SEARCH · Search NASA

Results for “thermochemical processing”

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.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 667 records · Page 37

All sources NASA NTRS DOE OSTI

DOE OSTI2021

Operating Characteristics of Metal Hydride-Based Solar Energy Storage Systems

Thermochemical energy storage systems, based on a high-temperature metal hydride coupled with a low-temperature metal hydride, represent a valid option to store thermal energy for concentrating solar power plant applications. The operating characteristics are investigated for a tandem hydride bed energy storage system, using a transient lumped parameter model developed to identify the technical performance of the proposed system. The results show that, without operational control, the system undergoes a thermal ratcheting process, causing the metal hydride concentrations to accumulate hydrogen in the high-temperature bed over time, and deplete hydrogen in the low temperature. This unbalanced system is compared with a ’thermally balanced’ system, where the thermal ratcheting is mitigated by thermally balancing the overall system. The analysis indicates that thermally balanced systems stabilize after the first few cycles and remain so for long-term operation, demonstrating their potential for practical thermal energy storage system applications.

25 ENERGY STORAGE↗

NASA NTRSDate not supplied

A Multi-Architecture Approach for Implicit Computational Fluid Dynamics on Unstructured Grids

High-performance computing (HPC) architectures are trending toward manycore paradigms such as graphics processing units (GPUs). Approximately half of the top 100 publicly disclosed supercomputers in the world utilize GPU accelerators for performance. This is in contrast to a decade ago, where there were only a few such machines in the top 100. It is not currently possible to compile and run legacy central processing unit (CPU) software efficiently on GPUs without significant refactoring. Though a number of frameworks offering performance portability exist, none offer a standardized specification that is supported by all major hardware vendors. Additionally, experiences show that obtaining a high percentage of peak performance often requires architecture-specific code. This work details a pragmatic multi-architecture computational fluid dynamics library focused on aerospace problems across the speed range from low subsonic to hypersonic flows involving thermochemical nonequilibrium. A thin abstraction layer above NVIDIA CUDA C++ is utilized, which enables primarily single-source software currently capable of running efficiently on multicore CPUs, NVIDIA GPUs, AMD GPUs, and Intel GPUs. Results on various problems of interest across the speed range are presented and performance is compared between various architectures.

GPU↗

NASA NTRSDate not supplied

A Multi-Architecture Approach for Implicit Computational Fluid Dynamics on Unstructured Grids

GPU↗

NASA NTRS1992

Thermochemical energy storage for a lunar base

A thermochemical solar energy storage concept involving the reversible reaction CaO + H2O yields Ca(OH)2 is proposed as a power system element for a lunar base. The operation and components of such a system are described. The CaO/H2O system is capable of generating electric power during both the day and night. Mass of the required amount of CaO is neglected since it is obtained from lunar soil. Potential technical problems, such as reactor design and lunar soil processing, are reviewed.

Perez-Davis, Marla E.↗

NASA NTRS2017

Fully Coupled Aero-Thermochemical-Elastic Simulations of an Eroding Graphite Nozzle

A multiphysics simulation capability has been developed that incorporates mutual interactions between aerodynamics, structural response from aero/thermal loading, ablation/pyrolysis, heating, and surface-to-surface radiation to perform high-fidelity, fully coupled aerothermoelastic ablation simulations, which to date had been unattainable. The multiphysics framework couples CHAR (a 3-D implicit charring ablator solver), Loci/CHEM (a computational fluid dynamics solver for high-speed chemically reacting flows), and Abaqus (a nonlinear structural dynamics solver) to create a fully coupled aerothermoelastic charring ablative solver. The solvers are tightly coupled in a fully integrated fashion to resolve the effects of the ablation pyrolysis and charring process and chemistry products upon the flow field, the changes in surface geometry due to recession upon the flow field, and thermal-structural analysis of the body from the induced aerodynamic heating from the flow field. The multiphysics framework was successfully demonstrated on a solid rocket motor graphite nozzle erosion application. Comparisons were made with available experimental data that measured the throat erosion during the motor firing. The erosion data is well characterized, as the test rig was equipped with a windowed nozzle section for real-time X-ray radiography diagnostics of the instantaneous throat variations for deducing the instantaneous erosion rates. The nozzle initially undergoes a nozzle contraction due to thermal expansion before ablation effects are able to widen the throat. A series of parameters studies were conducted using the coupled simulation capability to determine the sensitivity of the nozzle erosion to different parameters. The parameter studies included the shape of the nozzle throat (flat versus rounded), the material properties, the effect of the choice of turbulence model, and the inclusion or exclusion of the mechanical thermal expansion. Overall, the predicted results match the experiment very well, and the predictions were able to bound the data within acceptable limits.

Blades, E. L.↗

NASA NTRS1983

Review of alternative fuels data bases

Based on an analysis of the interaction of fuel physical and chemical properties with combustion characteristics and indicators, a ranking of the importance of various fuel properties with respect to the combustion process was established. This ranking was used to define a suite of specific experiments whose objective is the development of an alternative fuels design data base. Combustion characteristics and indicators examined include droplet and spray formation, droplet vaporization and burning, ignition and flame stabilization, flame temperature, laminar flame speed, combustion completion, soot emissions, NOx and SOx emissions, and the fuels' thermal and oxidative stability and fouling and corrosion characteristics. Key fuel property data is found to include composition, thermochemical data, chemical kinetic rate information, and certain physical properties.

Harsha, P. T.↗

DOE OSTI2014

“Conductive” yttria-stabilized zirconia as an epitaxial template for oxide heterostructures

We report an in situ thermochemical treatment that significantly increases the macroscopic electrical conductivity of insulating yttria-stabilized zirconia (YSZ) (001) single-crystalline substrates. We demonstrate the high-quality surface crystalline structure of the resulting “conductive” cYSZ (001) by low- and high-energy electron diffraction. Soft- and hard X-ray photoemission spectroscopy measurements reveal a sizable reduction of Zr cations to a metallic state and their homogeneous distribution within the cYSZ. We discuss the correlation between the microscopic chemical processes leading to the increased macroscopic metallicity. Finally, the heteroepitaxial growth of a functional magnetic oxide model system, ultrathin EuO on cYSZ (001), was demonstrated. cYSZ (001) thereby enables both high quality oxide heteroepitaxy and the advanced sample characterization by high electron-fluence characterization techniques.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

DOE OSTI2018

Element Distribution in the Silicomanganese Production Process

A pilot scale, silicomanganese alloy production campaign was performed in a 440 kVA, single phase electric furnace in order to establish an overview of the minor- and trace element contents in process input raw materials and their distribution in the resulting primary and secondary products. Samples of the in-going raw materials (manganese ore, coke, quartzite, and high carbon ferromanganese slag) and the out-going products (silicomanganese alloy, silicomanganese slag, and dust) were analyzed by inductively coupled plasma mass spectrometry. The distribution of 51 elements between the product phases was discussed in terms of their boiling temperatures, Gibbs energies of oxidation and activity coefficients of elements in the metal. A thermochemical simulation using the thermochemical software FactSage 7.1 was also carried out in order to model element phase distribution between the alloy, slag, and dust/gas. The correlation between the model and experimental element concentrations in the silicomanganese slag and dust is fair for most elements. However, in the metal phase, fewer elements show good correlation between modeled results and measured experimental concentrations. The discrepancy could be explained by a lack of accurate thermodynamic descriptions for several minor species in the database.

36 MATERIALS SCIENCE↗

NASA NTRS1987

Chemical interactions in Low Earth Orbit (LEO)

Although several observations of material changes on-orbit have been reported, mechanistic understanding has not yet become clear because new sets of non-intuitive processes are occurring on orbit. Reactant kinetic energy, low collision rates and surface/adsorbate interactions must be considered in the analysis of these observations. The specific example of oxide formation of elemental materials is examined in terms of thermodynamics and possible reaction pathways. On the basis of this approach, a rational trend emerges from the orbital behavior of these samples. The role of reactant kinetic energy as opposed to internal energy in chemiluminescent product formation is also presented. Development of a systematic thermochemical approach may be useful in making screening predictions of long-term material behavior on-orbit.

Green, B. D.↗

NASA NTRS2001

Simplified Analysis of Pulse Detonation Rocket Engine B1owdown Gasdynamics and Performance

Pulsed detonation rocket engines (PDREs) have generated considerable research interest in recent years as a chemical propulsion system potentially offering improved performance and reduced complexity compared to conventional rocket engines. The detonative mode of combustion employed by these devices offers a thermodynamic advantage over the constant-pressure deflagrative combustion mode used in conventional rocket engines and gas turbines. However, while this theoretical advantage has spurred a great deal of interest in building PDRE devices, the unsteady blowdown process intrinsic to the PDRE has made realistic estimates of the actual propulsive performance problematic. The recent review article by Kailasanath highlights some of the difficulties in comparing the available experimental measurements with numerical models. The goal of this paper is to improve understanding of PDRE blowdown gasdynamics and performance issues through use of a simplified model that captures the essential features of the unsteady blowdown process, and yet remains computationally inexpensive. The PDRE system studied here is highly idealized, consisting of a constant-area detonation tube with one end closed and the other end open to the environment. The tube is prefilled with a gaseous propellant mixture with no initial velocity or outflow to the environment. The detonation is initiated instantaneously at the closed end of the device. Chapman-Jouguet (C-J) post-detonation gas conditions are calculated using the CET89 version of the NASA thermochemical code. The I-D, unsteady method of characteristics is used to calculate the flowfield following the detonation front. See the compressible flow texts by Thompson and Zucrow and Hoffman for details of this method. Parametric studies of the effect of mixture stoichiometry, fill temperature, and blowdown pressure ratio on performance are reported. A comparison of the performance of an idealized straight-tube PDRE with a conventional steady-state rocket engine is provided. The effect of constant-gamma and equilibrium chemistry assumptions is also examined. Additionally, in order to form an assessment of the accuracy of the model, the flowfield time history is compared to experimental data from Stanford University.

Morris, Christopher I.↗

DOE OSTI2020

Thermodynamic and kinetic hydricity of transition metal hydrides

The prevalence of transition metal-mediated hydride transfer reactions in chemical synthesis, catalysis, and biology has inspired the development of methods for characterizing the reactivity of transition metal hydride complexes. Thermodynamic hydricity represents the free energy required for heterolytic cleavage of the metal–hydride bond to release a free hydride ion, H - , as determined through equilibrium measurements and thermochemical cycles. Kinetic hydricity represents the rate of hydride transfer from one species to another, as measured through kinetic analysis. This tutorial review describes the common methods for experimental and computational determination of thermodynamic and kinetic hydricity, including advice on best practices and precautions to help avoid pitfalls. The influence of solvation on hydricity is emphasized, including opportunities and challenges arising from comparisons across several different solvents. Connections between thermodynamic and kinetic hydricity are discussed, and opportunities for utilizing these connections to rationally improve catalytic processes involving hydride transfer are highlighted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1991

Chemical vapor deposition modeling: An assessment of current status

The shortcomings of earlier approaches that assumed thermochemical equilibrium and used chemical vapor deposition (CVD) phase diagrams are pointed out. Significant advancements in predictive capabilities due to recent computational developments, especially those for deposition rates controlled by gas phase mass transport, are demonstrated. The importance of using the proper boundary conditions is stressed, and the availability and reliability of gas phase and surface chemical kinetic information are emphasized as the most limiting factors. Future directions for CVD are proposed on the basis of current needs for efficient and effective progress in CVD process design and optimization.

Gokoglu, Suleyman A.↗

DOE OSTI2022

High Energy Systems for Transforming CO 2 to Valuable Products (Final Report)

The objective of this project is to develop the Direct E-Beam Synthesis (DEBS) process that uses high-energy electron beams (E-Beam) to break chemical bonds. This allows the production of valuable chemicals, such as acetic acid, methanol, and carbon monoxide, at relatively low severity (pressure near one atmosphere and temperatures <150°C) from near-pure CO 2 captured from a pulverized coal-fired power plant and methane, imported as natural gas. Creating such valuable products will offset the cost of carbon capture and storage. Through this project, we have designed, constructed, and operated an E-Beam reactor to examine the feasibility of performing dry reforming reaction without a catalyst using only DEBS. We have verified the production of syngas with 1:1 H2:CO ratio and calculated that the energy cost for conversion is about 5.2 eV/molecule of product for dry reforming reaction which is similar to the energy cost for conversion using conventional thermochemical conversion but under significantly milder conditions (room temperature and atmospheric pressure). We have performed a technoeconomic analysis (TEA) to estimate the total capital requirement and the cost of production for a 99.4 MMSCFD syngas production plant via non-catalytic Direct E-Beam Synthesis (DEBS) technology utilizing a high-energy electron beam (E-Beam) accelerator. No assumption is made for syngas utilization downstream, and the incoming reactants are pure CO 2 from carbon capture (assumed to be at zero cost) and natural gas. The Total As-Spent Cost (TASC) was calculated to be $\$242.5$ million, resulting in a levelized cost of syngas (LCOS) of $\$175.84$/tonne (metric) at a natural gas price of $\$6.24$/MMBTU1. The cost of syngas is primarily determined by the price of natural gas. If the cost of the CO 2 feedstock is assumed to be non-zero, then the price of the CO 2 feed also heavily influences the levelized cost of syngas. The potential impact on the cost of electricity from syngas revenue is significant. Following DOE NETL’s guidance, a lifecycle analysis (LCA) was conducted to compare the cradle-to-gate life cycle emissions of GTI Energy’s novel Direct E-Beam Synthesis (DEBS) process that produces syngas via the reaction of methane and carbon dioxide to the emissions of a state-of-the-art Steam Methane Reforming (SMR) process that also produces syngas via the reaction of methane and steam. The DEBS process results in less GHG emissions than SMR (with CO product as the basis of comparison). openLCA was used for the LCA and the results show that the total global warming potential (GWP) of DEBS is 0.981 kg CO 2 e per kg CO product, while the SMR process has a global warming potential of 2.573 kg CO 2 e per kg CO product. The ratio of the GWP of the proposed product system to the comparison product system is 0.381. This percent change is 61.9% lower GWP than SMR.

20 FOSSIL-FUELED POWER PLANTS↗

DOE OSTI2019

Decoding Proton-Coupled Electron Transfer with Potential–p K a Diagrams: Applications to Catalysis

The applied potential at which [Ni II (P 2 Ph N 2 Bn ) 2 ] 2+ (P 2 Ph N 2 Bn = 1,5-dibenzyl-3,7-diphenyl-1,5-diaza-3,7-diphosphacyclooctane) catalyzes hydrogen production is reported to vary as a function of proton source p K a in acetonitrile. Yet, most molecular catalysts exhibit catalytic onsets at p K a -independent potentials. Using experimentally determined thermochemical parameters associated with reduction and protonation, a coupled Pourbaix diagram is constructed for [Ni II (P 2 Ph N 2 Bn ) 2 ] 2+ . One layer describes proton-coupled electron transfer reactivity involving ligand-based protonation, and the second describes metal-based protonation. An overlay of this diagram with experimentally determined E cat/2 values spanning 15 p K a units, along with complementary stopped-flow rapid mixing experiments to detect reaction intermediates, supports a mechanism in which the proton-coupled electron transfer processes underpinning the p K a -dependent catalytic processes involve protonation of the ligand, not the metal center. For proton sources with p K a values in the range 6–10.6, the initial species formed is the doubly reduced, doubly protonated species [Ni 0 (P 2 Ph N 2 Bn H) 2 ] 2+ , despite a higher overpotential for this proton-coupled electron transfer reaction in comparison to forming the metal-protonated isomer. In this complex, each ligand is protonated in the exo position with the two amine moieties on each ligand binding a single proton and positioning it away from the metal center. This species undergoes very slow isomerization to form an endo-protonated hydride species [HNi II (P 2 Ph N 2 Bn )(P 2 Ph N 2 Bn H)] 2+ that can release hydrogen to close the catalytic cycle. Crucially, this slow isomerization does not perturb the initially established proton-coupled electron transfer equilibrium, placing catalysis under thermodynamic control. New details revealed about the reaction mechanism from the coupled Pourbaix diagram and the complementary stopped-flow studies lead to predictions as to how this p K a -dependent activity might be engendered in other molecular catalysts for multi-electron, multi-proton transformations.

08 HYDROGEN↗

NASA NTRS2004

Real-Time Measurements of Aft Dome Insulation Erosion on Space Shuttle Reusable Solid Rocket Motor

Real-time erosion of aft dome internal insulation was measured with internal instrumentation on a static test of a lengthened version of the Space Shuffle Reusable Solid Rocket Motor (RSRM). This effort marks the first time that real-time aft dome insulation erosion (Le., erosion due to the combined effects of thermochemical ablation and mechanical abrasion) was measured in this kind of large motor static test [designated as Engineering Test Motor number 3 (ETM3)I. This paper presents data plots of the erosion depth versus time. The data indicates general erosion versus time behavior that is in contrast to what would be expected from earlier analyses. Engineers have long known that the thermal environment in the aft dome is severe and that the resulting aft dome insulation erosion is significant. Models of aft dome erosion involve a two-step process of computational fluid dynamics (CFD) modeling and material ablation modeling. This modeling effort is complex. The time- dependent effects are difficult to verify with only prefire and postfire insulation measurements. Nozzle vectoring, slag accumulation, and changing boundary conditions will affect the time dependence of aft dome erosion. Further study of this data and continued measurements on future motors will increase our understanding of the aft dome flow and erosion environment.

McWhorter, Bruce↗

DOE OSTI2022

Synthesis and structure of high-purity BaCe 0.25 Mn 0.75 O 3 : an improved material for thermochemical water splitting

Solar thermochemical hydrogen production (STCH) via redox-active metal oxides is an approach for direct solar-driven hydrogen generation typically using a high-temperature redox cycle involving refractory oxides and steam. Typical cycles involve high-temperature reduction of oxides to form oxygen vacancies, followed by lower temperature reaction between oxygen vacancies and steam where the oxide is re-oxidized and the steam is reduced to hydrogen. Only a few materials have demonstrated reversible cycling under the typically harsh STCH conditions (e.g. 1500°C reduction, 900°C re-oxidation) and critical questions remain on the true reversibility of non-stoichiometric multi-cation oxide systems, significantly hampered by the lack of single-phase samples for these material systems. To date, most STCH processes have relied on CeO 2 as a benchmark active material, but more recently, the 12R phase of BaCe 0.25 Mn 0.75 O 3 (BCM) has demonstrated greater hydrogen-generation potential at lower peak temperatures. However, previous reports of 12R-BCM have included large fractions, > 10 wt%, of secondary phases, which complicate analysis of the stability and performance. A comprehensive understanding of the redox mechanism and reversibility of the process in BCM can only be achieved with nearly single-phase samples which, to date, have been difficult to produce. Here two approaches to BCM synthesis are reported: solid state and sol–gel-based routes. It is demonstrated that both routes can be tuned to produce the 12R structure with > 97 wt% yield when annealed ≥1450°C. Herein synchrotron-based diffraction measurements of rhombohedral 12R-BCM enabled characterization of the anisotropy between thermal expansion along the c-axis and within the ab plane. The impact of high-temperature redox cycling on the stability and phase fraction of the 12R-BCM polytype was also investigated. Our results offer two viable routes for synthesis of high-purity 12R-BCM critically needed for evaluating the efficacy of BCM as a STCH material and validate its ability to split water at lower temperatures over extended numbers of redox cycles.

08 HYDROGEN↗

DOE OSTI2019

Characterization of radiative heat transfer in a spark-ignition engine through high-speed experiments and simulations

A combined experimental and Large-Eddy Simulation (LES) study of molecular radiation is presented for combustion in a homogeneous pre-mixed spark-ignition engine. Molecular radiation can account for ~10% of the engine heat loss and could have a noticeable impact on the local conditions within the combustion chamber. The Transparent Combustion Chamber (TCC) engine, a single-cylinder two-valve research engine with a transparent liner and piston for optical access, was used for this study. High-speed infrared emission spectroscopy and radiative post-processing of LES calculations have been performed to gain insight into the timescales and magnitude of radiative emissions of molecular gases during the combustion process. Both the measurements and simulations show significant Cycle-to-Cycle Variations (CCV) of radiative emission. There is agreement in the instantaneous radiative spectrum of experiment and simulation, but the crank-angle development of the radiative spectrum shows disagreement. The strengths and limitations of the optical experiments and radiative simulations are seen in the results and suggest pathways for future efforts in characterizing the influence of molecular radiation. In particular, focusing on the relative changes of the spectral features will be important as they contain information about the thermochemical properties of the gas mixture.

02 PETROLEUM↗

DOE OSTI2016

Biomass conversion to produce hydrocarbon liquid fuel via hot-vapor filtered fast pyrolysis and catalytic hydrotreating

Lignocellulosic biomass conversion to produce biofuels has received significant attention because of the quest for a replacement for fossil fuels. Among the various thermochemical and biochemical routes, fast pyrolysis followed by catalytic hydrotreating is considered to be a promising near-term opportunity. This paper reports on experimental methods used 1) at the National Renewable Energy Laboratory (NREL) for fast pyrolysis of lignocellulosic biomass to produce bio-oils in a fluidized-bed reactor and 2) at Pacific Northwest National Laboratory (PNNL) for catalytic hydrotreating of bio-oils in a two-stage, fixed-bed, continuous-flow catalytic reactor. The configurations of the reactor systems, the operating procedures, and the processing and analysis of feedstocks, bio-oils, and biofuels are described in detail in this paper. We also demonstrate hot-vapor filtration during fast pyrolysis to remove fine char particles and inorganic contaminants from bio-oil. Representative results showed successful conversion of biomass feedstocks to fuel-range hydrocarbon biofuels and, specifically, the effect of hot-vapor filtration on bio-oil production and upgrading. As a result, the protocols provided in this report could help to generate rigorous and reliable data for biomass pyrolysis and bio-oil hydrotreating research.

09 BIOMASS FUELS↗