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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 595 records · Page 33
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Catalyst mixtures

Catalysts that include at least one catalytically active element and one helper catalyst can be used to increase the rate or lower the overpotential of chemical reactions. The helper catalyst can simultaneously act as a director molecule, suppressing undesired reactions and thus increasing selectivity toward the desired reaction. These catalysts can be useful for a variety of chemical reactions including, in particular, the electrochemical conversion of CO.sub.2 or formic acid. The catalysts can also suppress H.sub.2 evolution, permitting electrochemical cell operation at potentials below RHE. Chemical processes and devices using the catalysts are also disclosed, including processes to produce CO, OH.sup.-, HCO.sup.-, H.sub.2CO, (HCO.sub.2).sup.-, H.sub.2CO.sub.2, CH.sub.3OH, CH.sub.4, C.sub.2H.sub.4, CH.sub.3CH.sub.2OH, CH.sub.3COO.sup.-, CH.sub.3COOH, C.sub.2H.sub.6, O.sub.2, H.sub.2, (COOH).sub.2, or (COO.sup.-).sub.2, and a specific device, namely, a CO.sub.2 sensor.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Radiation Chemistry Research and Capabilities at Idaho National Laboratory

Radiation chemistry research and development to support the nuclear fuel cycle is a key role of the Fuel cycle Science and Technology Division at Idaho National Laboratory. Radiation chemistry research has primarily focused on solvent extraction processed being developed to support advanced aqueous recycle of spent nuclear fuel. This research is supported through a Co-60 Gamma irradiator and a radiolysis/hydrolysis test loop developed to support evaluation of the radiation chemistry of aqueous and organic phases while intimately mixed. Recently, research has expanded, through the Center for Radiation Chemistry Research, to include other area of radiation chemistry such as in solid phase adsorption, spent nuclear fuel, radiation kinetics modeling and formic acid degradation. Research advances will be detailed along with capabilities at INL as well as other institutions with which INL collaborates.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

Electrochemical Corrosion Analysis of Stainless Steels in LALM Pyrolysis Bio-Oil with Organic Corrodents

Pyrolysis bio-oils are corrosive to low alloy steels, e.g., 2.25Cr-1Mo, 5Cr-1Mo, and 9Cr-1Mo grades. To identify the alloys with sufficient bio-oil compatibility, several commercial stainless steels were examined in bio-oil using electrochemical impedance spectroscopy to semi quantitatively assess their corrosion resistance. Low-Ash Low-Moisture (LALM) bio-oil, produced from a forest residue feedstock by the National Renewable Energy Laboratory in Golden, CO, was used as a test liquid for electrochemical impedance spectroscopy measurements. Three organic corrodents, formic acid, catechol, and lactobionic acid, were added into LALM bio-oil to produce test liquids with intentionally increased corrosivity. Corrosion reaction resistance, determined from the impedance data, was used to evaluate the corrosion compatibility of each stainless steel in LALM bio-oil and LALM bio-oil + organic corrodent(s). The results from corrosion reaction resistance indicated that the critical Cr content of stainless steels for corrosion resistance would be greater than 14 wt % if Ni and Mo contents are low but can be as low as 12–13 wt % with appreciable amounts of Ni and Mo.

Jun, Jiheon↗
DOE OSTI2012

Mercury Reduction and Removal from High Level Waste at the Defense Waste Processing Facility - 12511

The Defense Waste Processing Facility processes legacy nuclear waste generated at the Savannah River Site during production of enriched uranium and plutonium required by the Cold War. The nuclear waste is first treated via a complex sequence of controlled chemical reactions and then vitrified into a borosilicate glass form and poured into stainless steel canisters. Converting the nuclear waste into borosilicate glass is a safe, effective way to reduce the volume of the waste and stabilize the radionuclides. One of the constituents in the nuclear waste is mercury, which is present because it served as a catalyst in the dissolution of uranium-aluminum alloy fuel rods. At high temperatures mercury is corrosive to off-gas equipment, this poses a major challenge to the overall vitrification process in separating mercury from the waste stream prior to feeding the high temperature melter. Mercury is currently removed during the chemical process via formic acid reduction followed by steam stripping, which allows elemental mercury to be evaporated with the water vapor generated during boiling. The vapors are then condensed and sent to a hold tank where mercury coalesces and is recovered in the tank's sump via gravity settling. Next, mercury is transferred from the tank sump to a purification cell where it is washed with water and nitric acid and removed from the facility. Throughout the chemical processing cell, compounds of mercury exist in the sludge, condensate, and off-gas; all of which present unique challenges. Mercury removal from sludge waste being fed to the DWPF melter is required to avoid exhausting it to the environment or any negative impacts to the Melter Off-Gas system. The mercury concentration must be reduced to a level of 0.8 wt% or less before being introduced to the melter. Even though this is being successfully accomplished, the material balances accounting for incoming and collected mercury are not equal. In addition, mercury has not been effectively purified and collected in the Mercury Purification Cell (MPC) since 2008. A significant cleaning campaign aims to bring the MPC back up to facility housekeeping standards. Two significant investigations are being undertaken to restore mercury collection. The SMECT mercury pump has been removed from the tank and will be functionally tested. Also, research is being conducted by the Savannah River National Laboratory to determine the effects of antifoam addition on the behavior of mercury. These path forward items will help us better understand what is occurring in the mercury collection system and ultimately lead to an improved DWPF production rate and mercury recovery rate. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Combining CO2 Electrolysis with Biological Upgrading to Fuels and Chemicals: Turning Waste into Fuels

The utilization of flue gas-derived CO2 presents an opportunity to enhance carbon utilization in the bioethanol industry, contributing to the production of valuable products. In the context of a 90 million-gallon-per-year corn ethanol plant generating approximately 30 tons per hour of 99% pure CO2, a collaborative effort involving six national laboratories has been established. This initiative, known as the CO2 Reduction and Upgrading for e-Fuels (CO2RUe) Consortium, is funded by the Department of Energy's BioEnergy Technologies Office (BETO). The primary objective of the CO2RUe Consortium is to explore innovative approaches to harness CO2 as a valuable feedstock. This interdisciplinary consortium integrates electrochemistry with biological upgrading techniques, aiming to yield sustainable, value-added products and aviation fuels. The presentation will delve into the recent advancements in the realms of electrochemistry and biological upgrading, with a specific focus on formic acid and CO. Additionally, the talk will include an analysis of future electricity grid scenarios, technoeconomic evaluations, and life-cycle assessments. These assessments aim to provide a comprehensive understanding of the impacts of various conversion pathways on both cost and carbon intensity. The CO2RUe Consortium is at the forefront of steering the development of economically favorable and sustainable processes for CO2 utilization. The presentation will showcase the consortium's progress in driving the advancement of technology and processes, emphasizing the economic viability and sustainability of CO2 utilization within the broader context of the bioethanol industry.

biological upgrading↗
DOE OSTI2022

Hydroxyl radical yields in the heavy ion radiolysis of water

Scavenging experiments coupled with Monte Carlo track structure and kinetics simulations have been used to determining and understand the yields of hydroxyl radicals in the radiolysis of water with protons and carbon ions. Carbon dioxide production from aerated formic acid solutions with concentrations ranging from 10-3 to 1 mol./dm3 was used as a probe of the time dependence of the hydroxyl radical yield from about 5 ns to 1 ?s. Numerical extrapolation of the results at slightly different ion energies in combination with data from gamma radiolysis experiments allows a systematic analysis of both track average and track segment yields, with considerable track chemistry found to occur on the nanosecond to microsecond time scale. Track chemistry calculations utilizing Monte Carlo track structure simulations and nonhomogeneous independent reaction times diffusion-reaction modeling of product yields reproduce experimental observations. Subsequently, the track simulation methods were used to predict hydroxyl radical kinetics in deaerated and aerated water at neutral pH. Taken with literature data for helium ion beam studies, the results offer insight into the potential for indirect radiation induced damage to biological systems for light ions with very different track structures.

38 - RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCL↗
DOE OSTI2017

Glycolic acid physical properties and impurities assessment

This document has been revised due to recent information that the glycolic acid used in Savannah River National Laboratory (SRNL) experiments contains both formaldehyde and methoxyacetic acid. These impurities were in the glycolic acid used in the testing included in this report and in subsequent testing using DuPont (now called Chemours) supplied Technical Grade 70 wt% glycolic acid. However, these impurities were not reported in earlier revisions. Additional data concerning the properties of glycolic acid have also been added to this report. The Defense Waste Processing Facility (DWPF) is planning to implement a nitric-glycolic acid flowsheets to increase attainment to meet closure commitment dates during Sludge Batch 9. In fiscal year 2009, SRNL was requested to determine the physical properties of formic and glycolic acid blends. Blends of formic acid in glycolic acid were prepared and their physical properties tested. Increasing amounts of glycolic acid led to increases in blend density, viscosity and surface tension as compared to the 90 wt% formic acid that is currently used at DWPF. These increases are small, however, and are not expected to present any difficulties in terms of processing. The effect of sulfur impurities in Technical Grade glycolic acid was studied for its impact on DWPF glass quality. While the glycolic acid specification allows for more sulfate than the current formic acid specification, the ultimate impact is expected to be on the order of 0.033 wt% sulfur in glass. Note that lower sulfur content glycolic acid could likely be procured at some increased cost if deemed necessary. A paper study on the effects of radiation on glycolic acid was performed. The analysis indicates that substitution of glycolic acid for formic acid would not increase the radiolytic production rate of H2 and cause an adverse effect in the Slurry Receipt and Adjustment Tank (SRAT) or Slurry Mix Evaporator (SME) process. It has been cited that glycolic acid solutions that are depleted of O2 when subjected to large radiation doses produced considerable quantities of a non-diffusive polymeric material. Considering a constant air purge is maintained in the SRAT and the solution is continuously mixed, oxygen depletion seems unlikely, however, if this polymer is formed in the SRAT solution, the rheology of the solution may be affected and pumping of the solution may be hindered. However, an irradiation test with a simulated SRAT product supernate containing glycolic acid in an oxygen depleted atmosphere found no evidence of polymerization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1990

Sources and sinks of formic, acetic, and pyruvic acids over central Amazonia. II - Wet season

Potential sources and sinks of formic, acetic, and pyruvic acids over the Amazon forest were investigated using a photochemical model and data collected on gas phase concentrations of these acids in the forest canopy, boundary layer, and free troposphere over the central Amazon Basin during the 1987 wet season. It was found that the atmospheric reactions previously suggested in the literature as sources of carboxylic acids (i.e., the gas phase decomposition of isoprene, the reaction between CH3CO3 and a peroxide, and aqueous phase oxidation of CH2O) appear to be too slow to explain the observed concentrations, suggesting that other atmospheric reactions, so far unidentified, could make a major contribution to the carboxylic acid budgets.

Talbot, R. W.↗
DOE OSTI2012

Corrosion Studies Of Raw And Treated Biomass-Derived Pyrolysis Oils

Rapid pyrolysis of biomass generates a liquid with properties that are particularly attractive for production of hydrocarbons that could be substituted for liquid fuels derived from petroleum. However, the high oxygen content of the biomass derived liquids presents a number of problems because of the high water content and the considerable concentration of carboxylic acids. Measurements of total acid number (TAN) of pyrolysis oil (bio-oil) samples show that values in the 90-100 range are fairly common. This level of acidity has been shown to cause corrosion problems that have to be addressed in the selection of structural materials that are used in the production, subsequent processing, storage and transport of the pyrolysis oils. Chemical analyses have been performed and laboratory corrosion studies have been conducted in order to assess the aggressiveness of the raw pyrolysis oil from several sources as well as the corrosion caused by a bio-oil that has been treated to reduce the acid and oxygen content. Components of biomass pyrolyzers have also been fabricated from various candidate alloys, and these components have been exposed for extended periods during operation of the pyrolyzers. This paper will report on results of these analyses and corrosion studies.

02 PETROLEUM↗
DOE OSTI2013

Flammability Control In A Nuclear Waste Vitrification System

The Defense Waste Processing Facility at the Savannah River Site processes high-level radioactive waste from the processing of nuclear materials that contains dissolved and precipitated metals and radionuclides. Vitrification of this waste into borosilicate glass for ultimate disposal at a geologic repository involves chemically modifying the waste to make it compatible with the glass melter system. Pretreatment steps include removal of excess aluminum by dissolution and washing, and processing with formic and nitric acids to: 1) adjust the reduction-oxidation (redox) potential in the glass melter to reduce radionuclide volatility and improve melt rate; 2) adjust feed rheology; and 3) reduce by steam stripping the amount of mercury that must be processed in the melter. Elimination of formic acid in pretreatment has been studied to eliminate the production of hydrogen in the pretreatment systems, which requires nuclear grade monitoring equipment. An alternative reductant, glycolic acid, has been studied as a substitute for formic acid. However, in the melter, the potential for greater formation of flammable gases exists with glycolic acid. Melter flammability is difficult to control because flammable mixtures can be formed during surges in offgases that both increase the amount of flammable species and decrease the temperature in the vapor space of the melter. A flammable surge can exceed the 60% of the LFL with no way to mitigate it. Therefore, careful control of the melter feed composition based on scaled melter surge testing is required. The results of engineering scale melter tests with the formic-nitric flowsheet and the use of these data in the melter flammability model are presented.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS1989

Mars, clays and the origins of life

To detect life in the Martian soil, tests were designed to look for respiration and photosynthesis. Both tests (labeled release, LR, and pyrolytic release, PR) for life in the Martian soils were positive. However, when the measurement for organic molecules in the soil of Mars was made, none were found. The interpretation given is that the inorganic constituents of the soil of Mars were responsible for these observations. The inorganic analysis of the soil was best fitted by a mixture of minerals: 60 to 80 percent clay, iron oxide, quartz, and soluble salts such as halite (NaCl). The minerals most successful in simulating the PR and LR experiments are iron-rich clays. There is a theory that considers clays as the first organisms capable of replication, mutation, and catalysis, and hence of evolving. Clays are formed when liquid water causes the weathering of rocks. The distribution of ions such as aluminum, magnesium, and iron play the role of bases in the DNA. The information was stored in the distribution of ions in the octahedral and tetrahedral molecules, but that they could, like RNA and DNA, replicate. When the clays replicated, each sheet of clay would be a template for a new sheet. The ion substitutions in one clay sheet would give rise to a complementary or similar pattern on the clay synthesized on its surface. It was theorized that it was on the surface of replicating iron-rich clays that carbon dioxide would be fixed in the light into organic acids such as formic or oxalic acid. If Mars had liquid water during a warm period in its past, clay formation would have been abundant. These clays would have replicated and evolved until the liquid water was removed due to cooling of Mars. It is entirely possible that the Viking mission detected life on Mars, but it was clay life that awaits the return of water to continue its evolution into life based on organic molecules.

Hartman, Hyman↗
DOE OSTI2016

Interactions of methylamine and ammonia with atmospheric nucleation precursor H{sub 2}SO{sub 4} and common organic acids: Thermodynamics and atmospheric implications

Interactions of the two common atmospheric bases, ammonia (NH{sub 3}) and methylamine MA (CH{sub 3}NH{sub 2}), which are considered to be important stabilizers of binary clusters in the Earth’s atmosphere, with H{sub 2}SO{sub 4}, the key atmospheric precursor, and 14 common atmospheric organic acids (COA) (formic (CH{sub 2}O{sub 2}), acetic (C{sub 2}H{sub 4}O{sub 2}), oxalic (C{sub 2}H{sub 2}O{sub 4}), malonic (C{sub 3}H{sub 4}O{sub 4}), succinic (C{sub 4}H{sub 6}O{sub 4}), glutaric acid (C{sub 5}H{sub 8}O{sub 4}), adipic (C{sub 6}H{sub 10}O{sub 4}), benzoic (C{sub 6}H{sub 5}COOH), phenylacetic (C{sub 6}H{sub 5}CH{sub 2}COOH), pyruvic (C{sub 3}H{sub 4}O{sub 3}), maleic acid (C{sub 4}H{sub 4}O{sub 4}), malic (C{sub 4}H{sub 6}O{sub 5}), tartaric (C{sub 4}H{sub 6}O{sub 6}) and pinonic acid (C{sub 10}H{sub 16}O{sub 3})) have been studied using the composite high-accuracy G3MP2 method. The thermodynamic stability of mixed (COA) (H{sub 2}SO{sub 4}), (COA)(B1) and (COA)(B2) dimers and (COA) (H{sub 2}SO{sub 4}) (B1) and (COA) (H{sub 2}SO{sub 4}) (B1) trimers, where B1 and B2 represent methylamine (CH{sub 3}NH{sub 2}) and ammonia (NH{sub 3}), respectively, have been investigated and their impacts on the thermodynamic stability of clusters containing H{sub 2}SO{sub 4} have been analyzed. It has been shown that in many cases the interactions of H{sub 2}SO{sub 4} with COA, ammonia and methylamine lead to the formation of heteromolecular dimers and trimers, which are certainly more stable than (H{sub 2}SO{sub 4}){sub 2} and (H{sub 2}SO{sub 4}){sub 3}. It has also been found that free energies of (COA) (H{sub 2}SO{sub 4})+ CH{sub 3}NH{sub 2}⇔(COA) (H{sub 2}SO{sub 4})(CH{sub 3}NH{sub 2}) reactions exceed 10-15 kcal mol{sup −1}. This is a clear indication that mixed trimers composed of COA, H{sub 2}SO{sub 4} and methylamine are very stable and can thus serve as possible nucleation sites. The present study leads us to conclude that the interactions of COA coexisting with H{sub 2}SO{sub 4} and common atmospheric bases in the Earth’s atmosphere may be an important factor affecting the stability of nucleating sulfuric acid clusters and that the impacts of COA on atmospheric nucleation should be studied in further details.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Corrosion Behavior of a Reactive Bond Between Stainless Steel and a Cast AlCeMg Alloy

Corrosion is a longstanding issue for metal components, especially those used in heat exchanger applications. Al–Ce–Mg alloys may provide a potential solution to this problem due to their good mechanical properties and potential reaction bonding with other metals. The reaction bonding involves a “reactive” bond that occurs upon casting of Al–Ce–Mg alloy over stainless steel (SS). Here this study examined the corrosion response of Al–2Ce–6Mg (atomic percent)/(SS) reactive bond interfaces after samples were completely submerged in nitric, sulfuric, formic, and mixed acids for 267 h. Scanning electron microscopy revealed that in the as-cut condition, reactive bond formations were seen frequently throughout the length of the casting and maintained a secure bond between the alloy and the SS tubes. Furthermore, the nitric, sulfuric, and the mixed acids did not have a deleterious effect on the reactive bond structure. However, formic acid did produce changes in both the microstructural appearance and the elemental profile across the bond due to the formation of corrosion reaction products on the acid-exposed surface.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Corrosion Resistance of an AlCeMg/Stainless-Steel Reactive Bond

A major issue for metal components in many industries is corrosion as it can substantially reduce their lifetime. This issue is especially problematic for materials used in heat exchanger applications. Al–Ce–Mg alloys, which exhibit corrosion resistance and can reactively bond with other metals, may be a viable solution to this problem. This investigation studied the corrosion behavior of Al–2Ce–6Mg (atomic percent)/stainless-steel (SS) reactive bond interfaces after full immersion in nitric, sulfuric, formic, and mixed acid for 267 h. This particular Al–Ce–Mg alloy was chosen due to its good castability. The results of scanning electron microscope characterization showed that reactive bond formations repeatedly occurred throughout the length of the casting in the as-cut samples and that these formations maintained a secure bonding between the alloy and the stainless-steel tubes. Transmission electron microscopy results showed that there was a clear compositional and microstructural transition across the reactive bond. The results of the immersion tests indicated that the nitric, sulfuric, and the mixed acid did not have an observably negative effect on the reactive bond structure. As for the sample exposed to formic acid only, noticable changes were seen in both the microstructural appearance and the elemental profile across the bond, suggesting that oxide formation occurred.

Brechtl, Jamieson [ORNL] (ORCID:0000000217394283)↗
DOE OSTI2025

Carboxylic acid induced restructuring of the Fe 3 O 4 (001) surface

The redox properties of Fe 3 O 4 surfaces are central to many catalytic processes and enable dynamic, reduction-induced morphological restructuring during reactions. Here, we investigate the structural changes of the Fe 3 O 4 (001) surface during the decomposition of formic and acetic acids using scanning tunneling microscopy, X-ray photoelectron spectroscopy, and density functional theory (DFT) calculations. Both acids readily deprotonate, forming ordered carboxylate overlayers on the surface. Product formation pathways involve the removal of lattice oxygen, resulting in extensive surface restructuring. For formic acid, only a modest level of surface oxygen removal (∼3%) is observed, resulting in elongated pits along the octahedral Fe rows and exhibiting an aspect ratio of ∼3. In contrast, acetic acid induces more extensive reduction, with the removal of ∼20% of surface oxygen, yielding significantly larger pits while maintaining a similar aspect ratio. Repeated exposure to acetic acid further enlarges the pits, indicating preferential etching at step edges. DFT calculations reveal a mechanistic sequence in which lattice oxygen removal destabilizes adjacent Fe atoms, promoting their migration into the bulk and subsequent pit propagation and step edge formation. Together, these findings provide atomistic insights into the coupling between carboxylic acid conversion and oxide surface restructuring, underscoring the strong interplay between redox chemistry and morphological changes on catalytically active Fe 3 O 4 surfaces.

Ortiz-Garcia, José J. [Pacific Northwest National ↗
DOE OSTI2022

Modeling the Solvation and Acidity of Carboxylic Acids Using an Ab Initio Deep Neural Network Potential

Formic and acetic acid constitute the simplest of carboxylic acids, yet they exhibit fascinating chemistry in the condensed phase such as proton transfer and dimerization. The go-to method of choice for modeling these rare events have been accurate but expensive ab-initio molecular dynamics simulations. Here, we present a deep neural network potential trained using accurate ab-initio data that can be used in tandem with enhanced-sampling methods to perform an efficient exploration of the free-energy surface of aqueous solutions of weak carboxylic acids. In particular, we show that our model captures proton dissociation and provides a good estimate of the pK a , as well as the dimerization of formic and acetic acid. This provides a suitable starting point for applications in different research areas where computational efficiency coupled with the accuracy of ab-initio methods is required.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗