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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 649 records · Page 36
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

A systematic retrieval analysis of secondary eclipse spectra. III. Diagnosing chemical disequilibrium in planetary atmospheres

Chemical disequilibrium has recently become a relevant topic in the study of the atmospheres of transiting extrasolar planets, brown dwarfs, and directly imaged exoplanets. We present a new way of assessing whether or not a Jovian-like atmosphere is in chemical disequilibrium from observations of detectable or inferred gases such as H{sub 2}O, CH{sub 4}, CO, and H{sub 2}. Our hypothesis, based on previous kinetic modeling studies, is that cooler atmospheres will show stronger signs of disequilibrium than hotter atmospheres. We verify this with chemistry-transport models and show that planets with temperatures less than ∼1200 K are likely to show the strongest signs of disequilibrium due to the vertical quenching of CO, and that our new approach is able to capture this process. We also find that in certain instances a planetary composition may appear in equilibrium when it actually is not due to the degeneracy in the shape of the vertical mixing ratio profiles. We determine the state of disequilibrium in eight exoplanets using the results from secondary eclipse temperature and abundance retrievals. We find that all of the planets in our sample are consistent with thermochemical equilibrium to within 3σ. Future observations are needed to further constrain the abundances in order to definitively identify disequilibrium in exoplanet atmospheres.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2017

Optimizing Biorefinery Design and Operations via Linear Programming Models

The ability to assess and optimize economics of biomass resource utilization for the production of fuels, chemicals and power is essential for the ultimate success of a bioenergy industry. The team of authors, consisting of members from the National Renewable Energy Laboratory (NREL) and the Idaho National Laboratory (INL), has developed simple biorefinery linear programming (LP) models to enable the optimization of theoretical or existing biorefineries. The goal of this analysis is to demonstrate how such models can benefit the developing biorefining industry. It focuses on a theoretical multi-pathway, thermochemical biorefinery configuration and demonstrates how the biorefinery can use LP models for operations planning and optimization in comparable ways to the petroleum refining industry. Using LP modeling tools developed under U.S. Department of Energy's Bioenergy Technologies Office (DOE-BETO) funded efforts, the authors investigate optimization challenges for the theoretical biorefineries such as (1) optimal feedstock slate based on available biomass and prices, (2) breakeven price analysis for available feedstocks, (3) impact analysis for changes in feedstock costs and product prices, (4) optimal biorefinery operations during unit shutdowns / turnarounds, and (5) incentives for increased processing capacity. These biorefinery examples are comparable to crude oil purchasing and operational optimization studies that petroleum refiners perform routinely using LPs and other optimization models. It is important to note that the analyses presented in this article are strictly theoretical and they are not based on current energy market prices. The pricing structure assigned for this demonstrative analysis is consistent with $4 per gallon gasoline, which clearly assumes an economic environment that would favor the construction and operation of biorefineries. The analysis approach and examples provide valuable insights into the usefulness of analysis tools for maximizing the potential benefits of biomass utilization for production of fuels, chemicals and power.

09 BIOMASS FUELS↗
NASA NTRS1980

A hybrid water-splitting cycle using copper sulfate and mixed copper oxides

The Institute of Gas Technology has derived and developed a hybrid thermochemical water-splitting cycle based on mixed copper oxides and copper sulfate. Similar to other metal oxide-metal sulfate cycles that use a metal oxide to 'concentrate' electrolytically produced sulfuric acid, this cycle offers the advantage of producing oxygen (to be vented) and sulfur dioxide (to be recycled) in separate steps, thereby eliminating the need of another step to separate these gases. The conceptual process flow-sheet efficiency of the cycle promises to exceed 50%. It has been completely demonstrated in the laboratory with recycled materials. Research in the electrochemical oxidation of sulfur dioxide to produce sulfuric acid and hydrogen performed at IGT indicates that the cell performance goals of 200 mA/sq cm at 0.5 V will be attainable using relatively inexpensive electrode materials.

Schreiber, J. D.↗
NASA NTRS1985

Chemical evolution of the Earth: Equilibrium or disequilibrium process?

To explain the apparent chemical incompatibility of the Earth's core and mantle or the disequilibrium process, various core forming mechanisms have been proposed, i.e., rapid disequilibrium sinking of molten iron, an oxidized core or protocore materials, and meteorite contamination of the upper mantle after separation from the core. Adopting concepts used in steady state thermodynamics, a method is devised for evaluating how elements should distribute stable in the Earth's interior for the present gradients of temperature, pressure, and gravitational acceleration. Thermochemical modeling gives useful insights into the nature of chemical evolution of the Earth without overly speculative assumptions. Further work must be done to reconcile siderophile elements, rare gases, and possible light elements in the outer core.

Sato, M.↗
NASA NTRS1982

Thermochemical tests on resins: Char resistance of selected phenolic cured epoxides

Curing epoxy resins with novalac phenolic resins is a feasible approach for increasing intact char of the resin system. Char yields above 40% at 700 C were achieved with epoxy novalac (DEN 438)/novalac phenolic (BRWE 5833) resin systems with or without catalyst such as ethyl tri-phenyl phosphonium iodide. These char yields are comparable to commercially used epoxy resin systems like MY-720/DDS/BF3. Stable prepregs are easily made from a solvent solution of the epoxy/phenolic system and this provides a feasible process for fabrication of same into commercial laminates.

Keck, F. L.↗
DOE OSTI2018

Partial flocculation for spray drying of spherical mixed metal oxide particles

Abstract Particles are an important design consideration for many proposed solar thermochemical water splitting reactor concepts. These particles must maintain physical integrity and chemical performance at very high temperatures (>900°C) while flowing within a system. Spray drying is a commonly used, scalable method to produce solid spherical particles that have the best opportunity to meet these requirements. Spray drying is used to produce hercynite (FeAl 2 O 4 ) particles using pH ‐modification of a charge‐stabilized sol. This process involves inducing partial flocculation in nanoparticle suspensions to yield larger particles that are spherical and structurally robust. A commercial boehmite suspension is characterized along with a mixture of the boehmite suspension with an iron oxide suspension. Zeta potential near zero and peak yield stress measurements at the same pH indicate flocculation, but associated sedimentation behavior is not observed. The behavior of both the boehmite‐only and mixed suspensions both seem to be driven by the behavior of the boehmite suspension alone. Spray dried particles from the mixed suspension at the critical pH gave significantly larger and more spherical particles, which also indicates flocculation. This relatively simple technique shows promise for new mixed‐metal material formulations and scalable applications.

Ehrhart, Brian D.↗
DOE OSTI2015

Development and Optimization of a Flocculation Procedure for Improved Solid-Liquid Separation of Digested Biomass

One viable treatment method for conversion of lignocellulosic biomass to biofuels begins with saccharification (thermochemical pretreatment and enzymatic hydrolysis), followed by fermentation or catalytic upgrading to fuels such as ethanol, butanol, or other hydrocarbons. The post-hydrolysis slurry is typically 4-8 percent insoluble solids, predominantly consisting of lignin. Suspended solids are known to inhibit fermentation as well as poison catalysts and obstruct flow in catalyst beds. Thus a solid-liquid separation following enzymatic hydrolysis would be highly favorable for process economics, however the material is not easily separated by filtration or gravimetric methods. Use of a polyacrylamide flocculant to bind the suspended particles in a corn stover hydrolyzate slurry into larger flocs (1-2mm diameter) has been found to be extremely helpful in improving separation. Recent and ongoing research on novel pretreatment methods yields hydrolyzate material with diverse characteristics. Therefore, we need a thorough understanding of rapid and successful flocculation design in order to quickly achieve process design goals. In this study potential indicators of flocculation performance were investigated in order to develop a rapid analysis method for flocculation procedure in the context of a novel hydrolyzate material. Flocculation conditions were optimized on flocculant type and loading, pH, and mixing time. Filtration flux of the hydrolyzate slurry was improved 170-fold using a cationic polyacrylamide flocculant with a dosing of approximately 22 mg flocculant/g insoluble solids at an approximate pH of 3. With cake washing, sugar recovery exceeded 90 percent with asymptotic yield at 15 L wash water/kg insoluble solids.

09 BIOMASS FUELS↗
DOE OSTI2024

ZeroCAL: Eliminating Carbon Dioxide Emissions from Limestone’s Decomposition to Decarbonize Cement Production

Limestone (calcite, CaCO 3 ) is an abundant and cost-effective source of calcium oxide (CaO) for cement and lime production. However, the thermochemical decomposition of limestone (~800 °C, 1 bar) to produce lime (CaO) results in substantial carbon dioxide (CO 2(g) ) emissions and energy use, i.e., ~1 tonne [t] of CO 2 and ~1.4 MWh per t of CaO produced. Here, we describe a new pathway to use CaCO 3 as a Ca source to make hydrated lime (portlandite, Ca(OH) 2 ) at ambient conditions (p, T) while nearly eliminating process CO 2(g) emissions (as low as 1.5 mol. % of the CO 2 in the precursor CaCO 3 , equivalent to 9 kg of CO 2(g) per t of Ca(OH) 2 ) within an aqueous flowelectrolysis/ pH-swing process that coproduces hydrogen (H 2(g) ) and oxygen (O 2(g) ). Because Ca(OH) 2 is a zero-carbon precursor for cement and lime production, this approach represents a significant advancement in the production of zero-carbon cement. The Zero CArbon Lime (ZeroCAL) process includes dissolution, separation/recovery, and electrolysis stages according to the following steps: (Step 1) chelator (e.g., ethylenediaminetetraacetic acid, EDTA)-promoted dissolution of CaCO 3 and complexation of Ca 2+ under basic (>pH 9) conditions, (Step 2a) Ca enrichment and separation using nanofiltration (NF), which allows separation of the Ca-EDTA complex from the accompanying bicarbonate (HCO 3 – ) species, (Step 2b) acidity-promoted decomplexation of Ca from EDTA, which allows near-complete chelator recovery and the formation of a Ca-enriched stream, and (Step 3) rapid precipitation of Ca(OH) 2 from the Ca-enriched stream using electrolytically produced alkalinity. These reactions can be conducted in a seawater matrix yielding coproducts including hydrochloric acid (HCl) and sodium bicarbonate (NaHCO 3 ), resulting from electrolysis and limestone dissolution, respectively. Careful analysis of the reaction stoichiometries and energy balances indicates that approximately 1.35 t of CaCO 3 , 1.09 t of water, 0.79 t of sodium chloride (NaCl), and ~2 MWh of electrical energy are required to produce 1 t of Ca(OH) 2 , with significant opportunity for process intensification. This approach has major implications for decarbonizing cement production within a paradigm that emphasizes the use of existing cement plants and electrification of industrial operations, while also creating approaches for alkalinity production that enable cost-effective and scalable CO 2 mineralization via Ca(OH) 2 carbonation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Impact of feedstock quality and variation on biochemical and thermochemical conversion

The production of biofuels from lignocellulosic feedstock is attracting considerable attention in the United States and globally as a strategy to diversify energy resources, spur regional economic development and reduce greenhouse gas emissions. Because of the wide variation in feedstock types, compositions and content of convertible organics, there is a growing need to better understand correlations among feedstock quality attributes and conversion performance. Knowledge of the feedstock impact on conversion is essential to supply quality controlled, uniform and on-spec feedstocks to biorefineries. This review paper informs the development of meaningful feedstock quality specifications for different conversion processes. Discussions are focused on how compositional properties of feedstocks affect various unit operations in biochemical conversion processes, fast pyrolysis and hydrothermal liquefaction. In addition, future perspectives are discussed that focus on the challenges and prospects of addressing compositionally intrinsic inhibitors through feedstock preprocessing at regionally distributed depots. As a result, such preprocessing depots may allow for the commoditization of lignocellulosic feedstock and realization of stable, cost-effective and quality controlled biomass supply systems.

09 BIOMASS FUELS↗
DOE OSTI2015

Lithium formate ion clusters formation during electrospray ionization: Evidence of magic number clusters by mass spectrometry and ab initio calculations

Small cationic and anionic clusters of lithium formate were generated by electrospray ionization and their fragmentations were studied by tandem mass spectrometry (collision-induced dissociation with N{sub 2}). Singly as well as multiply charged clusters were formed in both positive and negative ion modes with the general formulae, (HCOOLi){sub n}Li{sup +}, (HCOOLi){sub n}Li{sub m}{sup m+}, (HCOOLi){sub n}HCOO{sup −}, and (HCOOLi){sub n}(HCOO){sub m}{sup m−}. Several magic number cluster (MNC) ions were observed in both the positive and negative ion modes although more predominant in the positive ion mode with (HCOOLi){sub 3}Li{sup +} being the most abundant and stable cluster ion. Fragmentations of singly charged positive clusters proceed first by the loss of a dimer unit ((HCOOLi){sub 2}) followed by the loss of monomer units (HCOOLi) although the former remains the dominant dissociation process. In the case of positive cluster ions, all fragmentations lead to the magic cluster (HCOOLi){sub 3}Li{sup +} as the most abundant fragment ion at higher collision energies which then fragments further to dimer and monomer ions at lower abundances. In the negative ion mode, however, singly charged clusters dissociated via sequential loss of monomer units. Multiply charged clusters in both positive and negative ion modes dissociated mainly via Coulomb repulsion. Quantum chemical calculations performed for smaller cluster ions showed that the trimer ion has a closed ring structure similar to the phenalenylium structure with three closed rings connected to the central lithium ion. Further additions of monomer units result in similar symmetric structures for hexamer and nonamer cluster ions. Thermochemical calculations show that trimer cluster ion is relatively more stable than neighboring cluster ions, supporting the experimental observation of a magic number cluster with enhanced stability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Strengths, challenges, and opportunities for hydrothermal pretreatment in lignocellulosic biorefineries

Pretreatment prior to or during biological conversion is required to achieve high sugar yields essential to economic production of fuels and chemicals from low cost, abundant lignocellulosic biomass. Aqueous thermochemical pretreatments achieve this performance objective from pretreatment coupled with subsequent enzymatic hydrolysis, but chemical pretreatment can also suffer from additional costs for exotic materials of construction, the need to recover or neutralize the chemicals, introduction of compounds that inhibit downstream operations, and waste disposal, as well as for the chemicals themselves. The simplicity of hydrothermal pretreatment with just hot water offers the potential to greatly improve the cost of the entire conversion process if sugar degradation during pretreatment, production of un-fermentable oligomers, and the amount of expensive enzymes needed to obtain satisfactory yields from hydrothermally pretreated solids can be reduced. Biorefinery economics would also benefit if value could be generated from lignin and other components that are currently fated to be burned for power. However, achieving these goals will no doubt require development of advanced hydrothermal pretreatment configurations. For example, passing water through a stationary bed of lignocellulosic biomass in a flowthrough configuration achieves very high yields of hemicellulose sugars, removes more than 75% of the lignin for potential valorization, and improves sugar release from the pretreated solids with lower enzyme loadings. Unfortunately, the large quantities of water needed to achieve this performance result in very dilute sugars, high energy costs for pretreatment and product recover, and large amounts of oligomers. Furthermore, improving our understanding of hydrothermal pretreatment fundamentals is needed to gain insights into R&D opportunities to improve performance, and help identify novel configurations that lower capital and operating costs and achieve higher yields.

09 BIOMASS FUELS↗
NASA NTRS1993

Evaporation in equilibrium, in vacuum, and in hydrogen gas

Evaporation experiments were conducted for SiO2 in three different conditions: in equilibrium, in vacuum, and in hydrogen gas. Evaporation rate in vacuum is about two orders of magnitude smaller than that in equilibrium, which is consistent with previous works. The rate in hydrogen gas changes depending on hydrogen pressure. The rate at 10 exp -7 bar of hydrogen pressure is as small as that of free evaporation, but at 10 exp -5 bar of hydrogen pressure it is larger than that in equilibrium. In equilibrium and in vacuum, the evaporation rate is limited by decomposition of SiO2 on the crystal surface, but it is limited by a diffusion process for evaporation in hydrogen gas. Therefore, evaporation rate of minerals in the solar nebula can be shown neither by that in equilibrium nor by that in vacuum. The maximum temperature of the solar nebula at the midplane at 2-3 AU where chondrites are believed to have originated is calculated to be as low as 150 K, 1500 K, or in between them. The temperature is, in any case, not high enough for total evaporation of the interstellar materials. Therefore, evaporation of interstellar materials is one of the most important processes for the origin and fractionation of solid materials. The fundamental process of evaporation of minerals has been intensively studied for these several years. Those experiments were carried out either in equilibrium or in vacuum; however, evaporation in the solar nebula is in hydrogen (and much smaller amount of helium) gas. In order to investigate evaporation rate and compositional (including isotopic) fractionation during evaporation, vaporization experiments for various minerals in various conditions are conducted. At first, SiO2 was adopted for a starting material, because thermochemical data and its nature of congruent vaporization are well known. Experiments were carried out in a vacuum furnace system.

Nagahara, Hiroko↗
NASA NTRS1998

A Computational Chemistry Database for Semiconductor Processing

The concept of 'virtual reactor' or 'virtual prototyping' has received much attention recently in the semiconductor industry. Commercial codes to simulate thermal CVD and plasma processes have become available to aid in equipment and process design efforts, The virtual prototyping effort would go nowhere if codes do not come with a reliable database of chemical and physical properties of gases involved in semiconductor processing. Commercial code vendors have no capabilities to generate such a database, rather leave the task to the user of finding whatever is needed. While individual investigations of interesting chemical systems continue at Universities, there has not been any large scale effort to create a database. In this presentation, we outline our efforts in this area. Our effort focuses on the following five areas: 1. Thermal CVD reaction mechanism and rate constants. 2. Thermochemical properties. 3. Transport properties.4. Electron-molecule collision cross sections. and 5. Gas-surface interactions.

Jaffe, R.↗
DOE OSTI2024

Perspective on Lignin Conversion Strategies That Enable Next Generation Biorefineries

The valorization of lignin, a currently underutilized component of lignocellulosic biomass, has attracted attention to promote a stable and circular bioeconomy. Successful approaches including thermochemical, biological, and catalytic lignin depolymerization have been demonstrated, enabling opportunities for lignino-refineries and lignocellulosic biorefineries. Although significant progress in lignin valorization has been made, this review describes unexplored opportunities in chemical and biological routes for lignin depolymerization and thereby contributes to economically and environmentally sustainable lignin-utilizing biorefineries. This review also highlights the integration of chemical and biological lignin depolymerization and identifies research gaps while also recommending future directions for scaling processes to establish a lignino-chemical industry.

09 BIOMASS FUELS↗
NASA NTRS1989

Theoretical characterization of selected regions of the ground state potential surface of N2H2

The results of CASSCF/multireference contracted CI calculations with large atomic natural orbital basis sets are presented for selected regions of the N2H2 potential surface. The calculations focused on the addition of an H atom to HN2. This process involves four channels. Approach of the H atom along the HN bond leads to N2 + H2 with no barrier (H abstraction), while approach of the H atom to the other three positions leads to trans-HNNH, cis-HNNH, and NNH2, which are stable minima. These calculations provide the most accurate energetics for these three stable species obtained to date. Combining the results of these calculations with previous results for HN2 provides accurate thermochemical data on these important molecules.

Walch, Stephen P.↗
NASA NTRS1995

A perspective on computational aerothermodynamics: Current modeling difficulties

Future hypersonic vehicles are going to be designed largely with computational fluid dynamic methods based on appropriate physical models. The question on how much of this design process can be completed with the present state of computational aerothermodynamics is addressed. Some limitations of current models are discussed. It is shown that much more research is required before it will be possible to accurately design a hypersonic vehicle for all of its flight conditions. The quantities that must be computed accurately so that a minimum weight hypersonic vehicle can be designed are discussed. The use of computational fluid dynamics methods coupled with current thermochemical models in order to compute the quantities under specific flow conditions is considered.

Candler, Graham V.↗
DOE OSTI2012

Influence of HTR core inlet and outlet temperatures on hydrogen generation efficiency using the sulfur-iodine water-splitting cycle

The performance of hydrogen production via thermochemical cycles is typically evaluated using thermal efficiency. In this study, the sulfur-iodine cycle with heat supplied by a high-temperature reactor (HTR) is analyzed. Two cases are examined: one flow sheet designed by General Atomics in the United States, the other by Commissariat a l'energie atomique et aux energies alternatives in France. In each case, HTR helium inlet and outlet temperatures are specified. Differences in these temperature specifications lead to process variations between the limy sheets and in how the hydrogen processes interface with the nuclear heat source. Two principal conclusions result from the analysis. First, the thermal efficiency tends to plateau above a certain outlet helium temperature. This is a characteristic effect of the method of Ozturk et al. for sulfuric acid decomposition. Second, it is clear that it is impractical to discuss efficiencies for the hydrogen process that are independent of defined operating parameters of the HTR. (authors)

08 HYDROGEN↗
DOE OSTI2015

Strategic supply system design – a holistic evaluation of operational and production cost for a biorefinery supply chain

Abstract Pioneer cellulosic biorefineries across the United States rely on a conventional feedstock supply system based on one‐year contracts with local growers, who harvest, locally store, and deliver feedstock in low‐density format to the conversion facility. While the conventional system is designed for high biomass yield areas, pilot scale operations have experienced feedstock supply shortages and price volatilities due to reduced harvests and competition from other industries. Regional supply dependency and the inability to actively manage feedstock stability and quality, provide operational risks to the biorefinery, which translate into higher investment risk. The advanced feedstock supply system based on a network of depots can mitigate many of these risks and enable wider supply system benefits. This paper compares the two concepts from a system‐level perspective beyond mere logistic costs. It shows that while processing operations at the depot increase feedstock supply costs initially, they enable wider system benefits including supply risk reduction (leading to lower interest rates on loans), industry scale‐up, conversion yield improvements, and reduced handling equipment and storage costs at the biorefinery. When translating these benefits into cost reductions per liter of gasoline equivalent ( LGE ), we find that total cost reductions between –$0.46 to –$0.21 per LGE for biochemical and –$0.32 to –$0.12 per LGE for thermochemical conversion pathways are possible. Naturally, these system level benefits will differ between individual actors along the feedstock supply chain. Further research is required with respect to depot sizing, location, and ownership structures. Published 2015. This article is a U.S. Government work and is in the public domain in the USA. Biofuels, Bioproducts and Biorefining published by Society of Industrial Chemistry and John Wiley & Sons Ltd.

09 BIOMASS FUELS↗