National Library of Energy BETA

Sample records for oxygenate methyl tertiary

  1. State Restrictions on Methyl Tertiary Butyl Ether (released in AEO2006)

    Reports and Publications

    2006-01-01

    By the end of 2005, 25 states had barred, or passed laws banning, any more than trace levels of methyl tertiary butyl ether (MTBE) in their gasoline supplies, and legislation to ban MTBE was pending in 4 others. Some state laws address only MTBE; others also address ethers such as ethyl tertiary butyl ether (ETBE) and tertiary amyl methyl ether (TAME). Annual Energy Outlook 2006 assumes that all state MTBE bans prohibit the use of all ethers for gasoline blending.

  2. Enhanced diisobutene production in the presence of methyl tertiary butyl ether

    DOE Patents [OSTI]

    Smith, Jr., Lawrence A. (Bellaire, TX)

    1983-01-01

    In the liquid phase reaction of isobutene in the presence of resin cation exchange resins with itself in a C.sub.4 hydrocarbon stream to form dimers, the formation of higher polymers, oligomers, and co-dimer by-products is suppressed by the presence of 0.0001 to 1 mole per mole of isobutene of methyl tertiary butyl ether.

  3. Enhanced diisobutene production in the presence of methyl tertiary butyl ether

    DOE Patents [OSTI]

    Smith, L.A. Jr.

    1983-03-01

    In the liquid phase reaction of isobutene in the presence of resin cation exchange resins with itself in a C[sub 4] hydrocarbon stream to form dimers, the formation of higher polymers, oligomers, and co-dimer by-products is suppressed by the presence of 0.0001 to 1 mole per mole of isobutene of methyl tertiary butyl ether. 1 fig.

  4. Oxygenates du`jour...MTBE? Ethanol? ETBE?

    SciTech Connect (OSTI)

    Wolfe, R.

    1995-12-31

    There are many different liquids that contain oxygen which could be blended into gasoline. The ones that have been tried and make the most sense are in the alcohol (R-OH) and ether (R-O-R) chemical family. The alcohols considered are: methanol (MeOH), ethanol (EtOH), tertiary butyl alcohol (TBA). The ethers are: methyl tertiary butyl ether (MTBE), ethyl tertiary butyl ether (ETBE), tertiary amyl methyl ether (TAME), tertiary amyl ethyl ether (TAEE), di-isopropyl ether (DIPE). Of the eight oxygenates listed above, the author describes the five that are still waiting for widespread marketing acceptance (methanol, TBA, TAME, TAEE, and DIPE). He then discusses the two most widely used oxygenates in the US, MTBE and ethanol, along with the up-and-coming ethanol ether, ETBE. Selected physical properties for all of these oxygenates can be found in Table 2 at the end of this paper. A figure shows a simplified alcohol/ether production flow chart for the oxygenates listed above and how they are interrelated.

  5. Oxygenate Supply/Demand Balances in the Short-Term Integrated Forecasting Model (Released in the STEO March 1998)

    Reports and Publications

    1998-01-01

    The blending of oxygenates, such as fuel ethanol and methyl tertiary butyl ether (MTBE), into motor gasoline has increased dramatically in the last few years because of the oxygenated and reformulated gasoline programs. Because of the significant role oxygenates now have in petroleum product markets, the Short-Term Integrated Forecasting System (STIFS) was revised to include supply and demand balances for fuel ethanol and MTBE. The STIFS model is used for producing forecasts in the Short-Term Energy Outlook. A review of the historical data sources and forecasting methodology for oxygenate production, imports, inventories, and demand is presented in this report.

  6. MTBE, Oxygenates, and Motor Gasoline (Released in the STEO October 1999)

    Reports and Publications

    1999-01-01

    The blending of methyl tertiary butyl ether (MTBE) into motor gasoline has increased dramatically since it was first produced 20 years ago. MTBE usage grew in the early 1980's in response to octane demand resulting initially from the phaseout of lead from gasoline and later from rising demand for premium gasoline. The oxygenated gasoline program stimulated an increase in MTBE production between 1990 and 1994. MTBE demand increased from 83,000 in 1990 to 161,000 barrels per day in 1994. The reformulated gasoline (RFG) program provided a further boost to oxygenate blending. The MTBE contained in motor gasoline increased to 269,000 barrels per day by 1997.

  7. Activation of water soluble amines by halogens for trapping methyl radioactive iodine from air streams

    DOE Patents [OSTI]

    Deitz, Victor R.; Blachly, Charles H.

    1977-01-01

    Gas adsorbent charcoals impregnated with an aqueous solution of the reaction product of a tertiary amine and elemental iodine or bromine are better than 99 per cent efficient in trapping methyl iodine.sup.131. The chemical addition of iodine or bromine to the tertiary amine molecule increases the efficiency of the impregnated charcoal as a trapping agent, and in conjunction with the high flash point of the tertiary amine raises the ignition temperature of the impregnated charcoal.

  8. Fuel Ethanol Oxygenate Production

    Gasoline and Diesel Fuel Update

    Product: Fuel Ethanol Methyl Tertiary Butyl Ether Merchant Plants Captive Plants Period-Unit: Monthly-Thousand Barrels Monthly-Thousand Barrels per Day Annual-Thousand Barrels Annual-Thousand Barrels per Day Download Series History Download Series History Definitions, Sources & Notes Definitions, Sources & Notes Show Data By: Product Area Mar-16 Apr-16 May-16 Jun-16 Jul-16 Aug-16 View History U.S. 30,812 28,059 30,228 30,258 31,251 31,669 1981-2016 East Coast (PADD 1) 804 725 734 812 862

  9. Combustion characterization of methylal in reciprocating engines

    SciTech Connect (OSTI)

    Dodge, L.; Naegeli, D.

    1994-06-01

    Methylal, CH{sub 3}OCH{sub 2}OCH{sub 3}, also known as dimethoxy-methane, is unique among oxygenates in that it has a low autoignition temperature, no carbon-carbon bonds, and is soluble in middle distillate fuels. Because of these properties, methylal has been shown to be a favorable fuel additive for reducing smoke in diesel engines. Recent measurements of ignition delay times indicate that methylal has a cetane number in the range of 45-50, which is compatible with diesel fuels. Engine tests have shown that adding methylal to diesel fuel significantly reduces smoke emissions. Gaseous emissions and combustion efficiencies obtained with methylal/diesel fuel blends remain essentially the same as those measured using neat diesel fuel. Lubricity measurements of methylal/diesel fuel blends with a ball on cylinder lubrication evaluator (BOCLE) show that methylal improves the lubricity of diesel fuel. Even though additions of methylal lower the fuel viscosity, the results of the BOCLE tests indicate that the methylal/diesel fuel blends cause less pump wear than neat diesel fuel. The one drawback is that methylal has a low boiling point (42{degrees}C) and a relatively high vapor pressure. As a result, it lowers the flash point of diesel fuel and causes a potential fuel tank flammability hazard. One solution to this increased volatility is to make polyoxymethylenes with the general formula of CH{sub 3}O(CH{sub 2}O){sub x}CH{sub 3} where x > 2. The molecules are similar to methylal, but have higher molecular weights and thus higher viscosities and substantially lower vapor pressures. Therefore, their flash points will be compatible with regular diesel fuel. The polyoxymethylenes are expected to have combustion properties similar to methylal. It is theorized that by analogy with hydrocarbons, the ignition quality (i.e., cetane number) of the polyoxymethylenes will be better than that of methylal.

  10. Total Blender Net Input of Petroleum Products

    U.S. Energy Information Administration (EIA) (indexed site)

    Normal Butane Isobutane Other Liquids OxygenatesRenewables Oxygenates (excl. Fuel Ethanol) Methyl Tertiary Butyl Ether (MTBE) All Other Oxygenates Renewable Fuels (incl. Fuel Ethanol...

  11. Methylal and Methylal-Diesel Blended Fuels from Use In Compression-Ignition Engines

    SciTech Connect (OSTI)

    Keith D. Vertin; James M. Ohi; David W. Naegeli; Kenneth H. Childress; Gary P. Hagen; Chris I. McCarthy; Adelbert S. Cheng; Robert W. Dibble

    1999-05-05

    Gas-to-liquids catalytic conversion technologies show promise for liberating stranded natural gas reserves and for achieving energy diversity worldwide. Some gas-to-liquids products are used as transportation fuels and as blendstocks for upgrading crude derived fuels. Methylal (CH{sub 3}-O-CH{sub 2}-O-CH{sub 3}) also known as dimethoxymethane or DMM, is a gas-to-liquid chemical that has been evaluated for use as a diesel fuel component. Methylal contains 42% oxygen by weight and is soluble in diesel fuel. The physical and chemical properties of neat methylal and for blends of methylal in conventional diesel fuel are presented. Methylal was found to be more volatile than diesel fuel, and special precautions for distribution and fuel tank storage are discussed. Steady state engine tests were also performed using an unmodified Cummins 85.9 turbocharged diesel engine to examine the effect of methylal blend concentration on performance and emissions. Substantial reductions of particulate matter emissions h ave been demonstrated 3r IO to 30% blends of methylal in diesel fuel. This research indicates that methylal may be an effective blendstock for diesel fuel provided design changes are made to vehicle fuel handling systems.

  12. Oxygen analyzer

    DOE Patents [OSTI]

    Benner, William H.

    1986-01-01

    An oxygen analyzer which identifies and classifies microgram quantities of oxygen in ambient particulate matter and for quantitating organic oxygen in solvent extracts of ambient particulate matter. A sample is pyrolyzed in oxygen-free nitrogen gas (N.sub.2), and the resulting oxygen quantitatively converted to carbon monoxide (CO) by contact with hot granular carbon (C). Two analysis modes are made possible: (1) rapid determination of total pyrolyzable oxygen obtained by decomposing the sample at 1135.degree. C., or (2) temperature-programmed oxygen thermal analysis obtained by heating the sample from room temperature to 1135.degree. C. as a function of time. The analyzer basically comprises a pyrolysis tube containing a bed of granular carbon under N.sub.2, ovens used to heat the carbon and/or decompose the sample, and a non-dispersive infrared CO detector coupled to a mini-computer to quantitate oxygen in the decomposition products and control oven heating.

  13. An Experimental and Kinetic Modeling Study of Methyl Decanoate Combustion

    SciTech Connect (OSTI)

    Sarathy, S M; Thomson, M J; Pitz, W J; Lu, T

    2010-02-19

    Biodiesel is typically a mixture of long chain fatty acid methyl esters for use in compression ignition engines. Improving biofuel engine performance requires understanding its fundamental combustion properties and the pathways of combustion. This research study presents new combustion data for methyl decanoate in an opposed-flow diffusion flame. An improved detailed chemical kinetic model for methyl decanoate combustion is developed, which serves as the basis for deriving a skeletal mechanism via the direct relation graph method. The novel skeletal mechanism consists of 648 species and 2998 reactions. This mechanism well predicts the methyl decanoate opposed-flow diffusion flame data. The results from the flame simulations indicate that methyl decanoate is consumed via abstraction of hydrogen atoms to produce fuel radicals, which lead to the production of alkenes. The ester moiety in methyl decanoate leads to the formation of low molecular weight oxygenated compounds such as carbon monoxide, formaldehyde, and ketene.

  14. Oxygen analyzer

    DOE Patents [OSTI]

    Benner, W.H.

    1984-05-08

    An oxygen analyzer which identifies and classifies microgram quantities of oxygen in ambient particulate matter and for quantitating organic oxygen in solvent extracts of ambient particulate matter. A sample is pyrolyzed in oxygen-free nitrogen gas (N/sub 2/), and the resulting oxygen quantitatively converted to carbon monoxide (CO) by contact with hot granular carbon (C). Two analysis modes are made possible: (1) rapid determination of total pyrolyzable obtained by decomposing the sample at 1135/sup 0/C, or (2) temperature-programmed oxygen thermal analysis obtained by heating the sample from room temperature to 1135/sup 0/C as a function of time. The analyzer basically comprises a pyrolysis tube containing a bed of granular carbon under N/sub 2/, ovens used to heat the carbon and/or decompose the sample, and a non-dispersive infrared CO detector coupled to a mini-computer to quantitate oxygen in the decomposition products and control oven heating.

  15. Apolipoprotein AI tertiary structures determine stability and

    Office of Scientific and Technical Information (OSTI)

    phospholipid-binding activity of discoidal high-density lipoprotein particles of different sizes (Journal Article) | SciTech Connect Apolipoprotein AI tertiary structures determine stability and phospholipid-binding activity of discoidal high-density lipoprotein particles of different sizes Citation Details In-Document Search Title: Apolipoprotein AI tertiary structures determine stability and phospholipid-binding activity of discoidal high-density lipoprotein particles of different sizes

  16. untitled

    Gasoline and Diesel Fuel Update

    of "other" hydrocarbons and oxygenates include hydrogen and oxygenates especially fuel ethanol and methyl tertiary butyl ether (MTBE). The adjustment is equal to the...

  17. Cooperative Tertiary Interaction Network Guides RNA Folding

    SciTech Connect (OSTI)

    Behrouzi, Reza; Roh, Joon Ho; Kilburn, Duncan; Briber, R.M.; Woodson, Sarah A.

    2013-04-08

    Noncoding RNAs form unique 3D structures, which perform many regulatory functions. To understand how RNAs fold uniquely despite a small number of tertiary interaction motifs, we mutated the major tertiary interactions in a group I ribozyme by single-base substitutions. The resulting perturbations to the folding energy landscape were measured using SAXS, ribozyme activity, hydroxyl radical footprinting, and native PAGE. Double- and triple-mutant cycles show that most tertiary interactions have a small effect on the stability of the native state. Instead, the formation of core and peripheral structural motifs is cooperatively linked in near-native folding intermediates, and this cooperativity depends on the native helix orientation. The emergence of a cooperative interaction network at an early stage of folding suppresses nonnative structures and guides the search for the native state. We suggest that cooperativity in noncoding RNAs arose from natural selection of architectures conducive to forming a unique, stable fold.

  18. Oxygenates from synthesis gas

    SciTech Connect (OSTI)

    Falter, W.; Keim, W.

    1994-12-31

    The direct synthesis of oxygenates starting from synthesis gas is feasible by homogeneous and heterogeneous catalysis. Homogeneous Rh and Ru based catalysts yielding methyl formate and alcohols will be presented. Interestingly, modified heterogeneous catalysts based on {open_quotes}Isobutyl Oel{close_quotes} catalysis, practized in Germany (BRD) up to 1952 and in the former DDR until recently, yield isobutanol in addition to methanol. These {open_quotes}Isobutyl Oel{close_quotes} catalysts are obtained by adding a base such as Li < Na < K < Cs to a Zn-Cr{sub 2}O{sub 3} methanol catalyst. Isobutanol is obtained in up to 15% yield. Our best catalyst a Zr-Zn-Mn-Li-Pd catalyst produced isobotanol up to 60% at a rate of 740g isobutanol per liter catalyst and hour.

  19. Ethanol Demand in United States Production of Oxygenate-limited Gasoline

    SciTech Connect (OSTI)

    Hadder, G.R.

    2000-08-16

    Ethanol competes with methyl tertiary butyl ether (MTBE) to satisfy oxygen, octane, and volume requirements of certain gasolines. However, MTBE has water quality problems that may create significant market opportunities for ethanol. Oak Ridge National Laboratory (ORNL) has used its Refinery Yield Model to estimate ethanol demand in gasolines with restricted use of MTBE. Reduction of the use of MTBE would increase the costs of gasoline production and possibly reduce the gasoline output of U.S. refineries. The potential gasoline supply problems of an MTBE ban could be mitigated by allowing a modest 3 vol percent MTBE in all gasoline. In the U.S. East and Gulf Coast gasoline producing regions, the 3 vol percent MTBE option results in costs that are 40 percent less than an MTBE ban. In the U.S. Midwest gasoline producing region, with already high use of ethanol, an MTBE ban has minimal effect on ethanol demand unless gasoline producers in other regions bid away the local supply of ethanol. The ethanol/MTBE issue gained momentum in March 2000 when the Clinton Administration announced that it would ask Congress to amend the Clean Air Act to provide the authority to significantly reduce or eliminate the use of MTBE; to ensure that air quality gains are not diminished as MTBE use is reduced; and to replace the existing oxygenate requirement in the Clean Air Act with a renewable fuel standard for all gasoline. Premises for the ORNL study are consistent with the Administration announcement, and the ethanol demand curve estimates of this study can be used to evaluate the impact of the Administration principles and related policy initiatives.

  20. Cytotoxic and DNA-damaging effects of methyl tert-butyl ether and its metabolites on HL-60 cells in vitro

    SciTech Connect (OSTI)

    Tang, G.H.; Shen, Y.; Shen, H.M.

    1996-12-31

    Methyl tert-butyl ether (MTBE) is a widely used oxygenate in unleaded gasoline; however, few studies have been conducted on the toxicity of this compound. This study evaluates the cytotoxic and DNA-damaging effects of MTBE and its metabolites in a human haemopoietic cell line, HL-60. The metabolites of MTBE studied include tertiary butyl alcohol (TBA), {alpha}-hydroxyisobutyric acid (HIBA), and formaldehyde. Comet assay is used to assess DNA damage, and the cytotoxicity is investigated by lactate dehydrogenease (LDH) release. The results show no significant cytotoxic effects of MTBE, TBA, and HIBA over a concentration ranging from 1 to 30 mM. Formaldehyde, in contrast, causes a substantial LDH release at a concentration of 5 {mu}M. Hydrogen peroxide, a known oxidative agent, at concentrations ranging from 10 to 100 {mu}M, produces a significant dose-related increase in DNA damage, whereas a much higher concentration of MTBE (1 to 30 mM) is required to produce a similar observation. The genotoxic effects of TBA and HIBA appear to be identical to that of MTBE. Conversely, DNA damage is observed for formaldehyde at a relatively low concentration range (5 to 100 {mu}M). These findings suggest that MTBE and its metabolites, except formaldehyde, have relatively low cytotoxic and genotoxic effects. 16 refs., 4 figs.

  1. Controlling DNA Methylation

    U.S. Department of Energy (DOE) all webpages (Extended Search)

    Controlling DNA Methylation Though life on earth is composed of a diverse range of organisms, some with many different types of tissues and cells, all these are encoded by a molecule we call DNA. The information required to build a protein is stored in DNA within the cells. Not all the message in the DNA is used in each cell and not all the message is used all the time. During cell differentiation, the cells become dedicated for their specific function which involves selectively activating some

  2. Aqueous flooding methods for tertiary oil recovery

    DOE Patents [OSTI]

    Peru, Deborah A.

    1989-01-01

    A method of aqueous flooding of subterranean oil bearing formation for tertiary oil recovery involves injecting through a well into the formation a low alkaline pH aqueous sodium bicarbonate flooding solution. The flooding solution's pH ranges from about 8.25 to 9.25 and comprises from 0.25 to 5 weight percent and preferably about 0.75 to 3.0 weight percent of sodium bicarbonate and includes a petroleum recovery surfactant of 0.05 to 1.0 weight percent and between 1 and 20 weight percent of sodium chloride. After flooding, an oil and water mixture is withdrawn from the well and the oil is separated from the oil and water mixture.

  3. Artificial oxygen transport protein

    DOE Patents [OSTI]

    Dutton, P. Leslie

    2014-09-30

    This invention provides heme-containing peptides capable of binding molecular oxygen at room temperature. These compounds may be useful in the absorption of molecular oxygen from molecular oxygen-containing atmospheres. Also included in the invention are methods for treating an oxygen transport deficiency in a mammal.

  4. Solid state oxygen sensor

    DOE Patents [OSTI]

    Garzon, F.H.; Chung, B.W.; Raistrick, I.D.; Brosha, E.L.

    1996-08-06

    Solid state oxygen sensors are provided with a yttria-doped zirconia as an electrolyte and use the electrochemical oxygen pumping of the zirconia electrolyte. A linear relationship between oxygen concentration and the voltage arising at a current plateau occurs when oxygen accessing the electrolyte is limited by a diffusion barrier. A diffusion barrier is formed herein with a mixed electronic and oxygen ion-conducting membrane of lanthanum-containing perovskite or zirconia-containing fluorite. A heater may be used to maintain an adequate oxygen diffusion coefficient in the mixed conducting layer. 4 figs.

  5. Solid state oxygen sensor

    DOE Patents [OSTI]

    Garzon, Fernando H.; Chung, Brandon W.; Raistrick, Ian D.; Brosha, Eric L.

    1996-01-01

    Solid state oxygen sensors are provided with a yttria-doped zirconia as an electrolyte and use the electrochemical oxygen pumping of the zirconia electrolyte. A linear relationship between oxygen concentration and the voltage arising at a current plateau occurs when oxygen accessing the electrolyte is limited by a diffusion barrier. A diffusion barrier is formed herein with a mixed electronic and oxygen ion-conducting membrane of lanthanum-containing perovskite or zirconia-containing fluorite. A heater may be used to maintain an adequate oxygen diffusion coefficient in the mixed conducting layer.

  6. Solid state oxygen sensor

    DOE Patents [OSTI]

    Garzon, Fernando H.; Brosha, Eric L.

    1997-01-01

    A potentiometric oxygen sensor is formed having a logarithmic response to a differential oxygen concentration while operating as a Nernstian-type sensor. Very thin films of mixed conducting oxide materials form electrode services while permitting diffusional oxygen access to the interface between the zirconia electrolyte and the electrode. Diffusion of oxygen through the mixed oxide is not rate-limiting. Metal electrodes are not used so that morphological changes in the electrode structure do not occur during extended operation at elevated temperatures.

  7. Global prevalence and distribution of genes and microorganisms involved in mercury methylation

    SciTech Connect (OSTI)

    Podar, Mircea; Gilmour, C C; Brandt, Craig C; Bullock, Allyson L; Brown, Steven D; Crable, Bryan R; Palumbo, Anthony Vito; Somenahally, Anil C; Elias, Dwayne A

    2015-01-01

    Mercury methylation produces the neurotoxic, highly bioaccumulative methylmercury (MeHg). Recent identification of the methylation genes (hgcAB) provides the foundation for broadly evaluating microbial Hg-methylation potential in nature without making explicit rate measurements. We queried hgcAB diversity and distribution in all available microbial metagenomes, encompassing most environments. The genes were found in nearly all anaerobic, but not in aerobic, environments including oxygenated layers of the open ocean. Critically, hgcAB was effectively absent in ~1500 human microbiomes, suggesting a low risk of endogenous MeHg production. New potential methylation habitats were identified, including invertebrate guts, thawing permafrost, coastal dead zones , soils, sediments, and extreme environments, suggesting multiple routes for MeHg entry into food webs. Several new taxonomic groups potentially capable of Hg-methylation emerged, including lineages having no cultured representatives. We begin to address long-standing evolutionary questions about Hg-methylation and ancient carbon fixation mechanisms while generating a new global view of Hg-methylation potential.

  8. Global prevalence and distribution of genes and microorganisms involved in mercury methylation

    DOE PAGES-Beta [OSTI]

    Podar, Mircea; Gilmour, C. C.; Brandt, Craig C.; Soren, Allyson; Brown, Steven D.; Crable, Bryan R.; Palumbo, Anthony Vito; Somenahally, Anil C.; Elias, Dwayne A.

    2015-10-09

    Mercury methylation produces the neurotoxic, highly bioaccumulative methylmercury (MeHg). Recent identification of the methylation genes (hgcAB) provides the foundation for broadly evaluating microbial Hg-methylation potential in nature without making explicit rate measurements. We first queried hgcAB diversity and distribution in all available microbial metagenomes, encompassing most environments. The genes were found in nearly all anaerobic, but not in aerobic, environments including oxygenated layers of the open ocean. Critically, hgcAB was effectively absent in ~1500 human microbiomes, suggesting a low risk of endogenous MeHg production. New potential methylation habitats were identified, including invertebrate guts, thawing permafrost, coastal dead zones, soils, sediments,more » and extreme environments, suggesting multiple routes for MeHg entry into food webs. Several new taxonomic groups potentially capable of Hg-methylation emerged, including lineages having no cultured representatives. We then begin to address long-standing evolutionary questions about Hg-methylation and ancient carbon fixation mechanisms while generating a new global view of Hg-methylation potential.« less

  9. Global prevalence and distribution of genes and microorganisms involved in mercury methylation

    SciTech Connect (OSTI)

    Podar, Mircea; Gilmour, C. C.; Brandt, Craig C.; Soren, Allyson; Brown, Steven D.; Crable, Bryan R.; Palumbo, Anthony Vito; Somenahally, Anil C.; Elias, Dwayne A.

    2015-01-01

    Mercury methylation produces the neurotoxic, highly bioaccumulative methylmercury (MeHg). Recent identification of the methylation genes (hgcAB) provides the foundation for broadly evaluating microbial Hg-methylation potential in nature without making explicit rate measurements. We first queried hgcAB diversity and distribution in all available microbial metagenomes, encompassing most environments. The genes were found in nearly all anaerobic, but not in aerobic, environments including oxygenated layers of the open ocean. Critically, hgcAB was effectively absent in ~1500 human microbiomes, suggesting a low risk of endogenous MeHg production. New potential methylation habitats were identified, including invertebrate guts, thawing permafrost, coastal dead zones, soils, sediments, and extreme environments, suggesting multiple routes for MeHg entry into food webs. Several new taxonomic groups potentially capable of Hg-methylation emerged, including lineages having no cultured representatives. We then begin to address long-standing evolutionary questions about Hg-methylation and ancient carbon fixation mechanisms while generating a new global view of Hg-methylation potential.

  10. Oxygen partial pressure sensor

    DOE Patents [OSTI]

    Dees, D.W.

    1994-09-06

    A method for detecting oxygen partial pressure and an oxygen partial pressure sensor are provided. The method for measuring oxygen partial pressure includes contacting oxygen to a solid oxide electrolyte and measuring the subsequent change in electrical conductivity of the solid oxide electrolyte. A solid oxide electrolyte is utilized that contacts both a porous electrode and a nonporous electrode. The electrical conductivity of the solid oxide electrolyte is affected when oxygen from an exhaust stream permeates through the porous electrode to establish an equilibrium of oxygen anions in the electrolyte, thereby displacing electrons throughout the electrolyte to form an electron gradient. By adapting the two electrodes to sense a voltage potential between them, the change in electrolyte conductivity due to oxygen presence can be measured. 1 fig.

  11. Oxygen partial pressure sensor

    DOE Patents [OSTI]

    Dees, Dennis W.

    1994-01-01

    A method for detecting oxygen partial pressure and an oxygen partial pressure sensor are provided. The method for measuring oxygen partial pressure includes contacting oxygen to a solid oxide electrolyte and measuring the subsequent change in electrical conductivity of the solid oxide electrolyte. A solid oxide electrolyte is utilized that contacts both a porous electrode and a nonporous electrode. The electrical conductivity of the solid oxide electrolyte is affected when oxygen from an exhaust stream permeates through the porous electrode to establish an equilibrium of oxygen anions in the electrolyte, thereby displacing electrons throughout the electrolyte to form an electron gradient. By adapting the two electrodes to sense a voltage potential between them, the change in electrolyte conductivity due to oxygen presence can be measured.

  12. EPA`s proposed renewable oxygenate requirement (ROR): Pros and cons

    SciTech Connect (OSTI)

    Czeskleba, H.M.

    1995-12-31

    In December 1993, the US Environmental Protection Agency (EPA) released its final rule that sets for the details for requirements to sell reformulated gasoline (RFG) in certain ozone non-attainment areas. At the same time, EPA also issued a proposed rule to require that 30% of the oxygen required in RFG be based on a renewable oxygenate. Renewables include ethanol and its ether derivatives such as ethyl tertiary butyl ether (ETBE). The RFG rule is a final rule, while the Renewable Oxygenate Requirement (ROR) rule is a proposed rule yet to be finalized and subject to revision. Included in this paper are brief reviews of Ashland petroleum Company`s ethanol usage, oxygenated fuel and reformulated gasoline blending economics, and some comments on the EPA proposed renewable oxygenate requirement.

  13. Integrated turbomachine oxygen plant

    SciTech Connect (OSTI)

    Anand, Ashok Kumar; DePuy, Richard Anthony; Muthaiah, Veerappan

    2014-06-17

    An integrated turbomachine oxygen plant includes a turbomachine and an air separation unit. One or more compressor pathways flow compressed air from a compressor through one or more of a combustor and a turbine expander to cool the combustor and/or the turbine expander. An air separation unit is operably connected to the one or more compressor pathways and is configured to separate the compressed air into oxygen and oxygen-depleted air. A method of air separation in an integrated turbomachine oxygen plant includes compressing a flow of air in a compressor of a turbomachine. The compressed flow of air is flowed through one or more of a combustor and a turbine expander of the turbomachine to cool the combustor and/or the turbine expander. The compressed flow of air is directed to an air separation unit and is separated into oxygen and oxygen-depleted air.

  14. Oxygen ion conducting materials

    DOE Patents [OSTI]

    Carter, J. David; Wang, Xiaoping; Vaughey, John; Krumpelt, Michael

    2004-11-23

    An oxygen ion conducting ceramic oxide that has applications in industry including fuel cells, oxygen pumps, oxygen sensors, and separation membranes. The material is based on the idea that substituting a dopant into the host perovskite lattice of (La,Sr)MnO.sub.3 that prefers a coordination number lower than 6 will induce oxygen ion vacancies to form in the lattice. Because the oxygen ion conductivity of (La,Sr)MnO.sub.3 is low over a very large temperature range, the material exhibits a high overpotential when used. The inclusion of oxygen vacancies into the lattice by doping the material has been found to maintain the desirable properties of (La,Sr)MnO.sub.3, while significantly decreasing the experimentally observed overpotential.

  15. Oxygen ion conducting materials

    DOE Patents [OSTI]

    Vaughey, John; Krumpelt, Michael; Wang, Xiaoping; Carter, J. David

    2005-07-12

    An oxygen ion conducting ceramic oxide that has applications in industry including fuel cells, oxygen pumps, oxygen sensors, and separation membranes. The material is based on the idea that substituting a dopant into the host perovskite lattice of (La,Sr)MnO.sub.3 that prefers a coordination number lower than 6 will induce oxygen ion vacancies to form in the lattice. Because the oxygen ion conductivity of (La,Sr)MnO.sub.3 is low over a very large temperature range, the material exhibits a high overpotential when used. The inclusion of oxygen vacancies into the lattice by doping the material has been found to maintain the desirable properties of (La,Sr)MnO.sub.3, while significantly decreasing the experimentally observed overpotential.

  16. Oxygen ion conducting materials

    DOE Patents [OSTI]

    Vaughey, John; Krumpelt, Michael; Wang, Xiaoping; Carter, J. David

    2003-01-01

    An oxygen ion conducting ceramic oxide that has applications in industry including fuel cells, oxygen pumps, oxygen sensors, and separation membranes. The material is based on the idea that substituting a dopant into the host perovskite lattice of (La,Sr)MnO.sub.3 that prefers a coordination number lower than 6 will induce oxygen ion vacancies to form in the lattice. Because the oxygen ion conductivity of (La,Sr)MnO.sub.3 is low over a very large temperature range, the material exhibits a high overpotential when used. The inclusion of oxygen vacancies into the lattice by doping the material has been found to maintain the desirable properties of (La,Sr)MnO.sub.3, while significantly decreasing the experimentally observed overpotential.

  17. Oxygen-Enriched Combustion

    Energy.gov [DOE]

    This tip sheet discusses how an increase in oxygen in combustion air can reduce the energy loss in the exhaust gases and increase process heating system efficiency.

  18. Solid state oxygen sensor

    DOE Patents [OSTI]

    Garzon, F.H.; Brosha, E.L.

    1997-12-09

    A potentiometric oxygen sensor is formed having a logarithmic response to a differential oxygen concentration while operating as a Nernstian-type sensor. Very thin films of mixed conducting oxide materials form electrode services while permitting diffusional oxygen access to the interface between the zirconia electrolyte and the electrode. Diffusion of oxygen through the mixed oxide is not rate-limiting. Metal electrodes are not used so that morphological changes in the electrode structure do not occur during extended operation at elevated temperatures. 6 figs.

  19. High Selectivity Oxygen Delignification

    SciTech Connect (OSTI)

    Lucian A. Lucia

    2005-11-15

    Project Objective: The objectives of this project are as follows: (1) Examine the physical and chemical characteristics of a partner mill pre- and post-oxygen delignified pulp and compare them to lab generated oxygen delignified pulps; (2) Apply the chemical selectivity enhancement system to the partner pre-oxygen delignified pulps under mill conditions (with and without any predetermined amounts of carryover) to determine how efficiently viscosity is preserved, how well selectivity is enhanced, if strength is improved, measure any yield differences and/or bleachability differences; and (3) Initiate a mill scale oxygen delignification run using the selectivity enhancement agent, collect the mill data, analyze it, and propose any future plans for implementation.

  20. Detailed Chemical Kinetic Reaction Mechanism for Biodiesel Components Methyl Stearate and Methyl Oleate

    SciTech Connect (OSTI)

    Naik, C; Westbrook, C K; Herbinet, O; Pitz, W J; Mehl, M

    2010-01-22

    New chemical kinetic reaction mechanisms are developed for two of the five major components of biodiesel fuel, methyl stearate and methyl oleate. The mechanisms are produced using existing reaction classes and rules for reaction rates, with additional reaction classes to describe other reactions unique to methyl ester species. Mechanism capabilities were examined by computing fuel/air autoignition delay times and comparing the results with more conventional hydrocarbon fuels for which experimental results are available. Additional comparisons were carried out with measured results taken from jet-stirred reactor experiments for rapeseed methyl ester fuels. In both sets of computational tests, methyl oleate was found to be slightly less reactive than methyl stearate, and an explanation of this observation is made showing that the double bond in methyl oleate inhibits certain low temperature chain branching reaction pathways important in methyl stearate. The resulting detailed chemical kinetic reaction mechanism includes more approximately 3500 chemical species and more than 17,000 chemical reactions.

  1. EXTRACTION OF TETRAVALENT PLUTONIUM VALUES WITH METHYL ETHYL KETONE, METHYL ISOBUTYL KETONE ACETOPHENONE OR MENTHONE

    DOE Patents [OSTI]

    Seaborg, G.T.

    1961-08-01

    A process is described for extracting tetravalent plutonium from an aqueous acid solution with methyl ethyl ketone, methyl isobutyl ketone, or acetophenone and with the extraction of either tetravalent or hexavalent plutonium into menthone. (AEC)

  2. Process for conversion of lignin to reformulated, partially oxygenated gasoline

    DOE Patents [OSTI]

    Shabtai, Joseph S. (Salt Lake City, UT); Zmierczak, Wlodzimierz W. (Salt Lake City, UT); Chornet, Esteban (Golden, CO)

    2001-01-09

    A high-yield process for converting lignin into reformulated, partially oxygenated gasoline compositions of high quality is provided. The process is a two-stage catalytic reaction process that produces a reformulated, partially oxygenated gasoline product with a controlled amount of aromatics. In the first stage of the process, a lignin feed material is subjected to a base-catalyzed depolymerization reaction, followed by a selective hydrocracking reaction which utilizes a superacid catalyst to produce a high oxygen-content depolymerized lignin product mainly composed of alkylated phenols, alkylated alkoxyphenols, and alkylbenzenes. In the second stage of the process, the depolymerized lignin product is subjected to an exhaustive etherification reaction, optionally followed by a partial ring hydrogenation reaction, to produce a reformulated, partially oxygenated/etherified gasoline product, which includes a mixture of substituted phenyl/methyl ethers, cycloalkyl methyl ethers, C.sub.7 -C.sub.10 alkylbenzenes, C.sub.6 -C.sub.10 branched and multibranched paraffins, and alkylated and polyalkylated cycloalkanes.

  3. Optical oxygen concentration monitor

    DOE Patents [OSTI]

    Kebabian, P.

    1997-07-22

    A system for measuring and monitoring the concentration of oxygen uses as a light source an argon discharge lamp, which inherently emits light with a spectral line that is close to one of oxygen`s A-band absorption lines. In a preferred embodiment, the argon line is split into sets of components of shorter and longer wavelengths by a magnetic field of approximately 2,000 Gauss that is parallel to the light propagation from the lamp. The longer wavelength components are centered on an absorption line of oxygen and thus readily absorbed, and the shorter wavelength components are moved away from that line and minimally absorbed. A polarization modulator alternately selects the set of the longer wavelength, or upshifted, components or the set of the shorter wavelength, or downshifted, components and passes the selected set to an environment of interest. After transmission over a path through that environment, the transmitted optical flux of the argon line varies as a result of the differential absorption. The system then determines the concentration of oxygen in the environment based on the changes in the transmitted optical flux between the two sets of components. In alternative embodiments modulation is achieved by selectively reversing the polarity of the magnetic field or by selectively supplying the magnetic field to either the emitting plasma of the lamp or the environment of interest. 4 figs.

  4. Regional prospectivity of Mesozoic and Tertiary in the eastern Adriatic and adjacent area

    SciTech Connect (OSTI)

    Scott, J.; Dolan, P.; Lunn, G. )

    1988-08-01

    Post-Hercynian deposits in the eastern Adriatic and the adjacent external zones of the Dinarides and Albanian Hellenides may be subdivided into four facies groups. (1) Permian-Lower Triassic clastics and carbonates with some evaporites, (2) Middle Triassic-lower Tertiary carbonate platform facies with associated continental margin deeper marine sequences, (3) Upper Cretaceous-lower Tertiary flysch, and (4) middle Tertiary molasse and postorogenic Neogene sediments. The Permian to lower Tertiary section was deposited during the complex Alpine cycle, while the upper Tertiary section is the product of post-Alpine deposition. This depositional history during markedly different tectonic regimes creates two groups of petroleum plays in the eastern Adriatic: (1) Alpine cycle plays in the Permian to lower Tertiary in the thrust-faulted and folded foreland of Adria and (2) post-Alpine plays in upper Tertiary postorogenic or late synorogenic basins. Around the Adriatic, the post-Alpine plays have so far proved the most successful. Major production occurs in the onshore Po basin and its extension beneath the Adriatic. Some of this production is from deep Alpine-cycle reservoirs, but the bulk is from the upper Tertiary-Quaternary. Similar horizons produce onshore and offshore the central-southern Adriatic coast of Italy. Major Tertiary production also occurs to the northeast in the Pannonian basin of Yugoslavia and Hungary from Miocene and younger sequences. Onshore Albania produces significant quantities of hydrocarbons; although data are scarce, much of this production is presumably from upper Tertiary molasse or lower Tertiary flysch.

  5. Monolithic solid electrolyte oxygen pump

    DOE Patents [OSTI]

    Fee, Darrell C.; Poeppel, Roger B.; Easler, Timothy E.; Dees, Dennis W.

    1989-01-01

    A multi-layer oxygen pump having a one-piece, monolithic ceramic structure affords high oxygen production per unit weight and volume and is thus particularly adapted for use as a portable oxygen supply. The oxygen pump is comprised of a large number of small cells on the order of 1-2 millimeters in diameter which form the walls of the pump and which are comprised of thin, i.e., 25-50 micrometers, ceramic layers of cell components. The cell components include an air electrode, an oxygen electrode, an electrolyte and interconnection materials. The cell walls form the passages for input air and for exhausting the oxygen which is transferred from a relatively dilute gaseous mixture to a higher concentration by applying a DC voltage across the electrodes so as to ionize the oxygen at the air electrode, whereupon the ionized oxygen travels through the electrolyte and is converted to oxygen gas at the oxygen electrode.

  6. Method and apparatus for secondary and tertiary recovery of hydrocarbons

    SciTech Connect (OSTI)

    Rivas, N.; Beichel, R.

    1987-07-07

    This patent describes an apparatus for secondary and tertiary recovery of hydrocarbons from oil fields comprising: a. a bipropellant generator capable of producing exhaust gases at supercritical pressures and temperatures; b. transport means for carrying the exhaust gases into a well bore, at least a portion of the well bore extending into a hydrocarbon bearing formation from which hydrocarbons are to be recovered; c. means for introducing water into the transport means; and d. a water cooling jacket extending into at least the upper portion of the well bore, the center of the cooling jacket receiving the exhaust gases from the transport means, means being provided for the introduction of chemical additives through a portion of the cooling jacket. A process is described for secondary and tertiary recovery of hydrocarbons from geological formations comprising: a. providing a well bore extending at least into the strata of the geologic formation containing the hydrocarbons to be recovered; b. providing at least the upper portion of the well bore with a cooling jacket, the cooling jacket being provided with a central, open portion; c. generating gases at supercritical temperatures and pressures; d. introducing water into the supercritical gases to form steam; e. forcing the mixture of supercritical combustion gases and steam through the central open portion of the cooling jacket and the well bore into the hydrocarbon strata; and f. adding chemical additives to the mixture of combustion gases and steam below the cooling jacket.

  7. Optical oxygen concentration monitor

    DOE Patents [OSTI]

    Kebabian, Paul

    1997-01-01

    A system for measuring and monitoring the concentration of oxygen uses as a light source an argon discharge lamp, which inherently emits light with a spectral line that is close to one of oxygen's A-band absorption lines. In a preferred embodiment, the argon line is split into sets of components of shorter and longer wavelengths by a magnetic field of approximately 2000 Gauss that is parallel to the light propagation from the lamp. The longer wavelength components are centered on an absorption line of oxygen and thus readily absorbed, and the shorter wavelength components are moved away from that line and minimally absorbed. A polarization modulator alternately selects the set of the longer wavelength, or upshifted, components or the set of the shorter wavelength, or downshifted, components and passes the selected set to an environment of interest. After transmission over a path through that environment, the transmitted optical flux of the argon line varies as a result of the differential absorption. The system then determines the concentration of oxygen in the environment based on the changes in the transmitted optical flux between the two sets of components. In alternative embodiments modulation is achieved by selectively reversing the polarity of the magnetic field or by selectively supplying the magnetic field to either the emitting plasma of the lamp or the environment of interest.

  8. High pressure oxygen furnace

    DOE Patents [OSTI]

    Morris, D.E.

    1992-07-14

    A high temperature high pressure oxygen furnace having a hybrid partially externally heated construction is disclosed. A metallic bar fabricated from an alloy having a composition of at least 45% nickel, 15% chrome, and 10% tungsten is utilized, the preferred alloy including 55% nickel, 22% chrome, 14% tungsten, 2% molybdenum, 3% iron (maximum) and 5% cobalt (maximum). The disclosed alloy is fabricated into 11/4 inch bar stock and has a length of about 17 inches. This bar stock is gun drilled for over 16 inches of its length with 0.400 inch aperture to define a closed high temperature, high pressure oxygen chamber. The opposite and closed end of the bar is provided with a small support aperture into which both a support and a thermocouple can be inserted. The closed end of the gun drilled bar is inserted into an oven, preferably heated by standard nickel chrome electrical elements and having a heavily insulated exterior. 5 figs.

  9. High pressure oxygen furnace

    DOE Patents [OSTI]

    Morris, Donald E.

    1992-01-01

    A high temperature high pressure oxygen furnace having a hybrid partially externally heated construction is disclosed. A metallic bar fabricated from an alloy having a composition of at least 45% nickel, 15% chrome, and 10% tungsten is utilized (the preferred alloy including 55% nickel, 22% chrome, 14% tungsten, 2% molybdenum, 3% iron (maximum) and 5% cobalt (maximum). The disclosed alloy is fabricated into 11/4 inch bar stock and has a length of about 17 inches. This bar stock is gun drilled for over 16 inches of its length with 0.400 inch aperture to define a closed high temperature, high pressure oxygen chamber. The opposite and closed end of the bar is provided with a small support aperture into which both a support and a thermocouple can be inserted. The closed end of the gun drilled bar is inserted into an oven, preferably heated by standard nickel chrome electrical elements and having a heavily insulated exterior.

  10. Fuel cell oxygen electrode

    DOE Patents [OSTI]

    Shanks, H.R.; Bevolo, A.J.; Danielson, G.C.; Weber, M.F.

    An oxygen electrode for a fuel cell utilizing an acid electrolyte has a substrate of an alkali metal tungsten bronze of the formula: A/sub x/WO/sub 3/ where A is an alkali metal and x is at least 0.2, which is covered with a thin layer of platinum tungsten bronze of the formula: Pt/sub y/WO/sub 3/ where y is at least 0.8.

  11. Fuel cell oxygen electrode

    DOE Patents [OSTI]

    Shanks, Howard R.; Bevolo, Albert J.; Danielson, Gordon C.; Weber, Michael F.

    1980-11-04

    An oxygen electrode for a fuel cell utilizing an acid electrolyte has a substrate of an alkali metal tungsten bronze of the formula: A.sub.x WO.sub.3 where A is an alkali metal and x is at least 0.2, which is covered with a thin layer of platinum tungsten bronze of the formula: Pt.sub.y WO.sub.3 where y is at least 0.8.

  12. Oxygen Transport Ceramic Membranes

    SciTech Connect (OSTI)

    S. Bandopadhyay; T. Nithyanantham; X.-D Zhou; Y-W. Sin; H.U. Anderson; Alan Jacobson; C.A. Mims

    2005-08-01

    The present quarterly report describes some of the investigations on the structural properties of dense OTM bars provided by Praxair and studies on newer composition of Ti doped LSF. In the previous research, the reference point of oxygen occupancy was determined and verified. In the current research, the oxygen occupancy was investigated at 1200 C as a function of oxygen activity and compared with that at 1000 C. The cause of bumps at about 200 C was also investigated by using different heating and cooling rates during TGA. The fracture toughness of LSFT and dual phase membranes at room temperature is an important mechanical property. Vicker's indentation method was used to evaluate this toughness. Through this technique, a K{sub Ic} (Mode-I Fracture Toughness) value is attained by means of semi-empirical correlations between the indentation load and the length of the cracks emanating from the corresponding Vickers indentation impression. In the present investigation, crack propagation behavior was extensively analyzed in order to understand the strengthening mechanisms involved in the non-transforming La based ceramic composites. Cracks were generated using Vicker's indenter and used to identify and evaluate the toughening mechanisms involved. Preliminary results of an electron microscopy study of the origin of the slow kinetics on reduction of ferrites have been obtained. The slow kinetics appear to be related to a non-equilibrium reduction pathway that initially results in the formation of iron particles. At long times, equilibrium can be reestablished with recovery of the perovskite phase. Modeling of the isotopic transients on operating membranes (LSCrF-2828 at 900 C) and a ''frozen'' isotope profile have been analyzed in conjunction with a 1-D model to reveal the gradient in oxygen diffusivity through the membrane under conditions of high chemical gradients.

  13. Oxygen Transport Ceramic Membranes

    SciTech Connect (OSTI)

    S. Bandopadhyay; T. Nithyanantham; X.-D Zhou; Y-W. Sin; H.U. Anderson; Alan Jacobson; C.A. Mims

    2005-02-01

    The present quarterly report describes some of the investigations on the structural properties of dense OTM bars provided by Praxair and studies on newer composition of Ti doped LSF. The in situ electrical conductivity and Seebeck coefficient measurements were made on LSFT at 1000 and 1200 C over the oxygen activity range from air to 10{sup -15} atm. The electrical conductivity measurements exhibited a p to n type transition at an oxygen activity of 1 x 10{sup -10} at 1000 C and 1 x 10{sup -6} at 1200 C. Thermogravimetric studies were also carried out over the same oxygen activities and temperatures. Based on the results of these measurements, the chemical and mechanical stability range of LSFT were determined and defect structure was established. The studies on the fracture toughness of the LSFT and dual phase membranes exposed to air and N{sub 2} at 1000 C was done and the XRD and SEM analysis of the specimens were carried out to understand the structural and microstructural changes. The membranes that are exposed to high temperatures at an inert and a reactive atmosphere undergo many structural and chemical changes which affect the mechanical properties. A complete transformation of fracture behavior was observed in the N{sub 2} treated LSFT samples. Further results to investigate the origin of the slow kinetics on reduction of ferrites have been obtained. The slow kinetics appear to be related to a non-equilibrium reduction pathway that initially results in the formation of iron particles. At long times, equilibrium can be reestablished with recovery of the perovskite phase. Recent results on transient kinetic data are presented. The 2-D modeling of oxygen movement has been undertaken in order to fit isotope data. The model is used to study ''frozen'' profiles in patterned or composite membranes.

  14. Experimental study of the oxidation of methyl oleate in a jet-stirred reactor

    SciTech Connect (OSTI)

    Bax, Sarah; Hakka, Mohammed Hichem; Glaude, Pierre-Alexandre; Herbinet, Olivier; Battin-Leclerc, Frederique

    2010-06-15

    The experimental study of the oxidation of a blend containing n-decane and a large unsaturated ester, methyl oleate, was performed in a jet-stirred reactor over a wide range of temperature covering both low and high temperature regions (550-1100 K), at a residence time of 1.5 s, at quasi atmospheric pressure with high dilution in helium (n-decane and methyl oleate inlet mole fractions of 1.48 x 10{sup -3} and 5.2 x 10{sup -4}) and under stoichiometric conditions. The formation of numerous reaction products was observed. At low and intermediate temperatures, the oxidation of the blend led to the formation of species containing oxygen atoms like cyclic ethers, aldehydes and ketones deriving from n-decane and methyl oleate. At higher temperature, these species were not formed anymore and the presence of unsaturated species was observed. Because of the presence of the double bond in the middle of the alkyl chain of methyl oleate, the formation of some specific products was observed. These species are dienes and esters with two double bonds produced from the decomposition paths of methyl oleate and some species obtained from the addition of H-atoms, OH and HO{sub 2} radicals to the double bond. Experimental results were compared with former results of the oxidation of a blend of n-decane and methyl palmitate performed under similar conditions. This comparison allowed highlighting the similarities and the differences in the reactivity and in the distribution of the reaction products for the oxidation of large saturated and unsaturated esters. (author)

  15. Oxygen Transport Membranes

    SciTech Connect (OSTI)

    S. Bandopadhyay

    2008-08-30

    The focus of this research was to develop new membrane materials by synthesizing different compounds and determining their defect structures, crystallographic structures and electrical properties. In addition to measuring electrical conductivity, oxygen vacancy concentration was also evaluated using thermogravimetry, Neutron diffraction and Moessbauer Spectroscopy. The reducing conditions (CO{sub 2}/CO/H{sub 2} gas mixtures with steam) as encountered in a reactor environment can be expected to have significant influence on the mechanical properties of the oxides membranes. Various La based materials with and without Ti were selected as candidate membrane materials for OTM. The maximum electrical conductivity of LSF in air as a function of temperature was achieved at < 600 C and depends on the concentration of Sr (acceptor dopant). Oxygen occupancy in LSF was estimated using Neutron diffractometry and Moessbauer Spectroscopy by measuring magnetic moment changes depending on the Fe{sup 3+} and Fe{sup 4+} ratio. After extensive studies of candidate materials, lanthanum ferrites (LSF and LSFT) were selected as the favored materials for the oxygen transport membrane (OTM). LSF is a very good material for an OTM because of its high electronic and oxygen ionic conductivity if long term stability and mechanical strength are improved. LSFT not only exhibits p-type behavior in the high oxygen activity regime, but also has n-type conduction in reducing atmospheres. Higher concentrations of oxygen vacancies in the low oxygen activity regime may improve the performance of LSFT as an OTM. The hole concentration is related to the difference in the acceptor and donor concentration by the relation p = [Sr'{sub La}]-[Ti{sm_bullet}{sub Fe}]. The chemical formulation predicts that the hole concentration is, p = 0.8-0.45 or 0.35. Experimental measurements indicated that p is about {approx} 0.35. The activation energy of conduction is 0.2 eV which implies that LSCF conducts via the

  16. Oxygen Transport Ceramic Membranes

    SciTech Connect (OSTI)

    S. Bandopadhyay; N. Nagabhushana; T. Nithyanantham; X.-D Zhou; Y-W. Sin; H.U. Anderson; Alan Jacobson; C.A. Mims

    2005-02-01

    The present quarterly report describes some of the investigations on the structural properties of dense OTM bars provided by Praxair and studies on newer composition of Ti doped LSF. Thermogravimetric analysis (TGA) was carried out on La{sub 0.2}Sr{sub 0.8}Fe{sub 0.55}Ti{sub 0.45}O{sub 3-{delta}} to investigate oxygen deficiency ({delta}) of the sample. The TGA was performed in a controlled atmosphere using oxygen, argon, carbon monoxide and carbon dioxide with adjustable gas flow rates. In this experiment, the weight loss and gain of La{sub 0.2}Sr{sub 0.8}Fe{sub 0.55}Ti{sub 0.45}O{sub 3-{delta}} was directly measured by TGA. The weight change of the sample was evaluated at between 600 and 1250 C in air or 1000 C as a function of oxygen partial pressure. The oxygen deficiencies calculated from TGA data as a function of oxygen activity and temperature will be estimated and compared with that from neutron diffraction measurement in air. The LSFT and LSFT/CGO membranes were fabricated from the powder obtained from Praxair Specialty Ceramics. The sintered membranes were subjected to microstructure analysis and hardness analysis. The LSFT membrane is composed of fine grains with two kinds of grain morphology. The grain size distribution was characterized using image analysis. In LSFT/CGO membrane a lot of grain pullout was observed from the less dense, porous phase. The hardness of the LSFT and dual phase membranes were studied at various loads. The hardness values obtained from the cross section of the membranes were also compared to that of the values obtained from the surface. An electrochemical cell has been designed and built for measurements of the Seebeck coefficient as a function of temperature and pressure. Measurements on La{sub 0.2}Sr{sub 0.8}Fe{sub 0.55}Ti{sub 0.45}O{sub 3-{delta}} as a function of temperature an oxygen partial pressure are reported. Further analysis of the dilatometry data obtained previously is presented. A series of isotope transients

  17. APPENDXD.CHP:Corel VENTURA

    Annual Energy Outlook

    Report The Form EIA-819, "Monthly Oxygenate Report" provides production data for fuel ethanol and methyl tertiary butyl ether (MTBE). End-of-month stock data held at ethanol...

  18. Conservation and Functional Importance of Carbon-Oxygen Hydrogen Bonding in AdoMet-Dependent Methyltransferases

    SciTech Connect (OSTI)

    Horowitz, Scott; Dirk, Lynnette M.A.; Yesselman, Joseph D.; Nimtz, Jennifer S.; Adhikari, Upendra; Mehl, Ryan A.; Scheiner, Steve; Houtz, Robert L.; Al-Hashimi, Hashim M.; Trievel, Raymond C.

    2013-09-06

    S-Adenosylmethionine (AdoMet)-based methylation is integral to metabolism and signaling. AdoMet-dependent methyltransferases belong to multiple distinct classes and share a catalytic mechanism that arose through convergent evolution; however, fundamental determinants underlying this shared methyl transfer mechanism remain undefined. A survey of high-resolution crystal structures reveals that unconventional carbon–oxygen (CH···O) hydrogen bonds coordinate the AdoMet methyl group in different methyltransferases irrespective of their class, active site structure, or cofactor binding conformation. Corroborating these observations, quantum chemistry calculations demonstrate that these charged interactions formed by the AdoMet sulfonium cation are stronger than typical CH···O hydrogen bonds. Biochemical and structural studies using a model lysine methyltransferase and an active site mutant that abolishes CH···O hydrogen bonding to AdoMet illustrate that these interactions are important for high-affinity AdoMet binding and transition-state stabilization. Further, crystallographic and NMR dynamics experiments of the wild-type enzyme demonstrate that the CH···O hydrogen bonds constrain the motion of the AdoMet methyl group, potentially facilitating its alignment during catalysis. Collectively, the experimental findings with the model methyltransferase and structural survey imply that methyl CH···O hydrogen bonding represents a convergent evolutionary feature of AdoMet-dependent methyltransferases, mediating a universal mechanism for methyl transfer.

  19. OXYGEN TRANSPORT CERAMIC MEMBRANES

    SciTech Connect (OSTI)

    Dr. Sukumar Bandopadhyay; Dr. Nagendra Nagabhushana

    2000-10-01

    This is the third quarterly report on oxygen Transport Ceramic Membranes. In the following, the report describes the progress made by our university partners in Tasks 1 through 6, experimental apparatus that was designed and built for various tasks of this project, thermodynamic calculations, where applicable and work planned for the future. (Task 1) Design, fabricate and evaluate ceramic to metal seals based on graded ceramic powder/metal braze joints. (Task 2) Evaluate the effect of defect configuration on ceramic membrane conductivity and long term chemical and structural stability. (Task 3) Determine materials mechanical properties under conditions of high temperatures and reactive atmospheres. (Task 4) Evaluate phase stability and thermal expansion of candidate perovskite membranes and develop techniques to support these materials on porous metal structures. (Task 5) Assess the microstructure of membrane materials to evaluate the effects of vacancy-impurity association, defect clusters, and vacancy-dopant association on the membrane performance and stability. (Task 6) Measure kinetics of oxygen uptake and transport in ceramic membrane materials under commercially relevant conditions using isotope labeling techniques.

  20. Composite oxygen transport membrane

    DOE Patents [OSTI]

    Christie, Gervase Maxwell; Lane, Jonathan A.

    2014-08-05

    A method of producing a composite oxygen ion membrane and a composite oxygen ion membrane in which a porous fuel oxidation layer and a dense separation layer and optionally, a porous surface exchange layer are formed on a porous support from mixtures of (Ln.sub.1-xA.sub.x).sub.wCr.sub.1-yB.sub.yO.sub.3-.delta. and a doped zirconia. In the porous fuel oxidation layer and the optional porous surface exchange layer, A is Calcium and in the dense separation layer A is not Calcium and, preferably is Strontium. Preferred materials are (La.sub.0.8Ca.sub.0.2).sub.0.95Cr.sub.0.5Mn.sub.0.5O.sub.3-.delta. for the porous fuel oxidation and optional porous surface exchange layers and (La.sub.0.8Sr.sub.0.2).sub.0.95Cr.sub.0.5Fe.sub.0.5O.sub.3-.delta. for the dense separation layer. The use of such materials allows the membrane to sintered in air and without the use of pore formers to reduce membrane manufacturing costs. The use of materials, as described herein, for forming the porous layers have application for forming any type of porous structure, such as a catalyst support.

  1. High Selectivity Oxygen Delignification

    SciTech Connect (OSTI)

    Arthur J. Ragauskas Lucian A. Lucia Hasan Jameel

    2005-09-30

    The overall objective of this program was to develop improved extended oxygen delignification (EOD) technologies for current U.S. pulp mill operations. This was accomplished by: (1) Identifying pulping conditions that optimize O and OO performance; (2) Identifying structural features of lignin that enhance reactivity towards EOD of high kappa pulps; (3) Identifying factors minimizing carbohydrate degradation and improve pulp strength of EOD high kappa pulps; (4) Developing a simple, reproducible method of quantifying yield gains from EOD; and (5) Developing process conditions that significantly reduce the capital requirements of EOD while optimizing the yield benefits. Key research outcomes included, demonstrating the use of a mini-O sequence such as (E+O)Dkf:0.05(E+O) or Dkf:0.05(E+O)(E+O) without interstage washing could capture approximately 60% of the delignification efficiency of a conventional O-stage without the major capital requirements associated with an O-stage for conventional SW kraft pulps. The rate of formation and loss of fiber charge during an O-stage stage can be employed to maximize net fiber charge. Optimal fiber charge development and delignification are two independent parameters and do not parallel each other. It is possible to utilize an O-stage to enhance overall cellulosic fiber charge of low and high kappa SW kraft pulps which is beneficial for physical strength properties. The application of NIR and multi-variant analysis was developed into a rapid and simple method of determining the yield of pulp from an oxygen delignification stage that has real-world mill applications. A focus point of this program was the demonstration that Kraft pulping conditions and oxygen delignification of high and low-kappa SW and HW pulps are intimately related. Improved physical pulp properties and yield can be delivered by controlling the H-factor and active alkali charge. Low AA softwood kraft pulp with a kappa number 30 has an average improvement of 2% in

  2. Nanofluid of graphene-based amphiphilic Janus nanosheets for tertiary or

    Office of Scientific and Technical Information (OSTI)

    enhanced oil recovery: High performance at low concentration (Journal Article) | SciTech Connect Nanofluid of graphene-based amphiphilic Janus nanosheets for tertiary or enhanced oil recovery: High performance at low concentration Citation Details In-Document Search This content will become publicly available on January 12, 2017 Title: Nanofluid of graphene-based amphiphilic Janus nanosheets for tertiary or enhanced oil recovery: High performance at low concentration Authors: Luo, Dan ;

  3. West Hackberry Tertiary Project. Annual report, September 3, 1997--September 2, 1998

    SciTech Connect (OSTI)

    Gillham, T.H.

    1997-09-10

    The following report is the Project Management Plan for the fifth year of the West Hackberry Tertiary Project. The West Hackberry Tertiary Project is one of four mid-term projects selected by the United States Department of Energy (DOE) as part of the DOE`s Class 1 Program for the development of advance recovery technologies in fluvial dominated deltaic reservoirs. The West Hackberry Tertiary Project is a field test of the idea that air injection can be combined with the Double Displacement Process to produce a low cost tertiary recovery process which is economic at current oil prices. The Double Displacement Process is the gas displacement of a water invaded oil column for the purpose of recovering tertiary oil by gravity drainage. The Double Displacement Process is based upon the concept that in fields such as West Hackberry waterdrive recoveries are typically 50%-60% of the original oil in place while gravity drainage recoveries average 80%-90% of the original oil in place. Therefore, by injecting a gas into a watered out reservoir, a gas cap will form an additional oil can be recovered due to gravity drainage. Although the Double Displacement Process has been shown to be successful in recovering tertiary oil in other fields, this project will be the first to utilize air injection in the Double Displacement Process. The use of air injection in this process combines the benefits of air`s low cost and universal accessibility with the potential for accelerated oil recovery due to the combustion process. If successful, this project will demonstrate that the use of air injection in the Double Displacement Process will result in an economically viable tertiary process in reservoirs where tertiary oil recovery is presently uneconomical.

  4. Utilization of Renewable Oxygenates as Gasoline Blending Components

    SciTech Connect (OSTI)

    Yanowitz, J.; Christensen, E.; McCormick, R. L.

    2011-08-01

    This report reviews the use of higher alcohols and several cellulose-derived oxygenates as blend components in gasoline. Material compatibility issues are expected to be less severe for neat higher alcohols than for fuel-grade ethanol. Very little data exist on how blending higher alcohols or other oxygenates with gasoline affects ASTM Standard D4814 properties. Under the Clean Air Act, fuels used in the United States must be 'substantially similar' to fuels used in certification of cars for emission compliance. Waivers for the addition of higher alcohols at concentrations up to 3.7 wt% oxygen have been granted. Limited emission testing on pre-Tier 1 vehicles and research engines suggests that higher alcohols will reduce emissions of CO and organics, while NOx emissions will stay the same or increase. Most oxygenates can be used as octane improvers for standard gasoline stocks. The properties of 2-methyltetrahydrofuran, dimethylfuran, 2-methylfuran, methyl pentanoate and ethyl pentanoate suggest that they may function well as low-concentration blends with gasoline in standard vehicles and in higher concentrations in flex fuel vehicles.

  5. Researchers Directly Observe Oxygen Signature in the Oxygen-evolving

    U.S. Department of Energy (DOE) all webpages (Extended Search)

    Complex of Photosynthesis Researchers Directly Observe Oxygen Signature in the Oxygen-evolving Complex of Photosynthesis Arguably the most important chemical reaction on earth is the photosynthetic splitting of water to molecular oxygen by the Mn-containing oxygen-evolving complex (Mn-OEC) in the protein known as photosystem II (PSII). It is this reaction which has, over the course of some 3.8 billion years, gradually filled our atmosphere with O2 and consequently enabled and sustained the

  6. West Hackberry tertiary project. Annual report, September 3, 1994--September 2, 1995

    SciTech Connect (OSTI)

    Gillham, T.; Cerveny, B.; Turek, E.

    1996-05-01

    The West Hackberry Tertiary Project is a field test of the idea that air injection can be combined with the Double Displacement Process to produce a low cost tertiary recovery process which is economic at current oil prices. The Double Displacement Process is the gas displacement of a water invaded oil column for the purpose of recovering tertiary oil by gravity drainage. The Double Displacement Process is based upon the concept that in fields such as West Hackberry waterdrive recoveries are typically 50%-60% of the original oil in place while gravity drainage recoveries average 80%-90% of the original oil in place. Therefore, by injecting a gas into a watered out reservoir, a gas cap will form and additional oil can be recovered due to gravity drainage. Although the Double Displacement Process has been shown to be successful in recovering tertiary oil in other fields, this project will be the first to utilize air injection in the Double Displacement Process. The use of air injection in this process combines the benefits of air`s low cost and universal accessibility with the potential for accelerated oil recovery due to the combustion process. If successful, this project will demonstrate that the use of air injection in the Double Displacement Process will result in an economically viable tertiary process in reservoirs where tertiary oil recovery is presently uneconomical.

  7. Oxygen Transport Ceramic Membranes

    SciTech Connect (OSTI)

    S. Bandopadhyay; N. Nagabhushana; X.-D Zhou; Q. Cai; J. Yang; W.B. Yelon; W.J. James; H.U. Anderson; Alan Jacobson; C.A. Mims

    2004-05-01

    The present quarterly report describes some of the investigations on the structural properties of dense OTM bars provided by Praxair and studies on newer composition of Ti doped LSF. In this report, in situ neutron diffraction was used to characterize the chemical and structural properties of La{sub 0.2}Sr{sub 0.8}Fe{sub 0.55}Ti{sub 0.45}O{sub 3-{delta}} (here after as L2SF55T) specimen, which was subject to measurements of neutron diffraction from room temperature to 900 C. It was found that space group of R3c yielded a better refinement than a cubic structure of Pm3m. Oxygen occupancy was nearly 3 in the region from room temperature to 700 C, above which the occupancy decreased due to oxygen loss. Dense OTM bars provided by Praxair were loaded to fracture at varying stress rates. Studies were done at room temperature in air and at 1000 C in a specified environment to evaluate slow crack growth behavior. The X-Ray data and fracture mechanisms points to non-equilibrium decomposition of the LSFCO OTM membrane. The non-equilibrium conditions could probably be due to the nature of the applied stress field (stressing rates) and leads to transition in crystal structures and increased kinetics of decomposition. The formations of a Brownmillerite or Sr2Fe2O5 type structures, which are orthorhombic are attributed to the ordering of oxygen vacancies. The cubic to orthorhombic transitions leads to 2.6% increase in strains and thus residual stresses generated could influence the fracture behavior of the OTM membrane. Continued investigations on the thermodynamic properties (stability and phase-separation behavior) and total conductivity of prototype membrane materials were carried out. The data are needed together with the kinetic information to develop a complete model for the membrane transport. Previously characterization, stoichiometry and conductivity measurements for samples of La{sub 0.2}Sr{sub 0.8}Fe{sub 0.55}Ti{sub 0.45}O{sub 3-{delta}} were reported. In this report

  8. Radiation chemistry of alternative fuel oxygenates -- Substituted ethers

    SciTech Connect (OSTI)

    Mezyk, S. P.; Cooper, W. J.; Bartels, D. M.; Tobien, T.; O'Shea, K. E.

    1999-11-15

    The electron beam process, an advanced oxidation and reduction technology, is based in the field of radiation chemistry. Fundamental to the development of treatment processes is an understanding of the underlying chemistry. The authors have previously evaluated the bimolecular rate constants for the reactions of methyl tert-butyl ether (MTBE) and with this study have extended their studies to include ethyl tert-butyl ether (ETBE), di-isopropyl ether (DIPE) and tert-amyl methyl ether (TAME) with the hydroxyl radical, hydrogen atom and solvated electron using pulse radiolysis. For all of the oxygenates the reaction with the hydroxyl radical appears to be of primary interest in the destruction of the compounds in water. The rates with the solvated electron are limiting values as the rates appear to be relatively low. The hydrogen atom rate constants are relatively low, coupled with the low yield in radiolysis, they concluded that these are of little significance in the destruction of the alternative fuel oxygenates (and MTBE).

  9. Impact of oxygenates on petroleum refining, review and forecast

    SciTech Connect (OSTI)

    Unzelman, G.H.

    1995-09-01

    During the coming decade, oxygenates will continue to impact light oil processing and will steadily change the composition of the US gasoline pool. There are several major driving forces that will sustain the gradual influx of oxygen to US gasoline toward the regulatory limits: (1) the positive environmental characteristics of oxygenated compounds, (2) the high-octane quality of ethers that promote elimination of less desirable hydrocarbons and (3) the competitive need for ultra-clean gasoline to compete with alternatives. From 1995 forward, conventional gasoline will gradually shift to RFG (reformulated gasoline) containing a minimum of 2 wt% oxygen and less aromatics. As a result some processing changes, already in motion in the refining industry, will continue. For example, less severe naphtha reforming and cracking innovations to yield more feed for etherification and alkylation. While alternative fuel and vehicle technology will continue to develop, oxygenates in US gasoline will contribute the major alternative dimension to transportation fuel in the foreseeable future. With RFG, internal-combustion engine emissions will be progressively less toxic and lower in photochemical reactivity. The oxygenate mix will favor methyl ethers in spite of the recent methanol price spike. Ethyl ethers will be used on a more limited basis for specific situations where lower volatility and feedstock economics are an advantage. Downstream blending of ethanol will supplement ethers blended at the refinery in situations where economics are more favorable than refinery ethers. Long-range survival of ethanol, as a direct blending agent or feedstock for refinery ethers, depends on one or more of several factors: future crude oil costs, longevity of subsidies and/or mandates, and new production technology based on cellulose yielding ethanol economically competitive with hydrocarbons.

  10. Oxygen-reducing catalyst layer

    DOE Patents [OSTI]

    O'Brien, Dennis P.; Schmoeckel, Alison K.; Vernstrom, George D.; Atanasoski, Radoslav; Wood, Thomas E.; Yang, Ruizhi; Easton, E. Bradley; Dahn, Jeffrey R.; O'Neill, David G.

    2011-03-22

    An oxygen-reducing catalyst layer, and a method of making the oxygen-reducing catalyst layer, where the oxygen-reducing catalyst layer includes a catalytic material film disposed on a substrate with the use of physical vapor deposition and thermal treatment. The catalytic material film includes a transition metal that is substantially free of platinum. At least one of the physical vapor deposition and the thermal treatment is performed in a processing environment comprising a nitrogen-containing gas.

  11. EIA-819, Monthly Oxygenate Report ...

    U.S. Department of Energy (DOE) all webpages (Extended Search)

    (EIA) Form EIA-819, "Monthly Biofuel and Oxygenate Report," is used to collect data on ethanol production capacity, as well as stocks, receipts, inputs, production, and blending of...

  12. Oxygenate Supply/Demand Balances

    Annual Energy Outlook

    Related EIA Short-Term Forecast Analysis Products * ... and Price Outlook for Reformulated Motor Gasoline, 1995 Introduction The blending of oxygenates, such as fuel ethanol ...

  13. Ab initio metadynamics simulations of oxygen/ligand interactions in organoaluminum clusters

    SciTech Connect (OSTI)

    Alnemrat, Sufian; Hooper, Joseph P.

    2014-10-14

    Car-Parrinello molecular dynamics combined with a metadynamics algorithm is used to study the initial interaction of O{sub 2} with the low-valence organoaluminum clusters Al{sub 4}Cp{sub 4} (Cp=C{sub 5}H{sub 5}) and Al{sub 4}Cp{sub 4}{sup *} (Cp{sup *}=C{sub 5}[CH{sub 3}]{sub 5}). Prior to reaction with the aluminum core, simulations suggest that the oxygen undergoes a hindered crossing of the steric barrier presented by the outer ligand monolayer. A combination of two collective variables based on aluminum/oxygen distance and lateral oxygen displacement was found to produce distinct reactant, product, and transition states for this process. In the methylated cluster with Cp{sup *} ligands, a broad transition state of 45 kJ/mol was observed due to direct steric interactions with the ligand groups and considerable oxygen reorientation. In the non-methylated cluster the ligands distort away from the oxidizer, resulting in a barrier of roughly 34 kJ/mol with minimal O{sub 2} reorientation. A study of the oxygen/cluster system fixed in a triplet multiplicity suggests that the spin state does not affect the initial steric interaction with the ligands. The metadynamics approach appears to be a promising means of analyzing the initial steps of such oxidation reactions for ligand-protected clusters.

  14. Low temperature synthesis of methyl formate

    DOE Patents [OSTI]

    Mahajan, Devinder; Slegeir, William A.; Sapienza, Richard S.; O'Hare, Thomas E.

    1986-01-01

    A gas reaction process for the preferential production of methyl formate over the co-production of methanol wherein the reactant ratio of CO/H.sub.2 is upgraded and this reaction takes place at low temperatures of 50.degree.-150.degree. C. and moderate pressures of .gtoreq.100 psi.

  15. Oxygen Transport Ceramic Membranes

    SciTech Connect (OSTI)

    S. Bandopadhyay; N. Nagabhushana; X.-D Zhou; Q. Cai; J. Yang; W.B. Yelon; W.J. James; H.U. Anderson; Alan Jacobson; C.A. Mims

    2004-10-01

    The present quarterly report describes some of the investigations on the structural properties of dense OTM bars provided by Praxair and studies on newer composition of Ti doped LSF. In this report, Moessbauer spectroscopy was used to study the local environmentals of LSFT with various level of oxygen deficiency. Ionic valence state, magnetic interaction and influence of Ti on superexchange are discussed Stable crack growth studies on Dense OTM bars provided by Praxair were done at elevated temperature, pressure and elevated conditions. Post-fracture X-ray data of the OTM fractured at 1000 C in environment were refined by FullProf code and results indicate a distortion of the parent cubic perovskite to orthorhombic structure with reduced symmetry. TGA-DTA studies on the post-fracture samples also indicated residual effect arising from the thermal and stress history of the samples. An electrochemical cell has been designed and built for measurements of the Seebeck coefficient as a function of temperature and pressure. The initial measurements on La{sub 0.2}Sr{sub 0.8}Fe{sub 0.55}Ti{sub 0.45}O{sub 3-{delta}} are reported. Neutron diffraction measurements of the same composition are in agreement with both the stoichiometry and the kinetic behavior observed in coulometric titration measurements. A series of isotope transients under air separation mode (small gradient) were completed on the membrane of LSCrF-2828 at 900 C. Low pO{sub 2} atmospheres based on with CO-CO{sub 2} mixtures have also been admitted to the delivery side of the LSCrF-2828 membrane to produce the gradients which exist under syngas generation conditions. The COCO{sub 2} mixtures have normal isotopic {sup 18}O abundances. The evolution of {sup 18}O on the delivery side in these experiments after an {sup 18}O pulse on the air side reveals a wealth of information about the oxygen transport processes.

  16. Modulation of histone methylation and MLH1 gene silencing by...

    Office of Scientific and Technical Information (OSTI)

    ... Subject: 60 APPLIED LIFE SCIENCES; ARGININE; CARCINOGENS; CHROMIUM; DNA DAMAGES; GENES; HUMAN POPULATIONS; LUNGS; LYSINE; METHYLATION; NEOPLASMS; OCCUPATIONAL EXPOSURE; PROMOTERS ...

  17. Oxygen Transport Ceramic Membranes

    SciTech Connect (OSTI)

    S. Bandopadhyay; N. Nagabhushana; X.-D Zhou; W.B. Yelon; H.U. Anderson; Alan Jacobson; C.A. Mims

    2004-02-01

    The present quarterly report describes some of the investigations on the structural properties of dense OTM bars provided by Praxair and initial studies on newer composition of Ti doped LSF. Dense OTM bars provided by Praxair were loaded to fracture at varying stress rates. Studies were done at room temperature in air and at 1000 C in a specified environment to evaluate slow crack growth behavior. In addition, studies were also begun to obtain reliable estimates of fracture toughness and stable crack growth in specific environments. Newer composition of Ti doped LSF membranes were characterized by neutron diffraction analysis. Quench studies indicated an apparent correlation between the unit cell volume and oxygen occupancy. The studies however, indicated an anomaly of increasing Fe/Ti ratio with change in heat treatment. Ti doped LSF was also characterized for stoichiometry as a function of temp and pO{sub 2}. The non stoichiometry parameter {delta} was observed to increase almost linearly on lowering pO{sub 2} until a ideal stoichiometric composition of {delta} = 0.175 was approached.

  18. Oxygen detection using evanescent fields

    DOE Patents [OSTI]

    Duan, Yixiang; Cao, Weenqing

    2007-08-28

    An apparatus and method for the detection of oxygen using optical fiber based evanescent light absorption. Methylene blue was immobilized using a sol-gel process on a portion of the exterior surface of an optical fiber for which the cladding has been removed, thereby forming an optical oxygen sensor. When light is directed through the optical fiber, transmitted light intensity varies as a result of changes in the absorption of evanescent light by the methylene blue in response to the oxygen concentration to which the sensor is exposed. The sensor was found to have a linear response to oxygen concentration on a semi-logarithmic scale within the oxygen concentration range between 0.6% and 20.9%, a response time and a recovery time of about 3 s, ant to exhibit good reversibility and repeatability. An increase in temperature from 21.degree. C. to 35.degree. C. does not affect the net absorption of the sensor.

  19. Synthesis of Methyl Methacrylate from Coal-Derived Syngas

    SciTech Connect (OSTI)

    Gerald N. Choi; James J. Spivey; Jospeh R. Zoeller; Makarand R. Gogate; Richard D. Colberg; Samuel S. Tam

    1998-04-17

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel collectively are developing a novel three-step process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas that consists of the steps of synthesis of a propionate, its condensation with formaldehyde to form methacrylic acid (MAA), and esterification of MAA with methanol to produce MMA. RTI has completed the research on the three-step methanol-based route to MMA. Under an extension to the original contract, RTI is currently evaluating a new DME-based process for MMA. The key research need for DME route is to develop catalysts for DME partial oxidation reactions and DME condensation reactions. Over the last month, RTI has finalized the design of a fixed-bed microreactor system for DME partial oxidation reactions. RTI incorporated some design changes to the feed blending system, so as to be able to blend varying proportions of DME and oxygen. RTI has also examined the flammability limits of DME-air mixtures. Since the lower flammability limit of DME in air is 3.6 volume percent, RTI will use a nominal feed composition of 1.6 percent in air, which is less than half the lower explosion limit for DME-air mixtures. This nominal feed composition is thus considered operationally safe, for DME partial oxidation reactions. RTI is also currently developing an analytical system for DME partial oxidation reaction system.

  20. Mixed oxygen ion/electron-conducting ceramics for oxygen separation

    SciTech Connect (OSTI)

    Stevenson, J.W.; Armstrong, B.L.; Armstrong, T.R.; Bates, J.L.; Pederson, L.R.; Weber, W.J.

    1995-05-01

    Solid mixed-conducting electrolytes in the series La{sub l-x}A{sub x}Co{sub l-y}Fe{sub y}O{sub 3-{delta}} (A = Sr,Ca,Ba) are potentially useful as passive membranes to separate high purity oxygen from air and as cathodes in fuel cells. All of the compositions studied exhibited very high electrical conductivities. At lower temperatures, conductivities increased with increasing temperature, characterized by activation energies of 0.05 to 0.16 eV that are consistent with a small polaron (localized electronic carrier) conduction mechanism. At higher temperatures, electronic conductivities tended to decrease with increasing temperature, which is attributed to decreased electronic carrier populations associated with lattice oxygen loss. Oxygen ion conductivities were higher than that of yttria stabilized zirconia and increased with the cobalt content and also increased with the extent of divalent A-site substitution. Thermogravimetric studies were conducted to establish the extent of oxygen vacancy formation as a function of temperature, oxygen partial pressure, and composition. These vacancy populations strongly depend on the extent of A-site substitution. Passive oxygen permeation rates were established for each of the compositions as a function of temperature and oxygen partial pressure gradient. For 2.5 mm thick membranes in an oxygen vs nitrogen partial pressure gradient, oxygen fluxes at 900 C ranged from approximately 0.3 sccm/cm{sup 2} for compositions high in iron and with low amounts of strontium A-site substitution to approximately 0.8 sccm/cm{sup 2} for compositions high in cobalt and strontium. A-site substitution with calcium instead of strontium resulted in substantially lower fluxes.

  1. Oxygen Transport Ceramic Membranes

    SciTech Connect (OSTI)

    S. Bandopadhyay; T. Nithyanantham; X.-D Zhou; Y-W. Sin; H.U. Anderson; Alan Jacobson; C.A. Mims

    2005-11-01

    The present quarterly report describes some of the investigations on the structural properties of dense OTM bars provided by Praxair and studies on newer composition of Ti doped LSF. In the current research, the electrical conductivity and Seebeck coefficient were measured as a function of temperature in air. Based on these measurements, the charge carrier concentration, net acceptor dopant concentration, activation energy of conduction and mobility were estimated. The studies on the fracture toughness of the LSFT and dual phase membranes at room temperature have been completed and reported previously. The membranes that are exposed to high temperatures at an inert and a reactive atmosphere undergo many structural and chemical changes which affects the mechanical properties. To study the effect of temperature on the membranes when exposed to an inert environment, the membranes (LAFT and Dual phase) were heat treated at 1000 C in air and N{sub 2} atmosphere and hardness and fracture toughness of the membranes were studied after the treatment. The indentation method was used to find the fracture toughness and the effect of the heat treatment on the mechanical properties of the membranes. Further results on the investigation of the origin of the slow kinetics on reduction of ferrites have been obtained. The slow kinetics appears to be related to a non-equilibrium reduction pathway that initially results in the formation of iron particles. At long times, equilibrium can be reestablished with recovery of the perovskite phase. 2-D modeling of oxygen movement has been undertaken in order to fit isotope data. The model will serve to study ''frozen'' profiles in patterned or composite membranes.

  2. Oxygen Transport Ceramic Membranes

    SciTech Connect (OSTI)

    S. Bandopadhyay; N. Nagabhushana

    2003-08-07

    In the present quarter, experiments are presented on ceramic/metal interactions of Zirconia/ Ni-B-Si system and with a thin Ti coating deposited on zirconia surface. Existing facilities were modified for evaluation of environmental assisted slow crack growth and creep in flexural mode. Processing of perovskites of LSC, LSF and LSCF composition were continued for evaluation of mechanical properties as a function of environment. These studies in parallel to those on the LSFCO composition is expect to yield important information on questions such as the role of cation segregation and the stability of the perovskite structure on crack initiation vs. crack growth. Studies have been continued on the La{sub 1-x}Sr{sub x}FeO{sub 3-d} composition using neutron diffraction and TGA studies. A transition from p-type to n-type of conductor was observed at relative low pO{sub 2}, at which the majority carriers changed from the holes to electrons because of the valence state decreases in Fe due to the further loss of oxygen. Investigation on the thermodynamic properties of the membrane materials are continued to develop a complete model for the membrane transport. Data obtained at 850 C show that the stoichiometry in La{sub 0.2}Sr{sub 0.8}Fe{sub 0.8}Cr{sub 0.2}O{sub 3-x} vary from {approx}2.85 to 2.6 over the pressure range studied. From the stoichiometry a lower limit of 2.6 corresponding to the reduction of all Fe{sup 4+} to Fe{sup 3+} and no reduction of Cr{sup 3+} is expected.

  3. Fabrication of superhydrophilic and antireflective silica coatings on poly(methyl methacrylate) substrates

    SciTech Connect (OSTI)

    Geng, Zhi; He, Junhui; Xu, Ligang

    2012-06-15

    Graphical abstract: Self-cleaning and antireflection properties were successfully achieved by assembling (PDDA/S-20){sub n} coatings on PMMA substrates followed by oxygen plasma treatment. Highlights: ► Porous silica coatings were created by layer-by-layer assembly on PMMA substrates. ► Silica coatings were treated by oxygen plasma. ► Porous silica coatings were highly antireflective and superhydrophilic on PMMA substrates. -- Abstract: Silica nanoparticles of ca. 20 nm in size were synthesized, from which hierarchically porous silica coatings were fabricated on poly(methyl methacrylate) (PMMA) substrates via layer-by-layer (LbL) assembly followed by oxygen plasma treatment. These porous silica coatings were highly transparent and superhydrophilic. The maximum transmittance reached as high as 99%, whereas that of the PMMA substrate is only 92%. After oxygen plasma treatment, the time for a water droplet to spread to a contact angle of lower than 5° decreased to as short as 0.5 s. Scanning and transmission electron microscopy were used to observe the morphology and structure of nanoparticles and coating surfaces. Transmission and reflection spectra were recorded on UV–vis spectrophotometer. Surface wettability was studied by a contact angle/interface system. The influence of mesopores on the transmittance and wetting properties of coatings was discussed on the basis of experimental observations.

  4. Tension-compression-tension tertiary twins in coarse-grained polycrystalline pure magnesium at room temperature

    DOE PAGES-Beta [OSTI]

    Yu, Qin; Jiang, Yanyao; Wang, Jian

    2015-04-07

    Using electron backscatter diffraction, the microstructural features of tension–compression–tension (T–C–T) tertiary twins are studied in coarse-grained pure polycrystalline magnesium subjected to monotonic compression along the extrusion direction in ambient air. T–C–T tertiary twins are developed due to the formation of a compression–tension double twin inside a primary tension twin. All the observed T–C–T twin variants are of TiCjTj type. TiCi+1Ti+1 (or TiCi–1Ti–1) variants are observed more frequently than TiCi+2Ti+2 (or TiCi–2Ti–2) variants. Moreover, the number of tertiary twin lamellae increases with the applied compressive strain.

  5. Oxygen Transport Ceramic Membranes

    SciTech Connect (OSTI)

    S. Bandopadhyay; N. Nagabhushana; Thomas W. Eagar; Harold R. Larson; Raymundo Arroyave; X.-D Zhou; Y.-W. Shin; H.U. Anderson; Nigel Browning; Alan Jacobson; C.A. Mims

    2003-11-01

    The present quarterly report describes some of the initial studies on newer compositions and also includes newer approaches to address various materials issues such as in metal-ceramic sealing. The current quarter's research has also focused on developing a comprehensive reliability model for predicting the structural behavior of the membranes in realistic conditions. In parallel to industry provided compositions, models membranes have been evaluated in varying environment. Of importance is the behavior of flaws and generation of new flaws aiding in fracture. Fracture mechanics parameters such as crack tip stresses are generated to characterize the influence of environment. Room temperature slow crack growth studies have also been initiated in industry provided compositions. The electrical conductivity and defect chemistry of an A site deficient compound (La{sub 0.55}Sr{sub 0.35}FeO{sub 3}) was studied. A higher conductivity was observed for La{sub 0.55}Sr{sub 0.35}FeO{sub 3} than that of La{sub 0.60}Sr{sub 0.40}FeO{sub 3} and La{sub 0.80}Sr{sub 0.20}FeO{sub 3}. Defect chemistry analysis showed that it was primarily contributed by a higher carrier concentration in La{sub 0.55}Sr{sub 0.35}FeO{sub 3}. Moreover, the ability for oxygen vacancy generation is much higher in La{sub 0.55}Sr{sub 0.35}FeO{sub 3} as well, which indicates a lower bonding strength between Fe-O and a possible higher catalytic activity for La{sub 0.55}Sr{sub 0.35}FeO{sub 3}. The program continued to investigate the thermodynamic properties (stability and phase separation behavior) and total conductivity of prototype membrane materials. The data are needed together with the kinetic information to develop a complete model for the membrane transport. Previous report listed initial measurements on a sample of La{sub 0.2}Sr{sub 0.8}Fe{sub 0.55}Ti{sub 0.45}O{sub 3-x} prepared in-house by Praxair. Subsequently, a second sample of powder from a larger batch of sample were characterized and compared with

  6. A lithium oxygen secondary battery

    SciTech Connect (OSTI)

    Semkow, K.W.; Sammells, A.F.

    1987-08-01

    In principle the lithium-oxygen couple should provide one of the highest energy densities yet investigated for advanced battery systems. The problem to this time has been one of identifying strategies for achieving high electrochemical reversibilities at each electrode under conditions where one might anticipate to also achieve long materials lifetimes. This has been addressed in recent work by us via the application of stabilized zirconia oxygen vacancy conducting solid electrolytes, for the effective separation of respective half-cell reactions.

  7. Oxygen Transport Ceramic Membranes

    SciTech Connect (OSTI)

    S. Bandopadhyay; N. Nagabhushana; X.-D Zhou; Q. Cai; J. Yang; W.B. Yelon; W.J. James; H.U. Anderson; Alan Jacobson; C.A. Mims

    2004-05-01

    the LSCrF-2828 membrane to produce the gradients which exist under syngas generation conditions. The CO-CO{sub 2} mixtures have normal isotopic {sup 18}O abundances. The evolution of {sup 18}O on the delivery side in these experiments after an {sup 18}O pulse on the air side reveals a wealth of information about the oxygen transport processes.

  8. Platinum Monolayer Electrocatalysts for Oxygen Reduction Reaction...

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Platinum Monolayer Electrocatalysts for Oxygen Reduction Reaction Platinum Monolayer Electrocatalysts for Oxygen Reduction Reaction Download presentation slides from the June 19, ...

  9. Oxygen Transport Ceramic Membranes

    SciTech Connect (OSTI)

    S. Bandopadhyay; T. Nithyanantham; X.-D Zhou; Y-W. Sin; H.U. Anderson; Alan Jacobson; C.A. Mims

    2005-05-01

    been admitted to the delivery side of the LSCrF-2828 membrane to produce the gradients which exist under syngas generation conditions. The CO-CO{sub 2} mixtures have normal isotopic {sup 18}O abundances. The evolution of {sup 18}O on the delivery side in these experiments after an {sup 18}O pulse on the air side reveals a wealth of information about the oxygen transport processes.

  10. EVALUATING AN INNOVATIVE OXYGEN SENSOR FOR REMOTE SUBSURFACE OXYGEN MEASUREMENTS

    SciTech Connect (OSTI)

    Millings, M; Brian Riha, B; Warren Hyde, W; Karen Vangelas, K; Brian02 Looney, B

    2006-10-12

    Oxygen is a primary indicator of whether anaerobic reductive dechlorination and similar redox based processes contribute to natural attenuation remedies at chlorinated solvent contaminated sites. Thus, oxygen is a viable indicator parameter for documenting that a system is being sustained in an anaerobic condition. A team of researchers investigated the adaptation of an optical sensor that was developed for oceanographic applications. The optical sensor, because of its design and operating principle, has potential for extended deployment and sensitivity at the low oxygen levels relevant to natural attenuation. The results of the research indicate this tool will be useful for in situ long-term monitoring applications, but that the traditional characterization tools continue to be appropriate for characterization activities.

  11. Lithium Methyl Carbonate as a Reaction Product of Metallic Lithiumand...

    Office of Scientific and Technical Information (OSTI)

    Lithium methyl carbonate is only one of the components, the others being lithium oxalate and lithium methoxide. Authors: Zhuang, Guorong V. ; Yang, Hui ; Ross Jr., Philip N. ; Xu, ...

  12. Conversion of Levulinic Acid to Methyl Tetrahydrofuran - Energy...

    U.S. Department of Energy (DOE) all webpages (Extended Search)

    acid is a highly desirable renewable chemical platform, which, using this process, can be converted into Methyl Tetrahydrofuran (Me-THF) with reasonable yield. The...

  13. Facies and diagenesis of upper Tertiary-Pleistocene platform carbonates in a 300m borehole, southern Ambergris Caye, Belize

    SciTech Connect (OSTI)

    Burtnett, C.A.

    1996-12-31

    Well cuttings from an {approx}300 m-deep borehole drilled by the Belize government on Ambergris Caye were examined for inferred depositional environments, mineralogy, and stable oxygen-carbon isotopic compositions. The recovered section composes carbonates of the Barton Creek and (?)Sand Hill Formations, presumably of upper-most Tertiary to Pleistocene age. Location of the wellbore to the west of the exposed Pleistocene and superposed Holocene platform margin reef suggests continuous platform deposition. Comparison to modem facies indicates that the entire section is, in fact, mostly outer-shelf reef and immediate back-reef facies. Four unconformities are recognized in the upper 150 m of section on the basis of microbreccias and calcretes, and they truncate stacked, shallowing-upward cycles within the section. Depleted {delta}{sup 18}O and {delta}{sup 13}C compositions of whole-rock samples from the upper 150 m, which are highly porous and LMC-dominated, range from -2.5 to -5 {per_thousand} and -3 to -7 {per_thousand} (PDB), respectively. Unconformities are therefore believed to be subaerial exposure surfaces. Dolomite (replacive and cement) occurs below 150 m within HMC-dominated limestones that also contain aragonite. Dolomite generally increases with depth from 8-28%, its composition varies from Ca{sub 51-57}, and its mean isotopic composition is {delta}{sup 18}O = 3.2 {per_thousand} and {delta}{sup 13}C = 2.5 o/oo. There are no depth-related trends in dolomite stoichiometry or isotopic composition. Although the timing and site of dolomitization are not known, available data suggest formation from circulating marine fluids of near-normal composition.

  14. Facies and diagenesis of upper Tertiary-Pleistocene platform carbonates in a 300m borehole, southern Ambergris Caye, Belize

    SciTech Connect (OSTI)

    Burtnett, C.A. )

    1996-01-01

    Well cuttings from an [approx]300 m-deep borehole drilled by the Belize government on Ambergris Caye were examined for inferred depositional environments, mineralogy, and stable oxygen-carbon isotopic compositions. The recovered section composes carbonates of the Barton Creek and ( )Sand Hill Formations, presumably of upper-most Tertiary to Pleistocene age. Location of the wellbore to the west of the exposed Pleistocene and superposed Holocene platform margin reef suggests continuous platform deposition. Comparison to modem facies indicates that the entire section is, in fact, mostly outer-shelf reef and immediate back-reef facies. Four unconformities are recognized in the upper 150 m of section on the basis of microbreccias and calcretes, and they truncate stacked, shallowing-upward cycles within the section. Depleted [delta][sup 18]O and [delta][sup 13]C compositions of whole-rock samples from the upper 150 m, which are highly porous and LMC-dominated, range from -2.5 to -5 [per thousand] and -3 to -7 [per thousand] (PDB), respectively. Unconformities are therefore believed to be subaerial exposure surfaces. Dolomite (replacive and cement) occurs below 150 m within HMC-dominated limestones that also contain aragonite. Dolomite generally increases with depth from 8-28%, its composition varies from Ca[sub 51-57], and its mean isotopic composition is [delta][sup 18]O = 3.2 [per thousand] and [delta][sup 13]C = 2.5 o/oo. There are no depth-related trends in dolomite stoichiometry or isotopic composition. Although the timing and site of dolomitization are not known, available data suggest formation from circulating marine fluids of near-normal composition.

  15. Theoretical spectroscopic characterization at low temperatures of S-methyl thioformate and O-methyl thioformate

    SciTech Connect (OSTI)

    Senent, M. L.; Puzzarini, C.; Hochlaf, M.; Domínguez-Gómez, R.; Carvajal, M.

    2014-09-14

    Highly correlated ab initio methods are employed to determine spectroscopic properties at low temperatures of two S-analogs of methyl formate: S-methyl thioformate CH{sub 3}-S-CHO (MSCHO) and O-methyl thioformate CH{sub 3}-O-CHS (MOCHS). Both species are detectable and they are expected to play an important role in Astrochemistry. Molecular properties are compared with those of the O-analog, methyl formate. Both isomers present two conformers cis and trans. cis-CH{sub 3}-S-CHO represents the most stable structure lying 4372.2 cm{sup −1} below cis-CH{sub 3}-O-CHS. The energy difference between the cis and trans forms is drastically lower for MSCHO (1134 cm{sup −1}) than for MOCHS (1963.6 cm{sup −1}). Harmonic and anharmonic fundamentals and the corresponding intensities, as well as the rotational constants for the ground vibrational and first excited torsional states and the centrifugal distortions constants, are provided. Low torsional energy levels have been obtained by solving variationally a two dimensional Hamiltonian expressed in terms of the two torsional degrees of freedom. The corresponding 2D potential energy surfaces have been computed at the CCSD(T)/aug-cc-pVTZ level of theory. The methyl torsional barriers V{sub 3}(cis) are determined to be 139.7 cm{sup −1} (CH{sub 3}-S-CHO) and 670.4 cm{sup −1} (CH{sub 3}-O-CHS). The A/E splitting of ground torsional state has been estimated to be 0.438 cm{sup −1} for CH{sub 3}-S-CHO and negligible for CH{sub 3}-O-CHS.

  16. Production of methyl-vinyl ketone from levulinic acid

    DOE Patents [OSTI]

    Dumesic, James A.; West; Ryan M.

    2011-06-14

    A method for converting levulinic acid to methyl vinyl ketone is described. The method includes the steps of reacting an aqueous solution of levulinic acid, over an acid catalyst, at a temperature of from room temperature to about 1100 K. Methyl vinyl ketone is thereby formed.

  17. Host cells and methods for producing 3-methyl-2-buten-1-ol, 3-methyl-3-buten-1-ol, and 3-methyl-butan-1-ol

    DOE Patents [OSTI]

    Chou, Howard H.; Keasling, Jay D.

    2011-07-26

    The invention provides for a method for producing a 5-carbon alcohol in a genetically modified host cell. In one embodiment, the method comprises culturing a genetically modified host cell which expresses a first enzyme capable of catalyzing the dephosphorylation of an isopentenyl pyrophosphate (IPP) or dimethylallyl diphosphate (DMAPP), such as a Bacillus subtilis phosphatase (YhfR), under a suitable condition so that 5-carbon alcohol is 3-methyl-2-buten-1-ol and/or 3-methyl-3-buten-1-ol is produced. Optionally, the host cell may further comprise a second enzyme capable of reducing a 3-methyl-2-buten-1-ol to 3-methyl-butan-1-ol, such as a reductase.

  18. Methods for separating oxygen from oxygen-containing gases

    DOE Patents [OSTI]

    Mackay, Richard; Schwartz, Michael; Sammells, Anthony F.

    2000-01-01

    This invention provides mixed conducting metal oxides particularly useful for the manufacture of catalytic membranes for gas-phase oxygen separation processes. The materials of this invention have the general formula: A.sub.x A'.sub.x A".sub.2-(x+x') B.sub.y B'.sub.y B".sub.2-(y+y') O.sub.5+z ; where x and x' are greater than 0; y and y' are greater than 0; x+x' is less than or equal to 2; y+y' is less than or equal to 2; z is a number that makes the metal oxide charge neutral; A is an element selected from the f block lanthanide elements; A' is an element selected from Be, Mg, Ca, Sr, Ba and Ra; A" is an element selected from the f block lanthanides or Be, Mg, Ca, Sr, Ba and Ra; B is an element selected from the group consisting of Al, Ga, In or mixtures thereof; and B' and B" are different elements and are independently selected from the group of elements Mg or the d-block transition elements. The invention also provides methods for oxygen separation and oxygen enrichment of oxygen deficient gases which employ mixed conducting metal oxides of the above formula. Examples of the materials used for the preparation of the membrane include A.sub.x Sr.sub.x' B.sub.y Fe.sub.y' Co.sub.2-(y+y') O.sub.5+z, where x is about 0.3 to about 0.5, x' is about 1.5 to about 1.7, y is 0.6, y' is between about 1.0 and 1.4 and B is Ga or Al.

  19. Field pilot tests for tertiary recovery using butane and propane injection

    SciTech Connect (OSTI)

    Pacheco, E.F.; Garcia, A.I.

    1981-01-01

    This work describes a pilot project for tertiary recovery of liquid hydrocarbons through LPG injection in water-out sections of the Bolivar reservoir in La Pena Field, Santa Cruz, Boliva. The promising results obtained in the initial field miscibility tests, as well as the results from a mathematical model built to stimulate and evaluate the tertiary recovery project, directed subsequent work into a cyclic scheme for enhanced recovery. This scheme is explained and injection production data is presented. Field facilities built to handle both the injected LPG and the produced oil-LPG mixture are described. The oil/LPG ratio and the LPG recovered/injected fraction are the main factors measured in this to make further considerations for a full scale project.

  20. Characterization of molybdenum interfacial crud in a uranium mill that employs tertiary-amine solvent extraction

    SciTech Connect (OSTI)

    Moyer, B.; McDowell, W.J.

    1983-01-01

    In the present work, samples of a molybdenum-caused green gummy interfacial crud from an operating western US uranium mill have been physically and chemically examined. Formaton of cruds of this description has been a long-standing problem in the use of tertiary amine solvent extraction for the recovery of uranium from low-grade ores (Amex Process). The crud is essentially an organic-continuous dispersion containing about 10 wt % aqueous droplets and about 37 wt % greenish-yellow crystalline solids suspended in kerosene-amine process solvent. The greenish-yellow crystals were found to be a previously unknown double salt of tertiary amine molybdophosphate with three tertiary amine chlorides having the empirical formula (R/sub 3/NH)/sub 3/(PMo/sub 12/O/sub 40/).3(R/sub 3/NH)Cl. To confirm the identification of the compound, a pure trioctylamine (TOA) analog was synthesized. In laboratory extraction experiments, it was demonstrated that organic-soluble amine molydophosphate forms slowly upon contact of TOA solvent with dilute sulfuric acid solutions containing low concentrations of molybdate and phosphate. If the organic solutions of amine molybdophosphate were then contacted with aqueous NaCl solutions, a greenish-yellow precipitate of (TOAH)/sub 3/(PMo/sub 12/O/sub 40/).3(TOAH)Cl formed at the interface. The proposed mechanism for the formation of the crud under process conditions involves build up of molybdenum in the solvent, followed by reaction with extracted phosphate to give dissolved amine molybdophosphate. The amine molybdophosphate then co-crystallizes with amine chloride, formed during the stripping cycle, to give the insoluble double salt, which precipitates as a layer of small particles at the interface. The proposed solution to the problem is the use of branched-chain, instead of straight-chain, tertiary amine extractants under the expectation that branching would increase the solubility of the double salt. 2 figures, 5 tables.

  1. Laramide thrusting and Tertiary deformation Tierra Caliente, Michoacan and Guerrero States, southwestern Mexico

    SciTech Connect (OSTI)

    Johnson, C.A.; Harrison, C.G.A. ); Lang, H. ); Barros, J.A.; Cabral-Cano, E.

    1990-05-01

    Field investigations and detailed interpretations of Landsat Thematic Mapper images are in progress to improve understanding of regional structure and tectonics of the southernmost extension of the North American cordillera. Two areas have been selected within the Ciudad Altamirano 1:250,000 topographical sheet for geologic mapping and structural interpretation at 1:50,000 scale. The authors results to date require modification of previous ideas concerning the style and timing of deformations, the role and timing of terrane accretion in the overall tectonic history of the region, and the importance of southern Mexico to investigations of the tectonic evolution of the plates in the region. The relative sequence of deformation in the area correlates well with variations in relative motion between North America and plates in the Pacific. Post-Campanian thrusts and generally eastward-verging folds deformed the Mesozoic sequence during the (Laramide equivalent) Hidalgoan orogeny, associated with high-velocity east-west convergence with the Farallon plate that began about 70 Ma. The resulting unconformity was covered by the Tertiary Balsas Formation, a thick sequence of mostly continental clastics. The Tertiary stratigraphy is regionally and sometimes locally variable, but it can be divided into two members. The lower member is relatively volcanic poor and more deformed, and it lies below a regionally significant mid-Tertiary unconformity, which may mark a change to northeast-directed convergence with the Farallon plate sometime prior to 40 Ma. Continued mid-Tertiary deformation in southern Mexico may be related to eastward movement of the Chortis block and the resulting truncation of the Pacific margin of Mexico. The authors also suggest a tentative correlation between the volcaniclastic member of the Lower Cretaceous San Lucas Formation and the protolith of the Roca Verde metamorphics to the east.

  2. Catalyst containing oxygen transport membrane

    DOE Patents [OSTI]

    Christie, Gervase Maxwell; Wilson, Jamie Robyn; van Hassel, Bart Antonie

    2012-12-04

    A composite oxygen transport membrane having a dense layer, a porous support layer and an intermediate porous layer located between the dense layer and the porous support layer. Both the dense layer and the intermediate porous layer are formed from an ionic conductive material to conduct oxygen ions and an electrically conductive material to conduct electrons. The porous support layer has a high permeability, high porosity, and a high average pore diameter and the intermediate porous layer has a lower permeability and lower pore diameter than the porous support layer. Catalyst particles selected to promote oxidation of a combustible substance are located in the intermediate porous layer and in the porous support adjacent to the intermediate porous layer. The catalyst particles can be formed by wicking a solution of catalyst precursors through the porous support toward the intermediate porous layer.

  3. Composite oxygen ion transport element

    DOE Patents [OSTI]

    Chen, Jack C.; Besecker, Charles J.; Chen, Hancun; Robinson, Earil T.

    2007-06-12

    A composite oxygen ion transport element that has a layered structure formed by a dense layer to transport oxygen ions and electrons and a porous support layer to provide mechanical support. The dense layer can be formed of a mixture of a mixed conductor, an ionic conductor, and a metal. The porous support layer can be fabricated from an oxide dispersion strengthened metal, a metal-reinforced intermetallic alloy, a boron-doped Mo.sub.5Si.sub.3-based intermetallic alloy or combinations thereof. The support layer can be provided with a network of non-interconnected pores and each of said pores communicates between opposite surfaces of said support layer. Such a support layer can be advantageously employed to reduce diffusion resistance in any type of element, including those using a different material makeup than that outlined above.

  4. Spherules from the Cretaceous/Tertiary boundary clay at Gubbio, Italy: the problem of outcrop contamination

    SciTech Connect (OSTI)

    Montanari, A.

    1986-12-01

    Surficial outcrop contamination has occurred in some well-known stratigraphic sections of carbonate rocks in the northern Apennines. A critical case involves several contaminated clay partings, including the Cretaceous/Tertiary boundary clay in the classic Bottaccione section near Gubbio, Italy. These clay layers contain shiny spherules which, in several recent studies, have been said to consist of volcanic glass and have been used to support the hypothesis that the terminal Cretaceous mass extinction was caused by widespread volcanism. Laboratory tests, however, indicate that these shiny spherules are made of HF-insoluble and combustible material and are therefore of recent biological origin. These objects were introduced into the Cretaceous/Tertiary boundary clay and other clay layers from the surrounding soil along with abundant detrital contaminants derived from erosion of the middle Miocene flysch exposed at the head of the Bottaccione Gorge. They are completely different from the altered and flattened microtektitelike spheroids that are found only in the iridium-rich Cretaceous/Tertiary boundary clay and that provide strong evidence for a large impact.

  5. West Hackberry Tertiary Project. Quarterly technical progress report, January 1, 1996--March 31, 1996

    SciTech Connect (OSTI)

    Gillham, T.; Cerveny, B.; Turek, E.

    1996-04-10

    The goal of the West Hackberry Tertiary Project is to demonstrate the technical and economic feasibility of combining air injection with the Double Displacement Process for tertiary oil recovery. The Double Displacement Process is the gas displacement of a water invaded oil column for the purpose of recovering oil through gravity drainage. The novel aspect of this project is the use of air as the injection fluid. The target reservoir for the project is the Camerina C-1,2,3 sand located on the West Flank of West Hackberry Field in Cameron Parish, Louisiana. If successful, this project will demonstrate that the use of air injection in the Double Displacement Process can economically recover oil in reservoirs where tertiary oil recovery is presently uneconomic. The first quarter of 1996 was outstanding both in terms of volume of air injected and low cost operations. More air was injected during this quarter than in any preceding quarter. The compressors experienced much improved run time with minimal repairs. Low operating costs resulted from no repairs required for injection or production wells. A discussion of the following topics are contained herein: (1) performance summary for the injection and production wells, (2) air compressor operations, (3) updated bottom hole pressure data, (4) technology transfer activities and (5) plans for the upcoming quarter.

  6. Tension-compression-tension tertiary twins in coarse-grained polycrystalline pure magnesium at room temperature

    SciTech Connect (OSTI)

    Yu, Qin; Jiang, Yanyao; Wang, Jian

    2015-04-07

    Using electron backscatter diffraction, the microstructural features of tension–compression–tension (T–C–T) tertiary twins are studied in coarse-grained pure polycrystalline magnesium subjected to monotonic compression along the extrusion direction in ambient air. T–C–T tertiary twins are developed due to the formation of a compression–tension double twin inside a primary tension twin. All the observed T–C–T twin variants are of TiCjTj type. TiCi+1Ti+1 (or TiCi–1Ti–1) variants are observed more frequently than TiCi+2Ti+2 (or TiCi–2Ti–2) variants. Moreover, the number of tertiary twin lamellae increases with the applied compressive strain.

  7. Dcm methylation is detrimental to plasmid transformation in Clostridium thermocellum

    SciTech Connect (OSTI)

    Guss, Adam M; Olson, Daniel G.; Caiazza, Nicky; Lynd, Lee R

    2012-01-01

    BACKGROUND: Industrial production of biofuels and other products by cellulolytic microorganisms is of interest but hindered by the nascent state of genetic tools. Although a genetic system for Clostridium thermocellum DSM1313 has recently been developed, available methods achieve relatively low efficiency and similar plasmids can transform C. thermocellum at dramatically different efficiencies. RESULTS: We report an increase in transformation efficiency of C. thermocellum for a variety of plasmids by using DNA that has been methylated by Escherichia coli Dam but not Dcm methylases. When isolated from a dam+ dcm+ E. coli strain, pAMG206 transforms C. thermocellum 100-fold better than the similar plasmid pAMG205, which contains an additional Dcm methylation site in the pyrF gene. Upon removal of Dcm methylation, transformation with pAMG206 showed a four- to seven-fold increase in efficiency; however, transformation efficiency of pAMG205 increased 500-fold. Removal of the Dcm methylation site from the pAM205 pyrF gene via silent mutation resulted in increased transformation efficiencies equivalent to that of pAMG206. Upon proper methylation, transformation efficiency of plasmids bearing the pMK3 and pB6A origins of replication increased ca. three orders of magnitude. CONCLUSION: E. coli Dcm methylation decreases transformation efficiency in C. thermocellum DSM1313. The use of properly methylated plasmid DNA should facilitate genetic manipulation of this industrially relevant bacterium.

  8. Role of methyl groups in dynamics and evolution of biomolecules

    SciTech Connect (OSTI)

    Nickels, Jonathan D [ORNL; Curtis, J. E. [National Institute of Standards and Technology (NIST), Gaithersburg, MD; Oneill, Hugh [Oak Ridge National Laboratory (ORNL); Sokolov, Alexei P [ORNL

    2012-01-01

    Recent studies have discovered strong differences between the dynamics of nucleic acids (RNA and DNA) and proteins, especially at low hydration and low temperatures. This difference is caused primarily by dynamics of methyl groups that are abundant in proteins, but are absent or very rare in RNA and DNA. In this paper, we present a hypothesis regarding the role of methyl groups as intrinsic plasticizers in proteins and their evolutionary selection to facilitate protein dynamics and activity. We demonstrate the profound effect methyl groups have on protein dynamics relative to nucleic acid dynamics, and note the apparent correlation of methyl group content in protein classes and their need for molecular flexibility. Moreover, we note the fastest methyl groups of some enzymes appear around dynamical centers such as hinges or active sites. Methyl groups are also of tremendous importance from a ydrophobicity/folding/entropy perspective. These significant roles, however, complement our hypothesis rather than preclude the recognition of methyl groups in the dynamics and evolution of biomolecules.

  9. Phase 2 Methyl Iodide Deep-Bed Adsorption Tests

    SciTech Connect (OSTI)

    Soelberg, Nick; Watson, Tony

    2014-09-01

    Nuclear fission produces fission products (FPs) and activation products, including iodine-129, which could evolve into used fuel reprocessing facility off-gas systems, and could require off-gas control to limit air emissions to levels within acceptable emission limits. Research, demonstrations, and some reprocessing plant experience have indicated that diatomic iodine can be captured with efficiencies high enough to meet regulatory requirements. Research on the capture of organic iodides has also been performed, but to a lesser extent. Several questions remain open regarding the capture of iodine bound in organic compounds. Deep-bed methyl iodide adsorption testing has progressed according to a multi-laboratory methyl iodide adsorption test plan. This report summarizes the second phase of methyl iodide adsorption work performed according to this test plan using the deep-bed iodine adsorption test system at the Idaho National Laboratory (INL), performed during the second half of Fiscal Year (FY) 2014. Test results continue to show that methyl iodide adsorption using AgZ can achieve total iodine decontamination factors (DFs, ratios of uncontrolled and controlled total iodine levels) above 1,000, until breakthrough occurred. However, mass transfer zone depths are deeper for methyl iodide adsorption compared to diatomic iodine (I2) adsorption. Methyl iodide DFs for the Ag Aerogel test adsorption efficiencies were less than 1,000, and the methyl iodide mass transfer zone depth exceeded 8 inches. Additional deep-bed testing and analyses are recommended to (a) expand the data base for methyl iodide adsorption under various conditions specified in the methyl iodide test plan, and (b) provide more data for evaluating organic iodide reactions and reaction byproducts for different potential adsorption conditions.

  10. Oxygen permeation and coal-gas-assisted hydrogen production using...

    Office of Scientific and Technical Information (OSTI)

    Oxygen permeation and coal-gas-assisted hydrogen production using oxygen transport membranes Citation Details In-Document Search Title: Oxygen permeation and coal-gas-assisted ...

  11. The mechanisms of oxygen reduction and evolution reactions in...

    U.S. Department of Energy (DOE) all webpages (Extended Search)

    and evolution reactions in nonaqueous lithium-oxygen batteries A mechanistic understanding of the oxygen reductionevolution reaction in non-aqueous lithium-oxygen batteries. ...

  12. Laboratory measurements of parameters affecting wet deposition of methyl iodide

    SciTech Connect (OSTI)

    Maeck, W.J.; Honkus, R.J.; Keller, J.H.; Voilleque, P.G.

    1984-09-01

    The transfer of gaseous methyl iodide (CH/sub 3/I) to raindrops and the initial retention by vegetation of CH/sub 3/I in raindrops have been studied in a laboratory experimental program. The measured air-to-drop transfer parameters and initial retention factors both affect the wet deposition of methyl iodide onto vegetation. No large effects on the air-to-drop transfer due to methyl iodide concentration, temperature, acidity, or rain type were observed. Differences between laboratory measurements and theoretical values of the mass transfer coefficient were found. Pasture grass, lettuce, and alfalfa were used to study the initial retention of methyl iodide by vegetation. Only a small fraction of the incident CH/sub 3/I in raindrops was held by any of the three vegetation types.

  13. Distributions of methyl group rotational barriers in polycrystalline organic solids

    SciTech Connect (OSTI)

    Beckmann, Peter A. E-mail: wangxianlong@uestc.edu.cn; Conn, Kathleen G.; Division of Education and Human Services, Neumann University, One Neumann Drive, Aston, Pennsylvania 19014-1298 ; Mallory, Clelia W.; Department of Chemistry, Bryn Mawr College, 101 North Merion Ave., Bryn Mawr, Pennsylvania 19010-2899 ; Mallory, Frank B.; Rheingold, Arnold L.; Rotkina, Lolita; Wang, Xianlong E-mail: wangxianlong@uestc.edu.cn

    2013-11-28

    We bring together solid state {sup 1}H spin-lattice relaxation rate measurements, scanning electron microscopy, single crystal X-ray diffraction, and electronic structure calculations for two methyl substituted organic compounds to investigate methyl group (CH{sub 3}) rotational dynamics in the solid state. Methyl group rotational barrier heights are computed using electronic structure calculations, both in isolated molecules and in molecular clusters mimicking a perfect single crystal environment. The calculations are performed on suitable clusters built from the X-ray diffraction studies. These calculations allow for an estimate of the intramolecular and the intermolecular contributions to the barrier heights. The {sup 1}H relaxation measurements, on the other hand, are performed with polycrystalline samples which have been investigated with scanning electron microscopy. The {sup 1}H relaxation measurements are best fitted with a distribution of activation energies for methyl group rotation and we propose, based on the scanning electron microscopy images, that this distribution arises from molecules near crystallite surfaces or near other crystal imperfections (vacancies, dislocations, etc.). An activation energy characterizing this distribution is compared with a barrier height determined from the electronic structure calculations and a consistent model for methyl group rotation is developed. The compounds are 1,6-dimethylphenanthrene and 1,8-dimethylphenanthrene and the methyl group barriers being discussed and compared are in the 212 kJ?mol{sup ?1} range.

  14. Rape oil methyl ester (RME) and used cooking oil methyl ester (UOME) as alternative fuels

    SciTech Connect (OSTI)

    Hohl, G.H.

    1995-12-31

    The author presents a review about the fleet tests carried out by the Austrian Armed Forces concerning the practical application of a vegetable oil, i.e Rape Oil Methyl Ester (RME) and Used Cooking Oil Methyl Ester (UOME) as alternative fuels for vehicles under military conditions, and reviews other research results carried out in Austria. As a result of over-production in Western European agriculture, the increase in crop yields has led to tremendous surpluses. Alternative agricultural products have been sought. One alternative can be seen in biological fuel production for tractors, whereby the farmer is able to produce his own fuel supply as was the case when he previously provided self-made feed for his horses. For the market introduction different activities were necessary. A considerable number of institutes and organizations including the Austrian Armed Forces have investigated, tested and developed these alternative fuels. The increasing disposal problems of used cooking oil have initiated considerations for its use. The recycling of this otherwise waste product, and its preparation for use as an alternative fuel to diesel oil, seems to be most promising.

  15. Phytoremediation of ionic and methyl mercury pollution

    SciTech Connect (OSTI)

    Meagher, R.B.

    1998-06-01

    'The long-term objective of the research is to manipulate single-gene traits into plants, enabling them to process heavy metals and remediate heavy-metal pollution by resistance, sequestration, removal, and management of these contaminants. The authors are focused on mercury pollution as a case study of this plant genetic engineering approach. The working hypothesis behind this proposal was that transgenic plants expressing both the bacterial organo mercury lyase (merB) and the mercuric ion reductase gene (merA) will: (A) remove the mercury from polluted sites and (B) prevent methyl mercury from entering the food chain. The results from the research are so positive that the technology will undoubtedly be applied in the very near future to cleaning large mercury contaminates sites. Many such sites were not remediable previously due to the excessive costs and the negative environmental impact of conventional mechanical-chemical technologies. At the time this grant was awarded 20 months ago, the authors had successfully engineered a small model plant, Arabidopsis thaliana, to use a highly modified bacterial mercuric ion reductase gene, merA9, to detoxify ionic mercury (Hg(II)), reducing it to much less toxic and volatile metallic Hg(0) (Rugh et al., 1996). Seeds from these plants germinate, grow, and set seed at normal growth rates on levels of Hg(II) that are lethal to normal plants. In assays on transgenic seedlings suspended in a solution of Hg(II), 10 ng of Hg(0) was evolved per min per mg wet weight of plant tissue. At that time, the authors had no information on expression of merA in any other plant species, nor had the authors tested merB in any plant. However, the results were so startlingly positive and well received that they clearly presaged a paradigm shift in the field of environmental remediation.'

  16. Anastomosing grabens, low-angle faults, and Tertiary thrust( ) faults, western Markagunt Plateau, southwestern Utah

    SciTech Connect (OSTI)

    Maldonado, F.; Sable, E.G. )

    1993-04-01

    A structurally complex terrane composed of grabens and horsts, low-angle faults, Tertiary thrust( ) faults, gravity-slide blocks, and debris deposits has been mapped along the western Markagunt Plateau, east of Parowan and Summit, southwestern Utah. This terrane, structurally situated within the transition between the Basin and Range and Colorado Plateau provinces, contains Tertiary volcanic and sedimentary and Cretaceous sedimentary rocks. The structures are mostly Miocene to Oligocene but some are Pleistocene. The oldest structure is the Red Hills low-angle shear zone, interpreted as a shallow structure that decoupled an upper plate composed of a Miocene-Oligocene volcanic ash-flow tuff and volcaniclastic succession from a lower plate of Tertiary sedimentary rocks. The period of deformation on the shear zone is bracketed from field relationships between 22.5 and 20 Ma. The graben-horst system trends northeast and formed after about 20 Ma (and probably much later) based on displacement of dated dikes and a laccolith. The central part of the system contains many grabens that merge toward its southerly end to become a single graben. Within these grabens, (1) older structures are preserved, (2) debris eroded from horst walls forms lobe-shaped deposits, (3) Pleistocene basaltic cinder cones have localized along graben-bounding faults, and (4) rock units are locally folded suggesting some component of lateral translation along graben-bounding faults. Megabreccia deposits and landslide debris are common. Megabreccia deposits are interpreted as gravity-slide blocks of Miocene-Oligocene( ) age resulting from formation of the Red Hills shear zone, although some may be related to volcanism, and still others to later deformation. The debris deposits are landslides of Pleistocene-Pliocene( ) age possibly caused by continued uplift of the Markagunt Plateau.

  17. TABLE33.CHP:Corel VENTURA

    Gasoline and Diesel Fuel Update

    ethyl tertiary butyl ether (ETBE), tertiary amyl methyl ether (TAME), tertiary butyl alcohol (TBA), and other aliphatic alcohols and ethers intended for motor gasoline blending...

  18. TABLE34.CHP:Corel VENTURA

    Gasoline and Diesel Fuel Update

    ethyl tertiary butyl ether (ETBE), tertiary amyl methyl ether (TAME), tertiary butyl alcohol (TBA), and other aliphatic alcohols and ethers intended for motor gasoline blending...

  19. Properties of some ionic liquids based on1-methyl-3-octylimidazolium and 4-methyl-N-butylpyridinium cations.

    SciTech Connect (OSTI)

    Papaiconomou, Nicolas; Yakelis, Neal; Salminen, Justin; Bergman,Robert; Prausnitz, John M.

    2005-09-29

    Syntheses are reported for ionic liquids containing 1-methyl-3octylimidazolium and 4-methyl-N-butylpyridinium cations, and trifluoromethansulfonate, dicyanamide, bis(trifluoromethylsulfonyl)imide, and nonafluorobutanesulfonate anions. Densities, melting points and glass transition points, solubility in water as well as polarities have been measured. Ionic liquids based on pyridinium cations exhibit higher melting points, lower solubility in water, and higher polarity than those based on imidazolium cations.

  20. Synthesis of oxygenates from H{sub 2}/CO synthesis gas and use as fuel additives

    SciTech Connect (OSTI)

    Herman, R.G.; Klier, K.; Feeley, O.C.

    1994-12-31

    Alternative processes for synthesizing fuel-grade oxygenates are centered on conversion of synthesis gas into C{sub 1}-C{sub 8} alcohols and ethers. Over Cs/Cu/ZnO-based catalysts, mixtures of methanol/isobutanol are predominantly formed. It has been found that these alcohols can be directly coupled over certain strong acid organic-based catalysts to form unsymmetric C{sub 5} ethers, mainly the kinetically favored methyl isobutyl ether (MIBE) with some of the thermodynamically favored methyl tertiarybutyl ether (MTBE), the symmetric ethers of dimethylether (DME) and diisobutylether (DIBE), or selectively dehydrated to form isobutene over sulfated zirconia. Based on these reactions, a 2-stage, dual catalyst configuration can be utilized to give MTBE as the dominant ether product. The octane numbers and cetane ratings of the oxygenates have been determined and are compared, e.g. adding 10 vol% MIBE and MTBE to 82.3 MON gasoline altered the MON of the gasoline by -1.5 and +1.4 units, respectively, and MIBE has a high cetane number of 53, compared to 42 for typical U.S. diesel fuel.

  1. Oxygen ion-beam microlithography

    DOE Patents [OSTI]

    Tsuo, Y. Simon

    1991-01-01

    A method of providing and developing a resist on a substrate for constructing integrated circuit (IC) chips includes the following steps: of depositing a thin film of amorphous silicon or hydrogenated amorphous silicon on the substrate and exposing portions of the amorphous silicon to low-energy oxygen ion beams to oxidize the amorphous silicon at those selected portions. The nonoxidized portions are then removed by etching with RF-excited hydrogen plasma. Components of the IC chip can then be constructed through the removed portions of the resist. The entire process can be performed in an in-line vacuum production system having several vacuum chambers. Nitrogen or carbon ion beams can also be used.

  2. Oxygen ion-beam microlithography

    DOE Patents [OSTI]

    Tsuo, Y.S.

    1991-08-20

    A method of providing and developing a resist on a substrate for constructing integrated circuit (IC) chips includes the following steps: of depositing a thin film of amorphous silicon or hydrogenated amorphous silicon on the substrate and exposing portions of the amorphous silicon to low-energy oxygen ion beams to oxidize the amorphous silicon at those selected portions. The nonoxidized portions are then removed by etching with RF-excited hydrogen plasma. Components of the IC chip can then be constructed through the removed portions of the resist. The entire process can be performed in an in-line vacuum production system having several vacuum chambers. Nitrogen or carbon ion beams can also be used. 5 figures.

  3. Device and method for separating oxygen isotopes

    DOE Patents [OSTI]

    Rockwood, Stephen D.; Sander, Robert K.

    1984-01-01

    A device and method for separating oxygen isotopes with an ArF laser which produces coherent radiation at approximately 193 nm. The output of the ArF laser is filtered in natural air and applied to an irradiation cell where it preferentially photodissociates molecules of oxygen gas containing .sup.17 O or .sup.18 O oxygen nuclides. A scavenger such as O.sub.2, CO or ethylene is used to collect the preferentially dissociated oxygen atoms and recycled to produce isotopically enriched molecular oxygen gas. Other embodiments utilize an ArF laser which is narrowly tuned with a prism or diffraction grating to preferentially photodissociate desired isotopes. Similarly, desired mixtures of isotopic gas can be used as a filter to photodissociate enriched preselected isotopes of oxygen.

  4. Contiguous Platinum Monolayer Oxygen Reduction Electrocatalysts on

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    High-Stability-Low-Cost Supports | Department of Energy Contiguous Platinum Monolayer Oxygen Reduction Electrocatalysts on High-Stability-Low-Cost Supports Contiguous Platinum Monolayer Oxygen Reduction Electrocatalysts on High-Stability-Low-Cost Supports Presented at the Department of Energy Fuel Cell Projects Kickoff Meeting, September 1 - October 1, 2009 adzic_bnl_kickoff.pdf (4.62 MB) More Documents & Publications Platinum Monolayer Electrocatalysts for Oxygen Reduction Reaction

  5. Oxygen electrocatalysis on (001)-oriented manganese perovskite...

    Office of Scientific and Technical Information (OSTI)

    the nanoscale Citation Details In-Document Search Title: Oxygen electrocatalysis on (001)-oriented manganese perovskite films: Mn valency and charge transfer at the nanoscale ...

  6. Jupiter Oxygen Corporation | Open Energy Information

    Open Energy Information (Open El) [EERE & EIA]

    Place: Schiller Park, Illinois Zip: 60176 Product: Illinois-based oxy-fuel combustion company involved in the capture of CO2. References: Jupiter Oxygen Corporation1...

  7. Homogeneously dispersed, multimetal oxygen-evolving catalysts...

    Office of Scientific and Technical Information (OSTI)

    SciTech Connect Search Results Journal Article: Homogeneously dispersed, multimetal oxygen-evolving catalysts Citation ... Publication Date: 2016-03-24 OSTI Identifier: 1245398 Report ...

  8. DEVICE FOR CONTROL OF OXYGEN PARTIAL PRESSURE

    DOE Patents [OSTI]

    Bradner, H.; Gordon, H.S.

    1957-12-24

    A device is described that can sense changes in oxygen partial pressure and cause a corresponding mechanical displacement sufficient to actuate meters, valves and similar devices. A piston and cylinder arrangement contains a charge of crystalline metal chelate pellets which have the peculiar property of responding to variations in the oxygen content of the ambient atmosphere by undergoing a change in dimension. A lever system amplifies the relative displacement of the piston in the cylinder, and actuates the controlled valving device. This partial pressure oxygen sensing device is useful in controlled chemical reactions or in respiratory devices such as the oxygen demand meters for high altitude aircraft.

  9. Contiguous Platinum Monolayer Oxygen Reduction Electrocatalysts...

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    More Documents & Publications Platinum Monolayer Electrocatalysts for Oxygen Reduction Reaction Advanced Materials and Concepts for Portable Power Fuel Cells Catalysis Working ...

  10. Identification of an Archean marine oxygen oasis

    SciTech Connect (OSTI)

    Riding, Dr Robert E; Fralick, Dr Philip; Liang, Liyuan

    2014-01-01

    The early Earth was essentially anoxic. A number of indicators suggest the presence of oxygenic photosynthesis 2700 3000 million years (Ma) ago, but direct evidence for molecular oxygen (O2) in seawater has remained elusive. Here we report rare earth element (REE) analyses of 2800 million year old shallowmarine limestones and deep-water iron-rich sediments at Steep Rock Lake, Canada. These show that the seawater from which extensive shallow-water limestones precipitated was oxygenated, whereas the adjacent deeper waters where iron-rich sediments formed were not. We propose that oxygen promoted limestone precipitation by oxidative removal of dissolved ferrous iron species, Fe(II), to insoluble Fe(III) oxyhydroxide, and estimate that at least 10.25 M oxygen concentration in seawater was required to accomplish this at Steep Rock. This agrees with the hypothesis that an ample supply of dissolved Fe(II) in Archean oceans would have hindered limestone formation. There is no direct evidence for the oxygen source at Steep Rock, but organic carbon isotope values and diverse stromatolites in the limestones suggest the presence of cyanobacteria. Our findings support the view that during the Archean significant oxygen levels first developed in protected nutrient-rich shallow marine habitats. They indicate that these environments were spatially restricted, transient, and promoted limestone precipitation. If Archean marine limestones in general reflect localized oxygenic removal of dissolved iron at the margins of otherwise anoxic iron-rich seas, then early oxygen oases are less elusive than has been assumed.

  11. Evidence for temperate conditions along the Antarctic peninsula during the Early Tertiary

    SciTech Connect (OSTI)

    Zinsmeister, W.J.

    1985-01-01

    Several investigators based on deep sea glacial marine sediments from the southern oceans and volcanic sequences in West Antarctica have suggested extreme glacial conditions existed around Antarctica during the early Tertiary. Their data suggest ice sheets with ice shelves greater than those today were present on Antarctica by the late Eocene. If these data are correct, conditions during the Eocene along the Peninsula were similar to those that exist today. Late Eocene faunas and floras from Seymour Island indicate that conditions along the Peninsula were temperature. No paleontologic or geologic evidence have been obtained from Seymour Island (64/degree/18'S) to support the existence of glacial conditions along the northern part of the Peninsula during the early Tertiary. The presence of large quantities of fossil wood and plant debris in the upper Eocene sediments on Seymour Island indicates the presence of dense forests on the Peninsula during the Eocene. The discovery of marsupial and land birds remains on Seymour Island also indicate the presence of abundant terrestrial life on the Peninsula. The occurrence of an abundant marine life on Seymour Island supports the existence of temperate conditions along the Peninsula. Similarities of the Eocene faunas and floras with present day biotas from Tasmania, New Zealand and southern South America indicate that conditions along the Antarctic Peninsula during the late Eocene were comparable to present day mid latitudes of the southern hemisphere.

  12. Anaerobic Mercury Methylation and Demethylation by Geobacter bemidjiensis Bem

    DOE PAGES-Beta [OSTI]

    Lu, Xia; Liu, Yurong; Johs, Alexander; Zhao, Linduo; Wang, Tieshan; Yang, Ziming; Lin, Hui; Elias, Dwayne A.; Pierce, Eric M.; Liang, Liyuan; et al

    2016-03-28

    Two competing processes controlling the net production and bioaccumulation of neurotoxic methylmercury (MeHg) in natural ecosystems are microbial methylation and demethylation. Though mercury (Hg) methylation by anaerobic microorganisms and demethylation by aerobic Hg-resistant bacteria have both been extensively studied, little attention has been given to MeHg degradation by anaerobic bacteria, particularly the iron-reducing bacterium Geobacter bemidjensis Bem. Here we report, for the first time, that the strain G. bemidjensis Bem can methylate inorganic Hg and degrade MeHg concurrently under anoxic conditions. Our results suggest that G. bemidjensis cells utilize a reductive demethylation pathway to degrade MeHg, with elemental Hg(0) asmore » the major reaction product, possibly due to the presence of homologs encoding both organo-mercurial lyase (MerB) and mercuric reductase (MerA) in this organism. In addition, the cells can mediate multiple reactions including Hg/MeHg sorption, Hg reduction and oxidation, resulting in both time and concentration dependent Hg species transformations. Moderate concentrations (10 500 M) of Hg-binding ligands such as cysteine enhance Hg(II) methylation but inhibit MeHg degradation. These findings indicate a cycle of methylation and demethylation among anaerobic bacteria and suggest that mer-mediated demethylation may play a role in the net balance of MeHg production in anoxic water and sediments.« less

  13. Phytoremediation of Ionic and Methyl Mercury Pollution

    SciTech Connect (OSTI)

    Meagher, Richard B.

    2005-06-01

    control the chemical speciation, electrochemical state, transport, and aboveground binding of mercury in order to manage this toxicant. To advance this mercury phytoremediation strategy, our planned research focuses on the following Specific Aims: (1) to increase the transport of mercury to aboveground tissue; (2) to identify small mercury binding peptides that enhance hyperaccumulation aboveground; (3) to test the ability of multiple genes acting together to enhance resistance and hyperaccumulation; (4) to construct a simple molecular system for creating male/female sterility, allowing engineered grass, shrub, and tree species to be released indefinitely at contaminated sites; (5) to test the ability of transgenic cottonwood and rice plants to detoxify ionic mercury and prevent methylmercury release from contaminated sediment; and (6) to initiate field testing with transgenic cottonwood and rice for the remediation of methylmercury and ionic mercury. The results of these experiments will enable the phytoremediation of methyl- and ionic mercury by a wide spectrum of deep-rooted, fast-growing plants adapted to diverse environments. We have made significant progress on all six of these specific aims as summarized below.

  14. Nested methylation-specific polymerase chain reaction cancer detection method

    DOE Patents [OSTI]

    Belinsky, Steven A.; Palmisano, William A.

    2007-05-08

    A molecular marker-based method for monitoring and detecting cancer in humans. Aberrant methylation of gene promoters is a marker for cancer risk in humans. A two-stage, or "nested" polymerase chain reaction method is disclosed for detecting methylated DNA sequences at sufficiently high levels of sensitivity to permit cancer screening in biological fluid samples, such as sputum, obtained non-invasively. The method is for detecting the aberrant methylation of the p16 gene, O 6-methylguanine-DNA methyltransferase gene, Death-associated protein kinase gene, RAS-associated family 1 gene, or other gene promoters. The method offers a potentially powerful approach to population-based screening for the detection of lung and other cancers.

  15. OXYGEN ENHANCED COMBUSTION FOR NOx CONTROL

    SciTech Connect (OSTI)

    David R. Thompson; Lawrence E. Bool; Jack C. Chen

    2001-04-01

    This quarterly technical progress report will summarize work accomplished for the Program through the fourth quarter January-March 2001 in the following task areas: Task 1 - Oxygen Enhanced Combustion, Task 2 - Oxygen Transport Membranes and Task 4 - Program Management. This report will also recap the results of the past year. The program is proceeding in accordance with the objectives for the first year. OTM material characterization was completed. 100% of commercial target flux was demonstrated with OTM disks. The design and assembly of Praxair's single tube high-pressure test facility was completed. The production of oxygen with a purity of better than 99.5% was demonstrated. Coal combustion testing was conducted at the University of Arizona. Modest oxygen enhancement resulted in NOx emissions reduction. The injector for oxygen enhanced coal based reburning was conducted at Praxair. Combustion modeling with Keystone boiler was completed. Pilot-scale combustion test furnace simulations continued this quarter.

  16. Modelling Hydrogen Reduction and Hydrodeoxygenation of Oxygenates

    SciTech Connect (OSTI)

    Zhao, Y.; Xu, Q.; Cheah, S.

    2013-01-01

    Based on Density Functional Theory (DFT) simulations, we have studied the reduction of nickel oxide and biomass derived oxygenates (catechol, guaiacol, etc.) in hydrogen. Both the kinetic barrier and thermodynamic favorability are calculated with respect to the modeled reaction pathways. In early-stage reduction of the NiO(100) surface by hydrogen, the pull-off of the surface oxygen atom and simultaneous activation of the nearby Ni atoms coordinately dissociate the hydrogen molecules so that a water molecule can be formed, leaving an oxygen vacancy on the surface. In hydrogen reaction with oxygenates catalyzed by transition metals, hydrogenation of the aromatic carbon ring normally dominates. However, selective deoxygenation is of particular interest for practical application such as biofuel conversion. Our modeling shows that doping of the transition metal catalysts can change the orientation of oxygenates adsorbed on metal surfaces. The correlation between the selectivity of reaction and the orientation of adsorption are discussed.

  17. Oxygen ion-conducting dense ceramic

    DOE Patents [OSTI]

    Balachandran, Uthamalingam; Kleefisch, Mark S.; Kobylinski, Thaddeus P.; Morissette, Sherry L.; Pei, Shiyou

    1996-01-01

    Preparation, structure, and properties of mixed metal oxide compositions containing at least strontium, cobalt, iron and oxygen are described. The crystalline mixed metal oxide compositions of this invention have, for example, structure represented by Sr.sub..alpha. (Fe.sub.1-x Co.sub.x).sub..alpha.+.beta. O.sub..delta. where x is a number in a range from 0.01 to about 1, .alpha. is a number in a range from about 1 to about 4, .beta. is a number in a range upward from 0 to about 20, and .delta. is a number which renders the compound charge neutral, and wherein the composition has a non-perovskite structure. Use of the mixed metal oxides in dense ceramic membranes which exhibit oxygen ionic conductivity and selective oxygen separation, are described as well as their use in separation of oxygen from an oxygen-containing gaseous mixture.

  18. Oxygen ion-conducting dense ceramic

    DOE Patents [OSTI]

    Balachandran, Uthamalingam; Kleefisch, Mark S.; Kobylinski, Thaddeus P.; Morissette, Sherry L.; Pei, Shiyou

    1997-01-01

    Preparation, structure, and properties of mixed metal oxide compositions containing at least strontium, cobalt, iron and oxygen are described. The crystalline mixed metal oxide compositions of this invention have, for example, structure represented by Sr.sub..alpha. (Fe.sub.1-x Co.sub.x).sub..alpha.+.beta. O.sub..delta. where x is a number in a range from 0.01 to about 1, .alpha. is a number in a range from about 1 to about 4, .beta. is a number in a range upward from 0 to about 20, and .delta. is a number which renders the compound charge neutral, and wherein the composition has a non-perovskite structure. Use of the mixed metal oxides in dense ceramic membranes which exhibit oxygen ionic conductivity and selective oxygen separation, are described as well as their use in separation of oxygen from an oxygen-containing gaseous mixture.

  19. Methods for detection of methyl-CpG dinucleotides

    DOE Patents [OSTI]

    Dunn, John J

    2013-11-26

    The invention provides methods for enriching methyl-CpG sequences from a DNA sample. The method makes use of conversion of cytosine residues to uracil under conditions in which methyl-cytosine residues are preserved. Additional methods of the invention enable to preservation of the context of me-CpG dinucleotides. The invention also provides a recombinant, full length and substantially pure McrA protein (rMcrA) for binding and isolation of DNA fragments containing the sequence 5'-C.sup.MeCpGG-3'. Methods for making and using the rMcrA protein, and derivatives thereof are provided.

  20. Methods for detection of methyl-CpG dinucleotides

    DOE Patents [OSTI]

    Dunn, John J.

    2012-09-11

    The invention provides methods for enriching methyl-CpG sequences from a DNA sample. The method makes use of conversion of cytosine residues to uracil under conditions in which methyl-cytosine residues are preserved. Additional methods of the invention enable to preservation of the context of me-CpG dinucleotides. The invention also provides a recombinant, full length and substantially pure McrA protein (rMcrA) for binding and isolation of DNA fragments containing the sequence 5'-C.sup.MeCpGG-3'. Methods for making and using the rMcrA protein, and derivatives thereof are provided.

  1. Methods for detection of methyl-CpG dinucleotides

    DOE Patents [OSTI]

    Dunn, John J.

    2013-01-29

    The invention provides methods for enriching methyl-CpG sequences from a DNA sample. The method makes use of conversion of cytosine residues to uracil under conditions in which methyl-cytosine residues are preserved. Additional methods of the invention enable to preservation of the context of me-CpG dinucleotides. The invention also provides a recombinant, full length and substantially pure McrA protein (rMcrA) for binding and isolation of DNA fragments containing the sequence 5'-C.sup.MeCpGG-3'. Methods for making and using the rMcrA protein, and derivatives thereof are provided.

  2. Geometric and Electronic Structures of the Ni(I) and Methyl-Ni(III)

    U.S. Department of Energy (DOE) all webpages (Extended Search)

    Intermediates of Methyl-Coenzyme M Reductase 9 Geometric and Electronic Structures of the Ni(I) and Methyl-Ni(III) Intermediates of Methyl-Coenzyme M Reductase Methyl-coenzyme M reductase (MCR) from methanogenic archaea catalyzes the terminal step in biological methane synthesis. Using coenzyme B (CoBSH) as the two-electron donor, MCR reduces methyl-coenzyme M (methyl-SCoM) to form methane and the heterodisulfide product, CoBS-SCoM. MCR contains an essential redox active nickel tetrapyrrolic

  3. OXYGEN ENHANCED COMBUSTION FOR NOx CONTROL

    SciTech Connect (OSTI)

    David R. Thompson; Lawrence E. Bool; Jack C. Chen

    2004-04-01

    Conventional wisdom says adding oxygen to a combustion system enhances product throughput, system efficiency, and, unless special care is taken, increases NOx emissions. This increase in NOx emissions is typically due to elevated flame temperatures associated with oxygen use leading to added thermal NOx formation. Innovative low flame temperature oxy-fuel burner designs have been developed and commercialized to minimize both thermal and fuel NOx formation for gas and oil fired industrial furnaces. To be effective these systems require close to 100% oxy-fuel combustion and the cost of oxygen is paid for by fuel savings and other benefits. For applications to coal-fired utility boilers at the current cost of oxygen, however, it is not economically feasible to use 100% oxygen for NOx control. In spite of this conventional wisdom, Praxair and its team members, in partnership with the US Department of Energy National Energy Technology Laboratory, have developed a novel way to use oxygen to reduce NOx emissions without resorting to complete oxy-fuel conversion. In this concept oxygen is added to the combustion process to enhance operation of a low NOx combustion system. Only a small fraction of combustion air is replaced with oxygen in the process. By selectively adding oxygen to a low NOx combustion system it is possible to reduce NOx emissions from nitrogen-containing fuels, including pulverized coal, while improving combustion characteristics such as unburned carbon. A combination of experimental work and modeling was used to define how well oxygen enhanced combustion could reduce NOx emissions. The results of this work suggest that small amounts of oxygen replacement can reduce the NOx emissions as compared to the air-alone system. NOx emissions significantly below 0.15 lbs/MMBtu were measured. Oxygen addition was also shown to reduce carbon in ash. Comparison of the costs of using oxygen for NOx control against competing technologies, such as SCR, show that this

  4. Selective photooxidation of hydrocarbons in zeolites by oxygen

    DOE Patents [OSTI]

    Frei, Heinz; Blatter, Fritz; Sun, Hai

    1998-01-01

    A selective photooxidation process for the conversion of hydrocarbon molecules to partially oxygenated derivatives, which comprises the steps of adsorbing a hydrocarbon and oxygen onto a dehydrated zeolite support matrix to form a hydrocarbon-oxygen contact pair, and subsequently exposing the hydrocarbon-oxygen contact pair to visible light, thereby forming a partially oxygenated derivative.

  5. Tertiary and Quaternary Ammonium-Phosphate Ionic Liquids as Lubricant Additives

    DOE PAGES-Beta [OSTI]

    Barnhill, William C.; Luo, Huimin; Meyer, III, Harry M; Ma, Cheng; Chi, Miaofang; Papke, Brian L.; Qu, Jun

    2016-06-23

    In this work we investigated the feasibility of five quaternary (aprotic) and four tertiary (protic) ammonium ionic liquids (ILs) with an identical organophosphate anion as lubricant antiwear additives. Viscosity, oil solubility, thermal stability, and corrosivity of the candidate ILs were characterized and correlated to the molecular structure. The protic group exhibits higher oil solubility than the aprotic group, and longer alkyl chains seem to provide better oil solubility and higher thermal stability. Selected ILs were applied as oil additives in steel-cast iron tribological tests and demonstrated promising anti-scuffing and anti-wear functionality. The thickness, nanostructure, coverage and composition of the tribofilmmore » formed by the besting performing IL were revealed by surface characterization for mechanistic understanding of the tribochemical interactions between the IL and metal surface. Results provide fundamental insights of the correlations among the molecular structure, physiochemical properties and lubricating performance for ammonium-phosphate ILs.« less

  6. Microstructure design for fast oxygen conduction

    DOE PAGES-Beta [OSTI]

    Aidhy, Dilpuneet S.; Weber, William J.

    2015-11-11

    Research from the last decade has shown that in designing fast oxygen conducting materials for electrochemical applications has largely shifted to microstructural features, in contrast to material-bulk. In particular, understanding oxygen energetics in heterointerface materials is currently at the forefront, where interfacial tensile strain is being considered as the key parameter in lowering oxygen migration barriers. Nanocrystalline materials with high densities of grain boundaries have also gathered interest that could possibly allow leverage over excess volume at grain boundaries, providing fast oxygen diffusion channels similar to those previously observed in metals. In addition, near-interface phase transformations and misfit dislocations aremore » other microstructural phenomenon/features that are being explored to provide faster diffusion. In this review, the current understanding on oxygen energetics, i.e., thermodynamics and kinetics, originating from these microstructural features is discussed. Moreover, our experimental observations, theoretical predictions and novel atomistic mechanisms relevant to oxygen transport are highlighted. In addition, the interaction of dopants with oxygen vacancies in the presence of these new microstructural features, and their future role in the design of future fast-ion conductors, is outlined.« less

  7. Petrochemical feedstock from basic oxygen steel furnace

    SciTech Connect (OSTI)

    Greenwood, C.W.; Hardwick, W.E.

    1983-10-01

    Iron bath gasification in which coal, lime, steam and oxygen are injected into a bath of molten iron for the production of a medium-Btu gas is described. The process has its origin in basic oxygen steelmaking. It operates at high temperatures and is thus not restrictive on the type of coal used. The ash is retained in the slag. The process is also very efficient. The authors suggest that in the present economic climate in the iron and steel industry, such a plant could be sited where existing coal-handling, oxygen and steelmaking equipment are available.

  8. Infant sex-specific placental cadmium and DNA methylation associations

    SciTech Connect (OSTI)

    Mohanty, April F.; Farin, Fred M.; Bammler, Theo K.; MacDonald, James W.; Afsharinejad, Zahra; Burbacher, Thomas M.; Siscovick, David S.; and others

    2015-04-15

    Background: Recent evidence suggests that maternal cadmium (Cd) burden and fetal growth associations may vary by fetal sex. However, mechanisms contributing to these differences are unknown. Objectives: Among 24 maternal-infant pairs, we investigated infant sex-specific associations between placental Cd and placental genome-wide DNA methylation. Methods: We used ANOVA models to examine sex-stratified associations of placental Cd (dichotomized into high/low Cd using sex-specific Cd median cutoffs) with DNA methylation at each cytosine-phosphate-guanine site or region. Statistical significance was defined using a false discovery rate cutoff (<0.10). Results: Medians of placental Cd among females and males were 5 and 2 ng/g, respectively. Among females, three sites (near ADP-ribosylation factor-like 9 (ARL9), siah E3 ubiquitin protein ligase family member 3 (SIAH3), and heparin sulfate (glucosamine) 3-O-sulfotransferase 4 (HS3ST4) and one region on chromosome 7 (including carnitine O-octanoyltransferase (CROT) and TP5S target 1 (TP53TG1)) were hypomethylated in high Cd placentas. Among males, high placental Cd was associated with methylation of three sites, two (hypomethylated) near MDS1 and EVI1 complex locus (MECOM) and one (hypermethylated) near spalt-like transcription factor 1 (SALL1), and two regions (both hypomethylated, one on chromosome 3 including MECOM and another on chromosome 8 including rho guanine nucleotide exchange factor (GEF) 10 (ARHGEF10). Differentially methylated sites were at or close to transcription start sites of genes involved in cell damage response (SIAH3, HS3ST4, TP53TG1) in females and cell differentiation, angiogenesis and organ development (MECOM, SALL1) in males. Conclusions: Our preliminary study supports infant sex-specific placental Cd-DNA methylation associations, possibly accounting for previously reported differences in Cd-fetal growth associations across fetal sex. Larger studies are needed to replicate and extend these

  9. Low Temperature Autoignition of C8H16O2 Ethyl and Methyl Esters...

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Temperature Autoignition of C8H16O2 Ethyl and Methyl Esters in a Motored Engine Low Temperature Autoignition of C8H16O2 Ethyl and Methyl Esters in a Motored Engine qThe alkyl chain ...

  10. Phase 1 Methyl Iodide Deep-Bed Adsorption Tests

    SciTech Connect (OSTI)

    Nick Soelberg; Tony Watson

    2014-08-01

    Nuclear fission results in the production of fission products (FPs) and activation products including iodine-129, which could evolve into used fuel reprocessing facility off-gas systems, and could require off-gas control to limit air emissions to levels within acceptable emission limits. Research, demonstrations, and some reprocessing plant experience have indicated that diatomic iodine can be captured with efficiencies high enough to meet regulatory requirements. Research on the capture of organic iodides has also been performed, but to a lesser extent [Jubin 2012b]. Several questions remain open regarding the capture of iodine bound in organic compounds. Deep-bed methyl iodide adsorption testing has progressed according to a multi-laboratory methyl iodide adsorption test plan. This report summarizes the first phase of methyl iodide adsorption work performed according to this test plan using the deep-bed iodine adsorption test system at the Idaho National Laboratory (INL), performed during Fiscal Year (FY) 2013 and early FY-2014. Testing has been performed to address questions posed in the test plan, and followed the testing outline in the test plan. Tests established detection limits, developed procedures for sample analysis with minimal analytical interferences, and confirmed earlier results that show that the methyl iodide reacts when in contact with the AgZ sorbent, and not significantly in the gas flow upstream of the sorbent. The reaction(s) enable separation of the iodine from the organic moiety, so that the iodine can chemisorb onto the sorbent. The organic moiety can form other compounds, some of which are organic compounds that are detected and can be tentatively identified using GC-FID and GCMS. Test results also show that other gas constituents (NOx and/or H2O) can affect the methyl iodide reactions. With NOx and H2O present in the gas stream, the majority of uncaptured iodine exiting iodine-laden sorbent beds is in the form of I2 or HI, species that

  11. Methyl Formate Oxidation: Speciation Data, Laminar Burning Velocities, Ignition Delay Times and a Validated Chemical Kinetic Model

    SciTech Connect (OSTI)

    Dooley, S.; Burke, M. P.; Chaos, M.; Stein, Y.; Dryer, F. L.; Zhukov, V. P.; Finch, O.; Simmie, J. M.; Curran, H. J.

    2010-07-16

    The oxidation of methyl formate (CH{sub 3}OCHO) has been studied in three experimental environments over a range of applied combustion relevant conditions: 1. A variable-pressure flow reactor has been used to quantify reactant, major intermediate and product species as a function of residence time at 3 atm and 0.5% fuel concentration for oxygen/fuel stoichiometries of 0.5, 1.0, and 1.5 at 900 K, and for pyrolysis at 975 K. 2. Shock tube ignition delays have been determined for CH{sub 3}OCHO/O{sub 2}/Ar mixtures at pressures of ? 2.7, 5.4, and 9.2 atm and temperatures of 12751935 K for mixture compositions of 0.5% fuel (at equivalence ratios of 1.0, 2.0, and 0.5) and 2.5% fuel (at an equivalence ratio of 1.0). 3. Laminar burning velocities of outwardly propagating spherical CH{sub 3}OCHO/air flames have been determined for stoichiometries ranging from 0.81.6, at atmospheric pressure using a pressure-release-type high-pressure chamber. A detailed chemical kinetic model has been constructed, validated against, and used to interpret these experimental data. The kinetic model shows that methyl formate oxidation proceeds through concerted elimination reactions, principally forming methanol and carbon monoxide as well as through bimolecular hydrogen abstraction reactions. The relative importance of elimination versus abstraction was found to depend on the particular environment. In general, methyl formate is consumed exclusively through molecular decomposition in shock tube environments, while at flow reactor and freely propagating premixed flame conditions, there is significant competition between hydrogen abstraction and concerted elimination channels. It is suspected that in diffusion flame configurations the elimination channels contribute more significantly than in premixed environments.

  12. Determination of reactive oxygen species from ZnO micro-nano structures with shape-dependent photocatalytic activity

    SciTech Connect (OSTI)

    He, Weiwei; Zhao, Hongxiao; Jia, Huimin; Yin, Jun-Jie; Zheng, Zhi

    2014-05-01

    Graphical abstract: ZnO micro/nano structures with shape dependent photocatalytic activity were prepared by hydrothermal reaction. The generations of hydroxyl radical, superoxide and singlet oxygen from irradiated ZnO were identified precisely by electron spin resonance spectroscopy. The type of reactive oxygen species was determined by band gap structure of ZnO. - Highlights: ZnO micro/nano structures with different morphologies were prepared by solvothermal reaction. Multi-pod like ZnO structures exhibited superior photocatalytic activity. The generations of hydroxyl radical, superoxide and singlet oxygen from irradiated ZnO were characterized precisely by electron spin resonance spectroscopy. The type of reactive oxygen species was determined by band gap structure of ZnO. - Abstract: ZnO micro/nano structures with different morphologies have been prepared by the changing solvents used during their synthesis by solvothermal reaction. Three typical shapes of ZnO structures including hexagonal, bell bottom like and multi-pod formed and were characterized by scanning electron microscopy and X-ray diffraction. Multi pod like ZnO structures exhibited the highest photocatalytic activity toward degradation of methyl orange. Using electron spin resonance spectroscopy coupled with spin trapping techniques, we demonstrate an effective way to identify precisely the generation of hydroxyl radicals, superoxide and singlet oxygen from the irradiated ZnO multi pod structures. The type of reactive oxygen species formed was predictable from the band gap structure of ZnO. These results indicate that the shape of micro-nano structures significantly affects the photocatalytic activity of ZnO, and demonstrate the value of electron spin resonance spectroscopy for characterizing the type of reactive oxygen species formed during photoexcitation of semiconductors.

  13. OXYGEN ENHANCED COMBUSTION FOR NOx CONTROL

    SciTech Connect (OSTI)

    David R. Thompson; Lawrence E. Bool; Jack C. Chen

    2003-08-01

    This quarterly technical progress report will summarize work accomplished for the Program through the thirteenth quarter, April-June 2003, in the following task areas: Task 1--Oxygen Enhanced Combustion, Task 3--Economic Evaluation and Task 4--Program Management. The program is proceeding in accordance with project objectives. REI's model was modified to evaluate mixing issues in the upper furnace of a staged unit. Analysis of the results, and their potential application to this unit is ongoing. Economic evaluation continues to confirm the advantage of oxygen-enhanced combustion. A contract for a commercial demonstration has been signed with the Northeast Generation Services Company to supply oxygen and license the oxygen enhanced low NOx combustor technology for use at the 147-megawatt coal fired Mt. Tom Station in Holyoke, MA. Commercial proposals have been submitted. Economic analysis of a beta site test performance was conducted.

  14. Oxygen ion-conducting dense ceramic

    DOE Patents [OSTI]

    Balachandran, Uthamalingam; Kleefisch, Mark S.; Kobylinski, Thaddeus P.; Morissette, Sherry L.; Pei, Shiyou

    1998-01-01

    Preparation, structure, and properties of mixed metal oxide compositions and their uses are described. Mixed metal oxide compositions of the invention have stratified crystalline structure identifiable by means of powder X-ray diffraction patterns. In the form of dense ceramic membranes, the present compositions demonstrate an ability to separate oxygen selectively from a gaseous mixture containing oxygen and one or more other volatile components by means of ionic conductivities.

  15. OXYGEN ENHANCED COMBUSTION FOR NOx CONTROL

    SciTech Connect (OSTI)

    David R. Thompson; Lawrence E. Bool; Jack C. Chen

    2002-01-01

    This quarterly technical progress report will summarize work accomplished for the Program in the seventh quarter October-December 2001 in the following task areas: Task 1 - Oxygen Enhanced Combustion, Task 2 - Oxygen Transport Membranes, Task 3 - Economic Evaluation and Task 4 - Program Management. Computational fluid dynamic (CFD) modeling of oxygen injection strategies was performed during the quarter resulting in data that suggest the oxygen injection reduces NOx emissions while reducing LOI. Pilot-scale testing activities concluded at the University of Utah this quarter. Testing demonstrated that some experimental conditions can lead to NOx emissions well below the 0.15 lb/MMBtu limit. Evaluation of alternative OTM materials with improved mechanical properties continued this quarter. Powder procedure optimization continued and sintering trial began on an element with a new design. Several OTM elements were tested in Praxair's single tube high-pressure test facility under various conditions. A modified PSO1d element demonstrated stable oxygen product purity of >98% and oxygen flux of 68% of target. Updated test results and projected economic performance have been reviewed with the Utility Industrial Advisors. The economic comparison remains very favorable for O{sub 2} enhanced combustion. Discussions regarding possible Beta sites have been held with three other utilities in addition to the industrial advisors. Proposals will be prepared after the completion of full scale burner testing. Beta test cost estimating work has been initiated.

  16. OXYGEN ENHANCED COMBUSTION FOR NOx CONTROL

    SciTech Connect (OSTI)

    David R. Thompson; Lawrence E. Bool; Jack C. Chen

    2002-04-01

    This quarterly technical progress report will summarize work accomplished for the Program through the fourth quarter January-March 2002 in the following task areas: Task 1--Oxygen Enhanced Combustion, Task 2--Oxygen Transport Membranes, Task 3--Economic Evaluation and Task 4--Program Management. This report will also recap the results of the past year. The program is proceeding in accordance with the objectives for the second year. The first round of pilot scale testing with 3 bituminous coals was completed at the University of Utah. Full-scale testing equipment is in place and experiments are underway. Coal combustion lab-scale testing was completed at the University of Arizona. Modest oxygen enhancement resulted in NOx emissions reduction. Combustion modeling activities continued with pilot-scale combustion test furnace simulations. 75% of target oxygen flux was demonstrated with small PSO1 tube in Praxair's single tube high-pressure test facility. The production of oxygen with a purity of better than 99.999% was demonstrated. Economic evaluation has confirmed the advantage of oxygen-enhanced combustion. Two potential host sites have been identified.

  17. Magnetism in LithiumOxygen Discharge Product

    SciTech Connect (OSTI)

    Lu, Jun; Jung, Hun-Ji; Lau, Kah Chun; Zhang, Zhengcheng; Schlueter, John A.; Du, Peng; Assary, Rajeev S.; Greeley, Jeffrey P.; Ferguson, Glen A.; Wang, Hsien-Hau; Hassoun, Jusef; Iddir, Hakim; Zhou, Jigang; Zuin, Lucia; Hu, Yongfeng; Sun, Yang-Kook; Scrosati, Bruno; Curtiss, Larry A.; Amine, Khalil

    2013-05-13

    Nonaqueous lithiumoxygen batteries have a much superior theoretical gravimetric energy density compared to conventional lithium-ion batteries, and thus could render long-range electric vehicles a reality. A molecular-level understanding of the reversible formation of lithium peroxide in these batteries, the properties of major/minor discharge products, and the stability of the nonaqueous electrolytes is required to achieve successful lithiumoxygen batteries. We demonstrate that the major discharge product formed in the lithiumoxygen cell, lithium peroxide, exhibits a magnetic moment. These results are based on dc-magnetization measurements and a lithium oxygen cell containing an ether-based electrolyte. The results are unexpected because bulk lithium peroxide has a significant band gap. Density functional calculations predict that superoxide- type surface oxygen groups with unpaired electrons exist on stoichiometric lithium peroxide crystalline surfaces and on nanoparticle surfaces; these computational results are consistent with the magnetic measurement of the discharged lithium peroxide product as well as EPR measurements on commercial lithium peroxide. The presence of superoxide-type surface oxygen groups with spin can play a role in the reversible formation and decomposition of lithium peroxide as well as the reversible formation and decomposition of electrolyte molecules.

  18. Trapping radiodine, in the form of methyl iodide, on nuclear carbon

    SciTech Connect (OSTI)

    Nacapricha, D.; Taylor, C.

    1996-12-31

    Studies have been performed on potassium-iodide-impregnated charcoals of the type used in the nuclear industry for trapping radioiodine released during nuclear fission. The effects of various parameters on the trapping efficiency of methyl iodide have been investigated. A variation in particle size within a bulk charcoal caused poor precision in K value measurements because of differences in surface area, pore volume, and bed density, leading to differences in the deposition of the impregnant. Precision is improved by sieving the charcoal to a narrower size because smaller particles have a higher porosity. This finding is supported by surface area and pore measurements. Two methods of impregnation are compared by measuring K values and the deposition of potassium iodide. Charcoal impregnated by rotary evaporation exhibits both higher K values and higher potassium iodide contents than sprayed charcoal. Two designs of spraying drum are compared: a drum with helical vanes allows more efficient deposition and more uniform distribution of impregnant than a drum with axial vanes. A decrease in the K value with increasing humidity correlates with the available surface area. A similar correlation exists between water content and available pore volume. Aging of potassium-iodide-impregnated charcoal, caused by the formation of oxygen complexes on the surface, is associated with significant falls in K value. K values of charcoals also can be restored to at least their original values by heat treatment in the absence of air. 12 refs., 6 figs., 1 tab.

  19. Facile oxygen intercalation between full layer graphene and Ru...

    Office of Scientific and Technical Information (OSTI)

    Facile oxygen intercalation between full layer graphene and Ru(0001) under ambient ... Title: Facile oxygen intercalation between full layer graphene and Ru(0001) under ambient ...

  20. Webinar: Testing Oxygen Reduction Reaction Activity with the...

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Webinar: Testing Oxygen Reduction Reaction Activity with the Rotating Disc Electrode Technique Above is the video recording for the webinar, "Testing Oxygen Reduction Reaction ...

  1. Strain Control of Oxygen Vacancies in Epitaxial Strontium Cobaltite...

    Office of Scientific and Technical Information (OSTI)

    Strain Control of Oxygen Vacancies in Epitaxial Strontium Cobaltite Films Citation Details In-Document Search Title: Strain Control of Oxygen Vacancies in Epitaxial Strontium ...

  2. Oxygen Diffusion (OD) Dramatically Improves Wear-Resistance of...

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Oxygen Diffusion (OD) Dramatically Improves Wear-Resistance of Titanium Oxygen Diffusion (OD) Dramatically Improves Wear-Resistance of Titanium 2007 Diesel Engine-Efficiency & ...

  3. Pt3Re alloy nanoparticles as electrocatalysts for the oxygen...

    Office of Scientific and Technical Information (OSTI)

    Pt3Re alloy nanoparticles as electrocatalysts for the oxygen reduction reaction Citation ... on March 24, 2018 Title: Pt3Re alloy nanoparticles as electrocatalysts for the oxygen ...

  4. Oxygen Carriers for Solid Fuel Chemical Looping Combustion Process...

    U.S. Department of Energy (DOE) all webpages (Extended Search)

    Combustion Process Regenerable Mixed Copper-Iron-Inert Support Oxygen Carriers ... technology, "Regenerable Mixed Copper-Iron-Inert Support Oxygen Carriers for ...

  5. Virtual Oxygen Sensor for Innovative NOx and PM Emission Control...

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Virtual Oxygen Sensor for Innovative NOx and PM Emission Control Technologies Virtual Oxygen Sensor for Innovative NOx and PM Emission Control Technologies A virtual O2 sensor for ...

  6. Oxygen And Carbon Isotope Ratios Of Hydrothermal Minerals From...

    Open Energy Information (Open El) [EERE & EIA]

    Oxygen And Carbon Isotope Ratios Of Hydrothermal Minerals From Yellowstone Drill Cores Jump to: navigation, search OpenEI Reference LibraryAdd to library Journal Article: Oxygen...

  7. Artificial oxygen transport protein (Patent) | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    Patent: Artificial oxygen transport protein Citation Details In-Document Search Title: Artificial oxygen transport protein This invention provides heme-containing peptides capable...

  8. OXYGEN ENHANCED COMBUSTION FOR NOx CONTROL

    SciTech Connect (OSTI)

    Lawrence E. Bool; Jack C. Chen; David R. Thompson

    2000-07-01

    Increased environmental regulations will require utility boilers to reduce NO{sub x} emissions to less than 0.15lb/MMBtu in the near term. Conventional technologies such as Selective Catalytic Reduction (SCR) and Selective Non-Catalytic Reduction (SNCR) are unable to achieve these lowered emission levels without substantially higher costs and major operating problems. Oxygen enhanced combustion is a novel technology that allows utilities to meet the NO{sub x} emission requirements without the operational problems that occur with SCR and SNCR. Furthermore, oxygen enhanced combustion can achieve these NO{sub x} limits at costs lower than conventional technologies. The objective of this program is to demonstrate the use of oxygen enhanced combustion as a technical and economical method of meeting the EPA State Implementation Plan for NO{sub x} reduction to less than 0.15lb/MMBtu for a wide range of boilers and coal. The oxygen enhanced coal combustion program (Task 1) focused this quarter on the specific objective of exploration of the impact of oxygen enrichment on NO{sub x} formation utilizing small-scale combustors for parametric testing. Research efforts toward understanding any limitations to the applicability of the technology to different burners and fuels such as different types of coal are underway. The objective of the oxygen transport membrane (OTM) materials development program (Task 2.1) is to ascertain a suitable material composition that can be fabricated into dense tubes capable of producing the target oxygen flux under the operating conditions. This requires that the material have sufficient oxygen permeation resulting from high oxygen ion conductivity, high electronic conductivity and high oxygen surface exchange rate. The OTM element development program (Task 2.2) objective is to develop, fabricate and characterize OTM elements for laboratory and pilot reactors utilizing quality control parameters to ensure reproducibility and superior performance

  9. Direct Observation of the Oxygenated Species during Oxygen Reduction on a

    U.S. Department of Energy (DOE) all webpages (Extended Search)

    Platinum Fuel Cell Cathode | Stanford Synchrotron Radiation Lightsource Direct Observation of the Oxygenated Species during Oxygen Reduction on a Platinum Fuel Cell Cathode Friday, December 20, 2013 Fuel Cell Figure 1 Figure 1. In situ x-ray spectroscopy identification and DFT simulations of oxygenated intermediates on a platinum fuel-cell cathode. The study shows that two types of hydroxyl intermediates (non-hydrated OH and hydrated OH) with distinct activities coexist on a fuel-cell

  10. Chemically induced Parkinson's disease: intermediates in the oxidation of 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine to the 1-methyl-4-phenyl-pyridinium ion

    SciTech Connect (OSTI)

    Chacon, J.N.; Chedekel, M.R.; Land, E.J.; Truscott, T.G.

    1987-04-29

    Various unstable intermediate oxidation states have been postulated in the metabolic activation of 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine to the 1-methyl-4-phenyl pyridinium ion. We now report the first direct observation of these free radical intermediates by pulse radiolysis and flash photolysis. Studies are described of various reactions of such species, in particular with dopamine whose autoxidation to dopamine quinone is reported to be potentiated by 1-methyl-4-phenyl-1,2,3, 6-tetrahydropyridine.

  11. Oxygen generator for medical applications (USIC)

    SciTech Connect (OSTI)

    Staiger, C. L.

    2012-03-01

    The overall Project objective is to develop a portable, non-cryogenic oxygen generator capable of supplying medical grade oxygen at sufficient flow rates to allow the field application of the Topical Hyperbaric Oxygen Therapy (THOT{reg_sign}) developed by Numotech, Inc. This project was sponsored by the U.S. Department of Energy Global Initiatives for Proliferation Prevention (GIPP) and is managed by collaboration between Sandia National Laboratories (SNL), Numotech, Inc, and LLC SPE 'Spektr-Conversion.' The project had two phases, with the objective of Phase I being to develop, build and test a laboratory prototype of the membrane-pressure swing adsorber (PSA) system producing at 15 L/min of oxygen with a minimum of 98% oxygen purity. Phase II objectives were to further refine and identify the pre-requisites needed for a commercial product and to determine the feasibility of producing 15 L/min of oxygen with a minimum oxygen purity of 99%. In Phase I, Spektr built up the necessary infrastructure to perform experimental work and proceeded to build and demonstrate a membrane-PSA laboratory prototype capable of producing 98% purity oxygen at a flow rate of 5 L/min. Spektr offered a plausible path to scale up the process for 15 L/min. Based on the success and experimental results obtained in Phase I, Spektr performed work in three areas for Phase II: construction of a 15 L/min PSA; investigation of compressor requirements for the front end of the membrane/PSA system; and performing modeling and simulation of assess the feasibility of producing oxygen with a purity greater than 99%. Spektr successfully completed all of the tasks under Phase II. A prototype 15 L/min PSA was constructed and operated. Spektr determined that no 'off the shelf' air compressors met all of the specifications required for the membrane-PSA, so a custom compressor will likely need to be built. Modeling and simulation concluded that production of oxygen with purities greater than 99% was possible

  12. Refinery & Blenders Net Input of Crude Oil

    U.S. Energy Information Administration (EIA) (indexed site)

    Product: Total Crude Oil & Petroleum Products Crude Oil Natural Gas Plant Liquids and Liquefied Refinery Gases Pentanes Plus Liquefied Petroleum Gases Ethane Normal Butane Isobutane Other Liquids Hydrogen/Oxygenates/Renewables/Other Hydrocarbons Hydrogen Oxygenates (excl. Fuel Ethanol) Methyl Tertiary Butyl Ether (MTBE) All Other Oxygenates Renewable Fuels (incl. Fuel Ethanol) Fuel Ethanol Renewable Diesel Fuel Other Renewable Fuels Other Hydrocarbons Unfinished Oils (net) Unfinished Oils,

  13. Refinery Stocks of Crude Oil and Petroleum Products

    U.S. Energy Information Administration (EIA) (indexed site)

    Product: Crude Oil and Petroleum Products Crude Oil Petroleum Products Pentanes Plus Liquefied Petroleum Gases Ethane/Ethylene Propane/Propylene Normal Butane/Butylene Isobutane/Isobutylene Oxygenates/Renewables/Other Hydrocarbons Oxygenates (excl. Fuel Ethanol) Methyl Tertiary Butyl Ether (MTBE) All Other Oxygenates Renewable Fuels (incl. Fuel Ethanol) Fuel Ethanol Renewable Diesel Fuel Other Renewable Fuels Other Hydrocarbons Unfinished Oils Naphthas and Lighter Kerosene and Light Gas Oils

  14. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update

    Imports & Exports Definitions Key Terms Definition All Other Motor Gasoline Blending Components Naphthas (e.g. straight-run gasoline, alkylate, reformate, benzene, toluene, xylene) used for blending or compounding into finished motor gasoline. Includes receipts and inputs of Gasoline Treated as Blendstock (GTAB). Excludes conventional blendstock for oxygenate blending (CBOB), reformulated blendstock for oxygenate blending, oxygenates (e.g. fuel ethanol and methyl tertiary butyl ether),

  15. Total Crude Oil and Petroleum Products Exports

    U.S. Energy Information Administration (EIA) (indexed site)

    Exports Product: Total Crude Oil and Petroleum Products Crude Oil Natural Gas Plant Liquids and Liquefied Refinery Gases Pentanes Plus Liquefied Petroleum Gases Ethane/Ethylene Propane/Propylene Normal Butane/Butylene Isobutane/Isobutylene Other Liquids Hydrogen/Oxygenates/Renewables/Other Hydrocarbons Oxygenates (excl. Fuel Ethanol) Methyl Tertiary Butyl Ether (MTBE) Other Oxygenates Renewable Fuels (incl. Fuel Ethanol) Fuel Ethanol Biomass-Based Diesel Unfinished Oils Naphthas and Lighter

  16. Total Crude Oil and Petroleum Products Imports by Area of Entry

    U.S. Energy Information Administration (EIA) (indexed site)

    by Area of Entry Product: Total Crude Oil and Petroleum Products Crude Oil Natural Gas Plant Liquids and Liquefied Refinery Gases Pentanes Plus Liquefied Petroleum Gases Ethane Ethylene Propane Propylene Normal Butane Butylene Isobutane Isobutylene Other Liquids Hydrogen/Oxygenates/Renewables/Other Hydrocarbons Oxygenates (excl. Fuel Ethanol) Methyl Tertiary Butyl Ether (MTBE) Other Oxygenates Renewable Fuels (incl. Fuel Ethanol) Fuel Ethanol Biomass-Based Diesel Fuel Other Renewable Diesel Fuel

  17. Tropospheric oxidation mechanism of dimethyl ether and methyl formate

    SciTech Connect (OSTI)

    Good, D.A.; Francisco, J.S.

    2000-02-17

    The oxidation mechanism of dimethyl ether is investigated using ab initio methods. The structure and energetics of reactants, products, and transition structures are determined for all pathways involved in the oxidation mechanism. The detailed pathways leading to the experimentally observed products of dimethyl ether oxidation are presented. The energetics of over 50 species and transition structures involved in the oxidation process are calculated with G2 and G2(MP2) energies. The principal pathway following the initial attack of dimethyl ether (CH{sub 3}OCH{sub 3}) by the OH radical is the formation of the methoxymethyl radical (CH{sub 2}OCH{sub 3}). Oxidation steps lead to the formation of methyl formate, which is consistent with the experimentally observed products. Oxidation pathways of methyl formate are also considered.

  18. SYNTHESIS OF METHYL METHACRYLATE FROM COAL-DERIVED SYNGAS

    SciTech Connect (OSTI)

    Makarand R. Gogate; James J. Spivey; Joseph R. Zoeller; Richard D. Colberg; Gerald N. Choi; Samuel S. Tam

    1999-04-21

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel collectively are developing a novel three-step process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas that consists of the steps of synthesis of a propionate, its condensation with formaldehyde to form methacrylic acid (MAA), and esterification of MAA with methanol to produce MMA. The research team has completed the research on the three-step methanol-based route to MMA. Under an extension to the original contract, we are currently evaluating a new DME-based process for MMA. The key research need for DME route is to develop catalysts for DME partial oxidation reactions and DME condensation reactions. Over the last quarter (January-March/99), in-situ formaldehyde generation and condensation with methyl propionate were tested over various catalysts and reaction conditions. The patent application is in preparation and the results are retained for future reports.

  19. Supply Impacts of an MTBE Ban

    Reports and Publications

    2002-01-01

    This paper analyzes the supply impacts of removing methyl tertiary butyl ether (MTBE) from gasoline.

  20. Synthesis of 6-Methyl-9-n-propyldibenzothiophene-4-ol

    SciTech Connect (OSTI)

    Not Available

    1991-10-28

    The material presented here has been described to some extent in Status Reports 12, 13, and 14 and covers the progress toward the synthesis of the modified target molecules 9-isopropyl-4-methoxy-6-methyldibenzothiophene (13) and 9-isopropyl-6-methyldibenzothiophene-4-ol (14). It is divided into three parts: (a) Dehydrogenation experiments On tetrahydrodibenzothiophene 12. (b) methoxyl methyl cleavage of 13 to 14 using boron tribromide. (c) isolation and purification of methoxydibenzothiophene 13.

  1. FY-2015 Methyl Iodide Deep-Bed Adsorption Test Report

    SciTech Connect (OSTI)

    Soelberg, Nicholas Ray; Watson, Tony Leroy

    2015-09-30

    Nuclear fission produces fission and activation products, including iodine-129, which could evolve into used fuel reprocessing facility off-gas systems, and could require off-gas control to limit air emissions to levels within acceptable emission limits. Deep-bed methyl iodide adsorption testing has continued in Fiscal Year 2015 according to a multi-laboratory methyl iodide adsorption test plan. Updates to the deep-bed test system have also been performed to enable the inclusion of evaporated HNO3 and increased NO2 concentrations in future tests. This report summarizes the result of those activities. Test results showed that iodine adsorption from gaseous methyl iodide using reduced silver zeolite (AgZ) resulted in initial iodine decontamination factors (DFs, ratios of uncontrolled and controlled total iodine levels) under 1,000 for the conditions of the long-duration test performed this year (45 ppm CH3I, 1,000 ppm each NO and NO2, very low H2O levels [3 ppm] in balance air). The mass transfer zone depth exceeded the cumulative 5-inch depth of 4 bed segments, which is deeper than the 2-4 inch depth estimated for the mass transfer zone for adsorbing I2 using AgZ in prior deep-bed tests. The maximum iodine adsorption capacity for the AgZ under the conditions of this test was 6.2% (6.2 g adsorbed I per 100 g sorbent). The maximum Ag utilization was 51%. Additional deep-bed testing and analyses are recommended to (a) expand the data base for methyl iodide adsorption and (b) provide more data for evaluating organic iodide reactions and reaction byproducts for different potential adsorption conditions.

  2. OXYGEN ENHANCED COMBUSTION FOR NOx CONTROL

    SciTech Connect (OSTI)

    David R. Thompson; Lawrence E. Bool; Jack C. Chen

    2003-02-01

    This quarterly technical progress report will summarize work accomplished for the Program through the eleventh quarter, October-December 2002, in the following task areas: Task 1 - Oxygen Enhanced Combustion, Task 2 - Oxygen Transport Membranes, Task 3 - Economic Evaluation and Task 4 - Program Management. The program is proceeding in accordance with the objectives for the third year. Pilot scale experiments conducted at the University of Utah were aimed at confirming the importance of oxygen injection strategy for different types of burners. CFD modeling at REI was used to better understand the potential for increased corrosion under oxygen enhanced combustion conditions. Data from a full-scale demonstration test in Springfield, MO were analyzed. OTM element development continued with preliminary investigation of an alternative method of fabrication of PSO1d elements. OTM process development continued with long-term testing of a PSO1d element. Economic evaluation has confirmed the advantage of oxygen-enhanced combustion. Proposals have been submitted for two additional beta test sites. A first commercial proposal has been submitted. Economic analysis of a beta site test performance was conducted.

  3. OXYGEN ENHANCED COMBUSTION FOR NOx CONTROL

    SciTech Connect (OSTI)

    David R. Thompson; Lawrence E. Bool; Jack C. Chen

    2003-04-01

    This quarterly technical progress report will summarize work accomplished for the Program through the twelfth quarter, January-March 2003, in the following task areas: Task 1--Oxygen Enhanced Combustion, Task 2--Oxygen Transport Membranes, Task 3--Economic Evaluation and Task 4--Program Management. The program is proceeding in accordance with the objectives for the third year. Pilot scale experiments conducted at the University of Utah explored both the effectiveness of oxygen addition and the best way to add oxygen with a scaled version of Riley Power's newest low NOx burner design. CFD modeling was done to compare the REI's modeling results for James River Unit 3 with the NOx and LOI results obtained during the demonstration program at that facility. Investigation of an alternative method of fabrication of PSO1d elements was conducted. OTM process development work has concluded with the completion of a long-term test of a PSO1d element Economic evaluation has confirmed the advantage of oxygen-enhanced combustion. Proposals have been submitted for two additional beta test sites. Commercial proposals have been submitted. Economic analysis of a beta site test performance was conducted.

  4. Absorption process for producing oxygen and nitrogen and solution therefor

    DOE Patents [OSTI]

    Roman, I.C.; Baker, R.W.

    1990-09-25

    Process for the separation and purification of oxygen and nitrogen is disclosed which utilizes solutions of oxygen carriers to selectively absorb oxygen from a gaseous stream, leaving nitrogen as a byproduct. In the process, an oxygen carrier capable of reversibly binding molecular oxygen is dissolved in a solvent solution, which absorbs oxygen from an oxygen-containing gaseous feed stream such as atmospheric air and desorbs oxygen to a gaseous product stream. The feed stream is maintained at a sufficiently high oxygen pressure to keep the oxygen carrier in its oxygenated form during absorption, while the product stream is maintained at a sufficiently low oxygen pressure to keep the carrier in its deoxygenated form during desorption. In an alternate mode of operation, the carrier solution is maintained at a sufficiently low temperature and high oxygen pressure to keep the oxygen carrier in its oxygenated form during absorption, and at a sufficiently high temperature to keep the carrier in its deoxygenated form during desorption. Under such conditions, exceptionally high oxygen concentrations on the order of 95% to 99% are obtained, as well as a long carrier lifetime in excess of 3 months, making the process commercially feasible. 1 figure

  5. Absorption process for producing oxygen and nitrogen and solution therefor

    DOE Patents [OSTI]

    Roman, Ian C. [Wilmington, DE; Baker, Richard W. [Palo Alto, CA

    1990-09-25

    Process for the separation and purification of oxygen and nitrogen is disclosed which utilizes solutions of oxygen carriers to selectively absorb oxygen from a gaseous stream, leaving nitrogen as a byproduct. In the process, an oxygen carrier capable of reversibly binding molecular oxygen is dissolved in a solvent solution, which absorbs oxygen from an oxygen-containing gaseous feed stream such as atmospheric air and desorbs oxygen to a gaseous product stream. The feed stream is maintained at a sufficiently high oxygen pressure to keep the oxygen carrier in its oxygenated form during absorption, while the product stream is maintained at a sufficiently low oxygen pressure to keep the carrier in its deoxygenated form during desorption. In an alternate mode of operation, the carrier solution is maintained at a sufficiently low temperature and high oxygen pressure to keep the oxygen carrier in its oxygenated form during absorption, and at a sufficiently high temperature to keep the carrier in its deoxygenated form during desorption. Under such conditions, exceptionally high oxygen concentrations on the order of 95% to 99% are obtained, as well as a long carrier lifetime in excess of 3 months, making the process commercially feasible.

  6. Absorption process for producing oxygen and nitrogen and solution therefor

    DOE Patents [OSTI]

    Roman, Ian C.

    1984-01-01

    Process for the separation and purification of oxygen and nitrogen is disclosed which utilizes solutions of oxygen carriers to selectively absorb oxygen from a gaseous stream, leaving nitrogen as a byproduct. In the process, an oxygen carrier capable of reversibly binding molecular oxygen is dissolved in a solvent solution, which absorbs oxygen from an oxygen-containing gaseous feed stream such as atmospheric air and desorbs oxygen to a gaseous product stream. The feed stream is maintained at a sufficiently high oxygen pressure to keep the oxygen carrier in its oxygenated form during absorption, while the product stream is maintained at a sufficiently low oxygen pressure to keep the carrier in its deoxygenated form during desorption. In an alternate mode of operation, the carrier solution is maintained at a sufficiently low temperature and high oxygen pressure to keep the oxygen carrier in its oxygenated form during absorption, and at a sufficiently high temperature to keep the carrier in its deoxygenated form during desorption. Under such conditions, exceptionally high oxygen concentrations on the order of 95% to 99% are obtained, as well as a long carrier lifetime in excess of 3 months, making the process commercially feasible.

  7. Iridium profile for 10 million years across the Cretaceous-Tertiary boundary at Gubbio (Italy)

    SciTech Connect (OSTI)

    Alvarez, W.; Montanari, A. ); Asaro, F. )

    1990-12-21

    The iridium anomaly at the Cretaceous-Tertiary (KT) boundary was discovered in the pelagic limestone sequence at Gubbio on the basis of 12 samples analyzed by neutron activation analysis (NAA) and was interpreted as indicating impact of a large extraterrestrial object at exactly the time of the KT mass extinction. Continuing controversy over the shape of the Ir profile at the Gubbio KT boundary and its interpretation called for a more detailed follow-up study. Analysis of a 57-meter-thick, 10-million-year-old part of the Gubbio sequence using improved NAA techniques revealed that there is only one Ir anomaly at the KT boundary, but this anomaly shows an intricate fine structure, the origin of which cannot yet be entirely explained. The KT Ir anomaly peaks in a 1-centimeter-thick clay layer, where the average Ir concentration is 3,000 parts per trillion (ppt); this peak is flanked by tails with Ir concentrations of 20 to 80 ppt that rise above a background of 12 to 13 ppt. The fine structure of the tails is probably due in part to lateral reworking, diffusion, burrowing, and perhaps Milankovitch cyclicity.

  8. Synsedimentary tectonics in Late Cretaceous-Early Tertiary pelagic basin of northern Apennines, Italy

    SciTech Connect (OSTI)

    Montanari, A.; Chan, L.S.; Alvarez, W.

    1987-05-01

    The sequence of Upper Cretaceous-Lower Tertiary pelagic limestones in the Umbria-Marches Apennines of Italy have recorded, with remarkable continuity, the geologic history of an epeiric sea on the eastern continental margin of the Ligurian Ocean during a time of widespread tectonism in the western Tethys domain. Sedimentary facies and paleocurrent analyses indicate that intrabasinal depocenters and structural highs have formed in response to extensional tectonic movements which started to affect the central part of the paleobasin in the early Turonian. The topography of the paleobasin was probably controlled by a complex pattern of buried fault blocks formed during the passive margin phase of the western Tethys and then reactivated in the Turonian after a prolonged time (Aptian to Cenomanian) of tectonic quiescence. Calcareous turbidites essentially made of remobilized pelagic mud were generated on the newly formed intrabasinal slopes and deposited in the adjacent depocenters. Conspicuous sedimentary events such as maxima in turbiditic deposition and soft-sediment slumps in these intrabasinal depocenters are attributed to major syndepositional earthquakes of regional extent. A detailed event-stratigraphy based on these sedimentary features indicates that the level of syndepositional tectonic activity reached a peak in the late Maastrichtian-early Paleocene and rapidly diminished in the Eocene.

  9. Novel Membranes and Processes for Oxygen Enrichment

    SciTech Connect (OSTI)

    Lin, Haiqing

    2011-11-15

    The overall goal of this project is to develop a membrane process that produces air containing 25-35% oxygen, at a cost of $25-40/ton of equivalent pure oxygen (EPO2). Oxygen-enriched air at such a low cost will allow existing air-fueled furnaces to be converted economically to oxygen-enriched furnaces, which in turn will improve the economic and energy efficiency of combustion processes significantly, and reduce the cost of CO{sub 2} capture and sequestration from flue gases throughout the U.S. manufacturing industries. During the 12-month Concept Definition project: We identified a series of perfluoropolymers (PFPs) with promising oxygen/nitrogen separation properties, which were successfully made into thin film composite membranes. The membranes showed oxygen permeance as high as 1,200 gpu and oxygen/nitrogen selectivity of 3.0, and the permeance and selectivity were stable over the time period tested (60 days). We successfully scaled up the production of high-flux PFP-based membranes, using MTR's commercial coaters. Two bench-scale spiral-wound modules with countercurrent designs were made and parametric tests were performed to understand the effect of feed flow rate and pressure, permeate pressure and sweep flow rate on the membrane module separation properties. At various operating conditions that modeled potential industrial operating conditions, the module separation properties were similar to the pure-gas separation properties in the membrane stamps. We also identified and synthesized new polymers [including polymers of intrinsic microporosity (PIMs) and polyimides] with higher oxygen/nitrogen selectivity (3.5-5.0) than the PFPs, and made these polymers into thin film composite membranes. However, these membranes were susceptible to severe aging; pure-gas permeance decreased nearly six-fold within two weeks, making them impractical for industrial applications of oxygen enrichment. We tested the effect of oxygen-enriched air on NO{sub x} emissions using a

  10. Oxygen reduction reaction: A framework for success

    DOE PAGES-Beta [OSTI]

    Allendorf, Mark D.

    2016-05-06

    Oxygen reduction at the cathode of fuel cells typically requires a platinum-based material to catalyse the reaction, but lower-cost, more stable catalysts are sought. Here, an intrinsically conductive metal–organic framework based on cheaper elements is shown to be a durable, structurally well-defined catalyst for this reaction.

  11. Ammonia producing engine utilizing oxygen separation

    DOE Patents [OSTI]

    Easley, Jr., William Lanier; Coleman, Gerald Nelson; Robel, Wade James

    2008-12-16

    A power system is provided having a power source, a first power source section with a first intake passage and a first exhaust passage, a second power source section with a second intake passage and a second exhaust passage, and an oxygen separator. The second intake passage may be fluidly isolated from the first intake passage.

  12. Impact of Renewable Fuels Standard/MTBE Provisions of S. 1766

    Reports and Publications

    2002-01-01

    This service report addresses the Renewable Fuels Standard (RFS)/methyl tertiary butyl ether (MTBE) provisions of S. 1766. The 'S. 1766' Case reflects provisions of S. 1766 including a renewable fuels standard (RFS) reaching five billion gallons by 2012, a complete phase-out of MTBE within four years, and the option for states to waive the oxygen requirement for reformulated gasoline (RFG).

  13. Ozone-forming potential of a series of oxygenated organic compounds

    SciTech Connect (OSTI)

    Japar, S.M.; Wallington, T.J.; Rudy, S.J.; Chang, Tai Y. )

    1991-03-01

    An incremental reactivity approach has been used to assess the relative ozone-forming potentials of various important oxygenated fuels/fuel additives, i.e., tert-butyl alcohol (TBA), dimethyl ether (DME), diethyl ether (DEE), methyl tert-butyl ether (MTBE), and ethyl tert-butyl ether (ETBE), in a variety of environments. Calculations were performed using a single-cell trajectory model, combined with the Lurmann-Carter-Coyner chemical mechanism, with (NMOC)/(NO{sub x}) ratios ranging from 4 to 20. This work provides the first quantitative assessment of the air quality impact of release of these important oxygenated compounds. ETBE and DEE are the two most reactive compounds on a per carbon equivalent basis, while TBA is the least reactive species. At a (NMOC)/(NO{sub x}) ratio of 8, which is generally typical of polluted urban areas in the United States, TBA, DME, MTBE, and ETBE all have incremental reactivities less than or equal to that of the urban NMHC mix. Thus, use of these additives in fuels may have a beneficial impact on urban ozone levels.

  14. Impact of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Reaction Activity for Platinum Electrocatalysts

    SciTech Connect (OSTI)

    Christ, J. M.; Neyerlin, K. C.; Wang, H.; Richards, R.; Dinh, H. N.

    2014-10-30

    The impact of model membrane degradation compounds on the relevant electrochemical parameters for the oxygen reduction reaction (i.e. electrochemical surface area and catalytic activity), was studied for both polycrystalline Pt and carbon supported Pt electrocatalysts. Model compounds, representing previously published, experimentally determined polymer electrolyte membrane degradation products, were in the form of perfluorinated organic acids that contained combinations of carboxylic and/or sulfonic acid functionality. Perfluorinated carboxylic acids of carbon chain length C1 – C6 were found to have an impact on electrochemical surface area (ECA). The longest chain length acid also hindered the observed oxygen reduction reaction (ORR) performance, resulting in a 17% loss in kinetic current (determined at 0.9 V). Model compounds containing sulfonic acid functional groups alone did not show an effect on Pt ECA or ORR activity. Lastly, greater than a 44% loss in ORR activity at 0.9V was observed for diacid model compounds DA-Naf (perfluoro(2-methyl-3-oxa-5-sulfonic pentanoic) acid) and DA-3M (perfluoro(4-sulfonic butanoic) acid), which contained both sulfonic and carboxylic acid functionalities.

  15. Impact of Polymer Electrolyte Membrane Degradation Products on Oxygen Reduction Reaction Activity for Platinum Electrocatalysts

    DOE PAGES-Beta [OSTI]

    Christ, J. M.; Neyerlin, K. C.; Wang, H.; Richards, R.; Dinh, H. N.

    2014-10-30

    The impact of model membrane degradation compounds on the relevant electrochemical parameters for the oxygen reduction reaction (i.e. electrochemical surface area and catalytic activity), was studied for both polycrystalline Pt and carbon supported Pt electrocatalysts. Model compounds, representing previously published, experimentally determined polymer electrolyte membrane degradation products, were in the form of perfluorinated organic acids that contained combinations of carboxylic and/or sulfonic acid functionality. Perfluorinated carboxylic acids of carbon chain length C1 – C6 were found to have an impact on electrochemical surface area (ECA). The longest chain length acid also hindered the observed oxygen reduction reaction (ORR) performance, resultingmore » in a 17% loss in kinetic current (determined at 0.9 V). Model compounds containing sulfonic acid functional groups alone did not show an effect on Pt ECA or ORR activity. Lastly, greater than a 44% loss in ORR activity at 0.9V was observed for diacid model compounds DA-Naf (perfluoro(2-methyl-3-oxa-5-sulfonic pentanoic) acid) and DA-3M (perfluoro(4-sulfonic butanoic) acid), which contained both sulfonic and carboxylic acid functionalities.« less

  16. Oxygen-exchange Pathways in Aluminum Polyoxocations

    SciTech Connect (OSTI)

    Rustad, James R.; Loring, J. S.; Casey, William H.

    2004-07-15

    Using molecular dynamics simulations and electronic structure methods, we postulate a mechanism to explain the complicated reactivity trends that are observed for oxygen isotope exchange reactions between sites in aluminum polyoxocations of the E-Keggin type and bulk solution. Experimentally, the molecules have four nonequivalent oxygens that differ considerably in reactivity both within a molecule, and between molecules in the series: Al13, GaAl12, and GeAl12 [MO4Al12(OH)24(H2O)12 n*(aq); with M=Al(III) for Al13, n=7; M=Ga(III) for GaAl12, n=7; M=Ge(IV) for GeAl12, n=8]. We find that a partly dissociated, metastable intermediate molecule of expanded volume is necessary for exchange of both sets of u2-OH and that the steady-state concentration of this intermediate reflects the bond strengths between the central metal and the u4-O. Thus the central metal exerts extraordinary control over reactions at hydroxyl bridges, although these are three bonds away. This mechanism not only explains the reactivity trends for oxygen isotope exchange in u2-OH and u-OH2 sites in the E-Keggin aluminum molecules, but also explains the observation that the reactivities of minerals tend to reflect the presence of highly coordinated oxygens, such as the u4-O in boehmite, a-, and y-Al2O3 and their Fe(III) analogs. The partial dissociation of these highly coordinated oxygens, coupled with simultaneous activation and displacement of neighboring metal centers, may be a fundamental process by which metals atoms undergo ligand exchanges at mineral surfaces.

  17. Synthesis of oxygenate products for high volume fuels applications. Quarterly technical progress report, November 1, 1994--January 31, 1995

    SciTech Connect (OSTI)

    1995-03-08

    The objective of this project is to develop high yield syntheses of oxygenate products that are liquid at room temperature using as starting materials dimethy ether (DME) or methanol. The identified products include: Dimethyl Carbonate (DMC), 1,1-Dimethoxyethane (DMOE), C{sub 2}{sup +} Alcohols/Ethers (C{sub 2}AE). The technical strategy is outlined below: (A) Synthesis of DMC via oxidative carbonylation of DME instead of methanol. Since this synthesis would not co-produce water as a byproduct, there is a potential for very high DME conversions in contrast to the low (ca 20%) conversions obtained in conventional plants. Technical emphasis will be placed on development of a supported copper catalyst with a capability for cleavage of DME into its chemisorbed organic moieties. (B) Synthesis of 1,1-dimethoxymethane (DMOE) from acetylene/CO/H{sub 2} process streams obtained from commercial methane oxidative pyrolysis processes. In the overall processing scheme the syngas would be converted to DME. The wet acetylene stream would be partially condensed to retain an equivalent of water and then condensed with DME to produce EMOE. (C) Direct conversion of DME or DME/methanol to ethanol/propanol or their methyl ethers. Under the influence of functionalized alcohol condensation catalysts developed exclusively at Amoco it should be possible to achieve direct conversion of dimethyl ether (or methanol) to ethanol/propanol and/or the methyl ethers of these alcohols. Although this reaction is not currently known, a combination of key catalyst components from identified systems should result in a DME conversion catalyst to C{sub 2}+ oxygenates. (D) Reaction of DME or acetylene with synthesis gas (CO/H{sub 2}) or methanol. A variety of catalysts will be tested for conversion of acetylene/CO/H{sub 2} or acetylene/methanol to propylene and conversion of DME/CO/H{sub 2} or DME/methanol to dimenthyoxymethane (DMM) and/or other oxygenates.

  18. Methyl aryl ethers from coal liquids as gasoline extenders and octane improvers

    SciTech Connect (OSTI)

    Singerman, G.M.

    1980-11-01

    A mixture of methyl aryl ethers derived from the phenols present in direct liquefaction coal liquids shows considerable promise as a gasoline blending agent and octane improver. The mixture of methyl aryl ethers was blended at five volume percent with a commercial, unleaded gasoline. The properties and performance of the blend in a variety of laboratory and automotive tests is reported. The tests show that the mixture of methyl aryl ethers improves gasoline octane without degrading other gasoline properties.

  19. Dipole Alignment at the Carbon Nanotube and Methyl Ammonium Lead Iodide

    Office of Scientific and Technical Information (OSTI)

    Perovskite Interface (Technical Report) | SciTech Connect Dipole Alignment at the Carbon Nanotube and Methyl Ammonium Lead Iodide Perovskite Interface Citation Details In-Document Search Title: Dipole Alignment at the Carbon Nanotube and Methyl Ammonium Lead Iodide Perovskite Interface This work correlates resonant peaks from first principles calculation on ammonia (NH3) Nitrogen 1s x-ray absorption spectroscopy (XAS) within the methyl ammonium lead iodide perovskite (CH3NH3PbI3), and

  20. Oxygen-producing inert anodes for SOM process

    SciTech Connect (OSTI)

    Pal, Uday B

    2014-02-25

    An electrolysis system for generating a metal and molecular oxygen includes a container for receiving a metal oxide containing a metallic species to be extracted, a cathode positioned to contact a metal oxide housed within the container; an oxygen-ion-conducting membrane positioned to contact a metal oxide housed within the container; an anode in contact with the oxygen-ion-conducting membrane and spaced apart from a metal oxide housed within the container, said anode selected from the group consisting of liquid metal silver, oxygen stable electronic oxides, oxygen stable crucible cermets, and stabilized zirconia composites with oxygen stable electronic oxides.

  1. Methyl chloride via oxyhydrochlorination of methane. Quarterly technical progress report No. 13, October--December 1994

    SciTech Connect (OSTI)

    1995-02-01

    The purpose of this contract is to develop a process for converting light alkane gases to methyl chloride via oxyhydrochlorination using highly selective, stable catalysts in fixed-bed reactors designed to remove the large amount of heat generated, so as to control the reaction temperature. Further, the objective is to obtain the engineering data base necessary for developing a commercially feasible process and to evaluate t economics of the process. Significant progress was made in six different technical areas during this quarter. These key highlights are: (1) Evaluation of catalyst samples from UCI led to the ordering of the OHC PDU catalyst batch. This catalyst batch arrived, was screened and found to be defective, and was reordered. (2) Natural gas containing higher hydrocarbons was used as a methane source. The reactant mixture formed oxygenates at temperatures lower than observed in the past. Burning at such low temperatures seems to create a product stream containing very little CH{sub 2}Cl{sub 2}. (3) Although it has not been decided if the PDU will use natural gas from the plant or methane or natural gas from cylinders as a methane feed source, it was concluded that an adsorption unit to remove sulfur and higher hydrocarbons is not necessary at this time. (4) PDU construction was completed in December. The bulk of insulation work was completed at the end of November. Much effort has been put into pressure testing the PDU`s systems. The startup team has become adept at finding and correcting such leaks. (5) SOP writing for the PDU was completed this quarter with communication with the software programmer to insure agreement between the software and SOP.

  2. Vacuum ultraviolet and infrared spectra of condensed methyl acetate on cold astrochemical dust analogs

    SciTech Connect (OSTI)

    Sivaraman, B.; Nair, B. G.; Mason, N. J.; Lo, J.-I.; Cheng, B.-M.; Kundu, S.; Davis, D.; Prabhudesai, V.; Krishnakumar, E.; Raja Sekhar, B. N.

    2013-12-01

    Following the recent report of the first identification of methyl acetate (CH{sub 3}COOCH{sub 3}) in the interstellar medium (ISM), we have carried out vacuum ultraviolet (VUV) and infrared (IR) spectroscopy studies on methyl acetate from 10 K until sublimation in an ultrahigh vacuum chamber simulating astrochemical conditions. We present the first VUV and IR spectra of methyl acetate relevant to ISM conditions. Spectral signatures clearly showed molecular reorientation to have started in the ice by annealing the amorphous ice formed at 10 K. An irreversible phase change from amorphous to crystalline methyl acetate ice was found to occur between 110 K and 120 K.

  3. Protein arginine methyltransferase 1 regulates herpes simplex virus replication through ICP27 RGG-box methylation

    SciTech Connect (OSTI)

    Yu, Jungeun; Shin, Bongjin; Park, Eui-Soon; Yang, Sujeong; Choi, Seunga; Kang, Misun; Rho, Jaerang

    2010-01-01

    Protein arginine methylation is involved in viral infection and replication through the modulation of diverse cellular processes including RNA metabolism, cytokine signaling, and subcellular localization. It has been suggested previously that the protein arginine methylation of the RGG-box of ICP27 is required for herpes simplex virus type-1 (HSV-1) viral replication and gene expression in vivo. However, a cellular mediator for this process has not yet been identified. In our current study, we show that the protein arginine methyltransferase 1 (PRMT1) is a cellular mediator of the arginine methylation of ICP27 RGG-box. We generated arginine substitution mutants in this domain and examined which arginine residues are required for methylation by PRMT1. R138, R148 and R150 were found to be the major sites of this methylation but additional arginine residues serving as minor methylation sites are still required to sustain the fully methylated form of ICP27 RGG. We also demonstrate that the nuclear foci-like structure formation, SRPK interactions, and RNA-binding activity of ICP27 are modulated by the arginine methylation of the ICP27 RGG-box. Furthermore, HSV-1 replication is inhibited by hypomethylation of this domain resulting from the use of general PRMT inhibitors or arginine mutations. Our data thus suggest that the PRMT1 plays a key role as a cellular regulator of HSV-1 replication through ICP27 RGG-box methylation.

  4. Exploring the roles of DNA methylation in the metal-reducing bacterium Shewanella oneidensis MR-1

    SciTech Connect (OSTI)

    Bendall, Matthew L.; Luong, Khai; Wetmore, Kelly M.; Blow, Matthew; Korlach, Jonas; Deutschbauer, Adam; Malmstrom, Rex

    2013-08-30

    We performed whole genome analyses of DNA methylation in Shewanella 17 oneidensis MR-1 to examine its possible role in regulating gene expression and 18 other cellular processes. Single-Molecule Real Time (SMRT) sequencing 19 revealed extensive methylation of adenine (N6mA) throughout the 20 genome. These methylated bases were located in five sequence motifs, 21 including three novel targets for Type I restriction/modification enzymes. The 22 sequence motifs targeted by putative methyltranferases were determined via 23 SMRT sequencing of gene knockout mutants. In addition, we found S. 24 oneidensis MR-1 cultures grown under various culture conditions displayed 25 different DNA methylation patterns. However, the small number of differentially 26 methylated sites could not be directly linked to the much larger number of 27 differentially expressed genes in these conditions, suggesting DNA methylation is 28 not a major regulator of gene expression in S. oneidensis MR-1. The enrichment 29 of methylated GATC motifs in the origin of replication indicate DNA methylation 30 may regulate genome replication in a manner similar to that seen in Escherichia 31 coli. Furthermore, comparative analyses suggest that many 32 Gammaproteobacteria, including all members of the Shewanellaceae family, may 33 also utilize DNA methylation to regulate genome replication.

  5. Phase 1 Methyl Iodide Deep-Bed Adsorption Tests (Technical Report...

    Office of Scientific and Technical Information (OSTI)

    Tests established detection limits, developed procedures for sample analysis with minimal analytical interferences, and confirmed earlier results that show that the methyl iodide ...

  6. Accurate ab initio vibrational energies of methyl chloride

    SciTech Connect (OSTI)

    Owens, Alec; Yurchenko, Sergei N.; Yachmenev, Andrey; Tennyson, Jonathan; Thiel, Walter

    2015-06-28

    Two new nine-dimensional potential energy surfaces (PESs) have been generated using high-level ab initio theory for the two main isotopologues of methyl chloride, CH{sub 3}{sup 35}Cl and CH{sub 3}{sup 37}Cl. The respective PESs, CBS-35{sup  HL}, and CBS-37{sup  HL}, are based on explicitly correlated coupled cluster calculations with extrapolation to the complete basis set (CBS) limit, and incorporate a range of higher-level (HL) additive energy corrections to account for core-valence electron correlation, higher-order coupled cluster terms, scalar relativistic effects, and diagonal Born-Oppenheimer corrections. Variational calculations of the vibrational energy levels were performed using the computer program TROVE, whose functionality has been extended to handle molecules of the form XY {sub 3}Z. Fully converged energies were obtained by means of a complete vibrational basis set extrapolation. The CBS-35{sup  HL} and CBS-37{sup  HL} PESs reproduce the fundamental term values with root-mean-square errors of 0.75 and 1.00 cm{sup −1}, respectively. An analysis of the combined effect of the HL corrections and CBS extrapolation on the vibrational wavenumbers indicates that both are needed to compute accurate theoretical results for methyl chloride. We believe that it would be extremely challenging to go beyond the accuracy currently achieved for CH{sub 3}Cl without empirical refinement of the respective PESs.

  7. Evaluation of alternate routes for the synthesis of methyl methacrylate

    SciTech Connect (OSTI)

    Spivey, J.J.; Gogate, M.R.; Zoeller, J.R.; Colberg, R.D.; Choi, G.N.

    1998-12-31

    The use of coal-derived syngas to produce high value chemicals is an important means of upgrading this resource. One example of a chemical that can be produced from coal-derived syngas is methyl methacrylate (MMA). Poly-methyl methacrylate is widely used in coatings and in various industrial molded products. The most widely practiced commercial technology for the synthesis of MMA is the acetone cyanohydrin (ACH) process. This process requires handling of large quantities of toxic hydrogen cyanide and generates one mole of ammonium bisulfate waste per mole of MMA. This bisulfate must either be regenerated or discarded, either of which substantially increases the cost. The ACH technology is thus environmentally and economically untenable for any new MMA plant expansions that would be needed to meet increasing demand. The RTI-Eastman-Bechtel research team is developing an alternative, environmentally benign route to MMA consisting of three steps; (step 1) synthesis of a propionate from ethylene, carbon monoxide, and steam, (step 2) condensation of this propionate with formaldehyde, and (step 3) esterification of resulting methacrylic acid with methanol to form MMA. This paper describes the preliminary economics of the overall process compared to other emerging processes, and focuses on step 2, including long term testing of catalysts for the condensation of propionic acid with formaldehyde to form MAA.

  8. Differences in volatile methyl siloxane (VMS) profiles in biogas from landfills and anaerobic digesters and energetics of VMS transformations

    SciTech Connect (OSTI)

    Tansel, Berrin Surita, Sharon C.

    2014-11-15

    Highlights: • In the digester gas, D4 and D5 comprised the 62% and 27% if siloxanes, respectively. • In landfill gas, the bulk of siloxanes were TMSOH (58%) followed by D4 (17%). • Methane utilization may be a possible mechanism for TMSOH formation in the landfills. • The geometric configurations of D4 and D5 molecules make them very stable. - Abstract: The objectives of this study were to compare the types and levels of volatile methyl siloxanes (VMS) present in biogas generated in the anaerobic digesters and landfills, evaluate the energetics of siloxane transformations under anaerobic conditions, compare the conditions in anaerobic digesters and municipal solid waste (MSW) landfills which result in differences in siloxane compositions. Biogas samples were collected at the South District Wastewater Treatment Plant and South Dade Landfill in Miami, Florida. In the digester gas, D4 and D5 comprised the bulk of total siloxanes (62% and 27%, respectively) whereas in the landfill gas, the bulk of siloxanes were trimethylsilanol (TMSOH) (58%) followed by D4 (17%). Presence of high levels of TMSOH in the landfill gas indicates that methane utilization may be a possible reaction mechanism for TMSOH formation. The free energy change for transformation of D5 and D4 to TMSOH either by hydrogen or methane utilization are thermodynamically favorable. Either hydrogen or methane should be present at relatively high concentrations for TMSOH formation which explains the high levels present in the landfill gas. The high bond energy and bond distance of the Si–O bond, in view of the atomic sizes of Si and O atoms, indicate that Si atoms can provide a barrier, making it difficult to break the Si–O bonds especially for molecules with specific geometric configurations such as D4 and D5 where oxygen atoms are positioned inside the frame formed by the large Si atoms which are surrounded by the methyl groups.

  9. Use of Treated Municipal Wastewater as Power Plant Cooling System Makeup Water: Tertiary Treatment versus Expanded Chemical Regimen for Recirculating Water Quality Management

    SciTech Connect (OSTI)

    David Dzombak; Radisav Vidic; Amy Landis

    2012-06-30

    Treated municipal wastewater is a common, widely available alternative source of cooling water for thermoelectric power plants across the U.S. However, the biodegradable organic matter, ammonia-nitrogen, carbonate and phosphates in the treated wastewater pose challenges with respect to enhanced biofouling, corrosion, and scaling, respectively. The overall objective of this study was to evaluate the benefits and life cycle costs of implementing tertiary treatment of secondary treated municipal wastewater prior to use in recirculating cooling systems. The study comprised bench- and pilot-scale experimental studies with three different tertiary treated municipal wastewaters, and life cycle costing and environmental analyses of various tertiary treatment schemes. Sustainability factors and metrics for reuse of treated wastewater in power plant cooling systems were also evaluated. The three tertiary treated wastewaters studied were: secondary treated municipal wastewater subjected to acid addition for pH control (MWW_pH); secondary treated municipal wastewater subjected to nitrification and sand filtration (MWW_NF); and secondary treated municipal wastewater subjected nitrification, sand filtration, and GAC adsorption (MWW_NFG). Tertiary treatment was determined to be essential to achieve appropriate corrosion, scaling, and biofouling control for use of secondary treated municipal wastewater in power plant cooling systems. The ability to control scaling, in particular, was found to be significantly enhanced with tertiary treated wastewater compared to secondary treated wastewater. MWW_pH treated water (adjustment to pH 7.8) was effective in reducing scale formation, but increased corrosion and the amount of biocide required to achieve appropriate biofouling control. Corrosion could be adequately controlled with tolytriazole addition (4-5 ppm TTA), however, which was the case for all of the tertiary treated waters. For MWW_NF treated water, the removal of ammonia by

  10. OXYGEN ENHANCED COMBUSTION FOR NOx CONTROL

    SciTech Connect (OSTI)

    Lawrence E. Bool; Jack C. Chen; David R. Thompson

    2000-10-01

    This quarterly technical progress report will summarize work accomplished for the Program through the second quarter July--September 2000 in the following task areas: Task 1-Oxygen Enhanced Combustion, Task 2-Oxygen Transport Membranes and Task 4-Program Management. The program is proceeding in accordance with the objectives for the first year. OTM tube characterization is well underway, the design and assembly of the high pressure permeation test facility is complete and the facility will be in full operation during the next quarter. Combustion testing has been initiated at both the University of Arizona and Praxair. Testing at the University of Arizona has experienced some delays; steps have been take to get the test work back on schedule. Completion of the first phase of the testing is expected in next quarter. Combustion modeling has been started at both REI and Praxair, preliminary results are expected in the next quarter.

  11. Excess Oxygen Defects in Layered Cuprates

    DOE R&D Accomplishments [OSTI]

    Lightfoot, P.; Pei, S. Y.; Jorgensen, J. D.; Manthiram, A.; Tang, X. X.; Goodenough, J. B.

    1990-09-01

    Neutron powder diffraction has been used to study the oxygen defect chemistry of two non-superconducting layered cuprates, La{sub 1. 25}Dy{sub 0.75}Cu{sub 3.75}F{sub 0.5}, having a T{sup {asterisk}}- related structure, and La{sub 1.85}Sr{sub 1.15}Cu{sub 2}O{sub 6.25}, having a structure related to that of the newly discovered double-layer superconductor La{sub 2-x}Sr{sub x}CaCu{sub 2}O{sub 6}. The role played by oxygen defects in determining the superconducting properties of layered cuprates is discussed.

  12. Electrical insulator assembly with oxygen permeation barrier

    DOE Patents [OSTI]

    Van Der Beck, Roland R.; Bond, James A.

    1994-01-01

    A high-voltage electrical insulator (21) for electrically insulating a thermoelectric module (17) in a spacecraft from a niobium-1% zirconium alloy wall (11) of a heat exchanger (13) filled with liquid lithium (16) while providing good thermal conductivity between the heat exchanger and the thermoelectric module. The insulator (21) has a single crystal alumina layer (SxAl.sub.2 O.sub.3, sapphire) with a niobium foil layer (32) bonded thereto on the surface of the alumina crystal (26) facing the heat exchanger wall (11), and a molybdenum layer (31) bonded to the niobium layer (32) to act as an oxygen permeation barrier to preclude the oxygen depleting effects of the lithium from causing undesirable niobium-aluminum intermetallic layers near the alumina-niobium interface.

  13. Electrical insulator assembly with oxygen permeation barrier

    DOE Patents [OSTI]

    Van Der Beck, R.R.; Bond, J.A.

    1994-03-29

    A high-voltage electrical insulator for electrically insulating a thermoelectric module in a spacecraft from a niobium-1% zirconium alloy wall of a heat exchanger filled with liquid lithium while providing good thermal conductivity between the heat exchanger and the thermoelectric module. The insulator has a single crystal alumina layer (SxAl[sub 2]O[sub 3], sapphire) with a niobium foil layer bonded thereto on the surface of the alumina crystal facing the heat exchanger wall, and a molybdenum layer bonded to the niobium layer to act as an oxygen permeation barrier to preclude the oxygen depleting effects of the lithium from causing undesirable niobium-aluminum intermetallic layers near the alumina-niobium interface. 3 figures.

  14. Platinum Monolayer Electrocatalysts for Oxygen Reduction Reaction

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Platinum Monolayer Electrocatalysts for Oxygen Reduction Reaction Radoslav Adzic Co-workers: Jia Wang, Miomir Vukmirovic, Kotaro Sasaki, Stoyan Bliznakov, Yun Cai, Yu Zhang, Kurian Kuttiyiel, Kuanping Gong, YongMan Choi, Ping Liu, Hideo Naohara 1 Chemistry Department, Brookhaven National Laboratory, Upton, NY 11973 1 Toyota Motor Corporation, Susono, Japan Webinar June 19, 2012 Outline - Introduction on fuel cells, electrocatalysis, existing developments and remaining obstacles to

  15. A miniature inexpensive, oxygen sensing element

    SciTech Connect (OSTI)

    Arenz, R.W.

    1991-10-07

    An exhaustive study was conducted to determine the feasibility of Nernst-type oxygen sensors based on ceramics containing Bi{sub 2}O{sub 3}. The basic sensor design consisted of a ceramic sensing module sealed into a metal tube. The module accommodated an internal heater and thermocouple. Thermal-expansion-matched metals, adhesives, and seals were researched and developed, consistent with sequential firings during sensor assembly. Significant effort was devoted to heater design/testing and to materials' compatibility with Pt electrodes. A systematic approach was taken to develop all sensor components which led to several design modifications. Prototype sensors were constructed and exhaustively tested. It is concluded that development of Nerst-type oxygen sensors based on Bi{sub 2}O{sub 3} will require much further effort and application of specialized technologies. However, during the course of this 3-year program much progress was reported in the literature on amperometric-type oxygen sensors, and a minor effort was devoted here to this type of sensor based on Bi{sub 2}O{sub 3}. These studies were made on Bi{sub 2}O{sub 3}-based ceramic samples in a multilayer-capacitor-type geometry and amperometric-type oxygen sensing was demonstrated at very low temperatures ({approximately} 160{degree}C). A central advantage here is that these types of sensors can be mass-produced very inexpensively ({approximately} 20--50 cents per unit). Research is needed, however, to develop an optimum diffusion-limiting barrier coating. In summary, the original goals of this program were not achieved due to unforeseen problems with Bi{sub 2}O{sub 3}-based Nernst sensors. However, a miniature amperometric sensor base on Bi{sub 2}O{sub 3} was demonstrated in this program, and it is now seen that this latter sensor is far superior to the originally proposed Nernst sensor. 6 refs., 24 figs.

  16. Oxygen stabilized zirconium vanadium intermetallic compound

    DOE Patents [OSTI]

    Mendelsohn, Marshall H.; Gruen, Dieter M.

    1982-01-01

    An oxygen stabilized intermetallic compound having the formula Zr.sub.x OV.sub.y where x=0.7 to 2.0 and y=0.18 to 0.33. The compound is capable of reversibly sorbing hydrogen at temperatures from -196.degree. C. to 450.degree. C. at pressures down to 10.sup.-6 Torr. The compound is also capable of selectively sorbing hydrogen from gaseous mixtures in the presence of CO and CO.sub.2.

  17. Hydrogen (H2) Production by Oxygenic Phototrophs

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Production by Oxygenic Phototrophs Eric L. Hegg Michigan State University Great Lakes Bioenergy Research Center Bioresour. Technol. 2011, 102, 8589-8604 Major Challenges to H 2 Photoproduction Biological Challenges * Poor efficiency of H 2 production * Poor heterologous expression of H 2 -forming enzymes * Low quantum yields * Competition for reducing equivalents; poor electron coupling * Sensitivity of H 2 -forming enzymes to O 2 M. Ghirardi, Abstract #1751, Honolulu PRiME 2012 Technical

  18. OXYGEN ENHANCED COMBUSTION FOR NOx CONTROL

    SciTech Connect (OSTI)

    David R. Thompson; Lawrence E. Bool; Jack C. Chen

    2002-08-01

    This quarterly technical progress report will summarize work accomplished for the Program through the ninth quarter April-June 2002 in the following task areas: Task 1--Oxygen Enhanced Combustion, Task 2--Oxygen Transport Membranes, Task 3--Economic Evaluation and Task 4--Program Management. The program is proceeding in accordance with the objectives for the third year. Full-scale testing using the Industrial Boiler Simulation Facility (ISBF) at Alstom Power was completed. The pilot scale experiments to evaluate the effect of air preheat and transport air stoichiometric ratio (SR) on NOx emissions were conducted at the University of Utah. Combustion modeling activities continued with full-scale combustion test furnace simulations. An OTM element was tested in Praxair's single tube high-pressure test facility and two thermal cycles were completed. PSO1d elements of new dimension were tested resulting in a lower flux than previous PSO1d elements of different dimensions, however, no element deformation was observed. Economic evaluation has confirmed the advantage of oxygen-enhanced combustion. Two potential host beta sites have been identified and proposals submitted.

  19. DME-to-oxygenates process studies

    SciTech Connect (OSTI)

    Tartamella, T.L.; Sardesai, A.; Lee, S.; Kulik, C.J.

    1994-12-31

    The feasibility of the production of hydrocarbons from dimethyl ether (DNM) has been illustrated in a fixed bed micro-reactor as well as a bench scale fluidized bed reactor by the University of Akron/EPRI DME-to-Hydrocarbon (DTG) Process. The DTG process has distinct advantages over its methanol based counterpart. Specifically, the DTG process excels in the area of higher productivity, higher per-pass conversion, and lower heat duties than the MTG process. Also of special importance is the production of oxygenates -- including MTBE, ETBE, and TAME. DME may be reacted with isobutylene to produce a mixture of MTBE and ETBE. The properties of ETBE excel over MTBE in the areas of lower RVP and higher RON. According to industrial reports, MTBE is the fastest growing chemical (1992 US capacity 135,350 BPD, with expected growth of 34%/year to 1997). Also, recent renewed interest as an octane-enhancer and as a source of oxygen has spurred a growing interest in nonrefinery synthesis routes to ETBE. TAME, with its lower RVP and higher RON has proven useful as a gasoline blending agent and octane enhancer and may also be produced directly from DME. DME, therefore, serves as a valuable feedstock in the conversion of may oxygenates with wide-scale industrial importance. It should be also noted that the interest in the utilization of DME as process feedstock is based on the favorable process economics of EPRI/UA`s liquid phase DME process.

  20. Oxygen Catalysis: The Other Half of the Equation

    SciTech Connect (OSTI)

    Turner, J.

    2008-10-01

    Artificial photosynthesis--splitting water with light--is an attractive way to make hydrogen, but what happens to the oxygen? A catalyst that aids in the efficient production of gaseous oxygen improves the viability of this approach.

  1. Impact of interstitial oxygen on the electronic and magnetic...

    Office of Scientific and Technical Information (OSTI)

    interstitial oxygen on the electronic and magnetic structure in superconducting Fe 1 + y Te O x thin films Citation Details In-Document Search Title: Impact of interstitial oxygen...

  2. Quaternary and tertiary aldoxime antidotes for organophosphate exposure in a zebrafish model system

    SciTech Connect (OSTI)

    Schmidt, Hayden R.; Radić, Zoran; Taylor, Palmer; Fradinger, Erica A.

    2015-04-15

    The zebrafish is rapidly becoming an important model system for screening of new therapeutics. Here we evaluated the zebrafish as a potential pharmacological model for screening novel oxime antidotes to organophosphate (OP)-inhibited acetylcholinesterase (AChE). The k{sub i} values determined for chlorpyrifos oxon (CPO) and dichlorvos (DDVP) showed that CPO was a more potent inhibitor of both human and zebrafish AChE, but overall zebrafish AChE was less sensitive to OP inhibition. In contrast, aldoxime antidotes, the quaternary ammonium 2-PAM and tertiary amine RS-194B, showed generally similar overall reactivation kinetics, k{sub r}, in both zebrafish and human AChE. However, differences between the K{sub ox} and k{sub 2} constants suggest that zebrafish AChE associates more tightly with oximes, but has a slower maximal reactivation rate than human AChE. Homology modeling suggests that these kinetic differences result from divergences in the amino acids lining the entrance to the active site gorge. Although 2-PAM had the more favorable in vitro reactivation kinetics, RS-194B was more effective antidote in vivo. In intact zebrafish embryos, antidotal treatment with RS-194B rescued embryos from OP toxicity, whereas 2-PAM had no effect. Dechorionation of the embryos prior to antidotal treatment allowed both 2-PAM and RS-194B to rescue zebrafish embryos from OP toxicity. Interestingly, RS-194B and 2-PAM alone increased cholinergic motor activity in dechorionated embryos possibly due to the reversible inhibition kinetics, K{sub i} and αK{sub i}, of the oximes. Together these results demonstrate that the zebrafish at various developmental stages provides an excellent model for investigating membrane penetrant antidotes to OP exposure. - Highlights: • Zebrafish AChE shares significant structural similarities with human AChE. • OP-inhibited zebrafish and human AChE exhibit similar reactivation kinetics. • The zebrafish chorion is permeable to BBB penetrant and not

  3. Oxygen-Enriched Combustion for Military Diesel Engine Generators

    Energy.gov [DOE]

    Substantial increases in brake power and considerably lower peak pressure can result from oxygen-enriched diesel combustion

  4. Strain Control of Oxygen Vacancies in Epitaxial Strontium Cobaltite Films

    Office of Scientific and Technical Information (OSTI)

    (Journal Article) | SciTech Connect Strain Control of Oxygen Vacancies in Epitaxial Strontium Cobaltite Films Citation Details In-Document Search Title: Strain Control of Oxygen Vacancies in Epitaxial Strontium Cobaltite Films The ability to manipulate oxygen anion defects rather than metal cations in complex oxides can facilitate creating new functionalities critical for emerging energy and device technologies. However, the difficulty in activating oxygen at reduced temperatures hinders the

  5. Dilute Oxygen Combustion Phase IV Final Report

    SciTech Connect (OSTI)

    Riley, M.F.

    2003-04-30

    Novel furnace designs based on Dilute Oxygen Combustion (DOC) technology were developed under subcontract by Techint Technologies, Coraopolis, PA, to fully exploit the energy and environmental capabilities of DOC technology and to provide a competitive offering for new furnace construction opportunities. Capital cost, fuel, oxygen and utility costs, NOx emissions, oxide scaling performance, and maintenance requirements were compared for five DOC-based designs and three conventional air5-fired designs using a 10-year net present value calculation. A furnace direct completely with DOC burners offers low capital cost, low fuel rate, and minimal NOx emissions. However, these benefits do not offset the cost of oxygen and a full DOC-fired furnace is projected to cost $1.30 per ton more to operate than a conventional air-fired furnace. The incremental cost of the improved NOx performance is roughly $6/lb NOx, compared with an estimated $3/lb. NOx for equ8pping a conventional furnace with selective catalytic reduction (SCCR) technology. A furnace fired with DOC burners in the heating zone and ambient temperature (cold) air-fired burners in the soak zone offers low capital cost with less oxygen consumption. However, the improvement in fuel rate is not as great as the full DOC-fired design, and the DOC-cold soak design is also projected to cost $1.30 per ton more to operate than a conventional air-fired furnace. The NOx improvement with the DOC-cold soak design is also not as great as the full DOC fired design, and the incremental cost of the improved NOx performance is nearly $9/lb NOx. These results indicate that a DOC-based furnace design will not be generally competitive with conventional technology for new furnace construction under current market conditions. Fuel prices of $7/MMBtu or oxygen prices of $23/ton are needed to make the DOC furnace economics favorable. Niche applications may exist, particularly where access to capital is limited or floor space limitations

  6. Unexpected methyl migrations of ethanol dimer under synchrotron VUV radiation

    SciTech Connect (OSTI)

    Xiao, Weizhan; Hu, Yongjun E-mail: lssheng@ustc.edu.cn; Li, Weixing; Guan, Jiwen; Liu, Fuyi; Shan, Xiaobin; Sheng, Liusi E-mail: lssheng@ustc.edu.cn

    2015-01-14

    While methyl transfer is well known to occur in the enzyme- and metal-catalyzed reactions, the methyl transfer in the metal-free organic molecules induced by the photon ionization has been less concerned. Herein, vacuum ultraviolet single photon ionization and dissociation of ethanol dimer are investigated with synchrotron radiation photoionization mass spectroscopy and theoretical methods. Besides the protonated clusters cation (C{sub 2}H{sub 5}OH) ⋅ H{sup +} (m/z = 47) and the β-carbon-carbon bond cleavage fragment CH{sub 2}O ⋅ (C{sub 2}H{sub 5}OH)H{sup +} (m/z = 77), the measured mass spectra revealed that a new fragment (C{sub 2}H{sub 5}OH) ⋅ (CH{sub 3}){sup +} (m/z = 61) appeared at the photon energy of 12.1 and 15.0 eV, where the neutral dimer could be vertically ionized to higher ionic state. Thereafter, the generated carbonium ions are followed by a Wagner-Meerwein rearrangement and then dissociate to produce this new fragment, which is considered to generate after surmounting a few barriers including intra- and inter-molecular methyl migrations by the aid of theoretical calculations. The appearance energy of this new fragment is measured as 11.55 ± 0.05 eV by scanning photoionization efficiency curve. While the signal intensity of fragment m/z = 61 starts to increase, the fragments m/z = 47 and 77 tend to slowly incline around 11.55 eV photon energy. This suggests that the additional fragment channels other than (C{sub 2}H{sub 5}OH) ⋅ H{sup +} and CH{sub 2}O ⋅ (C{sub 2}H{sub 5}OH)H{sup +} have also been opened, which consume some dimer cations. The present report provides a clear description of the photoionization and dissociation processes of the ethanol dimer in the range of the photon energy 12-15 eV.

  7. Chemical diffusion of oxygen in tin dioxide: Effects of dopants and oxygen partial pressure

    SciTech Connect (OSTI)

    Kamp, B.; Merkle, R. . E-mail: s.weiglein@fkf.mpg.de; Lauck, R.; Maier, J.

    2005-10-15

    Tin dioxide SnO{sub 2-{delta}} is a pronounced n-type electron conductor due to its oxygen deficiency. This study investigates the rate of chemical diffusion of oxygen in SnO{sub 2-{delta}} single crystals, which is a crucial step in the overall stoichiometry change of the material. The chemical diffusion coefficient D{sup {delta}} was determined from conductivity- and EPR-relaxation methods. The temperature dependence was found to be D{sup {delta}}=exp(-4+/-2)cm{sup 2}s{sup -1}exp(-(1.1+/-0.3)eV/kT). The dependence on crystal orientation, dopant content and oxygen partial pressure was below experimental error. The latter observation leads to the conclusion that the chemical diffusion coefficient is close to the diffusion coefficient of oxygen vacancies. Along with the relaxation process resulting from the chemical diffusion of oxygen, additional processes were observed. One of these was attributed to complications in the defect chemistry of the material. The relevance of the results for the kinetics of drift processes of Taguchi sensors is discussed.

  8. Characterization of the Deltaproteobacteria in contaminated and uncontaminated stream sediments and identification of potential mercury methylators

    SciTech Connect (OSTI)

    Mosher, Jennifer; Vishnivetskaya, Tatiana A; Elias, Dwayne A; Podar, Mircea; Brooks, Scott C; Brown, Steven D; Brandt, Craig C; Palumbo, Anthony Vito

    2012-01-01

    Microbial communities were examined in surface stream sediments at 5 contaminated sites and 1 control site near Oak Ridge, TN, USA, to identify bacteria that could be contributing to mercury (Hg) methylation. The phylogenetic composition of the sediment bacterial community was examined over 3 quarterly sampling periods (36 samples) using 16S rRNA gene pyrosequencing. Only 3064 sequences (0.85% of the total community) were identified as Deltaproteobacteria, the only group known to methylate Hg, using the Ribosomal Database Project classifier at the 99% confidence threshold. Constrained ordination techniques indicated statistically significant positive linear correlations between Desulfobulbus spp., Desulfonema spp. and Desulfobacca spp. and methyl-Hg concentrations at the Hg-contaminated sites. In contrast, the distribution of organisms related to Byssovorax spp. was significantly correlated to inorganic carbon, nitrate and uranium concentrations but not to Hg or methyl-Hg. Overall, the abundance and richness of Deltaproteobacteria sequences were higher in uncontaminated sediments, while the majority of the members present at the contaminated sites were either known potential metal-reducers/methylators or metal tolerant species. Given the abundance relative to other known Hg methylators and the association with methyl-Hg, Desulfobulbus spp. is considered a prime candidate for involvement in Hg methylation in these streams.

  9. Methyl-CpG island-associated genome signature tags

    DOE Patents [OSTI]

    Dunn, John J

    2014-05-20

    Disclosed is a method for analyzing the organismic complexity of a sample through analysis of the nucleic acid in the sample. In the disclosed method, through a series of steps, including digestion with a type II restriction enzyme, ligation of capture adapters and linkers and digestion with a type IIS restriction enzyme, genome signature tags are produced. The sequences of a statistically significant number of the signature tags are determined and the sequences are used to identify and quantify the organisms in the sample. Various embodiments of the invention described herein include methods for using single point genome signature tags to analyze the related families present in a sample, methods for analyzing sequences associated with hyper- and hypo-methylated CpG islands, methods for visualizing organismic complexity change in a sampling location over time and methods for generating the genome signature tag profile of a sample of fragmented DNA.

  10. High Temperature Chemical Kinetic Combustion Modeling of Lightly Methylated Alkanes

    SciTech Connect (OSTI)

    Sarathy, S M; Westbrook, C K; Pitz, W J; Mehl, M

    2011-03-01

    Conventional petroleum jet and diesel fuels, as well as alternative Fischer-Tropsch (FT) fuels and hydrotreated renewable jet (HRJ) fuels, contain high molecular weight lightly branched alkanes (i.e., methylalkanes) and straight chain alkanes (n-alkanes). Improving the combustion of these fuels in practical applications requires a fundamental understanding of large hydrocarbon combustion chemistry. This research project presents a detailed high temperature chemical kinetic mechanism for n-octane and three lightly branched isomers octane (i.e., 2-methylheptane, 3-methylheptane, and 2,5-dimethylhexane). The model is validated against experimental data from a variety of fundamental combustion devices. This new model is used to show how the location and number of methyl branches affects fuel reactivity including laminar flame speed and species formation.

  11. Mechanism of singlet oxygen deactivation in an electric discharge oxygen – iodine laser

    SciTech Connect (OSTI)

    Azyazov, V N; Mikheyev, P A; Torbin, A P; Pershin, A A; Heaven, M C

    2014-12-31

    We have determined the influence of the reaction of molecular singlet oxygen with a vibrationally excited ozone molecule O{sub 2}(a {sup 1}Δ) + O{sub 3}(ν) → 2O{sub 2} + O on the removal rate of O{sub 2}(a {sup 1}Δ) in an electric-discharge-driven oxygen – iodine laser. This reaction has been shown to be a major channel of O{sub 2}(a {sup 1}Δ) loss at the output of an electric-discharge singlet oxygen generator. In addition, it can also contribute significantly to the loss of O{sub 2}(a {sup 1}Δ) in the discharge region of the generator. (lasers)

  12. Investigation of the electrocatalytic oxygen reduction and evolution reactions in lithium–oxygen batteries

    DOE PAGES-Beta [OSTI]

    Zheng, Dong; Zhang, Xuran; Qu, Deyu; Yang, Xiao -Qing; Lee, Hung -Sui; Qu, Deyang

    2015-04-21

    Oxygen reduction and oxygen evolution reactions were examined on graphite electrodes with different crystal orientations. The kinetics for the redox couple O2/O2•- are very fast, therefore no catalyst seems necessary to assist the charge transfer process. Apparently, the main source of the overpotential for the O2 reduction reaction is from mass diffusion. Li2O2 becomes soluble in non-aqueous electrolytes in the presence of the tetraethylammonium tetrafluoroborate additive. The soluble B-O22- ions can be oxidized electro-catalytically. The edge orientation of graphite demonstrates superior catalytic activity for the oxidation over basal orientation. The findings reveal an opportunity for recharging Li-air batteries efficiently andmore » a new strategy of developing the catalyst for oxygen evolution reaction.« less

  13. Investigation of the electrocatalytic oxygen reduction and evolution reactions in lithiumoxygen batteries

    SciTech Connect (OSTI)

    Zheng, Dong; Zhang, Xuran; Qu, Deyu; Yang, Xiao -Qing; Lee, Hung -Sui; Qu, Deyang

    2015-04-21

    Oxygen reduction and oxygen evolution reactions were examined on graphite electrodes with different crystal orientations. The kinetics for the redox couple O2/O2- are very fast, therefore no catalyst seems necessary to assist the charge transfer process. Apparently, the main source of the overpotential for the O2 reduction reaction is from mass diffusion. Li2O2 becomes soluble in non-aqueous electrolytes in the presence of the tetraethylammonium tetrafluoroborate additive. The soluble B-O22- ions can be oxidized electro-catalytically. The edge orientation of graphite demonstrates superior catalytic activity for the oxidation over basal orientation. The findings reveal an opportunity for recharging Li-air batteries efficiently and a new strategy of developing the catalyst for oxygen evolution reaction.

  14. Investigation of the electrocatalytic oxygen reduction and evolution reactions in lithium–oxygen batteries

    SciTech Connect (OSTI)

    Zheng, Dong; Zhang, Xuran; Qu, Deyu; Yang, Xiao -Qing; Lee, Hung -Sui; Qu, Deyang

    2015-04-21

    Oxygen reduction and oxygen evolution reactions were examined on graphite electrodes with different crystal orientations. The kinetics for the redox couple O2/O2•- are very fast, therefore no catalyst seems necessary to assist the charge transfer process. Apparently, the main source of the overpotential for the O2 reduction reaction is from mass diffusion. Li2O2 becomes soluble in non-aqueous electrolytes in the presence of the tetraethylammonium tetrafluoroborate additive. The soluble B-O22- ions can be oxidized electro-catalytically. The edge orientation of graphite demonstrates superior catalytic activity for the oxidation over basal orientation. The findings reveal an opportunity for recharging Li-air batteries efficiently and a new strategy of developing the catalyst for oxygen evolution reaction.

  15. Magnetic interaction in oxygenated alpha Fe-phthalocyanines

    SciTech Connect (OSTI)

    Kuzmann, Ern?, E-mail: kuzmann@caesar.elte.hu; Homonnay, Zoltn; Horvth, Attila [Institute of Chemistry, Etvs Lornd University, P.O. Box 32, 1512 Budapest (Hungary); Pechousek, Jiri; Cuda, Jan; Machala, Libor; Zoppellaro, Giorgio; Zboril, Radek [Regional Centre of Advanced Technologies and Materials, Departments of Experimental Physics and Physical Chemistry, Faculty of Science Palacky University, 17. Listopadu 1192/12, 771 46 Olomouc (Czech Republic); Yin, Houping; Wei, Yen [Department of Chemistry, Drexel University, Philadelphia, PA 19104 (United States); Klencsr, Zoltn [Research Centre for Natural Sciences, Hungarian Academy of Sciences, Budapest, 1117 (Hungary); Kubuki, Shiro [Department of Chemistry, Graduate School of Science and Engineering, Tokyo Metropolitan University, 1-1 Minami-Osawa, Hachi-Oji, Tokyo 192-0397 (Japan); Nath, Amar [Department of Chemistry, University of North Carolina, Asheville, NC 28804 (United States)

    2014-10-27

    Alpha iron phthalocyanines (?-FePc) oxygenated at low temperatures were investigated with the help of {sup 57}Fe Mssbauer spectroscopy, magnetization measurements (SQUID) and X-ray diffractometry (XRD). Mssbauer spectroscopy revealed that upon oxygenation of ?-FePc, new species were formed which could be associated with Fe{sup III}Pc oxygen adducts. Unexpectedly, magnetically split spectrum of oxygenated ?-FePc was observed below 20 K. In-field Mssbauer spectra in a 5 T external magnetic field at 5K and magnetization measurements indicate antiferromagnetic coupling in oxygenated ?-FePc.

  16. Cathode architectures for alkali metal / oxygen batteries

    SciTech Connect (OSTI)

    Visco, Steven J; Nimon, Vitaliy; De Jonghe, Lutgard C; Volfkovich, Yury; Bograchev, Daniil

    2015-01-13

    Electrochemical energy storage devices, such as alkali metal-oxygen battery cells (e.g., non-aqueous lithium-air cells), have a cathode architecture with a porous structure and pore composition that is tailored to improve cell performance, especially as it pertains to one or more of the discharge/charge rate, cycle life, and delivered ampere-hour capacity. A porous cathode architecture having a pore volume that is derived from pores of varying radii wherein the pore size distribution is tailored as a function of the architecture thickness is one way to achieve one or more of the aforementioned cell performance improvements.

  17. Oxygen stabilized zirconium-vanadium-iron alloy

    DOE Patents [OSTI]

    Mendelsohn, Marshall H.; Gruen, Dieter M.

    1982-01-01

    An oxygen stabilized intermetallic compound having the formula (Zr.sub.1-x Ti.sub.x).sub.2-u (V.sub.1-y Fe.sub.y)O.sub.z where x=0.0 to 0.9, y=0.01 to 0.9, z=0.25 to 0.5 and u=0 to 1. The compound is capable of reversibly sorbing hydrogen at temperatures from -196.degree. C. to 200.degree. C. at pressures down to 10.sup.-6 torr. The compound is suitable for use as a hydrogen getter in low pressure, high temperature applications such as magnetic confinement fusion devices.

  18. The Mechanisms of Oxygen Reduction and Evolution Reactions in Nonaqueous Lithium-Oxygen Batteries

    SciTech Connect (OSTI)

    Cao, Ruiguo; Walter, Eric D.; Xu, Wu; Nasybulin, Eduard N.; Bhattacharya, Priyanka; Bowden, Mark E.; Engelhard, Mark H.; Zhang, Jiguang

    2014-09-01

    The oxygen reduction/evolution reaction (ORR/OER) mechanisms in nonaqueous Li-O2 batteries have been investigated by using electron paramagnetic resonance spectroscopy in this work. We identified the superoxide radical anion (O2•-) as an intermediate in the ORR process using 5,5-dimethyl-pyrroline N-oxide as a spin trap, while no O2•- in OER was detected during the charge process. These findings provide insightful understanding on the fundamental oxygen reaction mechanisms in rechargeable nonaqueous Li-O2 batteries.

  19. Instabilities in a capacitively coupled oxygen plasma

    SciTech Connect (OSTI)

    Küllig, C. Wegner, Th. Meichsner, J.

    2015-04-15

    Periodic fluctuations in the frequency range from 0.3 to 3 kHz were experimentally investigated in capacitively coupled radio frequency (13.56 MHz) oxygen plasma. The Gaussian beam microwave interferometry directly provides the line integrated electron density fluctuations. A system of two Langmuir probes measured the floating potential spatially (axial, radial) and temporally resolved. Hence, the floating potential fluctuation development is mapped within the discharge volume and provides a kind of discharge breathing and no wave propagation. Finally, it was measured the optical emission pattern of atomic oxygen during the fluctuation as well as the RF phase resolved optical emission intensity at selected phase position of the fluctuation by an intensified charge-coupled device camera. The deduced excitation rate pattern reveals the RF sheath dynamics and electron heating mechanisms, which is changing between low and high electronegativity during a fluctuation cycle. A perturbation calculation was taken into account using a global model with 15 elementary collision processes in the balance equations for the charged plasma species (O{sub 2}{sup +}, e, O{sup −}, O{sub 2}{sup −}) and a harmonic perturbation. The calculated frequencies agree with the experimentally observed frequencies. Whereby, the electron attachment/detachment processes are important for the generation of this instability.

  20. Electrochemical oxygen pumps. Final CRADA report.

    SciTech Connect (OSTI)

    Carter, J. D. Noble, J.

    2009-10-01

    All tasks of the Work Plan of ISTC Project 2277p have been completed, thus: (1) techniques of chemical synthesis were developed for more than ten recipes of electrolyte based on cerium oxide doped with 20 mole% of gadolinium (CeGd)O{sub 2}, doped by more than 10 oxide systems including 6 recipes in addition to the Work Plan; (2) electric conductivity and mechanical strength of CeGd specimens with additions of oxide systems were performed, two candidate materials for the electrolyte of electrochemical oxygen pump (pure CeGd and CeGd doped by 0.2 wt% of a transition metal) were chosen; (3) extended studies of mechanical strength of candidate material specimens were performed at room temperature and at 400, 600, 800 C; (4) fixtures for determination of mechanical strength of tubes by external pressure above 40 atmospheres at temperature up to 700 C were developed and fabricated; and (5) technology of slip casting of tubes from pure (Ce,Gd)O{sub 2} and of (Ce,Gd)O{sub 2} doped by 0.2 wt% of a transition metal, withstanding external pressure of minimum 40 atmospheres at temperature up to 700 C was developed, a batch of tubes was sent for testing to Argonne National Laboratory; (6) technology of making nanopowder from pure (Ce,Gd)O{sub 2} was developed based on chemical synthesis and laser ablation techniques, a batch of nanopowder with the weight 1 kg was sent for testing to Argonne National Laboratory; (7) a business plan for establishing a company for making powders of materials for electrochemical oxygen pump was developed; and (8) major results obtained within the Project were reported at international conferences and published in the Russian journal Electrochemistry. In accordance with the Work Plan a business trip of the following project participants was scheduled for April 22-29, 2006, to Tonawanda, NY, USA: Manager Victor Borisov; Leader of technology development Gennady Studenikin; Leader of business planning Elena Zadorozhnaya; Leader of production Vasily

  1. Dilute Oxygen Combustion Phase 2 Final Report

    SciTech Connect (OSTI)

    Ryan, H.M.; Riley, M.F.; Kobayashi, H.

    2005-09-30

    A novel burner, in which fuel (natural gas) and oxidant (oxygen or air) are separately injected into a furnace, shows promise for achieving very low nitrogen oxide(s) (NOx) emissions for commercial furnace applications. The dilute oxygen combustion (DOC) burner achieves very low NOx through in-furnace dilution of the oxidant stream prior to combustion, resulting in low flame temperatures, thus inhibiting thermal NOx production. The results of a fundamental and applied research effort on the development of the DOC burner are presented. In addition, the results of a market survey detailing the potential commercial impact of the DOC system are disclosed. The fundamental aspects of the burner development project involved examining the flame characteristics of a natural gas turbulent jet in a high-temperature (~1366 K) oxidant (7-27% O2 vol. wet). Specifically, the mass entrainment rate, the flame lift-off height, the velocity field and major species field of the jet were evaluated as a function of surrounding-gas temperature and composition. The measured entrainment rate of the fuel jet decreased with increasing oxygen content in the surrounding high-temperature oxidant, and was well represented by the d+ scaling correlation found in the literature. The measured flame lift-off height decreased with increasing oxygen content and increasing temperature of the surrounding gas. An increase in surrounding-gas oxygen content and/or temperature inhibited the velocity decay within the jet periphery as a function of axial distance as compared to isothermal turbulent jets. However, the velocity measurements were only broadly represented by the d+ scaling correlation. Several DOC burner configurations were tested in a laboratory-scale furnace at a nominal firing rate of 185 kW (~0.63 MMBtu/h). The flue gas composition was recorded as a function of furnace nitrogen content, furnace temperature, burner geometric arrangement, firing rate, and fuel injection velocity. NOx emissions

  2. Dilute Oxygen Combustion Phase I Final Report

    SciTech Connect (OSTI)

    Ryan, H.M.; Riley, M.F.; Kobayashi, H.

    1997-10-31

    A novel burner, in which fuel (natural gas) and oxidant (oxygen or air) are separately injected into a furnace, shows promise for achieving very low nitrogen oxide(s) (NOx) emissions for commercial furnace applications. The dilute oxygen combustion (DOC) burner achieves very low NOx through in-furnace dilution of the oxidant stream prior to combustion, resulting in low flame temperatures, thus inhibiting thermal NOx production. The results of a fundamental and applied research effort on the development of the DOC burner are presented. In addition, the results of a market survey detailing the potential commercial impact of the DOC system are disclosed. The fundamental aspects of the burner development project involved examining the flame characteristics of a natural gas turbulent jet in a high-temperature (~1366 K) oxidant (7-27% O2 vol. wet). Specifically, the mass entrainment rate, the flame lift-off height, the velocity field and major species field of the jet were evaluated as a function of surrounding-gas temperature and composition. The measured entrainment rate of the fuel jet decreased with increasing oxygen content in the surrounding high-temperature oxidant, and was well represented by the d+ scaling correlation found in the literature. The measured flame lift-off height decreased with increasing oxygen content and increasing temperature of the surrounding gas. An increase in surrounding-gas oxygen content and/or temperature inhibited the velocity decay within the jet periphery as a function of axial distance as compared to isothermal turbulent jets. However, the velocity measurements were only broadly represented by the d+ scaling correlation. Several DOC burner configurations were tested in a laboratory-scale furnace at a nominal firing rate of 185 kW (~0.63 MMBtu/h). The flue gas composition was recorded as a function of furnace nitrogen content, furnace temperature, burner geometric arrangement, firing rate, and fuel injection velocity. NOx emissions

  3. Oxygen Handling and Cooling Options in High Temperature Electrolysis Plants

    SciTech Connect (OSTI)

    Manohar S. Sohal; J. Stephen Herring

    2008-07-01

    Idaho National Laboratory is working on a project to generate hydrogen by high temperature electrolysis (HTE). In such an HTE system, safety precautions need to be taken to handle high temperature oxygen at ~830°C. This report is aimed at addressing oxygen handling in a HTE plant.. Though oxygen itself is not flammable, most engineering material, including many gases and liquids, will burn in the presence of oxygen under some favorable physicochemical conditions. At present, an absolute set of rules does not exist that can cover all aspects of oxygen system design, material selection, and operating practices to avoid subtle hazards related to oxygen. Because most materials, including metals, will burn in an oxygen-enriched environment, hazards are always present when using oxygen. Most materials will ignite in an oxygen-enriched environment at a temperature lower than that in air, and once ignited, combustion rates are greater in the oxygen-enriched environment. Even many metals, if ignited, burn violently in an oxygen-enriched environment. However, these hazards do not preclude the operations and systems involving oxygen. Oxygen can be safely handled and used if all the materials in a system are not flammable in the end-use environment or if ignition sources are identified and controlled. In fact, the incidence of oxygen system fires is reported to be low with a probability of about one in a million. This report is a practical guideline and tutorial for the safe operation and handling of gaseous oxygen in high temperature electrolysis system. The intent is to provide safe, practical guidance that permits the accomplishment of experimental operations at INL, while being restrictive enough to prevent personnel endangerment and to provide reasonable facility protection. Adequate guidelines are provided to govern various aspects of oxygen handling associated with high temperature electrolysis system to generate hydrogen. The intent here is to present acceptable

  4. Efficiency evaluation of oxygen enrichment in energy conversion processes

    SciTech Connect (OSTI)

    Bomelburg, H.J.

    1983-12-01

    The extent to which energy conversion efficiencies can be increased by using oxygen or oxygen-enriched air for combustion was studied. Combustion of most fuels with oxygen instead of air was found to have five advantages: increases combustion temperature and efficiency, improves heat transfer at high temperatures, reduces nitrous oxide emissions, permits a high ration of exhaust gas recirculation and allows combustion of certain materials not combustible in air. The same advantages, although to a lesser degree, are apparent with oxygen-enriched air. The cost-effectiveness of the process must necessarily be improved by about 10% when using oxygen instead of air before such use could become justifiable on purely economic terms. Although such a modest increase appears to be attainable in real situations, this study ascertained that it is not possible to generally assess the economic gains. Rather, each case requires its own evaluation. For certain processes industry has already proven that the use of oxygen leads to more efficient plant operation. Several ideas for essentially new applications are described. Specifically, when oxygen is used with exhaust gas recirculation in external or internal combustion engines. It appears also that the advantages of pulse combustion can be amplified further if oxygen is used. When burning wet fuels with oxygen, direct steam generation becomes possible. Oxygen combustion could also improve processes for in situ gasification of coals, oil shales, peats, and other wet fuels. Enhanced oil recovery by fire flooding methods might also become more effective if oxygen is used. The cold energy contained in liquid oxygen can be substantially recovered in the low end of certain thermodynamic cycles. Further efforts to develop certain schemes for using oxygen for combustion appear to be justified from both the technical and economic viewpoints.

  5. SYNTHESIS OF METHYL METHACRYLATE FROM COAL-DERIVED SYNGAS

    SciTech Connect (OSTI)

    BEN W.-L. JANG; GERALD N. CHOI; JAMES J. SPIVEY; JOSPEH R. ZOELLER; RICHARD D. COLBERG

    1999-01-20

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel collectively are developing a novel three-step process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas that consists of the steps of synthesis of a propionate, its condensation with formaldehyde to form methacrylic acid (MAA), and esterification of MAA with methanol to produce MMA. The research team has completed the research on the three-step methanol-based route to MMA. Under an extension to the original contract, we are currently evaluating a new DME-based process for MMA. The key research need for DME route is to develop catalysts for DME partial oxidation reactions and DME condensation reactions. Over the last quarter(Oct.-Dec./98), we have investigated the condensation between methyl propionate and formaldehyde (MP/HCHO=4.5/1) at various reaction temperatures(280-360EC) over 5%, 10%, and 20% Nb O /SiO catalysts. The conversion of HCHO increases with reaction 2 5 2 temperature and niobium loading. MMA+MAA selectivity goes through a maximum with the temperature over both 10% and 20% Nb O /SiO . The selectivities to MMA+MAA are 67.2%, 2 5 2 72.3%and 58.1% at 320EC over 5%, 10%, 20% Nb O /SiO , respectively. However, the 2 5 2 conversion of formaldehyde decreases rapidly with time on stream. The results suggest that silica supported niobium catalysts are active and selective for condensation of MP with HCHO, but deactivation needs to be minimized for the consideration of commercial application. We have preliminarily investigated the partial oxidation of dimethyl ether(DME) over 5% Nb O /SiO catalyst. Reactant gas mixture of 0.1% DME, 0.1% O and balance nitrogen is 2 5 2 2 studied with temperature ranging from 200°C to 500°C. The conversion of DME first increases with temperature reaching an maximum at 400°C then decreases. The selectivity to HCHO also increases with reaction temperature first. But the selectivity to HCHO decreases at temperature above 350

  6. SYNTHESIS OF METHYL METHACRYLATE FROM COAL-DERIVED SYNGAS

    SciTech Connect (OSTI)

    Makarand R. Gogate; James J. Spivey; Joseph R. Zoeller; Richard D. Colberg; Gerald N. Choi

    1999-07-19

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel collectively are developing a novel three-step process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas that consists of the steps of synthesis of a propionate, its condensation with formaldehyde to form methacrylic acid (MAA), and esterification of MAA with methanol to produce MMA. The research team has completed the research on the three-step methanol-based route to MMA. Under an extension to the original contract, we are currently evaluating a new DME-based process for MMA. The key research need for DME route is to develop catalysts for DME partial oxidation reactions and DME condensation reactions. During the April-June quarter(04-06/99) the first in-situ formaldehyde generation from DME and condensation with methyl propionate is demonstrated and the results are summarized. The supported niobium catalyst shows better condensation activity, but supported tungsten catalyst has higher formaldehyde selectivity. The project team has also completed a 200-hour long term test of PA-HCHO condensation over 30% Nb{sub 2}O{sub 5}/SiO{sub 2}. Three activity cycles and two regeneration cycles were carried out. 30% Nb{sub 2}O{sub 5}/SiO{sub 2} showed similar MAA yields as 10% Nb{sub 2}O{sub 5}/SiO{sub 2} at 300 C. However, the deactivation appears to be slower with 30% Nb{sub 2}O{sub 5}/SiO{sub 2} than 10% Nb{sub 2}O{sub 5}/SiO{sub 2}. An detailed economic analysis of PA-HCHO condensation process for a 250 million lb/yr MMA plant is currently studied by Bechtel. Using the Amoco data-based azeotropic distillation model as the basis, an ASPEN flow sheet model was constructed to simulate the formaldehyde and propionic acid condensation processing section based on RTI's design data. The RTI MAA effluent azeotropic distillation column was found to be much more difficult to converge. The presence of non-condensible gases along with the byproduct DEK (both of which were not presented in

  7. Factors affecting the retention of methyl iodide by iodide-impregnated carbon

    SciTech Connect (OSTI)

    Hyder, M.L.; Malstrom, R.A.

    1990-12-31

    Iodide-impregnated activated carbon that had been in use for up to 30 months was studied to characterize those factors that affect its interaction with and retention of methyl iodide. Humidity and competing organic sorbents were observed to decrease the residence time of the methyl iodide on the carbon bed. Additionally, changes in the effective surface area and the loss of iodide from the surface are both important in determining the effectiveness of the carbon for retaining radioactive iodine from methyl iodide. A simple model incorporating both factors gave a fairly good fit to the experimental data.

  8. Factors affecting the retention of methyl iodide by iodide-impregnated carbon

    SciTech Connect (OSTI)

    Hyder, M.L.; Malstrom, R.A.

    1990-01-01

    Iodide-impregnated activated carbon that had been in use for up to 30 months was studied to characterize those factors that affect its interaction with and retention of methyl iodide. Humidity and competing organic sorbents were observed to decrease the residence time of the methyl iodide on the carbon bed. Additionally, changes in the effective surface area and the loss of iodide from the surface are both important in determining the effectiveness of the carbon for retaining radioactive iodine from methyl iodide. A simple model incorporating both factors gave a fairly good fit to the experimental data.

  9. Photochemistry of Methyl Bromide on the α-Cr2O3(0001) Surface

    SciTech Connect (OSTI)

    Henderson, Michael A.

    2010-09-30

    The photochemical properties of the Cr-terminated α-Cr2O3(0001) surface were explored using methyl bromide (CH3Br) as a probe molecule. CH3Br adsorbed and desorbed molecularly from the Cr-terminated α-Cr2O3(0001) surface without detectable thermal decomposition. Temperature programmed desorption (TPD) revealed a CH3Br desorption state at 240 K for coverages up to 0.5 ML, followed by more weakly bound molecules desorbing at 175 K for coverages up to 1 ML. Multilayer exposures led to desorption at ~130 K. The CH3Br sticking coefficient was unity at 105 K for coverages up to monolayer saturation, but decreased as the multilayer formed. In contrast, pre-oxidation of the surface (using an oxygen plasma source) led to capping of surface Cr3+ sites and near complete removal of CH3Br TPD states above 150 K. The photochemistry of chemisorbed CH3Br was explored on the Cr-terminated surface using post-irradiation TPD and photon stimulated desorption (PSD). Irradiation of adsorbed CH3Br with broad band light from a Hg arc lamp resulted in both photodesorption and photodecomposition of the parent molecule at a combined cross section of ~10-22 cm2. Parent PSD was indicative of molecular photodesorption, but CH3 was also detected in PSD and Br atoms were left on the surface, both reflective of photo-induced CH3-Br bond dissociation. Use of a 385 nm cut-off filter effectively shut down the photodissociation pathway but not the parent molecule photodesorption process. From these observations it is inferred that d-to-d transitions in α-Cr2O3, occurring at photon energies <3 eV, are not responsible for photodecomposition of 2 adsorbed CH3Br. It is unclear to what extent band-to-band versus direct CH3Br photolysis play in CH3-Br bond dissociation initiated by more energetic photons.

  10. Preliminary Study of Oxygen-Enhanced Longitudinal Relaxation in MRI: A Potential Novel Biomarker of Oxygenation Changes in Solid Tumors

    SciTech Connect (OSTI)

    O'Connor, James P.B.; Naish, Josephine H.; Parker, Geoff J.M.; Waterton, John C.; Watson, Yvonne; Jayson, Gordon C.; Buonaccorsi, Giovanni A.; Cheung, Sue; Buckley, David L.; McGrath, Deirdre M.; West, Catharine M.L.; Davidson, Susan E.; Roberts, Caleb; Mills, Samantha J.; Mitchell, Claire L.; Hope, Lynn; Ton, N. Chan; Jackson, Alan

    2009-11-15

    Purpose: There is considerable interest in developing non-invasive methods of mapping tumor hypoxia. Changes in tissue oxygen concentration produce proportional changes in the magnetic resonance imaging (MRI) longitudinal relaxation rate (R{sub 1}). This technique has been used previously to evaluate oxygen delivery to healthy tissues and is distinct from blood oxygenation level-dependent (BOLD) imaging. Here we report application of this method to detect alteration in tumor oxygenation status. Methods and materials: Ten patients with advanced cancer of the abdomen and pelvis underwent serial measurement of tumor R{sub 1} while breathing medical air (21% oxygen) followed by 100% oxygen (oxygen-enhanced MRI). Gadolinium-based dynamic contrast-enhanced MRI was then performed to compare the spatial distribution of perfusion with that of oxygen-induced DELTAR{sub 1}. Results: DELTAR{sub 1} showed significant increases of 0.021 to 0.058 s{sup -1} in eight patients with either locally recurrent tumor from cervical and hepatocellular carcinomas or metastases from ovarian and colorectal carcinomas. In general, there was congruency between perfusion and oxygen concentration. However, regional mismatch was observed in some tumor cores. Here, moderate gadolinium uptake (consistent with moderate perfusion) was associated with low area under the DELTAR{sub 1} curve (consistent with minimal increase in oxygen concentration). Conclusions: These results provide evidence that oxygen-enhanced longitudinal relaxation can monitor changes in tumor oxygen concentration. The technique shows promise in identifying hypoxic regions within tumors and may enable spatial mapping of change in tumor oxygen concentration.

  11. METHOD OF COMBINING HYDROGEN AND OXYGEN

    DOE Patents [OSTI]

    McBride, J.P.

    1962-02-27

    A method is given for the catalytic recombination of radiolytic hydrogen and/or deulerium and oxygen resulting from the subjection or an aqueous thorium oxide or thorium oxide-uranium oxide slurry to ionizing radiation. An improved catalyst is prepared by providing paliadium nitrate in an aqueous thorium oxide sol at a concentration of at least 0.05 grams per gram of thorium oxide and contacting the sol with gaseous hydrogen to form flocculated solids. The solids are then recovered and added to the slurry to provide a palladium concentration of 100 to 1000 parts per million. Recombination is effected by the calalyst at a rate sufficient to support high nuclear reactor power densities. (AEC)

  12. SUPPORTED DENSE CERAMIC MEMBRANES FOR OXYGEN SEPARATION

    SciTech Connect (OSTI)

    Timothy L. Ward

    2002-07-01

    Mixed-conducting ceramics have the ability to conduct oxygen with perfect selectivity at elevated temperatures, making them extremely attractive as membrane materials for oxygen separation and membrane reactor applications. While the conductivity of these materials can be quite high at elevated temperatures (typically 800-1000 C), much higher oxygen fluxes, or, alternatively, equivalent fluxes at lower temperatures, could be provided by supported thin or thick film membrane layers. Based on that motivation, the objective of this project was to explore the use of ultrafine aerosol-derived powder of a mixed-conducting ceramic material for fabrication of supported thick-film dense membranes. The project focused on the mixed-conducting ceramic composition SrCo{sub 0.5}FeO{sub x} (SCFO) because of the desirable permeability and stability of that material, as reported in the literature. Appropriate conditions to produce the submicron SrCo{sub 0.5}FeO{sub x} powder using aerosol pyrolysis were determined. Porous supports of the same composition were produced by partial sintering of a commercially obtained powder that possessed significantly larger particle size than the aerosol-derived powder. The effects of sintering conditions (temperature, atmosphere) on the porosity and microstructure of the porous discs were studied, and a standard support fabrication procedure was adopted. Subsequently, a variety of paste and slurry formulations were explored utilizing the aerosol-derived SCFO powder. These formulations were applied to the porous SCFO support by a doctor blade or spin coating procedure. Sintering of the supported membrane layer was then conducted, and additional layers were deposited and sintered in some cases. The primary characterization methods were X-ray diffraction and scanning electron microscopy, and room-temperature nitrogen permeation was used to assess defect status of the membranes.We found that non-aqueous paste/slurry formulations incorporating

  13. Thermochemistry of C-O, (CO)-O, and (CO)-C bond breaking in fatty acid methyl esters

    SciTech Connect (OSTI)

    Osmont, Antoine; Yahyaoui, Mohammed; Catoire, Laurent; Goekalp, Iskender; Swihart, Mark T.

    2008-10-15

    Density functional theory quantum chemical calculations corrected with empirical atomic increments have been used to examine C-O, (CO)-O, and (CO)-C bond scission enthalpies in gas-phase fatty acid methyl esters (FAMEs) present in biodiesel derived from rapeseed oil methyl ester and soybean oil methyl ester. Mechanistic information, currently not available elsewhere for these large species, is obtained based on thermochemical considerations and compared to thermochemical considerations reported for methyl butanoate, a small methyl ester sometimes used as a model for FAMEs. These results are compared to previously reported C-C and C-H bond scissions in these FAMEs, derived using this same protocol. (author)

  14. Dilute Oxygen Combustion - Phase 3 Report

    SciTech Connect (OSTI)

    Riley, Michael F.

    2000-05-31

    Dilute Oxygen Combustion (DOC) burners have been successfully installed and operated in the reheat furnace at Auburn Steel Co., Inc., Auburn, NY, under Phase 3 of the Dilute Oxygen Combustion project. Two new preheat zones were created employing a total of eight 6.5 MMBtu/hr capacity burners. The preheat zones provide a 30 percent increase in maximum furnace production rate, from 75 tph to 100 tph. The fuel rate is essentially unchanged, with the fuel savings expected from oxy-fuel combustion being offset by higher flue gas temperatures. When allowance is made for the high nitrogen level and high gas phase temperature in the furnace, measured NOx emissions are in line with laboratory data on DOC burners developed in Phase 1 of the project. Burner performance has been good, and there have been no operating or maintenance problems. The DOC system continues to be used as part of Auburn Steel's standard reheat furnace practice. High gas phase temperature is a result of the high firing density needed to achieve high production rates, and little opportunity exists for improvement in that area. However, fuel and NOx performance can be improved by further conversion on furnace zones to DOC burners, which will lower furnace nitrogen levels. Major obstacles are cost and concern about increased formation of oxide scale on the steel. Oxide scale formation may be enhanced by exposure of the steel to higher concentrations of oxidizing gas components (primarily products of combustion) in the higher temperature zones of the furnace. Phase 4 of the DOC project will examine the rate of oxide scale formation in these higher temperature zones and develop countermeasures that will allow DOC burners to be used successfully in these furnace zones.

  15. Dilute Oxygen Combustion Phase 3 Final Report

    SciTech Connect (OSTI)

    Riley, M.F.; Ryan, H.M.

    2000-05-31

    Dilute Oxygen Combustion (DOC) burners have been successfully installed and operated in the reheat furnace at Auburn Steel Co., Inc., Auburn, NY, under Phase 3 of the Dilute Oxygen Combustion project. Two new preheat zones were created employing a total of eight 6.5 MMBtu/hr capacity burners. The preheat zones provide a 30 percent increase in maximum furnace production rate, from 75 tph to 100 tph. The fuel rate is essentially unchanged, with the fuel savings expected from oxy-fuel combustion being offset by higher flue gas temperatures. When allowance is made for the high nitrogen level and high gas phase temperature in the furnace, measured NOx emissions are in line with laboratory data on DOC burners developed in Phase 1 of the project. Burner performance has been good and there have been no operating or maintenance problems. The DOC system continues to be used as part of Auburn Steel?s standard reheat furnace practice. High gas phase temperature is a result of the high firing density needed to achieve high production rates, and little opportunity exists for improvement in that area. However, fuel and NOx performance can be improved by further conversion of furnace zones to DOC burners, which will lower furnace nitrogen levels. Major obstacles are cost and concern about increased formation of oxide scale on the steel. Oxide scale formation may be enhanced by exposure of the steel to higher concentrations of oxidizing gas components (primarily products of combustion) in the higher temperature zones of the furnace. Phase 4 of the DOC project will examine the rate of oxide scale formation in these higher temperature zones and develop countermeasures that will allow DOC burners to be used successfully in these furnace zones.

  16. Review and reconnaissance of the hydrogeology of Tertiary sedimentary rocks in the vicinity of Frenchman Flat, Nevada Test Site

    SciTech Connect (OSTI)

    Prothro, L.B.; Drellack, S.L. Jr.

    1997-09-01

    Work is currently underway within the Underground Test Area (UGTA) subproject of the US Department of Energy/Nevada Operations Office Environmental Restoration Program to develop corrective action plans in support of the overall corrective action strategy for the Nevada Test Site (NTS) as established in the Federal Facility Agreement and Consent Order (FFACO, 1996). A closure plan is currently being developed for Frenchman Flat, which has been identified in the FFACO as a Corrective Action Unit (CAU). Part of this effort requires that hydrogeologic data be compiled for inclusion in a CAU-specific hydrologic flow and transport model that will be used to predict contaminant boundaries. Hydrogeologic maps and cross sections are currently being prepared for use in the model to define the nature and extent of aquifers and confining units that might influence the flow of contaminated groundwater from underground nuclear tests conducted in Frenchman Flat. During this effort, it has been found that older Tertiary-age sediments might be hydrogeologically important in the Frenchman Flat model area. Although the character and extent of these units are poorly known, there is reason to believe that in some parts of Frenchman Flat they may lie between the regional Lower Carbonate Aquifer (LCA) and the younger Tertiary saturated alluvium and volcanic units in which several underground nuclear tests were conducted. It was not possible to quickly determine their extent, or ascertain whether or not these units might act as confining units or aquifers. The work described in this report was done to gain a better understanding of the hydrogeology of these rocks.

  17. Renewed petroleum generation related to Tertiary intrusions and increased heat flow, western Permian basin, Texas and New Mexico

    SciTech Connect (OSTI)

    Barker, C.E.; Pawlewicz, M.J.

    1989-03-01

    Higher paleogeothermal gradients, commencing in the Tertiary after maximum burial, have caused renewed petroleum generation in the western Permian basin. Evidence for this reheating is two distinct trends in the mean random vitrinite reflectance (R/sub m/) and depth data compiled from over 40 wells. One group, with a 0.7% R/sub m//km gradient, is from the western edge of the basin; the other, with a 0.5% R/sub m//km gradient, is from the central and eastern portions. Post-Mississippian tilting produced greater subsidence and a thicker, mostly uneroded sedimentary section in the eastern portion of the Permian basin. Continued tilting prior to the Cretaceous caused uplift and erosion that exposed the Upper Permian section in the western part. Potassium-argon ages of igneous intrusions along the western edge of the basin show they were emplaced about 35 Ma, followed by Miocene to Holocene basin-and-range-type block faulting and associated high heat flow. Isopach-reflectance contours confirm this renewed heating is post-tectonic - that is, it occurred after eastward tilting and erosion had reduced burial depth. Maximum temperatures computed from R/sub m/-depth relationships infer that paleogeothermal gradients exceeded 40/degrees/C/km (2.2/degrees/F/100 ft) in the Tertiary. This reheating thermally matured rocks as young as Guadalupian in the western Permian basin and apparently caused a second episode of petroleum generation. By this time, however, the potential reservoir rocks and evaporite seals had been deeply eroded, resulting in poor conditions for trapping the renewed pulse of petroleum.

  18. Oxygen detected in atmosphere of Saturn's moon Dione

    U.S. Department of Energy (DOE) all webpages (Extended Search)

    Oxygen detected in atmosphere of Saturn's moon Dione Oxygen detected in atmosphere of Saturn's moon Dione Scientists and an international research team have announced discovery of molecular oxygen ions in the upper-most atmosphere of Dione. March 3, 2012 Los Alamos National Laboratory sits on top of a once-remote mesa in northern New Mexico with the Jemez mountains as a backdrop to research and innovation covering multi-disciplines from bioscience, sustainable energy sources, to plasma physics

  19. Elusive Oxygen Isotope Captured with Groundbreaking Sensitivity | The Ames

    U.S. Department of Energy (DOE) all webpages (Extended Search)

    Laboratory Elusive Oxygen Isotope Captured with Groundbreaking Sensitivity Oxygen is one of the most ubiquitous elements in chemistry and materials science, yet one of the most elusive elements for spectroscopic investigation by solid-state Nuclear Magnetic Resonance (SSNMR). Used to determine the structure of materials and chemicals on the atomic scale, SSNMR requires nuclei that have magnetic moments. Yet, less than four of every 10,000 oxygen nuclei are 17O, the only NMR-active isotope of

  20. Testing Oxygen Reduction Reaction Activity with the Rotating Disc Electrode

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Technique | Department of Energy Oxygen Reduction Reaction Activity with the Rotating Disc Electrode Technique Testing Oxygen Reduction Reaction Activity with the Rotating Disc Electrode Technique Presentation slides from the Fuel Cell Technologies Office webinar, "Testing Oxygen Reduction Reaction Activity with the Rotating Disc Electrode Technique," held March 12, 2013. Presenters were Shyam S. Kocha, National Renewable Energy Laboratory; Yannick Garsany, Naval Research

  1. Novel syngas-based process for methyl methacrylate

    SciTech Connect (OSTI)

    Gogate, M.R.; Spivey, J.J.; Zoeller, J.R.; Choi, G.N.; Tam, S.S.; Tischer, R.E.; Srivastava, R.D.

    1996-12-31

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel are developing a novel process for synthesis of methyl methacrylate (MMA) from coal-derived syngas, under a contract from the U.S. Department of Energy, Pittsburgh Energy Technology Center. This three-step process consists of synthesis of a propionate, its condensation with formaldehyde, and esterification of resulting methacrylic acid (MAA) with methanol to produce MMA. Eastman has focused on the research on propionate synthesis step. The resultant Mo catalysts work efficiently at much less severe conditions (170{degrees}C and 30 atm) than the conventional Ni catalysts (270{degrees}C and 180 atm). Bechtel has performed an extensive cost analysis, which shows that Eastman`s propionate synthesis process is competitive with other technologies to produce the anhydride. In the second step, RTI and Eastman have developed active and stable V-SI-P and Ta metal oxide catalysts for condensation reactions of propionates with formaldehyde. RTI has demonstrated a novel correlation among the catalyst acid-base properties, condensation reaction yield, and long-term catalyst activity. Current research focuses on enhancing the condensation reaction yields, acid-base properties, in situ condensation in a high- temperature, high-pressure (HTHP) slurry reactor, and alternate formaldehyde feedstocks. Based on Eastman and RTI laboratory reactor operating data, a cost estimate is also being developed for the integrated process.

  2. Advantages of Oxygenates Fuels over Gasoline in Direct Injection...

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Advantages of Oxygenates Fuels over Gasoline in Direct Injection Spark Ignition Engines Poster presented at the 16th Directions in Engine-Efficiency and Emissions Research (DEER) ...

  3. Strain control of oxygen vacancies in epitaxial strontium cobaltite...

    Office of Scientific and Technical Information (OSTI)

    Journal Article: Strain control of oxygen vacancies in epitaxial strontium cobaltite films ... This content will become publicly available on January 25, 2017 Title: Strain control of ...

  4. Hybrid System for Separating Oxygen from Air - Energy Innovation...

    U.S. Department of Energy (DOE) all webpages (Extended Search)

    components. The first component is a high efficiency membrane capable of separating argon and a portion of the nitrogen content from air, yielding an oxygen-enriched permeate...

  5. New Oxygen-Production Technology Proving Successful | Department...

    Energy.gov (indexed) [DOE]

    ITM Oxygen will enhance the performance of integrated gasification combined cycle (IGCC) power plants, as well as other gasification-based processes. The technology will also ...

  6. Catalytic reduction system for oxygen-rich exhaust

    DOE Patents [OSTI]

    Vogtlin, George E.; Merritt, Bernard T.; Hsiao, Mark C.; Wallman, P. Henrik; Penetrante, Bernardino M.

    1999-01-01

    Non-thermal plasma gas treatment is combined with selective catalytic reduction to enhance NO.sub.x reduction in oxygen-rich vehicle engine exhausts.

  7. Vehicle Technologies Office Merit Review 2014: Intake Air Oxygen...

    Energy Savers

    Review 2015: Intake Air Oxygen Sensor Vehicle Technologies Office Merit Review 2014: Advanced Combustion Concepts - Enabling Systems and Solutions (ACCESS) for High Efficiency...

  8. Vehicle Technologies Office Merit Review 2015: Intake Air Oxygen...

    Energy Savers

    Office Merit Review 2014: Intake Air Oxygen Sensor Bosch Powertrain Technologies Advanced Combustion Concepts - Enabling Systems and Solutions (ACCESS) for High Efficiency...

  9. Table 33. Oxygenated Motor Gasoline Prices by Grade, Sales Type...

    U.S. Energy Information Administration (EIA) (indexed site)

    - - - - - - - - - - - - See footnotes at end of table. 33. Oxygenated Motor Gasoline Prices by Grade, Sales Type, PAD District, and State 116 Energy Information...

  10. Table 33. Oxygenated Motor Gasoline Prices by Grade, Sales Type...

    U.S. Energy Information Administration (EIA) (indexed site)

    Information Administration Petroleum Marketing Annual 1995 Table 33. Oxygenated Motor Gasoline Prices by Grade, Sales Type, PAD District, and State (Cents per Gallon...

  11. Catalytic reduction system for oxygen-rich exhaust

    DOE Patents [OSTI]

    Vogtlin, G.E.; Merritt, B.T.; Hsiao, M.C.; Wallman, P.H.; Penetrante, B.M.

    1999-04-13

    Non-thermal plasma gas treatment is combined with selective catalytic reduction to enhance NO{sub x} reduction in oxygen-rich vehicle engine exhausts. 8 figs.

  12. Role of strain and conductivity in oxygen electrocatalysis on...

    Office of Scientific and Technical Information (OSTI)

    The slow kinetics of the oxygen reduction and evolution reactions (ORR, OER) hinder energy conversion and storage in alkaline fuel cells and electrolyzers employing abundant ...

  13. The Electronic Structure of Oxygen Atom Vacancy and Hydroxyl...

    Office of Scientific and Technical Information (OSTI)

    Title: The Electronic Structure of Oxygen Atom Vacancy and Hydroxyl Impurity Defects on Titanium Dioxide (110) Surface Introducing a charge into a solid such as a metal oxide ...

  14. Strain control of oxygen vacancies in epitaxial strontium cobaltite films

    DOE PAGES-Beta [OSTI]

    Jeen, Hyoung Jeen; Choi, Woo Seok; Reboredo, Fernando A.; Freeland, John W.; Eres, Gyula; Lee, Ho Nyung; Petrie, Jonathan R.; Mitra, Chandrima; Meyer, Tricia L.

    2016-01-25

    In this study, the ability to manipulate oxygen anion defects rather than metal cations in complex oxides can facilitate creating new functionalities critical for emerging energy and device technologies. However, the difficulty in activating oxygen at reduced temperatures hinders the deliberate control of important defects, oxygen vacancies. Here, strontium cobaltite (SrCoOx) is used to demonstrate that epitaxial strain is a powerful tool for manipulating the oxygen vacancy concentration even under highly oxidizing environments and at annealing temperatures as low as 300 °C. By applying a small biaxial tensile strain (2%), the oxygen activation energy barrier decreases by ≈30%, resulting inmore » a tunable oxygen deficient steady-state under conditions that would normally fully oxidize unstrained cobaltite. These strain-induced changes in oxygen stoichiometry drive the cobaltite from a ferromagnetic metal towards an antiferromagnetic insulator. The ability to decouple the oxygen vacancy concentration from its typical dependence on the operational environment is useful for effectively designing oxides materials with a specific oxygen stoichiometry.« less

  15. Oxygen-Enriched Combustion for Military Diesel Engine Generators...

    Energy.gov (indexed) [DOE]

    (196.85 KB) More Documents & Publications Development Methodology for Power-Dense Military Diesel Engine Oxygen-Enriched Combustion Emission Control Strategy for Downsized ...

  16. Ultrafast kinetics subsequent to shock compression in an oxygen...

    Office of Scientific and Technical Information (OSTI)

    to shock compression in an oxygen-balanced mixture of nitromethane and hydrogen peroxide Citation Details In-Document Search Title: Ultrafast kinetics subsequent to shock ...

  17. Ultrafast kinetics subsequent to shock in an unreacted, oxygen...

    Office of Scientific and Technical Information (OSTI)

    shock in an unreacted, oxygen balanced mixture of nitromethane and hydrogen peroxide Citation Details In-Document Search Title: Ultrafast kinetics subsequent to shock in an ...

  18. Selective reduction of NOx in oxygen rich environments with plasma...

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    environments with plasma-assisted catalysis: Catalyst development and mechanistic studies Selective reduction of NOx in oxygen rich environments with plasma-assisted catalysis: ...

  19. Discovery of oxygen in atmosphere could mean life for Saturn...

    U.S. Department of Energy (DOE) all webpages (Extended Search)

    is the possibility that on a moon with subsurface water, such as Jupiter's moon Europa, molecular oxygen could combine with carbon in subsurface lakes to form the building...

  20. Oxygen detected in atmosphere of Saturn's moon Dione

    U.S. Department of Energy (DOE) all webpages (Extended Search)

    is the possibility that on a moon with subsurface water, such as Jupiter's moon Europa, molecular oxygen could combine with carbon in subsurface lakes to form the building...

  1. Electrocatalyst for Oxygen Reduction with Reduced Platinum Oxidation...

    U.S. Department of Energy (DOE) all webpages (Extended Search)

    Electrocatalyst for oxygen reduction with reduced platinum oxidation and dissolution rates The invention relates to platinum-metal oxide composite particles and their use as...

  2. Probing oxygen vacancy concentration and homogeneity in solid...

    Office of Scientific and Technical Information (OSTI)

    Here, we develop an approach for direct mapping of oxygen vacancy concentrations based on local lattice parameter measurements by scanning transmission electron microscopy. The ...

  3. Oxidation State and Interfacial Effects on Oxygen Vacancies in...

    Office of Scientific and Technical Information (OSTI)

    Oxygen Vacancies in Tantalum Pentoxide. Abstract not provided. Authors: Bondi, Robert James ; Marinella, Matthew Publication Date: 2014-10-01 OSTI Identifier: 1184499 Report...

  4. Oxygen diffusion of anodic surface oxide film on titanium studied by Auger electron spectroscopy. [Oxygen diffusivity

    SciTech Connect (OSTI)

    Wang, P.S.; Wittberg, T.N.; Keil, R.G.

    1982-01-01

    TiO/sub 2/ films of about 1000 A were grown onto titanium foils anodically under galvanostatic conditions at 20 mA/cm/sup 2/ in saturated aqueous solutions of ammonium tetraborate. The samples were then aged at 450, 500, and 550/sup 0/C, and oxygen diffusion was observed by Auger electron spectroscopy (AES) profilings. The oxygen diffusivities were calculated by Fick's Second Law, using the Boltzmann-Matano solution, to be 9.4 x 10/sup -17/, 2.6 x 10/sup -16/, and 1.2 x 10/sup -15/ cm/sup 2//sec at 450, 500, and 550/sup 0/C, respectively. The diffusivities obtained by this method were also compared with those obtained using an exact solution to Fick's Second Law. The activation energy was calculated to be 30 kcal/mole.

  5. Optimized End-Stacking Provides Specificity of N-Methyl Mesoporphyrin...

    Office of Scientific and Technical Information (OSTI)

    Optimized End-Stacking Provides Specificity of N-Methyl Mesoporphyrin IX for Human Telomeric G-Quadruplex DNA Citation Details In-Document Search Title: Optimized End-Stacking ...

  6. Radio-methyl vorozole and methods for making and using the same

    DOE Patents [OSTI]

    Kim, Sung Won; Biegon, Anat; Fowler, Joanna S.

    2014-08-12

    Radiotracer vorozole compounds for in vivo and in vitro assaying, studying and imaging cytochrome P450 aromatase enzymes in humans, animals, and tissues and methods for making and using the same are provided. [N-radio-methyl] vorozole substantially separated from an N-3 radio-methyl isomer of vorozole is provided. Separation is accomplished through use of chromatography resins providing multiple mechanisms of selectivity.

  7. Radio-methyl vorozole and methods for making and using the same

    DOE Patents [OSTI]

    Kim, Sung Won; Biegon, Anat; Fowler, Joanna S.

    2014-08-05

    Radiotracer vorozole compounds for in vivo and in vitro assaying, studying and imaging cytochrome P450 aromatase enzymes in humans, animals, and tissues and methods for making and using the same are provided. [N-radio-methyl] vorozole substantially separated from an N-3 radio-methyl isomer of vorozole is provided. Separation is accomplished through use of chromatography resins providing multiple mechanisms of selectivity.

  8. Determination of Total Lipids as Fatty Acid Methyl Esters (FAME) by in situ

    Office of Scientific and Technical Information (OSTI)

    Transesterification: Laboratory Analytical Procedure (LAP) (Technical Report) | SciTech Connect Determination of Total Lipids as Fatty Acid Methyl Esters (FAME) by in situ Transesterification: Laboratory Analytical Procedure (LAP) Citation Details In-Document Search Title: Determination of Total Lipids as Fatty Acid Methyl Esters (FAME) by in situ Transesterification: Laboratory Analytical Procedure (LAP) This procedure is based on a whole biomass transesterification of lipids to fatty acid

  9. Dipole Alignment at the Carbon Nanotube and Methyl Ammonium Lead Trihalide

    Office of Scientific and Technical Information (OSTI)

    Perovskite Interface - Oral Presentation (Technical Report) | SciTech Connect Technical Report: Dipole Alignment at the Carbon Nanotube and Methyl Ammonium Lead Trihalide Perovskite Interface - Oral Presentation Citation Details In-Document Search Title: Dipole Alignment at the Carbon Nanotube and Methyl Ammonium Lead Trihalide Perovskite Interface - Oral Presentation This work correlates resonant peaks from first principles calculation on ammonia (NH3) Nitrogen 1s x-ray absorption

  10. Experimental and Kinetic Modeling Study of Extinction and Ignition of Methyl Decanoate in Laminar Nonpremixed Flows

    SciTech Connect (OSTI)

    Seshadri, K; Lu, T; Herbinet, O; Humer, S; Niemann, U; Pitz, W J; Law, C K

    2008-01-09

    Methyl decanoate is a large methyl ester that can be used as a surrogate for biodiesel. In this experimental and computational study, the combustion of methyl decanoate is investigated in nonpremixed, nonuniform flows. Experiments are performed employing the counterflow configuration with a fuel stream made up of vaporized methyl decanoate and nitrogen, and an oxidizer stream of air. The mass fraction of fuel in the fuel stream is measured as a function of the strain rate at extinction, and critical conditions of ignition are measured in terms of the temperature of the oxidizer stream as a function of the strain rate. It is not possible to use a fully detailed mechanism for methyl decanoate to simulate the counterflow flames because the number of species and reactions is too large to employ with current flame codes and computer resources. Therefore a skeletal mechanism was deduced from a detailed mechanism of 8555 elementary reactions and 3036 species using 'directed relation graph' method. This skeletal mechanism has only 713 elementary reactions and 125 species. Critical conditions of ignition were calculated using this skeletal mechanism and are found to agree well with experimental data. The predicted strain rate at extinction is found to be lower than the measurements. In general, the methyl decanoate mechanism provides a realistic kinetic tool for simulation of biodiesel fuels.

  11. Synthesis of Methyl Methacrylate From Coal-Derived Syngas

    SciTech Connect (OSTI)

    Ben W.-L. Jang; Gerald N. Choi; James J. Spivey; Jospeh R. Zoeller; Richard D. Colberg; Samuel S. Tam

    1998-07-27

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel collectively are developing a novel three-step process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas that consists of the steps of synthesis of a propionate, its condensation with formaldehyde to form methacrylic acid (MAA), and esterification of MAA with methanol to produce MMA. RTI has completed the research on the three-step methanol-based route to MMA. Under an extension to the original contract, RTI is currently evaluating a new DME-based process for MMA. The key research need for DME route is to develop catalysts for DME partial oxidation reactions and DME condensation reactions. Over the last quarter(April-June, 1998), RTI has modified the reactor system including a new preheater and new temperature settings for the preheater. Continuous condensation of formaldehyde with propionic acid were carried out over 10% Nb O /SiO at 300°C without 2 5 2 interruption. Five activity and four regeneration cycles have been completed without plugging or material balance problems. The results show that 10% Nb O /SiO deactivates slowly with time 2 5 2 but can be regenerated, at least four times, to 100% of its original activity with 2% O in nitrogen 2 at 400°C. The cycles continue with consistent 90-95% of carbon balance. The reaction is scheduled to complete with 6 activity cycles and 5 regenerations. Used catalysts will be analyzed with TGA and XPS to determine bulk and surface coke content and coke properties. RTI will start the investigation of effects of propionic acid/formaldehyde ratio on reaction activity and product selectivity over 20% Nb O /SiO catalysts.

  12. Low NOx combustion using cogenerated oxygen and nitrogen streams

    DOE Patents [OSTI]

    Kobayashi, Hisashi; Bool, Lawrence E.; Snyder, William J.

    2009-02-03

    Combustion of hydrocarbon fuel is achieved with less formation of NOx by feeding the fuel into a slightly oxygen-enriched atmosphere, and separating air into oxygen-rich and nitrogen-rich streams which are fed separately into the combustion device.

  13. Effects of oxygen and catalyst on tetraphenylborate decomposition rate

    SciTech Connect (OSTI)

    Walker, D.D.

    1999-12-15

    Previous studies indicate that palladium catalyzes rapid decomposition of alkaline tetraphenylborate slurries. Oxygen inhibits the reaction at low temperature (25 C), presumably by preventing activation of the catalyst. The present study investigated oxygen's inhibiting effectiveness at higher temperature (45 C) and catalyst concentrations.

  14. Palladium-cobalt particles as oxygen-reduction electrocatalysts

    DOE Patents [OSTI]

    Adzic, Radoslav; Huang, Tao

    2009-12-15

    The present invention relates to palladium-cobalt particles useful as oxygen-reducing electrocatalysts. The invention also relates to oxygen-reducing cathodes and fuel cells containing these palladium-cobalt particles. The invention additionally relates to methods for the production of electrical energy by using the palladium-cobalt particles of the invention.

  15. Device for measuring the total concentration of oxygen in gases

    DOE Patents [OSTI]

    Isaacs, Hugh S.; Romano, Anthony J.

    1977-01-01

    This invention provides a CO equilibrium in a device for measuring the total concentration of oxygen impurities in a fluid stream. To this end, the CO equilibrium is produced in an electrochemical measuring cell by the interaction of a carbon element in the cell with the chemically combined and uncombined oxygen in the fluid stream at an elevated temperature.

  16. Homogeneously dispersed, multimetal oxygen-evolving catalysts

    DOE PAGES-Beta [OSTI]

    Zhang, Bo; Zheng, Xueli; Voznyy, Oleksandr; Comin, Riccardo; Bajdich, Michal; Garcia-Melchor, Max; Han, Lili; Xu, Jixian; Liu, Min; Zheng, Lirong; et al

    2016-03-24

    Earth-abundant first-row (3d) transition-metal-based catalysts have been developed for the oxygen-evolution reaction (OER); however, they operate at overpotentials significantly above thermodynamic requirements. Density functional theory suggested that non-3d high-valency metals such as tungsten can modulate 3d metal oxides, providing near-optimal adsorption energies for OER intermediates. We developed a room-temperature synthesis to produce gelled oxy-hydroxide materials with an atomically homogeneous metal distribution. These gelled FeCoW oxy-hydroxide exhibits the lowest overpotential (191 mV) reported at 10 mA per square centimeter in alkaline electrolyte. Here, the catalyst shows no evidence of degradation following more than 500 hours of operation. X-ray absorption and computationalmore » studies reveal a synergistic interplay between W, Fe and Co in producing a favorable local coordination environment and electronic structure that enhance the energetics for OER.« less

  17. Nanoparticulate-catalyzed oxygen transfer processes

    DOE Patents [OSTI]

    Hunt, Andrew T.; Breitkopf, Richard C.

    2009-12-01

    Nanoparticulates of oxygen transfer materials that are oxides of rare earth metals, combinations of rare earth metals, and combinations of transition metals and rare earth metals are used as catalysts in a variety of processes. Unexpectedly large thermal efficiencies are achieved relative to micron sized particulates. Processes that use these catalysts are exemplified in a multistage reactor. The exemplified reactor cracks C6 to C20 hydrocarbons, desulfurizes the hydrocarbon stream and reforms the hydrocarbons in the stream to produce hydrogen. In a first reactor stage the steam and hydrocarbon are passed through particulate mixed rare earth metal oxide to crack larger hydrocarbon molecules. In a second stage, the steam and hydrocarbon are passed through particulate material that desulfurizes the hydrocarbon. In a third stage, the hydrocarbon and steam are passed through a heated, mixed transition metal/rare earth metal oxide to reform the lower hydrocarbons and thereby produce hydrogen. Stages can be alone or combined. Parallel reactors can provide continuous reactant flow. Each of the processes can be carried out individually.

  18. Willamette Oxygen Supplementation Studies : Annual Report 1994.

    SciTech Connect (OSTI)

    Ewing, R.D.; Ewing, S.K.; Sheahan, J.E.

    1994-09-01

    Hydropower development and operations in the Columbia River basin have caused the loss of 5 million to 11 million salmonids. An interim goal of the Northwest Power Planning Council is to reestablish these historical numbers by doubling the present runs from 2.5 million adult fish to 5.0 million adult fish. This increase in production will be accomplished through comprehensive management of both wild and hatchery fish, but artificial propagation will play a major role in the augmentation process. The current husbandry techniques in existing hatcheries require improvements that may include changes in rearing densities, addition of oxygen, removal of excess nitrogen, and improvement in raceway design. Emphasis will be placed on the ability to increase the number of fish released from hatcheries that survive to return as adults. Rearing density is one of the most important elements in fish culture. Fish culturists have attempted to rear fish in hatchery ponds at densities that most efficiently use the rearing space available. Such efficiency studies require a knowledge of cost of rearing and the return of adults to the fisheries and to the hatchery.

  19. Direct tuyere injection of oxygen for enhanced coal combustion

    SciTech Connect (OSTI)

    Riley, M.F.

    1996-12-31

    Injecting oxygen directly into the tuyere blowpipe can enhance the ignition and combustion of injected pulverized coal, allowing the efficient use of higher coal rates at high furnace production levels. The effects of direct oxygen injection have been estimated from an analysis of the factors controlling the dispersion, heating, ignition, and combustion of injected coal. Injecting ambient temperature oxygen offers mechanical improvements in the dispersion of coal but provides little thermochemical benefit over increased blast enrichment. Injecting hot oxygen through a novel, patented thermal nozzle lance offers both mechanical and thermochemical benefits over increased enrichment or ambient oxygen injection. Plans for pilot-scale and commercial-scale testing of this new lance are described.

  20. Novel catalysts for the environmentally friendly synthesis of methyl methacrylate

    SciTech Connect (OSTI)

    Spivey, J.J.; Gogate, M.R.; Zoeller, J.R.; Colberg, R.D.

    1997-11-01

    The development of a process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas can alleviate the environmental hazards associated with the current commercial MMA technology, the acetone cyanohydrin (ACH) process. A three-step syngas-based process consisted of synthesis of a propionic acid, its condensation with formaldehyde, and esterification of resulting methacrylic acid (MAA) to form MMA. The first two steps, propionic acid synthesis and condensation, are discussed here. The low-temperature, low-pressure process for single-step hydrocarbonylation of ethylene to propionic acid is carried out using a homogeneous iodine-promoted Mo(CO){sub 6} catalyst at pressures (30--70 atm) and temperatures (150--200 C) lower than those reported for other catalysts. Mechanistic investigations suggest that catalysis is initiated by a rate-limiting CO dissociation from Mo(CO){sub 6}. This dissociation appears to be followed by an inner electron-transfer process of an I atom from EtI to the coordinately unsaturated Mo(CO){sub 5}. This homogeneous catalyst for propionate synthesis represents the first case of an efficient carbonylation process based on Cr group metals. The condensation of formaldehyde with propionic acid is carried out by acid-base bifunctional catalysts. As a result of screening over 80 catalytic materials, group V metals supported on an amorphous silica are found to be most effective. A 20% Nb/SiO{sub 2} catalyst appears to be the most active and stable catalyst thus far. Preliminary relations among the reaction yield and catalyst properties indicate that a high surface area and a low overall surface acidity (<50 = mol of NH{sub 3}/g), with a high proportion of the acidity being weak (<350 C desorption of NH{sub 3}), are desirable. Long-term deactivation of V-Si-P, Nb-Si, and Ta-Si catalysts suggests that carbon deposition is the primary cause for activity decay, and the catalyst activity is partially restorable by oxidative regeneration.

  1. SYNTHESIS OF METHYL METHACRYLATE FROM COAL-DERIVED SYNGAS

    SciTech Connect (OSTI)

    BEN W.-L. JANG; GERALD N. CHOI; JAMES J. SPIVEY; JOSPEH R. ZOELLER; RICHARD D. COLBERG

    1998-10-20

    Research Triangle Institute (RTI), Eastman Chemical Company, and Bechtel collectively are developing a novel three-step process for the synthesis of methyl methacrylate (MMA) from coal-derived syngas that consists of the steps of synthesis of a propionate, its condensation with formaldehyde to form methacrylic acid (MAA), and esterification of MAA with methanol to produce MMA. RTI has completed the research on the three-step methanol-based route to MMA. Under an extension to the original contract, RTI is currently evaluating a new DME-based process for MMA. The key research need for DME route is to develop catalysts for DME partial oxidation reactions and DME condensation reactions. Over the last quarter (July-September, 1998), the project team has completed the continuous condensation of formaldehyde with propionic acid over 10% Nb{sub 2}O{sub 5}/SiO{sub 2} at 300 C. Six activity and five regeneration cycles have been completed. The results show that 10% Nb{sub 2}O{sub 5}/SiO{sub 2} deactivates slowly with time but can be regenerated to its original activity with 2% O{sub 2} in nitrogen over night at 400 C. We have investigated the effects of regeneration, propionic acid/formaldehyde ratio (PA/HCHO = 4.5/1 to 1.5/1) and reaction temperature(280-300 C) on reaction activity and product selectivity over 20% Nb{sub 2}O{sub 5}/SiO{sub 2} catalysts. The regeneration effect on 20% Nb{sub 2}O{sub 5}/SiO{sub 2} is similar to the effect on 10% Nb{sub 2}O{sub 5}/SiO{sub 2}. The regeneration can bring the deactivated catalyst to its original activity. However, the selectivity to MAA decreases with regeneration while the selectivity to DEK and CO{sub 2} increases. When PA/HCHO ratio is decreased from 4.5/1 to 2.25/1 then to 1.5/1 at 300 C the MAA yield decreases but the MAA selectivity first increases then decreases. Decreasing the reaction temperature from 300 C to 280 C decreases the MAA yield from 39.5% to 30.7% but increases the MAA selectivity from 73.7% to 82.2%. The

  2. Flammability of selected heat resistant alloys in oxygen gas mixtures

    SciTech Connect (OSTI)

    Zawierucha, R.; McIlroy, K.; Million, J.F.

    1995-12-31

    Within recent years, the use of oxygen has increased in applications where elevated temperatures and corrosion may be significant factors. In such situations, traditional alloys used in oxygen systems will not be adequate. Where alternative alloys must be utilized, based upon environmental requirements, it is essential that they may be characterized with respect to their ignition and combustion resistance in oxygen. Promoted ignition and promoted ignition-combustion are terms which have been used to describe a situation where a substance with low oxygen supports the combustion of a compatibility ignites and more ignition resistant material. In this paper, data will be presented on the promoted ignition-combustion behavior of selected heat resistant engineering alloys that may be considered for gaseous oxygen applications in severe environments. In this investigation, alloys have been evaluated via both flowing and static (fixed volume) approaches using a rod configuration. Oxygen-nitrogen gas mixtures with compositions ranging from approximately 40 to 99.7% oxygen at pressures of 3.55 to 34.6 MPa were used in the comparative studies.

  3. Enhancing perovskite electrocatalysis through strain tuning of oxygen deficiency

    DOE PAGES-Beta [OSTI]

    Barron, Sara C.; Lee, Ho Nyung; Petrie, Jonathan R.; Jeen, Hyoungjeen; Meyer, Tricia L.

    2016-05-27

    Oxygen vacancies in transition-metal oxides facilitate catalysis critical for energy storage and generation. However, promoting vacancies at the lower temperatures required for operation in devices such as metal–air batteries and portable fuel cells has proven elusive. Here we used thin films of perovskite-based strontium cobaltite (SrCoOx) to show that epitaxial strain is a powerful tool for manipulating the oxygen content under conditions consistent with the oxygen evolution reaction, yielding increasingly oxygen-deficient states in an environment where the cobaltite would normally be fully oxidized. The additional oxygen vacancies created through tensile strain enhance the cobaltite’s catalytic activity toward this important reactionmore » by over an order of magnitude, equaling that of precious-metal catalysts, including IrO2. Lastly, our findings demonstrate that strain in these oxides can dictate the oxygen stoichiometry independent of ambient conditions, allowing unprecedented control over oxygen vacancies essential in catalysis near room temperature.« less

  4. Vapor pressures of methyl tert-butyl ether, ethyl tert-butyl ether, isopropyl tert-butyl ether, tert-amyl methyl ether, and tert-amyl ethyl ether

    SciTech Connect (OSTI)

    Kraehenbuehl, M.A.; Gmehling, J. . Technische Chemie)

    1994-10-01

    The vapor pressures of methyl tert-butyl ether, ethyl tert-butyl ether, isopropyl tert-butyl ether, tert-amyl methyl ether, and tert-amyl ethyl ether were measured by ebulliometry or the static method in the pressure ranges 14--102 and 3--835 kPa (methyl tert-butyl ether), respectively. The data were correlated using the Antoine and Wagner equations. The experimental data of methyl tert-butyl ether and ethyl tert-butyl ether were compared with data available in the literature.

  5. Noble metal-free bifunctional oxygen evolution and oxygen reduction acidic media electro-catalysts

    DOE PAGES-Beta [OSTI]

    Patel, Prasad Prakash; Datta, Moni Kanchan; Velikokhatnyi, Oleg I.; Kuruba, Ramalinga; Damodaran, Krishnan; Jampani, Prashanth; Gattu, Bharat; Shanthi, Pavithra Murugavel; Damle, Sameer S.; Kumta, Prashant N.

    2016-07-06

    We report that identification of low cost, highly active, durable completely noble metal-free electro-catalyst for oxygen reduction reaction (ORR) in proton exchange membrane (PEM) fuel cells, oxygen evolution reaction (OER) in PEM based water electrolysis and metal air batteries remains one of the major unfulfilled scientific and technological challenges of PEM based acid mediated electro-catalysts. In contrast, several non-noble metals based electro-catalysts have been identified for alkaline and neutral medium water electrolysis and fuel cells. Furthermore, we report for the very first time, F doped Cu1.5Mn1.5O4, identified by exploiting theoretical first principles calculations for ORR and OER in PEM basedmore » systems. The identified novel noble metal-free electro-catalyst showed similar onset potential (1.43 V for OER and 1 V for ORR vs RHE) to that of IrO2 and Pt/C, respectively. The system also displayed excellent electrochemical activity comparable to IrO2 for OER and Pt/C for ORR, respectively, along with remarkable long term stability for 6000 cycles in acidic media validating theory, while also displaying superior methanol tolerance and yielding recommended power densities in full cell configurations.« less

  6. THERMOCHEMICAL CONVERSION OF FERMENTATION-DERIVED OXYGENATES TO FUELS

    SciTech Connect (OSTI)

    Ramasamy, Karthikeyan K.; Wang, Yong

    2013-06-01

    At present ethanol generated from renewable resources through fermentation process is the dominant biofuel. But ethanol suffers from undesirable fuel properties such as low energy density and high water solubility. The production capacity of fermentation derived oxygenates are projected to rise in near future beyond the current needs. The conversion of oxygenates to hydrocarbon compounds that are similar to gasoline, diesel and jet fuel is considered as one of the viable option. In this chapter the thermo catalytic conversion of oxygenates generated through fermentation to fuel range hydrocarbons will be discussed.

  7. Hydrogen Production Using Hydrogenase-Containing Oxygenic Photosynthetic Organisms

    DOE Patents [OSTI]

    Melis, A.; Zhang, L.; Benemann, J. R.; Forestier, M.; Ghirardi, M.; Seibert, M.

    2006-01-24

    A reversible physiological process provides for the temporal separation of oxygen evolution and hydrogen production in a microorganism, which includes the steps of growing a culture of the microorganism in medium under illuminated conditions to accumulate an endogenous substrate, depleting from the medium a nutrient selected from the group consisting of sulfur, iron, and/or manganese, sealing the culture from atmospheric oxygen, incubating the culture in light whereby a rate of light-induced oxygen production is equal to or less than a rate of respiration, and collecting an evolved gas. The process is particularly useful to accomplish a sustained photobiological hydrogen gas production in cultures of microorganisms, such as Chlamydomonas reinhardtii.

  8. Boron nitride nanosheets as oxygen-atom corrosion protective coatings

    SciTech Connect (OSTI)

    Yi, Min; Shen, Zhigang; Zhao, Xiaohu; Liang, Shuaishuai; Liu, Lei

    2014-04-07

    The research of two-dimensional nanomaterials for anticorrosion applications is just recently burgeoning. Herein, we demonstrate the boron nitride nanosheets (BNNSs) coatings for protecting polymer from oxygen-atom corrosion. High-quality BNNSs, which are produced by an effective fluid dynamics method with multiple exfoliation mechanisms, can be assembled into coatings with controlled thickness by vacuum filtration. After exposed in atom oxygen, the naked polymer is severely corroded with remarkable mass loss, while the BNNSs-coated polymer remains intact. Barrier and bonding effects of the BNNSs are responsible for the coating's protective performance. These preliminary yet reproducible results pave a way for resisting oxygen-atom corrosion.

  9. Hydrogen production using hydrogenase-containing oxygenic photosynthetic organisms

    DOE Patents [OSTI]

    Melis, Anastasios; Zhang, Liping; Benemann, John R.; Forestier, Marc; Ghirardi, Maria; Seibert, Michael

    2006-01-24

    A reversible physiological process provides for the temporal separation of oxygen evolution and hydrogen production in a microorganism, which includes the steps of growing a culture of the microorganism in medium under illuminated conditions to accumulate an endogenous substrate, depleting from the medium a nutrient selected from the group consisting of sulfur, iron, and/or manganese, sealing the culture from atmospheric oxygen, incubating the culture in light whereby a rate of light-induced oxygen production is equal to or less than a rate of respiration, and collecting an evolved gas. The process is particularly useful to accomplish a sustained photobiological hydrogen gas production in cultures of microorganisms, such as Chlamydomonas reinhardtii.

  10. Modelling oxygen self-diffusion in UO2 under pressure

    DOE PAGES-Beta [OSTI]

    Cooper, Michael William D.; Grimes, R. W.; Fitzpatrick, M. E.; Chroneos, A.

    2015-10-22

    Access to values for oxygen self-diffusion over a range of temperatures and pressures in UO2 is important to nuclear fuel applications. Here, elastic and expansivity data are used in the framework of a thermodynamic model, the cBΩ model, to derive the oxygen self-diffusion coefficient in UO2 over a range of pressures (0–10 GPa) and temperatures (300–1900 K). Furthermore, the significant reduction in oxygen self-diffusion as a function of increasing hydrostatic pressure, and the associated increase in activation energy, is identified.

  11. Solid phases of spatially nanoconfined oxygen: A neutron scattering study

    SciTech Connect (OSTI)

    Kojda, Danny [Helmholtz-Zentrum Berlin fr Materialien und Energie GmbH, 14109 Berlin (Germany) [Helmholtz-Zentrum Berlin fr Materialien und Energie GmbH, 14109 Berlin (Germany); Freie Universitt Berlin, 14195 Berlin (Germany); Wallacher, Dirk; Hofmann, Tommy, E-mail: tommy.hofmann@helmholtz-berlin.de [Helmholtz-Zentrum Berlin fr Materialien und Energie GmbH, 14109 Berlin (Germany)] [Helmholtz-Zentrum Berlin fr Materialien und Energie GmbH, 14109 Berlin (Germany); Baudoin, Simon; Hansen, Thomas [Institut Laue-Langevin, BP 156, 38042 Grenoble Cedex 9 (France)] [Institut Laue-Langevin, BP 156, 38042 Grenoble Cedex 9 (France); Huber, Patrick [Technische Universitt Hamburg-Harburg, 21073 Hamburg (Germany)] [Technische Universitt Hamburg-Harburg, 21073 Hamburg (Germany)

    2014-01-14

    We present a comprehensive neutron scattering study on solid oxygen spatially confined in 12 nm wide alumina nanochannels. Elastic scattering experiments reveal a structural phase sequence known from bulk oxygen. With decreasing temperature cubic ?-, orthorhombic ?- and monoclinic ?-phases are unambiguously identified in confinement. Weak antiferromagnetic ordering is observed in the confined monoclinic ?-phase. Rocking scans reveal that oxygen nanocrystals inside the tubular channels do not form an isotropic powder. Rather, they exhibit preferred orientations depending on thermal history and the very mechanisms, which guide the structural transitions.

  12. The use of nonmarine palynomorphs as correlation tools in rapidly deposited upper tertiary sediments of the Gulf of Mexico

    SciTech Connect (OSTI)

    Ravn, R.L. ); D'Ablaing, J.A. )

    1993-09-01

    Rapidly deposited upper Tertiary sediments can pose significant correlation problems for the biostratigrapher using foraminifera or calcareous nannoplankton because the abundance of marine organisms commonly is greatly diluted. In contrast, such sediments often contain abundant pollen and spores. This palynological population was collected by the proto-Mississippi and perhaps other rivers from a huge hinterland source area probably comparable to that of the Mississippi drainage today. The sediment therefore reflects a general floral population over a large region and may be expected to record important fluctuations in constituent elements of the flora due to climatic changes over time. A secondary overprint of physical sorting also may influence the relative distributions of certain forms. Although not strongly useful as an age-dating tool (the vast majority of forms occurring in Miocene or younger strata represent parent plant types that still exist today), these palynomorph populations do show strong potential as tools for correlation based on quantitative analyses. Palynological [open quotes]logs[close quotes] can be produced using inexpensive standard spreadsheet software and various mathematical evaluation techniques. An example from the Pliocene of offshore Louisiana demonstrates that numerous potential correlation horizons can be defined in a relatively brief time interval in a section in which standard marine microfossils are of little use owing to their scarcity.

  13. Oxygen enriched combustion system performance study. Phase 2: 100 percent oxygen enriched combustion in regenerative glass melters, Final report

    SciTech Connect (OSTI)

    Tuson, G.B.; Kobayashi, H.; Campbell, M.J.

    1994-08-01

    The field test project described in this report was conducted to evaluate the energy and environmental performance of 100% oxygen enriched combustion (100% OEC) in regenerative glass melters. Additional objectives were to determine other impacts of 100% OEC on melter operation and glass quality, and to verify on a commercial scale that an on-site Pressure Swing Adsorption oxygen plant can reliably supply oxygen for glass melting with low electrical power consumption. The tests constituted Phase 2 of a cooperative project between the United States Department of Energy, and Praxair, Inc. Phase 1 of the project involved market and technical feasibility assessments of oxygen enriched combustion for a range of high temperature industrial heating applications. An assessment of oxygen supply options for these applications was also performed during Phase 1, which included performance evaluation of a pilot scale 1 ton per day PSA oxygen plant. Two regenerative container glass melters were converted to 100% OEC operation and served as host sites for Phase 2. A 75 ton per day end-fired melter at Carr-Lowrey Glass Company in Baltimore, Maryland, was temporarily converted to 100% OEC in mid- 1990. A 350 tpd cross-fired melter at Gallo Glass Company in Modesto, California was rebuilt for permanent commercial operation with 100% OEC in mid-1991. Initially, both of these melters were supplied with oxygen from liquid storage. Subsequently, in late 1992, a Pressure Swing Adsorption oxygen plant was installed at Gallo to supply oxygen for 100% OEC glass melting. The particular PSA plant design used at Gallo achieves maximum efficiency by cycling the adsorbent beds between pressurized and evacuated states, and is therefore referred to as a Vacuum/Pressure Swing Adsorption (VPSA) plant.

  14. In-situ generation of oxygen-releasing metal peroxides

    DOE Patents [OSTI]

    Looney, Brian B.; Denham, Miles E.

    2007-01-09

    A method for remediation of contaminants in soil and groundwater is disclosed. The method generates oxygen releasing solids in groundwater or soil by injecting an aqueous energetic oxidant solution containing free radicals, oxidative conditions can be created within or ahead of a contaminant plume. Some contaminants may be remediated directly by reaction with the free radicals. Additionally and more importantly, the free radicals create an oxidative condition whereby native or injected materials, especially metals, are converted to peroxides. These peroxides provide a long-term oxygen reservoir, releasing oxygen relatively slowly over time. The oxygen can enhance microbial metabolism to remediate contaminants, can react with contaminant metals either to form immobile precipitants or to mobilize other metals to permit remediation through leaching techniques. Various injection strategies for injecting the energetic oxidant solution are also disclosed.

  15. IMPACT OF OXYGEN CONCENTRATION ON ZEBRA MUSSEL MORTALITY

    SciTech Connect (OSTI)

    Daniel P. Molloy

    2003-01-27

    These tests have indicated that the bacterium Pseudomonas fluorescens strain CL0145A is effective at killing zebra mussels in environments having dissolved oxygen (DO) concentrations ranging from very low to very high. The results suggest that the highest mussel kill can be achieved in moderately to highly aerated environments, while kill may be 0-20% lower under conditions of very low oxygen. For example, under highly oxygenated conditions 97% kill was achieved while conditions having low DO produced 79% mussel kill. Service water measured in a local power plant indicated that DO concentrations were in the range of 8-9 ppm (e.g., highly aerated) within their pipes. Therefore, we will not expect to see decreases in the efficacy of CL0145A treatments due to oxygen levels within such power plant pipes.

  16. Vehicle Technologies Office Merit Review 2014: Intake Air Oxygen Sensor

    Energy.gov [DOE]

    Presentation given by Robert Bosch at 2014 DOE Hydrogen and Fuel Cells Program and Vehicle Technologies Office Annual Merit Review and Peer Evaluation Meeting about intake air oxygen sensors.

  17. STUDY OF USING OXYGEN-ENRICHED COMBUSTION AIR FOR LOCOMOTIVE...

    Office of Scientific and Technical Information (OSTI)

    ... Evaluation o f Polymeric Membranes for Oxygen-Enrichment of Air, DOEAD- 127 10- 1, U S . ... fLom Gas Turbine Engines, Atmospheric Pollution by Aircraft Engines, AGARD CP-125, Paper ...

  18. An Oxygen Isotope Study Of Silicates In The Larderello Geothermal...

    Open Energy Information (Open El) [EERE & EIA]

    Silicates In The Larderello Geothermal Field, Italy Jump to: navigation, search OpenEI Reference LibraryAdd to library Journal Article: An Oxygen Isotope Study Of Silicates In The...

  19. Hybrid membrane--PSA system for separating oxygen from air

    DOE Patents [OSTI]

    Staiger, Chad L.; Vaughn, Mark R.; Miller, A. Keith; Cornelius, Christopher J.

    2011-01-25

    A portable, non-cryogenic, oxygen generation system capable of delivering oxygen gas at purities greater than 98% and flow rates of 15 L/min or more is described. The system consists of two major components. The first component is a high efficiency membrane capable of separating argon and a portion of the nitrogen content from air, yielding an oxygen-enriched permeate flow. This is then fed to the second component, a pressure swing adsorption (PSA) unit utilizing a commercially available, but specifically formulated zeolite compound to remove the remainder of the nitrogen from the flow. The system is a unique gas separation system that can operate at ambient temperatures, for producing high purity oxygen for various applications (medical, refining, chemical production, enhanced combustion, fuel cells, etc . . . ) and represents a significant advance compared to current technologies.

  20. Ultrafast kinetics subsequent to shock in an unreacted, oxygen...

    Office of Scientific and Technical Information (OSTI)

    subsequent to shock in an unreacted, oxygen balanced mixture of nitromethane and hydrogen peroxide Armstrong, M R; Zaug, J M; Grant, C D; Crowhurst, J C; Bastea, S 75...

  1. COLLATERAL EFFECTS ON SOLAR NEBULA OXYGEN ISOTOPES DUE TO INJECTION...

    Office of Scientific and Technical Information (OSTI)

    COLLATERAL EFFECTS ON SOLAR NEBULA OXYGEN ISOTOPES DUE TO INJECTION OF sup 26Al BY A NEARBY SUPERNOVA Citation Details In-Document Search Title: COLLATERAL EFFECTS ON SOLAR ...

  2. Oxygen Control of Atomic Structure and Physical Properties of...

    Office of Scientific and Technical Information (OSTI)

    Properties of SrRuO3 Surfaces Citation Details In-Document Search Title: Oxygen Control of Atomic Structure and Physical Properties of SrRuO3 Surfaces Authors: Tselev, ...

  3. Enhancing SNCR-aided combustion with oxygen addition

    DOE Patents [OSTI]

    Kobayashi, Hisashi; Wu, Kuang Tsai; Bool, III, Lawrence E.

    2004-03-09

    NOx emissions from combustion are reduced, NOx reduction efficiency by SNCR is improved, and other efficiencies are realized, by injecting oxygen into a fuel-rich combustion zone under controlled conditions.

  4. Role of an Oxygen Vacancy Nanostructure on the Switchable Photovoltaic...

    U.S. Department of Energy (DOE) all webpages (Extended Search)

    Role of an Oxygen Vacancy Nanostructure on the Switchable Photovoltaic Effect in BiFeO3 ... Moreover, a switchable photovoltaic effect and its diode effect have been demonstrated.2 ...

  5. Sensor Rapidly Measures the Concentration of Oxygen in Fluids...

    U.S. Department of Energy (DOE) all webpages (Extended Search)

    Compared to current sensor technology, such as universal exhaust gas oxygen sensors and ... mixture inside the intake manifold of an engine, to a transducer via a fiber optic cable. ...

  6. Vehicle Technologies Office Merit Review 2015: Intake Air Oxygen Sensor

    Office of Energy Efficiency and Renewable Energy (EERE)

    Presentation given by Robert Bosch at 2015 DOE Hydrogen and Fuel Cells Program and Vehicle Technologies Office Annual Merit Review and Peer Evaluation Meeting about intake air oxygen sensor.

  7. Hydrogen (H2) Production by Oxygenic Phototrophs | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Oxygenic Phototrophs Hydrogen (H2) Production by Oxygenic Phototrophs Presentation by Eric Hegg, Michigan State University, at the Biological Hydrogen Production Workshop held September 24-25, 2013, at the National Renewable Energy Laboratory in Golden, Colorado. bio_h2_workshop_hegg.pdf (1.07 MB) More Documents & Publications Renewable Hydrogen Production from Biological Systems Autofermentative Biological Hydrogen Production by Cyanobacteria 2013 Biological Hydrogen Production Workshop

  8. NETL Advances Copper-Hybrid Oxygen Carrier for Chemical Looping |

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Department of Energy Advances Copper-Hybrid Oxygen Carrier for Chemical Looping NETL Advances Copper-Hybrid Oxygen Carrier for Chemical Looping November 4, 2016 - 12:18pm Addthis NETL’s Chemical Looping Reactor Pilot-Scale Test Facility NETL's Chemical Looping Reactor Pilot-Scale Test Facility Back in February, we shared that DOE's National Energy Technology Laboratory (NETL) researchers were exploring the potential of using copper in a process known as chemical looping to capture

  9. Oxygen enhanced switching to combustion of lower rank fuels

    DOE Patents [OSTI]

    Kobayashi, Hisashi; Bool, III, Lawrence E.; Wu, Kuang Tsai

    2004-03-02

    A furnace that combusts fuel, such as coal, of a given minimum energy content to obtain a stated minimum amount of energy per unit of time is enabled to combust fuel having a lower energy content, while still obtaining at least the stated minimum energy generation rate, by replacing a small amount of the combustion air fed to the furnace by oxygen. The replacement of oxygen for combustion air also provides reduction in the generation of NOx.

  10. Method for making oxygen-reducing catalyst layers

    DOE Patents [OSTI]

    O'Brien, Dennis P.; Schmoeckel, Alison K.; Vernstrom, George D.; Atanasoski, Radoslav; Wood, Thomas E.; O'Neill, David G.

    2010-06-22

    Methods are provided for making oxygen-reducing catalyst layers, which include simultaneous or sequential stops of physical vapor depositing an oxygen-reducing catalytic material onto a substrate, the catalytic material comprising a transition metal that is substantially free of platinum; and thermally treating the catalytic material. At least one of the physical vapor deposition and the thermal treatment is performed in a processing environment comprising a nitrogen-containing gas.

  11. Distributed Reforming of Renewable Liquids via Water Splitting using Oxygen

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    Transport Membrane (OTM) (Presentation) | Department of Energy Renewable Liquids via Water Splitting using Oxygen Transport Membrane (OTM) (Presentation) Distributed Reforming of Renewable Liquids via Water Splitting using Oxygen Transport Membrane (OTM) (Presentation) Presented at the 2007 Bio-Derived Liquids to Hydrogen Distributed Reforming Working Group held November 6, 2007 in Laurel, Maryland. 11_anl_distributed_reforming_using_otm.pdf (809.59 KB) More Documents & Publications Cost

  12. Ultrafast kinetics subsequent to shock in an unreacted, oxygen balanced

    Office of Scientific and Technical Information (OSTI)

    mixture of nitromethane and hydrogen peroxide (Conference) | SciTech Connect kinetics subsequent to shock in an unreacted, oxygen balanced mixture of nitromethane and hydrogen peroxide Citation Details In-Document Search Title: Ultrafast kinetics subsequent to shock in an unreacted, oxygen balanced mixture of nitromethane and hydrogen peroxide Authors: Armstrong, M R ; Zaug, J M ; Grant, C D ; Crowhurst, J C ; Bastea, S Publication Date: 2014-06-24 OSTI Identifier: 1149544 Report Number(s):

  13. Oxygen-permeable ceramic membranes for gas separation

    SciTech Connect (OSTI)

    Balachandran, U.; Ma, B.; Maiya, P.S.; Dusek, J.T.; Mieville, R.L.; Picciolo, J.J.

    1998-02-01

    Mixed-conducting oxides have a wide range of applications, including fuel cells, gas separation systems, sensors, and electrocatalytic equipment. Dense ceramic membranes made of mixed-conducting oxides are particularly attractive for gas separation and methane conversion processes. Membranes made of Sr-Fe-Co oxide, which exhibits high combined electronic and oxygen ionic conductivities, can be used to selectively transport oxygen during the partial oxidation of methane to synthesis gas (syngas, i.e., CO + H{sub 2}). The authors have fabricated tubular Sr{sub 2}Fe{sub 2}CoO{sub 6+{delta}} membranes and tested them (some for more than 1,000 h) in a methane conversion reactor that was operating at 850--950 C. An oxygen permeation flux of {approx} 10 scc/cm{sup 2} {center_dot} min was obtained at 900 C in a tubular membrane with a wall thickness of 0.75 mm. Using a gas-tight electrochemical cell, the authors have also measured the steady-state oxygen permeability of flat Sr{sub 2}Fe{sub 2}CoO{sub 6+{delta}} membranes as a function of temperature and oxygen partial pressure(pO{sub 2}). Steady-state oxygen permeability increases with increasing temperature and with the difference in pO{sub 2} on the two sides of the membrane. At 900 C, an oxygen permeability of {approx} 2.5 scc/cm{sup 2} {center_dot} min was obtained in a 2.9-mm-thick membrane. This value agrees with that obtained in methane conversion reactor experiments. Current-voltage (I-V) characteristics determined in the gas-tight cell indicate that bulk effect, rather than surface exchange effect, is the main limiting factor for oxygen permeation of {approx} 1-mm-thick Sr{sub 2}Fe{sub 2}CoO{sub 6+{delta}} membranes at elevated temperatures (> 650 C).

  14. Crystal structure of 1-methyl-3-([2,2-dimethyl-4,6-dioxo-1,3-dioxane-5-ylidene]methyl)urea

    SciTech Connect (OSTI)

    Habibi, A. Ghorbani, H. S.; Bruno, G.; Rudbari, H. A.; Valizadeh, Y.

    2013-12-15

    The crystal structure of 1-Methyl-3-([2,2-dimethyl-4,6-dioxo-1,3-dioxane-5-ylidene]methyl)urea (C{sub 9}H{sub 12}N{sub 2}O{sub 5}) has been determined by single crystal X-ray diffraction analysis. The crystals are monoclinic, a = 5.3179(2), b = 18.6394(6), c =10.8124(3) , ? = 100.015(2), Z = 4, sp. gr. P2{sub 1}/c, R = 0.0381 for 2537 reflections with I > 2?(I). Except for C(CH{sub 3}){sub 2} group, the molecule is planar. The structure is stabilized by inter- and intramolecular N-H...O hydrogen bonds and weak C-H...O interactions.

  15. Polylactide?Poly(6-methyl-[espilson]-caprolactone)?Polylactide Thermoplastic Elastomers

    SciTech Connect (OSTI)

    Martello, Mark T.; Hillmyer, Marc A.

    2012-11-14

    Amorphous ABA type block aliphatic polyesters can be useful as degradable and biorenewable thermoplastic elastomers. These materials can be prepared by sequential ring-opening transesterification polymerization (ROTEP) reactions and can exhibit a range of physical properties and morphologies. In this work a set of amorphous polylactide-poly(6-methyl-{epsilon}-caprolactone)-polylactide aliphatic polyester ABA triblock copolymers were prepared by consecutive controlled ring-opening polymerizations. Ring-opening polymerization of neat 6-methyl-{epsilon}-caprolactone in the presence of 1,4-benzenedimethanol and tin(II) octoate afforded {alpha},{omega}-hydroxyl-terminated poly(6-methyl-{epsilon}-caprolactone). High conversions of 6-methyl-{epsilon}-caprolactone (>96%) afforded polymers with molar masses ranging from 12 to 98 kg mol{sup -1}, depending on monomer-to-initiator ratios, polymers with narrow, monomodal molecular weight distributions. An array of polylactide-poly(6-methyl-{epsilon}-caprolactone)-polylactide triblock copolymers with controlled molecular weights and narrow molecular weight distributions were synthesized using the telechelic poly(6-methyl-{epsilon}-caprolactone) samples as macroinitiators for the ring-opening polymerization of D,L-lactide. The morphological, thermal, and mechanical behaviors of these materials were explored. Several triblocks adopted well-ordered microphase-separated morphologies, and both hexagonally packed cylindrical and lamellar structures were observed. The Flory-Huggins interaction parameter was determined, x(T) = 61.2 T{sup -1} - 0.1, based on the order-to-disorder transition temperatures of two symmetric triblocks using the calculated mean field theory result. The elastomeric mechanical behavior of two high molecular weight triblocks was characterized by tensile and elastic recovery experiments.

  16. Synthesis Of [2h, 13c] And [2h3, 13c]Methyl Aryl Sulfides

    DOE Patents [OSTI]

    Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.

    2004-03-30

    The present invention is directed to labeled compounds, [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2, .sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfides wherein the .sup.13 C methyl group attached to the sulfur of the sulfide includes exactly one, two or three deuterium atoms and the aryl group is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 are each independently, hydrogen, a C.sub.1 -C.sub.4 lower alkyl, a halogen, an amino group from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each a C.sub.1 -C.sub.4 lower alkyl, a phenyl, or an alkoxy group. The present invention is also directed to processes of preparing [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2,.sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfides wherein the .sup.13 C methyl group attached to the sulfur of the sulfide includes exactly one, two or three deuterium atoms. The present invention is also directed to the labeled compounds of [.sup.2 H.sub.1, .sup.13 C]methyl iodide and [.sup.2 H.sub.2, .sup.13 C]methyl iodide.

  17. The role of DNA methylation in catechol-enhanced erythroid differentiation of K562 cells

    SciTech Connect (OSTI)

    Li, Xiao-Fei; Wu, Xiao-Rong; Xue, Ming; Wang, Yan; Wang, Jie; Li, Yang; Suriguga,; Zhang, Guang-Yao; Yi, Zong-Chun

    2012-11-15

    Catechol is one of phenolic metabolites of benzene in vivo. Catechol is also widely used in pharmaceutical and chemical industries. In addition, fruits, vegetables and cigarette smoke also contain catechol. Our precious study showed that several benzene metabolites (phenol, hydroquinone, and 1,2,4-benzenetriol) inhibited erythroid differentiation of K562 cells. In present study, the effect of catechol on erythroid differentiation of K562 cells was investigated. Moreover, to address the role of DNA methylation in catechol-induced effect on erythroid differentiation in K562 cells, methylation levels of erythroid-specific genes were analyzed by Quantitative MassARRAY methylation analysis platform. Benzidine staining showed that exposure to catechol enhanced hemin-induced hemoglobin accumulation in K562 cells in concentration- and time-dependent manners. The mRNA expression of erythroid specific genes, including ?-globin, ?-globin, ?-globin, erythroid 5-aminolevulinate synthase, erythroid porphobilinogen deaminase, and transcription factor GATA-1 genes, showed a significant concentration-dependent increase in catechol-treated K562 cells. The exposure to catechol caused a decrease in DNA methylation levels at a few CpG sites in some erythroid specific genes including ?-globin, ?-globin and erythroid porphobilinogen deaminase genes. These results indicated that catechol improved erythroid differentiation potency of K562 cells at least partly via up-regulating transcription of some erythroid related genes, and suggested that inhibition of DNA methylation might be involved in up-regulated expression of some erythroid related genes. -- Highlights: ? Catechol enhanced hemin-induced hemoglobin accumulation. ? Exposure to catechol resulted in up-regulated expression of erythroid genes. ? Catechol reduced methylation levels at some CpG sites in erythroid genes.

  18. Isomerization and dissociation in competition: The two-component dissociation rates of methyl propionate ions

    SciTech Connect (OSTI)

    Mazyar, O.A.; Baer, T.

    1999-03-04

    Threshold photoelectron-photoion coincidence (TPEPICO) spectroscopy has been used to investigate the unimolecular chemistry of gas-phase methyl propionate ions. This ion undergoes isomerization to a lower energy enol structure, CH{sub 3}CHC(OH)OCH{sub 3}{sup {sm_bullet}+}, via two different pathways involving two distonic isomers, {sup {sm_bullet}}CH{sub 2}CH{sub 2}C{sup +}(OH)OCH{sub 3} and CH{sub 3}CH{sub 2}C{sup +}(OH)OCH{sub 2}{sup {sm_bullet}}. This isomerization reaction is in competition with the direct CH{sub 3}O{sup {sm_bullet}} loss reaction, which leads to two-component dissociation rates of the methyl propionate ions. Detailed modeling of this complex reaction permitted the extraction of the dissociative photoionization threshold for methyl propionate, which at 0 K is 10.83 {+-} 0.01 eV, as well as the isomerization barrier between the distonic CH{sub 3}CH{sub 2}C{sup +}(OH)OCH{sub 2}{sup {sm_bullet}} and enol CH{sub 3}CHC(OH)OCH{sub 3}{sup {sm_bullet}+} ions of 8.5 kcal/mol (relative to the methyl propionate ion). By combining this with the 0 K heats of formation of methyl propionate and the methoxy radical, the authors derive a 0 K heat of formation of the product propanoyl ion of 147 kcal/mol. Also measured was the adiabatic ionization energy of methyl propionate, 10.03 {+-} 0.05 eV.

  19. Electrochemical transfer of oxygen during direct current arc welding

    SciTech Connect (OSTI)

    Kim, J.H.; Frost, R.H.; Olson, D.L.

    1994-12-31

    Weld metal oxygen content is important for control of weld metal microstructure and notch toughness. Low oxygen contents promote low toughness bainitic structures. Moderate oxygen levels favor a tough acicular ferrite structure, and high oxygen levels promote lower toughness grain boundary and Widmanstaetten side plate structures. The objective of this research was to examine electrochemical oxygen transfer as a function of welding process variables, polarity, and the relative importance of conduction across plasma-metal and slag-metal interfaces for: submerged arc welding (SAW), shielded metal arc welding (SMAW), and gas tungsten arc welding (GTAW) processes. SAW and SMAW were made in DCEN and DCEP polarities on structural steel and copper substrates. GTAW were made on steel substrates in DCEN polarity. The experimental results show that both thermochemical and electrochemical reactions are important for oxygen transfer, and that there are differences in the electrochemical reactions at slag-metal and plasma-metal interfaces. Both electrochemical and thermochemical reactions are significant for direct current arc welding processes. The arc plasma acts as an electrolyte for arc welding processes and electrochemical reactions occur at the plasma-metal interface have chemical effects opposite to those at the slag metal interface. This is caused by the fact that only positive ions exist in the arc plasma in large concentrations.

  20. Acute environmental toxicity and persistence of methyl salicylate: A chemical agent simulant. Final report

    SciTech Connect (OSTI)

    Cataldo, D.A.; Ligotke, M.W.; Harvey, S.D.; Fellows, R.J.; Li, S.W.

    1994-06-01

    The interactions of methyl salicylate with plant foliage and soils were assessed using aerosol/vapor exposure methods. Measurements of deposition velocity and residence times for soils and foliar surfaces are reported. Severe plant contact toxicity was observed at foliar mass-loading levels above 4 {mu}g/cm{sup 2} leaf; however, recovery was noted after four to fourteen days. Methyl salicylate has a short-term effect on soil dehydrogenase activity, but not phosphatase activity. Results of the earthworm bioassay indicated only minimal effects on survival.

  1. Structures, Phase Transitions and Tricritical Behavior of the Hybrid Perovskite Methyl Ammonium Lead Iodide

    Office of Scientific and Technical Information (OSTI)

    OPEN Received: 14 June 2016 Accepted: 03 October 2016 Published: 21 October 2016 Structures, Phase Transitions and Tricritical Behavior of the Hybrid Perovskite Methyl Ammonium Lead Iodide P. S. Whitfield1, N. Herron2, W. E. Guise3,4, K. Page1, Y. Q. Cheng1,1. Milas3 & M. K. Crawford3,5 We have examined the crystal structures and structural phase transitions of the deuterated, partially deuterated and hydrogenous organic-inorganic hybrid perovskite methyl ammonium lead iodide (MAPbl3) using

  2. MTBE Production Economics (Released in the STEO April 2001)

    Reports and Publications

    2001-01-01

    The purpose of this analysis is to evaluate the causes of methyl tertiary butyl ether (MTBE) price increases in 2000.

  3. Interaction of light with the ZnO surface: Photon induced oxygen breathing, oxygen vacancies, persistent photoconductivity, and persistent photovoltage

    SciTech Connect (OSTI)

    Gurwitz, Ron; Cohen, Rotem; Shalish, Ilan

    2014-01-21

    ZnO surfaces adsorb oxygen in the dark and emit CO{sub 2} when exposed to white light, reminiscent of the lungs of living creatures. We find that this exchange of oxygen with the ambient affects the integrity of the ZnO surface. Thus, it forms a basis for several interesting surface phenomena in ZnO, such as photoconductivity, photovoltage, and gas sensing, and has a role in ZnO electrical conduction. Using x-ray photoelectron spectroscopy on ZnO nanowires, we observed a decomposition of ZnO under white light and formation of oxygen-depleted surface, which explains photoconductivity by the electron donation of oxygen vacancies. Our findings suggest that the observed decomposition of the ZnO lattice may only take place due to photon-induced reduction of ZnO by carbon containing molecules (or carbo-photonic reduction), possibly from the ambient gas, accounting in a consistent way for both the reduced demands on the energy required for decomposition and for the observed emission of lattice oxygen in the form of CO{sub 2}. The formation of oxygen-vacancy rich surface is suggested to induce surface delta doping, causing accumulation of electrons at the surface, which accounts for both the increase in conductivity and the flattening of the energy bands. Using surface photovoltage spectroscopy in ultra high vacuum, we monitored changes in the deep level spectrum. We observe a wide optical transition from a deep acceptor to the conduction band, which energy position coincides with the position of the so called green luminescence in ZnO. This green transition disappears with the formation of surface oxygen vacancies. Since the oxygen vacancies are donors, while the green transition involves surface acceptors, the results suggest that the initial emission of oxygen originates at the defect sites of the latter, thereby eliminating each other. This suggests that the green transition originates at surface Zn vacancy acceptors. Removing an oxygen atom from a Zn vacancy

  4. Gravity and magnetic anomalies associated with Tertiary volcanism and a Proterozoic crustal boundary, Hopi Buttes volcanic field, Navajo Nation (Arizona)

    SciTech Connect (OSTI)

    Donovan-Ealy, P.F. . Geology Dept.); Hendricks, J.D. )

    1992-01-01

    The Hopi Buttes volcanic field is located in the Navajo Nation of northeastern Arizona, near the southern margin of the Colorado Plateau. Explosive phreatomagmatic eruptions from late Miocene to mid-Pliocene time produced more than 300 maar-diatremes and deposited limburgite tuffs and tuff breccia and monchiquite dikes, necks and flows within a roughly circular 2,500 km[sup 2] area. The volcanic and volcaniclastic rocks make up the middle member of the Bidahochi Formation, whose lower and upper members are lacustrine and fluvial, respectively. The Bidahochi Formation overlies gently dipping Mesozoic sedimentary rocks exposed in the southwestern portion of the volcanic field. Two significant gravity and magnetic anomalies appear within the Hopi Buttes volcanic field that are unlike the signatures of other Tertiary volcanic fields on the Colorado Plateau. A circular 20 mGal negative gravity anomaly is centered over exposed sedimentary rocks in the southwestern portion of the field. The anomaly may be due to the large volume of low density pyroclastic rocks in the volcanic field and/or extensive brecciation of the underlying strata from the violent maar eruptions. The second significant anomaly is the northeast-trending Holbrook lineament, a 5 km-wide gravity and magnetic lineament that crosses the southeastern part of the volcanic field. The lineament reflects substantial gravity and magnetic decreases of 1.67 mGals/km and 100 gammas/km respectively, to the southeast. Preliminary two-dimensional gravity and magnetic modeling suggests the lineament represents a major Proterozoic crustal boundary and may correlate with one of several Proterozoic faults exposed in the transition zone of central Arizona. Gravity modeling shows a 3--5 km step'' in the Moho near the crustal boundary. The decrease in depth of the Moho to the northwest indicates either movement along the fault or magmatic upwelling beneath the volcanic field.

  5. Stepwise DNA Methylation Changes Are Linked to Escape from Defined Proliferation Barriers and Mammary Epithelial Cell Immortalization

    SciTech Connect (OSTI)

    Novak, Petr; Jensen, Taylor J.; Garbe, James C.; Stampfer, Martha R.; Futscher, Bernard W.

    2009-04-20

    The timing and progression of DNA methylation changes during carcinogenesis are not completely understood. To develop a timeline of aberrant DNA methylation events during malignant transformation, we analyzed genome-wide DNA methylation patterns in an isogenic human mammary epithelial cell (HMEC) culture model of transformation. To acquire immortality and malignancy, the cultured finite lifespan HMEC must overcome two distinct proliferation barriers. The first barrier, stasis, is mediated by the retinoblastoma protein and can be overcome by loss of p16(INK4A) expression. HMEC that escape stasis and continue to proliferate become genomically unstable before encountering a second more stringent proliferation barrier, telomere dysfunction due to telomere attrition. Rare cells that acquire telomerase expression may escape this barrier, become immortal, and develop further malignant properties. Our analysis of HMEC transitioning from finite lifespan to malignantly transformed showed that aberrant DNA methylation changes occur in a stepwise fashion early in the transformation process. The first aberrant DNA methylation step coincides with overcoming stasis, and results in few to hundreds of changes, depending on how stasis was overcome. A second step coincides with immortalization and results in hundreds of additional DNA methylation changes regardless of the immortalization pathway. A majority of these DNA methylation changes are also found in malignant breast cancer cells. These results show that large-scale epigenetic remodeling occurs in the earliest steps of mammary carcinogenesis, temporally links DNA methylation changes and overcoming cellular proliferation barriers, and provides a bank of potential epigenetic biomarkers that mayprove useful in breast cancer risk assessment.

  6. Hydrogen-terminated silicon nanowire photocatalysis: Benzene oxidation and methyl red decomposition

    SciTech Connect (OSTI)

    Lian, Suoyuan; School of Chemical Engineering and Materials, Dalian Polytechnic University, Dalian 116034 ; Tsang, Chi Him A.; Centre of Super Diamond and Advanced Films, City University of Hong Kong, Hong Kong ; Kang, Zhenhui; Liu, Yang; Wong, Ningbew; Lee, Shuit-Tong; Centre of Super Diamond and Advanced Films, City University of Hong Kong, Hong Kong

    2011-12-15

    Graphical abstract: H-SiNWs can catalyze hydroxylation of benzene and degradation of methyl red under visible light irradiation. Highlights: Black-Right-Pointing-Pointer Hydrogen-terminated silicon nanowires were active photocatalyst in the hydroxylation of benzene under light. Black-Right-Pointing-Pointer Hydrogen-terminated silicon nanowires were also effective in the decomposition of methyl red dye. Black-Right-Pointing-Pointer The Si/SiO{sub x} core-shell structure is the main reason of the obtained high selectivity during the hydroxylation. -- Abstract: Hydrogen-terminated silicon nanowires (H-SiNWs) were used as heterogeneous photocatalysts for the hydroxylation of benzene and for the decomposition of methyl red under visible light irradiation. The above reactions were monitored by GC-MS and UV-Vis spectrophotometry, respectively, which shows 100% selectivity for the transformation of benzene to phenol. A complete decomposition of a 2 Multiplication-Sign 10{sup -4} M methyl red solution was achieved within 30 min. The high selectivity for the hydroxylation of benzene and the photodecomposition demonstrate the catalytic activity of ultrafine H-SiNWs during nanocatalysis.

  7. Surface control of epitaxial manganite films via oxygen pressure

    DOE PAGES-Beta [OSTI]

    Tselev, Alexander; Vasudevan, Rama K.; Gianfrancesco, Anthony G.; Qiao, Liang; Ganesh, Panchapakesan; Meyer, Tricia L.; Lee, Ho Nyung; Biegalski, Michael D.; Baddorf, Arthur P.; Kalinin, Sergei

    2015-03-11

    The trend to reduce device dimensions demands increasing attention to atomic-scale details of structure of thin films as well as to pathways to control it. We found that this is of special importance in the systems with multiple competing interactions. We have used in situ scanning tunneling microscopy to image surfaces of La5/8Ca3/8MnO3 films grown by pulsed laser deposition. The atomically resolved imaging was combined with in situ angle-resolved X-ray photoelectron spectroscopy. We find a strong effect of the background oxygen pressure during deposition on structural and chemical features of the film surface. Deposition at 50 mTorr of O2 leadsmore » to mixed-terminated film surfaces, with B-site (MnO2) termination being structurally imperfect at the atomic scale. Moreover, a relatively small reduction of the oxygen pressure to 20 mTorr results in a dramatic change of the surface structure leading to a nearly perfectly ordered B-site terminated surface with only a small fraction of A-site (La,Ca)O termination. This is accompanied, however, by surface roughening at a mesoscopic length scale. The results suggest that oxygen has a strong link to the adatom mobility during growth. The effect of the oxygen pressure on dopant surface segregation is also pronounced: Ca surface segregation is decreased with oxygen pressure reduction.« less

  8. Natural Ores as Oxygen Carriers in Chemical Looping Combustion

    SciTech Connect (OSTI)

    Tian, Hanjing; Siriwardane, Ranjani; Simonyi, Thomas; Poston, James

    2013-08-01

    Chemical looping combustion (CLC) is a combustion technology that utilizes oxygen from oxygen carriers (OC), such as metal oxides, instead of air to combust fuels. The use of natural minerals as oxygen carriers has advantages, such as lower cost and availability. Eight materials, based on copper or iron oxides, were selected for screening tests of CLC processes using coal and methane as fuels. Thermogravimetric experiments and bench-scale fixed-bed reactor tests were conducted to investigate the oxygen transfer capacity, reaction kinetics, and stability during cyclic reduction/oxidation reaction. Most natural minerals showed lower combustion capacity than pure CuO/Fe{sub 2}O{sub 3} due to low-concentrations of active oxide species in minerals. In coal CLC, chryscolla (Cu-based), magnetite, and limonite (Fe-based) demonstrated better reaction performances than other materials. The addition of steam improved the coal CLC performance when using natural ores because of the steam gasification of coal and the subsequent reaction of gaseous fuels with active oxide species in the natural ores. In methane CLC, chryscolla, hematite, and limonite demonstrated excellent reactivity and stability in 50-cycle thermogravimetric analysis tests. Fe{sub 2}O{sub 3}-based ores possess greater oxygen utilization but require an activation period before achieving full performance in methane CLC. Particle agglomeration issues associated with the application of natural ores in CLC processes were also studied by scanning electron microscopy (SEM).

  9. High fidelity modeling of thermal relaxation and dissociation of oxygen

    SciTech Connect (OSTI)

    Andrienko, Daniil A. Boyd, Iain D.

    2015-11-15

    A master equation study of vibrational relaxation and dissociation of oxygen is conducted using state-specific O{sub 2}–O transition rates, generated by extensive trajectory simulations. Both O{sub 2}–O and O{sub 2}–O{sub 2} collisions are concurrently simulated in the evolving nonequilibrium gas system under constant heat bath conditions. The forced harmonic oscillator model is incorporated to simulate the state-to-state relaxation of oxygen in O{sub 2}–O{sub 2} collisions. The system of master equations is solved to simulate heating and cooling flows. The present study demonstrates the importance of atom-diatom collisions due to the extremely efficient energy randomization in the intermediate O{sub 3} complex. It is shown that the presence of atomic oxygen has a significant impact on vibrational relaxation time at temperatures observed in hypersonic flow. The population of highly-excited O{sub 2} vibrational states is affected by the amount of atomic oxygen when modeling the relaxation under constant heat bath conditions. A model of coupled state-to-state vibrational relaxation and dissociation of oxygen is also discussed.

  10. Surface control of epitaxial manganite films via oxygen pressure

    SciTech Connect (OSTI)

    Tselev, Alexander; Vasudevan, Rama K.; Gianfrancesco, Anthony G.; Qiao, Liang; Ganesh, Panchapakesan; Meyer, Tricia L.; Lee, Ho Nyung; Biegalski, Michael D.; Baddorf, Arthur P.; Kalinin, Sergei

    2015-03-11

    The trend to reduce device dimensions demands increasing attention to atomic-scale details of structure of thin films as well as to pathways to control it. We found that this is of special importance in the systems with multiple competing interactions. We have used in situ scanning tunneling microscopy to image surfaces of La5/8Ca3/8MnO3 films grown by pulsed laser deposition. The atomically resolved imaging was combined with in situ angle-resolved X-ray photoelectron spectroscopy. We find a strong effect of the background oxygen pressure during deposition on structural and chemical features of the film surface. Deposition at 50 mTorr of O2 leads to mixed-terminated film surfaces, with B-site (MnO2) termination being structurally imperfect at the atomic scale. Moreover, a relatively small reduction of the oxygen pressure to 20 mTorr results in a dramatic change of the surface structure leading to a nearly perfectly ordered B-site terminated surface with only a small fraction of A-site (La,Ca)O termination. This is accompanied, however, by surface roughening at a mesoscopic length scale. The results suggest that oxygen has a strong link to the adatom mobility during growth. The effect of the oxygen pressure on dopant surface segregation is also pronounced: Ca surface segregation is decreased with oxygen pressure reduction.

  11. Oxygen electrode reaction in molten carbonate fuel cells

    SciTech Connect (OSTI)

    Appleby, A.J.; White, R.E.

    1992-07-07

    Molten carbonate fuel cell system is a leading candidate for the utility power generation because of its high efficiency for fuel to AC power conversion, capability for an internal reforming, and a very low environmental impact. However, the performance of the molten carbonate fuel cell is limited by the oxygen reduction reaction and the cell life time is limited by the stability of the cathode material. An elucidation of oxygen reduction reaction in molten alkali carbonate is essential because overpotential losses in the molten carbonate fuel cell are considerably greater at the oxygen cathode than at the fuel anode. Oxygen reduction on a fully-immersed gold electrode in a lithium carbonate melt was investigated by electrochemical impedance spectroscopy and cyclic voltammetry to determine electrode kinetic and mass transfer parameters. The dependences of electrode kinetic and mass transfer parameters on gas composition and temperature were examined to determine the reaction orders and the activation energies. The results showed that oxygen reduction in a pure lithium carbonate melt occurs via the peroxide mechanism. A mass transfer parameter, D{sub O}{sup 1/2}C{sub O}, estimated by the cyclic voltammetry concurred with that calculated by the EIS technique. The temperature dependence of the exchange current density and the product D{sub O}{sup 1/2}C{sub O} were examined and the apparent activation energies were determined to be about 122 and 175 kJ/ mol, respectively.

  12. Impaired methylation as a novel mechanism for proteasome suppression in liver cells

    SciTech Connect (OSTI)

    Osna, Natalia A.; White, Ronda L.; Donohue, Terrence M.; Beard, Michael R.; Tuma, Dean J.; Kharbanda, Kusum K.

    2010-01-08

    The proteasome is a multi-catalytic protein degradation enzyme that is regulated by ethanol-induced oxidative stress; such suppression is attributed to CYP2E1-generated metabolites. However, under certain conditions, it appears that in addition to oxidative stress, other mechanisms are also involved in proteasome regulation. This study investigated whether impaired protein methylation that occurs during exposure of liver cells to ethanol, may contribute to suppression of proteasome activity. We measured the chymotrypsin-like proteasome activity in Huh7CYP cells, hepatocytes, liver cytosols and nuclear extracts or purified 20S proteasome under conditions that maintain or prevent protein methylation. Reduction of proteasome activity of hepatoma cell and hepatocytes by ethanol or tubercidin was prevented by simultaneous treatment with S-adenosylmethionine (SAM). Moreover, the tubercidin-induced decline in proteasome activity occurred in both nuclear and cytosolic fractions. In vitro exposure of cell cytosolic fractions or highly purified 20S proteasome to low SAM:S-adenosylhomocysteine (SAH) ratios in the buffer also suppressed proteasome function, indicating that one or more methyltransferase(s) may be associated with proteasomal subunits. Immunoblotting a purified 20S rabbit red cell proteasome preparation using methyl lysine-specific antibodies revealed a 25 kDa proteasome subunit that showed positive reactivity with anti-methyl lysine. This reactivity was modified when 20S proteasome was exposed to differential SAM:SAH ratios. We conclude that impaired methylation of proteasome subunits suppressed proteasome activity in liver cells indicating an additional, yet novel mechanism of proteasome activity regulation by ethanol.

  13. An Exocyclic Methylene Group Acts As a Bioisostere of the 2′-Oxygen Atom in LNA

    SciTech Connect (OSTI)

    Seth, Punit P.; Allerson, Charles R.; Berdeja, Andres; Siwkowski, Andrew; Pallan, Pradeep S.; Gaus, Hans; Prakash, Thazha P.; Watt, Andrew T.; Egli, Martin; Swayze, Eric E.

    2010-12-07

    We show for the first time that it is possible to obtain LNA-like (Locked Nucleic Acid 1) binding affinity and biological activity with carbocyclic LNA (cLNA) analogs by replacing the 2{prime}-oxygen atom in LNA with an exocyclic methylene group. Synthesis of the methylene-cLNA nucleoside was accomplished by an intramolecular cyclization reaction between a radical at the 2{prime}-position and a propynyl group at the C-4{prime} position. Only methylene-cLNA modified oligonucleotides showed similar thermal stability and mismatch discrimination properties for complementary nucleic acids as LNA. In contrast, the close structurally related methyl-cLNA analogs showed diminished hybridization properties. Analysis of crystal structures of cLNA modified self-complementary DNA decamer duplexes revealed that the methylene group participates in a tight interaction with a 2{prime}-deoxyribose residue of the 5{prime}-terminal G of a neighboring duplex, resulting in the formation of a CH...O type hydrogen bond. This indicates that the methylene group retains a negative polarization at the edge of the minor groove in the absence of a hydrophilic 2{prime}-substituent and provides a rationale for the superior thermal stability of this modification. In animal experiments, methylene-cLNA antisense oligonucleotides (ASOs) showed similar in vivo activity but reduced toxicity as compared to LNA ASOs. Our work highlights the interchangeable role of oxygen and unsaturated moieties in nucleic acid structure and emphasizes greater use of this bioisostere to improve the properties of nucleic acids for therapeutic and diagnostic applications.

  14. Method and apparatus for producing oxygenates from hydrocarbons

    DOE Patents [OSTI]

    Kong, Peter C.; Lessing, Paul A.

    1995-01-01

    A chemical reactor for oxygenating hydrocarbons includes: a) a dielectric barrier discharge plasma cell, the plasma cell comprising a pair of electrodes having a dielectric material and void therebetween, the plasma cell comprising a hydrocarbon gas inlet feeding to the void; b) a solid oxide electrochemical cell, the electrochemical cell comprising a solid oxide electrolyte positioned between a porous cathode and a porous anode, an oxygen containing gas inlet stream feeding to the porous cathode side of the electrochemical cell; c) a first gas passageway feeding from the void to the anode side of the electrochemical cell; and d) a gas outlet feeding from the anode side of the electrochemical cell to expel reaction products from the chemical reactor. A method of oxygenating hydrocarbons is also disclosed.

  15. Method and apparatus for producing oxygenates from hydrocarbons

    DOE Patents [OSTI]

    Kong, P.C.; Lessing, P.A.

    1995-06-27

    A chemical reactor for oxygenating hydrocarbons includes: (a) a dielectric barrier discharge plasma cell, the plasma cell comprising a pair of electrodes having a dielectric material and void therebetween, the plasma cell comprising a hydrocarbon gas inlet feeding to the void; (b) a solid oxide electrochemical cell, the electrochemical cell comprising a solid oxide electrolyte positioned between a porous cathode and a porous anode, an oxygen containing gas inlet stream feeding to the porous cathode side of the electrochemical cell; (c) a first gas passageway feeding from the void to the anode side of the electrochemical cell; and (d) a gas outlet feeding from the anode side of the electrochemical cell to expel reaction products from the chemical reactor. A method of oxygenating hydrocarbons is also disclosed. 4 figs.

  16. Fuel and oxygen addition for metal smelting or refining process

    DOE Patents [OSTI]

    Schlichting, Mark R.

    1994-01-01

    A furnace 10 for smelting iron ore and/or refining molten iron 20 is equipped with an overhead pneumatic lance 40, through which a center stream of particulate coal 53 is ejected at high velocity into a slag layer 30. An annular stream of nitrogen or argon 51 enshrouds the coal stream. Oxygen 52 is simultaneously ejected in an annular stream encircling the inert gas stream 51. The interposition of the inert gas stream between the coal and oxygen streams prevents the volatile matter in the coal from combusting before it reaches the slag layer. Heat of combustion is thus more efficiently delivered to the slag, where it is needed to sustain the desired reactions occurring there. A second stream of lower velocity oxygen can be delivered through an outermost annulus 84 to react with carbon monoxide gas rising from slag layer 30, thereby adding still more heat to the furnace.

  17. Fuel and oxygen addition for metal smelting or refining process

    DOE Patents [OSTI]

    Schlichting, M.R.

    1994-11-22

    A furnace for smelting iron ore and/or refining molten iron is equipped with an overhead pneumatic lance, through which a center stream of particulate coal is ejected at high velocity into a slag layer. An annular stream of nitrogen or argon enshrouds the coal stream. Oxygen is simultaneously ejected in an annular stream encircling the inert gas stream. The interposition of the inert gas stream between the coal and oxygen streams prevents the volatile matter in the coal from combusting before it reaches the slag layer. Heat of combustion is thus more efficiently delivered to the slag, where it is needed to sustain the desired reactions occurring there. A second stream of lower velocity oxygen can be delivered through an outermost annulus to react with carbon monoxide gas rising from slag layer, thereby adding still more heat to the furnace. 7 figs.

  18. CRADA Final Report: Ionically Conductive Membranes Oxygen Separation

    SciTech Connect (OSTI)

    Visco, Steven J.

    2001-10-29

    Scientists at the Lawrence Berkeley National Laboratory (LBNL) in a collaborative effort with Praxair Corporation developed a bench-top oxygen separation unit capable of producing ultra-high purity oxygen from air. The device is based on thin-film electrolyte technology developed at LBNL as part of a solid oxide fuel cell program. The two teams first demonstrated the concept using planar ceramic disks followed by the development of tubular ceramic structures for the bench-top unit. The highly successful CRADA met all technical milestones on time and on budget. Due to the success of this program the industrial partner and the team at LBNL submitted a grant proposal for further development of the unit to the Advanced Technology Program administered by the National Institute of Standar~s. This proposal was selected for funding, and now the two teams are developing a precommercial oxygen separation unit under a 3-year, $6 million dollar program.

  19. Properties of reactive oxygen species by quantum Monte Carlo

    SciTech Connect (OSTI)

    Zen, Andrea; Trout, Bernhardt L.; Guidoni, Leonardo

    2014-07-07

    The electronic properties of the oxygen molecule, in its singlet and triplet states, and of many small oxygen-containing radicals and anions have important roles in different fields of chemistry, biology, and atmospheric science. Nevertheless, the electronic structure of such species is a challenge for ab initio computational approaches because of the difficulties to correctly describe the statical and dynamical correlation effects in presence of one or more unpaired electrons. Only the highest-level quantum chemical approaches can yield reliable characterizations of their molecular properties, such as binding energies, equilibrium structures, molecular vibrations, charge distribution, and polarizabilities. In this work we use the variational Monte Carlo (VMC) and the lattice regularized Monte Carlo (LRDMC) methods to investigate the equilibrium geometries and molecular properties of oxygen and oxygen reactive species. Quantum Monte Carlo methods are used in combination with the Jastrow Antisymmetrized Geminal Power (JAGP) wave function ansatz, which has been recently shown to effectively describe the statical and dynamical correlation of different molecular systems. In particular, we have studied the oxygen molecule, the superoxide anion, the nitric oxide radical and anion, the hydroxyl and hydroperoxyl radicals and their corresponding anions, and the hydrotrioxyl radical. Overall, the methodology was able to correctly describe the geometrical and electronic properties of these systems, through compact but fully-optimised basis sets and with a computational cost which scales as N{sup 3} ? N{sup 4}, where N is the number of electrons. This work is therefore opening the way to the accurate study of the energetics and of the reactivity of large and complex oxygen species by first principles.

  20. Mechanistic Study of Oxygen Atom Transfer Catalyzed by Rhenium Compounds

    SciTech Connect (OSTI)

    Xiaopeng Shan

    2003-08-05

    Two ionic and one neutral methyl(oxo)rhenium(V) compounds were synthesized and structurally characterized. They were compared in reactivity towards the ligands triphenylphosphane, pyridines, pyridine N-oxides. Assistance from Broensted bases was found on ligand displacement of ionic rhenium compounds as well as nucleophile assistance on oxidation of all compounds. From the kinetic data, crystal structures, and an analysis of the intermediates, a structural formula of PicH{sup +}3{sup -} and mechanisms of ligand displacement and oxidation were proposed.

  1. Site-Directed Mutagenesis of HgcA and HgcB Reveals Amino Acid Residues Important for Mercury Methylation

    DOE PAGES-Beta [OSTI]

    Smith, Steven D.; Bridou, Romain; Johs, Alexander; Parks, Jerry M.; Elias, Dwayne A.; Hurt, Richard A.; Brown, Steven D.; Podar, Mircea; Wall, Judy D.

    2015-02-27

    Methylmercury is a potent neurotoxin that is produced by anaerobic microorganisms from inorganic mercury by a recently discovered pathway. A two-gene cluster, consisting of hgcA and hgcB, encodes two of the proteins essential for this activity. hgcA encodes a corrinoid protein with a strictly conserved cysteine proposed to be the ligand for cobalt in the corrinoid cofactor, whereas hgcB encodes a ferredoxin-like protein thought to be an electron donor to HgcA. Deletion of either gene eliminates mercury methylation by the methylator Desulfovibrio desulfuricans ND132. Here, site-directed mutants of HgcA and HgcB were constructed to determine amino acid residues essential formore » mercury methylation. Mutations of the strictly conserved residue Cys93 in HgcA, the proposed ligand for the corrinoid cobalt, to Ala or Thr completely abolished the methylation capacity, but a His substitution produced measurable methylmercury. Mutations of conserved amino acids near Cys93 had various impacts on the methylation capacity but showed that the structure of the putative “cap helix” region harboring Cys93 is crucial for methylation function. In the ferredoxin-like protein HgcB, only one of two conserved cysteines found at the C terminus was necessary for methylation, but either cysteine sufficed. An additional, strictly conserved cysteine, Cys73, was also determined to be essential for methylation. Ultimately, this study supports the previously predicted importance of Cys93 in HgcA for methylation of mercury and reveals additional residues in HgcA and HgcB that facilitate the production of this neurotoxin.« less

  2. Site-Directed Mutagenesis of HgcA and HgcB Reveals Amino Acid Residues Important for Mercury Methylation

    SciTech Connect (OSTI)

    Smith, Steven D.; Bridou, Romain; Johs, Alexander; Parks, Jerry M.; Elias, Dwayne A.; Hurt, Richard A.; Brown, Steven D.; Podar, Mircea; Wall, Judy D.

    2015-02-27

    Methylmercury is a potent neurotoxin that is produced by anaerobic microorganisms from inorganic mercury by a recently discovered pathway. A two-gene cluster, consisting of hgcA and hgcB, encodes two of the proteins essential for this activity. hgcA encodes a corrinoid protein with a strictly conserved cysteine proposed to be the ligand for cobalt in the corrinoid cofactor, whereas hgcB encodes a ferredoxin-like protein thought to be an electron donor to HgcA. Deletion of either gene eliminates mercury methylation by the methylator Desulfovibrio desulfuricans ND132. Here, site-directed mutants of HgcA and HgcB were constructed to determine amino acid residues essential for mercury methylation. Mutations of the strictly conserved residue Cys93 in HgcA, the proposed ligand for the corrinoid cobalt, to Ala or Thr completely abolished the methylation capacity, but a His substitution produced measurable methylmercury. Mutations of conserved amino acids near Cys93 had various impacts on the methylation capacity but showed that the structure of the putative “cap helix” region harboring Cys93 is crucial for methylation function. In the ferredoxin-like protein HgcB, only one of two conserved cysteines found at the C terminus was necessary for methylation, but either cysteine sufficed. An additional, strictly conserved cysteine, Cys73, was also determined to be essential for methylation. Ultimately, this study supports the previously predicted importance of Cys93 in HgcA for methylation of mercury and reveals additional residues in HgcA and HgcB that facilitate the production of this neurotoxin.

  3. Electrochemical oxygen reduction catalysed by Ni3(hexaiminotriphenylene)2

    DOE PAGES-Beta [OSTI]

    Miner, Elise M.; Fukushima, Tomohiro; Sheberla, Dennis; Sun, Lei; Surendranath, Yogesh; Dinca, Mircea

    2016-03-08

    Control over the architectural and electronic properties of heterogeneous catalysts poses a major obstacle in the targeted design of active and stable non-platinum group metal electrocatalysts for the oxygen reduction reaction. Here we introduce Ni3(HITP)2 (HITP=2, 3, 6, 7, 10, 11-hexaiminotriphenylene) as an intrinsically conductive metal-organic framework which functions as a well-defined, tunable oxygen reduction electrocatalyst in alkaline solution. Ni3(HITP)2 exhibits oxygen reduction activity competitive with the most active non-platinum group metal electrocatalysts and stability during extended polarization. The square planar Ni-N4 sites are structurally reminiscent of the highly active and widely studied non-platinum group metal electrocatalysts containing M-N4 units.more » Ni3(HITP)2 and analogues thereof combine the high crystallinity of metal-organic frameworks, the physical durability and electrical conductivity of graphitic materials, and the diverse yet well-controlled synthetic accessibility of molecular species. As a result, such properties may enable the targeted synthesis and systematic optimization of oxygen reduction electrocatalysts as components of fuel cells and electrolysers for renewable energy applications.« less

  4. Blood storage device and method for oxygen removal

    DOE Patents [OSTI]

    Bitensky, Mark W.; Yoshida, Tatsuro

    2000-01-01

    The present invention relates to a storage device and method for the long-term storage of blood and, more particularly, to a blood storage device and method capable of removing oxygen from the stored blood and thereby prolonging the storage life of the deoxygenated blood.

  5. High-temperature potentiometric oxygen sensor with internal reference

    DOE Patents [OSTI]

    Routbort, Jules L.; Singh, Dileep; Dutta, Prabir K.; Ramasamy, Ramamoorthy; Spirig, John V.; Akbar, Sheikh

    2011-11-15

    A compact oxygen sensor is provided, comprising a mixture of metal and metal oxide an enclosure containing said mixture, said enclosure capable of isolating said mixture from an environment external of said enclosure, and a first wire having a first end residing within the enclosure and having a second end exposed to the environment. Also provided is a method for the fabrication of an oxygen sensor, the method comprising confining a metal-metal oxide solid mixture to a container which consists of a single material permeable to oxygen ions, supplying an electrical conductor having a first end and a second end, whereby the first end resides inside the container as a reference (PO.sub.2).sup.ref, and the second end resides outside the container in the atmosphere where oxygen partial pressure (PO.sub.2).sup.ext is to be measured, and sealing the container with additional single material such that grain boundary sliding occurs between grains of the single material and grains of the additional single material.

  6. Atomic oxygen patterning from a biomedical needle-plasma source

    SciTech Connect (OSTI)

    Kelly, Sen; Turner, Miles M.

    2013-09-28

    A plasma needle is a cold plasma source operating at atmospheric pressure. Such sources interact strongly with living cells, but experimental studies on bacterial samples show that this interaction has a surprising pattern resulting in circular or annular killing structures. This paper presents numerical simulations showing that this pattern occurs because biologically active reactive oxygen and nitrogen species are produced dominantly where effluent from the plasma needle interacts with ambient air. A novel solution strategy is utilised coupling plasma produced neutral (uncharged) reactive species to the gas dynamics solving for steady state profiles at the treated biological surface. Numerical results are compared with experimental reports corroborating evidence for atomic oxygen as a key bactericidal species. Surface losses are considered for interaction of plasma produced reactants with reactive solid and liquid interfaces. Atomic oxygen surface reactions on a reactive solid surface with adsorption probabilities above 0.1 are shown to be limited by the flux of atomic oxygen from the plasma. Interaction of the source with an aqueous surface showed hydrogen peroxide as the dominant species at this interface.

  7. Materials and methods for the separation of oxygen from air

    DOE Patents [OSTI]

    MacKay, Richard; Schwartz, Michael; Sammells, Anthony F.

    2003-07-15

    Metal oxides particularly useful for the manufacture of catalytic membranes for gas-phase oxygen separation processes having the formula: O.sub.5+z where: x and x' are greater than 0; y and y' are greater than 0; x+x' is equal to 2; y+y' is less than or equal to 2; z is a number that makes the metal oxide charge neutral; A is an element selected from the lanthanide elements; A' is an element selected from Be, Mg, Ca, Sr, Ba and Ra; A" is an element selected from the f block lanthanides, Be, Mg, Ca, Sr, Ba and Ra; B is an element selected from the group consisting of Al, Ga, In or mixtures thereof and B" is Co or Mg, with the exception that when B" is Mg, A' and A" are not Mg. The metal oxides are useful for preparation of dense membranes which may be formed from dense thin films of the mixed metal oxide on a porous metal oxide element. The invention also provides methods and catalytic reactors for oxygen separation and oxygen enrichment of oxygen deficient gases which employ mixed conducting metal oxides of the above formula.

  8. Proximal impact deposits at the Cretaceous-Tertiary boundary in the Gulf of Mexico: A restudy of DSDP Leg 77 Sites 536 and 540

    SciTech Connect (OSTI)

    Alvarez, W.; Asaro, F. ); Smit, J. ); Lowrie, W. ); Asaro, F. ); Margolis, S.V.; Claeys, P. ); Kastner, M. ); Hildebrand, A.R. )

    1992-08-01

    Restudy of Deep Sea Drilling Project Sites 536 and 540 in the southeast Gulf of Mexico gives evidence for a giant wave at Cretaceous-Tertiary boundary time. Five units are recognized: (1) Cenomanian limestone underlies a hiatus in which the five highest Cretaceous stages are missing, possibly because of catastrophic K-T erosion. (2) Pebbly mudstone, 45 m thick, represents a submarine landslide possibly of K-T age. (3) Current-bedded sandstone, more than 2.5 m thick, contains anomalous iridium, tektite glass, and shocked quartz; it is interpreted as ejecta from a nearby impact crater, reworked on the deep-sea floor by the resulting tsunami. (4) A 50-cm interval of calcareous mudstone containing small Cretaceous planktic foraminifera and the Ir peak is interpreted as the silt-size fraction of the Cretaceous material suspended by the impact-generated wave. (5) Calcareous mudstone with basal Tertiary forams and the uppermost tail of the Ir anomaly overlies the disturbed interval, dating the impact and wave event as K-T boundary age. Like Beloc in Haiti and Mimbral in Mexico, Sites 536 and 540 are consistent with a large K-T age impact at the nearby Chicxulub crater.

  9. Chemistry - Oxygen Vacancies and Catalysis on Ceria Surfaces

    SciTech Connect (OSTI)

    Campbell, Charles T.; Peden, Charles HF.

    2005-07-29

    Chemistry occurring at the surface of metal oxides is critical in a variety of industrial applications including catalysis and photocatalysis, optical display technology, solar energy devices and corrosion prevention. Defects have long been recognized to be the most reactive sites on the surfaces of many oxide materials. The most common types of defects present on the surfaces of metal oxides are oxygen vacancies and step edges. The nature of surface oxygen vacancies, and their number, distribution and diffusion across the surface of oxides, are thus issues of major scientific importance. One of the most interesting oxides in this respect is CeO2, since oxygen vacancies play the key role in giving this material it's industrially important ''oxygen-storage capacity''. This capacity makes modern automotive exhaust treatment catalysts containing CeO2 much more effective than their predecessors without CeO2. Ceria is also well known as a support which enhances the performance of transition metal catalysts, relative to other oxide supports, in a variety of other reactions including water-gas shift, steam reforming of oxygenates and PROX 1-7, all of which hold promise for enabling a hydrogen economy 1. Related to ceria's facile redox capacity (ability to rapidly form and eliminate oxygen vacancy defects) is the poorly understood observation that some less reducible oxides, such as zirconia (ZrO2), are used as additives that actually enhance this ''oxygen storage'' property of CeO2. In this issue, Esch and coworkers in Trieste, Italy report an exciting study that for the first time clearly elucidates the structure, distribution and formation of oxygen vacancies on a cerium oxide surface 8. They have elegantly combined beautiful, atomic-resolution imaging using scanning-tunneling microscopy (STM) on a ceria surface with state-of-the-art quantum mechanical calculations using Density Functional Theory (DFT) to raise our understanding of CeO2 surfaces to a much higher level

  10. Subtask 3.12 - Oxygen-Fired CFBC

    SciTech Connect (OSTI)

    Douglas Hajicek; Mark Musich; Ann Henderson

    2007-02-28

    Traditionally, air is used as the source of oxygen for firing a combustion system. A fully oxygen-fired circulating fluidized-bed combustion (CFBC) system would result in the production of a flue gas stream consisting of mostly carbon dioxide and water. The concentrated carbon dioxide stream would be available for sequestering or other purposes. Temperatures in an oxygen-blown CFBC system would be controlled by a combination of flue gas recycle, solids recirculation, and by appropriately sizing and locating the amount of heat-transfer surface required. Flue gas recycle provides the additional gas required for adequate fluidization and circulation of solids replacing the nitrogen that would be present in an air-blown system. The amount of flue gas recycle will determine how much of the remaining heat from the coal combustion will have to be removed. If the amount of flue gas recycle required by increasing solids recirculation and oxygen staging is limited, introducing the pure oxygen at multiple locations in the combustor to result in a more even temperature profile should result in a more compact system, thus reducing initial capital costs for construction. The overall efficiency of the process should be greater than that of an air-blown system since less fuel is required for the creation of the same amount of energy. The Energy & Environmental Research Center (EERC) is in a unique position to advance this technology. It has a world-class CFBC pilot plant, has experience with firing a wide range of fuels in our air-fired CFBC pilot plant, has prior experience with oxygen-firing a slagging furnace system in a pulverized coal-fired mode with a bituminous coal, and has all of the components required for oxygen-firing right next to the CFBC pilot plant already in place. An engineering study was performed to identify methods, an overall appropriate configuration, and an operating strategy for a fully oxygen-fired CFBC pilot plant by: (1) developing a plan to optimize

  11. Sub-crop geologic map of pre-Tertiary rocks in the Yucca Flat and northern Frenchman Flat areas, Nevada Test Site, southern Nevada

    SciTech Connect (OSTI)

    Cole, J.C.; Harris, A.G.; Wahl, R.R.

    1997-10-02

    This map displays interpreted structural and stratigraphic relations among the Paleozoic and older rocks of the Nevada Test Site region beneath the Miocene volcanic rocks and younger alluvium in the Yucca Flat and northern Frenchman Flat basins. These interpretations are based on a comprehensive examination and review of data for more than 77 drillholes that penetrated part of the pre-Tertiary basement beneath these post-middle Miocene structural basins. Biostratigraphic data from conodont fossils were newly obtained for 31 of these holes, and a thorough review of all prior microfossil paleontologic data is incorporated in the analysis. Subsurface relationships are interpreted in light of a revised regional geologic framework synthesized from detailed geologic mapping in the ranges surrounding Yucca Flat, from comprehensive stratigraphic studies in the region, and from additional detailed field studies on and around the Nevada Test Site. All available data indicate the subsurface geology of Yucca Flat is considerably more complicated than previous interpretations have suggested. The western part of the basin, in particular, is underlain by relics of the eastward-vergent Belted Range thrust system that are folded back toward the west and thrust by local, west-vergent contractional structures of the CP thrust system. Field evidence from the ranges surrounding the north end of Yucca Flat indicate that two significant strike-slip faults track southward beneath the post-middle Miocene basin fill, but their subsurface traces cannot be closely defined from the available evidence. In contrast, the eastern part of the Yucca Flat basin is interpreted to be underlain by a fairly simple north-trending, broad syncline in the pre-Tertiary units. Far fewer data are available for the northern Frenchman Flat basin, but regional analysis indicates the pre-Tertiary structure there should also be relatively simple and not affected by thrusting. This new interpretation has implications

  12. Spectroscopic investigation of the vibrational quasi-continuum arising from internal rotation of a methyl group

    SciTech Connect (OSTI)

    Hougen, J.T.

    1993-12-01

    The goal of this project is to use spectroscopic techniques to investigate in detail phenomena involving the vibrational quasi-continuum in a simple physical system. Acetaldehyde was chosen for the study because: (i) methyl groups have been suggested to be important promotors of intramolecular vibrational relaxation, (ii) the internal rotation of a methyl group is an easily describle large-amplitude motion, which should retain its simple character even at high levels of excitation, and (iii) the aldehyde carbonyl group offers the possibility of both vibrational and electronic probing. The present investigation of the ground electronic state has three parts: (1) understanding the {open_quotes}isolated{close_quotes} internal-rotation motion below, at, and above the top of the torsional barrier, (2) understanding in detail traditional (bond stretching and bending) vibrational fundamental and overtone states, and (3) understanding interactions involving states with multiquantum excitations of at least one of these two kinds of motion.

  13. Method of recycling lithium borate to lithium borohydride through methyl borate

    DOE Patents [OSTI]

    Filby, Evan E.

    1977-01-01

    This invention provides a method for the recycling of lithium borate to lithium borohydride which can be reacted with water to generate hydrogen for utilization as a fuel. The lithium borate by-product of the hydrogen generation reaction is reacted with hydrogen chloride and water to produce boric acid and lithium chloride. The boric acid and lithium chloride are converted to lithium borohydride through a methyl borate intermediate to complete the recycle scheme.

  14. Durability of Poly(Methyl Methacrylate) Lenses Used in Concentrating Photovoltaic Technology (Revised) (Presentation)

    SciTech Connect (OSTI)

    Miller, D. C.; Carloni, J. D.; Pankow, J. W.; Gjersing, E. L.; To, B.; Packard, C. E.; Kennedy, C. E.; Kurtz, S. R.

    2012-01-01

    Concentrating photovoltaic (CPV) technology recently gained interest based on its expected low levelized cost of electricity, high efficiency, and scalability. Many CPV systems employ Fresnel lenses composed of poly(methyl methacrylate) (PMMA) to obtain a high optical flux density on the cell. The optical and mechanical durability of these lenses, however, is not well established relative to the desired surface life of 30 years. Our research aims to quantify the expected lifetime of PMMA in key market locations (FL, AZ, and CO).

  15. Crystallization of lysozyme with (R)-, (S)- and (RS)-2-methyl-2, 4-pentanediol

    SciTech Connect (OSTI)

    Stauber, Mark; Jakoncic, Jean; Berger, Jacob; Karp, Jerome M.; Axelbaum, Ariel; Sastow, Dahniel; Buldyrev, Sergey V.; Hrnjez, Bruce J.; Asherie, Neer

    2015-03-01

    Crystallization of lysozyme with (R)-2-methyl-2, 4-pentanediol produces more ordered crystals and a higher resolution protein structure than crystallization with (S)-2-methyl-2, 4-pentanediol. The results suggest that chiral interactions with chiral additives are important in protein crystal formation. Chiral control of crystallization has ample precedent in the small-molecule world, but relatively little is known about the role of chirality in protein crystallization. In this study, lysozyme was crystallized in the presence of the chiral additive 2-methyl-2, 4-pentanediol (MPD) separately using the R and S enantiomers as well as with a racemic RS mixture. Crystals grown with (R)-MPD had the most order and produced the highest resolution protein structures. This result is consistent with the observation that in the crystals grown with (R)-MPD and (RS)-MPD the crystal contacts are made by (R)-MPD, demonstrating that there is preferential interaction between lysozyme and this enantiomer. These findings suggest that chiral interactions are important in protein crystallization.

  16. CMTM5 exhibits tumor suppressor activity through promoter methylation in oral squamous cell carcinoma

    SciTech Connect (OSTI)

    Zhang, Heyu; Nan, Xu; Li, Xuefen; Chen, Yan; Zhang, Jianyun; Sun, Lisha; Han, Wenlin; Li, Tiejun

    2014-05-02

    Highlights: • Down-regulation of CMTM5 expression in OSCC tissues was found. • The promoter methylation status of CMTM5 was measured. • CMTM5-v1 inhibited cell proliferation and migration and induced apoptosis. • CMTM5 might act as a putative tumor suppressor gene in OSCC. - Abstract: Oral squamous cell carcinoma (OSCC) is one of the most common types of malignancies in the head and neck region. CKLF-like MARVEL transmembrane domain-containing member 5 (CMTM5) has been recently implicated as a tumor suppressor gene in several cancer types. Herein, we examined the expression and function of CMTM5 in oral squamous cell carcinoma. CMTM5 was down-regulated in oral squamous cell lines and tumor samples from patients with promoter methylation. Treatment with the demethylating agent 5-aza-2′-deoxycytidine restored CMTM5 expression. In the OSCC cell lines CAL27 and GNM, the ectopic expression of CMTM5-v1 strongly inhibited cell proliferation and migration and induced apoptosis. In addition, CMTM5-v1 inhibited tumor formation in vivo. Therefore, CMTM5 might act as a putative tumor suppressor gene through promoter methylation in oral squamous cell carcinoma.

  17. Controlled temperature expansion in oxygen production by molten alkali metal salts

    DOE Patents [OSTI]

    Erickson, Donald C.

    1985-06-04

    A continuous process is set forth for the production of oxygen from an oxygen containing gas stream, such as air, by contacting a feed gas stream with a molten solution of an oxygen acceptor to oxidize the acceptor and cyclically regenerating the oxidized acceptor by releasing oxygen from the acceptor wherein the oxygen-depleted gas stream from the contact zone is treated sequentially to temperature reduction by heat exchange against the feed stream so as to condense out entrained oxygen acceptor for recycle to the process, combustion of the gas stream with fuel to elevate its temperature and expansion of the combusted high temperature gas stream in a turbine to recover power.

  18. Structural basis for recognition of hemi-methylated DNA by the SRA domain of human UHRF1.

    SciTech Connect (OSTI)

    Avvakumov, George V.; Walker, John R.; Xue, Sheng; Li, Yanjun; Duan, Shili; Bronner, Christian; Arrowsmith, Cheryl H.; Dhe-Paganon, Sirano

    2008-11-17

    Epigenetic inheritance in mammals is characterized by high-fidelity replication of CpG methylation patterns during development. UHRF1 (also known as ICBP90 in humans and Np95 in mouse) is an E3 ligase important for the maintenance of global and local DNA methylation in vivo. The preferential affinity of UHRF1 for hemi-methylated DNA over symmetrically methylated DNA by means of its SET and RING-associated (SRA) domain and its association with the maintenance DNA methyltransferase 1 (DNMT1) suggests a role in replication of the epigenetic code. Here we report the 1.7 {angstrom} crystal structure of the apo SRA domain of human UHRF1 and a 2.2 {angstrom} structure of its complex with hemi-methylated DNA, revealing a previously unknown reading mechanism for methylated CpG sites (mCpG). The SRA-DNA complex has several notable structural features including a binding pocket that accommodates the 5-methylcytosine that is flipped out of the duplex DNA. Two specialized loops reach through the resulting gap in the DNA from both the major and the minor grooves to read the other three bases of the CpG duplex. The major groove loop confers both specificity for the CpG dinucleotide and discrimination against methylation of deoxycytidine of the complementary strand. The structure, along with mutagenesis data, suggests how UHRF1 acts as a key factor for DNMT1 maintenance methylation through recognition of a fundamental unit of epigenetic inheritance, mCpG.

  19. Oxygen assisted interconnection of silver nanoparticles with femtosecond laser radiation

    SciTech Connect (OSTI)

    Huang, H.; Zhou, Y.; Duley, W. W.

    2015-12-14

    Ablation of silver (Ag) nanoparticles in the direction of laser polarization is achieved by utilizing femtosecond laser irradiation in air at laser fluence ranging from ∼2 mJ/cm{sup 2} to ∼14 mJ/cm{sup 2}. This directional ablation is attributed to localized surface plasmon induced localized electric field enhancement. Scanning electron microscopy observations of the irradiated particles in different gases and at different pressures indicate that the ablation is further enhanced by oxygen in the air. This may be due to the external heating via the reactions of its dissociation product, atomic oxygen, with the surface of Ag particles, while the ablated Ag is not oxidized. Further experimental observations show that the ablated material re-deposits near the irradiated particles and results in the extension of the particles in laser polarization direction, facilitating the interconnection of two well-separated nanoparticles.

  20. Bimetallic Fe-Ni Oxygen Carriers for Chemical Looping Combustion

    SciTech Connect (OSTI)

    Bhavsar, Saurabh; Veser, Goetz

    2013-11-06

    The relative abundance, low cost, and low toxicity of iron make Fe-based oxygen carriers of great interest for chemical looping combustion (CLC), an emerging technology for clean and efficient combustion of fossil and renewable fuels. However, Fe also shows much lower reactivity than other metals (such as Ni and Cu). Here, we demonstrate strong improvement of Fe-based carriers by alloying the metal phase with Ni. Through a combination of carrier synthesis and characterization with thermogravimetric and fixed-bed reactor studies, we demonstrate that the addition of Ni results in a significant enhancement in activity as well as an increase in selectivity for total oxidation. Furthermore, comparing alumina and ceria as support materials highlights the fact that reducible supports can result in a strong increase in oxygen carrier utilization.

  1. Residual Oxygen on Nb Heated to 500 C

    SciTech Connect (OSTI)

    Kirby, R.; King, F.K.; Padamsee, H.; /Cornell U., LEPP

    2005-06-10

    The superconducting accelerating cavities for the International Linear Collider will be constructed of high-residual resistivity ratio (RRR) niobium sheet. Excessive oxygen within the skin depth (several microns) will reduce the RRR and increase resistive losses. We measure the thickness of this oxide layer, following bakeout simulation, to be about 0.5 nm thick. The results suggest that this layer will very slowly disappear from the top five nm at 500 C.

  2. Excited states in the active media of oxygen - iodine lasers

    SciTech Connect (OSTI)

    Azyazov, V N

    2009-11-30

    A review of investigations of kinetic processes in active media oxygen - iodine lasers (OILs) performed in the last decade is presented. The mechanisms of pumping and quenching of electronically and vibrationally excited O{sub 2} and I{sub 2} molecules are considered, and dissociation mechanisms of I{sub 2} in the active medium of the OIL are analysed. The values of kinetic constants of processes proceeding in the active media of OILs are recommended. (review)

  3. Real Space Mapping of Oxygen Vacancy Diffusion and Electrochemical

    U.S. Department of Energy (DOE) all webpages (Extended Search)

    Transformations by Hysteretic Current Reversal Curve Measurements - Energy Innovation Portal Hydrogen and Fuel Cell Hydrogen and Fuel Cell Energy Storage Energy Storage Find More Like This Return to Search Real Space Mapping of Oxygen Vacancy Diffusion and Electrochemical Transformations by Hysteretic Current Reversal Curve Measurements Oak Ridge National Laboratory Contact ORNL About This Technology Technology Marketing SummaryElectrochemical energy storage and conversion systems based on

  4. K-shell auger decay of atomic oxygen

    SciTech Connect (OSTI)

    Stolte, W.C.; Lu, Y.; Samson, J.A.R.

    1997-04-01

    The aim of the present research is to understand the interaction between the ejected photoelectron and Auger electron produced by the Auger decay of a 1s hole in atomic oxygen, and to understand the influence this interaction has on the shape of the ionization cross sections. To accomplish this the authors have measured the relative ion yields (ion/photon) in the vicinity of the oxygen K-shell (525 - 533 eV) for O{sup +} and O{sup 2+}. The measurements were performed at the ALS on beamline, 6.3.2. The atomic oxygen was produced by passing molecular oxygen through a microwave-driven discharge. A Rydberg analysis of the two series leading to the [1s]2s{sup 2}2p{sup 4}({sup 4}P) and [1s]2s{sup 2}2p{sup 4}({sup 2}P) limits were obtained. This analysis shows some differences to the recently published results by Menzel et al. The energy position of the main 1s{sup 1}2s{sup 2}2p{sup 5}({sup 3}P) resonance differs by approximately 1 eV from the authors value, all members of the ({sup 2}P)np series differ by 0.3 eV, but the members of the ({sup 4}P)np series agree. The molecular resonance at 530.5 eV and those between 539 eV and 543 eV, measured with the microwave discharge off show identical results in both experiments.

  5. Observing Oxygen Atoms Move during Information Storage in Tantalum Oxide

    U.S. Department of Energy (DOE) all webpages (Extended Search)

    Memristors | Stanford Synchrotron Radiation Lightsource Observing Oxygen Atoms Move during Information Storage in Tantalum Oxide Memristors Saturday, April 30, 2016 Memristor technology, or resistive random access memory (RRAM), is a frontrunner for next generation computer memory, owing to the promise of long endurance, low power, nanoscale device size and fast operation.1 Memristor devices are typically made of a transition metal oxide sandwiched between two metallic electrodes, and

  6. Electrocatalyst for Oxygen Reduction with Reduced Platinum Oxidation and

    U.S. Department of Energy (DOE) all webpages (Extended Search)

    Dissolution Rates - Energy Innovation Portal Oxygen Reduction with Reduced Platinum Oxidation and Dissolution Rates Brookhaven National Laboratory Contact BNL About This Technology Publications: PDF Document Publication Electrodeposition of Pt onto RuO2 (110) Single-Crystal Surface (437 KB) <p> Results of a density functional theory calculation of atomic positions of platinum on an oxide surface, showing good agreement with experimental results.</p> Results of a density

  7. Atomically Precise Electrocatalyst for Oxygen Evolution Reaction | Stanford

    U.S. Department of Energy (DOE) all webpages (Extended Search)

    Synchrotron Radiation Lightsource Atomically Precise Electrocatalyst for Oxygen Evolution Reaction Thursday, March 31, 2016 Traditional heterogeneous catalysts contain a range of particles sizes, crystallographic faces, and surface structures. This heterogeneity makes catalysts design a challenge because the active sites responsible for catalytic activity are simply not known. An emerging class of "atomically-precise" nanocatalysts can help alleviate this problem because they form

  8. Controllable positive exchange bias via redox-driven oxygen migration

    DOE PAGES-Beta [OSTI]

    Gilbert, Dustin A.; Olamit, Justin; Dumas, Randy K.; Kirby, B. J.; Grutter, Alexander J.; Maranville, Brian B.; Arenholz, Elke; Borchers, Julie A.; Liu, Kai

    2016-03-21

    We report that ionic transport in metal/oxide heterostructures offers a highly effective means to tailor material properties via modification of the interfacial characteristics. However, direct observation of ionic motion under buried interfaces and demonstration of its correlation with physical properties has been challenging. Using the strong oxygen affinity of gadolinium, we design a model system of GdxFe1-x/NiCoO bilayer films, where the oxygen migration is observed and manifested in a controlled positive exchange bias over a relatively small cooling field range. The exchange bias characteristics are shown to be the result of an interfacial layer of elemental nickel and cobalt, amore » few nanometres in thickness, whose moments are larger than expected from uncompensated NiCoO moments. This interface layer is attributed to a redox-driven oxygen migration from NiCoO to the gadolinium, during growth or soon after. Ultimately, these results demonstrate an effective path to tailoring the interfacial characteristics and interlayer exchange coupling in metal/oxide heterostructures.« less

  9. Taguchi methods applied to oxygen-enriched diesel engine experiments

    SciTech Connect (OSTI)

    Marr, W.W.; Sekar, R.R.; Cole, R.L.; Marciniak, T.J.; Longman, D.E.

    1992-12-01

    This paper describes a test series conducted on a six-cylinder diesel engine to study the impacts of controlled factors (i.e., oxygen content of the combustion air, water content of the fuel, fuel rate, and fuel-injection timing) on engine emissions using Taguchi methods. Three levels of each factor were used in the tests. Only the main effects of the factors were examined; no attempt was made to analyze the interactions among the factors. It was found that, as in the case of the single-cylinder engine tests, oxygen in the combustion air was very effective in reducing particulate and smoke emissions. Increases in NO{sub x} due to the oxygen enrichment observed in the single-cylinder tests also occurred in the present six-cylinder tests. Water in the emulsified fuel was found to be much less effective in decreasing NO{sub x} emissions for the six-cylinder engine than it was for the single-cylinder engine.

  10. Taguchi methods applied to oxygen-enriched diesel engine experiments

    SciTech Connect (OSTI)

    Marr, W.W.; Sekar, R.R.; Cole, R.L.; Marciniak, T.J. ); Longman, D.E. )

    1992-01-01

    This paper describes a test series conducted on a six-cylinder diesel engine to study the impacts of controlled factors (i.e., oxygen content of the combustion air, water content of the fuel, fuel rate, and fuel-injection timing) on engine emissions using Taguchi methods. Three levels of each factor were used in the tests. Only the main effects of the factors were examined; no attempt was made to analyze the interactions among the factors. It was found that, as in the case of the single-cylinder engine tests, oxygen in the combustion air was very effective in reducing particulate and smoke emissions. Increases in NO[sub x] due to the oxygen enrichment observed in the single-cylinder tests also occurred in the present six-cylinder tests. Water in the emulsified fuel was found to be much less effective in decreasing NO[sub x] emissions for the six-cylinder engine than it was for the single-cylinder engine.

  11. How a weird Mars rock may be solid proof of an ancient oxygen...

    U.S. Department of Energy (DOE) all webpages (Extended Search)

    Weird Mars rock may be solid proof of ancient oxygen atmosphere How a weird Mars rock may be solid proof of an ancient oxygen atmosphere When researchers found a compound that ...

  12. Growth control of oxygen stoichiometry in homoepitaxial SrTiO3...

    Office of Scientific and Technical Information (OSTI)

    Growth control of oxygen stoichiometry in homoepitaxial SrTiO3 films by pulsed laser epitaxy in high vacuum Prev Next Title: Growth control of oxygen stoichiometry in ...

  13. Selectivity of Chemisorbed Oxygen in C-H Bond Activation and...

    Office of Scientific and Technical Information (OSTI)

    Selectivity of Chemisorbed Oxygen in C-H Bond Activation and CO Oxidation and Kinetic ... Title: Selectivity of Chemisorbed Oxygen in C-H Bond Activation and CO Oxidation and ...

  14. SYSTEM DESIGN AND ANALYSIS FOR CONCEPTUAL DESIGN OF OXYGEN-BASED...

    Office of Scientific and Technical Information (OSTI)

    DESIGN OF OXYGEN-BASED PC BOILER Citation Details In-Document Search Title: SYSTEM DESIGN AND ANALYSIS FOR CONCEPTUAL DESIGN OF OXYGEN-BASED PC BOILER The objective of the system ...

  15. Impact of ethanol and butanol as oxygenates on SIDI engine efficiency...

    Office of Energy Efficiency and Renewable Energy (EERE) (indexed site)

    ethanol and butanol as oxygenates on SIDI engine efficiency and emissions using steady-state and transient test procedures Impact of ethanol and butanol as oxygenates on SIDI engine ...

  16. Spatial and Functional Relationships Among Pol V-Associated loci, Pol IV-Dependent siRNAs, and Cytosine Methylation in the Arabidopsis Epigenome

    SciTech Connect (OSTI)

    Wierzbicki, A. T.; Cocklin, Ross; Mayampurath, Anoop; Lister, Ryan; Rowley, M. J.; Gregory, Brian D.; Ecker, Joseph R.; Tang, Haixu; Pikaard, Craig S.

    2012-08-15

    Multisubunit RNA polymerases IV and V (Pols IV and V) mediate RNA-directed DNA methylation and transcriptional silencing of retrotransposons and heterochromatic repeats in plants. We identified genomic sites of Pol V occupancy in parallel with siRNA deep sequencing and methylcytosine mapping, comparing wild-type plants with mutants defective for Pol IV, Pol V, or both Pols IV and V. Approximately 60% of Pol V-associated regions encompass regions of 24-nucleotide (nt) siRNA complementarity and cytosine methylation, consistent with cytosine methylation being guided by base-pairing of Pol IV-dependent siRNAs with Pol V transcripts. However, 27% of Pol V peaks do not overlap sites of 24-nt siRNA biogenesis or cytosine methylation, indicating that Pol V alone does not specify sites of cytosine methylation. Surprisingly, the number of methylated CHH motifs, a hallmark of RNA-directed de novo methylation, is similar in wild-type plants and Pol IV or Pol V mutants. In the mutants, methylation is lost at 50%-60% of the CHH sites that are methylated in the wild type but is gained at new CHH positions, primarily in pericentromeric regions. These results indicate that Pol IV and Pol V are not required for cytosine methyltransferase activity but shape the epigenome by guiding CHH methylation to specific genomic sites.

  17. Solid Oxide Fuel Cell Cathodes. Unraveling the Relationship Between Structure, Surface Chemistry and Oxygen Reduction

    SciTech Connect (OSTI)

    Gopalan, Srikanth

    2013-03-31

    In this work we have considered oxygen reduction reaction on LSM and LSCF cathode materials. In particular we have used various spectroscopic techniques to explore the surface composition, transition metal oxidation state, and the bonding environment of oxygen to understand the changes that occur to the surface during the oxygen reduction process. In a parallel study we have employed patterned cathodes of both LSM and LSCF cathodes to extract transport and kinetic parameters associated with the oxygen reduction process.

  18. Oxygen production by molten alkali metal salts using multiple absorption-desorption cycles

    DOE Patents [OSTI]

    Cassano, Anthony A.

    1985-01-01

    A continuous chemical air separation is performed wherein oxygen is recovered with a molten alkali metal salt oxygen acceptor in a series of absorption zones which are connected to a plurality of desorption zones operated in separate parallel cycles with the absorption zones. A greater recovery of high pressure oxygen is achieved at reduced power requirements and capital costs.

  19. Oxygen production by molten alkali metal salts using multiple absorption-desorption cycles

    DOE Patents [OSTI]

    Cassano, A.A.

    1985-07-02

    A continuous chemical air separation is performed wherein oxygen is recovered with a molten alkali metal salt oxygen acceptor in a series of absorption zones which are connected to a plurality of desorption zones operated in separate parallel cycles with the absorption zones. A greater recovery of high pressure oxygen is achieved at reduced power requirements and capital costs. 3 figs.

  20. The interaction of organic adsorbate vibrations with substrate lattice waves in methyl-Si(111)-(1??1)

    SciTech Connect (OSTI)

    Brown, Ryan D.; Hund, Zachary M.; Sibener, S. J.; Campi, Davide; Bernasconi, M.; OLeary, Leslie E.; Lewis, Nathan S.; Benedek, G.

    2014-07-14

    A combined helium atom scattering and density functional perturbation theory study has been performed to elucidate the surface phonon dispersion relations for both the CH{sub 3}-Si(111)-(1??1) and CD{sub 3}-Si(111)-(1??1) surfaces. The combination of experimental and theoretical methods has allowed characterization of the interactions between the low energy vibrations of the adsorbate and the lattice waves of the underlying substrate, as well as characterization of the interactions between neighboring methyl groups, across the entire wavevector resolved vibrational energy spectrum of each system. The Rayleigh wave was found to hybridize with the surface rocking libration near the surface Brillouin zone edge at both the M{sup }-point and K{sup }-point. The calculations indicated that the range of possible energies for the potential barrier to the methyl rotation about the Si-C axis is sufficient to prevent the free rotation of the methyl groups at a room temperature interface. The density functional perturbation theory calculations revealed several other surface phonons that experienced mode-splitting arising from the mutual interaction of adjacent methyl groups. The theory identified a Lucas pair that exists just below the silicon optical bands. For both the CH{sub 3}- and CD{sub 3}-terminated Si(111) surfaces, the deformations of the methyl groups were examined and compared to previous experimental and theoretical work on the nature of the surface vibrations. The calculations indicated a splitting of the asymmetric deformation of the methyl group near the zone edges due to steric interactions of adjacent methyl groups. The observed shifts in vibrational energies of the -CD{sub 3} groups were consistent with the expected effect of isotopic substitution in this system.

  1. Method and apparatus for producing oxygen and nitrogen and membrane therefor

    DOE Patents [OSTI]

    Roman, Ian C.; Baker, Richard W.

    1985-01-01

    Process and apparatus for the separation and purification of oxygen and nitrogen as well as a novel membrane useful therein are disclosed. The process utilizes novel facilitated transport membranes to selectively transport oxygen from one gaseous stream to another, leaving nitrogen as a byproduct. In the method, an oxygen carrier capable of reversibly binding molecular oxygen is dissolved in a polar organic membrane which separates a gaseous feed stream such as atmospheric air and a gaseous product stream. The feed stream is maintained at a sufficiently high oxygen pressure to keep the oxygen carrier in its oxygenated form at the interface of the feed stream with the membrane, while the product stream is maintained at a sufficiently low oxygen pressure to keep the carrier in its deoxygenated form at the interface of the product stream with the membrane. In an alternate mode of operation, the feed stream is maintained at a sufficiently low temperature and high oxygen pressure to keep the oxygen carrier in its oxygenated form at the interface of the feed stream with the membrane and the product stream is maintained at a sufficiently high temperature to keep the carrier in its deoxygenated form at the interface of the product stream with the membrane. Under such conditions, the carrier acts as a shuttle, picking up oxygen at the feed side of the membrane, diffusing across the membrane as the oxygenated complex, releasing oxygen to the product stream, and then diffusing back to the feed side to repeat the process. Exceptionally and unexpectedly high O.sub.2 /N.sub.2 selectivity, on the order of 10 to 30, is obtained, as well as exceptionally high oxygen permeability, on the order of 6 to 15.times.10.sup.-8 cm.sup.3 -cm/cm.sup.2 -sec-cmHg, as well as a long membrane life of in excess of 3 months, making the process commercially feasible.

  2. Method and apparatus for producing oxygen and nitrogen and membrane therefor

    DOE Patents [OSTI]

    Roman, I.C.; Baker, R.W.

    1985-09-17

    Process and apparatus for the separation and purification of oxygen and nitrogen as well as a novel membrane useful therein are disclosed. The process utilizes novel facilitated transport membranes to selectively transport oxygen from one gaseous stream to another, leaving nitrogen as a byproduct. In the method, an oxygen carrier capable of reversibly binding molecular oxygen is dissolved in a polar organic membrane which separates a gaseous feed stream such as atmospheric air and a gaseous product stream. The feed stream is maintained at a sufficiently high oxygen pressure to keep the oxygen carrier in its oxygenated form at the interface of the feed stream with the membrane, while the product stream is maintained at a sufficiently low oxygen pressure to keep the carrier in its deoxygenated form at the interface of the product stream with the membrane. In an alternate mode of operation, the feed stream is maintained at a sufficiently low temperature and high oxygen pressure to keep the oxygen carrier in its oxygenated form at the interface of the feed stream with the membrane and the product stream is maintained at a sufficiently high temperature to keep the carrier in its deoxygenated form at the interface of the product stream with the membrane. Under such conditions, the carrier acts as a shuttle, picking up oxygen at the feed side of the membrane, diffusing across the membrane as the oxygenated complex, releasing oxygen to the product stream, and then diffusing back to the feed side to repeat the process. Exceptionally and unexpectedly high O[sub 2]/N[sub 2] selectivity, on the order of 10 to 30, is obtained, as well as exceptionally high oxygen permeability, on the order of 6 to 15 [times] 10[sup [minus]8] cm[sup 3]-cm/cm[sup 2]-sec-cmHg, as well as a long membrane life of in excess of 3 months, making the process commercially feasible. 2 figs.

  3. Lithium cycling performance in improved lithium hexafluoroarsenate/2-Methyl tetrahydrofuran electrolytes

    SciTech Connect (OSTI)

    Desjardins, C.D.; Cadge, T.G.; Casey, E.J.; Donaldson, G.; Salter, R.S.

    1985-03-01

    Lithium hexafluoroarsenate/2-methyl tetrahydrofuran electrolytes have been prepared, purified, and evaluated using half-cell galvanostatic lithium cycling, cyclic voltammetry, plus colorimetric, gas chromatographic, and UV absorption techniques. Superior electrolytes have been prepared yielding reproducible cycling efficiencies in excess of 97%. Static aging trials at ambient temperature clearly demonstrate deterioration in cycling performance with time. This decline in performance is related to electrolyte degradation, possibly arising from the formation of peroxides. However, studies of various battery testing regimes on 1M LiAsF/sub 6//2Me-THF electrolyte support the system' battery potential with respect to both rate capability and shelf-life characteristics.

  4. Organic Carbon Transformation and Mercury Methylation in Tundra Soils from Barrow Alaska

    DOE Data Explorer [Office of Scientific and Technical Information (OSTI)]

    Liang, L.; Wullschleger, Stan; Graham, David; Gu, B.; Yang, Ziming

    2016-04-20

    This dataset includes information on soil labile organic carbon transformation and mercury methylation for tundra soils from Barrow, Alaska. The soil cores were collected from high-centered polygon (trough) at BEO and were incubated under anaerobic laboratory conditions at both freezing and warming temperatures for up to 8 months. Soil organic carbon including reducing sugars, alcohols, and organic acids were analyzed, and CH4 and CO2 emissions were quantified. Net production of methylmercury and Fe(II)/Fe(total) ratio were also measured and provided in this dataset.

  5. Continuous realtime radioiodine monitor employing on-line methyl iodide conversion

    SciTech Connect (OSTI)

    Fernandez, S.J.; Motes, B.G.

    1980-01-01

    An integrated /sup 14/C, /sup 129/I, and /sup 85/Kr monitor was proposed by Fernandez, et al. that separates /sup 129/I from /sup 85/Kr by selective permeation across thin silicone rubber membranes. Subsequent studies of the permeation of CH/sub 3/I and I/sub 2/ through silicone rubber membranes demonstrated that I/sub 2/ transport across the membranes is too slow to be useful in a realtime monitor. Transport of methyl iodide, however, is rapid and gives a separation factor of greater than 100 from /sup 85/Kr.

  6. Low-lying excited states and nonradiative processes of 9-methyl-2-aminopurine

    SciTech Connect (OSTI)

    Trachsel, Maria A.; Lobsiger, Simon; Schr, Tobias; Leutwyler, Samuel

    2014-01-28

    The UV spectrum of the adenine analogue 9-methyl-2-aminopurine (9M-2AP) is investigated with one- and two-color resonant two-photon ionization spectroscopy at 0.3 and 0.05 cm{sup ?1} resolution in a supersonic jet. The electronic origin at 32252 cm{sup ?1} exhibits methyl torsional subbands that originate from the 0A{sub 1}{sup ??} (l = 0) and 1E{sup ?} (l = 1) torsional levels. These and further torsional bands that appear up to 0{sub 0}{sup 0}+230 cm{sup ?1} allow to fit the threefold (V{sub 3}) barriers of the torsional potentials as |V{sub 3}{sup ??}|=50 cm{sup ?1} in the S{sub 0} and |V{sub 3}{sup ?}|=126 cm{sup ?1} in the S{sub 1} state. Using the B3LYP density functional and correlated approximate second-order coupled cluster CC2 methods, the methyl orientation is calculated to be symmetric relative to the 2AP plane in both states, with barriers of V{sub 3}{sup ??}=20 cm{sup ?1} and V{sub 3}{sup ?}=115 cm{sup ?1}. The 0{sub 0}{sup 0} rotational band contour is 75% in-plane (a/b) polarized, characteristic for a dominantly long-axis {sup 1}??{sup *} excitation. The residual 25% c-axis polarization may indicate coupling of the {sup 1}??{sup *} to the close-lying {sup 1}n?{sup *} state, calculated at 4.00 and 4.01 eV with the CC2 method. However, the CC2 calculated {sup 1}n? oscillator strength is only 6% of that of the {sup 1}??{sup *} transition. The {sup 1}??{sup *} vibronic spectrum is very complex, showing about 40 bands within the lowest 500 cm{sup ?1}. The methyl torsion and the low-frequency out-of-plane ?{sub 1}{sup ?} and ?{sub 2}{sup ?} vibrations are strongly coupled in the {sup 1}??{sup *} state. This gives rise to many torsion-vibration combination bands built on out-of-plane fundamentals, which are without precedence in the {sup 1}??{sup *} spectrum of 9H-2-aminopurine [S. Lobsiger, R. K. Sinha, M. Trachsel, and S. Leutwyler, J. Chem. Phys. 134, 114307 (2011)]. From the Lorentzian broadening needed to fit the 0{sub 0}{sup 0} contour of 9M-2AP

  7. Lattice Distortions and Oxygen Vacancies Produced in Au+-Irradiated Nanocrystalline Cubic Zirconia

    SciTech Connect (OSTI)

    Edmondson, P. D.; Weber, William J.; Namavar, Fereydoon; Zhang, Yanwen

    2011-07-13

    The oxygen ion conductivity, attributed to an oxygen vacancy mechanism, of yttria-stabilized zirconia membranes used in solid oxide fuel cells is restricted due to trapping limitations. In this work, a high concentration of oxygen vacancies has been deliberately introduced into nanocrystalline stabilizer-free zirconia through ion-irradiation. Oxygen vacancies with different charge states can be produced by varying irradiation temperatures. Due to the reduced trapping sites and high oxygen vacancy concentration, this work suggests that the efficiency of solid oxide fuel cells can be improved.

  8. Dietary administration of sodium arsenite to rats: Relations between dose and urinary concentrations of methylated and thio-metabolites and effects on the rat urinary bladder epithelium

    SciTech Connect (OSTI)

    Suzuki, Shugo; Arnold, Lora L.; Pennington, Karen L.; Chen, Baowei; Naranmandura, Hua; Le, X. Chris; Cohen, Samuel M.

    2010-04-15

    Based on epidemiological data, chronic exposure to high levels of inorganic arsenic in drinking water is carcinogenic to humans, inducing skin, urinary bladder and lung tumors. In vivo, inorganic arsenic is metabolized to organic methylated arsenicals including the highly toxic dimethylarsinous acid (DMA{sup III}) and monomethylarsonous acid (MMA{sup III}). Short-term treatment of rats with 100 mug/g trivalent arsenic (As{sup III}) as sodium arsenite in the diet or in drinking water induced cytotoxicity and necrosis of the urothelial superficial layer, with increased cell proliferation and hyperplasia. The objectives of this study were to determine if these arsenic-induced urothelial effects are dose responsive, the dose of arsenic at which urothelial effects are not detected, and the urinary concentrations of the arsenical metabolites. We treated female F344 rats for 5 weeks with sodium arsenite at dietary doses of 0, 1, 10, 25, 50, and 100 ppm. Cytotoxicity, cell proliferation and hyperplasia of urothelial superficial cells were increased in a dose-responsive manner, with maximum effects found at 50 ppm As{sup III}. There were no effects at 1 ppm As{sup III}. The main urinary arsenical in As{sup III}-treated rats was the organic arsenical dimethylarsinic acid (DMA{sup V}). The thio-metabolites dimethylmonothioarsinic acid (DMMTA{sup V}) and monomethylmonothioarsinic acid (MMMTA{sup V}) were also found in the urine of As{sup III}-treated rats. The LC{sub 50} concentrations of DMMTA{sup V} for rat and human urothelial cells in vitro were similar to trivalent oxygen-containing arsenicals. These data suggest that dietary As{sup III}-induced urothelial cytotoxicity and proliferation are dose responsive, and the urothelial effects have a threshold corresponding to the urinary excretion of measurable reactive metabolites.

  9. Oxygen vacancy ordering within anion-deficient Ceria

    SciTech Connect (OSTI)

    Hull, S.; Norberg, S.T.; Ahmed, I.; Eriksson, S.G.; Marrocchelli, D.; Madden, P.A.

    2009-10-15

    The structural properties of anion deficient ceria, CeO{sub 2-{delta}}, have been studied as a function of oxygen partial pressure, p(O{sub 2}), over the range 0>=log{sub 10p}(O{sub 2})>=-18.9 at 1273(2) K using the neutron powder diffraction technique. Rietveld refinement of the diffraction data collected on decreasing p(O{sub 2}) showed increases in the cubic lattice parameter, a, the oxygen nonstoichiometry, delta, and the isotropic thermal vibration parameters, u{sub Ce} and u{sub O}, starting at log{sub 10p}(O{sub 2}){approx}-11. The increases are continuous, but show a distinct kink at log{sub 10p}(O{sub 2}){approx}-14.5. Analysis of the total scattering (Bragg plus diffuse components) using reverse Monte Carlo (RMC) modelling indicates that the O{sup 2-} vacancies preferentially align as pairs in the <111> cubic directions as the degree of nonstoichiometry increases. This behaviour is discussed with reference to the chemical crystallography of the CeO{sub 2}-Ce{sub 2}O{sub 3} system at ambient temperature and, in particular, to the nature of the long-range ordering of O{sup 2-} vacancies within the crystal structure of Ce{sub 7}O{sub 12}. - Graphical abstract: Partial radial distribution function for oxygen vacancies within CeO{sub 1.710} at 1273 K (solid line) showing the increased tendency for local ordering in <111> directions compared to a random distribution (dashed line).

  10. Theory of long-lived nuclear spin states in methyl groups and quantum-rotor induced polarisation

    SciTech Connect (OSTI)

    Dumez, Jean-Nicolas; Håkansson, Pär; Mamone, Salvatore; Meier, Benno; Stevanato, Gabriele; Hill-Cousins, Joseph T.; Roy, Soumya Singha; Brown, Richard C. D.; Pileio, Giuseppe; Levitt, Malcolm H.

    2015-01-28

    Long-lived nuclear spin states have a relaxation time much longer than the longitudinal relaxation time T{sub 1}. Long-lived states extend significantly the time scales that may be probed with magnetic resonance, with possible applications to transport and binding studies, and to hyperpolarised imaging. Rapidly rotating methyl groups in solution may support a long-lived state, consisting of a population imbalance between states of different spin exchange symmetries. Here, we expand the formalism for describing the behaviour of long-lived nuclear spin states in methyl groups, with special attention to the hyperpolarisation effects observed in {sup 13}CH{sub 3} groups upon rapidly converting a material with low-barrier methyl rotation from the cryogenic solid state to a room-temperature solution [M. Icker and S. Berger, J. Magn. Reson. 219, 1 (2012)]. We analyse the relaxation properties of methyl long-lived states using semi-classical relaxation theory. Numerical simulations are supplemented with a spherical-tensor analysis, which captures the essential properties of methyl long-lived states.

  11. Oxygen transport in off-stoichiometric uranium dioxide mediated by defect clustering dynamics

    SciTech Connect (OSTI)

    Yu, Jianguo; Bai, Xian -Ming; El-Azab, Anter; Allen, Todd R.

    2015-03-05

    In this study, oxygen transport is central to many properties of oxides such as stoichiometric changes, phase transformation and ionic conductivity. In this paper, we report a mechanism for oxygen transport in uranium dioxide (UO2) in which the kinetics is mediated by defect clustering dynamics. In particular, the kinetic Monte Carlo (KMC) method has been used to investigate the kinetics of oxygen transport in UO2 under the condition of creation and annihilation of oxygen vacancies and interstitials as well as oxygen interstitial clustering, with variable offstoichiometry and temperature conditions. It is found that in hypo-stoichiometric UO2-x, oxygen transport is well described by the vacancy diffusion mechanism while in hyper-stoichiometric UO2+x, oxygen interstitial cluster diffusion contributes significantly to oxygen transport kinetics, particularly at high temperatures and high off-stoichiometry levels. It is also found that diinterstitial clusters and single interstitials play dominant roles in oxygen diffusion while other larger clusters have negligible contributions. However, the formation, coalescence and dissociation of these larger clusters indirectly affects the overall oxygen diffusion due to their interactions with mono and di-interstitials, thus providing a explanation of the experimental observation of saturation or even drop of oxygen diffusivity at high off-stoichiometry.

  12. Oxygen transport in off-stoichiometric uranium dioxide mediated by defect clustering dynamics

    SciTech Connect (OSTI)

    Yu, Jianguo Bai, Xian-Ming; El-Azab, Anter; Allen, Todd R.

    2015-03-07

    Oxygen transport is central to many properties of oxides such as stoichiometric changes, phase transformation, and ionic conductivity. In this paper, we report a mechanism for oxygen transport in uranium dioxide (UO{sub 2}) in which the kinetics is mediated by defect clustering dynamics. In particular, the kinetic Monte Carlo method has been used to investigate the kinetics of oxygen transport in UO{sub 2} under the condition of creation and annihilation of oxygen vacancies and interstitials as well as oxygen interstitial clustering, with variable off-stoichiometry and temperature conditions. It is found that in hypo-stoichiometric UO{sub 2?x}, oxygen transport is well described by the vacancy diffusion mechanism while in hyper-stoichiometric UO{sub 2+x}, oxygen interstitial cluster diffusion contributes significantly to oxygen transport kinetics, particularly at high temperatures and high off-stoichiometry levels. It is also found that di-interstitial clusters and single interstitials play dominant roles in oxygen diffusion while other larger clusters have negligible contributions. However, the formation, coalescence, and dissociation of these larger clusters indirectly affects the overall oxygen diffusion due to their interactions with mono and di-interstitials, thus providing an explanation of the experimental observation of saturation or even drop of oxygen diffusivity at high off-stoichiometry.

  13. Oxygen transport in off-stoichiometric uranium dioxide mediated by defect clustering dynamics

    DOE PAGES-Beta [OSTI]

    Yu, Jianguo; Bai, Xian -Ming; El-Azab, Anter; Allen, Todd R.

    2015-03-05

    In this study, oxygen transport is central to many properties of oxides such as stoichiometric changes, phase transformation and ionic conductivity. In this paper, we report a mechanism for oxygen transport in uranium dioxide (UO2) in which the kinetics is mediated by defect clustering dynamics. In particular, the kinetic Monte Carlo (KMC) method has been used to investigate the kinetics of oxygen transport in UO2 under the condition of creation and annihilation of oxygen vacancies and interstitials as well as oxygen interstitial clustering, with variable offstoichiometry and temperature conditions. It is found that in hypo-stoichiometric UO2-x, oxygen transport is wellmore » described by the vacancy diffusion mechanism while in hyper-stoichiometric UO2+x, oxygen interstitial cluster diffusion contributes significantly to oxygen transport kinetics, particularly at high temperatures and high off-stoichiometry levels. It is also found that diinterstitial clusters and single interstitials play dominant roles in oxygen diffusion while other larger clusters have negligible contributions. However, the formation, coalescence and dissociation of these larger clusters indirectly affects the overall oxygen diffusion due to their interactions with mono and di-interstitials, thus providing a explanation of the experimental observation of saturation or even drop of oxygen diffusivity at high off-stoichiometry.« less

  14. Leaner Lifted-Flame Combustion Enabled by the Use of an Oxygenated Fuel in an Optical CI Engine

    DOE PAGES-Beta [OSTI]

    Gehmlich, Ryan K.; Dumitrescu, Cosmin E.; Wang, Yefu; Mueller, Charles J.

    2016-04-05

    Leaner lifted-flame combustion (LLFC) is a mixing-controlled combustion strategy for compression-ignition engines that does not produce soot because the equivalence ratio at the lift-off length, Φ(H), is less than or equal to approximately two. In addition to preventing soot formation, LLFC can simultaneously control emissions of nitrogen oxides because it is tolerant to the use of exhaust-gas recirculation for lowering in-cylinder temperatures. LLFC can be achieved through the use of oxygenated fuels and enhanced fuel/charge-gas mixing upstream of the lift-off length. Enhanced mixing can be obtained via higher injection pressures, smaller injector orifice diameters, lower intake-manifold and coolant temperatures, and/ormore » more retarded injection timings. This study focuses on the effects of an oxygenated fuel blend (T50) made up of 50% by volume tri-propylene glycol mono-methyl ether with a #2 ULSD emissions-certification fuel (CFA), compared against baseline testing of the CFA fuel without the oxygenate. Experimental measurements include crank-angle resolved natural luminosity (NL) and chemiluminescence (CL) imaging diagnostics. EGR is simulated by adding nitrogen and carbon dioxide to the intake charge to produce a 16% intake-oxygen mole fraction (XO2), and results are compared against cases with no charge dilution (i.e., 21% XO2). Initial experiments with a two-hole tip achieved soot-free LLFC at low loads with the T50 fuel, 240 MPa injection pressure, 50 °C intake-manifold temperature (IMT), 95 °C coolant temperature, and -5 crank-angle degree (CAD) after top-dead-center (ATDC) start of combustion (SOC) timing. The strategy was extended to more moderate loads by employing a 6-hole injector tip, where lowering the IMT to 30 °C, reducing the coolant temperature to 85 °C, and retarding the SOC timing to +5 CAD ATDC resulted in sustained LLFC at both 21% and 16% XO2 at up to 6.2 bar gross indicated mean effective pressure (gIMEP) with T50. The

  15. Hydrogen and oxygen concentrations in IXCs: A compilation

    SciTech Connect (OSTI)

    Liljegren, L.M.; Terrones, G.T.; Melethil, P.K.

    1996-06-01

    This paper contains four reports and two internal letters that address the estimation of hydrogen and oxygen concentrations in ion exchange columns that treat the water of the K-East and K-West Basins at Hanford. The concern is the flammability of this mixture of gases and planning for safe transport during decommissioning. A transient will occur when the hydrogen filter is temporarily blocked by a sandbag. Analyses are provided for steady-state, transients, and for both wet and dry resins.

  16. Oxygen-stabilized zirconium-vanadium intermetallic compound

    DOE Patents [OSTI]

    Mendelsohn, M.H.; Gruen, D.M.

    1981-10-06

    An oxygen stabilized intermetallic compound having the formula Zr/sub x/OV/sub y/ where x = 0.7 to 2.0 and y = 0.18 to 0.33 is described. The compound is capable of reversibly sorbing hydrogen at temperatures from - 196/sup 0/C to 450/sup 0/C at pressures down to 10/sup -6/ Torr. The compound is also capable of selectively sorbing hydrogen from gaseous mixtures in the presence of CO and CO/sub 2/.

  17. Device for measuring oxygen activity in liquid sodium

    DOE Patents [OSTI]

    Roy, P.; Young, R.S.

    1973-12-01

    A composite ceramic electrolyte in a configuration (such as a closed end tube or a plate) suitable to separate liquid sodium from a reference electrode with a high impedance voltmeter connected to measure EMF between the sodium and the reference electrode as a measure of oxygen activity in the sodium is described. The composite electrolyte consists of zirconiacalcia with a bonded layer of thoria-yttria. The device is used with a gaseous reference electrode on the zirconia-calcia side and liquid sodium on the thoria-yttria side of the electrolyte. (Official Gazette)

  18. Thermochemical generation of hydrogen and oxygen from water

    DOE Patents [OSTI]

    Robinson, Paul R.; Bamberger, Carlos E.

    1982-01-01

    A thermochemical cyclic process for the production of hydrogen exploits the reaction between sodium manganate (NaMnO.sub.2) and titanium dioxide (TiO.sub.2) to form sodium titanate (Na.sub.2 TiO.sub.3), manganese (II) titanate (MnTiO.sub.3) and oxygen. The titanate mixture is treated with sodium hydroxide, in the presence of steam, to form sodium titanate, sodium manganate (III), water and hydrogen. The sodium titanate-manganate (III) mixture is treated with water to form sodium manganate (III), titanium dioxide and sodium hydroxide. Sodium manganate (III) and titanium dioxide are recycled following dissolution of sodium hydroxide in water.

  19. Thermochemical generation of hydrogen and oxygen from water

    DOE Patents [OSTI]

    Robinson, Paul R.; Bamberger, Carlos E.

    1981-01-01

    A thermochemical cyclic process for the production of hydrogen exploits the reaction between sodium manganate (NaMnO.sub.2) and titanium dioxide (TiO.sub.2) to form sodium titanate (Na.sub.2 TiO.sub.3), manganese (II) titanate (MnTiO.sub.3) and oxygen. The titanate mixture is treated with sodium hydroxide, in the presence of steam, to form sodium titanate, sodium manganate (III), water and hydrogen. The sodium titanate-manganate (III) mixture is treated with water to form sodium manganate (III), titanium dioxide and sodium hydroxide. Sodium manganate (III) and titanium dioxide are recycled following dissolution of sodium hydroxide in water.

  20. Method for providing oxygen ion vacancies in lanthanide oxides

    DOE Patents [OSTI]

    Kay, D. Alan R.; Wilson, William G.

    1989-12-05

    A method for desulfurization of fuel gases resulting from the incomplete combustion of sulfur containing hydrocarbons whereby the gases are treated with lanthanide oxides containing large numbers of oxygen-ion vacancies providing ionic porosity which enhances the ability of the lanthanide oxides to react more rapidly and completely with the sulfur in the fuel gases whereby the sulfur in such gases is reduced to low levels suitable for fuels for firing into boilers of power plants generating electricity with steam turbine driven generators, gas turbines, fuel cells and precursors for liquid fuels such as methanol and the like.

  1. Recent advances in the kinetics of oxygen reduction

    SciTech Connect (OSTI)

    Adzic, R.

    1996-07-01

    Oxygen reduction is considered an important electrocatalytic reaction; the most notable need remains improvement of the catalytic activity of existing metal electrocatalysts and development of new ones. A review is given of new advances in the understanding of reaction kinetics and improvements of the electrocatalytic properties of some surfaces, with focus on recent studies of relationship of the surface properties to its activity and reaction kinetics. The urgent need is to improve catalytic activity of Pt and synthesize new, possibly non- noble metal catalysts. New experimental techniques for obtaining new level of information include various {ital in situ} spectroscopies and scanning probes, some involving synchrotron radiation. 138 refs, 18 figs, 2 tabs.

  2. Commercialization Development of Oxygen Fired CFB for Greenhouse Gas Control

    SciTech Connect (OSTI)

    Nsakala ya Nsakala; Gregory N. Liljedahl; David G. Turek

    2007-03-31

    Given that fossil fuel fired power plants are among the largest and most concentrated producers of CO{sub 2} emissions, recovery and sequestration of CO{sub 2} from the flue gas of such plants has been identified as one of the primary means for reducing anthropogenic (i.e., man-made) CO{sub 2} emissions. In 2001, ALSTOM Power Inc. (ALSTOM) began a two-phase program to investigate the feasibility of various carbon capture technologies. This program was sponsored under a Cooperative Agreement from the US Department of Energy's National Energy Technology Laboratory (DOE). The first phase entailed a comprehensive study evaluating the technical feasibility and economics of alternate CO{sub 2} capture technologies applied to Greenfield US coal-fired electric generation power plants. Thirteen cases, representing various levels of technology development, were evaluated. Seven cases represented coal combustion in CFB type equipment. Four cases represented Integrated Gasification Combined Cycle (IGCC) systems. Two cases represented advanced Chemical Looping Combined Cycle systems. Marion, et al. reported the details of this work in 2003. One of the thirteen cases studied utilized an oxygen-fired circulating fluidized bed (CFB) boiler. In this concept, the fuel is fired with a mixture of oxygen and recirculated flue gas (mainly CO{sub 2}). This combustion process yields a flue gas containing over 80 percent (by volume) CO{sub 2}. This flue gas can be processed relatively easily to enrich the CO{sub 2} content to over 96 percent for use in enhanced oil or gas recovery (EOR or EGR) or simply dried for sequestration. The Phase I study identified the O{sub 2}-fired CFB as having a near term development potential, because it uses conventional commercial CFB technology and commercially available CO{sub 2} capture enabling technologies such as cryogenic air separation and simple rectification or distillation gas processing systems. In the long term, air separation technology

  3. Electrode Interface Dictates Oxygen Evolution from Lithium Peroxide in

    U.S. Department of Energy (DOE) all webpages (Extended Search)

    Li-O2 Batteries - Joint Center for Energy Storage Research December 16, 2014, Research Highlights Electrode Interface Dictates Oxygen Evolution from Lithium Peroxide in Li-O2 Batteries Isolation of the charge reaction from the discharge in Li-O2 cells by utilizing electrodes prefilled with commercial lithium peroxide provides a unique method to understand interfacial properties. OER is very facile on TiC, which lacks a significant oxide film and occurs at a much lower overpotential relative

  4. Oxygen transport membrane system and method for transferring heat to catalytic/process reactors

    DOE Patents [OSTI]

    Kelly, Sean M; Kromer, Brian R; Litwin, Michael M; Rosen, Lee J; Christie, Gervase Maxwell; Wilson, Jamie R; Kosowski, Lawrence W; Robinson, Charles

    2014-01-07

    A method and apparatus for producing heat used in a synthesis gas production is provided. The disclosed method and apparatus include a plurality of tubular oxygen transport membrane elements adapted to separate oxygen from an oxygen containing stream contacting the retentate side of the membrane elements. The permeated oxygen is combusted with a hydrogen containing synthesis gas stream contacting the permeate side of the tubular oxygen transport membrane elements thereby generating a reaction product stream and radiant heat. The present method and apparatus also includes at least one catalytic reactor containing a catalyst to promote the stream reforming reaction wherein the catalytic reactor is surrounded by the plurality of tubular oxygen transport membrane elements. The view factor between the catalytic reactor and the plurality of tubular oxygen transport membrane elements radiating heat to the catalytic reactor is greater than or equal to 0.5.

  5. Oxygen transport membrane system and method for transferring heat to catalytic/process reactors

    DOE Patents [OSTI]

    Kelly, Sean M.; Kromer, Brian R.; Litwin, Michael M.; Rosen, Lee J.; Christie, Gervase Maxwell; Wilson, Jamie R.; Kosowski, Lawrence W.; Robinson, Charles

    2016-01-19

    A method and apparatus for producing heat used in a synthesis gas production process is provided. The disclosed method and apparatus include a plurality of tubular oxygen transport membrane elements adapted to separate oxygen from an oxygen containing stream contacting the retentate side of the membrane elements. The permeated oxygen is combusted with a hydrogen containing synthesis gas stream contacting the permeate side of the tubular oxygen transport membrane elements thereby generating a reaction product stream and radiant heat. The present method and apparatus also includes at least one catalytic reactor containing a catalyst to promote the steam reforming reaction wherein the catalytic reactor is surrounded by the plurality of tubular oxygen transport membrane elements. The view factor between the catalytic reactor and the plurality of tubular oxygen transport membrane elements radiating heat to the catalytic reactor is greater than or equal to 0.5

  6. Production of FAME biodiesel in E. coli by direct methylation with an insect enzyme

    DOE PAGES-Beta [OSTI]

    Sherkhanov, Saken; Korman, Tyler P.; Clarke, Steven G.; Bowie, James U.

    2016-04-07

    Here, most biodiesel currently in use consists of fatty acid methyl esters (FAMEs) produced by transesterification of plant oils with methanol. To reduce competition with food supplies, it would be desirable to directly produce biodiesel in microorganisms. To date, the most effective pathway for the production of biodiesel in bacteria yields fatty acid ethyl esters (FAEEs) at up to ~1.5 g/L. A much simpler route to biodiesel produces FAMEs by direct S-adenosyl-L-methionine (SAM) dependent methylation of free fatty acids, but FAME production by this route has been limited to only ~16 mg/L. Here we employ an alternative, broad spectrum methyltransferase,more » Drosophila melanogaster Juvenile Hormone Acid O-Methyltransferase (DmJHAMT). By introducing DmJHAMT in E. coli engineered to produce medium chain fatty acids and overproduce SAM, we obtain medium chain FAMEs at titers of 0.56 g/L, a 35-fold increase over titers previously achieved. Although considerable improvements will be needed for viable bacterial production of FAMEs and FAEEs for biofuels, it may be easier to optimize and transport the FAME production pathway to other microorganisms because it involves fewer enzymes.« less

  7. Autoignition measurements and a validated kinetic model for the biodiesel surrogate, methyl butanoate

    SciTech Connect (OSTI)

    Dooley, S.; Curran, H.J.; Simmie, J.M.

    2008-04-15

    The autoignition of methyl butanoate has been studied at 1 and 4 atm in a shock tube over the temperature range 1250-1760 K at equivalence ratios of 1.5, 1.0, 0.5, and 0.25 at fuel concentrations of 1.0 and 1.5%. These measurements are complemented by autoignition data from a rapid compression machine over the temperature range 640-949 K at compressed gas pressures of 10, 20, and 40 atm and at varying equivalence ratios of 1.0, 0.5, and 0.33 using fuel concentrations of 1.59 and 3.13%. The autoignition of methyl butanoate is observed to follow Arrhenius-like temperature dependence over all conditions studied. These data, together with speciation data reported in the literature in a flow reactor, a jet-stirred reactor, and an opposed-flow diffusion flame, were used to produce a detailed chemical kinetic model. It was found that the model correctly simulated the effect of change in equivalence ratio, fuel fraction, and pressure for shock tube ignition delays. The agreement with rapid compression machine ignition delays is less accurate, although the qualitative agreement is reasonable. The model reproduces most speciation data with good accuracy. In addition, the important reaction pathways over each regime have been elucidated by both sensitivity and flux analyses. (author)

  8. Arbuzov rearrangement in alkoxy derivatives and chloro derivatives of methyl phosphonites

    SciTech Connect (OSTI)

    Livantsov, M.V.; Prishchenko, A.A.; Lutsenko, I.F.

    1987-10-20

    In a series of alkoxy- and chloro-substituted methyl phosphonites, the Arbuzov reaction is a preparative method for the synthesis of new types of functionally substituted methyl phosphinates. The Arbuzov reaction takes a new pathway in the case of dialkoxymethyl phosphonites, in which the phosphorus-carbon bond is ruptured at the stage where a quasiphosphonium compound forms, producing alkoxycarbonyl phosphonites that have not been available before. The IR spectra were obtained on UR-20 and IKS-22 instruments in a thin layer (NaCL). The PMR spectra were taken on a Tesla BS-497 spectrometer (100 MHz) in C/sub 6/D/sub 6/ and CDCl/sub 3/ solutions (20 to 30% concn.), with TMS as standard. The /sup 13/C NMR spectrum of phosphonite (XI) was obtained on a Varian FT-80A spectrometer (20 MHz) in an 80% solution in C/sub 6/D/sub 6/ and with TMS as standard. The /sup 31/P NMR spectra were obtained on JEOL 6-50OHL (24.3 MHz), Varian FT-80A (32.2 MHz), and JOEL FX-100 (42 MHz) spectrometers with an 85% solution of H/sub 3/PO/sub 4/ in D/sub 2/O as standard.

  9. Dipole Alignment at the Carbon Nanotube and Methyl Ammonium Lead Iodide Perovskite Interface

    SciTech Connect (OSTI)

    Przepioski, Joshua

    2015-08-28

    This work correlates resonant peaks from first principles calculation on ammonia (NH3) Nitrogen 1s x-ray absorption spectroscopy (XAS) within the methyl ammonium lead iodide perovskite (CH3NH3PbI3), and proposes a curve to determine the alignment of the methyl ammonium dipole if there exists angular dependence. The Nitrogen 1s XAS was performed at varying incident angles on the perovskite with and without a carbon nanotube (CNT) interface produced from an ultrasonic spray deposition. We investigated the peak contribution from PbI2 and the poly(9,9-dioctylfluorene- 2,7-diyl) with bipyridine (PFO-BPy) wrapped around the CNT, and used normalization techniques to better identify the dipole alignment. There was angular dependence on samples containing the CNT interface suggesting an existing dipole alignment, but there was no angular dependence on the perovskite samples alone; however, more normalization techniques and experimental work must be performed in order to ensure its validity and to better describe its alignment, and possible controlling factors.

  10. Methyl chloride via oxyhydrochlorination of methane: A building block for chemicals and fuels from natural gas

    SciTech Connect (OSTI)

    Benson, R.L.; Brown, S.S.D.; Ferguson, S.P.; Jarvis, R.F. Jr.

    1995-12-31

    The objectives of this program are to (a) develop a process for converting natural gas to methyl chloride via an oxyhydrochlorination route using highly selective, stable catalysts in a fixed-bed, (b) design a reactor capable of removing the large amount of heat generated in the process so as to control the reaction, (c) develop a recovery system capable of removing the methyl chloride from the product stream and (d) determine the economics and commercial viability of the process. The general approach has been as follows: (a) design and build a laboratory scale reactor, (b) define and synthesize suitable OHC catalysts for evaluation, (c) select first generation OHC catalyst for Process Development Unit (PDU) trials, (d) design, construct and startup PDU, (e) evaluate packed bed reactor design, (f) optimize process, in particular, product recovery operations, (g) determine economics of process, (h) complete preliminary engineering design for Phase II and (i) make scale-up decision and formulate business plan for Phase II. Conclusions regarding process development and catalyst development are presented.

  11. Characterization of the Deltaproteobacteria in Contaminated and Uncontaminated Surface Stream Sediments and Identification of Potential Mercury Methylators

    SciTech Connect (OSTI)

    Mosher, Jennifer J; Vishnivetskaya, Tatiana A; Elias, Dwayne A; Podar, Mircea; Brooks, Scott C; Brown, Steven D; Brandt, Craig C; Palumbo, Anthony Vito

    2012-01-01

    Microbial communities were examined in surface stream sediments at five contaminated sites and one control site near Oak Ridge, TN in order to identify bacteria that could be contributing to mercury methylation. The phylogenetic composition of the sediment bacterial community was examined over three quarterly sampling periods (36 samples) using 16s rRNA pyrosequencing. Only 3064 sequences (0.85 % of the total community) were identified as Deltaproteobacteria by the RDP classifier at the 99% confidence threshold. Constrained ordination techniques indicated significant positive correlations between Desulfobulbus spp., Desulfonema spp. and Desulfobacca spp. and methyl mercury concentrations in the contaminated sites. On the contrary, the distribution of organisms related to Byssovorax was significantly correlated to inorganic carbon, nitrate and uranium concentrations. Overall, the abundance and richness of Deltaproteobacteria sequences were higher in the sediments of the site, while the majority of the members present at the contaminated sites were either known metal reducers/methylators or metal tolerant species.

  12. Covalent Coupling of Organophosphorus Hydrolase Loaded Quantum Dots to Carbon Nanotube/Au Nanocomposite for Enhanced Detection of Methyl Parathion

    SciTech Connect (OSTI)

    Du, Dan; Chen, Wenjuan; Zhang, Weiying; Liu, Deli; Li, Haibing; Lin, Yuehe

    2010-02-15

    An amperometric biosensor for highly selective and sensitive determination of methyl parathion (MP) was developed based on dual signal amplification: (1) a large amount of introduced enzyme on the electrode surface and (2) synergistic effects of nanoparticles towards enzymatic catalysis. The fabrication process includes (1) electrochemical deposition of gold nanoparticles by a multi-potential step technique at multiwalled carbon nanotube (MWCNT) film pre-cast on a glassy carbon electrode and (2) immobilization of methyl parathion degrading enzyme (MPDE) onto a modified electrode through CdTe quantum dots (CdTe QDs) covalent attachment. The introduced MWCNT and gold nanoparticles significantly increased the surface area and exhibited synergistic effects towards enzymatic catalysis. CdTe QDs are further used as carriers to load a large amount of enzyme. As a result of these two important enhancement factors, the proposed biosensor exhibited extremely sensitive, perfectly selective, and rapid response to methyl parathion in the absence of a mediator.

  13. Oxygen transport properties estimation by DSMC-CT simulations

    SciTech Connect (OSTI)

    Bruno, Domenico; Frezzotti, Aldo; Ghiroldi, Gian Pietro

    2014-12-09

    Coupling DSMC simulations with classical trajectories calculations is emerging as a powerful tool to improve predictive capabilities of computational rarefied gas dynamics. The considerable increase of computational effort outlined in the early application of the method (Koura,1997) can be compensated by running simulations on massively parallel computers. In particular, GPU acceleration has been found quite effective in reducing computing time (Ferrigni,2012; Norman et al.,2013) of DSMC-CT simulations. The aim of the present work is to study rarefied Oxygen flows by modeling binary collisions through an accurate potential energy surface, obtained by molecular beams scattering (Aquilanti, et al.,1999). The accuracy of the method is assessed by calculating molecular Oxygen shear viscosity and heat conductivity following three different DSMC-CT simulation methods. In the first one, transport properties are obtained from DSMC-CT simulations of spontaneous fluctuation of an equilibrium state (Bruno et al, Phys. Fluids, 23, 093104, 2011). In the second method, the collision trajectory calculation is incorporated in a Monte Carlo integration procedure to evaluate the Taxman’s expressions for the transport properties of polyatomic gases (Taxman,1959). In the third, non-equilibrium zero and one-dimensional rarefied gas dynamic simulations are adopted and the transport properties are computed from the non-equilibrium fluxes of momentum and energy. The three methods provide close values of the transport properties, their estimated statistical error not exceeding 3%. The experimental values are slightly underestimated, the percentage deviation being, again, few percent.

  14. Fluorophore-based sensor for oxygen radicals in processing plasmas

    SciTech Connect (OSTI)

    Choudhury, Faraz A.; Shohet, J. Leon; Sabat, Grzegorz; Sussman, Michael R.; Nishi, Yoshio

    2015-11-15

    A high concentration of radicals is present in many processing plasmas, which affects the processing conditions and the properties of materials exposed to the plasma. Determining the types and concentrations of free radicals present in the plasma is critical in order to determine their effects on the materials being processed. Current methods for detecting free radicals in a plasma require multiple expensive and bulky instruments, complex setups, and often, modifications to the plasma reactor. This work presents a simple technique that detects reactive-oxygen radicals incident on a surface from a plasma. The measurements are made using a fluorophore dye that is commonly used in biological and cellular systems for assay labeling in liquids. Using fluorometric analysis, it was found that the fluorophore reacts with oxygen radicals incident from the plasma, which is indicated by degradation of its fluorescence. As plasma power was increased, the quenching of the fluorescence significantly increased. Both immobilized and nonimmobilized fluorophore dyes were used and the results indicate that both states function effectively under vacuum conditions. The reaction mechanism is very similar to that of the liquid dye.

  15. Nickel-hydrogen battery with oxygen and electrolyte management features

    DOE Patents [OSTI]

    Sindorf, John F.

    1991-10-22

    A nickel-hydrogen battery or cell having one or more pressure vessels containing hydrogen gas and a plurality of cell-modules therein. Each cell-module includes a configuration of cooperatively associated oxygen and electrolyte mangement and component alignment features. A cell-module having electrolyte includes a negative electrode, a positive electrode adapted to facilitate oxygen diffusion, a separator disposed between the positive and negative electrodes for separating them and holding electrolyte for ionic conductivity, an absorber engaging the surface of the positive electrode facing away from the separator for providing electrolyte to the positive electrode, and a pair of surface-channeled diffusion screens for enclosing the positive and negative electrodes, absorber, and separator and for maintaining proper alignment of these components. The screens, formed in the shape of a pocket by intermittently sealing the edges together along as many as three sides, permit hydrogen gas to diffuse therethrough to the negative electrodes, and prevent the edges of the separator from swelling. Electrolyte is contained in the cell-module, absorbhed by the electrodes, the separator and the absorber.

  16. MOLECULAR OXYGEN IN OORT CLOUD COMET 1P/HALLEY

    SciTech Connect (OSTI)

    Rubin, M.; Altwegg, K.; Dishoeck, E. F. van; Schwehm, G.

    2015-12-10

    Recently, the ROSINA mass spectrometer suite on board the European Space Agency's Rosetta spacecraft discovered an abundant amount of molecular oxygen, O{sub 2}, in the coma of Jupiter family comet 67P/Churyumov–Gerasimenko of O{sub 2}/H{sub 2}O = 3.80 ± 0.85%. It could be shown that O{sub 2} is indeed a parent species and that the derived abundances point to a primordial origin. Crucial questions are whether the O{sub 2} abundance is peculiar to comet 67P/Churyumov–Gerasimenko or Jupiter family comets in general, and also whether Oort cloud comets such as comet 1P/Halley contain similar amounts of molecular oxygen. We investigated mass spectra obtained by the Neutral Mass Spectrometer instrument during the flyby by the European Space Agency's Giotto probe of comet 1P/Halley. Our investigation indicates that a production rate of O{sub 2} of 3.7 ± 1.7% with respect to water is indeed compatible with the obtained Halley data and therefore that O{sub 2} might be a rather common and abundant parent species.

  17. Hydrogen and Oxygen Gas Monitoring System Design and Operation

    SciTech Connect (OSTI)

    Lee C. Cadwallader; Kevin G. DeWall; J. Stephen Herring

    2007-06-01

    This paper describes pertinent design practices of selecting types of monitors, monitor unit placement, setpoint selection, and maintenance considerations for gas monitors. While hydrogen gas monitors and enriched oxygen atmosphere monitors as they would be needed for hydrogen production experiments are the primary focus of this paper, monitors for carbon monoxide and carbon dioxide are also discussed. The experiences of designing, installing, and calibrating gas monitors for a laboratory where experiments in support of the DOE Nuclear Hydrogen Initiative (NHI) are described along with codes, standards, and regulations for these monitors. Information from the literature about best operating practices is also presented. The NHI program has two types of activities. The first, near-term activity is laboratory and pilot-plant experimentation with different processes in the kilogram per day scale to select the most promising types of processes for future applications of hydrogen production. Prudent design calls for indoor gas monitors to sense any hydrogen leaks within these laboratory rooms. The second, longer-term activity is the prototype, or large-scale plants to produce tons of hydrogen per day. These large, outdoor production plants will require area (or “fencepost”) monitoring of hydrogen gas leaks. Some processes will have oxygen production with hydrogen production, and any oxygen releases are also safety concerns since oxygen gas is the strongest oxidizer. Monitoring of these gases is important for personnel safety of both indoor and outdoor experiments. There is some guidance available about proper placement of monitors. The fixed point, stationary monitor can only function if the intruding gas contacts the monitor. Therefore, monitor placement is vital to proper monitoring of the room or area. Factors in sensor location selection include: indoor or outdoor site, the location and nature of potential vapor/gas sources, chemical and physical data of the

  18. Conceptual Design of Oxygen-Based PC Boiler

    SciTech Connect (OSTI)

    Andrew Seltzer; Zhen Fan

    2005-09-01

    Coal is presently the world's primary fuel for generating electrical power and, being more abundant and less expensive than oil or natural gas, is expected to continue its dominance into the future. Coal, however, is more carbon intensive than natural gas and oil and consequently coal-fired power plants are large point source emitters of carbon dioxide (CO{sub 2}). Since CO{sub 2} is a greenhouse gas, which may have an adverse impact on the world's climate/weather patterns, studies have been conducted to determine the feasibility and economic impact of capturing power plant CO{sub 2} emissions for pipeline transport to a sequestration/storage site. The stack gas that exhausts from a modern coal-fired power plant typically contains about 15% CO{sub 2} on a dry volume basis. Although there are numerous processes available for removing CO{sub 2} from gas streams, gas scrubbing with amine solvent is best suited for this application because of the large gas volumes and low CO{sub 2} concentrations involved. Unfortunately the energy required to regenerate the solvent for continued use as a capturing agent is large and imposes a severe energy penalty on the plant. In addition this ''back end'' or post combustion cleanup requires the addition of large vessels, which, in retrofit applications, are difficult to accommodate. As an alternative to post combustion scrubbing, Foster Wheeler (FW) has proposed that the combustion process be accomplished with oxygen rather than air. With all air nitrogen eliminated, a CO{sub 2}-water vapor rich flue gas will be generated. After condensation of the water vapor, a portion of the flue gas will be recirculated back to the boiler to control the combustion temperature and the balance of the CO{sub 2} will be processed for pipeline transport. This proposed oxygen-carbon dioxide (O{sub 2}/CO{sub 2}) combustion process eliminates the need for CO{sub 2} removal/separation and reduces the cost of supplying a CO{sub 2} rich stream for

  19. Oxygen-stabilized zirconium-vanadium-iron alloy

    DOE Patents [OSTI]

    Mendelsohn, M.H.; Gruen, D.M.

    1981-06-16

    An oxygen stabilized intermetallic compound is described which has the formula (Zr/sub 1-x/Ti/sub x/)/sub 2-u/(V/sub 1-y/Fe/sub y/)O/sub z/ where x = 0.0 to 0.9, y = 0.01 to 0.9, z = 0.25 to 0.5 and u = 0 to 1. The compound is capable of reversibly sorbing hydrogen at temperatures from -196/sup 0/C to 200/sup 0/C at pressures down to 10/sup -6/ torr. The compound is suitable for use as a hydrogen getter in low pressure, high temperature applications such as magnetic confinement fusion devices.

  20. Orbital reconstruction in a self-assembled oxygen vacancy nanostructure

    DOE PAGES-Beta [OSTI]

    Jang, H.; Kerr, G.; Lim, J. S.; Yang, C. -H.; Kao, C. -C.; Lee, J. -S.

    2015-07-27

    We demonstrate the microscopic role of oxygen vacancies spatially confined within nanometer inter-spacing (about 1nm) in BiFeO₃, using resonant soft X-ray scattering techniques and soft X-ray spectroscopy measurements. Such vacancy confinements and total number of vacancy are controlled by substitution of Ca²⁺ for Bi³⁺ cation. We found that by increasing the substitution, the in-plane orbital bands of Fe³⁺ cations are reconstructed without any redox reaction. It leads to a reduction of the hopping between Fe atoms, forming a localized valence band, in particular Fe 3d-electronic structure, around the Fermi level. This band localization causes to decrease the conductivity of themore » doped BiFeO₃ system.« less

  1. Orbital reconstruction in a self-assembled oxygen vacancy nanostructure

    SciTech Connect (OSTI)

    Jang, H.; Kerr, G.; Lim, J. S.; Yang, C. -H.; Kao, C. -C.; Lee, J. -S.

    2015-07-27

    We demonstrate the microscopic role of oxygen vacancies spatially confined within nanometer inter-spacing (about 1nm) in BiFeO₃, using resonant soft X-ray scattering techniques and soft X-ray spectroscopy measurements. Such vacancy confinements and total number of vacancy are controlled by substitution of Ca²⁺ for Bi³⁺ cation. We found that by increasing the substitution, the in-plane orbital bands of Fe³⁺ cations are reconstructed without any redox reaction. It leads to a reduction of the hopping between Fe atoms, forming a localized valence band, in particular Fe 3d-electronic structure, around the Fermi level. This band localization causes to decrease the conductivity of the doped BiFeO₃ system.

  2. Effects of Ionomer Morphology on Oxygen Reduction on Pt

    SciTech Connect (OSTI)

    Chlistunoff, Jerzy; Pivovar, Bryan

    2015-05-21

    In this paper, the oxygen reduction reaction (ORR) at the interface between platinum and Nafion 1100 equivalent weight was studied as a function of temperature (20–80 °C), humidity (10–100%), scan rate, the manner in which Nafion film was deposited, and the state of the Pt surface using ultramicroelectrodes employing cyclic voltammetry and chronoamperometry. ORR on smooth electrodes was strongly inhibited under specific conditions dependent on temperature, humidity, and scan rate. From the data presented, we postulate that dynamic changes in the molecular structure of the ionomer at the platinum interface result in differences in ORR voltammetry for films prepared and equilibrated under different conditions. The lack of similar changes for rough, platinized electrodes has been attributed to differences in initial ionomer structure and a higher energy barrier for ionomer restructuring. Finally, these model system studies yield insight into the ionomer-catalyst interface of particular interest for polymer electrolyte fuel cells.

  3. Willamette Hatchery Oxygen Supplementation Studies : Annual Report 1993.

    SciTech Connect (OSTI)

    Ewing, R.D.; Ewing, S.K.; Sheahan, J.E.

    1993-11-01

    Hydropower development and operations in the Columbia River basin have caused the loss of 5 million to 11 million salmonids. An interim goal of the Northwest Power Planning Council is to reestablish these historical numbers by doubling the present adult runs from 2.5 million to 5.0 million fish. This increase in production will be accomplished through comprehensive management of both wild and hatchery fish, but artificial propagation will play a major role in the augmentation process. The current husbandry techniques in existing hatcheries require improvements that may include changes in rearing densities, addition of oxygen, removal of excess nitrogen, and improvement in raceway design. Emphasis will be placed on the ability to increase the number of fish released from hatcheries that survive to return as adults.

  4. Complexes of self-interstitials with oxygen atoms in Ge

    SciTech Connect (OSTI)

    Khirunenko, L. I.; Pomozov, Yu. V.; Sosnin, M. G.; Abrosimov, N. V.; Riemann, H.

    2014-02-21

    Interactions of germanium self-interstitials with interstitial oxygen atoms in Ge subjected to irradiation at ?80 K and subsequently to annealing have been studied. To distinguish the processes involving vacancies and self-interstitials the doping with tin was used. It was shown that absorption lines with maximum at 602, 674, 713 and 803 cm{sup ?1} are self-interstitials-related. Two lines at 602 and 674, which develop upon annealing in the temperature range 180240 K, belong to IO complexes, while the bands at 713 and 803 cm{sup ?1}, which emerge after annealing at T>220 K, are associated with I{sub 2}O. It is argued that the annealing of IO occurs by two mechanisms: by dissociation and by diffusion.

  5. Development of a Supersonic Atomic Oxygen Nozzle Beam Source for Crossed Beam Scattering Experiments

    DOE R&D Accomplishments [OSTI]

    Sibener, S. J.; Buss, R. J.; Lee, Y. T.

    1978-05-01

    A high pressure, supersonic, radio frequency discharge nozzle beam source was developed for the production of intense beams of ground state oxygen atoms. An efficient impedance matching scheme was devised for coupling the radio frequency power to the plasma as a function of both gas pressure and composition. Techniques for localizing the discharge directly behind the orifice of a water-cooled quartz nozzle were also developed. The above combine to yield an atomic oxygen beam source which produces high molecular dissociation in oxygen seeded rare gas mixtures at total pressures up to 200 torr: 80 to 90% dissociation for oxygen/argon mixtures and 60 to 70% for oxygen/helium mixtures. Atomic oxygen intensities are found to be greater than 10{sup 17} atom sr{sup -1} sec{sup -1}. A brief discussion of the reaction dynamics of 0 + IC1 ..-->.. I0 + C1 is also presented.

  6. Measurement of the soot concentration and soot particle sizes in propane oxygen flames

    SciTech Connect (OSTI)

    Bockhorn, H.; Fetting, F.; Meyer, U.; Reck, R.; Wannemacher, G.

    1981-01-01

    Soot concentrations and particle sizes were measured by light scattering and probe measurements in the burnt gas region of atmospheric pressure propane-oxygen flames and propane-oxygen flames to which hydrogen or ammonia were added. The results show that the soot concentrations in propane-oxygen flames, to which hydrogen is added are lower compared to propane-oxygen flames. The decrease of soot concentration is much stronger when ammonia is added. Associated with the reduction of soot concentration is a reduction of mean particle size of the soot particles and a lower breadth of the particle size distributions. Electron micrographs of soot particles from the probe measurements showed that soot particles from flames with high soot concentrations (propane oxygen flames) are aggregates with chain or cluster structure while the structure of the particles from flames with lower soot concentration (propane oxygen flames with hydrogen or ammonia added) is more compact. 24 refs.

  7. Fast oxygen diffusion in bismuth oxide probed by quasielastic neutron scattering

    DOE PAGES-Beta [OSTI]

    Mamontov, Eugene

    2016-09-24

    In this paper, we present the first, to our knowledge, study of solid state oxygen translational diffusion by quasielastic neutron scattering. Such studies in the past might have been precluded by relatively low diffusivities of oxygen anions in the temperature range amenable to neutron scattering experiments. To explore the potential of the quasielastic scattering technique, which can deduce atomic diffusion jump length of oxygen anions through the momentum transfer dependence of the scattering signal, we have selected the fastest known oxygen conductor, bismuth oxide. Finally, we have found the oxygen anion jump length in excellent agreement with the nearest oxygen-vacancymore » distance in the anion sublattice of the fluorite-related structure of bismuth oxide.« less

  8. Origin of deep subgap states in amorphous indium gallium zinc oxide: Chemically disordered coordination of oxygen

    SciTech Connect (OSTI)

    Sallis, S.; Williams, D. S.; Butler, K. T.; Walsh, A.; Quackenbush, N. F.; Junda, M.; Podraza, N. J.; Fischer, D. A.; Woicik, J. C.; White, B. E.; Piper, L. F. J.

    2014-06-09

    The origin of the deep subgap states in amorphous indium gallium zinc oxide (a-IGZO), whether intrinsic to the amorphous structure or not, has serious implications for the development of p-type transparent amorphous oxide semiconductors. We report that the deep subgap feature in a-IGZO originates from local variations in the oxygen coordination and not from oxygen vacancies. This is shown by the positive correlation between oxygen composition and subgap intensity as observed with X-ray photoelectron spectroscopy. We also demonstrate that the subgap feature is not intrinsic to the amorphous phase because the deep subgap feature can be removed by low-temperature annealing in a reducing environment. Atomistic calculations of a-IGZO reveal that the subgap state originates from certain oxygen environments associated with the disorder. Specifically, the subgap states originate from oxygen environments with a lower coordination number and/or a larger metal-oxygen separation.

  9. Controlled temperature expansion in oxygen production by molten alkali metal salts

    DOE Patents [OSTI]

    Erickson, D.C.

    1985-06-04

    A continuous process is set forth for the production of oxygen from an oxygen containing gas stream, such as air, by contacting a feed gas stream with a molten solution of an oxygen acceptor to oxidize the acceptor and cyclically regenerating the oxidized acceptor by releasing oxygen from the acceptor wherein the oxygen-depleted gas stream from the contact zone is treated sequentially to temperature reduction by heat exchange against the feed stream so as to condense out entrained oxygen acceptor for recycle to the process, combustion of the gas stream with fuel to elevate its temperature and expansion of the combusted high temperature gas stream in a turbine to recover power. 1 fig.

  10. Heterogeneous catalyst for the production of acetic anhydride from methyl acetate

    DOE Patents [OSTI]

    Ramprasad, D.; Waller, F.J.

    1999-04-06

    This invention relates to a process for producing acetic anhydride by the reaction of methyl acetate, carbon monoxide, and hydrogen at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that contains an insoluble polymer having pendant quaternized phosphine groups, some of which phosphine groups are ionically bonded to anionic Group VIII metal complexes, the remainder of the phosphine groups being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for consecutive runs without loss in activity. Bifunctional catalysts for use in carbonylating dimethyl ether are also provided.

  11. Heterogeneous catalyst for the production of acetic anhydride from methyl acetate

    DOE Patents [OSTI]

    Ramprasad, Dorai; Waller, Francis Joseph

    1999-01-01

    This invention relates to a process for producing acetic anhydride by the reaction of methyl acetate, carbon monoxide, and hydrogen at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that contains an insoluble polymer having pendant quaternized phosphine groups, some of which phosphine groups are ionically bonded to anionic Group VIII metal complexes, the remainder of the phosphine groups being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for consecutive runs without loss in activity. Bifunctional catalysts for use in carbonylating dimethyl ether are also provided.

  12. Investigation of methyl decanoate combustion in an optical direct-injection diesel engine

    DOE PAGES-Beta [OSTI]

    Cheng, A. S.; Dumitrescu, Cosmin E.; Mueller, Charles J.

    2014-11-24

    In this study, an optically accessible heavy-duty diesel engine was used to investigate the impact of methyl decanoate (MD) on combustion and emissions. A specific goal of the study was to determine if MD could enable soot-free leaner-lifted flame combustion (LLFC) – a mode of mixing-controlled combustion associated with fuel-air equivalence ratios below approximately two. An ultra-low sulfur diesel certification fuel (CF) was used as the baseline fuel, and experiments were conducted at two fuel-injection pressures with three levels of charge-gas dilution. In addition to conventional pressure-based and engine-out emissions measurements, exhaust laser-induced incandescence, in-cylinder natural luminosity (NL), and in-cylindermore » chemiluminescence (CL) diagnostics were used to provide detailed insight into combustion processes.« less

  13. Crystallization of lysozyme with (R)-, (S)- and (RS)-2-methyl-2,4-pentanediol

    DOE PAGES-Beta [OSTI]

    Stauber, Mark; Jakoncic, Jean; Berger, Jacob; Karp, Jerome M.; Axelbaum, Ariel; Sastow, Dahniel; Buldyrev, Sergey V.; Hrnjez, Bruce J.; Asherie, Neer

    2015-03-01

    Chiral control of crystallization has ample precedent in the small-molecule world, but relatively little is known about the role of chirality in protein crystallization. In this study, lysozyme was crystallized in the presence of the chiral additive 2-methyl-2,4-pentanediol (MPD) separately using the R and S enantiomers as well as with a racemic RS mixture. Crystals grown with (R)-MPD had the most order and produced the highest resolution protein structures. This result is consistent with the observation that in the crystals grown with (R)-MPD and (RS)-MPD the crystal contacts are made by (R)-MPD, demonstrating that there is preferential interaction between lysozymemore » and this enantiomer. These findings suggest that chiral interactions are important in protein crystallization.« less

  14. Interactions in 1-ethyl-3-methyl imidazolium tetracyanoborate ion pair: Spectroscopic and density functional study

    SciTech Connect (OSTI)

    Mao, James X; Lee, Anita S; Kitchin, John R; Nulwala, Hunaid B; Luebke, David R; Damodaran, Krishnan

    2013-04-24

    Density Functional Theory is used to investigate a weakly coordinating room-temperature ionic liquid, 1-ethyl-3-methyl imidazolium tetracyanoborate ([Emim]{sup +}[TCB]{sup -}). Four locally stable conformers of the ion pair were located. Atoms-in-molecules (AIM) and electron density analysis indicated the existence of several hydrogen bonds. Further investigation through the Natural Bond Orbital (NBO) and Natural Energy Decomposition Analysis (NEDA) calculations provided insight into the origin of interactions in the [Emim]{sup +}[TCB]{sup -} ion pair. Strength of molecular interactions in the ionic liquid was correlated with frequency shifts of the characteristic vibrations of the ion pair. Harmonic vibrations of the ion pair were also compared with the experimental Raman and Infrared spectra. Vibrational frequencies were assigned by visualizing displacements of atoms around their equilibrium positions and through Potential Energy Distribution (PED) analysis.

  15. Tuning of cross-linking and mechanical properties of laser-deposited poly (methyl methacrylate) films

    SciTech Connect (OSTI)

    Sueske, Erik; Scharf, Thorsten; Krebs, Hans-Ulrich; Panchenko, Elena; Junkers, Thomas; Egorov, Mark; Buback, Michael; Kijewski, Harald

    2005-03-15

    The chemical composition, amount of cross-linking and its influence on the mechanical properties of poly(methyl methacrylate) (PMMA) thin films produced by pulsed laser deposition (PLD) at a wavelength of 248 nm under ultrahigh vacuum were investigated by infrared spectroscopy, scanning electron microscopy, size-exclusion chromatography, thermogravimetric analysis, and nanoindentation experiments. The films consist of two components, one fraction with a molecular weight well below that of the target material and a second fraction, which is cross-linked. Compared to bulk material, the Young's modulus of the film is increased. The amount of cross-linking in the film can be tuned by the applied laser fluence leading to changes of the mechanical properties.

  16. Methyl Chloride from Direct Methane Partial Oxidation: A High-Temperature Shilov-Like Catalytic System

    SciTech Connect (OSTI)

    Yongchun Tang; John Ma

    2012-03-23

    The intention of this study is to demonstrate and evaluate the scientific and economic feasibility of using special solvents to improve the thermal stability of Pt-catalyst in the Shilov system, such that a high reaction temperature could be achieved. The higher conversion rate (near 100%) of methyl chloride from partial oxidation of methane under the high temperature ({approx} 200 C) without significant Pt0 precipitation has been achieved. High concentration of the Cl- ion has been identified as the key for the stabilization of the Pt-catalysts. H/D exchange measurements indicated that the over oxidation will occur at the elevated temperature, developments of the effective product separation processes will be necessary in order to rationalize the industry-visible CH4 to CH3Cl conversion.

  17. Investigation of methyl decanoate combustion in an optical direct-injection diesel engine

    SciTech Connect (OSTI)

    Cheng, A. S.; Dumitrescu, Cosmin E.; Mueller, Charles J.

    2014-11-24

    In this study, an optically accessible heavy-duty diesel engine was used to investigate the impact of methyl decanoate (MD) on combustion and emissions. A specific goal of the study was to determine if MD could enable soot-free leaner-lifted flame combustion (LLFC) – a mode of mixing-controlled combustion associated with fuel-air equivalence ratios below approximately two. An ultra-low sulfur diesel certification fuel (CF) was used as the baseline fuel, and experiments were conducted at two fuel-injection pressures with three levels of charge-gas dilution. In addition to conventional pressure-based and engine-out emissions measurements, exhaust laser-induced incandescence, in-cylinder natural luminosity (NL), and in-cylinder chemiluminescence (CL) diagnostics were used to provide detailed insight into combustion processes.

  18. Mesoscale simulation of shocked poly-(4-methyl-1-pentene) (PMP) foams.

    SciTech Connect (OSTI)

    Schroen, Diana Grace; Flicker, Dawn G.; Haill, Thomas A.; Root, Seth; Mattsson, Thomas Kjell Rene

    2011-06-01

    Hydrocarbon foams are commonly used in HEDP experiments, and are subject to shock compression from tens to hundreds of GPa. Modeling foams is challenging due to the heterogeneous character of the foam. A quantitative understanding of foams under strong dynamic compression is sought. We use Sandia's ALEGRA-MHD code to simulate 3D mesoscale models of pure poly(4-methyl-1-petene) (PMP) foams. We employ two models of the initial polymer-void structure of the foam and analyze the statistical properties of the initial and shocked states. We compare the simulations to multi-Mbar shock experiments at various initial foam densities and flyer impact velocities. Scatter in the experimental data may be a consequence of the initial foam inhomogeneity. We compare the statistical properties the simulations with the scatter in the experimental data.

  19. Interfacial hydrothermal synthesis of SnO{sub 2} nanorods towards photocatalytic degradation of methyl orange

    SciTech Connect (OSTI)

    Hou, L.R. Lian, L.; Zhou, L.; Zhang, L.H.; Yuan, C.Z.

    2014-12-15

    Highlights: Efficient interfacial hydrothermal strategy was developed. 1D SnO{sub 2} nanorods as an advanced photocatalyst. SnO{sub 2} nanorods exhibit photocatalytic degradation of the MO. - Abstract: One-dimensional (1D) SnO{sub 2} nanorods (NRs) have been successfully synthesized by means of an efficient interfacial hydrothermal strategy. The resulting product was physically characterized by X-ray powder diffraction, scanning electron microscopy, transmission electron microscope, etc. The as-fabricated SnO{sub 2} NRs exhibited excellent photocatalytic degradation of the methyl orange with high degradation efficiency of 99.3% with only 60 min ultra violet light irradiation. Meanwhile, the 1D SnO{sub 2} NRs exhibited intriguing photostability after four recycles.

  20. Homogeneous Hydrogenation of CO? to Methyl Formate Utilizing Switchable Ionic Liquids

    SciTech Connect (OSTI)

    Yadav, Mahendra; Linehan, John C.; Karkamkar, Abhijeet J.; Van Der Eide, Edwin F.; Heldebrant, David J.

    2014-09-15

    Capture of CO? and subsequent hydrogenation allows for base/alcohol-catalyzed conversion of CO? to methylformate in one pot. The conversion of CO? proceeds via alkylcarbonates, to formate salts and then formate esters, which can be catalyzed by base and alcohol with the only byproduct being water. The system operates at mild conditions (300 psi H?, 140 C). Reactivity is strongly influenced by temperature and choice of solvent. In the presence of excess of base (DBU) formate is predominant product while in excess of methanol methyl formate is major product. 110 C yields formate salts, 140 C promotes methylformate. The authors acknowledge internal Laboratory Directed Re-search and Development (LDRD) funding from Pacific Northwest National Laboratory (PNNL). PNNL is operated by Battelle for the U.S. Department of Energy.

  1. Generation kinetics of color centers in irradiated poly(4-methyl-1-pentene)

    SciTech Connect (OSTI)

    Peng, J. S.; Li, C. L.; Lee, Sanboh; Chou, K. F.

    2011-09-15

    The transient absorbance of poly(4-methyl-1-pentene) (PMP) irradiated with gamma rays at elevated temperatures has been investigated. The absorbance in the ultraviolet and visible range increases with gamma ray dose. A bathochromic shift in transmission spectra emerges significantly upon irradiation. A first-order generation model is proposed to analyze the kinetics of color centers during annealing. The activation energy of the color center increases with increasing gamma ray dose. The equilibrium behavior of color centers in PMP is similar to that of vacancies in metals, and the formation energy of color centers in PMP decreases with increasing gamma ray dose. However, annealable color centers are not observed in this study.

  2. Direct observation of localized radial oxygen migration in functioning tantalum oxide memristors

    DOE PAGES-Beta [OSTI]

    Kumar, Suhas; Graves, Catherine E.; Strachan, John Paul; Grafals, Emmanuelle Merced; Arthur L. David Kilcoyne; Tyliszczak, Tolek; Weker, Johanna Nelson; Nishi, Yoshio; Williams, R. Stanley

    2016-02-02

    Oxygen migration in tantalum oxide, a promising next-generation storage material, is studied using in operando x-ray absorption spectromicroscopy and is used to microphysically describe accelerated evolution of conduction channel and device failure. Furthermore, the resulting ring-like patterns of oxygen concentration are modeled using thermophoretic forces and Fick diffusion, establishing the critical role of temperature-activated oxygen migration that has been under question lately.

  3. Oxygen's promise for groundwater cleanup a step closer with SRNL research

    Office of Scientific and Technical Information (OSTI)

    | OSTI, US Dept of Energy Office of Scientific and Technical Information Oxygen's promise for groundwater cleanup a step closer with SRNL research Back to the OSTI News Listing for 2008 Dr. Brian Looney Senior Advisory Engineer SRNL Savannah River National Laboratory researchers Brian Looney and Miles Denham have patented an invention for allowing permeation of a subsurface area with the right quantity of oxygen for effective groundwater remediation. Oxygen has long held promise as a means

  4. Blast furnace injection of massive quantities of coal with enriched air or pure oxygen

    SciTech Connect (OSTI)

    Ponghis, N.; Dufresne, P.; Vidal, R.; Poos, A. )

    1993-01-01

    An extensive study of the phenomena associated with the blast furnace injection of massive quantities of coal is described. Trials with conventional lances or oxy-coal injectors and hot blast at different oxygen contents - up to 40% - or with cold pure oxygen were realized at coal to oxygen ratios corresponding to a range of 150 to 440 kg. Pilot scale rigs, empty or filled with coke, as well as industrial blast furnaces were utilized.

  5. Lattice distortions and oxygen vacancies produced in Au+ irradiated nano-crystalline cubic zirconia

    SciTech Connect (OSTI)

    Edmondson, Philip D; Weber, William J; Namavar, Fereydoon; Zhang, Yanwen

    2011-01-01

    The structural impact of oxygen vacancies in nanocrystalline cubic zirconia is investigated. A non-equilibrium number of oxygen vacancies in introduced to the lattice by ion irradiation. The lattice is observed to be initially compressed, undergoes a relaxation at 0.7 displacements per atom (dpa), and experiences a contraction before reaching a temperature dependent steady state value at above 7 dpa. The level of lattice distortion is related to the charge state of the accumulating oxygen vacancies.

  6. Effect of cation ordering on oxygen vacancy diffusion pathways in double

    Office of Scientific and Technical Information (OSTI)

    perovskites (Journal Article) | DOE PAGES Effect of cation ordering on oxygen vacancy diffusion pathways in double perovskites Title: Effect of cation ordering on oxygen vacancy diffusion pathways in double perovskites Perovskite structured oxides (ABO3) are attractive for a number of technological applications, including as superionics because of the high oxygen conductivities they exhibit. Double perovskites (AA'BB'O6) provide even more flexibility for tailoring properties. Using

  7. Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO3 Perovskites

    Office of Scientific and Technical Information (OSTI)

    (Journal Article) | SciTech Connect Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO3 Perovskites Citation Details In-Document Search Title: Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO3 Perovskites Strain is known to greatly influence low temperature oxygen electro catalysis on noble metal films, leading to significant enhancements in bifunctional activity essential for fuel cells and Metal-air batteries. However, its catalytic impact on transition-metal oxide thin

  8. Reactions of methyl groups on a non-reducible metal oxide: The reaction of iodomethane on stoichiometric ?-Cr2O3(0001)

    SciTech Connect (OSTI)

    Dong, Yujung; Brooks, John D.; Chen, Tsung-Liang; Mullins, David R.; Cox, David F.

    2015-06-10

    The reaction of iodomethane on the nearly stoichiometric ?-Cr2O3(0001) surface produces gas phase ethylene, methane, and surface iodine adatoms. The reaction is first initiated by the dissociation of iodomethane into surface methyl fragments, -CH3, and iodine adatoms. Methyl fragments bound at surface Cr cation sites undergo a rate-limiting dehydrogenation reaction to methylene, =CH2. The methylene intermediates formed from methyl dehydrogenation can then undergo coupling reactions to produce ethylene via two principle reaction pathways: (1) direct coupling of methylene and (2) methylene insertion into the methyl surface bond to form surface ethyl groups which undergo ?-H elimination to produce ethylene. The liberated hydrogen also combines with methyl groups to form methane. Iodine adatoms from the dissociation of iodomethane deactivate the surface by simple site blocking of the surface Cr3+ cations.

  9. Reactions of methyl groups on a non-reducible metal oxide: The reaction of iodomethane on stoichiometric α-Cr2O3(0001)

    DOE PAGES-Beta [OSTI]

    Dong, Yujung; Brooks, John D.; Chen, Tsung-Liang; Mullins, David R.; Cox, David F.

    2015-06-10

    The reaction of iodomethane on the nearly stoichiometric α-Cr2O3(0001) surface produces gas phase ethylene, methane, and surface iodine adatoms. The reaction is first initiated by the dissociation of iodomethane into surface methyl fragments, -CH3, and iodine adatoms. Methyl fragments bound at surface Cr cation sites undergo a rate-limiting dehydrogenation reaction to methylene, =CH2. The methylene intermediates formed from methyl dehydrogenation can then undergo coupling reactions to produce ethylene via two principle reaction pathways: (1) direct coupling of methylene and (2) methylene insertion into the methyl surface bond to form surface ethyl groups which undergo β-H elimination to produce ethylene. Themore » liberated hydrogen also combines with methyl groups to form methane. Iodine adatoms from the dissociation of iodomethane deactivate the surface by simple site blocking of the surface Cr3+ cations.« less

  10. Enantioselective hydrogenation. III. Methyl pyruvate hydrogenation catalyzed by alkaloid-modified iridium

    SciTech Connect (OSTI)

    Simons, K.E.; Johnston, P.; Plum, H.; Wells, P.B.; Ibbotson, A.

    1994-12-01

    Enantioselective hydrogenation of methyl pyruvate, MeCOCOOMe to methyl lactate, MeCH(OH)COOMe, is catalyzed in solution at room temperature by supported iridium catalysts modified with cinchona alkaloids. Modification with cinchonidine or quinine yields R-lactate in excess, whereas modification with cinchonine or quinidine favors S-lactate formation. Ir/SiO{sub 2} catalysts (20%) calcined at 393 to 573 K and reduced at 523 to 593 K were highly active for racemic hydrogenation in the absence of a modifier (rates typically 1.8 mol h{sup -1} g{sub cat}{sup -1}) and were comparably active when modified with cinchonidine but gave an enantiomeric excess of about 30%. Use of higher calcination or reduction temperatures led to substantially inferior activity and selectivity. The high rates recorded for both racemic and enantioselective reactions are dependent on the catalysts being activated before use by a procedure involving exposure of the catalyst to air after the initial reduction. Use of a Cl-free precursor gave an Ir/SiO{sub 2} catalyst (20%) of superior activity but inferior enantioselectivity. Ir/CaCO{sub 3} (5%) was more active for racemic hydrogenation than for enantioselective hydrogenation, but provided the highest value of the enantiomeric excess 39%. Kinematics of reaction are reported. Exchange of H for D in 10,11-dihydrocinchonidine at room temperature over Ir/CaCO{sub 3} occurred in the quinoline moiety but not in the quinuclidine ring system, indicating that the alkaloid was adsorbed to the Ir surface via the interaction of its {pi}-electron system. For both silica-supported and calcium carbonate-supported Ir, the presence of chloride ion in the catalyst was advantageous for the achievement of enantioselectivity. 25 refs., 2 figs., 3 tabs.

  11. Noncovalently-functionalized reduced graphene oxide sheets by water-soluble methyl green for supercapacitor application

    SciTech Connect (OSTI)

    Ren, Xiaoying; Hu, Zhongai Hu, Haixiong; Qiang, Ruibin; Li, Li; Li, Zhimin; Yang, Yuying; Zhang, Ziyu; Wu, Hongying

    2015-10-15

    Graphical abstract: Electroactive methyl green (MG) is selected to functionalize reduced graphene oxide (RGO) through non-covalent modification and the composite achieves high specific capacitance, good rate capability and excellent long life cycle. - Highlights: • MG–RGO composites were firstly prepared through non-covalent modification. • The mass ratio in composites is a key for achieving high specific capacitance. • MG–RGO 5:4 exhibits the highest specific capacitance of 341 F g{sup −1}. • MG–RGO 5:4 shows excellent rate capability and long life cycle. - Abstract: In the present work, water-soluble electroactive methyl green (MG) has been used to non-covalently functionalize reduced graphene oxide (RGO) for enhancing supercapacitive performance. The microstructure, composition and morphology of MG–RGO composites are systematically characterized by UV–vis absorption, field emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and X-ray diffraction (XRD). The electrochemical performances are investigated by cyclic voltammetry (CV), galvanostatic charge/discharge and electrochemical impedance spectroscopy (EIS). The fast redox reactions from MG could generate additional pseudocapacitance, which endows RGO higher capacitances. As a result, the MG–RGO composite (with the 5:4 mass ratio of MG:RGO) achieve a maximum value of 341 F g{sup −1} at 1 A g{sup −1} within the potential range from −0.25 to 0.75 V and provide a 180% enhancement in specific capacitance in comparison with pure RGO. Furthermore, excellent rate capability (72% capacitance retention from 1 A g{sup −1} to 20 A g{sup −1}) and long life cycle (12% capacitance decay after 5000 cycles) are achieved for the MG–RGO composite electrode.

  12. Insights antifibrotic mechanism of methyl palmitate: Impact on nuclear factor kappa B and proinflammatory cytokines

    SciTech Connect (OSTI)

    Mantawy, Eman M.; Tadros, Mariane G.; Awad, Azza S.; Hassan, Dina A.A.; El-Demerdash, Ebtehal

    2012-01-01

    Fibrosis accompanies most chronic liver disorders and is a major factor contributing to hepatic failure. Therefore, the need for an effective treatment is evident. The present study was designed to assess the potential antifibrotic effect of MP and whether MP can attenuate the severity of oxidative stress and inflammatory response in chronic liver injury. Male albino rats were treated with either CCl{sub 4} (1 ml/kg, twice a week) and/or MP (300 mg/kg, three times a week) for six weeks. CCl{sub 4}-intoxication significantly increased liver weight, serum aminotransferases, total cholesterol and triglycerides while decreased albumin level and these effects were prevented by co-treatment with MP. As indicators of oxidative stress, CCl{sub 4}-intoxication caused significant glutathione depletion and lipid peroxidation while MP co-treatment preserved them within normal values. As markers of fibrosis, hydroxyproline content and ?-SMA expression increased markedly in the CCl{sub 4} group and MP prevented these alterations. Histopathological examination by both light and electron microscope further confirmed the protective efficacy of MP. To elucidate the antifibrotic mechanisms of MP, the expression of NF-?B, iNOS and COX-2 and the tissue levels of TNF-? and nitric oxide were assessed; CCl{sub 4} increased the expression of NF-?B and all downstream inflammatory cascade while MP co-treatment inhibited them. Collectively these findings indicate that MP possesses a potent antifibrotic effect which may be partly a consequence of its antioxidant and anti-inflammatory properties. -- Highlights: ? Methyl palmitate is free fatty acid methyl ester. ? It possesses a strong antifibrotic effect. ? It inhibits NF-?B and the consequent proinflammatory and oxidative stress response.

  13. Factors controlling reservoir quality in tertiary sandstones and their significance to geopressured geothermal production. Annual report, May 1, 1979-May 31, 1980

    SciTech Connect (OSTI)

    Loucks, R.G.; Richmann, D.L.; Milliken, K.L.

    1980-07-01

    Differing extents of diagenetic modification is the factor primarily responsible for contrasting regional reservoir quality of Tertiary sandstones from the Upper and Lower Texas Gulf Coast. Detailed comparison of Frio sandstones from the Chocolate Bayou/Danbury Dome area, Brazoria County, and Vicksburg sandstones from the McAllen Ranch Field area, Hidalgo County, reveals that extent of diagenetic modification is most strongly influenced by (1) detrital mineralogy and (2) regional geothermal gradients. Vicksburg sandstones from the McAllen Ranch Field area are less stable, chemically and mechanically, than Frio sandstones from the Chocolate Bayou/Danbury dome area. Vicksburg sandstones are mineralogically immature and contain greater proportions of feldspars and rock fragments than do Frio sandstones. Thr reactive detrital assemblage of Vicksubrg sandstones is highly susceptible to diagenetic modification. Susceptibility is enhanced by higher than normal geothermal gradients in the McAllen Ranch Field area. Thus, consolidation of Vicksburg sandstones began at shallower depth of burial and precipitation of authigenic phases (especially calcite) was more pervasive than in Frio sandstones. Moreover, the late-stage episode of ferroan calcite precipitation that occluded most secondary porosity in Vicksburg sandstones did not occur significantly in Frio sandstones. Therefore, regional reservoir quality of Frio sandstones from Brazoria County is far better than that characterizing Vicksburg sandstones from Hidalgo County, especially at depths suitable for geopressured geothermal energy production.

  14. Assessment of thermal evolution stages and oil-gas migration of carbonate source rocks of early tertiary in eastern Sichuan, China, by organic inclusion analysis

    SciTech Connect (OSTI)

    Shi Jixi; Li Benchao; Fu Jiamo

    1989-03-01

    The Jialinjiang Formation of early Tertiary in Sichuan, China, is a series of limestone and dolomite sediments deposited in a platform shoal environment. The diagenetic sequence and organic inclusions trapped in minerals of 95 samples from 20 drillings have been studied. At the late diagenetic stage, pale yellow organic inclusions consisted of liquid hydrocarbons disseminated in pore-infiltrating dolomite, and the homogeneous temperature of contemporaneous saline liquid inclusions possessing a low gas-liquid ratio was 86/degree/C. This indicates the evolution of the organic matter had gone over the oil generating threshold and oil formation had initiated. In the limestone formed at the late diagenetic stage, more brown-yellow organic inclusions were scattered and/or developed along with fissures, comprising 60-70% liquid hydrocarbons and 30-40% gaseous hydrocarbons. Contemporaneous saline liquid inclusions with gas-liquid ratios of 5-10% had homogeneous temperatures of 90/degree/-130/degree/C. These findings show that the organic material had entered a high evolution stage and oil migration had taken place on a large scale.

  15. NMR Analysis of Methyl Groups at 100-500 kDa: Model Systems and Arp2/3 Complex

    SciTech Connect (OSTI)

    Kreishman-Deitrick, Mara; Egile, Coumaran; Hoyt, David W.; Ford, Joseph J.; Rong, Li; Rosen, Michael K.

    2003-07-01

    Large macromolecular machines are among the most important and challenging targets for structural and mechanistic analyses. Consequently, there is great interest in development of NMR methods for the study of multicomponent systems in the 50-500 kDa range. Biochemical methods also must be developed in concert to produce such systems in selectively labeled form. Here, we present 1H/13C-HSQC spectra of protonated methyl groups in a model system that mimics molecular weights up to ~560 kDa. Signals from side chain methyl groups of Ile, Leu, and Val residues are clearly detectable at correlation times up to ~330 ns. We have also developed a biochemical procedure to produce the 240 kDa, heteroheptameric Arp2/3 actin nucleation complex selectively labeled at one subunit and obtained 1H/13C-HSQC spectra of this assembly. Sensitivity in spectra of both the Arp2/3 complex and the model system indicate that methyl groups will be useful sources of information in nonsymmetric systems with molecular weights greater than 600 kDa at concentrations less than 100 μM. Methyl analyses will complement TROSY and CRINEPT analyses of amides in NMR studies of structure and molecular interactions of extremely large macromolecules and assemblies.

  16. Determination of Total Lipids as Fatty Acid Methyl Esters (FAME) by in situ Transesterification: Laboratory Analytical Procedure (LAP)

    SciTech Connect (OSTI)

    Van Wychen, S.; Laurens, L. M. L.

    2013-12-01

    This procedure is based on a whole biomass transesterification of lipids to fatty acid methyl esters to represent an accurate reflection of the potential of microalgal biofuels. Lipids are present in many forms and play various roles within an algal cell, from cell membrane phospholipids to energy stored as triacylglycerols.

  17. Surface oxygen micropatterns on glow discharge polymer targets by photo irradiation

    DOE PAGES-Beta [OSTI]

    Reynolds, Hannah; Baxamusa, Salmaan; Haan, Steven W.; Fitzsimmons, Paul; Carlson, Lane; Farrell, Mike; Nikroo, Abbas; Watson, Brian J.

    2016-02-24

    Recent simulations predict surface oxygen may be a significant source of disruptive perturbations in the implosion process of glow-discharge polymers (GDP) ablators at the National Ignition Facility. GDP material held in ambient atmospheric conditions showed an increase in mass when stored in light transparent containers, which suggests that photo exposure is a driving force for oxygen absorption. To investigate if surface oxygen is a contributing factor of disruptive perturbations during implosion, we developed a method to imprint a periodic micropattern of oxygen on the surface of GDP and used it to fabricate a flat sample for empirical testing.

  18. First-Principle Investigation of Oxygen Defects in Metal/Oxide...

    U.S. Department of Energy (DOE) all webpages (Extended Search)

    First-Principle Investigation of Oxygen Defects in MetalOxideMetal Heterostructures: Structure, Energetics, and Transport in the Quantum Regime PI Name: Olle Heinonen PI Email: ...

  19. Cold-Start and Warm-Up Driveability Performance of Hybrid Electric Vehicles Using Oxygenated Fuels

    SciTech Connect (OSTI)

    Thornton, M.; Jorgensen, S.; Evans, B.; Wright, K.

    2003-11-01

    Provides analysis and results of the driveability performance testing from four hybrid electric vehicles--Honda Civic, Toyota Prius, and two Honda Insights--that used oxygenated fuels.

  20. Enhanced Bifunctional Oxygen Catalysis in Strained LaNiO3 Perovskites...

    Office of Scientific and Technical Information (OSTI)

    low temperature oxygen electro catalysis on noble metal films, leading to significant enhancements in bifunctional activity essential for fuel cells and Metal-air batteries. ...

  1. Growth control of oxygen stoichiometry in homoepitaxial SrTiO3...

    Office of Scientific and Technical Information (OSTI)

    Citation Details In-Document Search Title: Growth control of oxygen ... Type: Accepted Manuscript Journal Name: Scientific Reports Additional Journal Information: ...

  2. Low oxygen biomass-derived pyrolysis oils and methods for producing the same

    DOE Patents [OSTI]

    Marinangeli, Richard; Brandvold, Timothy A; Kocal, Joseph A

    2013-08-27

    Low oxygen biomass-derived pyrolysis oils and methods for producing them from carbonaceous biomass feedstock are provided. The carbonaceous biomass feedstock is pyrolyzed in the presence of a catalyst comprising base metal-based catalysts, noble metal-based catalysts, treated zeolitic catalysts, or combinations thereof to produce pyrolysis gases. During pyrolysis, the catalyst catalyzes a deoxygenation reaction whereby at least a portion of the oxygenated hydrocarbons in the pyrolysis gases are converted into hydrocarbons. The oxygen is removed as carbon oxides and water. A condensable portion (the vapors) of the pyrolysis gases is condensed to low oxygen biomass-derived pyrolysis oil.

  3. Task Technical Plan for Studies of Oxygen Consumption in the Catalyzed Hydrolysis of Tetraphenylborate Ion

    SciTech Connect (OSTI)

    Fink, S.D.

    1996-12-20

    This document presents the plan for studies of how dissolved oxygen affects the catalytic decomposition of the tetraphenylborate ion in alkaline aqueous solution.

  4. Computer Simulation of Defects and Oxygen Transport in Yttria-Stabilized Zirconia

    SciTech Connect (OSTI)

    Devanathan, Ram; Weber, William J.; Singhal, Subhash C.; Gale, Julian D.

    2006-06-15

    We have used molecular dynamics simulations and energy minimization calculations to examine defect energetics and oxygen diffusion in yttria-stabilized zirconia (YSZ). Oxygen vacancies prefer to be second nearest neighbors to yttrium dopants. The oxygen diffusion coefficient shows a peak at 8 mole % yttria consistent with experimental findings. The activation energy for oxygen diffusion varies from 0.6 to 1.0 eV depending on the yttria content. The Y-Vo-Y complex with a binding energy of -0.85 eV may play an important role in any conductivity degradation of YSZ.

  5. Oxygen-resistant hydrogenases and methods for designing and making same

    DOE Patents [OSTI]

    King, Paul; Ghirardi, Maria L; Seibert, Michael

    2009-03-10

    The invention provides oxygen- resistant iron-hydrogenases ([Fe]-hydrogenases) for use in the production of H2. Methods used in the design and engineering of the oxygen-resistant [Fe]-hydrogenases are disclosed, as are the methods of transforming and culturing appropriate host cells with the oxygen-resistant [Fe]-hydrogenases. Finally, the invention provides methods for utilizing the transformed, oxygen insensitive, host cells in the bulk production of H.sub.2 in a light catalyzed reaction having water as the reactant.

  6. Oxygen-resistant hydrogenases and methods for designing and making same

    DOE Patents [OSTI]

    King, Paul; Ghirardi, Maria Lucia; Seibert, Michael

    2014-03-04

    The invention provides oxygen-resistant iron-hydrogenases ([Fe]-hydrogenases) for use in the production of H.sub.2. Methods used in the design and engineering of the oxygen-resistant [Fe]-hydrogenases are disclosed, as are the methods of transforming and culturing appropriate host cells with the oxygen-resistant [Fe]-hydrogenases. Finally, the invention provides methods for utilizing the transformed, oxygen insensitive, host cells in the bulk production of H.sub.2 in a light catalyzed reaction having water as the reactant.

  7. Resistance-Based Ceramic Ho123 Ionic Conductor for Oxygen Gas...

    Office of Scientific and Technical Information (OSTI)

    The rod showed stable sensing characteristics with good electrical stability and reproducibility with higher sensitivity at low oxygen partial pressure. The sensing property is ...

  8. Nitrogen Oxides as a Chemistry Trap in Detonating Oxygen-Rich...

    Office of Scientific and Technical Information (OSTI)

    Conference: Nitrogen Oxides as a Chemistry Trap in Detonating Oxygen-Rich Materials Citation Details In-Document Search Title: Nitrogen Oxides as a Chemistry Trap in Detonating ...

  9. Miniature, Inexpensive, Amperometric Oxygen Sensor: Inventions and Innovation Sensors and Controls Project Fact Sheet

    SciTech Connect (OSTI)

    Wogsland, J.

    2001-01-25

    Project fact sheet written for the Inventions and Innovation Program about a new miniature oxygen sensor that costs less that conventional sensors.

  10. Anomalous expansion of the copper-apical-oxygen distance in supercondu...

    Office of Scientific and Technical Information (OSTI)

    Anomalous expansion of the copper-apical-oxygen distance in superconducting cuprate bilayers Citation Details In-Document Search Title: Anomalous expansion of the copper-apical-oxy...

  11. Webinar: Testing Oxygen Reduction Reaction Activity with the Rotating Disc Electrode Technique

    Energy.gov [DOE]

    Video recording of the Fuel Cell Technologies Office webinar, Testing Oxygen Reduction Reaction Activity with the Rotating Disc Electrode Technique, originally presented on March 12, 2013.

  12. Covalency in Metal-Oxygen Multiple Bonds Evaluated Using Oxygen K-edge Spectroscopy and Electronic Structure Theory

    SciTech Connect (OSTI)

    Minasian, Stefan G.; Keith, Jason M.; Batista, Enrique R.; Boland, Kevin S.; Bradley, Joseph A.; Daly, Scott R.; Kozimor, Stosh A.; Lukens, Wayne W.; Martin, Richard L.; Nordlund, Dennis; Seidler, Gerald T.; Shuh, David K.; Sokaras, Dimosthenis; Tyliszczak, Tolek; Wagner, Gregory L.; Weng, Tsu-Chein; Yang, Ping

    2014-01-01

    Advancing theories of how metal oxygen bonding influences metal oxo properties can expose new avenues for innovation in materials science, catalysis, and biochemistry. Historically, spectroscopic analyses of the transition metal peroxyanions, MO4x-, have formed the basis for new M O bonding theories. Herein, relative changes in M O orbital mixing in MO42- (M = Cr, Mo, W) and MO41- (M = Mn, Tc, Re) are evaluated for the first time by non-resonant inelastic X-ray scattering, X-ray absorption spectroscopy using fluorescence and transmission (via a scanning transmission X-ray microscope), and linear-response density functional theory. The results suggest that moving from Group 6 to Group 7 or down the triads increases M O e () mixing. Meanwhile, t2 mixing ( + ) remains relatively constant within the same Group. These unexpected changes in frontier orbital energy and composition are evaluated in terms of periodic trends in d orbital energy and radial extension.

  13. Synthesis of oxygenate products for high volume fuels applications. Quarterly status report No. 3 for the period April through June 1995

    SciTech Connect (OSTI)

    Not Available

    1995-09-26

    A rudimentary process variables study of the reaction of acetylene with methanol indicates high activity for the formation of ethanol, n- propanol, and i-butanol with a pure low temperature activated MgO catalyst. Initial results indicate that higher conversions and space- time yields may be obtainable by operation at higher temperatures and reactant feed rates, respectively. Also, ethanol formation was consistently observed to rise with decreasing reaction temperature between 454{degrees}C and 370{degrees}C. A 10% Al{sub 2}O{sub 3}/MgO catalyst exhibited high activity for methanol-dimethyl ether interconversion but was not very active for the condensation of these reactants to either the product alcohols or their methyl ethers. Neither catalyst exhibited significant activity for the condensation to dimethyl ether/water with acetylene to form such products. This lack of activity in the ether systems is attributed to insufficient hydrolysis of dimethyl ether to methanol, and it is expected that feeds containing additional water or methanol (which produces water via condensation) will exhibit higher activity. The aluminum- containing catalyst exhibited diminished condensation activity possibly as a result of deactivation of Mg sites by Al sites. The overall objective of this project is to develop catalyst and process technology for evaluation as potential routes for the production of high volume fuel oxygenates.

  14. Synthesis of oxygenate products for high volume fuels applications. Quarterly status report No. 4 for the period July through September 1995

    SciTech Connect (OSTI)

    Not Available

    1995-12-29

    A rudimentary process variables study of the reaction of acetylene with methanol indicates high activity for the formation of ethanol, n- propanol, and i-butanol with a pure low temperature activated MgO catalyst. Initial results indicate that higher conversions and space- time yields may be obtainable by operation at higher temperatures and reactant feed rates, respectively. Also, ethanol formation was consistently observed to rise with decreasing reaction temperature between 454{degrees}C and 370{degrees}C. A 10% Al{sub 2}O{sub 3}/MgO catalyst exhibited high activity for methanol-dimethyl ether interconversion but was not very active for the condensation of these reactants to either the product alcohols or their methyl ethers. Neither catalyst exhibited significant activity for the condensation of dimethyl ether/water with acetylene to form such products. This lack of activity in the ether systems us attributed to insufficient hydrolysis of dimethyl ether to methanol, and it is expected that feeds containing additional water or methanol (which produces water via condensation) will exhibit higher activity. The aluminum- containing catalyst exhibited diminished condensation activity possibly as the result of deactivation of Mg sites by Al sites. The overall objective of this project is to develop catalyst and process technology for evaluation as potential routes for the production of high volume fuel oxygenates.

  15. The combustion kinetics of coal chars in oxygen-enriched environments.

    SciTech Connect (OSTI)

    Shaddix, Christopher R.; Murphy, Jeffrey J.

    2004-09-01

    Oxygen-enhanced and oxygen-fired pulverized coal combustion is actively being investigated to achieve emission reductions and reductions in flue gas cleanup costs, as well as for coal-bed methane and enhanced oil recovery applications. To fully understand the results of pilot scale tests and to accurately predict scale-up performance through CFD modeling, accurate rate expressions are needed to describe coal char combustion under these unconventional combustion conditions. In the work reported here, the combustion rates of two pulverized coal chars have been measured in both conventional and oxygen-enriched atmospheres. A combustion-driven entrained flow reactor equipped with an optical particle-sizing pyrometry diagnostic and a rapid-quench sampling probe has been used for this investigation. Highvale subbituminous coal and a high-volatile eastern United States bituminous coal have been investigated, over oxygen concentrations ranging from 6 to 36 mol% and gas temperatures of 1320-1800 K. The results from these experiments demonstrate that pulverized coal char particles burn under increasing kinetic control in elevated oxygen environments, despite their higher burning rates in these environments. Empirical fits to the data have been successfully performed over the entire range of oxygen concentrations using a single-film oxidation model. Both a simple nth-order Arrhenius expression and an nth-order Langmuir-Hinshelwood kinetic equation provide good fits to the data. Local fits of the nth-order Arrhenius expression to the oxygen-enriched and oxygen-depleted data produce lower residuals in comparison to fits of the entire dataset. These fits demonstrate that the apparent reaction order varies from 0.1 under near-diffusion-limit oxygen-depleted conditions to 0.5 under oxygen-enriched conditions. Burnout predictions show good agreement with measurements. Predicted char particle temperatures tend to be low for combustion in oxygen-depleted environments.

  16. Oxygen isotope variability within Nautilus shell growth bands

    DOE PAGES-Beta [OSTI]

    Linzmeier, Benjamin J.; Kozdon, Reinhard; Peters, Shanan E.; Valley, John W.

    2016-04-21

    Nautilus is often used as an analogue for the ecology and behavior of extinct externally shelled cephalopods. Nautilus shell grows quickly, has internal growth banding, and is widely believed to precipitate aragonite in oxygen isotope equilibrium with seawater. Pieces of shell from a wild-caught Nautilus macromphalus from New Caledonia and from a Nautilus belauensis reared in an aquarium were cast in epoxy, polished, and then imaged. Growth bands were visible in the outer prismatic layer of both shells. The thicknesses of the bands are consistent with previously reported daily growth rates measured in aquarium reared individuals. In situ analysis ofmore » oxygen isotope ratios using secondary ion mass spectrometry (SIMS) with 10 μm beam-spot size reveals inter- and intra-band δ18O variation. In the wild-caught sample, a traverse crosscutting 45 growth bands yielded δ18O values ranging 2.5‰, from +0.9 to -1.6 ‰ (VPDB), a range that is larger than that observed in many serial sampling of entire shells by conventional methods. The maximum range within a single band (~32 μm) was 1.5‰, and 27 out of 41 bands had a range larger than instrumental precision (±2 SD = 0.6‰). The results from the wild individual suggest depth migration is recorded by the shell, but are not consistent with a simple sinusoidal, diurnal depth change pattern. In addition, to create the observed range of δ18O, however, this Nautilus must have traversed a temperature gradient of at least ~12°C, corresponding to approximately 400 m depth change. Isotopic variation was also measured in the aquarium-reared sample, but the pattern within and between bands likely reflects evaporative enrichment arising from a weekly cycle of refill and replacement of the aquarium water. Overall, this work suggests that depth migration behavior in ancient nektonic mollusks could be elucidated by SIMS analysis across individual growth bands.« less

  17. Comparative developmental toxicity of environmentally relevant oxygenated PAHs

    SciTech Connect (OSTI)

    Knecht, Andrea L.; Goodale, Britton C.; Truong, Lisa; Simonich, Michael T.; Swanson, Annika J.; Matzke, Melissa M.; Anderson, Kim A.; Waters, Katrina M.; Tanguay, Robert L.

    2013-09-01

    Oxygenated polycyclic aromatic hydrocarbons (OPAHs) are byproducts of combustion and photo-oxidation of parent PAHs. OPAHs are widely present in the environment and pose an unknown hazard to human health. The developing zebrafish was used to evaluate a structurally diverse set of 38 OPAHs for malformation induction, gene expression changes and mitochondrial function. Zebrafish embryos were exposed from 6 to 120 h post fertilization (hpf) to a dilution series of 38 different OPAHs and evaluated for 22 developmental endpoints. AHR activation was determined via CYP1A immunohistochemistry. Phenanthrenequinone (9,10-PHEQ), 1,9-benz-10-anthrone (BEZO), xanthone (XAN), benz(a)anthracene-7,12-dione (7,12-B[a]AQ), and 9,10-anthraquinone (9,10-ANTQ) were evaluated for transcriptional responses at 48 hpf, prior to the onset of malformations. qRT-PCR was conducted for a number of oxidative stress genes, including the glutathione transferase(gst), glutathione peroxidase(gpx), and superoxide dismutase(sod) families. Bioenergetics was assayed to measure in vivo oxidative stress and mitochondrial function in 26 hpf embryos exposed to OPAHs. Hierarchical clustering of the structure-activity outcomes indicated that the most toxic of the OPAHs contained adjacent diones on 6-carbon moieties or terminal, para-diones on multi-ring structures. 5-carbon moieties with adjacent diones were among the least toxic OPAHs while the toxicity of multi-ring structures with more centralized para-diones varied considerably. 9,10-PHEQ, BEZO, 7,12-B[a]AQ, and XAN exposures increased expression of several oxidative stress related genes and decreased oxygen consumption rate (OCR), a measurement of mitochondrial respiration. Comprehensive in vivo characterization of 38 structurally diverse OPAHs indicated differential AHR dependency and a prominent role for oxidative stress in the toxicity mechanisms. - Highlights: • OPAHs are byproducts of combustion present in the environment. • OPAHs pose a largely

  18. The effect of plutonium dioxide water surface coverage on the generation of hydrogen and oxygen

    SciTech Connect (OSTI)

    Veirs, Douglas K.; Berg, John M.; Crowder, Mark L.

    2012-06-20

    The conditions for the production of oxygen during radiolysis of water adsorbed onto plutonium dioxide powder are discussed. Studies in the literature investigating the radiolysis of water show that both oxygen and hydrogen can be generated from water adsorbed on high-purity plutonium dioxide powder. These studies indicate that there is a threshold in the amount of water below which oxygen is not generated. The threshold is associated with the number of monolayers of adsorbed water and is shown to occur at approximately two monolayers of molecularly adsorbed water. Material in equilibrium with 50% relative humidity (RH) will be at the threshold for oxygen generation. Using two monolayers of molecularly adsorbed water as the threshold for oxygen production, the total pressure under various conditions is calculated assuming stoichiometric production of hydrogen and oxygen. The specific surface area of the oxide has a strong effect on the final partial pressure. The specific surface areas resulting in the highest pressures within a 3013 container are evaluated. The potential for oxygen generation is mitigated by reduced relative humidity, and hence moisture adsorption, at the oxide surface which occurs if the oxide is warmer than the ambient air. The potential for oxygen generation approaches zero as the temperature difference between the ambient air and the material approaches 6 C.

  19. Low energy consumption method for separating gaseous mixtures and in particular for medium purity oxygen production

    DOE Patents [OSTI]

    Jujasz, Albert J.; Burkhart, James A.; Greenberg, Ralph

    1988-01-01

    A method for the separation of gaseous mixtures such as air and for producing medium purity oxygen, comprising compressing the gaseous mixture in a first compressor to about 3.9-4.1 atmospheres pressure, passing said compressed gaseous mixture in heat exchange relationship with sub-ambient temperature gaseous nitrogen, dividing the cooled, pressurized gaseous mixture into first and second streams, introducing the first stream into the high pressure chamber of a double rectification column, separating the gaseous mixture in the rectification column into a liquid oxygen-enriched stream and a gaseous nitrogen stream and supplying the gaseous nitrogen stream for cooling the compressed gaseous mixture, removing the liquid oxygen-enriched stream from the low pressure chamber of the rectification column and pumping the liquid, oxygen-enriched steam to a predetermined pressure, cooling the second stream, condensing the cooled second stream and evaporating the oxygen-enriched stream in an evaporator-condenser, delivering the condensed second stream to the high pressure chamber of the rectification column, and heating the oxygen-enriched stream and blending the oxygen-enriched stream with a compressed blend-air stream to the desired oxygen concentration.

  20. Study of using oxygen-enriched combustion air for locomotive diesel engines

    SciTech Connect (OSTI)

    Poola, R.B.; Sekar, R.; Assanis, D.N.; Cataldi, G.R.

    1996-12-31

    A thermodynamic simulation is used to study the effects of oxygen-enriched intake air on the performance and nitrogen oxide (NO) emissions of a locomotive diesel engine. The parasitic power of the air separation membrane required to supply the oxygen-enriched air is also estimated. For a given constraint on peak cylinder pressure, the gross and net power output of an engine operating under different levels of oxygen enrichment are compared with those obtained when a high-boost turbocharged engine is used. A 4% increase in peak cylinder pressure can result in an increase in net engine power of approximately 13% when intake air with an oxygen content of 28% by volume is used and fuel injection timing is retarded by 4 degrees. When the engine is turbocharged to a higher inlet boost, the same increase in peak cylinder pressure can improve power by only 4%. If part of the significantly higher exhaust enthalpies available as a result of oxygen enrichment are recovered, the power requirements of the air separator membrane can be met, resulting in substantial net power improvements. Oxygen enrichment with its attendant higher combustion temperatures, reduces emissions of particulates and visible smoke but increases NO emissions (by up to three times at 26% oxygen content). Therefore, exhaust gas after-treatment and heat recovery would be required if the full potential of oxygen enrichment for improving the performance of locomotive diesel engines is to be realized.