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159 records · Page 9

Advanced Processing of Coal and Coal Waste to Produce Graphite for Fast-Charging Lithium-Ion Battery Anode

The University of North Dakota (UND) Energy & Environmental Research Center (EERC), in collaboration with the UND Center for Process Engineering Research (CPER), conducted a project to validate two technologies capable of converting North Dakota lignite and lignite coal waste to high-quality graphite for fast-charging lithium-ion battery (LIB) anode. The project was conducted over about 3 years from April 7, 2022, to July 6, 2025. The two technological paths pursued in this project include path A – direct conversion of coal or coal waste to graphite by the upgraded carbon ores to products (UCOP) process being developed at the EERC and path B – lignite-derived coal tar pitch (CTP) conversion to graphite (CTP2G) process being developed at CPER. The results from this project validate the two technological approaches and are expected to be an integral part of a portfolio of emerging technologies for making high-quality graphite not only from North Dakota lignite, but from all ranks of U.S. domestic coal and coal waste resources. The quality of the graphite produced by these technologies is high enough for various applications, including batteries for the fast-growing electric vehicle industry, energy storage applications, electric arc furnace electrodes for steel production, and graphene production, among others. Although the two technologies can produce high-quality graphite, they are fundamentally different in that the UCOP technology provides a direct path to transform coal to graphite, while the CTP2G technology needs to go through a CTP intermediate and a coking process for the intermediate, which requires a special facility to accomplish. For application in the industry, the UCOP process is designed to be more flexible, with feedstock to include potentially any carbonaceous material such as all coal ranks and biochar, while the CTP2G process is designed to utilize CTP as the starting precursor. The key project accomplishments include the following: • Successful preparation of high-quality synthetic graphite from North Dakota lignite coal/coal wastes and lignite-derived CTP. • Patent application has been filed for the UCOP process and an internal invention disclosure has been filed for the CTP2G process. • The produced graphite performs better than a commercial battery-grade sample in LIB coin cells, especially fast-charging capability, stability, and long-duration cycling. • Coin-type Li-ion half-cells with CTP2G graphite showed excellent performance, with >370 mAh/g capacity, >90% initial coulombic efficiency, and 93%/67% retention at 1C/2C rate, which outperforms commercial graphite in charging speed, stability, and cycling. • Results of fabricated 18650 cells were consistent with the observations in coin cells. • Preliminary techno-economic analysis (TEA) estimates for the UCOP technology indicate a manufacturing cost of about $\$$39/kg based on 50-metric ton/year capacity. • Preliminary TEA estimates for the CTP2G technology indicate a market price of about $\$$7107/ton ($\$$7/kg) based on 22,000-ton/year production capacity.

01 COAL, LIGNITE, AND PEAT↗

Reconstruction of Thermal Protection System Aeroheating using a Green’s Function Approach

Inverse heat transfer (IHT) techniques are often used to reconstruct the surface heating conditions on spacecraft thermal protection systems (TPS) during atmospheric entry. Current IHT techniques for entry spacecraft applications, however, demand substantial computational resources, and are impractical for analyses such as uncertainty quantification and real-time health monitoring. In this paper, a Green’s function sensor fusion approach is used to reconstruct the TPS surface aeroheating conditions on experimental spaceflight and ground test systems from collocated temperature and heat flux sensors embedded in the TPS. The algorithm leverages Green’s functions to model the heat conduction within the spacecraft TPS and stabilizes the recovery of the surface heating condition using the direct heat flux sensor measurement. The algorithm is validated using arc-jet ground test data and applied to the reconstruction of the Mars 2020 backshell heating during Martian atmospheric entry. The performance of the algorithm is benchmarked against a current state-of-the-art IHT framework, FIAT_Opt. The Green’s function-based reconstruction algorithm recovers the net hot-wall heat flux absorbed by the TPS and the incident heat flux from the atmospheric entry environment in close agreement with FIAT_Opt. Notably, computation of the surface heating condition is completed in three orders of magnitude less time with the Green’s function sensor fusion approach using a consumer-grade PC, versus with FIAT_Opt running on a high performance computer cluster. The efficiency of the algorithm is leveraged to compute the uncertainty contributions of input parameters to the total uncertainty in reconstructed Mars 2020 backshell heating for the full atmospheric entry heat pulse. The sensitivity analysis uncovers that, at different times throughout the entry heat pulse, uncertainties in the TPS specific heat, thermal conductivity, and emissivity are all dominant drivers of the reconstruction uncertainty. These results demonstrate Green’s functions and sensor-fusion techniques as promising IHT approaches to reconstruct atmospheric entry environments from TPS-embedded measurements, and highlight how these techniques may give access to post-flight analyses previously hindered by the prohibitive cost of current methods.

Kenneth McAfee↗

Reconstruction of Thermal Protection System Aeroheating using a Green’s Function Approach

Inverse heat transfer (IHT) techniques are often used to reconstruct the surface heating conditions on spacecraft thermal protection systems (TPS) during atmospheric entry. Current IHT techniques for entry spacecraft applications, however, demand substantial computational resources, and are impractical for analyses such as uncertainty quantification and real-time health monitoring. In this paper, a Green’s function sensor fusion approach is used to reconstruct the TPS surface aeroheating conditions on experimental spaceflight and ground test systems from collocated temperature and heat flux sensors embedded in the TPS. The algorithm leverages Green’s functions to model the heat conduction within the spacecraft TPS and stabilizes the recovery of the surface heating condition using the direct heat flux sensor measurement. The algorithm is validated using arc-jet ground test data and applied to the reconstruction of the Mars 2020 backshell heating during Martian atmospheric entry. The performance of the algorithm is benchmarked against a current state-of-the-art IHT framework, FIAT_Opt. The Green’s function-based reconstruction algorithm recovers the net hot-wall heat flux absorbed by the TPS and the incident heat flux from the atmospheric entry environment in close agreement with FIAT_Opt. Notably, computation of the surface heating condition is completed in three orders of magnitude less time with the Green’s function sensor fusion approach using a consumer-grade PC, versus with FIAT_Opt running on a high performance computer cluster. The efficiency of the algorithm is leveraged to compute the uncertainty contributions of input parameters to the total uncertainty in reconstructed Mars 2020 backshell heating for the full atmospheric entry heat pulse. The sensitivity analysis uncovers that, at different times throughout the entry heat pulse, uncertainties in the TPS specific heat, thermal conductivity, and emissivity are all dominant drivers of the reconstruction uncertainty. These results demonstrate Green’s functions and sensor-fusion techniques as promising IHT approaches to reconstruct atmospheric entry environments from TPS-embedded measurements, and highlight how these techniques may give access to post-flight analyses previously hindered by the prohibitive cost of current methods.

Kenneth McAfee↗

Electrochemical-driven green recovery of lithium, graphite and cathode from lithium-ion batteries using water

The expected exponential increase in consumption of lithium-ion batteries (LIBs) would pose a unique challenge to the availability of near-critical resources like lithium and graphite in the upcoming decade. In this work, we present a lithium recovery process that utilizes a degradation mechanism, i.e., lithium plating, as a tool to concentrate metallic lithium at the anode/separator interface for convenient extraction at room temperature – using only water. Electrochemical characterization of fast charged (1–6 C) LIBs yielded a maximum capacity fade of 50% over ten cycles. The lithium plating was confirmed via voltage plateau analysis, coulombic efficiency, and DC resistance measurements. A maximum lithium plating condition was observed to exist between 4C and 5C, thereby limiting the energy consumption in the extraction process. Post-mortem film thickness measurement showed an incrementing film deposition with a maximum of 35 µm thickness. SEM and XPS analysis confirmed increasing concentration of a dense dendritic metallic lithium deposition on the anode/separator interface with C-rate. A green recovery process was adopted to extract the concentrated metallic lithium using distilled water. The lithium from the plated film, solid/electrolyte interface (SEI), electrolyte, anode, and cathode, was extracted as salts. A 37% improvement in lithium recoverability was achieved with fast charging under ambient conditions. XPS analysis showed ~92% of lithium yield with no residual lithium in the graphite. In addition, the battery-grade graphite was recovered with 97% purity after heat treatment of the washed anode film, and concentrated transition metals oxides in the cathode to 93% purity for convenient extraction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Crowd Sourcing Medical Data Collection Using Medical Students

OBJECTIVE We undertook an upgrade of the Evidence Library database of NASA HRP’s Integrated Medical Model, assessing 120 medical conditions which integrate with a novel probabilistic risk assessment (IMPACT) tool of medical risk and resource utilization for long duration exploration human spaceflight. This data collection process included a selection of these conditions crowd sourced over one year via three 4-week medical student electives at the University of Colorado School of Medicine (IDPT 8059 Space Medicine: Human Spaceflight Factors & Medical Risk Assessment). Students undertook a rapid systematic review of each medical condition, under close preceptors with backgrounds in clinical medicine, library science, epidemiology, biostatistics, and evidence-based medicine. As part of the elective, students also received instruction in core space medicine concepts, evidence based medicine and problem based learning sessions as a flight surgeon supporting a simulated Mars mission. METHODS The list of 120 medical conditions includes both common, terrestrial illness/injury (epistaxis, diverticulitis) as well as spaceflight-specific ones (space adaptation conditions, EVA-related injuries). A rapid systematic review process was developed that would allow students to find the data for determining disease incidence/prevalence, return to definitive care (often a surrogate such as hospitalization rates), loss of crew life, and treatment duration. Each data point required a tailored, specialized search process using different databases and corresponding specialized search filters. Databases were selected on their ability to provide high quality literature in an efficient manner and prioritized by their ability to provide graded evidence via a set rubrics specific to human spaceflight. Students were responsible for performing all literature searches and identifying the highest quality available evidence for each data point. Completed student data sheets underwent initial review by faculty preceptors followed by a secondary editing review by the ExMC Clinical Science Team. RESULTS Over the course of three electives, approximately 105 medical conditions were researched by students using spreadsheets with pre-crafted search strategies. Overall, this process was successful in allowing students to perform the preponderance of work to update incidence, treatment duration, return to definitive care, and loss of crew life data points. Students were successful in running searches, identifying the necessary data points within the literature, and determining the types of terrestrial data that most aligns with the astronaut population for successful completion of their tasks. Limitations included variable student experience with search methodologies [PubMed], differing values of evidence grading [best practice evidence based medicine vs. relevant to spaceflight], and students’ unfamiliarity with spaceflight specific conditions. CONCLUSION Finding the relevant literature for medical conditions in spaceflight within terrestrial databases in a systematic method is time consuming and not intuitive. However, the stepwise process that balanced sensitivity with specificity allowed for students to be highly successful in a short amount of time. Additionally, as the process was refined over the course of three electives, preceptors were better able to anticipate where students were likely to encounter barriers, which allowed the course to be adjusted to account for certain data points needing more time for completion. This replicable process may be an efficient way to accomplish rapid systematic reviews for a large volume of data in a short amount of time.

J Lemery↗

Educational Applications on the World Wide Web: An Example Using Amphion

There is a great deal of excitement about using the internet and the World Wide Web in education. There are such exciting possibilities and there is a wealth and variety of material up on the web. There are however many problems, problems of access and resources, problems of quality -- for every excellent resource there are many poor ones, and there are insufficiently explored problems of teacher training and motivation. For example, Wiesenmayer and Meadows report on a study of 347 West Virginia science teachers. These teachers were enrolled in a week-long summer workshop to introduce them to the internet and its educational potential. The teachers were asked to review science sites as to overall quality and then about their usefulness in their own classrooms. The teachers were enthusiastic about the web, and gave two-thirds of the sites high ratings, and essentially all the rest average ratings. But alarmingly, over 80% of these sites were viewed as having no direct applicability in the teacher's own classroom. This summer I was assigned to work on the Amphion project in the Automated Software Engineering Group under the leadership of Michael Lowry. I wished to find educational applications of the Amphion system, which in its current implementation can be used to create fortran programs and animations using the SPICE libraries created by the NAIF group at JPL. I wished to find an application which provided real added educational value, which was in line with educational curriculum standards and which would serve a documented need of the educational community. The application selected was teaching about the causes of the seasons -- at the approximately the fourth, fifth, sixth grade level. This topic was chosen because it is in line with national curriculum standards. The fourth, fifth, sixth grade level was selected to coincide with the grade level served by the Ames Aerospace Encounter, which services 10,000 children a year on field trips. The hope is that eventually the Ames Aerospace Encounter could be used as a test bed for the lessons developed. The topic is one which is difficult to teach and the necessity for new methods is documented in the educational literature. Current educational standards indicate that seasons should be part of the elementary school curriculum.

Friedman, Jane↗

Modeling the Skills and Practices of Scientists through an “All-Inclusive” Comparative Planetology Student Research Investigation

To effectively prepare the nation's future Science, Technology, Engineering, and Mathematics (STEM) workforce, students in today's classrooms need opportunities to engage in authentic experiences that model skills and practices used by STEM professionals. Relevant, real-world authentic research experiences allow students to behave as scientists as they model the process of science. This enables students to get a true sense of STEM-related professions and also allows them to develop the requisite knowledge, skills, curiosity, and creativity necessary for success in STEM careers. Providing professional development and opportunities to help teachers infuse research in the classroom is one of the primary goals of the Expedition Earth and Beyond (EEAB) program. EEAB, facilitated by the Astromaterials Research and Exploration Science (ARES) Directorate at the NASA Johnson Space Center, is an Earth and planetary science education program designed to inspire, engage, and educate teachers and students in grades 5-12 by getting them actively involved with exploration, discovery, and the process of science. The program combines the expertise of scientists and educators to ensure the professional development provided to classroom teachers is scientifically valid and also recognizes classroom constraints. For many teachers, facilitating research in the classroom can be challenging. In addition to addressing required academic standards and dealing with time constraints, challenges include structuring a research investigation the entire class can successfully complete. To build educator confidence, foster positive classroom research experiences, and enable teachers to help students model the skills and practices of scientists, EEAB has created an "allinclusive" comparative planetology research investigation activity. This activity addresses academic standards while recognizing students (and teachers) potentially lack experience with scientific practices involved in conducting research. Designed as an entry level research engagement investigation, the activity introduces, illustrates, and teaches the skills involved in each step of the research process. Students use astronaut photos, provided through the ARES Crew Earth Observations (CEO) payload on the International Space Station (ISS) as well as remote sensing imagery of other planetary worlds. By including all the necessary tools to complete the investigation, students can focus on gaining experience in the process of science. Additionally, students are able to extend their experience of modeling the skills and practices of scientists through the opportunity to request new data of Earth from the ISS. Professional development offered through in-person and webinar trainings, along with the resources provided, enable educators to gain first-hand experience implementing a structured research investigation in the classroom. Through data and feedback collected from teachers, this type of "all-inclusive" investigation activity aims to become a model that can be utilized for other research topics and STEM disciplines.

Graff, Paige↗

Coupling Waste Feedstocks to Microbial Protein Production in a Circular Food System

Global food production is a major contributor to greenhouse gas emissions, water consumption, and land use. As an alternative to conventional agriculture, the production of waste-derived microbial protein (MP) holds promise for reducing environmental impacts. MP can be mass-produced in volumetrically scalable fermentation processes on short time scales, enabling facile scale-up with lower greenhouse gas emissions, land use, and water impacts than animal and, in some cases, plant protein. MP can also be produced from waste feedstocks, diverting waste from landfills or the natural environment. This Perspective explores the availability and suitability of waste feedstocks for MP production, suggesting that MP generated from waste feedstocks in the United States could fulfill twice the current national protein demand. Here, we also discuss the biotechnological and separations processes required to produce food-grade MP for human consumption from waste. Key challenges include MP consistency, consumer and regulatory acceptance, and the process utilities (electricity, heat, and nutrients) that account for up to 85% of MP costs and most environmental impacts, all of which present opportunities for innovation in the microbiology and process design spaces. Overall, this work highlights the potential of MP to contribute to a more circular, resilient, and sustainable food system.

09 BIOMASS FUELS↗

Integrated Bosch Process System Models for In-Situ Oxygen and Carbon Production

In-Situ Resource Utilization (ISRU) technology is a vital component to NASA’s mission of a sustainable presence on the Moon and Mars. Local resources can be leveraged to reduce resupply frequency and mass. Elements of the Bosch process, combined with the carbothermal reduction process, can produce oxygen on the lunar surface with minimal consumables. The Bosch process can also produce oxygen on the Martian surface by using the CO 2 -rich environment. Between both systems, adsorption pump, solar thermal energy, carbon formation reactor, and water recovery subsystems are modeled and integrated to create a functional model in MATLAB software. The model is used to simulate performance of the system and reduce mass, power, and volume requirements. This integrated system model provides a tool to scale ISRU technologies for oxygen and carbon production. The MATLAB model is created by developing a system of independent subsystem models that are solved for their quasi-steady state values which can be integrated with respect to time to determine the change in current states. A flexible time stepping method is used to ensure a high level of accuracy during periods of rapid change while still making use of a simple explicit integration method. The flexible time step is calculated for each independent subsystem and the minimum value from those is used as the overall time step. A flexible time step is calculated by dividing a resolution value, or the maximum change per time step, by the variables current rate of change. The maximum value from all points in space is used for subsystem models that contain multiple values. The process is done for every variable that is being monitored in each subsystem and the global minimum is used as that iteration’s timestep. Several assumptions used in the MATLAB model for fluid flow dynamics, such as 1-D gas flow through the sorption pump, are supported by modeling in Ansys Fluent software. The Lunar oxygen production system is outlined in Fig. 1. The carbothermal reduction subsystem uses solar energy to heat a mixture of lunar regolith and carbon powder to produce carbon monoxide. To begin, the carbon monoxide feeds to the modified Bosch subsystem along with hydrogen gas. The reactants then enter the carbon formation reactor where water and carbon powder are produced. Solar thermal energy is used to add energy to the reactor, but waste heat from the carbothermal process is another potential heat source. The water is collected and electrolyzed to produce hydrogen which reenters the Bosch subsystem, and the oxygen is stored for downstream use. The carbon powder is collected and feeds back into the carbothermal subsystem. The Martian oxygen production system uses the full Bosch process and is outlined in Fig 2. A CO 2 adsorption pump thermally cycles to scrub and pressurize CO 2 from the environment. Along with an initial supply of hydrogen, the reactants enter the Reverse Water Gas Shift Reactor (RWGSR) which produces carbon monoxide and water. Carbon monoxide and unreacted hydrogen enter the carbon formation reactor to produce water and carbon powder. The water is collected from both reactors and electrolyzed to reintroduce hydrogen and store oxygen for propellant production or life support. Carbon is removed from the carbon formation reactor and stored. The adsorption pump utilizes rapid cycle temperature swings within a stack of zeolite coated surfaces. The subsystem model solves 1-D quasi-steady conservation laws of the quasi-steady form, shown in Eq. 1, for the gas stream and heat exchange liquid to predict performance parameters such as breakthrough capacity and optimum cycle time. The source term S is used to capture interactions between the fluid flows and the sorbent. A quasi-steady-state scheme is used where no time derivatives appear in the governing equations, except for those in the source terms. This results in an autonomous system, where ∂F/∂x = ƒ(F). The fluxes F are provided at the inlet, and an explicit method is used to solve for the spatial distribution of F. The heat and mass flows to the sorbent are then extracted from the source terms. These flows are numerically integrated to produce a 1-D solution for the system’s state as a function of both time and space. The body of the adsorption pump is separated into two semi-independent models: the heat exchanger fluid flow and gas flow through the zeolite coated surfaces. Both models are solved using the above-described method to find a 1-D solution as a function of space and interact only once a timestep is taken. The interaction point is the sorbent through which all heat transfer between the two models must occur. Sorbent mass adsorption is calculated using the Lagergren model, shown in Eq. 2, where the transfer coefficient, λ D , is found by solving a system of nondimensionalized equations derived by using the heat and mass transfer analogy for transport phenomena. Using Grade 544 Type 13X zeolite as the sorbent material, the equilibrium concentration, θ eq , is calculated using the k-site Langmuir isotherm and fit parameters. Additionally, the enthalpy of adsorption used in the model is computed by interpolation of available data [1]. The subsystem model was validated using the Rapid Cycle Temperature Swing Adsorption (RC-TSA) pump. The solar thermal energy subsystem focuses on a solar concentrator concept with a heat exchanger to heat the reactants before entering the carbon formation reactor. The subsystem model assumes a fixed solar flux and reflector efficiency to calculate the reactant temperature given the incoming temperature, pressure, and exchanger geometry. The receiver is a custom manufactured series of copper blocks with serpentine channels to increase its surface area and the residence time of the reactants to heat up to 550 °C. The subsystem model was validated using a heat exchanger developed at NASA Glenn Research Center (GRC). The solar thermal energy subsystem focuses on a solar concentrator concept with a heat exchanger to heat the reactants before entering the carbon formation reactor. The subsystem model assumes a fixed solar flux and reflector efficiency to calculate the reactant temperature given the incoming temperature, pressure, and exchanger geometry. The receiver is a custom manufactured series of copper blocks with serpentine channels to increase its surface area and the residence time of the reactants to heat up to 550 °C. The subsystem model was validated using a heat exchanger developed at NASA Glenn Research Center (GRC).

In situ Resource Utilization↗

Near-Critical CO 2 -Assisted Liquefaction-Extraction of Biomass and Wastes to Fuels and Value-Added Products

With the growing need for sustainable carbon-neutral liquid fuels, low-grade feedstocks, such as lignocellulosic biomass, and municipal solid wastes offer sufficient potential via thermochemical conversion. But the existing thermochemical means are limited in feed flexibility and scalability and require significant processing (energy and costs) of the intermediates. Bio-oil/biocrude intermediate from fast pyrolysis and hydrothermal techniques is impeded by issues of stability and oxygen content, along with hydrotreating viability. To address these issues, we investigated a novel pathway of near-critical CO 2 -assisted integrated liquefaction-extraction (NILE) technology in conceptual aspects for conversion of various biomass and municipal solid wastes into high-quality biocrude with high compatibility for co-hydrotreating with traditional fossil crude for liquid fuel needs in power and transportation sectors. Using supercritical CO 2 for dewatering wet feedstocks, for liquefaction, and extraction for lighter biocrude has produced biocrude with lower oxygen content by 50%, lowered metal content by 90%, stable viscosity, low acidity, and good aging stability compared to that produced from hydrothermal liquefaction along with higher hydrotreating and co-hydrotreating compatibility. Hydrotreating of the biocrude extract from supercritical CO 2 extraction also was feasible with no detected coke deposition, an oxygen content of 1%, and catalyst deactivation. Here, the validation and capabilities of the NILE concept urge for its further development to obtain sustainable liquid fuels with lower greenhouse gas emissions and costs.

09 BIOMASS FUELS↗

Restoration Hydro: A Watershed Approach to Standard Modular New Hydropower

The objectives of FOA DE- FOA-0001836- “Standard Modular Hydropower” included designing a standardized, modular, and environmentally compatible hydropower schematic for implementation in greenfield sites that generate up to 10 MW of capacity. Utilizing funds competitively awarded under DOE’s Water Power Technologies Office, the Natel Energy team developed a concept for modular new stream reach (NSR) hydropower that incorporates multi species upstream and downstream fish passage, improved river channel connectivity, and recreational modules. The in-stream design of the collective modules minimized site specific design and maximized the opportunities for modularity. Financial data was also presented using actual costs from regional suppliers, with figures provided in 2022 dollars. While the project team did not address potential permitting process improvements, the site selection criteria did consider established barriers to hydropower development such as tribal and preserved lands, interconnection proximity, and endangered species to exclude or deprioritize. The project’s design schematic met the objectives of the FOA, and presented a unique solution that targets alluvial pockets as natural features for sustainable development. Natel’s concept also incorporated the company's fish-safe Restoration Hydro Turbine for safe downstream passage, while featuring a rock arch that integrates fish passage, water, recreation, and grade control modules (including sediment). Alignment with the Department of Energy Office of Energy Efficiency and Renewable Energy (EERE) “Innovative Design Concepts for Standard Modular Hydropower and Pumped-Storage Hydropower” Program: According to the Hydropower Vision (DOE, 2016), approximately 16 GW of hydropower growth is possible with the development of technology solutions that balance efficiency, economics, and environmental sustainability. The desired outcome of the SMH program is transformational innovation specifically in the site identification, conceptual, and detailed design phases of technology development lifecycles (DOE, 2018). In developing the SMH design schematic, the team aimed to address the opportunities outlined in the Vision through an inverted design philosophy; rather than singularly prioritizing efficiency and power production, the team focused on integrating hydropower with restoration of degraded streams to optimal ecosystem function and provision of exceptional recreation value as design criteria. To achieve this, Restoration Hydro incorporates the principles of nature-based engineering (WWAP, 2018) and biomimicry (Biomimicry NL.) to strategically deploy complementary combinations of permanent, semi-permanent, and ephemeral low-head structures - such as natural and engineered log jams - that harness geomorphological and hydrological processes at the landscape-scale. Primary applications of Restoration Hydro include: 1) restoration of degraded watersheds’ natural ecological function and enhancement of hydrological connectivity; and 2) creation of associated co-benefits to hydro production, including increased groundwater recharge, improved sediment transport and management, improved water security and water quality. Restoration Hydro projects build upon proven watershed restoration engineering techniques by integrating hydropower turbines into low-head structures using innovative and evolving civil works concepts that facilitate fish and sediment passage, and in some cases create additional revenue-generating recreational opportunities. Powering low-head structures creates a directly monetizable layer of economic value in the form of flexible, reliable, renewable energy on top of the already high-value water, environmental and recreational benefits of watershed and river restoration. The approach aims to create a virtuous, self-reinforcing cycle whereby Restoration Hydro projects support the scaling of ecosystem restoration activities, creating a water-energy-carbon multiplier effect that, through the principles of adaptive change management: 1) improves the resilience of landscapes and downstream population centers for changing hydrological cycles; 2) creates a reliable energy resource that facilitates the integration of intermittent renewable power sources into grids; and 3) supports climate change mitigation through grid decarbonization and enhanced ecosystem carbon capture and retention.

13 HYDRO ENERGY↗

UT-GOM2-2 Preliminary Report: Terrebonne Basin Northern Gulf of Mexico, 30 July-28 September 2023

In the summer and fall of 2023, the Gulf of Mexico Deepwater Hydrate Coring Expedition (UT-GOM2-2) drilled, cored, made downhole measurements, and analyzed samples from the seafloor to the base of the gas hydrate stability zone in one location (Site H, WR313) in the Terrebonne basin, deepwater Gulf of Mexico. Analyses of data and samples from the expedition will inform biological, geochemical, and geomechanical models to constrain the role of gas hydrates in the carbon cycle and the potential for gas hydrates as an energy resource. Pressure and conventional cores were collected continuously to a depth of 155.1 meters below the seafloor (mbsf). At deeper depths, cores were taken periodically from hydrate-bearing sands and their bounding muds to a total depth of 861.3 mbsf. 162.6 m of conventional core and 54.8 m of pressure core were obtained. Twelve temperature measurements were made between 27.1 and 144.5 mbsf to determine the geothermal gradient. At the seafloor, more than 4 m of sandy silt of unknown origin was encountered. Beneath this sand, to a depth of ~200 mbsf, the section was composed of interbedded mud and biogenic carbonate ooze. The biogenic ooze correlated to low density and high porosity intervals observed in the previously acquired logging while drilling (LWD) data and as measured. Calcareous nannofossil biostratigraphy constrains the entire record to the Pleistocene (< 0.91 million years) with a pronounced increase in sedimentation rate with depth. Beneath 200 mbsf, the section was predominantly composed of mud with two thicker, hydrate-bearing coarse-grained intervals, which are commonly known as the Blue and Orange sands. The dissolved gas concentration was quantified from pressure cores. In the shallow section, dissolved methane concentration increased below the sulfate-methane transition zone (SMTZ) and reaches saturation (the limit of solubility for methane) at 147 mbsf. Gas expansion was very common in conventional and depressurized pressure (conventionalized) cores below the SMTZ. At deeper depths, the methane concentration within muds bounding the Blue and Orange reservoirs was generally found to be less than saturation. The dissolved and hydrate gas composition is consistent with a microbial source, containing greater than 99.99% methane and only trace concentrations of ethane, propane, and butane. The methane to ethane ratio (C 1 /C 2 ) and the methane to ethane plus propane (C 1 /(C 2 +C 3 )) decrease with depth down to at least 678 mbsf, mainly driven by the increase in ethane with depth. It is unclear if this trend continues through the Orange sand interval. The δ 13 C isotopic signature of methane ranges between -69.9 and -78.5 ‰ Vienna Pee Dee Belemnite (VPDB). Pressure core recovery of all sandy intervals was poor. However, pressure core logs of the Orange sand show intervals of low density and high velocity, which are indicative of high hydrate saturation. One core from within the Orange sand was composed of interbedded graded sandy silt and mud. The sandy silts from this core are composed of mainly quartz and feldspar with some lithics. Most of the recovered pressure core samples are maintained at near in-situ pressure and temperature (within the hydrate stability field) at the University of Texas Pressure Core Center awaiting analysis. In the shallow section, samples will be used to determine the flux of organic carbon through the basin system, find the rate at which that carbon was consumed, and understand the microbial population responsible for these processes. In the deeper section, samples from in and around the hydrate reservoirs will be used to determine the petrophysical properties of the reservoir and bounding seals in these systems.

03 NATURAL GAS↗

KSC Headquarters Building Area SWMU 104 Soil Interim Measure Report for LOC 2D and LOC 2E Kennedy Space Center, Florida

This Interim Measure (IM) Report for Location of Concern (LOC) 2D and LOC 2E summarizes the activities associated with implementation of an IM to address soil and concrete contamination at the Kennedy Space Center (KSC) Headquarters Building Area (KHQA) located at KSC, Florida. KHQA has been designated Solid Waste Management Unit (SWMU) 104 under KSC’s Resource Conservation and Recovery Act Corrective Action Program. The IM consisted of excavating/removing residual polychlorinated biphenyl (PCB) contamination in soil and concrete from two separate areas, LOC 2D and LOC 2E, which were associated with electrical transformer locations. IM activities were conducted in accordance with the Interim Measure Work Plan (IMWP), Revision 1, for KHQA dated June 2018, which was approved by the Florida Department of Environmental Protection in a correspondence letter dated April 2016 and the United States Environmental Protection Agency in a correspondence letter dated August 2018. The objective of the IM was to remove all remaining contaminated media with total PCB concentrations greater than the State of Florida Residential Soil Cleanup Target Level (RSCTL) (0.5 milligrams per kilogram [mg/kg]). This cleanup goal meets unrestrictive re-use conditions in Florida, and is below federal regulations for PCB Bulk Remediation Waste Cleanup of 1 mg/kg for high occupancy, unrestricted use areas, as outlined in 40 Code of Federal Regulations (CFR) 761.61(a). The timeline of the IM was coordinated with demolition of the former KSC Headquarters Building (demolished in 2021) in order to safely remove contaminated media after electrical equipment was de-energized and removed from the site. Excavation activities were conducted between January 10, 2022, and February 8, 2022, and included two waste streams for off-site disposal: (1) PCB-remediation waste greater than or equal to 50 mg/kg, and (2) PCB-remediation waste less than 50 mg/kg. A total of approximately 347 cubic yards (478 tons) of PCB-contaminated soil and concrete was initially removed from the LOC 2D and LOC 2E areas, as defined in the IMWP. An additional 4.35 tons of soil and concrete were removed based on verification sampling, which was conducted until the cleanup goal was achieved. The total area of excavation from both LOC 2D and LOC 2E was approximately 5,186 square feet (0.12 acres), and excavation depths ranged from 0.5 to 4.0 feet below land surface Excavated soils and concrete were stockpiled based on waste stream and subsequently transported and disposed of at Waste Connections of Osceola County, LLC – JED Landfill in St. Cloud, Florida (PCBs less than 50 mg/kg) or the Chemical Waste Management Landfill in Emelle, Alabama (PCBs greater than or equal to 50 mg/kg). Following excavation, clean backfill was brought to the site and provided to the Demolition Contractor to complete backfill and grading in conjunction with their final site restoration activities from building demolition. Post-IM groundwater sampling was conducted in May 2022 at three monitoring wells installed in April 2022 to confirm that PCBs did not leach into groundwater. These wells were installed where the highest PCB concentrations were detected at LOC 2D, LOC 2E, and from the Building Perimeter IM (previously completed in 2020). All PCB results in groundwater were non-detect. Volatile organic compounds were also analyzed based on potential past use of solvents in transformers with PCB-dielectric fluids and the potential release of dielectric fluids containing volatile organic compounds, and all results were non-detect. Based on completion of a successful IM at LOC 2D and LOC 2E, as well as previous remedial actions that have addressed other contamination at KHQA (SWMU 104), No Further Action without controls will be recommended for SWMU 104. NASA will submit separate Site Rehabilitation Completion Order request documentation for SWMU 104 to support an NFA without controls recommendation.

PCB↗

Pilot-Scale Testing of an Integrated Circuit for the Extraction of Rare Earth Minerals and Elements from Coal and Coal Byproducts Using Advanced Separation Technologies

The primary objective of this project was to develop and demonstrate an integrated pilot-scale circuitry for recovering high-value rare earth elements (REEs) from coal and coal byproducts. The target performance was to produce a mixed REE product with content of at least two percent by weight on a dry mass basis in a cost-effective and environmentally benign manner. During the first nine months of the project period (Phase 2 Budget Period 2), pilot plant construction was completed including all field site startup activities such as permitting, engineering design, procurement/bidding, unit fabrication, site construction, equipment installation, module assembly, safety training, and circuit shakedown. During the remaining 21 months of project period (Phase 2 Budget Period 3), detailed field-testing activities were performed including feedstock sample collection and preparation, exploratory testing, circuit modification, detailed parametric study, and performance optimization. A detailed techno-economic analysis was performed based on the pilot plant testing findings which provided various scenarios for REE production. The project successfully accomplished the proposed target performance by producing mixed rare earth oxide (REO) with greater than 90% purity by weight in a continuous pilot scale operation from two distinctly different coarse refuse materials (i.e., West Kentucky No. 13 and Fire Clay coal seams), and at least three secondary sources (i.e., heap leach process and naturally formed acid mine drainage system). Project partners included the University of Kentucky, Virginia Tech, West Virginia University, Alliance Coal, Blackhawk Mining, Mineral Refining Company, and Mineral Separation Technologies. The pilot scale test facility was constructed at a former mining complex owned by Alliance Natural Resource Partners (Alliance Coal). The site was rehabilitated to accommodate the equipment installation, construction and fabrication, electrical power requirement, water line management and containment. The process units constructed and installed included X-ray sorting unit, crushing and grinding unit, physical separation unit, acid leaching unit, solvent extraction unit, and wastewater management unit. A rare earth mineral concentration unit was constructed as a standalone unit for flexible operation. A detailed environmental assessment and control plan was carried out to identify and quantify any potential impacts of the pilot-scale processing circuitry on the human and eco-system health and well-being. Corresponding mitigation strategies and control measures were provided. A conceptual flowsheet was developed to effectively remove thorium and uranium from high purity rare earth oxide mix or any potential radionuclide enriched stream. The two distinct feedstock materials were secured from the Blackhawk Mining Complex in eastern Kentucky where the Fire Clay (Hazard No. 4) seam is processed. The West Kentucky No. 13 (Baker) coarse refuse material was collected from an active process stream at an Alliance coal preparation plant located in western Kentucky. Characterization analysis indicated that both of feed materials generated from the two sources contained >300 ppm of TREEs on a dry whole mass basis which met the requirements for a qualified feed stock. The two feedstocks were further upgraded using a dual x-ray sorter to prepare the feed material for hydrometallurgical circuit. Thermal treatment on feed material prior to leaching was found to: 1) improve the leaching recovery of REEs, 2) increase the leaching kinetics, and 3) allow the leaching reaction to occur at lower acidity. Roasting at 600°C was selected as the pre-treatment condition for both West Kentucky No. 13 and Fire Clay coarse refuse material. Over 40% of leaching recovery was achieved by roasting West Kentucky No. 13 material having a top particle size of 3 mm in the pilot scale operation using 1.2M sulfuric acid leaching at 75OC. Initial pilot scale testing involved continuous operation of the pilot plant for 94 hours. The leaching unit was operated at solid-to-liquid ratio of 1 to 10 (w/v) using 0.5M sulfuric acid solution at a temperature of 75°C. The continuous solvent extraction circuit utilized rougher and cleaner units with DEHPA and TBP as the extractants. An innovative stripping circuit was developed to accumulate the REE concentration in the stripping solution to a level above 600 ppm. A bleed stream from the recycled strip solution was treated using oxalic acid precipitation which produced a high grade rare earth oxalate. The oxalate product was roasted to remove the oxalate which produced a rare earth oxide product having a purity greater 90%. Due to high concentrations of contaminant ions in the pregnant leach solution (PLS), a modified flowsheet was developed that involved pre-concentration of the REEs using multiple stages of precipitation and redissolution. The advantage of this process was improved removal of contamination before the downstream purification process and a significant cost reduction relative to the circuit that utilized the solvent extraction process. The modified circuitry included processes involving leaching, multistage precipitation, redissolution, and oxalate precipitation followed by roasting of the oxalate product. The circuit produced a mixed REO that was 92.96% pure from the initial test. A detailed parametric test plan was carried out which involved varying key parameters including solids feed rate, acid flowrate, acid concentration, multistage precipitation pH, redissolution pH, oxalate precipitation dosage and pH. The response variables included REE recovery, contaminant recovery, REO product grade and overall chemical consumption. Test results indicated that the acid-to-solid ratio is the key parameter to leaching efficiency as performance deteriorated with an increase in solids concentration. The optimal pH determined for REE precipitation and redissolution was 6.5 and 2.5, respectively. Additional tests were conducted to further improve the flowsheet. Recirculating a portion of the PLS to the feed of the leach tanks improved the leaching performance by lowering the pH of the leaching system and reducing the contamination recovery by shortening the residence time. Moreover, the removal of Al prior to REE precipitation significantly reduced the oxalic acid consumption in the oxalate precipitation circuit. The modified circuit produced over 90% grade REO by weight from both West Kentucky No. 13 and Fire Clay coarse refuse material in pilot scale continuous test programs. A case analysis model was developed to project the REE and major contaminants concentration in each PLS stream based on the leaching condition, pH cut point, and oxalic acid dosage. A correlation was established using empirical and semi-empirical models. Using the models, chemical consumption required for each stage was predicted based on the projected performance of the hydrometallurgy circuit. After identifying the optimum conditions, validation tests were carried out for the treatment of both West Kentucky No. 13 and Fire Clay coarse refuse materials in the pilot plant. The actual circuit performance and chemical consumptions were very close to the model predictions. Other than the two coarse refuse sources, several secondary feedstocks were also tested in the pilot plant facility. A “heap leach” system was constructed using the coarse refuse material generated from cleaning the West Kentucky No. 13 seam coal. Using the two stage SX rougher and cleaner circuit, a concentrate with a grade >90% REO was produced while recovering >97% of the REEs from the heap leach PLS. Naturally generated acid mine drainage (AMD) from West Kentucky No.13 mine was processed using the multistage precipitation circuit in the pilot plant in a test conducted for a period of 32 hours. The final grade of the mix RE oxide produced from the AMD was 90.84% with an overall circuit recovery of 64%. The primary source of REE was the selective precipitation steps involving iron and aluminum rejection. The hydrophobic-hydrophilic separation (HHS) process was proven to effectively recover coal from fine waste materials. For REM recovery, the HHS process was able to produce concentrates at grades of approximately 1.8% REE on an ash basis; however, recovery values were typically low, <10%, under the optimal conditions determined in the laboratory-scale testing. Staged testing of the pilot-scale HHS process for coal recovery and semi-continuous laboratory testing for REM testing showed that a total concentration ratio of more than 15x was observed for the REM recovery process. A circuit simulation package was developed for REE extraction and purification using a spreadsheet-based platform (Microsoft Excel). The REESim circuit simulation package is configured to track the mass and volume flows of components passing through a series of unit operations specified and configured by the user. The mass rates can then be utilized by the user to determine important performance indicators such as product mass yields, concentrate purity levels, element-by-element recoveries, and so forth. The techno-economic analysis showed that the roasting and leaching operations were the most expensive capital items, each contributing approximately 30% to the total capital cost. One notable contributor to the high production costs was the low REE recovery observed in the pilot scale trials. The product basket price was shown to have a strong influence on the economic viability of the scenarios, with the scandium price being the most significant influencer. Operating cost was shown to be extremely sensitive to REE recovery, REE feed grade, and leaching acid consumption. An analysis of ten different scenarios for a 500 t/h commercial operation revealed that three were economically favorable, producing internal rates of return varying from 27.7% to 33.1% and payback periods of 4 to 5 years. The project successfully developed and demonstrated a process to recover REEs from coal and coal byproducts in a pilot-plant operation which consistently produced over 90% grade REO mix from varies types of feedstocks. Commercialization analysis showed that the technology readiness level successfully achieved TRL 6 at the end of the project and demonstrated the need and the potential for scaling the process to further advance the technologies toward the goal of providing a domestic supply of REEs at a commercial scale.

01 COAL, LIGNITE, AND PEAT↗

Subtask 1.3 – Integrated Carbon Capture and Storage for North Dakota Ethanol Production

The Energy & Environmental Research Center (EERC), in partnership with Red Trail Energy, LLC (RTE), a North Dakota ethanol producer; the North Dakota Industrial Commission (NDIC) Renewable Energy Program (REP); and the U.S. Department of Energy (DOE), conducted a feasibility and implementation study for a commercial carbon capture and storage (CCS) effort. This subtask provided technical support and developed recommended practices of how small-scale industrial CO2 emitters (<1,000,000 tonnes of CO2 emitted annually) may economically deploy CCS. The 64-million-gallon dry mill RTE ethanol facility, emitting an average 180,000 tonnes of CO2 annually, was the subject of the case study. The positive outcome of this research, which shows technical and economic potential for ethanol–CCS in North Dakota, has resulted in RTE acquiring an approved Permit to Drill on December 2, 2019, for a stratigraphic test well in early 2020, a necessary step toward a North Dakota CO2 Storage Facility Permit (SFP) for the RTE CCS effort. Outcomes include 1) validating the Broom Creek Formation as a regional target for CCS, 2) determining the full carbon life cycle of an industrial fuel production facility with CCS, 3) developing a field implementation plan (FIP) for small-scale CCS, and 4) determining the validity and pathway for using CCS to meet low-carbon fuel (LCF) standards. The technical team included the EERC, RTE, Trimeric Corporation, Schlumberger Carbon Services, and Computer Modelling Group (CMG). Findings from activities conducted November 2016 – May 2020 are summarized as follows. Several key steps have been accomplished toward validating the Broom Creek Formation as a CO2 injection and storage target at the RTE CCS site, including verification of the presence and structure of sandstone layers that may comprise the potential CO2 storage reservoir and the several thousand feet of overlying confining zone. Work included site characterization using existing data, interpretation of seismic data within the study area, and geologic modeling simulation of CO2 injection. Interpreted results estimate 3000 feet of confining zone between the Broom Creek Formation (storage target) and the lowermost underground source of drinking water (e.g., the Fox Hills Formation). The thickness of the Broom Creek injection target varies 230–420 ft within the survey area. Results were used to inform the location of a stratigraphic test well and associated characterization test program. No impediments were identified within the targeted CO2 storage complex that would prevent the project from moving forward. A stratigraphic test well is the next step to validate these results and to acquire remaining data necessary to develop a North Dakota CO2 SFP application. The EERC generated full carbon life cycle estimates for CCS integration with the RTE ethanol facility. Results indicated that an average 40% reduction in CO2 emissions is possible through CCS implementation. Approximately half of the carbon in the overall life cycle for a dry mill ethanol plant is generated through the fermentation process and emitted to the atmosphere; this is the CO2 stream targeted for CCS. The remaining carbon is attributed to corn feedstock farming (diesel, fertilizer), energy for fuel processing (natural gas, electricity), and transportation (diesel) of the fuel product. Life cycle carbon estimates are also affected by the anticipated energy consumption of a potential capture facility, which depend on the type of CO2 product generated. For example, a 30%–40% net CO2 emission reduction is estimated if a liquefied CO2 facility were incorporated compared to a 40%–50% net CO2 reduction if a supercritical “injection-grade” CO2 product is generated; i.e., more energy is required to further refine the CO2 stream, affecting the full carbon life cycle estimates. A CCS FIP was developed and initiated at the RTE CCS site, resulting in the development of several guidance documents: a CO2 Capture Process Design Package, a North Dakota CO2 geologic Storage Permits Template, and a Public Outreach Package for CCS in North Dakota. General FIP components include CO2 capture system, pipeline and well designs; monitoring, verification, and accounting (MVA) plans; geologic characterization and testing programs; and permitting and outreach plans. Vendor bids were also acquired for the CO2 liquefaction facility. Near-surface characterization (groundwater and soil gas sampling) and geologic characterization (seismic survey) were initiated to inform development of a UIC Class VI-compliant MVA plan compliant with a North Dakota CO2 SFP. Designs (well and geologic testing) were completed for a stratigraphic test well compliant with a North Dakota CO2 SFP. In addition, the outreach plan was executed, including community open houses, meetings with city/county/state officials, and development of public materials. Although other entities continued to mature incentive programs in 2019–2020, California and the Internal Revenue Service (IRS) currently provide the most advanced economic opportunities for CCS integrated with fuel production. The California Low-Carbon Fuel Standard (LCFS) adopted a CCS Protocol in January 2019, allowing submittal of a design-based pathway (DBP) application for an approved temporary (not certified) carbon intensity value for a fully engineered facility. An ethanol–CCS DBP application to the California LCFS Program (officially approved February 28, 2020) was developed to show that the RTE CCS effort meets LCFS requirements. The approved DBP provides confidence to advance the project and supports potential investments. Other entities continue to mature incentive programs. The IRS issued guidance in February 2020 that addresses the definition of beginning of construction and revenue procedure on partnerships for the Enhancement of Carbon Dioxide Sequestration Credit (a.k.a. Section 45Q) CCS tax credit program; the IRS anticipates issuing further guidance on issues such as secure geologic storage, utilization qualifications, and recapture of claimed credits. Maturing incentive programs coupled with workable permitting regulations provide confidence to advance CCS projects in North Dakota and support financial investment to proceed with designing, constructing, and implementing CCS projects at small-scale fuel production facilities. The largest hurdles for CCS implementation at small-scale industrial systems are often business/economic-related (i.e., not technical). Market uncertainty already exists for agriculture-based alternative fuels such as corn ethanol, for which production has increased by ~33%, and prices have correspondingly lowered since 2015. Passing the Section 45Q tax credit program improves economic feasibility for CCS but may require external investors for a small business to achieve maximum benefits. Public–private partnerships with NDIC and DOE have resulted in foundational technical and regulatory knowledge, growing stakeholder confidence, and a pathway to implementation that enables similar industrial CCS projects in the region to advance. This subtask was funded through the EERC–DOE Joint Program on Research and Development for Fossil Energy-Related Resources Cooperative Agreement No. DE-FE0024233. Nonfederal funding was provided by NDIC and RTE. The authors would also like to thank CMG, ESRI, IHS, Neuralog, and Schlumberger for allowing the use of their software packages in support of this work.

42 ENGINEERING↗