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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 379 records · Page 21

Electrical and Spectroscopic Diagnostics as Real‐Time Metallization Indicators During Hydrogen Plasma Smelting Reduction

This study investigates the hydrogen (H 2 ) plasma reduction process of direct-reduced-iron-grade hematite ore at different arc currents (100–200 A) in an Ar–5% H 2 atmosphere at 0.9 bar. Iron ore samples (10 g) were exposed to a plasma arc, and the reduction/metallization kinetics were analyzed over fixed time intervals. Electrical diagnostics revealed that the arc voltage exhibited takeover-mode oscillations which were suppressed at higher currents due to stronger electromagnetic coupling. The voltage dropped significantly as metallization approached ∼95%, linked to increased electrical conductivity of the metallic iron (Fe) in the ore as well as Fe evaporation into the arc, lowering the arc resistance. A simplified Elenbaas–Heller model supported this explanation and confirmed that Fe vapor concentration enhances plasma conductivity. Optical emission spectroscopy focused on the plasma–metal interface revealed the plasma's optically thick nature, as the primary Fe I 526.95 nm line experienced self-absorption. However, weaker Fe I lines (404.58, 438.35 nm) normalized to Ar I 696.5 nm provided a reliable proxy for metallization. These diagnostics, electrical and spectroscopic, effectively track metallization in real-time during H 2 plasma smelting reduction.

08 HYDROGEN↗

Acetate as a Platform for Carbon-Negative Production of Renewable Fuels and Chemicals (Final Technical Report)

This project was an industrial-academic collaboration between experts at the University of Wisconsin-Madison, the University of Kentucky, and LanzaTech, a world leader in the use of gas fermentation to sustainably produce fuels and chemicals. The project developed technologies to create an integrated process for converting carbon dioxide and renewable hydrogen into molecules that can be blended with liquid transportation fuels or used in an array of chemical applications. The project was motivated by the Program Objectives of eliminating carbon dioxide release in the production of chemicals by integrating the unique and efficient capabilities of two microorganisms into a single process. The first microbe, an acetogen, produces acetate from carbon dioxide and hydrogen while the second microbe upgrades acetate from acetogen fermentation permeates to higher-value chemical products. The carbon dioxide released in the upgrading process is recycled internally to produce more acetate. As such, the process can be designed to operate with zero carbon dioxide release and net positive carbon dioxide capture. The process has the potential to provide an alternative paradigm to the current bioeconomy – one in which acetate is the primary energy carrier instead of sugars. Our process by-passes photosynthesis and the barriers created by biomass as primary chemical feedstock. As such, the process can be scaled to meet existing sources of carbon dioxide emissions and located anywhere renewable hydrogen can be provided. Our work developed microorganisms with optimized metabolism for producing acetate and other microorganisms with improved conversion of acetate to dodecanol and dodecyl-acetate. We developed synthetic biology tools for a promising non-model bacterium that could enhance metabolic engineering efforts to convert acetate to chemical products. We conducted protein engineering studies to improve the activity of key enzymes involved in our metabolic pathways. We conducted a full technoeconomic analysis that set technical targets for each strain to meet economic goals. We identified key technical barriers in our process and proposed strategies to overcome them.

09 BIOMASS FUELS↗

Kinetics of furfural electrochemical hydrogenation and hydrogenolysis in acidic media on copper

Electrochemical processes can be implemented for the valorization of biomass-derived species such as furfural to generate fine chemicals and fuels. The electrochemical hydrogenation and hydrogenolysis (ECH) of furfural (FF) can produce furfuryl alcohol (FA) and 2-methylfuran (MF) as the major products over Cu catalysts in acidic conditions. The production of these species are in competition and the kinetics of these reactions should be studied so that the product distribution can be better controlled. In this work, the competing kinetics of furfural ECH to furfuryl alcohol and 2-methylfuran were studied on Cu in acidic media by using the applied cathodic potential, temperature, and initial concentration of furfural as probes. Furthermore, an increased temperature of the system was shown to promote the MF production in the range tested (15 °C and 45 °C), however the production of FA was decreased when the temperature was increased from 35 °C to 45 °C, due to significant promotion of side reactions. By varying the concentration of FF used in bulk electrolysis, we saw that the rates of reaction to FA and MF shift from positive order to zero order, suggesting a Langmuir–Hinshelwood or Eley–Rideal mechanism at –0.56 V vs. RHE and 25 °C. An analysis of the reaction mechanisms showed that a non-competitive Langmuir–Hinshelwood mechanism is likely occurring. In addition, we suggest the likely rate limiting steps based on the mechanisms are the first hydrogenation step of FF to C 4 H 3 O–CH 2 O to form FA, and the C–O cleavage of the C 4 H 3 O–CHOH intermediate to form MF.

09 BIOMASS FUELS↗

Green hydrogen from microalgal liquefaction byproducts with ammonia recovery and effluent recycle for developing circular processes

Hydrothermal liquefaction is a promising technology for microalgae-based biofuel production. However, hydrothermal liquefaction’s aqueous wastes have little established reuse, and contain significant fractions of toxic ammoniacal nitrogen. Careful reuse of this waste can assure microalgae-based biofuels are produced with less environmental impact and larger energy efficiency. Microbial electrolysis cells were investigated to valorize this waste product by converting the leftover organics into hydrogen and remove ammonia. Waste hydrothermal liquefaction aqueous phase from two microalgal strains, Tetraselmis sp. and Chlorella sp. were used as feedstocks for hydrogen production in microbial electrolysis cells. Chlorella and Tetraselmis aqueous phase-fed microbial electrolysis cells reach an average current density of 5.1 ± 0.19 A/m 2 and 3.8 ± 0.08 A/m 2 . Compound removal rates and mass removal percentages were also investigated for each feedstock. Additionally, acetic acid, propionic acid, ethanol, and glycerol were effectively removed from the aqueous byproduct. Further, microbial electrolysis cells separated up to 34.3% of ammoniacal nitrogen present in the aqueous phase. Charge transfer analysis indicated that proton transfer, not ammonium transfer, contributed to the majority of the hydrogen production in the cathode. Finally, the microbial electrolysis cell effluent was reused to grow the same microalgal strains, leading to the development of a circular biofuel production system. Microalgae regrowth studies using microbial electrolysis cell effluent showed nearly complete removal of total organic carbon, but significantly less removal of total nitrogen. Tetraselmis sp. growth occurred with the Tetraselmis-derived MEC effluent, however, the control medium without effluent produced the most growth. These findings support the possibility of a circular biofuel framework using MECs, but additional constraints, including the removal of inorganic contaminants, are necessary to realize the circular processes.

09 BIOMASS FUELS↗

Hydrogen from Carbonaceous Waste Material - Hydrogen Fuel Cells Prize Phase 2 Voucher: Cooperative Research and Development (Final Report)

NLR conducted a conceptual design study for scaling up biomass conversion technology from Green Fortress Engineering (GFE). GFE has proprietary technology where cellulosic biomass is thermally converted to a tar-free syngas. A ceramic membrane separation unit (MSU) previously developed with NLR can extract high-purity hydrogen from the syngas. The energy content of the retentate stream is sufficient to power the process with a gas-powered genset. Design details including mass and energy balances, process and instrumentation diagrams (P&ID), and major equipment schedules were delivered.

08 HYDROGEN↗

Hydrogen Dissociation Controls 1-Hexyne Selective Hydrogenation on Dilute Pd-in-Au Catalysts

Increasing the selectivity of the catalytic hydrogenation of alkynes to alkenes is of major importance for the processing of petrochemicals and the production of fine chemicals. Achieving high selectivity for alkene formation at high conversions, however, remains a long-standing challenge in heterogeneous catalysis. Here, the mechanism and origin of the high selectivity of dilute Pd-in-Au catalysts has been studied by a combination of first-principles calculations, microkinetic simulations, and isotopic exchange hydrogenation experiments using Pd 0.04 Au 0.96 nanoparticles embedded in raspberry colloid-templated silica. The Pd is predominantly in the form of isolated atoms, only surrounded by Au atoms, based on prior studies. The simulations indicate that the rate-limiting process for 1-hexyne hydrogenation on Pd monomers in Au(111) is H 2 dissociation, which has a large free energy barrier of 0.86 eV at 363 K and 0.2 bar of H 2 . The C–H bond formation steps, on the other hand, proceed with lower barriers, which contrasts with previous studies of extended Pd catalysts. The microkinetic simulations identify the sizable H 2 dissociation barrier and the small barrier for the hydrogenation of 1-hexyne as key factors that lead to a high selectivity for the production of 1-hexene from 1-hexyne, even at high conversion. The unconventional H 2 dissociation limiting process in combination with the low coverage of weakly bound hydrocarbon intermediates explains the near-zero order of 1-hexyne found experimentally. Furthermore, the partial hydrogenation of 1-hexyne to form 1-hexene is shown to be an irreversible process from our isotopic exchange hydrogenation experiments and is explained by the strongly exothermic nature of the reaction. Diluting active species, like Pd, in a less active host metal, like Au, hence appears promising as a means of tuning the binding energy of reactants and altering reaction profiles, leading to distinct kinetic behavior for an optimal catalytic activity and selectivity. Furthermore, the combination of microkinetic modeling, density functional theory calculations, and isotopic exchange experiments is thus demonstrated to be an effective approach to modeling important catalytic phenomena.

1-hexyne↗

High-salinity brine desalination with amine-based temperature swing solvent extraction: A molecular dynamics study

Solvent extraction desalination (SED) is a promising technique for efficiently treating high salinity brines. However, only a few studies in the literature have investigated the influence of the molecular characteristics of the organic solvents on the emergent performance of the separation process. Thus, in this work we investigate the influence of the molecular structure of four different secondary amines on the desalination process of a concentrated aqueous solution of NaCl. Molecular dynamics simulations and free energy calculations are used to obtain the thermodynamic and structural properties of the pure solvent bulk phase, as well as a homogeneous solvent-water bulk mixture. Furthermore, solvent-water and solvent-brine interfacial systems are used to explicitly analyze the water partitioning behavior in the relevant temperature range for SED. The water solubilization in these secondary amines is found to be an exothermic process. Additionally, although the hydrogen-bonding interaction between the water and solvent molecules are beneficial, this interaction is not necessarily the dominant factor for ranking the water solubility performance of the different solvents. Finally, the excess volume of mixing of the bulk solvent-water mixture, as well as the electrostatic surface features of the solvents are also found to provide important clues for screening solvent behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Chain-length-controllable upcycling of polyolefins to sulfate detergents

Escalating global plastic pollution and the depletion of fossil-based resources underscore the urgent need for innovative end-of-life plastic management strategies in the context of a circular economy. Thermolysis is capable of upcycling end-of-life plastics to intermediate molecules suitable for downstream conversion to eventually high-value chemicals, but tuning the molar mass distribution of the products is challenging. Here, in this study, we report a temperature-gradient thermolysis strategy for the conversion of polyethylene and polypropylene into hydrocarbons with tunable molar mass distributions. The whole thermolysis process is catalyst- and hydrogen-free. The thermolysis of polyethylene and polyethylene/polypropylene mixtures with tailored temperature gradients generated oil with an average chain length of ~C 14 . The oil featured a high concentration of synthetically useful α-olefins. Computational fluid dynamics simulations revealed that regulating the reactor wall temperature was the key to tuning the hydrocarbon distributions. Subsequent oxidation of the obtained α-olefins by sulfuric acid and neutralization by potassium hydroxide afforded sulfate detergents with excellent foaming behaviour and emulsifying capacity and low critical micelle concentration. Overall, this work provides a viable approach to producing value-added chemicals from end-of-life plastics, improving the circularity of the anthropogenic carbon cycle.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The effect of chemically preintercalated alkali ions on the structure of layered titanates and their electrochemistry in aqueous energy storage systems

We introduce a novel chemical preintercalation synthesis technique based on a hydrogen peroxide induced sol–gel process to obtain alkali ion containing ternary layered titanates (MTO, where M = Li, Na, K). Synthesis parameters leading to the formation of single-phase materials with homogeneous elemental distribution are reported for each of the preintercalated ions. Our analyses indicate that the interlayer spacing in the structure of the layered titanates increases with the increase of the radius of the hydrated preintercalated ion. Scanning and transmission electron microscopy imaging revealed morphological diversity: the LTO phase crystallized as nanoplates assembled in “peony-like” spherical agglomerates while NTO and KTO particles exhibited a one-dimensional nanobelt or wire-like morphology, with the KTO nanobelts being shorter and more aggregated than the NTO nanobelts. Structural refinement corroborated by electron diffraction and high-resolution transmission electron microscopy revealed that the structure of the LTO phase is built by stacking Ti–O layers containing a single straight layer of connected TiO 6 octahedra. The layers in NTO and KTO structures form differently and consist of double Ti–O layers with two titanium rows and ragged arrangement of units built by TiO6 octahedra. The NTO electrodes exhibited the highest electrochemical performance in cells with aqueous 1 M Na 2 SO 4 electrolyte, followed by the KTO electrodes and then LTO electrodes, and this trend is maintained at various scan rates. The established relationships between the structure and electrochemical performance reveal that, in addition to interlayer distance and chemistry of the interlayer region, the structure of the layers can play an important role in charge storage properties of layered oxide electrodes. The double Ti–O layers in the structure of NTO and KTO phases provide a larger number of redox centers which could contribute to the superior electrochemical performance as compared to the LTO electrodes. Our findings indicate that layered materials containing double transition metal oxide layers are promising candidates for exfoliation and assembly with electronically conductive layers with the aim to create 2D heterostructures with high electrochemical performance.

25 ENERGY STORAGE↗

The plasma–sheath transition and Bohm criterion in a high recycling divertor

The high recycling regime of a divertor is characterized by high plasma particle fluxes and low temperature at the target, where a strong hydrogen recirculation loop exists. Atomic processes in the high recycling regime, such as ion–neutral friction and radiation, can affect the plasma momentum and energy transport in the sheath transition region. Here, in this work, the plasma–sheath transition near a high recycling wall is investigated. The Bohm speed, which constraints the ion exit flow speed, is evaluated from a transport model that accounts for the effect of the anisotropic transport and atomic collisions in the transition layer. A first principles kinetic code vector particle-in-cell with the atomic collision package is used to investigate a 1D self-consistent slab plasma with a high recycling boundary for the tungsten and carbon divertors. The results demonstrate the accuracy of the Bohm speed model in predicting the ion exit flow speed in the transition region, as well as the reduction of the Bohm speed due to the ion–neutral friction. The effect of different wall materials, tungsten, and carbon, on the Bohm speed and near-wall plasma profile is shown.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Neutral Silicon Vacancy Centers in Undoped Diamond via Surface Control

Neutral silicon vacancy centers (SiV 0 ) in diamond are promising candidates for quantum applications; however, stabilizing SiV 0 requires high-purity, boron-doped diamond, which is not a readily available material. Here, we demonstrate an alternative approach via chemical control of the diamond surface. We use low-damage chemical processing and annealing in a hydrogen environment to realize reversible and highly stable charge state tuning in undoped diamond. The resulting SiV 0 centers display optically detected magnetic resonance and bulklike optical properties. Controlling the charge state tuning via surface termination offers a route for scalable technologies based on SiV 0 centers, as well as charge state engineering of other defects.

74 ATOMIC AND MOLECULAR PHYSICS↗

Impact of Nickel Ions on the Oxygen Reduction Reaction Kinetics of Pt and on Oxygen Diffusion through Ionomer Thin Films

The effects of dissolved nickel on the oxygen reduction reaction (ORR) kinetics and oxygen transport properties of perfluorosulfonic acid (PFSA) thin films were investigated using rotating disk electrode (RDE) measurements of ORR on a PFSA-coated platinum electrode. The electrochemical characterization in 0.1 M perchloric acid (HClO 4 ) with and without added Ni 2+ quantitatively measured the impact of ionic interactions between the Ni 2+ cations and sulfonate (SO 3 - ) anions on oxygen transport through the PFSA thin film. Cyclic voltammetry (CV) curves in deaerated electrolyte showed that Ni 2+ cations diffusing through the PFSA thin film interact with the Pt surface altering the hydrogen underpotential deposition and stripping processes and decreasing ORR kinetics. The RDE limiting current results point to reduced permeability of oxygen through PFSA-Ni 2+ compared to PFSA-H + . Furthermore, the results indicate that transition metals leached from Pt alloy catalyst may be detrimental not only to the intrinsic ORR kinetics of the PEFC cathode catalyst through loss of the ORR-enhancing transition metal, but may also inhibit the diffusion of oxygen to the catalytic sites and poison the ORR.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A set of test problems for nonlinear optimization

The software is a set of test problems for nonlinear optimization algorithms, including subroutines such as linear algebra routines and automatic differentiation algorithms. The test problems come from chemical engineering open literature, and describe optimization tasks related to the design and operation of processes such as carbon capture, Hydrogen production, heat exchange, and distillation.

Parker, Robert↗

Understanding Transient Combustion Phenomena in Low-NO x Gas Turbines

The goal of this work was to understand, quantify, and eventually predict combustion instability during operational transients in low-NO x gas turbine combustors. Transient operation is defined as a mode where one or more key operating parameters, including equivalence ratio, fuel composition, or fuel splitting between nozzles in a combustor, are varying in time. The timescale over which this variation occurs will be referred to as the transient timescale, the magnitude of the change in the transient parameter will be referred to as the transient amplitude, and the direction of the variation will be referred to as the transient direction. Transients occur regularly in power generation gas turbine operation. For example, load-following gas turbines vary load to meet power demands while accounting for variation in unsteady grid contributors like wind and solar power. Operators achieve this by varying equivalence ratio and fuel splitting inside the combustors to produce more or less power. Another example of transient operation is during fuel-switching operations, a particular issue for turbines operating with syngas fuels in a co-generation facility. In this case, the composition of the fuel stream may vary in time either as a result of fluctuations in the pipeline, or in the case of a co-generation plant, variations in feedstock or gasification processes. This fluctuation in fuel composition can have significant implications for combustion processes, particularly with high-hydrogen fuels. A small number of studies have investigated transient behavior in gas turbine combustors, particularly in the context of flame blow-off; here, investigators have typically focused on issues of transient amplitude, though without the depth and physics-based experimental design that is proposed in this program. To our knowledge, there have been no studies that have quantified the impact of the transient timescale on combustion. The work helped us understand the impact of several types of transients on combustion stability. Both static and dynamic combustion stability will be considered. The transients will be quantified using their amplitude, direction, and timescale, and we will consider transients in equivalence ratio, fuel composition, and fuel splitting. There were two main objectives of this work: 1. Provide a fundamental understanding of combustion stability during transient operation using data obtained from a number of high-speed diagnostic techniques on experimental configurations that capture important gas turbine combustor features and operating conditions. This goal was met in conjunction with our industrial partner, GE Global Research, with whom we worked closely throughout the program. 2. Develop a stability prediction framework that will allow for the prediction, and possible control, of instabilities as a function of the transient amplitude, direction, and timescale. This input/output model should be physics-based and allow for screening of operating conditions and prediction of unstable behavior at the end of a transient by monitoring combustor health and precursor signals during operation.

03 NATURAL GAS↗

Application of FARM to an IES scenario within the FORCE ecosystem

The FARM (Feasible Actuator Range Modifier) software module is a component of the RAVEN-based FORCE framework for analysis of Integrated Energy Systems (IES). FARM supports the HERON software module in the evaluation of the optimal dispatch by evaluating feasible set-points for the different IES unit components. Set-points are required to satisfy limits on both production variables (i.e., the variables to be optimized such as the electrical power, the hydrogen production rate, etc.) and process variables tied to the service life of equipment (e.g., steam flowrate, vessel pressure, turbine firing temperature, etc.). This problem is addressed by adopting a two-stage approach. First, the HERON power dispatcher determines set-points that meet the constraints on the former variables (e.g., power levels and power ramp rate limits). These constraints are called explicit constraints. Then, FARM adjusts these set-points to ensure the respect of the limits on the latter variables given the knowledge of the system physics acquired through machine learning algorithms. These constraints are called implicit constraints. From this standpoint, FARM constitutes a bridge between the HERON power dispatcher that adopts a simplified description of the IES unit (low-resolution physics) and the HYBRID high-fidelity models (high-resolution physics). The original version of the FARM software module (FARM-Alpha) was released by Argonne National Laboratory in January 2021. In the latest version of the code released in July 2022 (FARM-Delta), the Reference Governor (RG) algorithm was upgraded to a Multi-Input Multi-Output version from its original Single-Input Single-Output form. The RG algorithm acts to enforce constraints. With this improvement an IES unit is now treated as a single dynamic system from the standpoint of control. The crosstalk among components in an IES unit is now fully considered thereby ensuring a true optimization is obtained for those units that have multiple set-points. In this report, the capabilities of FARM-Delta operating within the FORCE ecosystem are demonstrated for an IES test case. The specific configuration of IES unit for this case was selected by the IES team with consultation from the Advanced Reactor IES Expert Group. A full TEA analysis that invoked HERON, HYBRID, FARM, and RAVEN was performed and serves to demonstrate how the latest modification to FARM algorithms (i.e., state variable selection, state-space matrices derivation, set-point verification) can shape setpoints that might otherwise compromise the health of equipment through accelerated wear and tear. In this specific test case, it was demonstrated that these algorithms ensure a more efficient utilization of steam resources to be shared by two different subsystems, namely Balance of Plant (BOP) and High-Temperature Steam Electrolysis (HTSE). Finally, some code improvements that can further enhance the user-friendliness are suggested.

97 MATHEMATICS AND COMPUTING↗

Implementation of a feature selection algorithm in FARM to identify important state variables and time-invariant matrices

The FARM (Feasible Actuator Range Modifier) software module is a component of the RAVEN-based FORCE framework for analysis of Integrated Energy Systems (IES). FARM aids the HERON software module in the evaluation of the optimal dispatch for the different IES components. Set-point trajectories are required to meet limits on both production variables (i.e., the variables to be optimized such as the electrical power, the hydrogen production rate, etc.) and process variables tied to the service life of equipment (e.g., steam flowrate, vessel pressure, turbine firing temperature, etc.). To evaluate the feasibility of HERON generated set-points and to do so in an acceptable time, FARM employs reduced order models to represent the dynamic behavior of the systems to be dispatched. These surrogate models take the form of a linear dynamic system with sets of Linear Parameter Varying (LPV) matrices that are mapped to the system operating space. These matrices are derived from the trajectories of system state variables and system output variables during transients. The accuracy of LPV matrices depends on the selection of state variables. In previous reports, state variables were selected by adopting a complicated workflow requiring multiple software licenses and an advanced level of user expertise. In this report, a new workflow that automates the state variable selection process is presented. It significantly reduces the frequency of user interventions and does not require multiple software licenses. Each module in the new workflow is described in detail, and the input / output examples in each step of the workflow are provided. It was demonstrated that this workflow can greatly reduce the complexity of the state variable selection process, and that the updated FARM-Gamma and FARM-Delta validators can benefit from this workflow when solving the power dispatch problem of a representative IES test case. Finally, some code improvements that can further enhance the efficiency are suggested.

42 ENGINEERING↗

Microwave-Assisted Catalytic Conversion of Tar Using Iron Catalyst Doped with Ni/La/Ce

The goal of this research is to study the microwave-assisted catalytic dry reforming of toluene using Fe/Al2O3 as a catalyst in the presence of various dopants such as Ni/La/Ce in a conventional fixed-bed reactor. Initial studies show that both CO2 and toluene conversion can be achieved up to 85% at 500 °C. Higher toluene conversion and syngas production was achieved under microwave conditions compared to conventional thermal conditions. The pre and post-reaction catalyst characterizations were performed using X-ray diffraction analysis (XRD) and thermogravimetric analysis (TGA). The tar analysis was performed using gas chromatography–mass spectrometry (GC-MS). The product gas mainly consisted of H2, CO, methane, propane, ethylene, and ethane along with small amounts of benzene, and naphthalene. The production of benzene indicates the hydrodemethylation (HDM) process of toluene, which requires hydrogen to initiate the reaction. The reaction pathway was proposed based on the observed product gas.

Linge Gowda, Anitha Shankara↗