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At least 343 records · Page 19

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DOE OSTI2022

Ultra-fast and Thick Boriding of Geothermal Casing to Enhance Reliability

Harnessing the heat that is continuously generated underneath the Earth’s crust (geothermal) is a clean and renewable source of energy. Geothermal energy can be used to heat and cool buildings, including greenhouses, and to generate electrical power. Compared to other renewable energy sources such as solar and wind, geothermal energy is more reliable because it is available all the time and versatile in its many forms of application and deployment. Nonetheless, the deployment and extensive use of geothermal energy still lags behind other renewable sources due to some technical, but mainly economic challenges. Upfront costs of geothermal power well development are relatively high. Some of this high cost is attributed to the use of expensive construction materials to ensure adequate performance during operation. For example, Inconel 625, super duplex 2507, and titanium alloy materials are used in downhole casings, piping, and other components exposed to brine solution to withstand harsh operating environments (high temperature and corrosive environments). Relatively low-cost carbon steel can be used in many of these components in geothermal power plants; however, they are susceptible to excessive corrosion, thereby limiting their useful lifespan. Ultra-fast boriding (UFB) surface treatment of carbon steel may drastically increase its corrosion resistance thereby providing a cost-effective material solution in geothermal applications. Scientists at Argonne National Laboratory (ANL) recently developed a technique to accelerate the boriding process using a high-temperature electrochemical process to produce relatively thick boride layers on various metal and alloy materials in minutes rather than the several hours it takes through the typical pack boriding process; hence, the process is designated UFB. The process uses molten borax salt at 900– 1000°C in an electrochemical cell in which the material to be borided is the cathode and a graphite plate is the anode. Continuous and durable boride layers with thicknesses of 100–300 µm have been produced on a variety of metals and alloys in one hour. Such a surface layer can indeed be a cost-effective pathway to prevent corrosion of casing materials in contact with the chemically aggressive and corrosive geothermal brine fluids.

15 GEOTHERMAL ENERGY↗

DOE OSTI2022

(Project 18-15531) Repair and Mitigation of Chloride-Induced Pitting and Chloride-Induced Stress Corrosion Cracking in Used Spent Nuclear Fuel Dry Cask Canister Materials (Final Technical Report)

Several experimental techniques were utilized to understand the corrosion and SCC performance of possible techniques for repairing cracks and pits in SS304 utilized for dry cask storage of spent nuclear fuel. The repairs examined included cold spray, FSW, soldering, and VFAW. The corrosion and SCC assessment techniques utilized for comparing repairs against the base material were 4-pt bending SCC testing in boiling MgCl 2 at stress levels between 0 MPa and 350 MPa, immersion testing in 40% RH brine solution meant to mimic a service-like environment, SSRT SCC testing in 40% RH brine solution. For FSW alone, scanning electrochemical cell microscopy and microelectrochemical syringe cell were utilized to understand the corrosion performance across the weld, in the retreating/advancing sides, and base material. Based on the results of this study, the FSW and cold spray repair techniques proved most viable for SCC repair in SS304 dry cask storage applications and continuing research is highly recommended to understand and quantify in further detail their SCC performance compared to unrepaired SS304. Additionally, solder and VFAW (patch or incline) would not be recommended based on the corrosion and SCC findings in this study.

42 ENGINEERING↗

DOE OSTI2023

NRAP-Open-IAM Multisegmented Wellbore Reduced-Order Model: Improvement and Quality Assurance

The multisegmented wellbore model (MSW) semi-analytically estimates the amount of CO 2 and brine leakage from a leaking legacy well by segmenting it into intervals to simulate site-specific stratigraphic and hydrogeologic properties. The model is a component of the National Risk Assessment Partnership Open-Source Integrated Assessment Model (NRAP-Open-IAM), which was developed to perform risk assessment for geologic CO 2 storage. The new wellbore leakage model, which uses deep learning networks for a caprock segment, was developed to enhance the analytical MSW. The model was trained and validated using a synthetic data set of Subsurface Transport Over Multiple Phases (STOMP) multiphase flow simulations from various geological, well attribute, and operational conditions to ensure its quality. The results demonstrate that the model is more accurate than the existing model in predicting the transport of two-phase fluids (brine and injected CO 2 ) through the well. This report provides a detailed explanation of the model development and quality assurance.

58 GEOSCIENCES↗

DOE OSTI2024

Magnetic Nanoparticle Extraction of Lithium from Produced Waters - CRADA 483 (Final Report)

The demand for lithium in the energy production industry is expected to increase sharply, development of simple and cost-effective techniques for lithium production and recovery from various lithium sources is essential. In this project, core/shell magnetic nanoparticles were successfully designed to selectively extract lithium from aqueous lithium sources as an extension of Pacific Northwest National Laboratory’s magnetic nanofluid extraction technology. The core/shell magnetic nanoparticles are composed of manganese oxide-based lithium ion sieve shells, which allow selective lithium uptake from brines with multiple coexisting ions, over iron oxide cores, which can respond to external magnetic fields for effective recovery and reuse of adsorbents from a liquid. The synthesized lithium ion-sieves and core/shell magnetic nanoparticles were characterized using several techniques to reveal their crystallinity and morphology. The lithium uptake properties of the lithium ion-sieves and core/shell magnetic nanoparticles were evaluated in terms of lithium adsorption capacity, removal percentage, selectivity, and cycling performance in simulated and natural brines. Magnetic properties of the core/shell magnetic nanoparticles were tested by measuring magnetic saturation, and magnetic response of colloidal solutions containing the core/shell magnetic nanoparticles was tested with permanent magnets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Plutonium Oxidation State Distribution in the Presence of WIPP-Relevant Organics and Iron Corrosion Products

The oxidation state and solubility of plutonium (Pu) in high ionic strength synthetic WIPP (Waste Isolation Pilot Plant) brines as a function of pC H+ in the presence and absence of WIPP-relevant organic ligands (EDTA [Ethylenediaminetetraacetic acid], oxalate, citrate, acetate) and iron corrosion products (magnetite and metallic iron) at 𝑇 = 23 ± 2 ∘C was thoroughly studied by long-term batch solubility experiments (between approximately 800-1,100 days) from an undersaturation approach. The oxidation state of Pu in the WIPP environment has been a topic of interest since the initial Compliance Certification Application (CCA). This study aims to investigate the solubility of Pu under the expected WIPP conditions and to determine the oxidation state of the solid phase that will control the solubility. One of the most important results of this study is that the Pu oxidation state was analyzed both from the surface area of the corrosion products and in the precipitated solid. The analysis of the Pu oxidation state on the surface of the iron mineral from the ongoing undersaturated experiments is more relevant to the performance assessment of nuclear waste disposal than short term batch (plutonium-iron phase) experiments. The X-ray Absorption Near-Edge Spectroscopy (XANES) analysis showed that Pu oxidation state is different on the metal surface and in the precipitated solid. Pu(III) is the dominant oxidation state in the metallic iron (Fe 0 ) system in the presence and absence of organics. Pu(IV) is the dominant oxidation state in the magnetite system in the presence and absence of organics. Also, organics stabilize Pu(IV) in the magnetite system. Analysis of Pu in the precipitated solid by Extended X-ray Absorption Fine Structure (EXAFS) analysis showed that Pu formed an inner-sphere complex with iron with minor amounts of PuO 2 present. X-ray diffraction (XRD) results indicate that metallic iron and magnetite did not oxidize in three years in the alkaline and high ionic strength system. Under these conditions (8 < pC H+ < 10 at T = (22 ± 2) °C under nitrogen atmosphere, the solubility of Pu changes by up to three orders of magnitude (10 -5 and 10 -8 M). The spread in solubility is highest at pC H+ = 9. Pu(III) and Pu(IV) showed different solubility behavior in the synthetic WIPP brine. A summary of the data collected in this report will be submitted to Sandia National Laboratories as part of a parameter update report which will outline the changes to the OXSTAT parameter for the 2026 Compliance Recertification Application (CRA-2026). The experiments performed were done according to the U.S. Department of Energy (DOE) approved Test Plan entitled “Effects of Radiolysis, Organic Complexation, and Redox Conditions on the Speciation and Oxidation State Distribution of Pu(III/IV)” (LCO-ACP-25). All data reported were obtained under the Los Alamos National Laboratory-Carlsbad Office (LANL-CO) Quality Assurance Program, which is compliant with the DOE Carlsbad Field Office, Quality Assurance Program Document (CBFO/QAPD).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2026

Bipolar Membranes Electrodialysis for Water Purification and Resource Recovery

Reverse osmosis concentrate (ROC) from inland brackish water desalination and wastewater recycling presents moderate salinity, posing significant challenges for treatment and disposal. Existing treatment technologies predominantly rely on energy-intensive thermal methods, large-area evaporation strategies, or deep-well disposal, which often result in the loss of water value. Electrified membrane brine treatment offers a promising alternative by utilizing renewable energy sources, enabling complete water recycling. This work proposes the development of next-generation bipolar membrane electrodialysis (BMED) systems capable of desalinating brine while simultaneously recovering valuable resources. However, several critical challenges remain in the areas of membrane engineering for BMED. These include: 1) decreased current efficiency during desalination due to the low conductivity of feed chambers, 2) fouling and scaling from multivalent ions and contaminants in the feed, and 3) the retention and carryover of ROC contaminants, including PFAS compounds. Our research focuses on the development of novel anion exchange membranes (AEMs) and cation exchange membranes (CEMs) based on synthesized multiblock copolymers. We investigate the effects of block length, ion exchange capacity (IEC), and polymer backbone structure on cation and anion transport (e.g., Na+, Cl-, OH-, H+) for both our synthesized membranes and commercial membranes. Fundamental properties of these membranes, such as water uptake, IEC, and ionic conductivity, are also evaluated to optimize performance for BMED applications.

08 HYDROGEN↗

DOE OSTI2020

Experimental Investigation of Inhibitive Drilling Fluids Performance: Case Studies from United States Shale Basins

Shale formations are attractive prospects due to their potential in oil and gas production. Some of the largest shale formations in the mainland US, such as the Tuscaloosa Marine Shale (TMS), have reserves estimated to be around 7 billion barrels. Despite their huge potential, shale formations present major concerns for drilling operators. These prospects have unique challenges because of all their alteration and incompatibility issues with drilling and completion fluids. Most shale formations undergo numerous chemical and physical alterations, making their interaction with the drilling and completion fluid systems very complex to understand. In this study, a high-pressure, high-temperature (HPHT) drilling simulator was used to mimic real time drilling operations to investigate the performance of inhibitive drilling fluid systems in two major shale formations (Eagle Ford Shale and Tuscaloosa Marine Shale). A series of drilling experiments using the drilling simulator and clay swelling tests were conducted to evaluate the drilling performance of the KCl drilling fluid and cesium formate brine systems and their effectiveness in minimizing drilling concerns. Cylindrical cores were used to mimic vertical wellbores. It was found that the inhibitive muds systems (KCl and cesium formate) provided improved drilling performance compared to conventional fluid systems. Among the inhibitive systems, the cesium formate brine showed the best drilling performances due to its low swelling rate and improved drilling performance.

04 OIL SHALES AND TAR SANDS↗

DOE OSTI2021

Concentrating lithium carbonate after regeneration of lithium sorbent

A system and method that includes flowing brine containing a metal ion through a reactor that includes porous particles having metal ion imprinted polymer having selective binding sites. The system and method further include discharging the brine from the reactor, contacting the porous particles with water, and pressurizing the reactor with carbon dioxide. The carbon dioxide reacts with the adsorbed metal ions to form a metal carbonate solution, where the metal carbonate solution can then be continuously purified with ion exchange. The method can include recycling eluent from the ion exchange back into the system for re-use. The method further includes depressurizing the reactor to precipitate metal carbonate from the metal carbonate solution and discharging the metal carbonate solution from the reactor.

Hornbostel, Marc↗

DOE OSTI2022

“Tailing” Phenomenon During Polymer Propagation at The Milne Point Polymer Flood

Chemical flooding simulators traditionally assume that polymer retention follows the Langmuir isotherm, while fractional-flow calculations assume concentration-independent retention. Both models predict a delay in propagation of the polymer front (in proportion to the retention value), followed by a rapid rise in produced polymer concentration to the injected level. In contrast, laboratory retention studies for the Milne Point polymer flood (North Slope of Alaska) consistently show virtually no delay in polymer propagation, a rapid rise in produced polymer to 70-90% of the injected concentration, followed by produced concentration gradually approaching the injected value over many pore volumes. From a practical viewpoint, this behavior means that retention causes no significant delay in propagation of the polymer bank (and therefore the oil bank), but the effective viscosity and displacement efficiency are less than originally planned. This paper explores why this polymer “tailing” phenomenon occurs. During core floods, effluent was analyzed for brine-tracer concentration, viscosity, total organic carbon, and total nitrogen. The latter three items allowed three independent measures of polymer concentration and polymer retention. Experiments were performed with Milne Point core material, oil, brine, and conditions. Mechanistic experiments were also performed with packs of glass beads with controlled levels of various minerals. In Milne Point cores, the presence of the tailing phenomenon was not sensitive to flow rate, polymer concentration, core heterogeneity, or whether the core was preserved, cleaned of oil, or cleaned and resaturated with oil, or cleaned, re-saturated and aged with oil. The three independent measures of polymer concentration confirmed that the tailing phenomenon was not an artifact associated with polymer degradation or detection interferences. Tailing was also observed during mechanistic floods using glassbead packs when sufficient levels of illite or kaolinite were present. This observation was consistent with high levels of illite noted in Milne Point cores. The tailing was not noted during mechanistic floods that contained beads with montmorillonite, chlorite, calcium carbonate, dolomite, siderite, pyrite, or calcium sulfate. A model is proposed to account for the tailing phenomenon. This work suggests that mineralogy analysis (especially for illite and kaolinite) may reveal whether tailing should be accounted for during simulations of polymer propagation/retention in a given field application.

Seright, Randy↗

DOE OSTI2022

A Technical-Economic Assessment of Brackish Water Treatment for Fossil Power Plant Cooling with Reduced Environmental Impact

The power sector accounts for approximately 40% of freshwater use in the U.S. Reusing non-traditional water resources is critical for alleviating water stress in the western United States. The purpose of this study is to conduct a techno-economic system analysis to evaluate the potential of brackish water treatment for wet cooling towers at existing thermo-electric generating units (EGUs). It aims to address current knowledge gaps in support of non-traditional water resources planning and the electric power industry's water decision- and policy making. An engineering-economic model was developed and combined with DuPont's water application value engine (WAVE) v1.82 to evaluate the viability of retrofitting reverse osmosis-based brackish water treatment systems to individual existing EGUs and then aggregating the unit-level results to the fleet level. In the base case, brackish water treatment can reduce freshwater consumption of electric generation units by 94–100% while increasing the cost of electric generation by approximately 10% and have marginal impacts on the units' parasitic loads. When zero liquid discharge systems are applied to brackish water brine treatment, the cost of electric generation and freshwater consumption savings and energy penalty to the power plant significantly increase. These costs are even higher than dry cooling deployment in lieu of wet cooling towers. The choice of freshwater savings between brackish water desalination and dry cooling deployment depends greatly on how the concentrated brines are managed. Multiple factors must be considered when supporting decision-making in water management and planning in power sectors, which include non-traditional water quantity and quality as well as trade-offs among technical performance, economics, and environmental impacts.

Wu, Zitao↗

DOE OSTI2022

Black-box optimization of a closed-circuit reverse osmosis system for desalination through extremum seeking control

We study the minimization of the cost function of a closed-circuit desalination reverse osmosis (CCRO) system, which is used for producing drinking water. The cost function is a trade-off between the specific energy consumption and the specific brine management cost. The extremum-seeking controller (ESC) manipulates the critical electric conductivity of the brine to minimize the cost function. Experiments were designed in which the composition of the feed salinity is increased to test the controller’s ability to converge to a new optimum. The ESC was able to shift the critical conductivity to a new optimum, which resulted in a 9% improvement in the cost function.

Chowdhury, Dhruba↗

DOE OSTI2024

Mineral and fluid transformation of hydraulically fractured shale: case study of Caney Shale in Southern Oklahoma

This study explores the geochemical reactions that can cause permeability loss in hydraulically fractured reservoirs. The experiments involved the reaction of powdered-rock samples with produced brines in batch reactor system at temperature of 95 °C and atmospheric pressure for 7-days and 30-days respectively. Results show changes in mineralogy and chemistry of rock and fluid samples respectively, therefore confirming chemical reactions between the two during the experiments. The mineralogical changes of the rock included decreases of pyrite and feldspar content, whilst carbonate and illite content showed an initial stability and increase respectively before decreasing. Results from analyses of post-reaction fluids generally corroborate the results obtained from mineralogical analyses. Integrating the results obtained from both rocks and fluids reveal a complex trend of reactions between rock and fluid samples which is summarized as follows. Dissolution of pyrite by oxygenated fluid causes transient and localized acidity which triggers the dissolution of feldspar, carbonates, and other minerals susceptible to dissolution under acidic conditions. The dissolution of minerals releases high concentrations of ions, some of which subsequently precipitate secondary minerals. On the field scale, the formation of secondary minerals in the pores and flow paths of hydrocarbons can cause significant reduction in the permeability of the reservoir, which will culminate in rapid productivity decline. This study provides an understanding of the geochemical rock–fluid reactions that impact long term permeability of shale reservoirs.

58 GEOSCIENCES↗

DOE OSTI2021

Energy efficient supercritical water desalination using a high-temperature heat pump: A zero liquid discharge desalination

Supercritical water desalination (SCWD) is zero liquid discharge technology that can potentially control the solubility of different electrolytes. However, SCWD is an energy-intensive process and requires high-quality thermal heat (> 450 °C). This study proposes the integration of a high-temperature heat pump to reduce the SCWD energy requirement. The integrated system energy consumption improves by 36% for 3.5% feed concentration and 14% for 20% feed, and the distillate cost reduces by 15% and 10%. Another benefit of the proposed integration is the system can be operated using only electricity as a heat source, as is the case with commonly used high-recovery thermal desalination technology. The integrated SCWD-heat pump system shows superior performance compared to the commercially used brine concentrator and crystallizer system. It is approximately 20% more energy-efficient for 25% feed concentration and 8% cheaper. Hence, the integrated SCWD-heat pump has the potential to outperform the pre-existing high-recovery desalination technology.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Selective recovery of critical materials in zero-liquid discharge supercritical water desalination

Zero-liquid discharge desalination techniques are being actively studied as alternative means to produce drinkable water and recover valuable resources without polluting the environment. Supercritical water desalination is one of such alternatives that can overcome the technical and environmental challenges in standard desalination techniques. In addition to these attractive features, this work explores the possibility of utilizing supercritical water desalination for the selective recovery of strategic (critical) materials as co-products. Here, to validate the technical and economic feasibility of the process, we prepared model brine solutions that consist of sodium, neodymium, and different anions and conducted a series of desalination experiments. The results were analyzed experimentally and theoretically and were utilized to evaluate the economic feasibility of the process. When a few tens or hundreds of parts-per-million critical materials are dissolved in the feed, the proposed method becomes more cost-effective in producing critical materials than existing technologies. In addition, it does not discharge any concentrated contaminants while producing drinkable water. These results suggest that supercritical water desalination can recover critical materials while producing freshwater in an economically feasible fashion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Combined chlorine dioxide–membrane distillation for the treatment of produced water

Membrane distillation (MD) is a promising technique for desalinating hypersaline brine, such as produced water (PW). To date, fouling and scaling have remained as major challenges for MD implementation. In this study, chlorine dioxide combined with induced air floatation (ClO 2 -IAF) was systematically investigated as a pretreatment prior to MD. First, the ClO 2 generation based on sodium chlorite and hydrochloric acid was optimized to maximize the on-demand ClO 2 production. The maximum production yield of 18.4% was obtained with 4wt.% NaClO 2 and 20wt.% HCl solutions, with a molar ratio of 1:1.25. Then, two real PW samples were pretreated, and removal efficiencies for total suspended solids (TSS), turbidity, iron, and total organic carbon (TOC) were comprehensively studied by varying the ClO 2 dosage between 6 and 91 mg/L. The ClO 2 -IAF pretreatment displayed TSS and turbidity removals above 90% and TOC removal close to 55%. Further, the PW constituents such as benzene, toluene, ethylbenzene, xylene (BTEX), and total petroleum hydrocarbons (TPH) were analyzed and quantified throughout the cascade of the treatments. The volatiles like BTEX were mainly removed by air floatation, while saturated hydrocarbons such as TPH were retained by the hydrophobic membrane. The MD long-term stability without any in-place cleaning was evaluated, and the membrane withstood for twenty two days without wetting, suggesting that optimizing oxidation pretreatment is critical for mitigating the fouling in MD. Results suggest that organic fouling in PW could be effectively reduced by the pretreatment, but further treatment is required to mitigate the scaling, which resulted in MD wetting.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Cost optimization of low-salt-rejection reverse osmosis

Low-salt-rejection reverse osmosis (LSRRO) is an emerging membrane-based desalination technology for concentrating brines with potentially lower energy consumption and cost than thermally driven processes. We assess the technoeconomic performance of LSRRO by using an optimization model that minimizes the levelized cost of water (LCOW). We develop detailed models for the RO module and other equipment using WaterTAP (Water treatment Technoeconomic Assessment Platform), an open-source simulation and optimization software for water treatment. We improve upon previous LSRRO cost optimization studies by optimizing the salt permeability for each stage, which has significant implications for technoeconomic performance. We present the cost-optimal design, operation, and performance for three cases: 35 g/L TDS feed at 70% recovery, 70 g/L at 55%, and 125 g/L at 35%. The cost-optimal LCOW and specific energy consumption (SEC) for these cases are 0.70, 1.89, and 7.41 $/m 3 and 3.9, 8.4, and 30.4 kWh/m 3 , respectively. For each case, we use sensitivity analyses to provide guidance on key factors that impact economic viability. We also present the cost-optimal LCOW and SEC for feed concentrations between 5 and 220 g/L TDS and recoveries between 30 and 90%. So, we compare LSRRO to other high-salinity desalination technologies and find that it may be cost-competitive below feed concentrations of 125 g/L.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2020

Brackish water desalination using reverse osmosis and capacitive deionization at the water-energy nexus

Here, we present a critical review of the reported performance of reverse osmosis (RO) and capacitive deionization (CDI) for brackish water (salinity < 5.0 g/L) desalination from the aspects of engineering, energy, economy and environment. We first illustrate the criteria and the key performance indicators to evaluate the performance of brackish water desalination. We then systematically summarize technological information of RO and CDI, focusing on the effect of key parameters on desalination performance, as well as energy-water efficiency, economic costs and environmental impacts (including carbon footprint). We provide in-depth discussion on the interconnectivity between desalination and energy, and the trade-off between kinetics and energetics for RO and CDI as critical factors for comparison. We also critique the results of technical-economic assessment for RO and CDI plants in the context of large-scale deployment, with focus on lifetime-oriented consideration to total costs, balance between energy efficiency and clean water production, and pretreatment/post-treatment requirements. Finally, we illustrate the challenges and opportunities for future brackish water desalination, including hybridization for energy-efficient brackish water desalination, co-removal of specific components in brackish water, and sustainable brine management with innovative utilization. Our study reveals that both RO and CDI should play important roles in water reclamation and resource recovery from brackish water, especially for inland cities or rural regions.

42 ENGINEERING↗

DOE OSTI2024

Review of solar-enabled desalination and implications for zero-liquid-discharge applications

Abstract The production of freshwater from desalinating abundant saline water on the planet is increasingly considered a climate change adaptation measure. Yet, there are challenges associated with the high cost, intensive energy demand, and environmental implications of desalination. Effective integration of solar energy generation and freshwater production can address both issues. This review article highlights recent key advances in such integration achieved in a joint-research university-national laboratory partnership under the auspices of the United States Department of Energy and parallel efforts worldwide. First, an overview of current and emerging desalination technologies and associated pretreatment, brine treatment, and valorization technologies that together can result in zero-liquid-discharge systems is presented, and their technological readiness levels are evaluated. Then, advanced modeling techniques and new software platforms that enable optimization of solar-desalination applications with the dual objective of cost and environmental impact minimization are discussed.

14 SOLAR ENERGY↗