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Results for “Chemical Fractionation”

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 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

High Yield, Economical and Environmentally Benign Production of Rare Earth Elements from Coal Ash [Abstract]

Fly ash stored in landfills and ponds across the United States is an attractive, abundant domestic resource for the cost-effective recovery of rare earth elements (REE) and other critical minerals (CM). Physical Sciences Inc. (PSI) and its team members, Winner Water Services (WWS) and University of Kentucky/Center for Applied Energy Research (UK/CAER) successfully executed a multiphase program that developed and demonstrated pilot plant operations for cost-effective and environmentally-friendly production of rare earth element oxide (REO) concentrates, and the critical minerals scandium and aluminum (in the forms of salts or oxide products). We constructed and operated a sub-scale (0.5 kg/day) micropilot facility to demonstrate the key physical and chemical processing operations, predict yields, and troubleshoot process bottlenecks. The project team then designed, constructed and operated two decoupled pilot plant operations: (1) an operational pilot plant for physical separation processes with a capacity of 0.4 metric tons per day (tpd) where we optimized processes to produce selected ash fractions as the feedstock for chemical processing as well as valuable byproducts such as cement substitute, cenospheres, magnetic ash and secondary fuel carbon, and (2) an operational pilot plant for chemical processing with a capacity of 0.5 tpd that developed optimized processes for the production of: (a) REO concentrates, (b) critical minerals recovery (Sc, Al), and (c) beneficiated ash as valuable byproduct suitable for cement applications.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2021

Deep Learning Coordinate-Free Quantum Chemistry

Computing quantum chemical properties of small molecules and polymers can provide insights valuable to physicists, chemists and biologists when designing new materials, catalysts, biological probes and drugs. Deep learning can compute quantum chemical properties accurately in a fraction of the time required by commonly used methods such as density functional theory (DFT). However, many of these deep learning architectures require energy minimized molecular geometries as input, which is also computationally expensive, and decreasing the reproducibility and throughput of these methods. In this study, we demonstrate that accurate quantum chemical computations can be performed without optimized geometries by operating in the coordinate-free domain using deep learning on graph encodings. Furthermore, we also find that the choice of graph-encoding architecture substantially affects the performance of these methods. The Wave architecture outperforms graph convolution architectures, particularly on complex molecules. Furthermore, the structures of these graph encoding architectures provide an opportunity to probe an important, outstanding question in quantum mechanics: What types of quantum chemical properties can be represented by local-variable models? We find that Wave, a local-variable model, is more accurately calculates quantum chemical properties. Graph convolutional architectures require global variables, and are not as effective as as Wave. We anticipate that coordinate-free, deep-learning models of quantum chemistry will become valuable tools in chemistry and biology, enabling researchers to rapidly screen chemical databases or identify new molecules using automated, de-novo design algorithms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1998

A Gas-Kinetic Scheme for Reactive Flows

In this paper, the gas-kinetic BGK scheme for the compressible flow equations is extended to chemical reactive flow. The mass fraction of the unburnt gas is implemented into the gas kinetic equation by assigning a new internal degree of freedom to the particle distribution function. The new variable can be also used to describe fluid trajectory for the nonreactive flows. Due to the gas-kinetic BGK model, the current scheme basically solves the Navier-Stokes chemical reactive flow equations. Numerical tests validate the accuracy and robustness of the current kinetic method.

Lian,Youg-Sheng↗
NASA NTRS1993

Low-energy ion implantation: Large mass fractionation of argon

The isotropic signatures of noble gases in the atmospheres of the Earth and other planets are considerably evolved when compared to signatures observed in the solar wind. The mechanisms driving the evolution of planetary volatiles from original compositions in the solar accretion disk are currently poorly understood. Modeling of noble-gas compositional histories requires knowledge of fractionating processes that may have operated through the evolutionary stages. Since these gases are chemically inert, information on noble-gas fractionation processes can be used as probes. The importance of understanding these processes extends well beyond 'noble-gas planetology.' Trapped argon acquired by low-energy implantation (approximately less than 100 eV) into solids is strongly mass fractionated (approximately greater than or equal to 3 percent/amu). This has potential implications for the origin and evolution of terrestrial planet atmospheres.

Ponganis, K. V.↗
DOE OSTI2023

Root traits of perennial C 4 grasses contribute to cultivar variations in soil chemistry and species patterns in particulate and mineral‐associated carbon pool formation

Abstract Recent studies have indicated that the C 4 perennial bioenergy crops switchgrass ( Panicum virgatum ) and big bluestem ( Andropogon gerardii ) accumulate significant amounts of soil carbon (C) owing to their extensive root systems. Soil C accumulation is likely driven by inter‐ and intraspecific variability in plant traits, but the mechanisms that underpin this variability remain unresolved. In this study we evaluated how inter‐ and intraspecific variation in root traits of cultivars from switchgrass (Cave‐in‐Rock, Kanlow, Southlow) and big bluestem (Bonanza, Southlow, Suther) affected the associations of soil C accumulation across soil fractions using stable isotope techniques. Our experimental field site was established in June 2008 at Fermilab in Batavia, IL. In 2018, soil cores were collected (30 cm depth) from all cultivars. We measured root biomass, root diameter, specific root length, bulk soil C, C associated with coarse particulate organic matter (CPOM) and fine particulate organic matter plus silt‐ and clay‐sized fractions, and characterized organic matter chemical class composition in soil using high‐resolution Fourier‐transform ion cyclotron resonance mass spectrometry. C 4 species were established on soils that supported C 3 grassland for 36 years before planting, which allowed us to use differences in the natural abundance of stable C isotopes to quantify C 4 plant‐derived C. We found that big bluestem had 36.9% higher C 4 plant‐derived C compared to switchgrass in the CPOM fraction in the 0–10 cm depth, while switchgrass had 60.7% higher C 4 plant‐derived C compared to big bluestem in the clay fraction in the 10–20 cm depth. Our findings suggest that the large root system in big bluestem helps increase POM‐C formation quickly, while switchgrass root structure and chemistry build a mineral‐bound clay C pool through time. Thus, both species and cultivar selection can help improve bioenergy management to maximize soil carbon gains and lower CO 2 emissions.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2022

Organic carbon content and turnover time in relation to pedogenic iron and aluminum in four temperate forest soils sampled in 2007

Soil organic carbon (SOC) can be stabilized via association with iron (Fe) and aluminum (Al) minerals. Fe and Al can be strong predictors of SOC storage and turnover in soils with relatively high extractable metals content and moderately acidic to circumneutral pH. Here we test whether pedogenic Fe and Al influence SOC content and turnover in soils with low Fe and Al content and acidic pH. In soils from four sites spanning three soil orders, we quantified the amount of Fe and Al in operationally-defined poorly crystalline and organically-complexed phases using selective chemical dissolution applied to the soil fraction containing mineral-associated carbon. We evaluated the correlations of Fe and Al concentrations, mean annual precipitation (MAP), mean annual temperature (MAT), and pH with SOC content and 14C-based turnover times. We found that poorly crystalline Fe and Al content predicted SOC turnover times (p < 0.0001) consistent with findings of previous studies, while organically-complexed Fe and Al content was a better predictor of SOC concentration (p < 0.0001). Greater site-level MAP (p < 0.0001) and colder site-level MAT (p < 0.0001) were correlated with longer SOC turnover times but were not correlated with SOC content. Our results suggest that poorly crystalline Fe and Al effectively slow the turnover of SOC in these acidic soils, even when their combined content in the soil is less than 2% by mass. However, in the strongly acidic Spodosol, organo-metal complexes tended to be less stable resulting in a more actively cycling mineral-associated SOC pool. We characterized mineralogy and carbon content in soils from four forested sites in the eastern deciduous forest zone that span three soil orders. Using selective chemical dissolution applied to the soil fraction containing mineral-associated carbon, we quantified the amount of Fe and Al in operationally-defined poorly crystalline and organically-complexed phases, and correlated these with previously published SOC content and 14C-based turnover times (McFarlane et al. 2013). This dataset comprises site characterization undertaken in 2007 (.png) and subsequent soil analyses (.csv containing C, Fe, Al, 14C-derived TurnoverTime) concluded in 2010.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

R-Value Measurements Performed on Actinide Targets Irradiated using the GODIVA IV Critical Assembly in FY22

The separation and characterization of two irradiated uranium targets, a depleted uranium (DU) and a highly enriched uranium (HEU) target as well as a plutonium (Pu) target, was conducted in April of 2022. The three targets were assembled at Los Alamos National Laboratory (LANL) and irradiated using the GODIVA critical assembly at the National Criticality Experiments Research Center (NCERC). Splits of the dissolved targets were received by Pacific Northwest National Laboratory (PNNL) after which the PNNL and LANL teams chemically separated the solutions using independent separation schemes and analyzed the separated fractions for short lived actinides and fission products. Chemical separations were traced with stable or radioactive tracers to allow for the determination of chemical yields, analyzing using either inductively coupled plasma optical emission spectroscopy (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS) or gamma emission analysis (GEA) depending on the nature of the tracer. The Pu target solution was traced with stable elements at LANL to follow elemental fractionation during a Pu removal step. Many analytical techniques were used by PNNL including kinetic phosphorescence analysis (KPA), ICP-OES, ICP-MS, GEA, and thermal ionization mass spectrometry (TIMS) depending on the analyte’s need.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS1976

Geochemistry of grain-size fractions of soils from the Taurus-Littrow valley floor

Results are presented for a study in which high-precision instrumental neutron activation analysis was applied to determine the abundances of seven rare-earth and nine other elements in two grain-size fractions (90 to 150 microns and less than 20 microns) of eight soils from the Taurus-Littrow Valley floor and one Apollo 11 bulk-soil fraction with grain sizes of less than 1 mm. Compositional differences between the two size fractions of two valley-floor soils are examined, and mixing of soil components is investigated. It is found that a five-component mixing model describes very adequately the chemical composition of bulk soils with grain sizes of less than 1 mm as mixtures of local Apollo 17 rock types (basalt, anorthositic gabbro, noritic breccia), orange glass, and meteorites, but does not describe well the chemical compositions of the other two size fractions. A ten-component model is used to show that the compositions of those two size fractions can be well represented as mixtures of the five components if the mineralogy and chemical composition of the basalt component are allowed to vary in the size fractions.

Korotev, R. L.↗
DOE OSTI2022

Computational Prediction of Water Sorption in Facilitated Transport Membranes

Polymeric facilitated transport membranes (FTMs) have emerged as an innovative class of promising carbon capture technology. Studies have shown that the transport properties of an FTM are significantly influenced by its water uptake. In order to better quantify FTM performance, we herein explore the potential of computational techniques to predict the equilibrium water uptake values of FTMs. Two prediction approaches were examined. First, the water sorption was explicitly simulated by iteratively conducting grand canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations. Second, the water sorption was predicted based on the chemical potential of the adsorbed water, which was calculated using the Widom insertion or continuous fractional component Monte Carlo (CFCMC) method. The chemical potential-based approach with CFCMC demonstrated good prediction of the equilibrium water uptake values of FTMs with poly(N-vinylformamide-co-vinylamine) as fixed-site carrier and 2-(1-piperazinyl)ethylamine sarcosinate as mobile carrier. The predicted water uptake values increased with increasing mobile carrier content and were in good agreement with the experimental values. Furthermore, the higher water uptake promoted the diffusion of CO 2 , N 2 , and mobile carrier as well as slightly stifled the sorption of N 2 . Such an approach significantly contributes to a more comprehensive theoretical evaluation of FTMs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2005

Association of Presolar Grains with Molecular Cloud Material in IDPs

Anhydrous interplanetary dust particles (IDPs) collected in the stratosphere appear chemically, mineralogically, and texturally primitive in comparison to meteorites. Particles that escape significant atmospheric entry heating have highly unequilibrated mineralogy, are volatile element rich, and, overall, appear to have escaped significant parent body hydrothermal alteration. These IDPs are comprised of the building blocks of the solar system. The strongest evidence that anhydrous IDPs are primitive is that they contain abundant stardust and molecular cloud material. In particular, presolar silicates were first identified in IDPs and are present in abundances (450-5,500 ppm) that are well above that observed in primitive meteorites (less than 170 ppm). The most fragile (cluster) IDPs also commonly exhibit large H and N isotopic anomalies that likely originated by isotopic fractionation during extremely low temperature chemical reactions in a presolar cold molecular cloud. The D/H ratios exceed that of most primitive meteorites, and in rare cases reach values directly observed from simple gas phase molecules in cold molecular clouds. The most extreme D- and N-15-enrichments are usually observed at the finest spatial scales (0.5-2 microns) that can be measured. These observations suggest that D and N-15 hotspots are in fact preserved nuggets of molecular cloud material, and that the materials within them also have presolar origins. The advanced capabilities of the NanoSIMS ion microprobe now enable us to test this hypothesis. Here, we report two recent examples of presolar silicates found to be directly associated with molecular cloud material.

Messenger, S.↗
DOE OSTI2022

R-Value Measurements Performed on Uranium Targets Irradiated with Fission Spectrum Neutrons FY 2021 for F2019 Project

The separation and characterization of two irradiated uranium targets, a depleted uranium (DU) and a highly enriched uranium (HEU) target, was conducted in April of 2021. The two targets were assembled at Los Alamos National Laboratory (LANL) and irradiated using the critical assembly at the National Criticality Experiments Research Center (NCERC). Splits of the dissolved targets were received by Pacific Northwest National Laboratory (PNNL) after which the PNNL and LANL teams chemically separated the solutions using independent separation schemes and analyzed the separated fractions for short lived actinides and fission products. Chemical separations at PNNL were traced with stable or radioactive tracers to allow for the determination of chemical yields, analyzing using either inductively coupled plasma optical emission spectroscopy (ICP-OES), inductively coupled plasma mass spectrometry (ICP-MS) or gamma emission analysis (GEA) depending on the nature of the tracer. Several other analytical techniques were used by PNNL including kinetic phosphorescence analysis (KPA) and thermal ionization mass spectrometry (TIMS) depending on the analyte’s need. Comparisons were made between current and historical PNNL and LANL, as well as literature values. Overall, there was agreement between the two laboratories for the bulk of analytes, with some notable exceptions such as 111 Ag, and 141,143,144 Ce. Included in these comparisons were the short-lived actinides 237 U, 239 Np, the fission products 89 Sr, 91 Y, 95/97 Zr, 99 Mo, 111 Ag, 115/115 mCd, 136/137 Cs, 140 Ba, 141/143/144 Ce, 147 Nd, 153 Sm, 156 Eu, and 161 Tb, providing both total atoms as well as the R-values. The data presented in this report represents the sixth NCERC irradiation of HEU and DU (FY13, FY14, FY15, FY17, FY18, FY21), and their subsequent separation and analysis.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
NASA NTRS2011

Composition of LHB Comets and Their Influence on the Early Earth Atmosphere Composition

Two main processes were responsible for the composition of this atmosphere: chemical evolution of the volatile fraction of the accretion material forming the planet and the delivery of gasses to the planetary surface by impactors during the late heavy bombardment (LHB). The amount and composition of the volatile fraction influences the outgassing of the Earth mantle during the last planetary formation period. A very weakened form of outgassing activity can still be observed today by examining the composition of volcanic gasses. An enlightenment of the second process is based on the sparse records of the LHB impactors resulting from the composition of meteorites, observed cometary comas, and the impact material found on the Moon. However, for an assessment of the influence of the outgassing on the one hand and the LHB event on the other, one has to supplement the observations with numerical simulations of the formation of volatiles and their incorporation into the accretion material which is the precursors of planetary matter, comets and asteroids. These simulations are performed with a combined hydrodynamic-chemical model of the solar nebula (SN). We calculate the chemical composition of the gas and dust phase of the SN. From these data, we draw conclusions on the upper limits of the water content and the amount of carbon and nitrogen rich volatiles incorporated later into the accretion material. Knowing these limits we determine the portion of major gas compounds delivered during the LHB and compare it with the related quantities of the outgassed species.

Tornow, C.↗
DOE OSTI2024

Vanishing adsorption limit of Riemann problem solutions for the polymer model

Here we examine the vanishing adsorption limit of solutions of Riemann problems for the Glimm–Isaacson model of chemical flooding of a petroleum reservoir. A contact discontinuity is deemed admissible if it is the limit of traveling waves or rarefaction waves for an augmented system that accounts for weak chemical adsorption onto the rock. We prove that this criterion justifies the admissibility criteria adopted previously by Keyfitz–Kranzer, Isaacson–Temple and de Souza–Marchesin, provided that the fractional flow function depends monotonically on chemical concentration. We also demonstrate that the adsorption criterion selects the undercompressive contact discontinuities required to solve the general Riemann problem in an example model with non-monotone dependence.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2022

From acetone fractionation to lignin-based phenolic and polyurethane resins

In this paper, acetone fractionation was used to increase the homogeneity of softwood kraft lignin for product development. The acetone soluble and insoluble fractions were analyzed in terms of elemental composition, chemical structure, and thermal properties. The phenolic hydroxyl content of the acetone soluble fraction increased by 24%. The acetone soluble fraction of kraft lignin was used to fully substitute phenol in phenolic resin formulation. The resulting formulated lignin-formaldehyde adhesive showed higher adhesion strength (4.3 MPa) compared to a lab formulated phenol-formaldehyde resin (3.4 MPa) with 100% wood failure after lap shear test. On the other hand, the acetone insoluble lignin fraction, which had 23% higher aliphatic hydroxyl content compared to the starting lignin, was used to entirely replace petroleum-based polyol in polyurethane resin formulation. Then a bio-derived solvent (dihydrolevoglucosenone, Cyrene) was used to dissolve the acetone insoluble lignin fraction to synthesize lignin-based polyurethane resin. Tailoring the structure of kraft lignin through solvent fractionation resulted in two fractions, which were used to replace 100% of two major petrochemicals (phenol and polyol) in the formulations of phenolic and PU resins, that would otherwise be challenging due to the heterogeneity of softwood kraft lignin.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Response of Pseudomonas putida to Complex, Aromatic-Rich Fractions from Biomass

There is strong interest in the valorization of lignin to produce valuable products; however, its structural complexity has been a conversion bottleneck. Chemical pretreatment liberates lignin-derived soluble fractions that may be upgraded by bioconversion. Here, cholinium ionic liquid pretreatment of sorghum produced soluble, aromatic-rich fractions that were converted by Pseudomonas putida (P. putida), a promising host for aromatic bioconversion. Growth studies and mutational analysis demonstrated that P. putida growth on these fractions was dependent on aromatic monomers but unknown factors also contributed. Proteomic and metabolomic analyses indicated that these unknown factors were amino acids and residual ionic liquid; the oligomeric aromatic fraction derived from lignin was not converted. A cholinium catabolic pathway was identified, and the deletion of the pathway stopped the ability of P. putida to grow on cholinium ionic liquid. This work demonstrates that aromatic-rich fractions obtained through pretreatment contain multiple substrates; conversion strategies should account for this complexity.

09 BIOMASS FUELS↗
DOE OSTI2027

A multi-region approach for the analysis of porous materials and gas-solid reactions using USAXS-SAXS-WAXS: application to CaO carbonation

The reaction rate of gas-solid non-catalytic reactions is typically investigated using reactant conversion data over time and ex-situ measurements of the porous solid reactant textural properties; these data enable the experimental estimation of the initial intrinsic reaction rate, whereas the evolution of the textural properties and the reaction rate over time are evaluated theoretically using reaction models. In this work, a different methodology is presented, based on: a) in-situ time-resolved USAXS-SAXS-WAXS measurements of the solid sample, and b) a multi-region modeling approach; this methodology allows for the estimation of the textural properties and the intrinsic reaction rate at any time during the reaction. Referring to a reaction in which a solid product is obtained from a solid reactant and a gaseous reactant, the porous particle is described as consisting of several distinct regions with different microstructural properties, and both a gas-solid reaction model and a SAXS model are derived and applied to the carbonation of porous CaO. The proposed reaction model highlights the role of the inaccessible reactant and accurately predicts the solid reactant conversion versus time profile. The SAXS model accurately predicts the measured linear trends of the Porod invariant and of the pre-factor of the power law scattering profile versus CaO mass fraction; in the absence of chemical reactions, the proposed equations extend classical SAXS theory to porous materials containing macropores and nonporous solid phases in addition to standard nanoscale inhomogeneous regions.

CO2 solid sorbents↗
DOE OSTI2025

Boron isotopic analysis in bulk silicate materials using the Neoma MS/MS MC-ICP-MS

Boron (B) isotopes are a valuable tracer with applications ranging from geological, environmental, and nuclear studies because B isotopic fractionation is highly sensitive to chemical processes yielding distinct isotopic trends in natural and anthropogenic systems. Despite this wide applicability, there remain relatively few measurements on well-described reference materials and in some cases, poor agreement between various methods. We report a method for boron isotope ratio measurement in solution on the Neoma MS/MS MC-ICP-MS specifically targeting bulk silicates. We evaluate the performance of the method and instrument as it relates to the measurement of the absolute boron isotope ratio ( 10 B/ 11 B). The results indicate that the method produces data in agreement with literature values and that the sample–standard bracketing technique is appropriate for the Neoma MS/MS MC-ICP-MS which has been in use for decades on previous generation instruments. Careful tuning of the MS/MS lenses is required to obtain precision comparable to non MS/MS equipped MC-ICP-MS. With careful tuning, internal and external precisions of ∼0.3‰ were achieved. However, when the MS/MS is not properly tuned external precisions exceed 3‰. Nevertheless, our results for IAEA B-6, BCR-2, BHVO-2 and W-2a reference materials overlap the 1σ range of previously reported 10 B/ 11 B. Data are reported for total boron quantities down to a few tens of nanograms. Our procedure yielded blanks as low as 3 ng but up to 29 ng, making blank corrections important for small samples sizes in the few 10s of nanogram range. We report B isotope ratios for AGV-2G, SL-1G, GSC-2G, GSD-2G, GSE-2G, RLS-132, RLS-140, NKT-1G, and T1-G glass reference materials that have not been previously reported in the literature.

Scott, Sean R. [Pacific Northwest National Laborat↗