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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 1,099 records · Page 61
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

Bio-Oil Separation and Stabilization by Near-Critical Propane Fractionation

Bio-oils produced by thermal process are promising sources of sustainable, low greenhouse gas alternative fuels. These thermal processes are also well suited to decentralized energy production due to low capital and operating costs. Algae feedstocks for bio-oil production are of particular interest, due in part to their high-energy growth yields. Further, algae can be grown in non-arable areas in fresh, brackish, salt water, or even waste water. Unfortunately, bio-oils produced by thermal processes present significant stability challenges. These oils have complex chemical compositions, are viscous, reactive, and thermally unstable. Further, the components within the oils are difficult to separate by fractional distillation. By far, the most effective separation and stabilization method has been solvent extraction. However, liquid phase extraction processes pose two main obstacles to commercialization; they require a significant amount of energy to remove and recover the solvent from the product, and they have a propensity for the solvent to become contaminated with minerals from the char and ash present in the original bio-oil. Separation and fractionation of thermally produced bio-oils using supercritical fluids (SCF) offers the advantages of liquid solvent extraction while drastically reducing energy demands and the predisposition to carry over solids into the extracted phase. SCFs are dense fluids with liquid-like solvent properties and gas-like transport properties. Further, SCF density and solvent strength can be tuned with minor adjustments in pressure, co-solvent addition, or gas anti-solvent addition. Catalytic pyrolysis oils were produced from Scenedesmus dimorphus algae using a fluid catalytic cracking catalyst. Bio-oil produced from catalytic fast pyrolysis (CFP) was separated using critical fluids. Propane extraction was performed at 65 °C at a fluid reduced pressure of 2.0 (85 bar) using an eight to one solvent to feed ratio by weight. Extraction of catalytic fast pyrolysis oil with near critical propane produced an oil extract that was physically and chemically different from and more stable than the original oil. The propane extract displayed lower viscosity and lower average molecular weight. The species present in the propane extract were likely the less polar that would be expected from using a non-polar solvent (propane). Carbonyl containing species in the extract were likely ketones and esters. The raffinate contained a higher amnount of OH bonded species along with the more polar more polar acids, amides, and alcohols. The higher concentration of nitrogen in the raffinate may confirm the presence of amides. Viscosity of the propane extract increased only half as much as that of the CFP bio-oil. Further, In situ NMR aging studies showed that the propane extract was more stable than the raw oil. In conclusion, propane extraction is a promising method to decrease the nitrogen content of bio-oils and to improve the stability of bio-oils obtained by the catalytic pyrolysis of algae based biomass.

09 BIOMASS FUELS↗
DOE OSTI2018

Arctic Methane, Carbon Aerosols, and Tracers Study Field Campaign Report

The Arctic Methane, Carbon Aerosols, and Tracers Study was a measurement campaign at the National Oceanic and Atmospheric Administration (NOAA) Barrow Observatory and U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) Climate Research Facility North Slope of Alaska (NSA) sites in Barrow (formerly known as Utqiagvik) that involved the deployment of instruments to measure CH4, black carbon (BC), and source tracers. The campaign ran from September 1, 2014 to September 1, 2016 and was extended until July 30, 2017. We deployed an in situ instrument to measure methane, the ratio of its isotopologues 13CH4/12CH4, and ethane. We deployed a second instrument to measure carbon monoxide, carbonyl sulfide (COS), carbon dioxide, and water vapor. We also deployed an in situ instrument to measure BC, a single-particle soot photometer (SP2), at the nearby NOAA Barrow Observatory, co-located with the other NOAA aerosol instruments. Changes in emissions across different regions and seasons will be inferred using atmospheric transport and inverse modeling techniques.

North Slope of Alaska, trace gases, black carbon, ↗
DOE OSTI2018

Rechargeable alkaline battery using organic materials as negative electrodes

An energy storage device may provide a positive electrode, an electrolyte, and a negative electrode. The energy storage device may utilize an aqueous alkaline electrolyte, which may be nonflammable. The energy storage device may utilize organic material(s) as the negative electrode, such as, but not limited to, poly(anthraquinonyl sulfide) (PAQS), organic carbonyl compounds, organosulfur compounds, redox polymers, or radical polymers.

25 ENERGY STORAGE↗
DOE OSTI2018

Carbon composition with hierarchical porosity, and methods of preparation

A method for fabricating a porous carbon material possessing a hierarchical porosity, the method comprising subjecting a precursor composition to a curing step followed by a carbonization step, the precursor composition comprising: (i) a templating component comprised of a block copolymer, (ii) a phenolic component, (iii) a dione component in which carbonyl groups are adjacent, and (iv) an acidic component, wherein said carbonization step comprises heating the precursor composition at a carbonizing temperature for sufficient time to convert the precursor composition to a carbon material possessing a hierarchical porosity comprised of mesopores and macropores. Also described are the resulting hierarchical porous carbon material, a capacitive deionization device in which the porous carbon material is incorporated, as well as methods for desalinating water by use of said capacitive deionization device.

Mayes, Richard T.↗
DOE OSTI2019

Aqueous energy storage devices with organic electrode materials

An aqueous metal-ion battery and a method for constructing same. In one embodiment, the battery includes an aqueous electrolyte and at least one electrode comprising at least one organic electrode material. A method comprises incorporating an organic electrode material into the electrode of an aqueous metal-ion battery. The organic electrode material further comprises at least one material chosen from carbonyl compounds.

Yao, Yan↗
DOE OSTI2020

Method for preparing bis-(silylalkyl)carbonate esters

Carbonate esters of Formula (I): (R1)(R2)(R3)Si—R4—O—C(═O)—O—R4—Si(R1)(R2)(R3) are prepared by reaction of a silyl-substituted alcohol of Formula (II): (R1)(R2)(R3)Si—R4—OH with an activated carbonyl compound of Formula (III): C(═O)Z2 in the presence of a catalyst (e.g., an bicyclic amidine, a bicyclic guanidine, or a phosphazene) in an aprotic solvent. In Formulas (I) and (II) each of R1 and R2 independently is alkyl; R3 is alkyl or —X1—Si(R5)(R6)(R7); X1 is O or alkylene; R4 is alkylene; and each R5, R6, and R7 independently is alkyl. In Formula (III), Z is 1-N-imidazolyl or 1-N-succinimidyl. In some embodiments, the catalyst used in the methods described herein comprises at least one base selected from the group consisting of a bicyclic amidine and a bicyclic guanidine. The reaction proceeds readily under both bulk and continuous flow reactor conditions.

25 ENERGY STORAGE↗
DOE OSTI2020

Carbon composition with hierarchical porosity, and methods of preparation

A method for fabricating a porous carbon material possessing a hierarchical porosity, the method comprising subjecting a precursor composition to a curing step followed by a carbonization step, the precursor composition comprising: (i) a templating component comprised of a block copolymer, (ii) a phenolic component, (iii) a dione component in which carbonyl groups are adjacent, and (iv) an acidic component, wherein said carbonization step comprises heating the precursor composition at a carbonizing temperature for sufficient time to convert the precursor composition to a carbon material possessing a hierarchical porosity comprised of mesopores and macropores. Also described are the resulting hierarchical porous carbon material, a capacitive deionization device in which the porous carbon material is incorporated, as well as methods for desalinating water by use of said capacitive deionization device.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Pyrolysis Vapor and Bio-Oil Preconditioning via Ex Situ Hydrodeoxygenation and Alkylation Using a Heteropolyacid Catalyst

Ex situ catalytic preconditioning of biomass pyrolysis vapors (partial deoxygenation) has the potential for both reducing the oxygen content and beneficially influencing the oxygen speciation of condense bio-oils for enhancement of downstream condensed phase upgrading processes. Here, condensed phase upgrading processes may refer to both coprocessing and hydroprocessing with vacuum gas-oil (VGO). Reduction of oxygen content to produce bio-oils with greater hydrophobicity can enhance VGO-solubility while tailoring of oxygen speciation by removal of reactive carbonyls (e.g., acetic acid) can lessen catalytic deactivation via coking reactions. 1,2 Furthermore, enhanced VGO-solubility and reduced coking leads to greater biogenic carbon incorporation in end-products from condensed phase upgrading processes. By leveraging the hydrodeoxygenation and alkylation activity of a titania-supported molybdenum-heteropolyacid (Mo-HPA/TiO2) catalyst, pyrolysis vapors and resulting condensed bio-oils were effectively preconditioned for downstream upgrading. 3 Data regarding the use of Mo-HPA/TiO2 for pyrolysis vapor preconditioning will be presented on, including method of employment, catalyst characterization, and impacts on bio-oil in relation to downstream condensed phase upgrading processes. Our approach is to: Compare Mo-HPA/TiO2 product distribution to HZSM-5; Investigate Mo-HPA/TiO2 regeneration and characterize changes in acid site character; Assess product differences in terms of enhanced VGO-solubility.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2020

Rechargeable alkaline battery using organic materials as negative electrodes

An energy storage device may provide a positive electrode, an electrolyte, and a negative electrode. The energy storage device may utilize an aqueous alkaline electrolyte, which may be nonflammable. The energy storage device may utilize organic material(s) as the negative electrode, such as, but not limited to, poly(anthraquinonyl sulfide) (PAQS), organic carbonyl compounds, organosulfur compounds, redox polymers, or radical polymers.

25 ENERGY STORAGE↗
DOE OSTI2021

BETO 2021 Peer Review - Analytical Development and Standardization for Biomass-Derived Thermochemical Liquids

This project began in FY14 to address the lack of standard chemical characterization analytical methods for bio-oils. Bio-oils are very complex and present numerous analytical challenges; yet reliable chemical information (quantification of both individual compounds and chemical functional groups) is needed to inform upgrading research and refinery co-processing. In this project, analysis needs are first determined from engaging the bioenergy community. Next, standard methods are developed to meet these needs, and then subsequently validated via inter-laboratory studies. Methods that are successfully validated (< 10% variability) are then shared as Laboratory Analytical Procedures (LAPs), which are free and publicly available. We have been tracking LAP use and have seen sustained usage as evidenced by an average of 500 pages views and 100 downloads per quarter, demonstrating the value of these methods to the bioenergy community. LAP methods that are particularly useful and reliable will be chosen for the next-level of standardization through ASTM. We have recently achieved approval by ASTM for our carbonyl titration method. This method (ASTM E3146) is the first example of an ASTM standard solely focused on the chemical characterization of bio-oils. Work in this project is meeting the analysis needs of the bioenergy community and will ultimately help enable the commoditization of bio-oils.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2021

Feedstock and Catalyst Impact on Bio-Oil Production and FCC Co-Processing to Fuels

NREL’s thermochemical biomass conversion research is focused on ex-situ upgrading of biomass fast-pyrolysis (FP) vapors as an efficient and economical route to completely biogenic pyrolysis-based fuel precursors, potential fuels, and value-added chemicals depending on catalyst choice and process conditions. In this approach, biomass vapors are generated via fast pyrolysis with destabilizing vapor components (char, inorganics, tar aerosols) removed by hot gas filtration to produce conditioned vapors more responsive to catalytic upgrading. A Davison Circulating Riser (DCR), a petroleum industry standard for fluidized catalytic cracking (FCC) catalyst evaluation, was coupled with a custom pyrolyzer system designed to produce consistent composition pyrolysis vapors as feed to the DCR. The coupled system is shown below (Figure 1). Pyrolysis vapors, derived from pure hardwood and softwood, were upgraded using commercially available and laboratory modified zeolite-based catalysts. Upgraded oils were analyzed via 31P and 13C NMR spectroscopy, GCxGC-TOF/MS, carbonyl and ultimate analysis (CHNO), and micro distillation to assess both oil chemistry and distillation behavior as they relate to catalyst and feedstock type for producing fungible hydrocarbon product liquids. Measured process parameters identified from technoeconomic process analysis included achieving oil oxygenate contents of 20% or less, carbon-conversion efficiencies of 30% or more, and catalyst coking rates of 10% or less. A proprietary modified zeolite catalyst from Johnson Matthey produced oils that met these requirements. Using the DCR equipped with a proprietary nozzle system, a second approach focused on reducing the carbon intensity of petroleum-derived hydrocarbon fuels by FCC co-processing these CFP oils with petroleum vacuum gas oil (VGO) to produce biogenic carbon containing fuels. The vapor-phase upgrading results demonstrated for the first time the feasibility of producing refinery-compatible hydrocarbon fuel intermediates entirely from biomass-derived fast-pyrolysis vapors using an industry-accepted DCR system for catalytic upgrading. The co-processing results demonstrated the feasibility of using CFP oils with VGO feeds in FCC refinery operations to produce biogenic carbon containing fuels.

bio-oil↗
DOE OSTI2022

Conversion of lignin to ionic liquids

Disclosed herein are lignin-derived ionic liquids and methods for preparing them. The methods include forming a reaction mixture comprising a lignin-derived starting material, a carbonyl compound, and an amine; maintaining the reaction mixture under conditions sufficient to form a lignin-derived aminophenol; and converting the lignin derived aminophenol to the lignin-derived ionic liquid. Monomeric phenols, oligomeric phenols, and polymeric phenols can be used as lignin-derived starting materials.

Dutta, Tanmoy↗
DOE OSTI2023

Method for conversion of diols to olefin products

A method for converting a diol in solution to an olefin fraction, the method comprising: (i) reacting a diol of the formula HO—R—OH in solution with a carbonyl-containing molecule of the formula: in the presence of an acid catalyst to result in a dioxolane molecule of the formula: wherein R is a hydrocarbon linker containing 1-12 carbon atoms, and R 1 and R 2 are independently selected from hydrogen atom and hydrocarbon groups containing 1-12 carbon atoms, wherein R 1 and R 2 optionally interconnect; (ii) removing the dioxolane molecule from the solution by phase separation; and (iii) contacting the dioxolane molecule with a metal-loaded zeolite at a temperature of 100-500° C. to convert the dioxolane molecule to an olefin fraction.

Li, Zhenglong↗
DOE OSTI2018

In Situ Quantification of [Re(CO) 3 ] + by Fluorescence Spectroscopy in Simulated Hanford Tank Waste

A pretreatment protocol is presented that allows for the quantitative conversion and subsequent in situ spectroscopic analysis of [Re(CO)3]+ species in simulated Hanford tank waste. The protocol encompasses adding a simulated waste sample containing the non-emissive [Re(CO)3]+ species to a developer solution that enables the rapid, quantitative conversion of the non-emissive species to a luminescent species which can then be detected spectroscopically. The [Re(CO)3]+ species concentration in an alkaline, simulated Hanford tank waste supernatant can be quantified by the standard addition method. In a test case, the [Re(CO)3]+ species was measured to be at a concentration of 38.9 µM, which was a difference of 2.01% from the actual concentration of 39.7 µM.

fluorescence detection↗
DOE OSTI2021

Backbonding in Thorium(IV) and Uranium(IV) Diarsenido Complexes with t BuNC and CO

The coordination of tBuNC and CO with the diarsenido complexes (C 5 Me 5 ) 2 An(η 2 -As 2 Mes 2 ), An=Th, U, has been investigated. For the first time, a comparison between isostructural complexes of Th IV and U IV has been possible with CO; density functional calculations indicated an appreciable amount of π backbonding that originates from charge transfer from an actinide-arsenic sigma bond. The calculated CO stretching frequencies in the Th IV and U IV diarsenido complexes are consistent with the experimental measurements, both show large shifts to lower frequency. We demonstrate that the π backbonding is crucial to explaining the red shifts of CO frequency upon An IV complex formation. Interestingly, this interaction essentially correlates to the parallel orientation of π*(C-O) orbitals relative to the An-As bond.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Stabilization of Softwood-Derived Pyrolysis Oils for Continuous Bio-oil Hydroprocessing

The use of fast pyrolysis as a potential renewable liquid transportation fuel alternative to crude oil depends on successful catalytic upgrading to produce a refinery-ready product with oxygen content and qualities (i.e. specific functional group or compound content) that is compatible with the product’s proposed insertion point. Catalytic upgrading of bio-oil requires high temperature and pressure, while similar to crude oil hydrotreating, is not as straightforward for the thermally unstable pyrolysis oil. For years, a two-temperature zone, downflow trickle bed reactor was the state-of-the art for continuous operation. However, pressure excursion due to plug formation still occurred, typically at the high temperature transition zone, leading to a process shutdown within 140 h. Recently, a bio-oil pre-treatment process, together with a robust commercial catalyst, was found to be enabling the continuous operation of the two-zone hydroprocessing system. Here, we report the results on pre-treating bio-oil at 413 K and 8.4 MPa of flowing H2 (500 L H2/L bio-oil, 0.5 L bio-oil/L catalyst bed) and the attempts to characterize this oil product to understand the chemistry which enabled the long-term processing of bio-oil.

carbonyls↗
DOE OSTI2013

Oxidative stress suppresses the cellular bioenergetic effect of the 3-mercaptopyruvate sulfurtransferase/hydrogen sulfide pathway

Highlights: •Oxidative stress impairs 3-MST-derived H{sub 2}S production in isolated enzyme and in isolated mitochondria. •This impairs the stimulatory bioenergetic effects of H{sub 2}S in hepatocytes. •This has implications for the pathophysiology of diseases with oxidative stress. -- Abstract: Recent data show that lower concentrations of hydrogen sulfide (H{sub 2}S), as well as endogenous, intramitochondrial production of H{sub 2}S by the 3-mercaptopyruvate (3-MP)/3-mercaptopyruvate sulfurtransferase (3-MST) pathway serves as an electron donor and inorganic source of energy to support mitochondrial electron transport and ATP generation in mammalian cells by donating electrons to Complex II. The aim of our study was to investigate the role of oxidative stress on the activity of the 3-MP/3-MST/H{sub 2}S pathway in vitro. Hydrogen peroxide (H{sub 2}O{sub 2}, 100–500 μM) caused a concentration-dependent decrease in the activity of recombinant mouse 3-MST enzyme. In mitochondria isolated from murine hepatoma cells, H{sub 2}O{sub 2} (50–500 μM) caused a concentration-dependent decrease in production of H{sub 2}S from 3-MP. In cultured murine hepatoma cells H{sub 2}O{sub 2}, (3–100 μM), did not result in overall cytotoxicity, but caused a partial decrease in basal oxygen consumption and respiratory reserve rapacity. The positive bioenergetic effect of 3-MP (100–300 nM) was completely abolished by pre-treatment of the cells with H{sub 2}O{sub 2} (50 μM). The current findings demonstrate that oxidative stress inhibits 3-MST activity and interferes with the positive bioenergetic role of the 3-MP/3-MST/H{sub 2}S pathway. These findings may have implications for the pathophysiology of various conditions associated with increased oxidative stress, such as various forms of critical illness, cardiovascular diseases, diabetes or physiological aging.

60 APPLIED LIFE SCIENCES↗