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All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Anhydrous vs Hydrated f-Element Acetate Polymers Dictated by the Stoichiometry of Protic Acidic/Basic Azole Mixtures

Continuing our investigations of ionic liquid (IL) based routes to a library of f-element/soft donor complexes which could be studied crystallographically, we have explored the dissolution of f-element salts in protic imidazole-based ILs containing only soft donors at high temperatures to drive off volatiles, including water and carboxylic or mineral acids. Here we present our results, reacting acidic and basic azoles in 1:3 or 1:1 stoichiometric compositions at elevated temperature, followed by saturation with Nd(OAc) 3 ·xH 2 O or Ce(OAc) 3 ·xH 2 O, which led to 13 new metal–acetate polymeric complexes identified by single-crystal X-ray diffraction. We found that the diversity in coordination modes of the simple acetate ligand that interfere with substitution of the softer N donors led to several readily crystallizable complexes forming two distinct groups with respect to f-element interaction with the ionic liquid precursors. When the acidic/basic azole ratio was 1:3, acetate and a neutral basic azole were found to be coordinated to the metal centers but no water, although in one case (2) water was observed in the secondary coordination sphere: [Ce(μ 2 -OAc) 3 (C 1 im)] n (1, C 1 im = 1-methylimidazole), [Nd(μ 2 -(OAc) 3 (C 1 im)] n ·nH 2 O (2), [Ce(μ 2 -OAc) 3 (C 2 im)] n (3, C 2 im = 1-ethylimidazole), [Ln(μ 2 -OAc) 3 DMF] n (Ln = Nd (4), Ce (5); dimethylformamide (DMF) was substituted for the azole mixture), and [Nd(μ 2 -OAc) 3 (C 4 im)] n (6, C 4 im = 1-butylimidazole). However, when the stoichiometric ratio was 1:1, water was always observed coordinated to the metal ions with the acidic azole included in the structure as a solvate or cocrystal, despite a higher reaction temperature: [Nd(μ 2 -OAc) 3 (OH 2 )] n ·n(1,2,3-Taz) (7, 1,2,3-Taz = 1,2,3-triazole), [Ln(μ 2 -OAc) 3 (OH 2 )] n ·n(4,5-DCim) (Ln = Nd (8), Ce (9), 4,5-DCim = 4,5-dicyanoimidazole), [Ln(μ 2 -OAc) 3 (OH 2 )] n ·n(3,5-diNH 2 -1,2,4-Taz) (Ln = Nd (10), Ce (11), 3,5-diNH 2 -1,2,4-Taz = 3,5-diamino-1,2,4-triazole), [Ce(μ 2 -OAc) 3 (OH 2 )] n ·n(3-NH 2 -1,2,4-Taz) (12, 3-NH 2 -1,2,4-Taz = 3-amino-1,2,4-triazole), and [Nd(μ 2 -OAc) 3 (OH 2 )] n ·n(5-NH 2 -Tz) (13, 5-NH2-Tz = 5-aminotetrazole). All of the compounds retain the Ln:OAc– ratio of 1:3 and form 1D polymeric chains; however, they exhibit a variety of coordination modes affecting the degree of chain condensation. The isolation of both hydrated and anhydrous products revealed different abilities of the investigated soft N-donors to compete with O-donors finding their place in the coordination sphere of the lanthanide or in the crystal lattice.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Subsurface electrical conductivity across the BEO site inferred using a capacitively coupled resistivity survey in May 2013, Utqiagvik, Alaska

Multiple transects across and around the Barrow Environmental Observatory (BEO) site were surveyed using a capacitively coupled resistivity tool to infer the subsurface electrical conductivity in the top ~6 m in order to improve the understanding of heterogeneity in ice and salinity content. This work was led by the environmental geophysics team from Lawrence Berkeley National Laboratory as part of the Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic). The acquisition was performed in May 2013 using a capacitively coupled resistivity tool (OhmMapper from Geometrics, Inc) mounted behind a sled hooked to a snowmobile. Twenty-eight ~750 m long transects cover the NGEE intensive site (polygon areas A, B, C, D) in the BEO with a measurement (apparent resistivity for 5 different geometries) taken every 1.5 to 2 m. The survey also includes other transects that have been acquired along Electrical Resistivity Tomography (ERT) transects previously acquired at the site (Site 0, AB, and BD), and several long transects (up to 7 km each) around the BEO site crossing several Drained Thawed Lake Basins (DTLB). The various transects acquired during this survey cover a distance of about 100 km. All the datasets are provided with the acquisition geometry and the associated subsurface apparent electrical conductivity. In addition, the 28 transects at the BEO intensive site were inverted to infer the subsurface electrical conductivity. Unprocessed and processed data products are included in this package. This metadata document contains a description of the survey and processing steps and the inferred products.The Next-Generation Ecosystem Experiments: Arctic (NGEE Arctic) was a 15-year research effort (2012-2027) to reduce uncertainty in Earth System Models by developing a predictive understanding of carbon-rich Arctic ecosystems and feedbacks to climate. NGEE Arctic was supported by the Department of Energy’s Office of Biological and Environmental Research. The NGEE Arctic project had two field research sites: 1) located within the Arctic polygonal tundra coastal region on the Barrow Environmental Observatory (BEO) and the North Slope near Utqiagvik (Barrow), Alaska, and 2) multiple areas in the discontinuous permafrost region of the Seward Peninsula north of Nome, Alaska. Through observations, experiments, and synthesis with existing datasets, NGEE Arctic provided an enhanced knowledge base for multi-scale modeling and contributed to improved process representation at global pan-Arctic scales within the Department of Energy’s Earth system Model (the Energy Exascale Earth System Model, or E3SM), and specifically within the E3SM Land Model component (ELM).

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

The Uranium-Containing and Thorium-Containing Anions Studied by Photoelectron Spectroscopy

An in-depth knowledge of actinide chemistry is fundamental to many aspects of nuclear science and technology, including the synthesis and processing of materials and the remediation of waste disposal sites. Among the actinides, the chemical bonding behaviors of actinium and thorium resemble those of the transition metals; the 5f-electrons of protactinium, uranium, neptunium, and plutonium often play important roles in their bonding; and among the still heavier elements, their bonding tends to mimic the lanthanide elements in terms of electron shielding and their f-electron contributions. Bonding that involves 5f-electrons, however, is especially important, in part because of the significance of uranium and plutonium, but also because these elements are among the few where f-electron participation in bonding is relatively common. This work focused on studying uranium-containing and thorium-containing anions in the gas phase using negative ion photoelectron spectroscopy. Since this technique directly probed valence electrons, it was uniquely positioned to address open questions regarding molecular bonding and electron configurations. A particularly important issue concerned how bonding in actinide-containing molecules was affected by modifications to their actinide atoms’ environment, i.e., due to their interaction with ligands. A closely related question was how actinide atoms’ suborbitals were qualitatively reordered and their energies quantitatively shifted as a result of their ligated environments. These were especially relevant issues in regard to uranium due to it having multiple possible oxidation states (OS) and the potential for 5f electron participation in bonding. The effects of ligands on oxidation states and 5f-orbital energies in uranium bonding was expected to be pronounced. Both ligands and excess electrons were seen as probes of actinide atoms within actinide-containing molecules. Our strategy for advancing knowledge of chemical bonding in the actinide-containing species utilized the synergy between experiments and theory, where in some cases experimental results validated theory and where in others computational results assisted in interpreting experiments. Calculations on actinide systems are terrifically challenging due to large spin-orbit interactions, relativistic effects, and just the sheer number of electrons involved. Even in the simplest species, e.g., U and U2, the most sophisticated, modern calculations carried out by the most experienced theorists often only approximate experimentally-measured values, such as electron affinities. For theory to provide confident predictions that can be used to solve real problems it needed an iterative and ultimately corrective mechanism by which its methods can develop further. Experiments can be used to identify when theory has failed; whereupon the subsequent process of using the experiment-theory interplay can be used to find the cause of the failure. Upon fixing it in one case, different test species can be proposed and studied by the experiment-theory combination to determine whether the problem has been corrected. Thus, experiments not only measure the values of molecular properties, they also provide navigational 3 beacons that keep computations off the reefs in an otherwise dark sea with few reference points. Experimental measurements in the actinide field are not only important, they are in actuality essential to computational progress. While it was not always possible to compare the theoreticallydetermined quantity of interest directly with the same experimentally-measured observable, it was usually possible to compare consequential properties that are both calculable and measurable. In the work completed here electron affinities and electronic state spacings were often sensitive consequential parameters. Reasonable agreement between measured and computational values signaled that a calculation that was very likely to be on-track. We had established collaborative relationships with five computational groups, all of which have expertise in computational actinide chemistry. Their PI’s are L. Cheng, D. Dixon, L. Gagliardi, K. Peterson, and B. Vlaisavljevich. Our close interaction with our theory partners led to us suggesting systems to them and them to us. This reciprocal interaction between our experimental and their computational results was among the most important strengths of this work and was a thread woven throughout. Even though anion photoelectron spectroscopic studies are conducted on anions, much of the information that they provide, pertains to the electronic structure of the neutral counterparts of those anions; among these are electron affinities and electronically excited state spacings. Our experimental tools included several specialized ion sources for forming the anionic species of interest, a mass spectrometer for identifying and mass-selecting them, and an anion photoelectron spectrometer for determining their electron affinities (EA) and characterizing the electronic states of the selected anions’ neutral counterparts. Anion photoelectron spectroscopy is conducted by crossing a mass-selected beam of anions with a fixed-frequency laser beam and energy-analyzing the resultant photodetached electrons. The photodetachment process is governed by the energyconserving relationship: hν = EBE + EKE, where hν is the photon’s energy, EBE is the electron binding (photodetachment transition) energy, and EKE is the electron’s kinetic energy. In our apparatus mass-selection is accomplished via time-of-flight mass spectrometry (TOF-MS), electron energy analysis is achieved with either a magnetic bottle or by velocity mapped imaging. Photodetachment of electrons from anions is implemented via either Nd:YAG or excimer lasers. The photodetachment transition energy, i.e., the EBE, between the ground vibrational and electronic state of an anion and the ground vibrational and electronic state of that anion’s neutral counterpart is the adiabatic electron affinity (EA) of that neutral molecule. Likewise, photodetachment transitions between the ground vibrational and electronic state of an anion and the various electronically-excited states of that anion’s corresponding neutral map the electronic spectrum of that neutral species, i.e., the spectral spacings in the photoelectron spectrum are a mirror image of the neutral’s electronic spectrum. It was, of course, crucial to be able to form the anionic species of interest. There, we had a particularly broad field of anion sources from which to choose. These included several variants of pulsed laser vaporization (LV), laser photoemission, infrared desorption plus photoemission, pulsed arc discharge (PACIS), electrospray ionization (ESI), and Rydberg electron transfer (RET). Each of these anion sources were readily combined with, i.e., connected to, the anion photoelectron spectroscopic portion of our apparatus as described above. Among the sources that utilize lasers, visible light for LV sources as well as IR for desorption sources are provided by Nd:YAG lasers. Ultraviolet photons are provided by both Nd:YAG and excimer lasers, whereas the excitation wavelengths for RET experiments come from two Nd:YAG-pumped dye lasers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

DOE Award No.: DE-FE0023919 Phase 3 Scientific/Technical Report

This is the Phase 3 Report for the ‘Deepwater Methane Hydrate Characterization and Scientific Assessment or Genesis of Methane Hydrates in the Gulf of Mexico (GOM2)’ research project (DOE Award No. DE-FE0023919). The report summarizes activities from January 16, 2018 to September 30, 2019. The project is led by the University of Texas at Austin (UT). The objective is to gain insight into the nature, formation, occurrence and physical properties of methane hydrate-bearing sediments for the purpose of methane hydrate resource appraisal through the planning and execution of drilling, coring, logging, testing and analytical activities that assess the geologic occurrence, regional context, and characteristics of marine methane hydrate deposits in the Gulf of Mexico outer continental shelf (OCS). We determined that it would not be possible to pursue the project with the International Ocean Discovery Program (IODP) and then developed a revised science and operations plan to maximize the science using a commercial vessel within the budget that is available. We improved the scientific capability of the UT pressure core center by adding the ability to X-ray pressure cores, and the ability to cut and store multiple core samples for experimental analysis. We transferred pressure cores to peer institutions, including the National Energy Technology Lab (NETL) the United States Geological Survey (USGS Woods Hole). We made advances in understanding the composition and source of gasses locked in the methane hydrate from Green Canyon 955 (GC-955). We developed approaches to determine the in-situ salinity of hydrate-bearing samples, revealing that the in situ salinity of the GC 955 reservoir is just above that of seawater. We determined that the GC-955 hydrate reservoir is composed of sandy silt with a high concentration of hydrate interbedded with clayey silt with no hydrate present. We determined that some or all of the intervals bounding the hydrate reservoir are composed of material similar to the reservoir (sandy silt with hydrate and clayey silt with no hydrate), but with a lower net to gross. We determined that the reservoir effective permeability at a hydrate saturation of ~80-90 % is ~0.1 mD (or 1.0×10-16 m2) to ~0.5 mD (or 5.0×10-16 m2) and the intrinsic permeability is ~12 mD (or 1.2×10-14 m2). The GC-955 reservoir in-situ porosity of sandy silt is 0.38 to 0.40 and is largely independent of effective stress, and that the porosity of clayey silt is 0.33 at an in situ effective stress of 3.8 MPa to ~0.37 at zero effective stress. We developed a systematic, repeatable approach to studying hydrate reservoir properties by reconstituting individual lithofacies from dissociated pressure cores. We determined index properties of GC-955 reservoir, including liquid limit and plasticity, porosity, capillary behavior, and particle size distribution. We developed a more robust pressure coring technology. We finalized and published the UT-GOM2-1 Expedition Volume and we finalized a dedicated volume on the UT-GOM2-1 expedition that will be published in the American Association of Petroleum Geologists Bulletin (AAPG) in spring 2020.

03 NATURAL GAS↗
DOE OSTI2020

Accelerating Nuclear Facility Mission Completion Through an Improved Chemical Hazard Control Strategy - 20460

Code of Federal Regulation (CFR) 10 CFR 830, Nuclear Safety Management [1], explicitly identifies hazardous materials in addition to radioactive materials when establishing the scope of materials that must be evaluated in Hazard Category (HC) 1, 2, and 3 nuclear facilities. This inclusion has led to a near decade-long progression of more and more rigorous application of chemical hazard controls in these facilities. The progressive addition of more rigorous chemical hazard controls has occurred across the Department of Energy (DOE) Complex, having been driven by contractors and regulators alike. However, chemical hazards in other DOE facilities have been, and continue to be, controlled using traditional industrial safety centered strategies. Thus, identical chemical hazards are controlled using dramatically different approaches based solely on the facility type. Not only are the controls different, the analysis and derivation rigor and requirements are also significantly different. In particular, chemical control derivation and application in non-nuclear facilities are much less onerous than the comprehensive hazard analysis process used in nuclear facilities, even in circumstances in which chemicals are not initiators to, or do not exacerbate a nuclear event. While the derivation and control approaches used in these two types of facilities are disparate, the safety results are similarly effective based on a review of reported chemical events from 2014 through 2018. While both approaches achieve comparable safety outcomes, the approach used in nuclear facilities results in significantly greater preparation costs and implementation costs. Furthermore, the problem with the differing approach is not relegated to the control preparation and implementation burden. The operational impact of potentially unnecessary controls slows mission completion without a corresponding increase in safety, not to mention the dilution of the importance of Technical Safety Requirements. The proposed solution must first include a critical and thorough examination of DOE Complex and top-tier chemical industry chemical hazard control practices, coupled with a similar examination of the driving facility regulatory requirements. Results from the examination can then be used to fuel a bold departure from current chemical control practices in Hazard Category 1, 2, and 3 nuclear facilities. Development of an improved and consistent chemical hazard control process would follow, one that continues to ensure safety while accelerating mission completion and significantly reducing the burden associated with chemical hazard control development and implementation. The improved process must establish a hierarchy where radiological hazards are addressed using safety class and safety significant controls and chemical hazards are addressed using overarching safety management programs (with limited unique exceptions). The improved Hazard Category 1,2, and 3 nuclear facility chemical hazard control strategy, while compliant with 10 CFR 830 [1], would be founded on the requirements in 10 CFR 851, Worker Safety and Health Program [2], and the complementary DOE O 151.1D, Comprehensive Emergency Management System [3]. In this way, the Hazard Category 1, 2, and 3 nuclear facility chemical hazard control strategy would, wherever appropriate, be the same process used at other DOE Complex facilities. Ultimately, the improved process will maintain safety and significantly reduce costs and life cycle risk through faster mission completion. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2022

Robust Carbon Dioxide Plume Imaging Using Joint Tomographic Inversion of Seismic Onset Time and Distributed Pressure and Temperature Measurements (Final Report)

We develop and demonstrate rapid and cost-effective methodologies for spatiotemporal tracking of CO2 plumes during geologic sequestration using joint inversion of seismic data and distributed pressure and temperature measurements. Key elements of our methodology are: (a) a computationally efficient approach to pressure and temperature propagation, (b) analysis of time lapse seismic data using a novel ‘seismic onset time’ approach to detect fluid front propagation, and (c) data assimilation and uncertainty assessment via joint inversion of pressure, temperature and time lapse seismic data, and (d) validating the numerical tomographic inversion using a CO2 injection demonstration projects, specifically data collected from the from the Petra Nova Parish Holdings CCUS project in the West Ranch Field, Texas and the Chester-16 reef CO2 injection site in Northern Michigan which is part of the DOE Midwestern Carbon Sequestration Project. The research team is led by Texas A&M University and includes Battelle as a subcontractor with support from Shell, Anadarko, Chevron and JX Nippon. A carbon dioxide (CO2) water-alternating-gas (WAG) pilot was conducted to gain insights into tertiary oil recovery potential via CO2 flood in the West Ranch Field as part of the Petra Nova project, the world’s largest post-combustion CO2 capture and utilization initiative. With a fluvial formation geology and large contrasts in permeability, this is a challenging and novel application of CO2 enhanced oil recovery (EOR). We build a predictive dynamic model of the subsurface that incorporates the multiphase and compositional data acquired during the pilot operation. The calibrated model is used for the carbon dioxide plume imaging. The study began with an initialization of the pilot sector model extracted from a calibrated full-field model. The pilot model calibration follows a two-step hierarchical workflow. First, we performed a large-scale update of the permeability distribution by integrating available bottomhole pressure and multiphase production data. In the second step, local permeability field is fine-tuned using a streamline-based method to match CO2 breakthrough times at the producers. The predictive capability of the calibrated model was verified through two blind validation tests: (1) the model showed good agreement with saturation logs acquired at two observation wells; and (2) the model reproduced the CO2 recovery as a fraction of the injected CO2. The use of seismic onset times has shown great promise for integrating near-continuous seismic surveys for updating geologic models. In this study, we analyze the impact of seismic survey frequency on the onset time approach aiming to extend the application of onset time to infrequent seismic surveys. In addition, we quantitatively examine the nonlinearity of the onset time method and compare it to the commonly used amplitude inversion method. We carry out a sensitivity analysis of seismic survey frequency based on the complete seismic survey data (over 175 surveys) of steam injection in a heavy oil reservoir (Peace River Unit) in Canada. Our results show that an adequate onset time map can be obtained from the infrequent seismic surveys by interpolation between seismic surveys as long as there is no change in the dominant underlying physics between the successive surveys. The study also shows that nonlinearity of the onset time method can be -smaller than that of the amplitude inversion method by several orders of magnitude. Application to the Brugge benchmark case shows that the onset time method obtains comparable permeability update as the traditional seismic amplitude inversion method with faster computation and improved convergence characteristics. We extend the streamline-based data integration approach to incorporate distributed temperature sensor (DTS) data using the concept of thermal tracer travel time. Then, a hierarchical workflow composed of evolutionary and streamline methods is employed to jointly history match the DTS and pressure data. Finally, CO2 saturation and streamline maps are used to visualize the CO2 plume movement during the sequestration process. The hierarchical workflow is applied to a carbon sequestration project in a carbonate reef reservoir within the Northern Niagaran Pinnacle Reef Trend in Michigan, USA. The monitoring data set consists of distributed temperature sensing (DTS) data acquired at the injection well and a monitoring well, flowing bottom-hole pressure data at the injection well, and time-lapse pressure measurements at several locations along the monitoring well. The history matching results indicate that the CO2 movement is mostly restricted to the intended zones of injection which is consistent with an independent warm-back analysis of the temperature data. In addition to employing simulation models and inverse methods for CO2 plume imaging, we also initialized a data-driven technology for detecting inter-well connectivity based on production and pressure data. Our machine-learning framework is built on the statistical recurrent unit (SRU) model and interprets well-based injection/production data into inter-well connectivity without relying on a geologic model. We test it on synthetic and field-scale CO2 EOR projects utilizing the water-alternating-gas (WAG) process. The validation of the proposed data-driven inter-well connectivity assessment is performed using synthetic data from simulation models where inter-well connectivity can be easily measured using the streamline-based flux allocation. The SRU model is shown to offer excellent prediction performance on the synthetic case. Despite significant measurement noise and frequent well shut-ins imposed in the field-scale case, the SRU model offers good prediction accuracy, the overall relative error of the phase production rates at most producers ranges from 10% to 30%. It is shown that the dominant connections identified by the data-driven method and streamline method are in close agreement. Texas A&M University, the lead organization in the project, was primarily responsible for the development of tomographic approaches for CO2 plume mapping in conjunction with distributed pressure, temperature and seismic onset time data. Battelle, as a subcontractor, was primarily responsible for the development of analytical and empirical methods for analyzing transient injection rate and pressure data from point/line sources such as injection and monitoring wells. An additional area of emphasis for Battelle was the use of machine learning for such tasks as inferring reservoir connectivity information from injection-production data, and identifying variable importance for machine learning-based proxy models developed from full-physics simulations. The two organizations also collaborated on the application of the tomographic inversion methodology for a field data set.

02 PETROLEUM↗
DOE OSTI2026

Reproducibility, Replicability, and Research Quality in Homogeneous Catalysis

Researchers from all sectors of homogeneous catalysis convened in response to concerns regarding reproducibility in science to analyze the issue and provide recommendations. In addition to an in- person workshop, the group engaged the broader homogeneous catalysis community through a webinar series and virtually during the workshop. Results of the project affirm that homogeneous catalysis is not in a reproducibility crisis, as evidenced by the field’s current and past contributions to society that have led to economic growth and advances in a range of industries from agriculture to consumer goods to human health. However, it is not uncommon for researchers to encounter obstacles related to reproducibility. Ensuring reproducibility remains the responsibility of the community, both in current work and in training future researchers. This report is intended to engage key stakeholders, including disciplinary societies, publishers, employers, research leaders, and researchers, in practices that maximize reproducible homogeneous catalysis and ensure continued innovation and translatable discoveries. Recommendations made herein are also framed to be applicable beyond homogeneous catalysis, empowering the broader chemical if not scientific community.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Nanostructures for Electrical Energy Storage (NEES) (2020 Final Technical Report)

Nanostructures for Electrical Energy Storage (NEES, www.efrc.umd.edu) was an Energy Frontier Research Center supported by the DOE Office of Science, Basic Energy Sciences, from 8/1/2009 to 7/31/2020. Led by the University of Maryland, NEES enjoyed extensive collaborations with its funded partners, including two DOE Laboratories and six universities. The NEES vision has been to reveal a set of scientific insights and design principles that can underpin a next-generation electrical energy storage approach, building on advances in nanoscale science and technology to achieve simultaneous high power and high energy over extended charge/discharge cycling. The vision is motivated by the recognition that scaling into the nano regime opens the door to new physical phenomena and that the tools enlisted in nanoscale research provide major new opportunities for the synthesis not only of materials at molecular scale but for structures at nano scale and above. NEES has translated this vision into its research program based on two observations. First, while the behavior of ions and electrons in electrolytes and in electrode materials is crucial to electrical energy storage (or more appropriately electrochemical energy storage), it is the transport of ion and electron charge between different structural components of a storage device that ultimately determine its performance. With it well recognized that the choice of electrode materials typically constrain ion transport kinetics as well as maximum ion concentration, the search for better electrode materials has been a primary driver of battery research. At the same time the synthesis of electrodes is typically based on aggregation of particles with varying size, shape, and orientation in the electrode. Together with the presence of additional materials to impart electrical conductivity and cohesion to the composite electrode, change in electrode materials is necessarily accompanied by structural changes at the nano/micro scale that are difficult to categorize and manage. From the beginning, NEES’ vision has been to create and study simpler, highly controlled spatial arrangements of known materials as battery components (electrodes, current collectors, and electrolyte) and to understand how design and structure above the molecular scale determines the energy storage performance available from known materials. Second, advances in nanoscience dramatically expanded the portfolio of synthesis methods, structural motifs, and new phenomena available for research. Some of these gave rapid access to new building blocks at the deep nanoscale (e.g., carbon nanotubes grown by self-assembly, nanoscale arrays formed by electrochemical self-alignment, monolayer films controlled by self-limiting reaction). Such advances served as the enabler for the NEES vision to be pursued experimentally through study of 3D structures created and controlled at the nano, micro, and meso scales. Here, we use meso as in the BES MESO Report, implying not only intermediate or varying length scales, but very much the way behavior is influenced by other factors including aggregation of nanocomponents at different densities and spatial configurations, statistical variations in the aggregates, hierarchical architectures in which they can be assembled, or local 3D configurations that result from the architectures. Over its life cycle, NEES has pursued two overarching goals: (1) to understand the scientific fundamentals of electrochemical storage from the nanoscale to the mesoscale; and (2) to create and learn from innovative, controlled, heterogeneous nanostructures, where such nanostructures can enable the first goal and serve as models for future paradigms in energy storage. Specific goals have included: Synthesize heterogeneous nanostructures comprised of multiple materials arranged in controlled fashion and characterize their behavior; Demonstrate and elucidate design principles for achieving simultaneous high power and high energy; Develop materials processes which enable precision control of thin layers and 3D structures; Investigate the impact of artificial interphases on electrode stability during ion insertion/deinsertion; Create dense arrays of nanostructures to understand how the architecture of these assemblies, along with nanostructure design, influences energy storage behavior at the mesoscale; Identify and understand the consequences of nanoconfinement and local inhomogeneities in 3D mesoscale arrays; Develop and apply computational models to stimulate, guide and interpret experiments.

25 ENERGY STORAGE↗
DOE OSTI2020

Dynamic Behavior of Natural Seep Vents: Analysis of Field and Laboratory Observations and Modeling (Final Scientific/Technical Report)

In this project, we have analyzed data collected by the U.S. Department of Energy (DOE), National Energy Technology Laboratory (NETL) in a high pressure water tunnel (HPWT) and data from two research cruises to natural seeps in the Gulf of Mexico to adapt and validate a numerical model to predict the dynamics of natural seeps in the deep oceans. The HPWT data include video observations of the shrinkage rate of individual methane and natural gas bubbles under simulated deep-water conditions. Field data were collected during two cruises by the Gulf Integrated Spill Research (GISR) Consortium led by Texas A&M University and funded by the Gulf of Mexico Research Initiative (GoMRI). These data included in situ observations from a remotely operated vehicle (ROV) of gas bubbles at two natural seep sites in the Gulf and acoustic observations of the natural seep bubble flares in the ocean water column. The acoustic data were from multibeam echosounders, one mounted in a forward-looking orientation on the ROV and another mounted down-looking in the haul of the ship. All of these laboratory and field data were focused on the dynamics of natural gas bubbles at temperatures and pressures favorable for clathrate hydrate formation between the gas and water. Our analyses of this data focused on understanding the mechanisms responsible for gas bubble dissolution within the hydrate stability zone (HSZ) of the oceans. Ice-like hydrate shells may form on the bubble-water interface under these conditions, and it was unknown how this might affect the mass transfer of gas into the ocean. We were able to extract bubble shrinkage rates from the HPWT datasets. Using this data we determined that mass transfer coefficients with and without a hydrate shell match empirical values for bubbles in contaminated systems (so-called dirty bubbles contaminated by naturally occurring surfactants). We also showed that free gas, and not gas hydrate, is the dominant dissolving phase when the hydrate sub-cooling is below 11 degree Celsius (temperature difference between hydrate the hydrate formation temperature and ambient temperator) or the pressure is reducing as bubbles rise through the ocean water column. Using this mass transfer model, our numerical model of bubble dissolution matched the over 200 HPWT experiments with an average error of 10% for predicting the bubble size at the end of an experiment. From field data in the literature, we also observed that gas bubbles dissolve faster when they are initially released, following mass transfer coefficients for so-called clean-bubbles (those not yet contaminated by surfactants). Shortly after release within the HSZ, a hydrate shell forms on the bubble-water interface, and the mass transfer reduces to rates matching those of dirty bubbles. We correlated this transition time from clean to dirty bubble behavior with the initial bubble surface area and the hydrate sub-cooling. With this model for hydrate formation time and using the mass transfer coefficients deduced from the HPWT data, we validated our numerical model for predicting the rise heights of natural seep flares in the oceans. Flare heights are commonly observed in haul-mounted acoustic multibeam data. The numerical model predicts bubbles to rise high in the ocean water column owing to the slower mass transfer rates for dirty bubbles that accompany the majority of their rise time. We found that the numerical model predictions matched the observed flare heights within 5% to 10% accuracy when we compared the rise heights of the largest bubbles released from the seafloor with the bubbles acoustically visible in the multibeam data. Bubbles become acoustically transparent as they shrink to sizes of order 1 mm in diameter for the multibeam frequencies used in the field. The forward-looking multibeam on the ROV also provided data on the lateral spreading of bubbles in natural seep flares. Our analysis of this data showed that spreading follows a diffusion process, with the effective diffusivity correlating with the wobbling length scale of these ellipsoidal bubbles. When we apply this diffusivity in a random displacement model of bubble spreading, our numerical simulations match closely the lateral spread observed by the M3 in the ocean water column. Finally, we compared the seep model predictions for the acoustic properties of these natural seep plumes with that observed by the acoustic instruments in the field. The M3 and EM 302 observations were converted to relative values of target strength using a calibration we obtained in the laboratory for the M3 and using an algorithm from the manufacturer for the EM 302. Comparing the numerical seep model to these data, we obtain good agreement over the whole height of rise of these bubble flares. This further validates the numerical model. Overall, our validated seep model captures the key dynamics of gas bubbles released from natural seeps in the oceans and helps to predict the fate of methane in the water column.

03 NATURAL GAS↗
DOE OSTI2023

Rapid AI-based Dissection of Ashes using Raman and XRF Spectroscopy (RADAR-X)

Waste-to-energy (WTE) facilities incinerate ~35 million tons of municipal solid waste annually in the United States. The incineration process reduces the mass and the volume of the waste fraction by over 75 and 95%, respectively. The fraction left after incineration remains as ash residues and is referred to as WTE ash, compromising of bottom and fly ash. In the United States, ~10 million tons of WTE ashes are generated annually and predominantly landfilled because of the lack of secondary end-use pathways. This incurs a significant financial burden (landfilling costs) on U.S. WTE facilities and also results in the loss of materials to the landfill. The primary objective of this research is to understand better the elemental and mineralogical composition of WTE ashes from diverse origins and find composition dependent upcycling pathways for diverting these ashes from landfills. This primary objective was addressed through three research tasks –(Task I) An AI-led Multi-Modal Approach for Compositional Analysis, (Task II) Developing a Dissolution-Based Test for Real Time Analysis, and (Task III) Establishing composition-dependent end uses. The chemical composition of WTE ash is dependent on two factors, i.e., the input waste composition and the operational parameters of a WTE facility (combustion conditions). Amongst these two factors, the input waste composition will likely show spatial and temporal variation. As a result, the chemical composition of WTE ash will also fluctuate. To understand the spatial and temporal variation in WTE ash composition, in Task I, we collected 128 ash samples (62 bottom ash and 66 fly ash samples) from 11 WTE facilities located in 11 U.S. states and characterized them via X-ray Fluorescence, powder X-ray Diffraction, and Raman Spectroscopy. The findings from this extensive characterization work indicated that the key elements in WTE fly ashes are Ca, Cl (greater than 10 wt. %), Si, S, K, Zn ( between 1 and 10 wt. %), Mg, Al, P, Ti, Fe, Cu, Br, and Pb (between 0.1 and 1 wt. %). Similarly, the key elements in WTE bottom ash fraction finer than 45μm are Ca (greater than 10 wt. %), Mg, Al, Si, S, Cl, K, Ti, Fe, Zn (between 1 and 10 wt. %), P, V, Cr, Mn, Cu, Br, and Pb (between 0.1 and 1 wt. %). Here, we note that the dominant fraction of WTE bottom ash is the coarse fraction. The coarse WTE bottom ash fraction (rich in silicon) was not characterized in this study because of excessive grinding requirements and their unsuitability as a supplementary cementitious material due to their coarse nature. The elements in WTE bottom ashes are present as calcite, anhydrite, vaterite, hydroxyapatite, quartz, bassanite, gehlenite, akermanite, hydrocalumite, and portlandite. Similarly, the mineralogical species present in WTE fly ashes are calcium chloride hydroxide, halite, calcite, anhydrite, sylvite, hydrocalumite, vaterite, hannebachite, quartz, and bassanite. Temporal variation in ash composition may also result in significant fluctuations in chemical compositions. Therefore, a WTE facility may need to monitor the ash composition (elemental and mineralogical composition) in real time. In Task I, we evaluated the possibility of using a portable X-ray fluorescence (XRF) spectrometer to monitor the elemental composition in real-time. Specifically, we collected XRF data on identical specimens via a portable XRF spectrometer (low-end) and a lab-based benchtop XRF spectrometer (high-end). The collected data was used to train an A.I. algorithm (portable XRF data as an input and benchtop XRF data as an output) to predict accurate elemental composition using portable XRF data. Finally, we developed a 2-minute photobleaching protocol to monitor the mineralogical characteristics of WTE ashes via Raman spectroscopy. Overall, the activities in Task I improved our understanding of ash composition and developed techniques to monitor elemental and mineralogical composition in near real-time. Based on the findings of Task I, we find that WTE ashes exhibit wide variability in mineralogy. For ICP-based elemental analysis, all the mineralogical species in WTE ashes must be brought into solution. This is traditionally accomplished with acid digestion using a combination of multiple acids. However, acid digestion with multiple acids is time-consuming and often fails to ensure complete digestion of the ash matrix. To address this limitation, in Task II, we developed an alkali-fusion-based digestion protocol using a combination of lithium tetraborate, lithium metaborate, and their combinations as possible alkali fluxes for digesting WTE ashes entirely and rapidly. The validity of the developed method was evaluated on two standard ash specimens, i.e., SRM 1633c coal fly ash and BCR-176R incineration fly ash specimen. The findings suggest that the developed protocol can ensure complete digestion of elements such as Al, Ba, Ca, Cr, Cu, Mg, Mn, P, Sr, V, Zn, Be, K, and rare earth elements. The recent changes in the energy market towards renewables and increased metal recycling have resulted in reduced supplies of supplementary cementitious materials (coal fly ash and slag). Therefore, in Task III, we evaluated the possibility of employing WTE ashes as SCMs. As the chemical composition of WTE ashes varies temporally (on an hourly basis), there was also a need to develop tests that can evaluate the suitability of material to act as supplementary cementitious material rapidly, i.e., in a few minutes. Therefore, in Task II, we also developed a rapid test to assess the suitability of a material to act as an SCM in 5 minutes. This represents a significant advance over the state-of-the-art R 3 test, which takes ~144 hours. This test was initially validated on amorphous aluminosilicates, such as calcined clays, and could be extended to evaluate other industrial by-products, such as WTE ashes. In Task III, we evaluated the possibility of employing WTE ashes for two applications, i.e., as an SCM and a lime substitute for clay stabilization. The findings from Task I indicated that WTE ashes are enriched in chlorine and, therefore, cannot be used directly as an SCM due to corrosion-related risks and altered hydration kinetics. Accordingly, we developed an ash treatment protocol to reduce the solubility of chlorine-containing species in WTE ashes. The developed treatment protocol also immobilized lead in certain mineral forms. As a result of the treatment, WTE ashes can be used as SCMs without any corrosion or heavy metal leaching concerns. The second application examined in this study was clay stabilization. WTE ashes are calcium-rich and can be an adequate lime replacement for clay stabilization. Our findings reveal that the sum of the concentrations of Ca(OH) 2 and CaClOH controls the clay stabilization capability of WTE ashes. In summary, in this work, we evaluated the elemental and mineralogical characteristics of U.S. WTE ashes from diverse origins and developed tests to evaluate the chemical characteristics of these ashes in real time through a portable XRF and a benchtop Raman spectrometer. Based on the chemical characteristics of these ashes, we developed an ash treatment process to enable the use of WTE ashes as an SCM and also evaluated the possibility of employing these ashes for clay stabilization. Overall, the findings from this work enables the diversion of WTE ashes from landfills for multiple end-uses, i.e., as an SCM or a lime substitute for clay stabilization.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Emissions mitigation technology for advanced water-lean solvent-based CO 2 capture processes

This technical final report submitted to DOE/NETL presents all the research activities performed during the entirety of DE-FE0031660 project-Emissions Mitigation Technology for Advanced Water-Lean Solvent-Based CO 2 Capture Processes which spans from October 2018 through March 2022. RTI International has been conducting studies from fundamental and operational aspects to reduce the overall amine emissions from the advanced Water-Lean Solvent (WLS) systems, specifically RTI’s Non-Aqueous Solvent (NAS). This technical final report will highlight the key findings from project which align closely to the project objectives which are: Identify the contribution of vapor loss, entrainment, and aerosols to the overall emissions of water-lean systems; Determine the significance of CO 2 capture system operating parameters to the amine emissions; Develop an emissions model based on critical operating parameters; Evaluate the effectiveness of emissions mitigation devices to reduce the amine emissions to <1 ppm under flue coal-fired flue gas; and, Determine the contribution of the ECTs to the overall CO 2 capture cost. The following are the key findings based on numerous tests using both lab-scale setups and parametric testing performed at RTI’s Bench-scale Gas Absorption System (BsGAS). During the BP1, the aerosol generation system and monitoring equipment were installed at BsGAS to produce and determine the aerosol characteristics during the NAS CO 2 capture process. The aerosol produced by this setup produced aerosols with the peak diameter and concentration of 50 micron and 1.2E10 7 cm -3 , respectively. These particle sizes and concentrations are matched to those observed in the actual coal-fired power plant flue gases and expected to be found at the absorber inlet of the CO 2 capture system. Over 1,300 hours of parametric testing have been conducted to evaluate the impact of the aerosols and operating conditions during the CO 2 capture with NAS on the overall amine emissions in the treated flue gas. At the worse condition tested, the presence of the aerosols in the flue gas could increase the overall emissions by 10X compared to the baseline emissions from NAS’s vapor pressure. CO 2 capture rate was found to be a main factor impacting the overall emissions as well as aerosol size and concentrations in the absorber off-gas. The higher CO 2 capture rate, the higher amine emissions in the treated gas. The temperature difference between the temperature bulge seen in the absorber and the water wash temperature also impacts the particle growth where the larger the temperature difference, the more amine emissions from aerosols in the treated gas. The majority of the aerosols did not grow substantially in the system, and the particle concentrations remained nearly constant between the absorber inlet and wash outlet. Only a small portion of the particles were found to grow significantly. The high efficiency demister with mesh size of 5-10 micron can be installed to remove a portion of the aerosols from the gas stream leaving the water wash. Overall, these results from parametric testing have established the emission baseline and validate our assumption on the need of emission control technologies (ECT) in order to minimize the emissions from the baseline NAS CO 2 capture process. Over 2,000 of BsGAS operating hours was used to investigate a handful of process improvements which led to a selection of the vital few changes that effectively control the amine emissions. These process improvements are lime-coated-filters for absorber gas inlet, advanced demister at the top of the absorber, a second water wash with amine recovery unit were designed, installed, and tested at BsGAS at the end of BP1. The result showed that the NAS CO 2 capture process with these additional emission control devices could lower the amine emission in the treated gas to about 1 ppm using a simulated coal-fire flue gas stream. The main contributor in lowering the amine emission came from the second water wash with amine recovery unit where the amine concentration in the scrubbing water was kept below 2 wt% through a continuous amine removal via an adsorbent bed, resulting in a low amine vapor pressure. The adsorbent bed was regenerated via a direct steam regeneration and the recover amine was returned to the absorber to minimize wastewater and makeup amine. A flue gas generation system was designed and installed during the first half of BP2 to support the emission testing using a real coal-derived flue gas. The system is capable of generating both coal- and natural gas- derived flue gases with the composition of the gaseous species highly resemble to that of the power plant flue gases. The particulates detected in the coal-derived flue gas showed the mean diameter of 1 micron. The CO 2 capture operating was then proceed using the real coal-derived flue gas where the amine emission was controlled to be about 0-3 ppm for the total run time of about 200 hours. Similar testing was conducted with natural gas-derived flue gas and the result showed a highly amine emission of 30 ppm under the total run time of 200 hours. The Principal Component Analysis (PCA) and the Partial Least Squares Projection to Latent Structures (PLS) techniques were applied to the parametric testing data to derive a multivariate statistical model. The model was validated and trained with half of the data collected, and the predictive ability of the model was evaluated using the remaining half of the data. The resulting empirical model was capable of predicting the overall emissions from the NAS process without the ECTs with ±15% accuracy (average absolute deviation, AAD) in BP1. As more emission data were obtained under the real coal-flue gas in the BP2, the model incorporated these new set of data to reflect the final process configuration, operating parameters, and amine emission. This results in the updated empirical model predicting the amine emission from the NAS CO 2 capture process with 84% goodness-of-fit (R 2 ), 85% predictability (Q 2 ), and 15% AAD. The study evaluates the use of RTI’s Non-Aqueous Solvent technology for 90% CO 2 capture from a net 650 MWe pulverized coal power plant, downstream of the flue-gas desulfurization unit. The captured CO 2 has a purity of > 95% CO 2 , and is dried, compressed to 15.3 MPa (2,215 psia), ready for sequestration. The analysis uses Case B12B from the DOE Baseline study on Bituminous Coal, Revision 4 where the Cansolv CO 2 capture plant is replaced by the RTI CO 2 Capture plant. The CO 2 capture plant has been sized to capture >90% CO 2 from flue gas derived from a net 650 MWe supercritical pulverized coal power plant. The CO 2 capture plant is equipped with emission control technologies that limits the amine emissions to < 1 ppm. Two different cases were evaluated for the technoeconomic study. The key difference between the two cases is the regenerator pressure. In Case 1, the regenerator operates at 0.195 MPa (28.3 psia), whereas in Case 2, the regenerator pressure is 0.44 MPa (64 psia) thus removing the need for the first stage of compression of the eight-stage compression train. Results from the TEA are compared against the DOE reference cases for SCPC plant with and without CO 2 Capture (Case B12A and Case B12B of the DOE Baseline study, respectively). Case 2 with CO 2 regeneration at higher pressure results in the lower cost of CO 2 capture. The total capital cost of the capture process has been estimated using 2018 dollars in Aspen Process Economic Analyzer and was estimated to be $579 MM. The capture plant operation leads to a total parasitic power loss rate of 96 MWe, resulting in a decrease in pulverized coal power plant efficiency of 7.8% points. The resulting cost of electric power increases from 64.4 mills/kWh, for no capture, to 97.5 mills/kWh, with 90% capture, an increase of 51% in the COE. The cost of capturing 90% CO 2 was estimated to be $38.2/tonne-CO 2 , and meets the DOE target of $40/t-CO 2 . Emission control technologies (ECT) investigated in this project includes a second water wash with use of activated carbon beds for removal of amine from the wash water prior to recirculation in the water wash. These ECT allow operation of the CO 2 capture plant with < 1 ppm amine emissions with the treated flue gas and contributes to $2.4/t-CO 2 captured. Amine emissions derived from thermal and oxidative degradations were investigated under this project along with the emissions derived from aerosols for the NAS system. The thermally degraded of the lean NAS showed less than 4% decreased of the original total amine content in the NAS at 150 °C while the result obtained at 120 °C showed no drop in total amine content, suggesting that thermal degradation of the NAS is minimal. These results also suggested that the thermally degraded species are not likely formed and contributed to the emissions due to the low regeneration temperature of the NAS at 90-105 °C. The oxidative degradation, on the other hand, could become problematic as some of these oxidative degraded species were observed during the NAS-5 testing at National Carbon Capture Center (NCCC) and SINTEF in our previous project. The rapid screening of selected inhibitors suggested that oxidative degradation of NAS can be suppressed using thiol containing compounds in amounts of at least 1 mol%. The detailed mechanistic degradation pathway was conceived for a specific amine used in NAS formulation during BP2. he reduction of the nitrosamines caused by the NO x present in the flue gas was also examined. The study suggested that the thermo-chemical treatment of the NAS solvent would be a more effective and economically viable compared to removing NO x at the DCC.

01 COAL, LIGNITE, AND PEAT↗