enhanced pool boiling process enables the compact design of flooded evaporators, which substantially reduces the refrigerant charge. High-porosity metal foam, with a large surface-area-to-volume ratio, could provide an extended heat transfer area and a high-density of nucleation sites. This study experimentally investigated the pool boiling heat transfer and flow characteristics on metal-foam enhanced tube bundles. The enhanced bundle consists of four aluminum tubes with aluminum foam brazed around the outer surface, which are horizontally mounted in a staggered arrangement. The results showed that the metal-foam enhanced tube bundles improved the heat transfer coefficient by 100-160% with a lower wall temperature difference of 1-10°C, compared to the baseline. In addition, the tube pitch played a significant role in determining the pool boiling behavior of the tube bundles.

Yang, Cheng-Min↗

Impact of exposure to brine/CO 2 on the mechanical and transport properties of the Mt. Simon Sandstone

When sandstone rocks are exposed to CO 2 -saturated brine, their transport and mechanical properties can, potentially, change due to chemical reactions as a result of such exposure. This paper investigates changes in the flow-through characteristics, porosity, and the mechanical properties of Mt. Simon Sandstone samples caused by such exposure to brine/CO 2 . A core, extracted from the Mt. Simon formation, was first characterized for its porosity and relevant transport properties, and it was then aged for over 500 hr in CO 2 -saturated brine at formation-relevant pressure, temperature, and confining stress conditions. The deformation of the sample was measured in situ during aging via strain gauges attached to the core's surface. Following the aging experiment, the sample's porosity and transport properties were again analyzed. Our experiments show that both the porosity and permeability of the Mt. Simon sandstone sample increase due to exposure to brine/CO 2 , with the impact on permeability being more significant. The deformation measurements employing strain gauges indicate a weakening of the core material. Analysis of the composition of the brine at the conclusion of the testing reveals changes, specifically, an increase in the concentration of several of the cations. These changes are indicative of mineral/clay dissolution, consistent with the porosity, permeability, and strain gauge measurements.

58 GEOSCIENCES↗

NRAP-Open-IAM Multisegmented Wellbore Reduced-Order Model

Geologic carbon storage is one of the promising strategies to mitigate climate change by reducing the emission of carbon dioxide to the atmosphere. As part of the National Risk Assessment Partnership (NRAP), a systems-level stochastic analysis tool called the open source integrated assessment model, NRAP-Open-IAM, has been developed to estimate and manage the risk of containment loss at a geological carbon sequestration site. NRAP-Open-IAM contains several wellbore leakage model components that estimate the fluid leak rate that may occur through compromised legacy wells due to the increase in pressure resulting from CO 2 injection activities. Coupled to a reservoir component model, these components estimate the leakage of CO 2 and/or brine from a storage reservoir to overlying aquifer layers and the atmosphere through legacy wells. This report presents the theoretical framework and quality testing of the multisegmented wellbore reduced-order model. The model allows for segmenting of the legacy wells passing through the overlying stratigraphy into several intervals to simulate a site’s specific stratigraphic and hydrogeologic properties. For quality assurance, the analytical model is validated against numerical reservoir flow simulations for single and multiple aquifer(s) models. The results indicate that the model accurately predicts the transport of two-phase fluids (brine and injected CO 2 ) through the well over time. A detailed description of the model helps users to understand the model and provides a basis for future improvements.

58 GEOSCIENCES↗

Dataset documenting reaction-induced changes to five fractured foamed wellbore cement cores during CO2 fluid flow

This dataset consists of reconstructed CT scans for four fractured foamed cement cores, generated in the lab using Portland Class H cement, and associated processed data. The cements were exposed to reactive brines, and CT scans were take at different time points through the experiment. The CT imaging allows for the tracking of dissolution-induced changes to fracture morphology, as well as alteration and dissolution in the cement matrix.

Computed Tomography↗

Treatment of brackish water reverse osmosis brine using only solar energy

Post-treatment of brine produced by reverse osmosis (RO) is a great challenge as it often requires high energy input and works under extreme operating conditions. In this study, brine from a RO plant in El Paso, TX USA was successfully treated using a pilot-scale nanophotonics enhanced solar membrane distillation (NESMD) system. The novel NESMD reactor has a nanophotonic membrane surface area of 0.2 m 2 and an internal heat recovery system to recover the latent heat released during vapor condensation. By utilizing a sweeping gas operational mode under real solar irradiation (585–827 W m -2 ), the NESMD realized successful desalination of RO brine with the membrane flux reaching 0.45–0.65 kg m -2 h -1 and total dissolved solids (TDS) removal greater than 99.5% without an external heat condenser. The decrease in the feed flow rate to the evaporation channel of the NESMD system led to an increase in the gained output ratio (GOR) from 0.35 to 0.62. We report to the best of our knowledge, this is the largest photothermal reactor utilized for the desalination of real RO brine under practical solar irradiation. Compared with conventional brine treatment processes that require high temperature or pressure, the NESMD desalinates RO brine at near-ambient temperature and pressure with free solar energy, providing a promising approach for water desalination, and RO brine post treatment.

42 ENGINEERING↗

Advanced Brine Processing to Enable U.S. Lithium Independence (CRADA Report)

Current production of LiOH, which is needed to make Li-ion battery cathode active materials, utilizes a multistep process including solar evaporation, precipitation with Na 2 CO 3 and then conversion to LiOH using Ca(OH) 2 . This process requires a large amount of land area for solar evaporation, the right weather conditions, and chemicals for the conversion process that result in NaCl and CaCO 3 waste products. The production of Ca(OH) 2 is very energy intensive and evolves significant quantities of CO 2 . An alternative process flow utilizing direct lithium extraction techniques, followed by a chemical free conversion process can have benefits in reducing the needed land requirements and chemicals for traditional brine processing. There are many potential direct lithium extraction technologies that are currently being developed. The direct lithium extraction process from typical brine sources will produce a LiCl solution with some impurities including typically high concentrations of Na. This brine then needs to be converted to LiOH for use in battery cathode production. Ideally this conversion could occur without the use of additional chemicals. Electrochemistry can do this conversion either via electrolysis or bipolar membrane electrodialysis (BPED) to produce LiOH and HCl in solution. BPED utilized bipolar membranes to split water, which has a reduced potential as compared to splitting water at electrodes into hydrogen and oxygen gas. This reduced potential required results in a significant energy savings for BPED over electrolysis methods. This CRADA project aimed to develop such an integrated process using direct lithium extraction followed by BPED to produce a LiOH solution. That solution can then be crystallized into battery grade LiOH. In particular, Albemarle utilized a direct lithium extraction process to produce a concentrated LiCl solution that could be used for the BPED process. The BPED process was first tested using various LiCl solutions with impurity ions added at bench scale to understand the effects of impurities and determine processing parameters. Then testing was performed using the direct lithium extracted brine at the bench scale before scaling the process up. After the process was scaled up a long duration test was carried out to estimate the lifetime of the membranes, which is key to the economics of the BPED process.

25 ENERGY STORAGE↗