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At least 775 records · Page 43

Spent-fuel recycling molecule degradation product standards can be produced with preparative liquid chromatography

Solvent systems used for spent nuclear fuel separation schemes are subject to intense radiation fields from the spent fuel, resulting in a degradation of separation performance over time from both the radiolytic destruction of active compounds (extractants, holdback agents, etc.) and the production of degradation compounds (compounds produced from the destruction of the active compounds). Development of a quantitative understanding of the effects of radiolysis on separations is impeded by a near-complete lack of availability of degradation products from chemical manufacturers. Synthesis of these degradation products through traditional means is both cost and time prohibitive, inhibiting advancement of new fuel separation processes. We hypothesize that comprehensive sets of degradation products can be synthesized using preparative radiolysis, and purified using high performance liquid chromatography in quantities sufficient for unequivocal identification and subsequent use as quantitative analytical studies. Achieving this objective will facilitate development of a much more accurate understanding of radiolysis reactions and their effects on solvent extraction processes, positioning Idaho National Laboratory (INL) in a leadership role in the science of fuel cycle separations. We propose producing these degradation compounds by irradiating concentrated samples of solvent ligands in the INL gamma irradiator, separating the resulting mixture with preparative chromatography, and removing the mobile phase in the separated fractions with a vacuum concentrator. This will yield milligram to gram quantities of purified degradation products, sufficient for fundamental research, at a fraction of the time and cost of synthesis. Facile production of separation molecule degradation products at minimal cost will enable the fundamental research that will accelerate the development of fuel cycles that will ensure the competitiveness of nuclear energy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bio-oil production from biomass via supercritical fluid extraction

Supercritical fluid extraction is used for producing bio-fuel from biomass. Supercritical fluid extraction process under supercritical conditions is the thermally disruption process of the lignocellulose or other organic materials at 250-400 °C temperature range under high pressure (4-5 MPa). Supercritical fluid extraction trials were performed in a cylindrical reactor (75 mL) in organic solvents (acetone, ethanol) under supercritical conditions with (calcium hydroxide, sodium carbonate) and without catalyst at the temperatures of 250, 275 and 300 °C. The produced liquids at 300 °C in supercritical liquefaction were analyzed and characterized by elemental, GC-MS and FT-IR. 36 and 37 different types of compounds were identified by GC-MS obtained in acetone and ethanol respectively.

09 BIOMASS FUELS↗

Flow-through compression cell for small-angle and ultra-small-angle neutron scattering measurements

In situ measurements of geological materials under compression and with hydrostatic fluid pressure are important in understanding their behavior under field conditions, which in turn provides critical information for application-driven research. In particular, understanding the role of nano- to micro-scale porosity in the subsurface liquid and gas flow is critical for the high-fidelity characterization of the transport and more efficient extraction of the associated energy resources. In other applications, where parts are produced by the consolidation of powders by compression, the resulting porosity and crystallite orientation (texture) may affect its in-use characteristics. Small-angle neutron scattering (SANS) and ultra SANS are ideal probes for characterization of these porous structures over the nano to micro length scales. Here we show the design, realization, and performance of a novel neutron scattering sample environment, a specially designed compression cell, which provides compressive stress and hydrostatic pressures with effective stress up to 60 MPa, using the neutron beam to probe the effects of stress vectors parallel to the neutron beam. In conclusion, we demonstrate that the neutron optics is suitable for the experimental objectives and that the system is highly stable to the stress and pressure conditions of the measurements.

47 OTHER INSTRUMENTATION↗

A Novel Hollow Fiber Membrane Reactor for High Purity H 2 Generation from Thermal Catalytic NH 3 Decomposition (Final Report)

Ammonia (NH 3 ), as a promising carbon neutral liquid fuel (CNLF) and an effective H 2 source, can be synthesized from air and water (N 2 extracted from air and H 2 from water) using renewable energy sources. To produce H 2 as an intermediate, it is essential to develop effective and economic NH 3 decomposition technologies. We have been developing an innovative hollow fiber membrane reactor for high purity H 2 generation from thermal catalytic NH 3 decomposition. The objective of the proposed research is to fabricate a compact and robust prototype with high energy efficiency (>80%) to deliver high purity (>99%) H2 at high rate per volume (>0.15 g H 2 /h/cm 3 ) from NH3 decomposition at low temperature (<450 °C) and high conversion (>99%). Our overall technical approach is to effectively combine an active catalyst for NH 3 decomposition with a selective H 2 membrane separation process in a novel, compact modular system to generate high purity H 2 and simultaneously achieve high NH 3 conversion and optimize the entire system energy efficiency. This novel integrated membrane reactor design, together with low-cost, highly active Ru-based catalyst, makes it most appropriate for the project objective. The proposed applied research and development work, therefore, represents an innovative and transformational solution to H 2 generation from thermal catalytic NH 3 decomposition. During the course of our research we i) synthesized and characterized ruthenium(Ru)-based catalysts, evaluated their catalytic performance for NH 3 decomposition and optimized the catalyst composition and performance based on machine learning, ii) prepared SAPO-34, MFI membranes on α-alumina hollow fibers and measured their performance for H 2 /N 2 , H 2 /N 2 /NH 3 separation and evaluated carbon molecular sieve (CMS) and Pd/Ag membranes for H 2 /N 2 , H 2 /N 2 /NH 3 separation at different conditions, iii) designed and evaluated several types of membrane reactors for H 2 production from NH 3 decomposition, and iv) evaluated the H 2 delivery cost base on catalysts development, membrane development and membrane reactor. For 3,1,12 RuYK catalyst, H 2 productivity of 6.35 mmol/min/gcat with NH 3 conversion of 95~98% was achieved at 5 bar and 400 °C; for SAPO-34 membrane, the best membrane showed H 2 permeance of 7.56×10 -7 mol/(m 2 ∙s∙Pa) and H 2 /N 2 selectivity of 23.1 at 20 °C; For CMS and Pd/Ag membranes, both showed superior stability for 71%H 2 /24%N 2 /5%NH 3 mixture separation at 450 °C and 7 bar for over 120 h; for the membrane reactor, high H 2 purity of >99.99% with NH 3 conversion of >99.4% were achieved in Pd/Ag membrane reactor at 450 °C, and the NH 3 concentration was always below 10 ppb in H 2 product. The H 2 generation rate was calculated to be as high as 0.47 g/h/cm 3 and the energy efficiency was calculated to be 88%. The membrane reactor showed superior stability for over 370 h and high H 2 purity, H 2 production rate and NH 3 conversion. Based on calculation, the H 2 delivery cost can be as low as $3.66/kg.

08 HYDROGEN↗

An effective QWBA/UHPLC-MS/tissue punch approach: solving a pharmacokinetic issue via quantitative Met-ID

Methods to provide absolute quantitation of the administered drug and corresponding metabolites in tissue in a spatially resolved manner is a challenging but much needed necessity in pharmaceutical research. Quantitative whole-body autoradiography (QWBA) after a single-dose intravenous (3 mg/kg) and extravascular (30 mg/kg) administrations of an in vitro metabolically stable test compound (structure not reported here) indicated quick tissue distribution and excretion. Good bioavailability and short in vivo half-lives were determined formerly for the same test compound. For closing gaps in the understanding of pharmacokinetic data and in vitro results, radioactive hot spots on whole-body tissue sections had been profiled. Punches from selected tissue regions containing high radioactivity in the tissue sections previously analyzed by QWBA were extracted by a highly organic solvent and analyzed without any consecutive sample preparation step, applying ultra high performance liquid chromatography-mass spectrometry (UHPLC-MS) and off-line radioanalysis to maximize signal levels for metabolite identification and profiling. The analysis revealed that the test compound was metabolized intensively by phase I reactions in vivo and the metabolites formed were excreted in bile and in urine. The predominant metabolites showed abundant signal intensities both by MS and by radioanalysis but the MS signal intensities generally underestimated the real abundances of metabolites relative to the unchanged drug. In this work we illustrate that maximizing the sensitivity of tissue punch radioanalysis and the combination with UHPLC-MS leads to a better insight of pharmacokinetic processes by providing quantitative data with high molecular selectivity.

60 APPLIED LIFE SCIENCES↗

Determination of the gram-positive bacterial content of soils and sediments by analysis of teichoic acid components

Many gram-positive bacteria form substituted polymers of glycerol and ribitol phosphate esters known as teichoic acids. Utilizing the relative specificity of cold concentrated hydrofluoric acid in the hydrolysis of polyphosphate esters it proved possible to quantitatively assay the teichoic acid-derived glycerol and ribitol from gram-positive bacteria added to various soils and sediments. The lipids are first removed from the soils or sediments with a one phase chloroform-methanol extraction and the lipid extracted residue is hydrolyzed with cold concentrated hydrofluoric acid. To achieve maximum recovery of the teichoic acid ribitol, a second acid hydrolysis of the aqueous extract is required. The glycerol and ribitol are then acetylated after neutralization and analyzed by capillary gas-liquid chromatography. This technique together with measures of the total phospholipid, the phospholipid fatty acid, the muramic acid and the hydroxy fatty acids of the lipopolysaccharide lipid A of the gram-negative bacteria makes it possible to describe the community structure environmental samples. The proportion of gram-positive bacteria measured as the teichoic acid glycerol and ribitol is higher in soils than in sediments and increases with depth in both.

Ribitol/analogs & derivatives↗

Purification Procedures for Single-Wall Carbon Nanotubes

This report summarizes the comparison of a variety of procedures used to purify carbon nanotubes. Carbon nanotube material is produced by the arc process and laser oven process. Most of the procedures are tested using laser-grown, single-wall nanotube (SWNT) material. The material is characterized at each step of the purification procedures by using different techniques including scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), Raman, X-ray diffractometry (XRD), thermogravimetric analysis (TGA), nuclear magnetic resonance (NMR), and high-performance liquid chromatography (HPLC). The identified impurities are amorphous and graphitic carbon, catalyst particle aggregates, fullerenes, and hydrocarbons. Solvent extraction and low-temperature annealing are used to reduce the amount of volatile hydrocarbons and dissolve fullerenes. Metal catalysts and amorphous as well as graphitic carbon are oxidized by reflux in acids including HCl, HNO3 and HF and other oxidizers such as H2O2. High-temperature annealing in vacuum and in inert atmosphere helps to improve the quality of SWNTs by increasing crystallinity and reducing intercalation.

Gorelik, Olga P.↗

A Search for Amino Acids and Nucleobases in the Martian Meteorite Roberts Massif 04262 Using Liquid Chromatography-Mass Spectrometry

The investigation into whether Mars contains signatures of past or present life is of great interest to science and society. Amino acids and nucleobases are compounds that are essential for all known life on Earth and are excellent target molecules in the search for potential Martian biomarkers or prebiotic chemistry. Martian meteorites represent the only samples from Mars that can be studied directly in the laboratory on Earth. Here, we analyzed the amino acid and nucleobase content of the shergottite Roberts Massif (RBT) 04262 using liquid chromatography-mass spectrometry. We did not detect any nucleobases above our detection limit in formic acid extracts; however, we did measure a suite of protein and nonprotein amino acids in hot-water extracts with high relative abundances of beta-alanine and gamma-amino-eta-butyric acid. The presence of only low (to absent) levels of several proteinogenic amino acids and a lack of nucleobases suggest that this meteorite fragment is fairly uncontaminated with respect to these common biological compounds. The distribution of straight-chained amine-terminal eta-omega-amino acids in RBT 04262 resembled those previously measured in thermally altered carbonaceous meteorites. A carbon isotope ratio of -24(0/00) +/- 6(0/00) for beta-alanine in RBT 04262 is in the range of reduced organic carbon previously measured in Martian meteorites (Steele et al. 2012). The presence of eta-omega-amino acids may be due to a high temperature Fischer-Tropschtype synthesis during igneous processing on Mars or impact ejection of the meteorites from Mars, but more experimental data are needed to support these hypotheses.

Laboratory analysis↗

Techniques for Liquid Rocket Combustion Spontaneous Stability and Rough Combustion Assessments

This work presents techniques for liquid rocket engine combustion stability assessments with respect to spontaneous stability and rough combustion. Techniques covering empirical parameter extraction, which were established in prior works, are applied for three additional programs: the F-1 Gas Generator (F1GG) component test program, the RS-84 preburner component test program, and the Marshall Integrated Test Rig (MITR) program. Stability assessment parameters from these programs are compared against prior established spontaneous stability metrics and updates are identified. Also, a procedure for comparing measured with predicted mode shapes is presented, based on an extension of the Modal Assurance Criterion (MAC).

Kenny, R. J.↗

X-ray Induced Cycling of Rare-Earth Elements between Bulk and Interfacial Liquid

Reversible cycling of rare-earth elements between an aqueous electrolyte solution and its free surface is achieved by X-ray exposure. This exposure alters the competitive equilibrium between lanthanide ions bound to a chelating ligand, diethylenetriamine pentaacetic acid (DTPA), in the bulk solution and to insoluble monolayers of extractant di-hexadecyl phosphoric acid (DHDP) at its surface. Evidence for the exposure-induced temporal variations in the lanthanide surface density is provided by X-ray fluorescence near total reflection measurements. Comparison of results when X-rays are confined to the aqueous surface region to results when X-rays transmit into the bulk solution suggests the importance of aqueous radiolysis in the adsorption cycle. Amine binding sites in DTPA are identified as a likely target of radiolysis products. The molecules DTPA and DHDP are like those used in the separation of lanthanides from ores and in the reprocessing of nuclear fuel. Furthermore, these results suggest that an external source of X-rays can be used to drive rare-earth element separations. More generally, use of X-rays to controllably dose a liquid interface with lanthanides could trigger a range of interfacial processes, including enhanced metal ion extraction, catalysis, and materials synthesis.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Beneficiation and extraction of nonterrestrial materials, part 2

A review of options for processing extraterrestrial materials was dominated by industrial materials scientist who tried to identify which processes utilizing space materials could be implemented in the near term. The most practical process seem to us to be the extraction of lunar oxygen and the extraction of metals and ceramics from the residues of the reduction process. The growth of space activity will be accompanied by increased demand for liquid oxygen for each round trip to the Moon. The oxygen and the intermediary product water will be needed for the life support at the base. The reduced metals and ceramics may be considered byproducts or may develop into primary products. Some of the same processes would be directly applicable to recovery of products from asteroids. We also discussed other processes for directly utilizing asteroid metals. Some of the topics covered include beneficiation and oxygen extraction methods, metallurgy, and extraterrestrial cement.

Agosto, William N.↗

Liquid-Liquid Separation Process

The 3M Company, in collaboration with the National Renewable Energy Laboratory (NREL) and others, will develop the concept of the membrane solvent-extraction (MSE) technology for water removal and verify the technology at a pilot scale for bio-ethanol production to increase energy and water savings.

09 BIOMASS FUELS↗

Extraction of Dry Leaf Spectral Features from Reflectance Spectra of Green Vegetation

Reflectance spectra of green vegetation in the 1.4-2.5 micrometer region are dominated by liquid water absorptions. In this article, we describe the analysis of a set of reflectance spectra of green vegetation, dry vegetation, and liquid water measured in a laboratory using a nonlinear least squares spectral matching technique. We conclude that both the liquid water and the dry materials contribute to the reflectance spectra of green vegetation in the 1.0-2.5 micrometer region. Our matching of data acquired with the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) over two vegetated areas in Oregon Transect with a pure water spectrum also shows a residual absorption feature near 1.72 micrometers.

Gao, Bo-Cai↗

Understanding Self-Assembly and the Stabilization of Liquid/Liquid Interfaces: The Importance of Ligand Tail Branching and Oil-Phase Solvation

Organophosphorus-based ligands represent a versatile set of solvent extraction reagents whose chemical makeup plays an important role in extraction mechanism. We hypothesize that the branching of the extractant hydrophobic tail and its oil-phase solvation affect the liquid/liquid interfacial structure. Understanding the structure mediated adsorption and interfacial ordering becomes key in designing ligands with enhanced selectivity and efficiency for targeted extractions. We employed vibrational sum frequency generation spectroscopy and interfacial tension measurements to extract thermodynamic adsorption energies, map interfacial ordering, and rationalize disparate behaviors of model di-(2-ethylhexyl) phosphoric acid and dioctyl phosphoric acid ligands at the hexadecane water interface. With increased surface loading, ligands with branched hydrophobic tails formed stable interfaces at much lower concentrations than those observed for ligands with linear alkyl tails. The lack of an oil phase and associated solvation results in markedly different interfacial properties, and thus measurements made at air/liquid surfaces cannot be assumed to correlate with the processes occurring at buried liquid/liquid interfaces. Here, we attribute these differences in the surface mediated self-assembly to key variations in hydrophobic interactions and tail solvation taking place in the oil phase demonstrating that interactions in both the polar and nonpolar phases are essential to understand self-assembly and function.

36 MATERIALS SCIENCE↗

Formation and Survival of Amino Acids in Space

The detection of deuterium enrichments in meteoritic hydroxy and amino acids demonstrates that there is a connection between organic material in the interstellar medium and in primitive meteorites. It has generally been assumed that such molecules formed via reactions of small deuterium enriched insterstellar precursors in liquid water on a large asteroidal or cometary parent body. We have recently show that the W photolysis of interstellar/presolar ices can produce the amino acids alanine, serine, and glycine, as well as hydroxy acids, and glycerol, all of which have been extracted from the Murchison meteorite. Thus, some of the probiologically interesting organic compounds, compounds found in meteorites may have formed in presolar ice and have not solely been a product of parent body liquid water chemistry. We will report on our isotopic labeling studies of the mechanism of formation of these interesting compounds, and on astrophysically relevant kinetic studies UV photodecomposition of amino acid precursors in the solid state. This is our first year of exobiology funding on this project.

Bernstein, M. P.↗

Formation and Survival of Amino Acids in Space

The detection of deuterium enrichments in meteoritic hydroxy and amino acids demonstrates that there is a connection between organic material in the interstellar medium and in piimitive meteorites. It has generally been assumed that such molecules formed via reactions of small deuterium enriched insterstellar precursors in liquid water on a large asteroidal or cometary parent body. We have recently show that the W photolysis of interstellar/presolar ices can produce the amino acids alanine, serine, and glycine, as well as hydroxy acids, and glycerol, all of which have been extracted from the Murchison meteorite. Thus, some of the probiologically interesting organic compounds compounds found in meteorites may have formed in presolar ice and have not solely been a product of parent body liquid water chemistry. We will report on our isotopic labeling studies of the mechanism of formation of these inteiesting compounds, and on astrophysically relevant kinetic studies UV photo-decomposition of amino acid precursors in the solid state. This is our first year of exobiology funding on this project.

Bernstein, M. P.↗

Microgravity Liquid-Gas Two-Phase Flow: Review of Pressure Drop and Heat Transfer Correlations and Guidelines for Equipment Operability

In this report we have catalogued the flow regimes observed in microgravity, summarized correlations for the pressure drop and rate of heat transfer that are commonly used, and discuss the validation of a few correlations from available experimental results. Two-phase flow through some specific components such as bends, tees, filters and pumps are discussed from a physical perspective to guide the designer on how reduced gravity might affect their performance. Phase separation in zero gravity is addressed through the behavior and basic design concepts for devices based on passive centrifugal action, capillary forces, gas extraction through a membrane installed in a channel wall and the use of a syringe with a perforated piston to remove bubbles from small liquid volumes. We address the common instabilities that develop in flow loops owing exclusively to the two-phase nature of the flow, e.g., Ledinegg instability and concentration waves. Finally we briefly review flow metering and gauging; two-phase flow through porous media, where pressure drop and flow regime map correlations in zero-g are a current research topic; and basic operation principles of heat pipes and capillary pumped loops.

liquid-gas↗