National Library of Energy BETA

Sample records for aliphatic alco hol

  1. Process for producing peracids from aliphatic hydroxy carboxylic acids

    DOE Patents [OSTI]

    Chum, H.L.; Palasz, P.D.; Ratcliff, M.A.

    1984-12-20

    A process is described for producing peracids from lactic acid-containing solutions derived from biomass processing systems. It consists of adjusting the pH of the solution to about 8 to 9 and removing alkaline residue fractions therefrom to form a solution comprised substantially of lower aliphatic hydroxy acids. The solution is oxidized to produce volatile lower aliphatic aldehydes. The aldehydes are removed as they are generated and converted to peracids.

  2. Process for producing peracids from aliphatic hydroxy carboxylic acids

    DOE Patents [OSTI]

    Chum, Helena L.; Ratcliff, Matthew A.; Palasz, Peter D.

    1986-01-01

    A process for producing peracids from lactic acid-containing solutions derived from biomass processing systems comprising: adjusting the pH of the solution to about 8-9 and removing alkaline residue fractions therefrom to form a solution comprised substantially of lower aliphatic hydroxy acids; oxidizing the solution to produce volatile lower aliphatic aldehydes; removing said aldehydes as they are generated; and converting said aldehydes to peracids.

  3. Aerobic microorganism for the degradation of chlorinated aliphatic hydrocarbons

    DOE Patents [OSTI]

    Fliermans, Carl B.

    1989-01-01

    A chlorinated aliphatic hydrocarbon-degrading microorganism, having American Type Culture Collection accession numbers ATCC 53570 and 53571, in a biologically pure culture aseptically collected from a deep subsurface habitat and enhanced, mineralizes trichloroethylene and tetrachloroethylene to HCl, H.sub.2 O and Co.sub.2 under aerobic conditions stimulated by methane, acetate, methanol, tryptone-yeast extract, propane and propane-methane.

  4. Process for the synthesis of aliphatic alcohol-containing mixtures

    DOE Patents [OSTI]

    Greene, M.I.; Gelbein, A.P.

    1984-10-16

    A process for the synthesis of mixtures which include saturated aliphatic alcohols is disclosed. In the first step of the process, the first catalyst activation stage, a catalyst, which comprises the oxides of copper, zinc, aluminum, potassium and one or two additional metals selected from the group consisting of chromium, magnesium, cerium, cobalt, thorium and lanthanum, is partially activated. In this step, a reducing gas stream, which includes hydrogen and at least one inert gas, flows past the catalyst at a space velocity of up to 5,000 liters (STP) per hour, per kilogram of catalyst. The partially activated catalyst is then subjected to the second step of the process, second-stage catalyst activation. In this step, the catalyst is contacted by an activation gas stream comprising hydrogen and carbon monoxide present in a volume ratio of 0.5:1 and 4:1, respectively, at a temperature of 200 to 450 C and a pressure of between 35 and 200 atmospheres. The activation gas flows at a space velocity of from 1,000 to 20,000 liters (STP) per hour, per kilogram of catalyst. Second-stage activation continues until the catalyst is contacted with at least 500,000 liters (STP) of activation gas per kilogram of catalyst. The fully activated catalyst, in the third step of the process, contacts a synthesis gas stream comprising hydrogen and carbon monoxide.

  5. Process for the synthesis of aliphatic alcohol-containing mixtures

    DOE Patents [OSTI]

    Greene, Marvin I.; Gelbein, Abraham P.

    1984-01-01

    A process for the synthesis of mixtures which include saturated aliphatic alcohols is disclosed. In the first step of the process, the first catalyst activation stage, a catalyst, which comprises the oxides of copper, zinc, aluminum, potassium and one or two additional metals selected from the group consisting of chromium, magnesium, cerium, cobalt, thorium and lanthanum, is partially activated. In this step, a reducing gas stream, which includes hydrogen and at least one inert gas, flows past the catalyst at a space velocity of up to 5,000 liters (STP) per hour, per kilogram of catalyst. The partially activated catalyst is then subjected to the second step of the process, second-stage catalyst activation. In this step, the catalyst is contacted by an activation gas stream comprising hydrogen and carbon monoxide present in a volume ratio of 0.5:1 and 4:1, respectively, at a temperature of 200.degree. to 450.degree. C. and a pressure of between 35 and 200 atmospheres. The activation gas flows at a space velocity of from 1,000 to 20,000 liters (STP) per hour, per kilogram of catalyst. Second-stage activation continues until the catalyst is contacted with at least 500,000 liters (STP) of activation gas per kilogram of catalyst. The fully activated catalyst, in the third step of the process, contacts a synthesis gas stream comprising hydrogen and carbon monoxide.

  6. Shape memory polymers based on uniform aliphatic urethane networks

    SciTech Connect (OSTI)

    Wilson, T S; Bearinger, J P; Herberg, J L; Marion III, J E; Wright, W J; Evans, C L; Maitland, D J

    2007-01-19

    Aliphatic urethane polymers have been synthesized and characterized, using monomers with high molecular symmetry, in order to form amorphous networks with very uniform supermolecular structures which can be used as photo-thermally actuable shape memory polymers (SMPs). The monomers used include hexamethylene diisocyanate (HDI), trimethylhexamethylenediamine (TMHDI), N,N,N{prime},N{prime}-tetrakis(hydroxypropyl)ethylenediamine (HPED), triethanolamine (TEA), and 1,3-butanediol (BD). The new polymers were characterized by solvent extraction, NMR, XPS, UV/VIS, DSC, DMTA, and tensile testing. The resulting polymers were found to be single phase amorphous networks with very high gel fraction, excellent optical clarity, and extremely sharp single glass transitions in the range of 34 to 153 C. Thermomechanical testing of these materials confirms their excellent shape memory behavior, high recovery force, and low mechanical hysteresis (especially on multiple cycles), effectively behaving as ideal elastomers above T{sub g}. We believe these materials represent a new and potentially important class of SMPs, and should be especially useful in applications such as biomedical microdevices.

  7. Process for removing halogenated aliphatic and aromatic compounds from petroleum products

    DOE Patents [OSTI]

    Googin, John M.; Napier, John M.; Travaglini, Michael A.

    1983-01-01

    A process for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contacting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible compound, such as, water or a polyhydroxy compound, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of water or polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the water or polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds and the low polar or nonpolar solvent are separated by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered from recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced.

  8. Process for removing halogenated aliphatic and aromatic compounds from petroleum products

    DOE Patents [OSTI]

    Googin, J.M.; Napier, J.M.; Travaglini, M.A.

    1983-09-20

    A process is described for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contacting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible compound, such as, water or a polyhydroxy compound, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of water or polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the water or polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds and the low polar or nonpolar solvent are separated by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered from recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced. 1 fig.

  9. Gas phase heterogeneous catalytic oxidation of alkanes to aliphatic ketones and/or other oxygenates

    DOE Patents [OSTI]

    Lin, Manhua; Wang, Xiang; Yeom, Younghoon

    2015-03-17

    A catalyst, its method of preparation and its use for producing aliphatic ketones by subjecting alkanes C.sub.3 to C.sub.9 to a gas phase catalytic oxidation in the presence of air or oxygen, and, optionally, steam and/or one or more diluting gases. The catalyst comprises a catalytically active mixed metal oxide phase and a suitable support material onto and/or into which the active catalytic phase id dispersed.

  10. Gas phase heterogeneous catalytic oxidation of alkanes to aliphatic ketones and/or other oxygenates

    DOE Patents [OSTI]

    Lin, Manhua; Wang, Xiang; Yeom, Younghoon

    2015-09-29

    A catalyst, its method of preparation and its use for producing aliphatic ketones by subjecting alkanes C.sub.3 to C.sub.9 to a gas phase catalytic oxidation in the presence of air or oxygen, and, optionally, steam and/or one or more diluting gases. The catalyst comprises a catalytically active mixed metal oxide phase and a suitable support material onto and/or into which the active catalytic phase is dispersed.

  11. Process for removing halogenated aliphatic and aromatic compounds from petroleum products. [Polychlorinated biphenyls; methylene chloride; perchloroethylene; trichlorofluoroethane; trichloroethylene; chlorobenzene

    DOE Patents [OSTI]

    Googin, J.M.; Napier, J.M.; Travaglini, M.A.

    1982-03-31

    A process for removing halogenated aliphatic and aromatic compounds, e.g., polychlorinated biphenyls, from petroleum products by solvent extraction. The halogenated aliphatic and aromatic compounds are extracted from a petroleum product into a polar solvent by contracting the petroleum product with the polar solvent. The polar solvent is characterized by a high solubility for the extracted halogenated aliphatic and aromatic compounds, a low solubility for the petroleum product and considerable solvent power for polyhydroxy compound. The preferred polar solvent is dimethylformamide. A miscible polyhydroxy compound, such as, water, is added to the polar extraction solvent to increase the polarity of the polar extraction solvent. The halogenated aliphatic and aromatic compounds are extracted from the highly-polarized mixture of polyhydroxy compound and polar extraction solvent into a low polar or nonpolar solvent by contacting the polyhydroxy compound-polar solvent mixture with the low polar or nonpolar solvent. The halogenated aliphatic and aromatic compounds in the low polar or nonpolar solvent by physical means, e.g., vacuum evaporation. The polar and nonpolar solvents are recovered for recycling. The process can easily be designed for continuous operation. Advantages of the process include that the polar solvent and a major portion of the nonpolar solvent can be recycled, the petroleum products are reclaimable and the cost for disposing of waste containing polychlorinated biphenyls is significantly reduced. 2 tables.

  12. Amperometric detection and electrochemical oxidation of aliphatic amines and ammonia on silver-lead oxide thin-film electrodes

    SciTech Connect (OSTI)

    Ge, Jisheng

    1996-01-08

    This thesis comprises three parts: Electrocatalysis of anodic oxygen-transfer reactions: aliphatic amines at mixed Ag-Pb oxide thin-film electrodes; oxidation of ammonia at anodized Ag-Pb eutectic alloy electrodes; and temperature effects on oxidation of ethylamine, alanine, and aquated ammonia.

  13. Kinetics of the transformation of halogenated aliphatic compounds by iron sulfide

    SciTech Connect (OSTI)

    Butler, E.C.; Hayes, K.F.

    2000-02-01

    The objectives of the experiments described here were 2-fold: first, to assess the relative rates and products of transformation of a variety of halogenated aliphatics by the soil mineral FeS under a uniform set of experimental conditions and, second, to establish whether there exists a relationship between rate constants for these transformations and free energy or molecular parameters. The transformation of nine halogenated aliphatic compounds by 10 g/L (0.5 m{sup 2}/L) FeS at pH 8.3 was studied in batch experiments. These compounds were as follows: pentachloroethane (PCA), 1,1,2,2- and 1,1,1,2-tetrachloroethanes (1122-TeCA and 1112-TeCA), 1,1,1- and 1,1,2-trichloroethanes (111-TCA and 112-TCA), 1,1- and 1,2-dichloroethanes (11-DCA and 12-DCA), carbon tetrachloride (CT), and tribromomethane (TBM). 11-DCA, 12-DCA, and 112-TCA showed no appreciable transformation by FeS over approximately 120 days, but the other compounds were transformed with half-lives of hours to days. PCA and 1122-TeCA underwent dehydrohalogenation faster than FeS-mediated reductive dehalogenation reactions under the conditions of these experiments. The remaining compounds for which significant transformation was observed underwent FeS-mediated reactions more rapidly than hydrolysis or dehydrohalogenation. For 1112-TeCA, the dihaloelimination product (1,1-dichloroethylene) was the only reaction product detected. For 111-TCA, CT, and TBM, hydrogenolysis products were the only products detected, although their mass recoveries were considerably less than 100%. Two simple log-linear correlations between rate constants and either one-electron reduction potentials or homolytic bond dissociation enthalpies were developed, with coefficients of determination (R{sup 2} values) of 0.48 and 0.82, respectively. These findings are consistent with a rate-limiting step involving homolytic bond dissociation. However, neither correlation accurately described the reactivity of all the compounds that were studied

  14. Materials Data on U2AlCo3 (SG:194) by Materials Project

    DOE Data Explorer [Office of Scientific and Technical Information (OSTI)]

    Kristin Persson

    2015-03-08

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  15. Materials Data on U2AlCo2 (SG:127) by Materials Project

    DOE Data Explorer [Office of Scientific and Technical Information (OSTI)]

    Kristin Persson

    2015-03-08

    Computed materials data using density functional theory calculations. These calculations determine the electronic structure of bulk materials by solving approximations to the Schrodinger equation. For more information, see https://materialsproject.org/docs/calculations

  16. ROMP Crosslinkers for the Preparation of Aliphatic Aerogels ...

    Office of Scientific and Technical Information (OSTI)

    Laboratory (LLNL), Livermore, CA Sponsoring Org: USDOE Country of Publication: United States Language: English Subject: 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY

  17. ROMP Crosslinkers for the Preparation of Aliphatic Aerogels ...

    Office of Scientific and Technical Information (OSTI)

    DOE Contract Number: AC52-07NA27344 Resource Type: Journal Article Resource Relation: Journal Name: Journal of Non-Crystalline Solids, vol. 408, na, January 15, 2014, pp. 98-101 ...

  18. Sandia Energy Biomass

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    Lignin-Feasting Microbe Holds Promise for Biofuels http:energy.sandia.govlignin-feasting-microbe-holds-promise-for-biofuels http:energy.sandia.govlignin-feasting-microbe-hol...

  19. 2009 Publications | Stanford Synchrotron Radiation Lightsource

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    09 Publications Journal Papers J. Abendroth, A. C. Kreger and W. G. J. Hol, "The Dimer Formed by the Periplasmic Domain of EpsL from the Type 2 Secretion System of Vibrio parahaemolyticus", J. Struct. Biol. 168, 313 (2009) doi: 10.1016/j.jsb.2009.07.022 J. Abendroth, D. D. Mitchell, K. V. Korotkov, T. L. Johnson, A. Kreger, M. Sandkvist and W. G. J. Hol, "The Three-dimensional Structure of the Cytoplasmic Domains of EpsF from the Type 2 Secretion System of Vibrio cholerae",

  20. NATIONAL LF.hD COMPANY OF C4IIO

    Office of Legacy Management (LM)

    ... In the piercing operation tl vntponcnt of the rotat.i.lg force force8 the solid work pit y:ic:rcini: pof.nt which fcms a holJ.ow tube. The metal dis cbmter o,f the war& piece ...

  1. Deuterium separation by infrared-induced addition reaction

    DOE Patents [OSTI]

    Marling, John B.

    1977-01-01

    A method for deuterium enrichment by the infrared-induced addition reaction of a deuterium halide with an unsaturated aliphatic compound. A gaseous mixture of a hydrogen halide feedstock and an unsaturated aliphatic compound, particularly an olefin, is irradiated to selectively vibrationally excite the deuterium halide contained therein. The excited deuterium halide preferentially reacts with the unsaturated aliphatic compound to produce a deuterated addition product which is removed from the reaction mixture.

  2. TABLE33.CHP:Corel VENTURA

    Gasoline and Diesel Fuel Update (EIA)

    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...

  3. TABLE34.CHP:Corel VENTURA

    Gasoline and Diesel Fuel Update (EIA)

    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...

  4. Metal-sulfur type cell having improved positive electrode

    DOE Patents [OSTI]

    Dejonghe, Lutgard C.; Visco, Steven J.; Mailhe, Catherine C.; Armand, Michel B.

    1989-01-01

    An novel metal-sulfur type cell operable at a temperature of 200.degree. C. or less with an energy density of 150 Whrs/Kg or better is disclosed characterized by an organo-sulfur cathode formed from an organic-sulfur compound having the general formula, in its charged state, of (R(S).sub.y).sub.n wherein y=1 to 6; n=2 to 20; and R is one or more different aliphatic or aromatic organic moieties having 1 to 20 carbon atoms, which may include one or more oxygen, sulfur, or nitrogen heteroatoms when R comprisises one of more aromatic rings, or one or more oxygen, sulfur, nitrogen, or fluorine atoms associtated with the chain when R comprises an aliphatic chain, wherein the aliphatic group may be linear or branched, saturated or unsaturated, and wherein either the aliphatic chain or the aromatic ring may have substituted groups thereon.

  5. Metal-sulfur type cell having improved positive electrode

    DOE Patents [OSTI]

    DeJonghe, L.C.; Visco, S.J.; Mailhe, C.C.; Armand, M.B.

    1988-03-31

    A novel metal-sulfur type cell operable at a temperature of 200/degree/C or less with an energy density of 150 Whrs/Kg or better is disclosed characterized by an organo-sulfur cathode formed from an organic-sulfur compound having the general formula, in its charged state, of (R(S)/sub y/)n wherein y = 1 to 6; n = 2 to 20; and R is one or more different aliphatic or aromatic organic moieties having 1 to 20 carbon atoms, which may include one or more oxygen, sulfur, or nitrogen heteroatoms when R comprises one or more aromatic rings, or one or more oxygen, sulfur, nitrogen, or fluorine atoms associated with the chain when R comprises an aliphatic chain, wherein the aliphatic group may be linear or branched, saturated or unsaturated, and wherein either the aliphatic chain or the aromatic ring may have substituted groups thereon. 4 figs.

  6. Process for reducing organic compounds with calcium, amine, and alcohol

    DOE Patents [OSTI]

    Benkeser, R.A.; Laugal, J.A.; Rappa, A.

    1985-08-06

    Olefins are produced by contacting an organic compound having at least one benzene ring with calcium metal, ethylenediamine, a low molecular weight aliphatic alcohol, and optionally a low molecular weight aliphatic primary amine, and/or an inert, abrasive particulate substance. The reduction is conducted at temperatures ranging from about [minus]10 C to about 30 C or somewhat higher. Substantially all of the organic compounds are converted to corresponding cyclic olefins, primarily diolefins.

  7. Process for reducing organic compounds with calcium, amine, and alcohol

    DOE Patents [OSTI]

    Benkeser, Robert A.; Laugal, James A.; Rappa, Angela

    1985-01-01

    Olefins are produced by contacting an organic compound having at least one benzene ring with calcium metal, ethylenediamine, a low molecular weight aliphatic alcohol, and optionally a low molecular weight aliphatic primary amine, and/or an inert, abrasive particulate substance. The reduction is conducted at temperatures ranging from about -10.degree. C. to about 30.degree. C. or somewhat higher. Substantially all of the organic compounds are converted to corresponding cyclic olefins, primarily diolefins.

  8. Decontamination performance of selected in situ technologies for jet fuel contamination. Master's thesis

    SciTech Connect (OSTI)

    Chesley, G.D.

    1993-01-01

    Specific study of jet fuel is warranted because of the quantitive and qualitative component differences between jet fuel and other hydrocarbon fuels. Quantitatively, jet fuel contains a larger aliphatic or saturate fraction and a smaller aromatic fraction than other fuels (i.e. heating oil and diesel oil) in the medium-boiling-point-distillate class of fuels. Since the aliphatic and aromatic fractions of fuel are not equally susceptible to biodegradation, jet fuel decontamination using biodegradation may be different from other fuels.

  9. LANL: AOT & LANSCE The Pulse May 2012

    Broader source: All U.S. Department of Energy (DOE) Office Webpages (Extended Search)

    2 Los Alamos National Laboratory * Est. 1943 The Pulse-Newsletter of the Los Alamos Neutron Science Center and Accelerator Operations and Technology Division I N S I D E 2 From Steve'S DeSk 3 experimentS hint that the atomic nucleuS Still holDS Some SurpriSeS 4 Spin anD orbital orDering in Y 1-x la x vo 3 5 probing manganite FilmS chemical uniFor- mitY with polarizeD neutronS 6 heaDS up! By Diana Del Mauro ADEPS Communications As joint Accelerator Operations and Technology (AOT) deputy division

  10. Synthesis of pore-variable mesoporous CdS and evaluation of its photocatalytic activity in degrading methylene blue

    SciTech Connect (OSTI)

    Zhang, Wei-Min; Jiang, Yao-Quan; Cao, Xiao-Yan; Chen, Meng; Ge, Dong-Lai; Sun, Zhong-Xi

    2013-10-15

    Graphical abstract: - Highlights: Self-templated synthesis of tubular CdS. Cadmium complexes of aliphatic acids sustain the network of mesoporous structures. Aliphatic acids affect the phase composition and particle size. Pore size and volume vary with aliphatic acids having different hydrocarbonyl. - Abstract: In this study, mesoporous CdS polycrystallites have been synthesized using aliphatic acids of hexanoic acid, octanoic acid, and oleic acid as coordinating and capping agents, respectively. The fibrous Cdfatty acid salts act as a template to form the tubular CdS. The organic species are found to be necessary for maintaining the network of mesoporous CdS. The characterization results indicate that the shorter carbon chain length in aliphatic acids favors the wurtzite phase and particle size growth the specific surface area, pore diameter and pore volume show a monotonic raise with increasing carbon chain. The photocatalytic activities of mesoporous CdS tubes exhibit much higher efficiency than those of nanosized CdS powders in decolorizing methylene blue under simulated visible light.

  11. Lithium/organosulfur redox cell having protective solid electrolyte barrier formed on anode and method of making same

    DOE Patents [OSTI]

    De Jonghe, Lutgard C.; Visco, Steven J.; Liu, Meilin; Mailhe, Catherine C.

    1990-01-01

    A lithium/organosulfur redox cell is disclosed which comprises a solid lium anode, a liquid organosulfur cathode, and a barrier layer formed adjacent a surface of the solid lithium anode facing the liquid organosulfur cathode consisting of a reaction product of the lithium anode with the organosulfur cathode. The organosulfur cathode comprises a material having the formula (R(S).sub.y).sub.N where y=1 to 6, n=2 to 20 and R is one or more different aliphatic or aromatic organic moieties having 1 to 20 carbon atoms, which may include one or more oxygen, sulfur, nitrogen, or fluorine atoms associated with the chain when R comprises an aliphatic chain, wherein the linear chain may be linear or branched, saturated or unsaturated, and wherein either the aliphatic chain or the aromatic ring may have substituted groups thereon.

  12. Biomass conversion to mixed alcohols

    SciTech Connect (OSTI)

    Holtzapple, M.T.; Loescher, M.; Ross, M.

    1996-10-01

    This paper discusses the MixAlco Process which converts a wide variety of biomass materials (e.g. municipal solid waste, sewage sludge, agricultural residues) to mixed alcohols. First, the biomass is treated with lime to enhance its digestibility. Then, a mixed culture of acid-forming microorganisms converts the lime-treated biomass to volatile fatty acids (VFA) such as acetic, propionic, and butyric acids. To maintain fermentor pH, a neutralizing agent (e.g. calcium carbonate or lime) is added, so the fermentation actually produces VFA salts such as calcium acetate, propionate, and butyrate. The VFA salts are recovered and thermally converted to ketones (e.g. acetone, methylethyl ketone, diethyl ketone) which are subsequently hydrogenated to mixed alcohols (e.g. isopropanol, isobutanol, isopentanol). Processing costs are estimated at $0.72/gallon of mixed alcohols making it potentially attractive for transportation fuels.

  13. PRODUCTION OF FLUOROCARBONS

    DOE Patents [OSTI]

    Sarsfield, N.F.

    1949-06-21

    This patent pertains to a process for recovering fluorocarbons from a liquid mixture of hydrocarbons with partially and completely fluorinated products thereof. It consists of contacting the mxture in the cold with a liquid which is a solvent for the hydrocarbons and which is a nonsolvent for the fluorocarbons, extracting the hydrocarbons, separating the fluorocarbon-containing layer from the solvent-containing layer, and submitting the fluorocarbon layer to fractlonal distillation, to isolate the desired fluorocarbon fraction. Suitable solvents wnich may be used in the process include the lower aliphatic alcohols, and the lower aliphatic ketones.

  14. Sprayable titanium composition

    DOE Patents [OSTI]

    Tracy, Chester E.; Kern, Werner; Vibronek, Robert D.

    1980-01-01

    The addition of 2-ethyl-1-hexanol to an organometallic titanium compound dissolved in a diluent and optionally containing a lower aliphatic alcohol spreading modifier, produces a solution that can be sprayed onto a substrate and cured to form an antireflection titanium oxide coating having a refractive index of from about 2.0 to 2.2.

  15. Process for the extraction of strontium from acidic solutions

    DOE Patents [OSTI]

    Horwitz, E.P.; Dietz, M.L.

    1993-01-01

    The invention is a process for selectively extracting strontium values from aqueous nitric acid waste solutions containing these and other fission product values. The extractant solution is a macrocyclic polyether in an aliphatic hydrocarbon diluent containing a phase modifier. The process will selectively extract strontium values from nitric acid solutions which are up to 6 molar in nitric acid.

  16. SOLVENT EXTRACTION PROCESS FOR PROTACTINIUM

    DOE Patents [OSTI]

    Hyde, E.K.; Katzin, L.I.; Wolf, M.J.

    1961-04-01

    A process is described for separating protactinium from thorium present together as the nitrates in a 0.1 to 10 N nitric acid solution. The separation is carried out by extraction with an aliphatic alcohol, ketone, and/or ester having at least six carbon atoms, such as n-amyl acetate, 2-ethyl hexanol, and diisopropyl ketone.

  17. Process for the extraction of strontium from acidic solutions

    DOE Patents [OSTI]

    Horwitz, E.P.; Dietz, M.L.

    1994-09-06

    The invention is a process for selectively extracting strontium values from aqueous nitric acid waste solutions containing these and other fission product values. The extractant solution is a macrocyclic polyether in an aliphatic hydrocarbon diluent containing a phase modifier. The process will selectively extract strontium values from nitric acid solutions which are up to 6 molar in nitric acid. 4 figs.

  18. Surface chemistry control for selective fossil resin flotation

    DOE Patents [OSTI]

    Miller, J.D.; Yi, Y.; Yu, Q.

    1994-06-07

    A froth flotation method is disclosed for separating fine particles of fossil resin by use of frothing reagents which include an aliphatic organic compound having a polar group and containing not more than four carbon atoms. Butanol is an effective frothing reagent in this method. 12 figs.

  19. Surface chemistry control for selective fossil resin flotation

    DOE Patents [OSTI]

    Miller, Jan D.; Yi, Ye; Yu, Qiang

    1994-01-01

    A froth flotation method is disclosed for separating fine particles of fossil resin from by use of frothing reagents which include an aliphatic organic compound having a polar group and containing not more than four carbon atoms. Butanol is an effective frothing reagent in this method.

  20. Process for the extraction of strontium from acidic solutions

    DOE Patents [OSTI]

    Horwitz, E. Philip; Dietz, Mark L.

    1994-01-01

    The invention is a process for selectively extracting strontium values from aqueous nitric acid waste solutions containing these and other fission product values. The extractant solution is a macrocyclic polyether in an aliphatic hydrocarbon diluent containing a phase modifier. The process will selectively extract strontium values from nitric acid solutions which are up to 6 molar in nitric acid.

  1. Flexible moldable conductive current-limiting materials

    DOE Patents [OSTI]

    Shea, John Joseph; Djordjevic, Miomir B.; Hanna, William Kingston

    2002-01-01

    A current limiting PTC device (10) has two electrodes (14) with a thin film of electric conducting polymer material (20) disposed between the electrodes, the polymer material (20) having superior flexibility and short circuit performance, where the polymer material contains short chain aliphatic diepoxide, conductive filler particles, curing agent, and, preferably, a minor amount of bisphenol A epoxy resin.

  2. Coal liquefaction process using pretreatment with a binary solvent mixture

    DOE Patents [OSTI]

    Miller, Robert N.

    1986-01-01

    An improved process for thermal solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a hydrogen donor solvent comprises pretreating the coal with a binary mixture of an aromatic hydrocarbon and an aliphatic alcohol at a temperature below 300.degree. C. before the hydroliquefaction step. This treatment generally increases both conversion of coal and yields of oil.

  3. Process and catalyst for carbonylating olefins

    DOE Patents [OSTI]

    Zoeller, J.R.

    1998-06-02

    Disclosed is an improved catalyst system and process for preparing aliphatic carbonyl compounds such as aliphatic carboxylic acids, alkyl esters of aliphatic carboxylic acids and anhydrides of aliphatic carboxylic acids by carbonylating olefins in the presence of a catalyst system comprising (1) a first component selected from at least one Group 6 metal, i.e., chromium, molybdenum, and/or tungsten and (2) a second component selected from at least one of certain halides and tertiary and quaternary compounds of a Group 15 element, i.e., nitrogen, phosphorus and/or arsenic, and (3) as a third component, a polar, aprotic solvent. The process employing the improved catalyst system is carried out under carbonylating conditions of pressure and temperature discussed herein. The process constitutes and improvement over known processes since it can be carried out at moderate carbonylation conditions without the necessity of using an expensive noble metal catalyst, volatile, toxic materials such as nickel tetracarbonyl, formic acid or a formate ester. Further, the addition of a polar, aprotic solvent to the catalyst system significantly increases, or accelerates, the rate at which the carbonylation takes place.

  4. Catalytic hydroprocessing of chlorinated hydrocarbons

    SciTech Connect (OSTI)

    Allen, D.T.

    1996-12-31

    Catalytic hydroprocessing is a promising technology for the treatment or recycling of chlorinated organic waste streams. This paper will describe the hydroprocessing kinetics and reaction pathways of chlorinated aromatics and aliphatics. The compounds investigated include chlorinated benzenes, chlorinated phenols, chlorinated pyridinols, perchloroethylene, trichloroethyene, and dichloroethylenes. Experiments were performed over a NiMo/Al{sub 2}O{sub 3} catalyst in the temperature range of 175{degrees}C to 350{degrees}C. For the chlorinated benzenes, removal of chlorine proceeded at comparable rates for all species from hexachlorobenzene to chlorobenzene. For the chlorophenols and chloropyridinols, dechlorination proceeded at a much higher rate than deoxygenation. Rates of dechlorination of aliphatics were approximately an order of magnitude faster than the rates for aromatics. 10 refs., 4 figs., 1 tab.

  5. Extraction chemistry of fermentation product carboxylic acid

    SciTech Connect (OSTI)

    Kertes, A.S.; King, C.J.

    1986-02-01

    Within the framework of a program aiming to improve the existing extractive recovery technology of fermentation products, the state of the art is critically reviewed. The acids under consideration are propionic, lactic, pyruvic, succinic, fumaric, maleic, malic, itaconic, tartaric, citric, and isocitric, all obtained by the aerobic fermentation of glucose via the glycolytic pathway and glyoxylate bypass. With no exception, it is the undissociated monomeric acid that is extracted into carbon-bonded and phosphorus-bonded oxygen donor extractants. In the organic phase, the acids are usually dimerized. The extractive transfer process obeys the Nernst law, and the measured partition coefficients range from about 0.003 for aliphatic hydrocarbons to about 2 to 3 for aliphatic alcohols and ketones to about 10 or more for organophosphates. Equally high distribution ratios are measured when long-chain tertiary amines are employed as extractants, forming bulky salts preferentially soluble in the organic phase. 123 references.

  6. PRODUCTION OF FLUORINE-CONTAINING HYDROCARBON

    DOE Patents [OSTI]

    Sarsfield, N.F.

    1949-08-01

    This patent relates to improvements in the production of fluorine- containing hydrocarbon derivatives. The process for increasing the degree of fluorination of a fluorochlorohydrocarbon comprises subjecting a highly fluorinated fluorochlorohydrocarbon to the action of a dehydrochlorinating agent, and treating the resulting unsaturated body with fluorine, cobalt trifluoride, or silver difluoride. A number of reagents are known as dehydrochlorinaling agents, including, for example, the caustic alkalies, either in an anhydrous condition or dissolved in water or a lower aliphatic alcohol.

  7. SEPARATION OF PLUTONIUM FROM ELEMENTS HAVING AN ATOMIC NUMBER NOT LESS THAN 92

    DOE Patents [OSTI]

    Fitch, F.T.; Russell, D.S.

    1958-09-16

    other elements having atomic numbers nnt less than 92, It has been proposed in the past to so separate plutonium by solvent extraction iato an organic solvent using triglycoldichlcride as the organic solvent. The improvement lies in the discovery that triglycoldichloride performs far more efflciently as an extractant, wher certain second organie compounds are added to it. Mentioned as satisfactory additive compounds are benzaldehyde, saturated aliphatic aldehydes containtng at least twc carbon atoms, and certain polyhydric phenols.

  8. Polyestercarbonates which exhibit improved processibility

    DOE Patents [OSTI]

    Krabbenhoft, Herman Otto (Scotia, NY)

    1999-01-01

    The invention relates to a polyestercarbonate polymer which comprises repeating units of a mono-unsaturated aliphatic dicarboxylic acid having about 12 to about 20 carbon atoms. Preferred dicarboxylic acids for incorporation into the polymer are cis-octadec-9-enedioic acid or trans-octadec-9-enedioic acid. The use of these mono-unsaturated acids results in polymers with lower glass transition temperatures, and enhances processibility.

  9. Nanofluids and a method of making nanofluids for ground source heat pumps and other applications

    DOE Patents [OSTI]

    Olson, John Melvin

    2013-11-12

    This invention covers nanofluids. Nanofluids are a combination of particles between 1 and 100 nanometers, a surfactant and the base fluid. The nanoparticles for this invention are either pyrogenic nanoparticles or carbon nanotubes. These nanofluids improve the heat transfer of the base fluids. The base fluid can be ethylene glycol, or propylene glycol, or an aliphatic-hydrocarbon based heat transfer fluid. This invention also includes a method of making nanofluids. No surfactant is used to suspend the pyrogenic nanoparticles in glycols.

  10. Coal liquefaction process using pretreatment with a binary solvent mixture

    DOE Patents [OSTI]

    Miller, R.N.

    1986-10-14

    An improved process for thermal solvent refining or hydroliquefaction of non-anthracitic coal at elevated temperatures under hydrogen pressure in a hydrogen donor solvent comprises pretreating the coal with a binary mixture of an aromatic hydrocarbon and an aliphatic alcohol at a temperature below 300 C before the hydroliquefaction step. This treatment generally increases both conversion of coal and yields of oil. 1 fig.

  11. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    Input Definitions Key Terms Definition Barrel A unit of volume equal to 42 U.S. gallons. Blending Plant A facility which has no refining capability but is either capable of producing finished motor gasoline through mechanical blending or blends oxygenates with motor gasoline. Conventional Blendstock for Oxygenate Blending (CBOB) Motor gasoline blending components intended for blending with oxygenates to produce finished conventional motor gasoline. Fuel Ethanol An anhydrous denatured aliphatic

  12. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    Oxygenate Production Definitions Key Terms Definition Barrel A unit of volume equal to 42 U.S. gallons. Captive Refinery Oxygenate Plants Oxygenate production facilities located within or adjacent to a refinery complex. Fuel Ethanol An anhydrous denatured aliphatic alcohol intended for gasoline blending as described in Oxygenates definition. Gasohol A blend of finished motor gasoline containing alcohol (generally ethanol but sometimes methanol) at a concentration of 10 percent or less by volume.

  13. Motor fuel additive and ori-inhibited motor fuel composition

    SciTech Connect (OSTI)

    Sung, R.L.

    1989-09-26

    This patent describes a composition. It is obtained by reacting, at a temperature of 30{sup 0}C-200C 0.5-2.5 moles of one or more aliphatic carboxylic acids selected from the group consisting of formic, acetic, propionic, butyric, isobutyric, valeric, pivalic, acrylic, propiolie, methacylic, crotonic, isocrfotonic, maleic and fumaric acid; and 0.5-1.5 moles of a polyoxyalkylene diamine.

  14. Intrinsic and accelerated anaerobic biodegradation of perchloroethylene in groundwater

    SciTech Connect (OSTI)

    Buchanan, R.J. Jr.; Ellis, D.E.; Odom, J.M.; Lee, M.D.; Mazierski, P.F.

    1995-12-31

    The DuPont Niagara Falls Plant is located in a heavily industrialized area of Niagara Falls, New York, adjacent to the Niagara River. The plant has been in continuous operation since 1898 and manufactured various organic and inorganic chemicals. Chlorinated solvents were produced from 1930 to 1975 at the plant. Numerous hydrogeologic investigations have described the subsurface hydrogeology and indicated that the groundwater underlying the plant was impacted by a variety of chlorinated aliphatic hydrocarbons in a wide range of concentrations. DuPont initiated in-field evaluations to determine whether biological reductive anaerobic dechlorination was occurring naturally and, if so, whether such dechlorination could be enhanced in situ. A field program was subsequently implemented could be enhanced in situ. A field program was subsequently implemented in a preselected area of the plant through use of an in situ borehole bioreactor to attempt to stimulate indigenous biological reductive dechlorination of chlorinated aliphatics by the addition of yeast extract (substrate) and sulfate (electron acceptor). At this location, a very active microbial population developed, which reduced the in situ concentrations of chlorinated aliphatic compounds by more than 94%, but did not increase the typical biological degradation products. This may have been due to an alternative biological degradation pathway or to very rapid biological kinetics. Efforts to elucidate this mechanism have been initiated under a separate laboratory program.

  15. Molecular and crystal structure of n-hexyloxybenzoic anhydride at low and room temperatures

    SciTech Connect (OSTI)

    Konstantinov, I. I.; Churakov, A. V.; Kuz'mina, L. G.

    2010-09-15

    The crystal and molecular structures of n-hexyloxybenzoic anhydride, C{sub 6}H{sub 13}-O-C{sub 6}H{sub 4}-C(O)-O-C(O)-C{sub 6}H{sub 4}-C{sub 6}H{sub 13}, at low (120 K) and room (296 K) temperatures have been investigated. The molecule has an asymmetric bent structure. The dihedral angle between the benzene ring planes is 48.5 deg. The aliphatic chain on one side of the molecule has a transoid orientation with respect to the 'internal' C4 atom of the closest benzene ring, whereas the aliphatic chain on the other side has a cissoid orientation with respect to the analogous C(4A) atom. The crystal packing does not exhibit any pronounced separation of the crystal space into closely packed aromatic or loosely packed aliphatic regions. No weak directional interactions are observed in the packing; this fact explains the absence of liquid-crystal properties for this compound.

  16. Land subsidence associated with hydrocarbon production, Texas Gulf Coast

    SciTech Connect (OSTI)

    Kreitler, C.W.; White, W.A.; Akhter, M.S.

    1988-01-01

    Although ground-water withdrawal has been the predominant cause of land subsidence in the Texas Gulf Coast, localized subsidence and faulting have also resulted from hydrocarbon production. Subsidence was documented as early as the 1920s over the Goose Creek field. Since then, subsidence and/or faulting have been identified over the Saxet, South Houston, Chocolate Bayou, Hastings, Alco-Mag, Clinton, Mykawa, Blue Ridge, Webster, and Caplen oil fields. Oil-production-related subsidence over these fields generally creates few environmental or engineering problems. One exception is the subsidence and faulting over the Caplen oil field on Bolivar Peninsula, where more than 1,000 ac of saltwater marsh has been replaced by subaqueous flats. Subsidence may be occurring over other fields but has not been identified because of limited releveled benchmark data. An evaluation of drill-stem and bottom-hole pressure data for the Frio Formation in Texas indicates extensive depressurization presumably from hydrocarbon production. Nearly 12,000 measurements from a pressure data base of 17,000 measurements indicate some depressurization. Some of the Frio zones have pressure declines of more than 1,500 psi from original hydrostatic conditions. Subsidence and faulting may be associated with these fields in the Frio as well as other Tertiary formations where extensive hydrocarbon production and subsequent depressurization have occurred.

  17. Land subsidence caused by withdrawal of oil and gas in the Gulf coastal plain - The Houston, Texas, case history

    SciTech Connect (OSTI)

    Holzer, T.L. )

    1990-09-01

    The extensive network of geodetic leveling lines in the Houston-Galveston, Texas, area, where at least 110 oil and gas fields have been developed, provides the most comprehensive opportunity in the Gulf Coast to search for the occurrence of land subsidence caused by withdrawal of oil and gas. Although the evaluation is complicated by regional subsidence caused by a decline of ground-water level in aquifers beneath the area, subsidence caused by oil and gas withdrawal can be examined by searching for local increases of subsidence at oil and gas fields crossed by leveling lines. Twenty-nine fields are crossed by lines with repeated leveling surveys. Subsidence profiles across these fields indicate local increases of subsidence at six fields-Alco-Mag, Chocolate Bayou, Goose Creek, Hastings, Mykawa, and South Houston. Although ground-water withdrawal is undoubtedly the most important factor contributing to the total subsidence at each field, oil and gas withdrawal may be partly responsible for the local increases. Except for Chocolate Bayou, the volume of petroleum production at each field was sufficient to account for the increase. The volume of petroleum production, however, in general is not a reliable index for predicting the local increase because land within many fields with significant production did not show local increases of subsidence. With the exception of the 1 m subsidence caused by petroleum withdrawal at Goose Creek (1917-1925), local increases of subsidence were less than 0.3 m.

  18. Hydroprocessing carbonaceous feedstocks containing asphaltenes

    SciTech Connect (OSTI)

    Kuehler, C.W.

    1983-05-03

    A liquid hydrocarbonaceous feedstock containing asphaltenes and optionally solids is hydroprocessed by passing the feedstock through a catalytic reaction zone in the presence of a catalyst bed containing a solid hydroprocessing catalyst under hydroprocessing conditions to produce a hydrocarbonaceous effluent containing solids. Plugging of the catalyst bed is avoided by controlling the severity of the hydroprocessing conditions in the catalytic reaction zone to maintain the aliphatic hydrogen concentration of the liquid effluent sufficiently low to prevent substantial precipitation of asphaltenes within the catalytic reaction zone.

  19. Degradation problems with the solvent extraction organic at Roessing uranium

    SciTech Connect (OSTI)

    Munyungano, Brodrick; Feather, Angus; Virnig, Michael

    2008-07-01

    Roessing Uranium Ltd recovers uranium from a low-grade ore in Namibia. Uranium is recovered and purified from an ion-exchange eluate in a solvent-extraction plant. The solvent-extraction plant uses Alamine 336 as the extractant for uranium, with isodecanol used as a phase modifier in Sasol SSX 210, an aliphatic hydrocarbon diluent. Since the plant started in the mid 1970's, there have been a few episodes where the tertiary amine has been quickly and severely degraded when the plant was operated outside certain operating parameters. The Rossing experience is discussed in more detail in this paper. (authors)

  20. Shock temperature as a criterion for the detonability of LNG/LPG constituents

    SciTech Connect (OSTI)

    Michels, H.J. . Dept. of Chemical Engineering and Chemical Technology); Rashidi, F. )

    1992-12-01

    Detonation limit data obtained at ambient conditions for some aliphatic LNG/LNG constituents with oxygen and nitrogen (air) have been analyzed in search of a single critical parameter for detonation propagation. It was established the shock, rather than C-J reaction temperatures, provides a firm basis for marginal detonability prediction and that, furthermore, classical reaction mechanisms and relatively simple calculation methods can be used for their reliable evaluation. In this paper the result is used to formulate a criterion, for predicting composition limits to detonation. For the systems investigated, this criterion is accurate to within approximately 0.2% for fuel-lean and around 1% for fuel-rich mixtures.

  1. Kinetic data base for combustion modeling

    SciTech Connect (OSTI)

    Tsang, W.; Herron, J.T.

    1993-12-01

    The aim of this work is to develop a set of evaluated rate constants for use in the simulation of hydrocarbon combustion. The approach has been to begin with the small molecules and then introduce larger species with the various structural elements that can be found in all hydrocarbon fuels and decomposition products. Currently, the data base contains most of the species present in combustion systems with up to four carbon atoms. Thus, practically all the structural grouping found in aliphatic compounds have now been captured. The direction of future work is the addition of aromatic compounds to the data base.

  2. URANIUM SEPARATION PROCESS

    DOE Patents [OSTI]

    Hyde, E.K.; Katzin, L.I.; Wolf, M.J.

    1959-07-14

    The separation of uranium from a mixture of uranium and thorium by organic solvent extraction from an aqueous solution is described. The uranium is separrted from an aqueous mixture of uranium and thorium nitrates 3 N in nitric acid and containing salting out agents such as ammonium nitrate, so as to bring ihe total nitrate ion concentration to a maximum of about 8 N by contacting the mixture with an immiscible aliphatic oxygen containing organic solvent such as diethyl carbinol, hexone, n-amyl acetate and the like. The uranium values may be recovered from the organic phase by back extraction with water.

  3. Selective aerobic alcohol oxidation method for conversion of lignin into simple aromatic compounds

    DOE Patents [OSTI]

    Stahl, Shannon S; Rahimi, Alireza

    2015-03-03

    Described is a method to oxidize lignin or lignin sub-units. The method includes oxidation of secondary benzylic alcohol in the lignin or lignin sub-unit to a corresponding ketone in the presence of unprotected primarily aliphatic alcohol in the lignin or lignin sub-unit. The optimal catalyst system consists of HNO.sub.3 in combination with another Bronsted acid, in the absence of a metal-containing catalyst, thereby yielding a selectively oxidized lignin or lignin sub-unit. The method may be carried out in the presence or absence of additional reagents including TEMPO and TEMPO derivatives.

  4. BARIUM RECOVERY PROCESS

    DOE Patents [OSTI]

    Blanco, R.E.

    1959-07-21

    A method of separating barium from nuclear fission products is described. In accordance with the invention, barium may be recovered from an acidic solution of neutron-irradiated fissionable material by carrying ihe barium cut of solution as a sulfate with lead as a carrier and then dissolving the barium-containing precipitate in an aqueous solution of an aliphatic diamine chelating reagent. The barium values together with certain other metallic values present in the diamine solution are then absorbed onto a cation exchange resin and the barium is selectively eluted from the resin bed with concentrated nitric acid.

  5. Molecular Recognition: Preparation and Characterization of Two Tripodal Anion Receptors

    SciTech Connect (OSTI)

    Shokri, Alireza; Deng, Shihu; Wang, Xue B.; Kass, Steven R.

    2014-03-01

    Two new tripodal hydroxyl-based anion receptors (1 and 2) are reported and their molecular complexes with Cl, H2PO4 , and OAc along with the (M1) ion of 1 were characterized by negative ion photoelectron spectroscopy in the gas phase and by binding constant determinations in four solvents (i.e., CDCl3, CD2Cl2, CD3COCD3, and CD3CN). An intramolecular hydrogen bond network (HBN) in hexaol 1 was found to diminish its binding whereas the triol 2 is the strongest aliphatic hydroxyl-based receptor to date.

  6. Glassy dynamics of hydrogen-bonded heteroditopic molecules

    SciTech Connect (OSTI)

    Lou, Nan; Wang, Yangyang; Li, Haixia; Sokolov, Alexei P; Xiong, Huiming

    2012-01-01

    A self-complementary heteroditopic molecule composed of thymine and diamidopyridine end groups and a flexible aliphatic interconnecting chain has been synthesized. The glassy dynamics of this hydrogen-bonded supramolecule have been investigated by using dielectric and rheological measurements, in combination with infra-red spectroscopy and solid-state 13C NMR experiments. Decoupling of main dielectric relaxation from viscosity has been found in the vicinity of the glass transition and the temperature dependence of viscosity appears to be stronger than that of dielectric relaxation. The unusual dynamic decoupling phenomenon is ascribed to the chemical/dynamic heterogeneity and formation of hydrogen bonds in the supramolecules.

  7. Selective Sorbents For Purification Of Hydrocarbons

    DOE Patents [OSTI]

    Yang, Ralph T.; Yang, Frances H.; Takahashi, Akira; Hernandez-Maldonado, Arturo J.

    2006-04-18

    A method for removing thiophene and thiophene compounds from liquid fuel includes contacting the liquid fuel with an adsorbent which preferentially adsorbs the thiophene and thiophene compounds. The adsorption takes place at a selected temperature and pressure, thereby producing a non-adsorbed component and a thiophene/thiophene compound-rich adsorbed component. The adsorbent includes either a metal or a metal ion that is adapted to form p-complexation bonds with the thiophene and/or thiophene compounds, and the preferential adsorption occurs by p-complexation. A further method includes selective removal of aromatic compounds from a mixture of aromatic and aliphatic compounds.

  8. Selective sorbents for purification of hydrocarbons

    DOE Patents [OSTI]

    Yang, Ralph T.; Yang, Frances H.; Takahashi, Akira; Hernandez-Maldonado, Arturo J.

    2006-05-30

    A method for removing thiophene and thiophene compounds from liquid fuel includes contacting the liquid fuel with an adsorbent which preferentially adsorbs the thiophene and thiophene compounds. The adsorption takes place at a selected temperature and pressure, thereby producing a non-adsorbed component and a thiophene/thiophene compound-rich adsorbed component. The adsorbent includes either a metal or a metal cation that is adapted to form .pi.-complexation bonds with the thiophene and/or thiophene compounds, and the preferential adsorption occurs by .pi.-complexation. A further method includes selective removal of aromatic compounds from a mixture of aromatic and aliphatic compounds.

  9. Selective sorbents for purification of hydrocartons

    DOE Patents [OSTI]

    Yang, Ralph T.; Yang, Frances H.; Takahashi, Akira; Hermandez-Maldonado, Arturo J.

    2006-12-12

    A method for removing thiophene and thiophene compounds from liquid fuel includes contacting the liquid fuel with an adsorbent which preferentially adsorbs the thiophene and thiophene compounds. The adsorption takes place at a selected temperature and pressure, thereby producing a non-adsorbed component and a thiophene/thiophene compound-rich adsorbed component. The adsorbent includes either a metal or a metal ion that is adapted to form .pi.-complexation bonds with the thiophene and/or thiophene compounds, and the preferential adsorption occurs by .pi.-complexation. A further method includes selective removal of aromatic compounds from a mixture of aromatic and aliphatic compounds.

  10. Selective sorbents for purification of hydrocarbons

    DOE Patents [OSTI]

    Yang, Ralph T.; Hernandez-Maldonado, Arturo J.; Yang, Frances H.; Takahashi, Akira

    2006-08-22

    A method for removing thiophene and thiophene compounds from liquid fuel includes contacting the liquid fuel with an adsorbent which preferentially adsorbs the thiophene and thiophene compounds. The adsorption takes place at a selected temperature and pressure, thereby producing a non-adsorbed component and a thiophene/thiophene compound-rich adsorbed component. The adsorbent includes either a metal or a metal cation that is adapted to form .pi.-complexation bonds with the thiophene and/or thiophene compounds, and the preferential adsorption occurs by .pi.-complexation. A further method includes selective removal of aromatic compounds from a mixture of aromatic and aliphatic compounds.

  11. Photodetachment and electron reactivity in 1-methyl-1-butyl-pyrrolidinium bis(trifluoromethylsulfonyl)amide

    SciTech Connect (OSTI)

    Molins i Domenech, Francesc; FitzPatrick, Benjamin; Healy, Andrew T.; Blank, David A.

    2012-07-21

    The transient absorption spectrum in the range 500 nm-1000 nm was measured with ultrafast time resolution on a flowing neat, aliphatic, room-temperature ionic liquid following anion photodetachment. In this region the spectrum was shown to be a combination of absorption from the electron and the hole. Spectrally-resolved electron quenching determined a bimodal shape for the hole spectrum in agreement with recent computational predictions on a smaller aliphatic ionic liquid [Margulis et al., J. Am. Chem. Soc. 133, 20186 (2011)]. For time delays beyond 15 ps, spectral evolution qualitatively agrees with recent radiolysis experiments [Wishart et al., Faraday Discuss. 154, 353 (2012)]. However, the shape of the spectrum is different, reflecting the contrast in ionization energy between the two methods. Previously unobserved reactivity of the electron was found with a time constant of 300 fs. The results demonstrate solvent control of the rate coefficient for reaction between the electron and proton, with a rapid decline in the rate within the first picosecond.

  12. Ionic Liquid–Solute Interactions Studied by 2D NOE NMR Spectroscopy

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Khatun, Sufia; Castner, Edward W.

    2014-11-26

    Intermolecular interactions between a Ru²⁺(bpy)₃ solute and the anions and cations of four different ionic liquids (ILs) are investigated by 2D NMR nuclear Overhauser effect (NOE) techniques, including {¹H-¹⁹F} HOESY and {¹H-¹H} ROESY. Four ILs are studied, each having the same bis(trifluoromethylsulfonyl)amide anion in common. Two of the ILs have aliphatic 1-alkyl-1-methylpyrrolidinium cations, while the other two ILs have aromatic 1-alkyl-3-methylimidazolium cations. ILs with both shorter (butyl) and longer (octyl or decyl) cationic alkyl substituents are studied. NOE NMR results suggest that the local environment of IL anions and cations near the Ru²⁺(bpy)₃ solute is rather different from the bulkmore » IL structure. The solute-anion and solute-cation interactions are significantly different both for ILs with short vs long alkyl tails and for ILs with aliphatic vs aromatic cation polar head groups. In particular, the solute-anion interactions are observed to be about 3 times stronger for the cations with shorter alkyl tails relative to the ILs with longer alkyl tails. The Ru²⁺(bpy)₃ solute interacts with both the polar head and the nonpolar tail groups of the 1- butyl-1-methylpyrrolidinium cation but only with the nonpolar tail groups of the 1-decyl-1-methylpyrrolidinium cation.« less

  13. Probing the molecular design of hyper-branched aryl polyesters towards lubricant applications

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Robinson, Joshua W.; Zhou, Yan; Bhattacharya, Priyanka; Erck, Robert; Qu, Jun; Bays, J. Timothy; Cosimbescu, Lelia

    2016-01-05

    We report novel polymeric materials that may be used as viscosity index improvers (VII) for lubricant applications. Our efforts included probing the comb-burst hyper-branched aryl polyester architecture for beneficial viscosity and friction behavior when utilized as an additive in a group I oil. The monomer was designed as to undergo polymerization via polycondensation within the architectural construct (AB2), typical of hyperbranched polymers. The monomer design was comprised of aliphatic arms (12 or 16 methylenes) to provide the necessary lipophilicity to achieve solubility in a non-polar medium. Once polymerized, via catalyst and heat, the surface alcohols were functionalized with fatty acidsmore » (lauric and palmitic). Controlling the aliphatic nature of the internal arms and peripheral end-groups provided four unique flexible polymer designs. Changing the reaction time and concentration provided opportunities to investigate the influence of molecular weight and branching density on oil-solubility, viscosity, and friction. Oil-solubility was found to decrease with fewer internal carbons, but the number of internal carbons appears to have little influence on the bulk solution viscosity. Increased branching and degree of polymerization, and thus molecular weight, were found to reduce the solubility of these systems in the base oil. At concentrations of 2 wt % in a group I base oil, these polymer additives demonstrated improved viscosity index and reduced friction coefficient, validating the basic approach.« less

  14. Crosslinked Polyamide

    DOE Patents [OSTI]

    Huang, Zhi H.; McDonald, William F.; Wright, Stacy C.; Taylor, Andrew C.

    2002-06-04

    A crosslinked polyamide material and a process for preparing the crosslinked polyamide material are disclosed. The crosslinked polyamide material comprises a crosslinked chemical combination of (1) a polyamide of the formula: ##STR1## wherein n is between about 50 and 10,000, wherein each R is between 1 and 50 carbon atoms alone and is optionally substituted with heteroatoms, oxygen, nitrogen, sulfur, or phosphorus and combinations thereof, wherein multiple of the R are in vertically aligned spaced relationship along a backbone forming the polyamide, and wherein two or more of the R contain an amino group; and (2) a crosslinking agent containing at least two functional groups capable of reacting with the amino groups of the polyamide. In one embodiment of the invention, the crosslinking agent is an aliphatic or aromatic isocyanate compound having 2 or more --N.dbd.C.dbd.O groups. In another embodiment of the invention, the crosslinking agent is an aliphatic aldehyde or aromatic aldehyde compound having 2 or more --CHO groups. In still another embodiment of the invention, the crosslinking agent is selected from a phosphine having the general formula (A).sub.2 P(B) and mixtures thereof, wherein A is hydroxyalkyl, and B is hydroxyalkyl, alkyl, or aryl. In yet another embodiment of the invention, the crosslinking agent is selected from the group consisting of epoxy resins having more than one epoxide group per molecule.

  15. Characterization of the surface properties of Illinois basin coals. Final technical report, September 1, 1991--August 31, 1992

    SciTech Connect (OSTI)

    Demir, I.; Harvey, R.D.; Lizzio, A.A.

    1992-12-31

    Surface area and pore volume distributions, surface charge, and surface chemical structure of the eight coals in the Illinois Basin Coal Sample Program (IBCSP) were determined. The IBC-101 coal has the lowest total and micropore (3.5-20.0 {Angstrom}) surface areas. The IBC-103 coal has the lowest mesopore (20-500 {Angstrom}) surface area. The mesopore surface areas of IBC-101, IBC-102, and IBC-107 coals are higher than the other four coals. Pore volume in pores <1800 {Angstrom} in diameter varies almost five-fold with IBC-103 coal having the lowest value. These differences may affect the reactivity of these coals during cleaning, conversion, and combustion processes. Surface charge and isoelectric points vary among the samples. The isoelectric point, where processes such as agglomeration and dewatering is most efficient, shifted to higher pH values for some of the samples upon exposure to air oxidation at room temperature. Diffuse reflectance infrared spectroscopy (DRIS) data indicate that the surfaces of the IBCSP coals contain aromatic hydrocarbon components, aliphatic hydrocarbons, and an aldehyde group. Ball-mill grinding reduced the organic hydroxyls and thus enriched relative concentrations of nonpolar aliphatic functional groups in the samples. The room temperature air oxidation did not cause any significant change on the surface chemical structure of the coals.

  16. October 1999 Groundwater Sampling and Data Analysis, Distler Brickyard Site, Hardin County, Kentucky

    SciTech Connect (OSTI)

    J. P. Martin, L. N. Peterson; C. J. Taylor

    2000-03-01

    This report describes the results of a sampling event conducted at the Distler Brickyard Superfund Site, Hardin County, Kentucky, October 1999. The purpose of the sampling event was to evaluate the extent of natural biodegradation of chlorinated aliphatic hydrocarbons (CAH) occurring at the Site. Sampling locations were selected to evaluate three areas of the suspected CAH plume: the source area, an axial cross-section, and a downgradient transect. Due to inadequate recharge to and the poor physical condition of some monitoring wells at the Site, the sampling approach was modified to reflect wells that could be sampled. Results indicate that natural anaerobic degradation of chlorinated aliphatic hydrocarbons is occurring in the presumed source area around monitoring well GW-11. The primary contaminant of concern, trichloroethene, migrates downgradient from the source area into the Coarse Grained Alluvium Aquifer at concentrations slightly greater than the Maximum Contaminant Level (MCL). Based on the available, the following hypothesis is proposed: the source area has been remediated through soil removal activities and subsequent anaerobic reductive dechlorination. If this is the case, this Site may be a good candidate for implementation of a monitored natural attenuation remedy. However, more data are necessary before this hypothesis can be confirmed.

  17. Aromatic and polycyclic aromatic hydrocarbon formation in a laminar premixed n-butane flame

    SciTech Connect (OSTI)

    Marinov, N.M.; Pitz, W.J.; Westbrook, C.K.; Vincitore, A.M.; Castaldi, M.J.; Senkan, S.M.; Melius, C.F.

    1998-07-01

    Experimental and detailed chemical kinetic modeling work has been performed to investigate aromatic and polycyclic aromatic hydrocarbon (PAH) formation pathways in a premixed, rich, sooting, n-butane-oxygen-argon burner stabilized flame. An atmospheric pressure, laminar flat flame operated at an equivalence ratio of 2.6 was used to acquire experimental data for model validation. Gas composition analysis was conducted by an on-line gas chromatograph/mass spectrometer technique. Measurements were made in the main reaction and post-reaction zones for a number of low molecular weight species, aliphatics, aromatics, and polycyclic aromatic hydrocarbons (PAHs) ranging from two to five-fused aromatic rings. Reaction flux and sensitivity analysis were used to help identify the important reaction sequences leading to aromatic and PAH growth and destruction in the n-butane flame. Reaction flux analysis showed the propargyl recombination reaction was the dominant pathway to benzene formation. The consumption of propargyl by H atoms was shown to limit propargyl, benzene, and naphthalene formation in flames as exhibited by the large negative sensitivity coefficients. Naphthalene and phenanthrene production was shown to be plausibly formed through reactions involving resonantly stabilized cyclopentadienyl and indenyl radicals. Many of the low molecular weight aliphatics, combustion by-products, aromatics, branched aromatics, and PAHs were fairly well simulated by the model. Additional work is required to understand the formation mechanisms of phenyl acetylene, pyrene, and fluoranthene in the n-butane flame. 73 refs.

  18. The Influence of Process Conditions on the Chemical Composition of Pine Wood Catalytic Pyrolysis Oils

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Pereira, J.; Agblevor, F. A.; Beis, S. H.

    2012-01-01

    Pine wood samples were used as model feedstock to study the properties of catalytic fast pyrolysis oils. The influence of two commercial zeolite catalysts (BASF and SudChem) and pretreatment of the pine wood with sodium hydroxide on pyrolysis products were investigated. The pyrolysis oils were first fractionated using column chromatography and characterized using GC-MS. Long chain aliphatic hydrocarbons, levoglucosan, aldehydes and ketones, guaiacols/syringols, and benzenediols were the major compounds identified in the pyrolysis oils. The catalytic pyrolysis increased the polycyclic hydrocarbons fraction. Significant decreases in phthalate derivatives using SudChem and long chain aliphatics using BASF catalyst were observed. Significant amountsmore » of aromatic heterocyclic hydrocarbons and benzene derivatives were formed, respectively, using BASF and SudChem catalysts. Guaiacyl/syringyl and benzenediols derivatives were partly suppressed by the zeolite catalysts, while the sodium hydroxide treatment enriched phenolic derivatives. Zeolite catalyst and sodium hydroxide were employed together; they showed different results for each catalyst.« less

  19. Computational Study of Bond Dissociation Enthalpies for Substituted $\\beta$-O-4 Lignin Model Compounds

    SciTech Connect (OSTI)

    Younker, Jarod M; Beste, Ariana; Buchanan III, A C

    2011-01-01

    The biopolymer lignin is a potential source of valuable chemicals. Phenethyl phenyl ether (PPE) is representative of the dominant $\\beta$-O-4 ether linkage. Density functional theory (DFT) is used to calculate the Boltzmann-weighted carbon-oxygen and carbon-carbon bond dissociation enthalpies (BDEs) of substituted PPE. These values are important in order to understand lignin decomposition. Exclusion of all conformers that have distributions of less than 5\\% at 298 K impacts the BDE by less than 1 kcal mol$^{-1}$. We find that aliphatic hydroxyl/methylhydroxyl substituents introduce only small changes to the BDEs (0-3 kcal mol$^{-1}$). Substitution on the phenyl ring at the $ortho$ position substantially lowers the C-O BDE, except in combination with the hydroxyl/methylhydroxyl substituents, where the effect of methoxy substitution is reduced by hydrogen bonding. Hydrogen bonding between the aliphatic substituents and the ether oxygen in the PPE derivatives has a significant influence on the BDE. CCSD(T)-calculated BDEs and hydrogen bond strengths of $ortho$-substituted anisoles when compared with M06-2X values confirm that the latter method is sufficient to describe the molecules studied and provide an important benchmark for lignin model compounds.

  20. Ionic Liquid–Solute Interactions Studied by 2D NOE NMR Spectroscopy

    SciTech Connect (OSTI)

    Khatun, Sufia; Castner, Edward W.

    2014-11-26

    Intermolecular interactions between a Ru²⁺(bpy)₃ solute and the anions and cations of four different ionic liquids (ILs) are investigated by 2D NMR nuclear Overhauser effect (NOE) techniques, including {¹H-¹⁹F} HOESY and {¹H-¹H} ROESY. Four ILs are studied, each having the same bis(trifluoromethylsulfonyl)amide anion in common. Two of the ILs have aliphatic 1-alkyl-1-methylpyrrolidinium cations, while the other two ILs have aromatic 1-alkyl-3-methylimidazolium cations. ILs with both shorter (butyl) and longer (octyl or decyl) cationic alkyl substituents are studied. NOE NMR results suggest that the local environment of IL anions and cations near the Ru²⁺(bpy)₃ solute is rather different from the bulk IL structure. The solute-anion and solute-cation interactions are significantly different both for ILs with short vs long alkyl tails and for ILs with aliphatic vs aromatic cation polar head groups. In particular, the solute-anion interactions are observed to be about 3 times stronger for the cations with shorter alkyl tails relative to the ILs with longer alkyl tails. The Ru²⁺(bpy)₃ solute interacts with both the polar head and the nonpolar tail groups of the 1- butyl-1-methylpyrrolidinium cation but only with the nonpolar tail groups of the 1-decyl-1-methylpyrrolidinium cation.

  1. Zinc ferrite nanoparticle as a magnetic catalyst: Synthesis and dye degradation

    SciTech Connect (OSTI)

    Mahmoodi, Niyaz Mohammad

    2013-10-15

    Graphical abstract: Photocatalytic degradation of Reactive Red 198 and Reactive Red 120 by the synthesized zinc ferrite nanoparticle. - Highlights: Magnetic zinc ferrite nanoparticle was synthesized and characterized. Photocatalytic dye degradation by magnetic nanoparticle was studied. Formate, acetate and oxalate were detected as dominant dye degradation aliphatic intermediates. Nitrate and sulfate ions were detected as mineralization products of dyes. Zinc ferrite nanoparticle was an effective magnetic photocatalyst to degrade dyes. - Abstract: In this paper, magnetic zinc ferrite (ZnFe{sub 2}O{sub 4}) nanoparticle was synthesized and its photocatalytic dye degradation ability from colored wastewater was studied. Reactive Red 198 (RR198) and Reactive Red 120 (RR120) were used as model dyes. The characteristics of ZnFe{sub 2}O{sub 4} were investigated using Fourier transform infrared (FTIR), X-ray diffraction (XRD) and scanning electron microscope (SEM). Photocatalytic dye degradation by ZnFe{sub 2}O{sub 4} was studied by UVvis spectrophotometer and ion chromatography (IC). The effects of ZnFe{sub 2}O{sub 4} dosage, initial dye concentration and salt on dye degradation were evaluated. Formate, acetate and oxalate anions were detected as dominant aliphatic intermediate. Inorganic anions (nitrate and sulfate anions) were detected as dye mineralization products. The results indicated that ZnFe{sub 2}O{sub 4} could be used as a magnetic photocatalyst to degrade dyes from colored wastewater.

  2. Molecular Siganture and Sources of Biochemical Recalcitrance of Organic C in Amozonian Dark Earths

    SciTech Connect (OSTI)

    Solomon,D.; Lehmann, J.; Thies, J.; Schafer, T.; Liang, B.; Kinyangi, J.; Neves, E.; Peterson, J.; Liuzao, F.; Skjemstad, J.

    2007-01-01

    Amazonian Dark Earths (ADE) are a unique type of soils developed through intense anthropogenic activities that transformed the original soils into Anthrosols throughout the Brazilian Amazon Basin. We conducted a comparative molecular-level investigation of soil organic C (SOC) speciation in ADE (ages between 600 and 8700 years B.P.) and adjacent soils using ultraviolet photo-oxidation coupled with {sup 13}C cross polarization-magic angle spinning nuclear magnetic resonance (CP-MAS NMR), synchrotron-based Fourier transform infrared-attenuated total reflectance (Sr-FTIR-ATR) and C (1s) near edge X-ray absorption fine structure (NEXAFS) spectroscopy to obtain deeper insights into the structural chemistry and sources of refractory organic C compounds in ADE. Our results show that the functional group chemistry of SOC in ADE was considerably different from adjacent soils. The SOC in ADE was enriched with: (i) aromatic-C structures mostly from H- and C-substituted aryl-C, (ii) O-rich organic C forms from carboxylic-C, aldehyde-C, ketonic-C and quinine-C, and (iii) diverse group of refractory aliphatic-C moieties. The SOC in adjacent soils was predominantly composed of O-alkyl-C and methoxyl-C/N-alkyl-C structures and elements of labile aliphatic-C functionalities. Our study suggests that the inherent molecular structures of organic C due to selective accumulation of highly refractory aryl-C structures seems to be the key factor for the biochemical recalcitrance and stability of SOC in ADE. Anthropogenic enrichment with charred carbonaceous residues from biomass-derived black C (BC) is presumed to be the precursor of these recalcitrant polyaromatic structures. Our results also highlight the complementary role that might be played by organic C compounds composed of O-containing organic C moieties and aliphatic-C structures that persisted for millennia in these anthropic soils as additional or secondary sources of chemical recalcitrance of SOC in ADE. These organic C

  3. Shape memory polymers

    DOE Patents [OSTI]

    Wilson, Thomas S.; Bearinger, Jane P.

    2015-06-09

    New shape memory polymer compositions, methods for synthesizing new shape memory polymers, and apparatus comprising an actuator and a shape memory polymer wherein the shape memory polymer comprises at least a portion of the actuator. A shape memory polymer comprising a polymer composition which physically forms a network structure wherein the polymer composition has shape-memory behavior and can be formed into a permanent primary shape, re-formed into a stable secondary shape, and controllably actuated to recover the permanent primary shape. Polymers have optimal aliphatic network structures due to minimization of dangling chains by using monomers that are symmetrical and that have matching amine and hydroxyl groups providing polymers and polymer foams with clarity, tight (narrow temperature range) single transitions, and high shape recovery and recovery force that are especially useful for implanting in the human body.

  4. N,N'-DICYCLOHEXYL-N"-ISOTRIDECYLGUANIDINE AS SUPPRESSOR FOR THE NEXT GENERATION CAUSTIC SIDE SOLVENT EXTRACTION (NG-CSSX) PROCESS

    SciTech Connect (OSTI)

    Duncan, Nathan C; Roach, Benjamin D; Williams, Neil J; Bonnesen, Peter V; Rajbanshi, Arbin; Moyer, Bruce A

    2012-01-01

    ABSTRACT The purity, concentration, and source of the N,N'-dicyclohexyl-N"-isotridecylguanidine (DCiTG) suppressor (guanidine) used in the NG-CSSX process were found to influence solvent performance. As the starting isotridecanol used in the preparation of DCiTG is comprised of a mixture of branched-chain aliphatic alcohols, varying in composition with manufacturer, the resulting DCiTG itself is a mixture. Thus, it is necessary to address how the solvent performance will be affected by the different preparations of the DCiTG solvent component. In this study, four preparations of DCiTG from three sources were analyzed and evaluated for purity and performance, both in the absence and presence of an anionic surfactant impurity.

  5. An Assessment of the Stability and the Potential for In-Situ Synthesis of Regulated Organic Compounds in High Level Radioactive Waste Stored at Hanford, Richland, Washington

    SciTech Connect (OSTI)

    Wiemers, K.D.; Babad, H.; Hallen, R.T.; Jackson, L.P.; Lerchen, M.E.

    1999-01-04

    The stability assessment examined 269 non-detected regulated compounds, first seeking literature references of the stability of the compounds, then evaluating each compound based upon the presence of functional groups using professional judgment. Compounds that could potentially survive for significant periods in the tanks (>1 year) were designated as stable. Most of the functional groups associated with the regulated organic compounds were considered unstable under tank waste conditions. The general exceptions with respect to functional group stability are some simple substituted aromatic and polycyclic aromatic compounds that resist oxidation and the multiple substituted aliphatic and aromatic halides that hydrolyze or dehydrohalogenate slowly under tank waste conditions. One-hundred and eighty-one (181) regulated, organic compounds were determined as likely unstable in the tank waste environment.

  6. Water soluble laser dyes

    DOE Patents [OSTI]

    Hammond, Peter R.; Feeman, James F.; Field, George F.

    1998-01-01

    Novel water soluble dyes of the formula I are provided ##STR1## wherein R.sup.1 and R.sup.4 are alkyl of 1 to 4 carbon atoms or hydrogen; or R.sup.1 -R.sup.2 or R.sup.2 -R.sup.4 form part of aliphatic heterocyclic rings; R.sup.2 is hydrogen or joined with R.sup.1 or R.sup.4 as described above; R.sup.3 is --(CH.sub.2).sub.m --SO.sub.3.sup.-, where m is 1 to 6; X is N, CH or ##STR2## where Y is 2 --SO.sub.3.sup.- ; Z is 3, 4, 5 or 6 --SO.sub.3.sup.-. The novel dyes are particularly useful as the active media in water solution dye lasers.

  7. Clean, premium-quality chars: Demineralized and carbon enriched. [Quarterly] technical report, March 1, 1993--May 31, 1993

    SciTech Connect (OSTI)

    Smith, G.V.; Malhotra, V.M.; Wiltowski, T.; Myszka, E.

    1993-09-01

    The overall objective of this two-year project is to evaluate methods of preparing demineralized and carbon enriched chars from Illinois Basin coals. There are two processing steps: physical cleaning of the coal and devolatilization under different environments to form chars. Two differents techniques were used, in-situ Diffuse Reflectance FTIR measurements and BTU measurements. Experiments were performed with coals IBC-101, 102, and 104 as received and after cleaning. DR-FTIR spectrums helped to explain the possible existing chemical bonds in the coal structure as well as their changes during drying and mild pyrolysis. Drying coal causes hydrogen bonds between water and coal to be broken. Liquids produced above 500{degrees}C are much higher in aromatic content, thus, effectively reducing the concentration of aliphatic groups in the overall liquid yield. BTU values of coals after methane treatment are higher than after helium treatment.

  8. Sulfur Speciation of Different Kerogens using XANES Spectroscopy

    SciTech Connect (OSTI)

    Wiltfong,R.; Mitra-Kirtley, S.; Mullins, O.; Andrews, B.; Fujisawa, G.; Larsen, J.

    2005-01-01

    X-ray absorption near-edge structure (XANES) methodology has been employed to quantify the different sulfur structures present in three Type I and three Type II kerogens. Kerogens from the Green River (3), Bakken (1), Woodford (1), and Indiana limestone (1) formations were studied. Both aliphatic (sulfide) and aromatic (thiophene) forms of sulfur exist in all these kerogen samples. Except for Woodford, all of the kerogens contain oxidized functional groups. Sulfur in Types I and II kerogens mimics the carbon chemistry in that the sulfur structures are more aromatic in Type II than in Type I. It was impossible to differentiate elemental sulfur from pyrite in these samples by using K-edge XANES.

  9. Nonhazardous solvent composition and method for cleaning metal surfaces

    DOE Patents [OSTI]

    Googin, John M.; Simandl, Ronald F.; Thompson, Lisa M.

    1993-01-01

    A solvent composition for displacing greasy and oily contaminants as well as water and/or aqueous residue from metallic surfaces, especially surfaces of radioactive materials so that such surfaces can be wiped clean of the displaced contaminants, water and/or aqueous residue. The solvent composition consists essentially of a blend of nonpolar aliphatic hydrocarbon solvent having a minimum flash point of about 140.degree. F. and 2 to 25 volume percent of a polar solvent having a flash point sufficiently high so as to provide the solvent composition with a minimum flash point of at least 140.degree. F. The solvent composition is nonhazardous so that when it is used to clean the surfaces of radioactive materials the waste in the form of paper or cloth wipes, lab coats and the like used in the cleaning operation is not considered to be mixed waste composed of a hazardous solvent and a radioactive material.

  10. Nonhazardous solvent composition and method for cleaning metal surfaces

    DOE Patents [OSTI]

    Googin, J.M.; Simandl, R.F.; Thompson, L.M.

    1993-05-04

    A solvent composition for displacing greasy and oily contaminants as well as water and/or aqueous residue from metallic surfaces, especially surfaces of radioactive materials so that such surfaces can be wiped clean of the displaced contaminants, water and/or aqueous residue. The solvent composition consists essentially of a blend of nonpolar aliphatic hydrocarbon solvent having a minimum flash point of about 140 F and 2 to 25 volume percent of a polar solvent having a flash point sufficiently high so as to provide the solvent composition with a minimum flash point of at least 140 F. The solvent composition is nonhazardous so that when it is used to clean the surfaces of radioactive materials the waste in the form of paper or cloth wipes, lab coats and the like used in the cleaning operation is not considered to be mixed waste composed of a hazardous solvent and a radioactive material.

  11. Surfactant-modified zeolites as permeable barriers to organic and inorganic groundwater contaminants

    SciTech Connect (OSTI)

    Bowman, R.S.; Sullivan, E.J.

    1995-10-01

    We have shown in laboratory experiments that natural zeolites treated with hexadecyltrimethylammonium (HDTMA) are effective sorbents for nonpolar organics, inorganic cations, and inorganic anions. Due to their low cost ({approximately}$0.75/kg) and granular nature, HDTMA-zeolites appear ideal candidates for reactive, permeable subsurface barriers. The HDTMA-zeolites are stable over a wide range of pH (3-13), ionic strength (1 M Cs{sup +} or Ca{sup 2+}), and in organic solvents. Surfactant-modified zeolites sorb nonpolar organics (benzene, toluene, xylene, chlorinated aliphatics) via a partitioning mechanism, inorganic cations (Pb{sup 2+}) via ion exchange and surface complexation, and inorganic anions (CrO{sub 4}{sup 2-}, SeO{sub 4}{sup 2-}, SO{sub 4}{sup 2-}) via surface precipitation.The goal of this work is to demonstrate the use of surfactant-modified zeolite as a permeable barrier to ground water contaminants.

  12. Substantially isotactic, linear, alternating copolymers of carbon monoxide and an olefin

    DOE Patents [OSTI]

    Sen, Ayusman; Jiang, Zhaozhong

    1996-01-01

    The compound, [Pd(Me-DUPHOS)(MeCN).sub.2 ](BF.sub.4).sub.2, [Me-DUPHOS: 1,2-bis(2,5-dimethylphospholano)benzene] is an effective catalyst for the highly enantioselective, alternating copolymerization of olefins, such as aliphatic .alpha.-olefins, with carbon monoxide to form optically active, isotactic polymers which can serve as excellent starting materials for the synthesis of other classes of chiral polymers. For example, the complete reduction of a propylene-carbon monoxide copolymer resulted in the formation of a novel, optically active poly(1,4-alcohol). Also, the previously described catalyst is a catalyst for the novel alternating isomerization cooligomerization of 2-butene with carbon monoxide to form optically active, isotactic poly(1,5-ketone)

  13. Substantially isotactic, linear, alternating copolymers of carbon monoxide and an olefin

    DOE Patents [OSTI]

    Sen, A.; Jiang, Z.

    1996-05-28

    The compound, [Pd(Me-DUPHOS)(MeCN){sub 2}](BF{sub 4}){sub 2}, [Me-DUPHOS: 1,2-bis(2,5-dimethylphospholano)benzene] is an effective catalyst for the highly enantioselective, alternating copolymerization of olefins, such as aliphatic {alpha}-olefins, with carbon monoxide to form optically active, isotactic polymers which can serve as excellent starting materials for the synthesis of other classes of chiral polymers. For example, the complete reduction of a propylene-carbon monoxide copolymer resulted in the formation of a novel, optically active poly(1,4-alcohol). Also, the previously described catalyst is a catalyst for the novel alternating isomerization cooligomerization of 2-butene with carbon monoxide to form optically active, isotactic poly(1,5-ketone).

  14. Reduction of Aromatic Hydrocarbons by Zero-Valent Iron and Palladium Catalyst

    SciTech Connect (OSTI)

    Kim, Young-Hun; Shin, Won Sik; Ko, Seok-Oh; Kim, Myung-Chul

    2004-03-31

    Permeable reactive barrier (PRB) is an alternative technology for soil and groundwater remediation. Zero valent iron, which is the most popular PRB material, is only applicable to halogenated aliphatic organics and some heavy metals. The objective of this study was to investigate reductive dechlorination of halogenated compounds and reduction of non-halogenated aromatic hydrocarbons using zero valent metals (ZVMs) and catalysts as reactive materials for PRBs. A group of small aromatic hydrocarbons such as monochlorophenols, phenol and benzene were readily reduced with palladium catalyst and zero valent iron. Poly-aromatic hydrocarbons (PAHs) were also tested with the catalysts and zero valent metal combinations. The aromatic rings were reduced and partly reduced PAHs were found as the daughter compounds. The current study demonstrates reduction of aromatic compounds by ZVMs and modified catalysts and implicates that PRB is applicable not only for halogenated organic compounds but nonhalogenated aromatic compounds such as PAHs.

  15. Method and composition for testing for the presence of an alkali metal

    DOE Patents [OSTI]

    Guon, Jerold

    1981-01-01

    A method and composition for detecting the presence of an alkali metal on the surface of a body such as a metal plate, tank, pipe or the like is provided. The method comprises contacting the surface with a thin film of a liquid composition comprising a light-colored pigment, an acid-base indicator, and a nonionic wetting agent dispersed in a liquid carrier comprising a minor amount of water and a major amount of an organic solvent selected from the group consisting of the lower aliphatic alcohols, ketones and ethers. Any alkali metal present on the surface in elemental form or as an alkali metal hydroxide or alkali metal carbonate will react with the acid-base indicator to produce a contrasting color change in the thin film, which is readily discernible by visual observation or automatic techniques.

  16. A study of poplar organosolv lignin after melt rheology treatment as carbon fiber precursors

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Sun, Qining; Khunsupat, Ratayakorn; Akato, Kokouvi; Tao, Jingming; Labbe, Nicole; Gallego, Nidia C.; Bozell, Joseph J.; Rials, Timothy G.; Tuskan, Gerald A.; Tschaplinski, Timothy J.; et al

    2016-06-16

    Lignins from various poplar genotypes were isolated by using organosolv fractionation and subjected to rheological treatment at various temperatures. Physicochemical characterization of the lignin variants shows a broad distribution of glass transition temperatures, melt viscosity, and pyrolysis char residues. Rheological treatment at 170 °C induces lignin repolymerization accompanied with an increase in condensed linkages, molecular weights, and viscosities. In contrast, rheology testing at 190 °C results in the decrease in lignin aliphatic and phenolic hydroxyl groups, β-O-aryl ether linkages, molecular weights, and viscosity values. Lignin under air cooling generates more oxygenated and condensed compounds, but lower amounts of ether linkagesmore » than lignin cooled under nitrogen. Here, lignin with a lower syringyl/guaiacyl ratio tends to form more cross-linkages along with higher viscosity values, higher molecular weight and larger amounts of condensed bonds.« less

  17. Azacoumarin dye lasers

    DOE Patents [OSTI]

    Hammond, Peter R.; Atkins, Ronald L.; Henry, Ronald A.; Fletcher, Aaron N.

    1978-01-01

    A dye laser comprising a laser dye solution of a compound having the general structure: ##STR1## wherein at least one of the 5, 6 and 8 ring positions is occupied by a nitrogen atom in lieu of the corresponding CR group and X is OH, alkoxy, or amino including amino substituted by at least one of the following: alkyl, aryl, acyl, aracyl, a group which taken together with the nitrogen atom of the amino group forms a heterocyclic ring, or part of one or two 5 or 6 membered aliphatic heterocyclic rings attached to ring A at positions 6 or 8 or both depending on where the N in ring A is located. R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.8 are hydrogen or other groups as defined below. The compounds lase in the blue-green to near ultraviolet region.

  18. Azaquinolone dye lasers

    DOE Patents [OSTI]

    Hammond, Peter R.; Atkins, Ronald L.; Henry, Ronald A.; Fletcher, Aaron N.

    1978-01-01

    A dye laser comprising a laser dye solution of a compound having the general structure: ##STR1## wherein at least one of the 5, 6 and 8 ring positions is occupied by a nitrogen atom in lieu of the corresponding CR group and X is OH, alkoxy, or amino including amino substituted by at least one of the following: alkyl, aryl, acyl, aracyl, a group which taken together with the nitrogen atom of the amino group forms a heterocyclic ring, or part of one or two 5 or 6 membered aliphatic heterocyclic rings attached to ring A at positions 6 or 8 or both depending on where the N in ring A is located. R.sub.1, R.sub.3, R.sub.4, R.sub.5, R.sub.6 and R.sub.8 are hydrogen or other groups as defined below. The compounds lase in the blue to near ultraviolet region.

  19. Interactions between silver nanoparticles and polyvinyl alcohol nanofibers

    SciTech Connect (OSTI)

    Chou, H. L.; Wu, C. M.; Lin, F. D.; Rick, J.

    2014-08-15

    The interaction of polyvinylalcohol (PVA) nanofibers with silver (Ag) nanoparticles (mean diameter 8nm) has been modeled using density functional theory (DFT) calculations. The physical adsorption of PVA through the hydroxyl group, to the Ag, and its corresponding molecular orientation was compared with experimental results obtained from surface-enhanced Raman scattering (SERS) studies of the same material. A good agreement was found between the computational model of the vibrational spectrum of the adsorbate and the experimentally observed SERS. In general, aliphatic capping molecules are used to passivate the surface of Ag{sub 55} nanocrystals (55 = atomic number of Ag). In this study, a DFT simulation was employed to show binding energies and electron contour map analyses of Ag{sub 55} with PVA. Here we show that the PVA interacts with the Ag nanoparticle's surface, through the OH group, thereby contributing significantly to the increase in SERS activity.

  20. Water soluble laser dyes

    DOE Patents [OSTI]

    Hammond, P.R.; Feeman, J.F.; Field, G.F.

    1998-08-11

    Novel water soluble dyes of the formula 1 are provided by the formula described in the paper wherein R{sup 1} and R{sup 4} are alkyl of 1 to 4 carbon atoms or hydrogen; or R{sup 1}--R{sup 2} or R{sup 2}--R{sup 4} form part of aliphatic heterocyclic rings; R{sup 2} is hydrogen or joined with R{sup 1} or R{sup 4} as described above; R{sup 3} is --(CH{sub 2}){sub m}--SO{sub 3}{sup {minus}}, where m is 1 to 6; X is N, CH or formula 2 given in paper where Y is 2 --SO{sub 3}{sup {minus}} ; Z is 3, 4, 5 or 6 --SO{sub 3}{sup {minus}}. The novel dyes are particularly useful as the active media in water solution dye lasers.

  1. Analysis of low molecular weight hydrocarbons including 1,3-butadiene in engine exhaust gases using an aluminum oxide porous-layer open-tubular fused-silica column

    SciTech Connect (OSTI)

    Pelz, N.; Dempster, N.M.; Shore, P.R. )

    1990-05-01

    A method for the quantitative analysis of individual hydrocarbons in the C1-C8 range emitted in engine exhaust gases is described. The procedure provides base-line or near base-line resolution of C4 components including 1,3-butadiene. With a run time of less than 50 min, the light aromatics (benzene, toluene, ethyl benzene, p- and m-xylene, and o-xylene) are resolved during the same analysis as aliphatic hydrocarbons in the C1-C8 range. It is shown that typical 1,3-butadiene levels in engine exhaust are about 5 ppm at each of two engine conditions. Aromatic hydrocarbon levels show a dependence on engine operating conditions, benzene being about 20 ppm at high speed and about 40 ppm at idle.

  2. Urethane-based stabilizers for radiation-crosslinked polyethylene. [Electron beams

    SciTech Connect (OSTI)

    Shkolnik, S.; Rajbenbach, L.A.

    1982-11-01

    Unsaturated urethane-based stabilizers for use in radiation-crosslinked polyethylene were synthesized. Aromatic amine moieties were attached to allylic and acrylic monomers by means of aromatic or aliphatic diisocyanates. The synthesized stabilizers were incorporated in high-density polyethylene films which were subjected to electron beam irradiation. The oxidative stability of the films prior to and after extraction was determined by DTA in the temperature range 185-210/sup 0/C and compared with samples treated with commercial amine-bearing antioxidants. Tensile strength and gel content were also determined. Best results were obtained with a stabilizer prepared from equimolecular amounts of allyl alcohol, tolylene-2,4-diisocyanate and N-phenyl-1,4-phenylenediamine. Estimated lifetimes at 70/sup 0/C of stabilized irradiated polyethylene samples were calculated.

  3. FERRATES: SYNTHESIS, PROPERTIES AND APPLICATIONS IN WATER AND WASTEWATER TREATMENT.

    SciTech Connect (OSTI)

    CABELLI, D.E.; SHARMA, V.K.

    2006-05-19

    The higher oxidation states of iron (Fe(VI) and Fe(V) in particular) have been shown to be strongly oxidizing in enzymatic systems, where they can carry out aliphatic hydrogen abstraction. In addition, they have been postulated as intermediates in Fenton-type systems. Fe(VI) itself is relatively stable and has been shown to have potential as an oxidant in the so-called ''green'' treatment of polluted waters. By contrast, Fe(V) is a relatively short-lived transient when produced in aqueous solution in the absence of strongly bonding ligands other than hydroxide, a feature that has limited studies of its reactivity. Fe(VI) has been proposed to be useful in battery design and a very interesting study suggested that ferrate may be able to oxidize insoluble chromium to chromate and thus serve to remove chromium contamination in the Hanford radioactive waste tanks.

  4. Spectroscopic study on deuterated benzenes. I. Microwave spectra and molecular structure in the ground state

    SciTech Connect (OSTI)

    Kunishige, Sachi; Katori, Toshiharu; Baba, Masaaki; Nakajima, Masakazu; Endo, Yasuki

    2015-12-28

    We observed microwave absorption spectra of some deuterated benzenes and accurately determined the rotational constants of all H/D isotopomers in the ground vibrational state. Using synthetic analysis assuming that all bond angles are 120°, the mean bond lengths were obtained to be r{sub 0}(C–C) = 1.3971 Å and r{sub 0}(C–H) = r{sub 0}(C–D) = 1.0805 Å. It has been concluded that the effect of deuterium substitution on the molecular structure is negligibly small and that the mean bond lengths of C–H and C–D are identical unlike small aliphatic hydrocarbons, in which r{sub 0}(C–D) is about 5 mÅ shorter than r{sub 0}(C–H). It is considered that anharmonicity is very small in the C–H stretching vibration of aromatic hydrocarbons.

  5. Reactor and method for hydrocracking carbonaceous material

    DOE Patents [OSTI]

    Duncan, Dennis A.; Beeson, Justin L.; Oberle, R. Donald; Dirksen, Henry A.

    1980-01-01

    Solid, carbonaceous material is cracked in the presence of hydrogen or other reducing gas to provide aliphatic and aromatic hydrocarbons of lower molecular weight for gaseous and liquid fuels. The carbonaceous material, such as coal, is entrained as finely divided particles in a flow of reducing gas and preheated to near the decomposition temperature of the high molecular weight polymers. Within the reactor, small quantities of oxygen containing gas are injected at a plurality of discrete points to burn corresponding amounts of the hydrogen or other fuel and elevate the mixture to high temperatures sufficient to decompose the high molecular weight, carbonaceous solids. Turbulent mixing at each injection point rapidly quenches the material to a more moderate bulk temperature. Additional quenching after the final injection point can be performed by direct contact with quench gas or oil. The reactions are carried out in the presence of a hydrogen-containing reducing gas at moderate to high pressure which stabilizes the products.

  6. Method and apparatus for synthesizing hydrocarbons

    DOE Patents [OSTI]

    Colmenares, C.A.; Somorjai, G.A.; Maj, J.J.

    1985-04-16

    A method and apparatus for synthesizing a mixture of aliphatic alcohols having five carbons or less is disclosed. An equal molar ratio of CO and H/sub 2/ gases is caused to pass through a ThO/sub 2/ catalyst having a surface area of about 80 to 125 m/sup 2//g. The catalyst further optionally includes Na ions present as substitutional cations in an amount of about 5 to 10 atom %. At a temperature of about 570 to 630/sup 0/K, and at pressures of about 20 to 50 atm, methanol and isobutanol are the predominant products and are produced in amounts of about 90 wt % of the total hydrocarbon mixture. 6 figs.

  7. Field Sampling Plan for the Distler Brickyard Superfund Site, Hardin County, Kentucky

    SciTech Connect (OSTI)

    J. P. Martin; L. N. Peterson; C. J. Taylor

    1999-08-01

    This plan describes the field and analytical activities to be conducted at the Distler Brickyard Superfund Site, Hardin County, Kentucky, in order to evaluate natural attenuation processes within the aquifer system. Sampling will consist of a single round to take place in October 1999. Analytes will consist of the contaminants of concern (chlorinated aliphatic hydrocarbons), electron donors (non-chlorinated organic compounds), oxidation-reduction indicators, and water quality parameters. These activities are conducted in order to evaluate the water quality parameters. These activities are conducted in order to evaluate the extent to which natural attenuation processes, in the form of anaerobic reductive dechlorination, may be taking place in the aquifer system. These data will then be used to select the appropriate remediation technology for this site.

  8. Protein Vivisection Reveals Elusive Intermediates in Folding

    SciTech Connect (OSTI)

    Zheng, Zhongzhou; Sosnick, Tobin R. (UC)

    2010-05-25

    Although most folding intermediates escape detection, their characterization is crucial to the elucidation of folding mechanisms. Here, we outline a powerful strategy to populate partially unfolded intermediates: A buried aliphatic residue is substituted with a charged residue (e.g., Leu {yields} Glu{sup -}) to destabilize and unfold a specific region of the protein. We applied this strategy to ubiquitin, reversibly trapping a folding intermediate in which the {beta}5-strand is unfolded. The intermediate refolds to a native-like structure upon charge neutralization under mildly acidic conditions. Characterization of the trapped intermediate using NMR and hydrogen exchange methods identifies a second folding intermediate and reveals the order and free energies of the two major folding events on the native side of the rate-limiting step. This general strategy may be combined with other methods and have broad applications in the study of protein folding and other reactions that require trapping of high-energy states.

  9. Superacid Catalyzed Depolymerization and Conversion of Coals. Final Technical Report. [HF:BF{sub 2}/H{sub 2}

    DOE R&D Accomplishments [OSTI]

    Olah, G.

    1980-01-01

    We were interested in applying superacid catalyzed cleavage-depolymerization and ionic hydrogenation low temperature conversion of coal to liquid hydrocarbon, as well as obtaining information about the reactions involved and the structure of intermediates of the coal liquefaction process. In order to show the feasibility of our proposed research we have carried out preliminary investigation in these areas. Preceding our work there was no practical application of a superacid system to coal liquefaction. We carried out an extensive study of the potential of the HF:BF{sub 3}/H{sub 2} system for coal hydroliquefaction. Under varying conditions of reactant ratio, reaction time and temperature, we were able to obtain over 95% pyridine extractible product by treating coal in HF:BF{sub 3}:H{sub 2} system at approx. 100 degrees C for 4 hours. The coal to acid ratio was 1:5 and FB{sub 3} at 900 psi and H{sub 2} at 500 psi were used. These are extremely encouraging results in that the conditions used are drastically milder than those used in any known process, such as Exxon donor solvent and related processes. The cyclohexane extractibility of the treated coal was as high as 27% and the yield of liquid distillate at 400 degrees C/5 x 10{sup -3}/sup torr/ was approx. 30%. The infrared spectrum of product coal, extracts and distillates were distinctly different from the starting coal and show a significant increase in the amount of saturates. The {sup 1}H NMR spectrum of cyclohexane extract of the treated coal shows essentially all aliphatic photons. The spectra of other treated coal extracts show increased amounts and types of aliphatic protons as well as significant amounts of protons bound to unsaturated sites. This again indicates that the HF-BF{sub 3} system is depolymerizing the coal to small fragments which are soluble in non-polar solvents.

  10. Systematic modulation and enhancement of CO{sub 2} : N{sub 2} selectivity and water stability in an isoreticular series of bio-MOF-11 analogues

    SciTech Connect (OSTI)

    Li, Tao; Chen, De-Li; Sullivan, Jeanne E.; Kozlowski, Mark T.; Johnson, J Karl; Rosi, Nathaniel L.

    2013-02-01

    An isoreticular series of cobalt-adeninate bio-MOFs (bio-MOFs 11-14) is reported. The pores of bio-MOFs 11-14 are decorated with acetate, propionate, butyrate, and valerate, respectively. The nitrogen (N{sub 2}) and carbon dioxide (CO{sub 2}) adsorption properties of these materials are studied and compared. The isosteric heats of adsorption for CO{sub 2} are calculated, and the CO{sub 2}:N{sub 2} selectivities for each material are 10 determined. As the lengths of the aliphatic chains decorating the pores in bio-MOFs 11-14 increase, the BET surface areas decrease from 1148 m{sup 2}/g to 17 m{sup 2}/g while the CO{sub 2}:N{sub 2} selectivities predicted from ideal adsorbed solution theory at 1 bar and 273 K for a 10:90 CO{sub 2}:N{sub 2} mixture range from 73:1 for bio-MOF-11 to 123:1 for bio-MOF-12 and finally to 107:1 for bio-MOF-13. At 298 K, the selectivities are 43:1 for bio-MOF-11, 52:1 for bio-MOF-12, and 40:1 for bio-MOF-13. Additionally, it is shown that 15 bio-MOF-14 exhibits a unique molecular sieving property that allows it to adsorb CO{sub 2} but not N{sub 2} at 273 and 298 K. Finally, the water stability of bio-MOFs 11-14 increases with increasing aliphatic chain length. Bio-MOF-14 exhibits no loss of crystallinity or porosity after soaking in water for one month.

  11. Genes involved in long-chain alkene biosynthesis in Micrococcus luteus

    SciTech Connect (OSTI)

    Beller, Harry R.; Goh, Ee-Been; Keasling, Jay D.

    2010-01-07

    Aliphatic hydrocarbons are highly appealing targets for advanced cellulosic biofuels, as they are already predominant components of petroleum-based gasoline and diesel fuels. We have studied alkene biosynthesis in Micrococcus luteus ATCC 4698, a close relative of Sarcina lutea (now Kocuria rhizophila), which four decades ago was reported to biosynthesize iso- and anteiso branched, long-chain alkenes. The underlying biochemistry and genetics of alkene biosynthesis were not elucidated in those studies. We show here that heterologous expression of a three-gene cluster from M. luteus (Mlut_13230-13250) in a fatty-acid overproducing E. coli strain resulted in production of long-chain alkenes, predominantly 27:3 and 29:3 (no. carbon atoms: no. C=C bonds). Heterologous expression of Mlut_13230 (oleA) alone produced no long-chain alkenes but unsaturated aliphatic monoketones, predominantly 27:2, and in vitro studies with the purified Mlut_13230 protein and tetradecanoyl-CoA produced the same C27 monoketone. Gas chromatography-time of flight mass spectrometry confirmed the elemental composition of all detected long-chain alkenes and monoketones (putative intermediates of alkene biosynthesis). Negative controls demonstrated that the M. luteus genes were responsible for production of these metabolites. Studies with wild-type M. luteus showed that the transcript copy number of Mlut_13230-13250 and the concentrations of 29:1 alkene isomers (the dominant alkenes produced by this strain) generally corresponded with bacterial population over time. We propose a metabolic pathway for alkene biosynthesis starting with acyl-CoA (or -ACP) thioesters and involving decarboxylative Claisen condensation as a key step, which we believe is catalyzed by OleA. Such activity is consistent with our data and with the homology (including the conserved Cys-His-Asn catalytic triad) of Mlut_13230 (OleA) to FabH (?-ketoacyl-ACP synthase III), which catalyzes decarboxylative Claisen condensation during

  12. 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.

  13. Metagenomics, metatranscriptomics and single cell genomics reveal functional response of active Oceanospirillales to Gulf oil spill

    SciTech Connect (OSTI)

    Mason, Olivia U.; Hazen, Terry C.; Borglin, Sharon; Chain, Patrick S. G.; Dubinsky, Eric A.; Fortney, Julian L.; Han, James; Holman, Hoi-Ying N.; Hultman, Jenni; Lamendella, Regina; Mackelprang, Rachel; Malfatti, Stephanie; Tom, Lauren M.; Tringe, Susannah G.; Woyke, Tanja; Zhou, Jizhong; Rubin, Edward M.; Jansson, Janet K.

    2012-06-12

    The Deepwater Horizon oil spill in the Gulf of Mexico resulted in a deep-sea hydrocarbon plume that caused a shift in the indigenous microbial community composition with unknown ecological consequences. Early in the spill history, a bloom of uncultured, thus uncharacterized, members of the Oceanospirillales was previously detected, but their role in oil disposition was unknown. Here our aim was to determine the functional role of the Oceanospirillales and other active members of the indigenous microbial community using deep sequencing of community DNA and RNA, as well as single-cell genomics. Shotgun metagenomic and metatranscriptomic sequencing revealed that genes for motility, chemotaxis and aliphatic hydrocarbon degradation were significantly enriched and expressed in the hydrocarbon plume samples compared with uncontaminated seawater collected from plume depth. In contrast, although genes coding for degradation of more recalcitrant compounds, such as benzene, toluene, ethylbenzene, total xylenes and polycyclic aromatic hydrocarbons, were identified in the metagenomes, they were expressed at low levels, or not at all based on analysis of the metatranscriptomes. Isolation and sequencing of two Oceanospirillales single cells revealed that both cells possessed genes coding for n-alkane and cycloalkane degradation. Specifically, the near-complete pathway for cyclohexane oxidation in the Oceanospirillales single cells was elucidated and supported by both metagenome and metatranscriptome data. The draft genome also included genes for chemotaxis, motility and nutrient acquisition strategies that were also identified in the metagenomes and metatranscriptomes. These data point towards a rapid response of members of the Oceanospirillales to aliphatic hydrocarbons in the deep sea.

  14. Chemical changes to nonagrregtaed particulate soil organic matter following grassland-to woodland transition ina subtropical savanna.

    SciTech Connect (OSTI)

    Filley, T. R.; Boutton, T. W.; Liao, J. D.; Jastrow, J. D.; Gamblin, D. E.; Biosciences Division; Purdue Univ.; Texas A&M

    2008-07-19

    Encroachment of thorn woodlands into grasslands of southern Texas has resulted in greater aboveground and belowground biomass and greater soil organic carbon (SOC) stocks. Our previous studies showed that a large percentage of the SOC accrued under invading woody clusters was not stabilized within protective soil aggregates or on mineral-surfaces. Here we evaluated lignin and cutin- and suberin-derived substituted fatty acid (SFA) chemistry to determine if the accrual of nonaggregated particulate organic matter (POM) in woodlands was promoted by inherently greater recalcitrance of tissues from woody versus grass species, and if there was selective input of aboveground versus belowground plant carbon to POM. Woody clusters exhibited reduced concentrations of cutin-derived SFA and cinnamyl phenols within surface litter compared to fresh aboveground plant material. However, root litter exhibited relatively minor changes in biopolymer chemistry compared to fresh root tissue, suggesting it was either more stable or was refreshed at a greater rate. Between 14 and 105 years of woody plant encroachment, SFA in free POM fractions appeared to be consistently derived from root material while SFA within intraaggregate POM were increasingly derived from cutin sources. In addition, the shift from herbaceous to woody input was accompanied by enrichment in the amount of cutin and suberin-derived aliphatics with respect to lignin in both root and surface litter as well as nonaggregated POM. Woody plant encroachment at this site results in the rapid accrual of POM pools that are biochemically recalcitrant, providing a mechanism by which soil organic carbon can accumulate in this sandy soil system. Our results also lend further credence to the hypothesis that aliphatic biopolymers, particularly root-derived suberin, are important components of long-term soil organic carbon stabilization.

  15. Biomarker analysis of Upper Permian lacustrine oil shales, Junggar basin, NW China

    SciTech Connect (OSTI)

    Carroll, A. )

    1990-05-01

    Upper Permian lacustrine oil shales containing up to 34% TOC (total organic carbon) underlie approximately 50,000 km{sup 2} of the Junggar basin in western China, and appear to be the principal source of oils in the giant Karamay field in the northwestern Junggar and in several recent discoveries in other areas of the basin. The siliceous oil shales were deposited in a sediment-starved foreland basin during a period of predominantly humid climate. Previous biomarker studies of crude oils from Karamay field have documented an abundance of {beta}-carotane (which in some cases dominates the aliphatic hydrocarbon distribution) and gammacerane, suggesting a source bed deposited under hypersaline conditions. However, relatively complete outcrop exposures of finely laminated oil shales in the southern Junggar conspicuously lack evaporites, extensive dessication horizons, or other sedimentological evidence of playa lake environments. Indeed, the aliphatic hydrocarbon distribution in bitumen extracts from southern Junggar oil shales appear characteristic of freshwater to brakish water deposition of organic matter in an anoxic lake. Normal alkanes show a slight odd-over-even preference with relatively low levels of the C{sub 22}, n-alkane, pristane/phytane ratios close to unity, low {beta}-carotane and gammacerane levels, and the absence of C{sub 34}-C{sub 35} hopanes. This apparent difference in source bed depositional environments may be due to tectonic partitioning between separate depocenters of the Late Permian Junggar basin. Alternatively, hypersaline oil shale facies may be limited to deeper basinal areas, whereas upslope southern Junggar sediments record highstands in lake level or influx of fresh water from the adjacent drainage areas.

  16. Fluoroalkyl and Alkyl Chains Have Similar Hydrophobicities in Binding to the “Hydrophobic Wall” of Carbonic Anhydrase

    SciTech Connect (OSTI)

    J Mecinovic; P Snyder; K Mirica; S Bai; E Mack; R Kwant; D Moustakas; A Heroux; G Whitesides

    2011-12-31

    The hydrophobic effect, the free-energetically favorable association of nonpolar solutes in water, makes a dominant contribution to binding of many systems of ligands and proteins. The objective of this study was to examine the hydrophobic effect in biomolecular recognition using two chemically different but structurally similar hydrophobic groups, aliphatic hydrocarbons and aliphatic fluorocarbons, and to determine whether the hydrophobicity of the two groups could be distinguished by thermodynamic and biostructural analysis. This paper uses isothermal titration calorimetry (ITC) to examine the thermodynamics of binding of benzenesulfonamides substituted in the para position with alkyl and fluoroalkyl chains (H{sub 2}NSO{sub 2}C{sub 6}H{sub 4}-CONHCH{sub 2}(CX{sub 2}){sub n}CX{sub 3}, n = 0-4, X = H, F) to human carbonic anhydrase II (HCA II). Both alkyl and fluoroalkyl substituents contribute favorably to the enthalpy and the entropy of binding; these contributions increase as the length of chain of the hydrophobic substituent increases. Crystallography of the protein-ligand complexes indicates that the benzenesulfonamide groups of all ligands examined bind with similar geometry, that the tail groups associate with the hydrophobic wall of HCA II (which is made up of the side chains of residues Phe131, Val135, Pro202, and Leu204), and that the structure of the protein is indistinguishable for all but one of the complexes (the longest member of the fluoroalkyl series). Analysis of the thermodynamics of binding as a function of structure is compatible with the hypothesis that hydrophobic binding of both alkyl and fluoroalkyl chains to hydrophobic surface of carbonic anhydrase is due primarily to the release of nonoptimally hydrogen-bonded water molecules that hydrate the binding cavity (including the hydrophobic wall) of HCA II and to the release of water molecules that surround the hydrophobic chain of the ligands. This study defines the balance of enthalpic and

  17. Detection of high molecular weight organic tracers in vegetation smoke samples by high-temperature gas chromatography-mass spectrometry

    SciTech Connect (OSTI)

    Elias, V.O.; Simoneit, B.R.T. ); Pereira, A.S.; Cardoso, J.N. ); Cabral, J.A. )

    1999-07-15

    High-temperature high-resolution gas chromatography (HTGC) is an established technique for the separation of complex mixtures of high molecular weight (HMW) compounds which do not elute when analyzed on conventional GC columns. The combination of this technique with mass spectrometry is not so common and application to aerosols is novel. The HTGC and HTGC-MS analyses of smoke samples taken by particle filtration from combustion of different species of plants provided the characterization of various classes of HMW compounds reported to occur for the first time in emissions from biomass burning. Among these components are a series of wax esters with up to 58 carbon numbers, aliphatic hydrocarbons, triglycerides, long chain methyl ketones, alkanols and a series of triterpenyl fatty acid esters which have been characterized as novel natural products. Long chain fatty acids with more than 32 carbon numbers are not present in the smoke samples analyzed. The HMW compounds in smoke samples from the burning of plants from Amazonia indicate the input of directly volatilized natural products in the original plants during their combustion. However, the major organic compounds extracted from smoke consist of a series of lower molecular weight polar components, which are not natural products but the result of the thermal breakdown of cellulose and lignin. In contrast, the HMW natural products may be suitable tracers for specific sources of vegetation combustion because they are emitted as particles without thermal alternation in the smoke and can thus be related directly to the original plant material.

  18. Wet oxidation of an azo dye: Lumped kinetics in batch and mixed flow reactors

    SciTech Connect (OSTI)

    Donlagic, J.; Levec, J.

    1999-12-01

    Oxidation of a dilute aqueous solution of a model azo dye pollutant (Orange II) was studied in batch and continuous well-mixed (CSTR) reactors. Both reactors operate at 200--250 C, and total pressures up to 50 bar and at oxygen partial pressure from 10 to 30 bar. The model pollutant concentrations were in a range between 100 and 1,000 mg/L, which may be found in industrial wastewaters. The dye oxidation undergoes parallel-consecutive reaction pathways, in which it first decomposes thermally and oxidatively to aromatic intermediates and via organic acids to the final product carbon dioxide. To develop a kinetic equation capable of predicting organic carbon reduction, all organic species present in solution were lumped by total organic carbon (TOC). The lumped oxidation rate in batch reactor exhibited second-order behavior, whereas in the CSTR is was found linearly proportional to its TOC concentration. The lump behavior in batch reactor was dominated by the refractory low molecular mass aliphatic acids formed during the oxidation.

  19. Yellow phosphorus process to convert toxic chemicals to non-toxic products

    DOE Patents [OSTI]

    Chang, S.G.

    1994-07-26

    The present invention relates to a process for generating reactive species for destroying toxic chemicals. This process first contacts air or oxygen with aqueous emulsions of molten yellow phosphorus. This contact results in rapid production of abundant reactive species such as O, O[sub 3], PO, PO[sub 2], etc. A gaseous or liquid aqueous solution organic or inorganic chemicals is next contacted by these reactive species to reduce the concentration of toxic chemical and result in a non-toxic product. The final oxidation product of yellow phosphorus is phosphoric acid of a quality which can be recovered for commercial use. A process is developed such that the byproduct, phosphoric acid, is obtained without contamination of toxic species in liquids treated. A gas stream containing ozone without contamination of phosphorus containing species is also obtained in a simple and cost-effective manner. This process is demonstrated to be effective for destroying many types of toxic organic, or inorganic, compounds, including polychlorinated biphenyls (PCB), aromatic chlorides, amines, alcohols, acids, nitro aromatics, aliphatic chlorides, polynuclear aromatic compounds (PAH), dyes, pesticides, sulfides, hydroxyamines, ureas, dithionates and the like. 20 figs.

  20. Structural Transformation of Isolated Poplar and Switchgrass Lignins from Dilute Acid Pretreatment

    SciTech Connect (OSTI)

    Sun, Qining; Pu, Yunqiao; Meng, Xianzhi; Wells, Tyrone; Ragauskas, Arthur J.

    2015-08-27

    A key step in conversion of cellulosic biomass into sustainable fuels and chemicals is thermochemical pretreatment to reduce plant cell wall recalcitrance. Obtaining an improved understanding of the fundamental chemistry of lignin, the most recalcitrant component of biomass, during pretreatment is critical to the continued development of renewable biofuel production. To examine the intrinsic chemistry of lignin during dilute acid pretreatment (DAP), lignin was isolated from poplar and switchgrass using a cellulolytic enzyme system and then treated under DAP conditions. These results highlight that lignin is subjected to depolymerization reactions within the first 2 min of dilute acid pretreatment and these changes are accompanied by increased generation of aliphatic and phenolic hydroxyl groups of lignin. This is followed by a competing set of depolymerization and repolymerization reactions that lead to a decrease in the content of guaiacyl lignin units and an increase in condensed lignin units as the reaction residence time is extended beyond 5 min. Finally, we showed that a detailed comparison of changes in functional groups and molecular weights of cellulolytic enzyme lignins with different structural parameters, related to the recalcitrant properties of lignin, could be successfully altered during DAP conditions.

  1. Nitrous oxide production from radiolysis of simulted high-level nuclear waste solutions

    SciTech Connect (OSTI)

    Walker, D.D.; Hobbs, D.T.; Tiffany, J.B.; Bibler, N.E.; Meisel, D.

    1992-07-01

    Nitrous oxide gas (N{sub 2}O) is produced by the radiolysis of aqueous nitrate or nitrite solutions in the presence of organic compounds. When ethylenediaminetetraacetic acid (EDTA) or N- (2-hydroxyethyl)-ethylenediaminetriacetic acid (HEDTA) is present, the G-value for hydrogen increases and N{sub 2}O become the major gaseous product (G=0.54). A survey of organic compounds indicates the amount of N{sub 2}O formed depends on the structure of the organic. With highly oxidized organics (carbonate, formate, acetate and oxalate), little or no N{sub 2}O is formed. Aromatic and aliphatic organics (sodium tetraphenylborate, benzene, phenol, n-paraffin, and tributylphosphate) produce small amounts of N{sub 2}O. Water soluble, easily oxidized organics (methanol, ethanol, isopropanol, n-butanol, acetone, and ethylene glycol) produce large amounts of N{sub 2}O relative to the previous two categories. Nitrous oxide production is not greatly affected by pH between neutral and pH=13, but increases significantly in acid solution. The G-value for N{sub 2}O production in 10 wt% potassium tetraphenylborate slurries has been measured under process conditions important at the Savannah River Site.

  2. Nitrous oxide production from radiolysis of simulted high-level nuclear waste solutions

    SciTech Connect (OSTI)

    Walker, D.D.; Hobbs, D.T.; Tiffany, J.B.; Bibler, N.E. ); Meisel, D. )

    1992-01-01

    Nitrous oxide gas (N{sub 2}O) is produced by the radiolysis of aqueous nitrate or nitrite solutions in the presence of organic compounds. When ethylenediaminetetraacetic acid (EDTA) or N- (2-hydroxyethyl)-ethylenediaminetriacetic acid (HEDTA) is present, the G-value for hydrogen increases and N{sub 2}O become the major gaseous product (G=0.54). A survey of organic compounds indicates the amount of N{sub 2}O formed depends on the structure of the organic. With highly oxidized organics (carbonate, formate, acetate and oxalate), little or no N{sub 2}O is formed. Aromatic and aliphatic organics (sodium tetraphenylborate, benzene, phenol, n-paraffin, and tributylphosphate) produce small amounts of N{sub 2}O. Water soluble, easily oxidized organics (methanol, ethanol, isopropanol, n-butanol, acetone, and ethylene glycol) produce large amounts of N{sub 2}O relative to the previous two categories. Nitrous oxide production is not greatly affected by pH between neutral and pH=13, but increases significantly in acid solution. The G-value for N{sub 2}O production in 10 wt% potassium tetraphenylborate slurries has been measured under process conditions important at the Savannah River Site.

  3. Ras-GTP dimers activate the mitogen-activated protein kinase (MAPK) pathway

    SciTech Connect (OSTI)

    Nan, Xiaolin; Tamgney, Tanja M.; Collisson, Eric A.; Lin, Li -Jung; Pitt, Cameron; Galeas, Jacqueline; Lewis, Sophia; Gray, Joe W.; McCormick, Frank; Chu, Steven

    2015-06-16

    Rat sarcoma (Ras) GTPases regulate cell proliferation and survival through effector pathways including Raf-MAPK, and are the most frequently mutated genes in human cancer. Although it is well established that Ras activity requires binding to both GTP and the membrane, details of how Ras operates on the cell membrane to activate its effectors remain elusive. Efforts to target mutant Ras in human cancers to therapeutic benefit have also been largely unsuccessful. Here we show that Ras-GTP forms dimers to activate MAPK. We used quantitative photoactivated localization microscopy (PALM) to analyze the nanoscale spatial organization of PAmCherry1-tagged KRas 4B (hereafter referred to KRas) on the cell membrane under various signaling conditions. We found that at endogenous expression levels KRas forms dimers, and KRasG12D, a mutant that constitutively binds GTP, activates MAPK. Overexpression of KRas leads to formation of higher order Ras nanoclusters. Conversely, at lower expression levels, KRasG12D is monomeric and activates MAPK only when artificially dimerized. Moreover, dimerization and signaling of KRas are both dependent on an intact CAAX (C, cysteine; A, aliphatic; X, any amino acid) motif that is also known to mediate membrane localization. These results reveal a new, dimerization-dependent signaling mechanism of Ras, and suggest Ras dimers as a potential therapeutic target in mutant Ras-driven tumors.

  4. Single gene insertion drives bioalcohol production by a thermophilic archaeon

    SciTech Connect (OSTI)

    Basen, M; Schut, GJ; Nguyen, DM; Lipscomb, GL; Benn, RA; Prybol, CJ; Vaccaro, BJ; Poole, FL; Kelly, RM; Adams, MWW

    2014-12-09

    Bioethanol production is achieved by only two metabolic pathways and only at moderate temperatures. Herein a fundamentally different synthetic pathway for bioalcohol production at 70 degrees C was constructed by insertion of the gene for bacterial alcohol dehydrogenase (AdhA) into the archaeon Pyrococcus furiosus. The engineered strain converted glucose to ethanol via acetate and acetaldehyde, catalyzed by the host-encoded aldehyde ferredoxin oxidoreductase (AOR) and heterologously expressed AdhA, in an energy-conserving, redox-balanced pathway. Furthermore, the AOR/AdhA pathway also converted exogenously added aliphatic and aromatic carboxylic acids to the corresponding alcohol using glucose, pyruvate, and/or hydrogen as the source of reductant. By heterologous coexpression of a membrane-bound carbon monoxide dehydrogenase, CO was used as a reductant for converting carboxylic acids to alcohols. Redirecting the fermentative metabolism of P. furiosus through strategic insertion of foreign genes creates unprecedented opportunities for thermophilic bioalcohol production. Moreover, the AOR/AdhA pathway is a potentially game-changing strategy for syngas fermentation, especially in combination with carbon chain elongation pathways.

  5. The effect of feedstock additives on FCC catalyst deactivation

    SciTech Connect (OSTI)

    Hughes, R.; Koon, C.L.; McGhee, B.

    1995-12-31

    Fluid catalytic cracking is a major petroleum refining process and because of this the deactivation of FCC catalysts by coke deposition has been the subject of considerable investigation during the past 50 years. Nevertheless, a lack of understanding of the fundamental understanding of processes leading to coke formation still exists. Basic studies using Zeolites have usually involved excessively high levels of coke deposits compared to normal FCC operation. The present study addresses coke formation at realistic levels of 0.5 to 1.0% w/w using a standard MAT reactor in which concentrations of 1% and 10% of various additives were added to the n-hexadecane feedstock. These additives included, quinoline, phenanthrene, benzofuran, thianaphthene and indene. The coke formed was characterised by mass spectrometry and was significantly aliphatic in nature, the amount formed increasing in the order quinoline, phenanthrene, thianaphthene, benzofuran, indene. Quinoline acts primarily as a poison, whereas the other additives tend to promote coke formation in n-hexadecane cracking.

  6. Clean, premium-quality chars: Demineralized and carbon enriched. Final technical report, 1 September, 1992--31 August, 1993

    SciTech Connect (OSTI)

    Smith, G.V.; Malhotra, V.M.; Wiltowski, T.

    1993-12-31

    The overall objective of this two-year project was to evaluate methods of preparing demineralized and carbon enriched chars from Illinois Basin coals. The two processing steps, physical cleaning and devolatilization under different environments, led to the following results. Cleaning coal incompletely removes mineral matter which decreases catalytic activity and increases micropore structure. Water forms hydrogen bonds to oxygen functional groups in coal, and during drying, coals undergo structural changes which affect mild gasification. When methane reacts wit coal, devolatilization and carbon deposition occur, the rates of which depend on temperature and amount of ash. Thermal decomposition of IBC-101 coal starts at 300 C, which is much lower than previously believed, but maximum yields of liquids occur at 500 C for IBC-101 coal and at 550 C for IBC-102 coal. Aliphatic-to-aromatic ratios increase with increasing pyrolysis temperatures to 300 C and then decrease; therefore, liquids formed during gasification of 550 C or higher contain mainly aromatic compounds. Btu values of chars are higher after methane treatment than after helium treatment.

  7. Energetics and dynamics of solvent reorganization in charge-transfer excited states

    SciTech Connect (OSTI)

    Kozik, M.; Sutin, N.; Winkler, J.R.

    1989-01-01

    The dynamics of solvation of the Ru(bpy){sub 2}(CN){sub 2} metal-to-ligand charge-transfer excited state have been examined in a series of aliphatic alcohols. Steady-state emission spectra recorded at low temperature ({approx} 10 K) and at room temperature were used to resolve internal-mode and solvent contributions to the emission bandshape. Time-resolved emission spectra were fit to a model that takes into account internal-mode distortions as well as time-dependent broadening and shifts in emission maxima. A single- exponential solvent relaxation function does not adequately describe the temporal development of the emission profile of Ru(bpy){sub 2}(CN){sub 2} in alcohols. The evolution of the emission spectrum is clearly biphasic, and can be reasonably fit with a biexponential function. The slower of the two relaxation times is comparable to the longest longitudinal relaxation time reported for the bulk solvent. These slower components, however, represent less than half of the overall approach to equilibrium. Local heating due to above-threshold excitation, and local solvent relaxation are two likely sources of the faster dynamics. 25 refs., 3 figs., 2 tabs.

  8. Interactions of a designed peptide with lipopolysaccharide: Bound conformation and anti-endotoxic activity

    SciTech Connect (OSTI)

    Bhunia, Anirban; Chua, Geok Lin; Domadia, Prerna N.; Warshakoon, Hemamali; Cromer, Jens R.; David, Sunil A.; Bhattacharjya, Surajit

    2008-05-09

    Designed peptides that would selectively interact with lipopolysaccharide (LPS) or endotoxin and fold into specific conformations could serve as important scaffolds toward the development of antisepsis compounds. Here, we describe solution structure of a designed amphipathic peptide, H{sub 2}N-YVKLWRMIKFIR-CONH{sub 2} (YW12D) in complex with endotoxin as determined by transferred nuclear Overhauser effect spectroscopy. The conformation of the isolated peptide is highly flexible, but undergoes a dramatic structural stabilization in the presence of LPS. Structure calculations reveal that the peptide presents two amphipathic surfaces in its bound state to LPS whereby each surface is characterized by two positive charges and a number of aromatic and/or aliphatic residues. ITC data suggests that peptide interacts with two molecules of lipid A. In activity assays, YW12D exhibits neutralization of LPS toxicity with very little hemolysis of red blood cells. Structural and functional properties of YW12D would be applicable in designing low molecular weight non-toxic antisepsis molecules.

  9. Experimental and modeling investigation of aromatic and polycyclic aromatic hydrocarbon formation in a premixed ethylene flame

    SciTech Connect (OSTI)

    Castaldi, M.J.; Marinov, N.M.; Melius, C.F.

    1996-02-01

    Experimental and detailed chemical kinetic modeling has been performed to investigate aromatic and polyaromatic hydrocarbon formation pathways in a rich, sooting, ethylene-oxygen-argon premixed flame. An atmospheric pressure, laminar flat flame operated at an equivalence ratio of 2.5 was used to acquire experimental data for model validation. Gas composition analysis was conducted by an on-line gas chromatograph/mass spectrometer (GC/MS) technique. Measurements were made in the flame and post-flame zone for a number of low molecular weight species, aliphatics, aromatics and polycyclic aromatic hydrocarbons (PAHs) ranging from two to five-aromatic fused rings. The modeling results show the key reaction sequences leading to aromatic and polycyclic aromatic hydrocarbon growth involve the combination of resonantly stabilized radicals. In particular, propargyl and 1-methylallenyl combination reactions lead to benzene and methyl substituted benzene formation, while polycyclic aromatics are formed from cyclopentadienyl radicals and fused rings that have a shared C{sub 5} side structure. Naphthalene production through the reaction step of cyclopentadienyl self-combination and phenanthrene formation from indenyl and cyclopentadienyl combination were shown to be important in the flame modeling study. The removal of phenyl by O{sub 2} leading to cyclopentadienyl formation is expected to play a pivotal role in the PAH or soot precursor growth process under fuel-rich oxidation conditions.

  10. Effect of Ligands on Characteristics of (CdSe)13 Quantum Dot

    SciTech Connect (OSTI)

    Gao, Yang; Zhou, Bo; Kang, Seung-gu; Xin, Minsi; Yang, Ping; Dai, Xing; Wang, Zhigang; Zhou, Ruhong

    2014-01-01

    The widespread applications of quantum dots (QDs) have spurred an increasing interest in the study of their coating ligands, which can not only protect the electronic structures of the central QDs, but also control their permeability through biological membranes with both size and shape. In this work, we have used density functional theory (DFT) to investigate the electronic structures of (CdSe)13 passivated by OPMe2(CH2)nMe ligands with different lengths and various numbers of branches (Me=methyl group, n = 0, 1-3). Our results show that the absorption peak in the ultraviolet-visible (UV-vis) spectra displays a clear blue-shift, on the scale of ~100 nm, upon the binding of ligands. Once the total number of ligands bound with (CdSe)13 reached a saturated number (9 or 10), no more blue-shift occurred in the absorption peak in the UV-vis spectra. On the other hand, the aliphatic chain length of ligands has a negligible effect on the optical properties of the QD core. Analyses of the bonding characteristics confirm that optical transitions are dominantly governed by the central QD core rather than the organic passivation. Interestingly, the density of states (DOS) share similar characteristics as vibrational spectra, even though there is no coordination vibration mode between the ligands and the central QD. These findings might provide insights on the material design for the passivation of quantum dots for biomedical applications.

  11. α, α', α", α'"-meso-tetrahexyltetramethyl-calix[4]pyrrole: An easy-to-prepare, isomerically pure anion extractant with enhanced solubility in organic solvents

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Williams, Neil J.; Bryantsev, Vyacheslav S.; Custelcean, Radu; Seipp, Charles A.; Moyer, Bruce A.

    2016-01-29

    α, α', α", α'"-meso-Tetrahexyltetramethyl-calix[4]pyrrole is easily obtained as a single diastereomer in a one-pot reaction. It exhibits enhanced solubility in organic solvents, including aliphatic solvents, relative to its parent meso-octamethylcalix[4]pyrrole (1). Somewhat surprisingly, the tetrahexyl derivative 2 complexes with tributylmethylammonium chloride in chloroform more strongly than does 1 as shown by NMR titrations. However, 1 and 2 exhibit comparable complexation strength in extraction experiments, the difference between the NMR and extraction results being attributed to the effect of organic-phase water in the extraction systems. Mass-action analysis indicates the formation of the predominant complex TBMA+(1 or 2)Cl– in both NMR andmore » extraction systems, and equilibrium constants are reported. x-Ray crystal structures were obtained for the free ligand 2 and its complex with tetramethylammonium chloride. In addition, the free ligand crystallises in the 1,3-alt conformation with equatorial hexyl arms. In the chloride complex with 2 in its cone conformation, the hexyl arms adopt an axial orientation, enveloping the anion. DFT calculations show this binding conformation to be the most stable, mostly owing to destabilising steric interactions involving the pyrrole C–H and alkyl C–H groups positioned equatorially.« less

  12. Characteristics of carbonized sludge for co-combustion in pulverized coal power plants

    SciTech Connect (OSTI)

    Park, Sang-Woo; Jang, Cheol-Hyeon

    2011-03-15

    Co-combustion of sewage sludge can destabilize its combustion profile due to high volatility, which results in unstable flame. We carried out fuel reforming for sewage sludge by way of carbonization at pyrolysis temperature of 300-500 deg. C. Fuel characteristics of carbonized sludge at each temperature were analyzed. As carbonization temperature increased, fuel ratio increased, volatile content reduced, and atomic ratio relation of H/C and O/C was similar to that of lignite. The analysis result of FT-IR showed the decrease of aliphatic C-H bond and O-C bond in carbonization. In the analysis result of TG-DTG, the thermogravimetry reduction temperature of carbonized sludge (CS400) was proven to be higher than that of dried sludge, but lower than that of sub-bituminous coal. Hardgrove grindability index increased in proportion to fuel ratio increase, where the carbonized sludge value of 43-110 was similar or higher than the coal value of 49-63. As for ash deposits, slagging and fouling index were higher than that of coal. When carbonized sludge (CS400) and coal were co-combusted in 1-10% according to calorific value, slagging tendency was low in all conditions, and fouling tendency was medium or high according to the compositions of coal.

  13. Mechanisms, Chemistry, and Kinetics of Anaerobic Biodegradation of cis-Dichloroethene and Vinyl Chloride

    SciTech Connect (OSTI)

    McCarty, P.L.; Spormann, A.M.

    2000-12-01

    Anaerobic biological processes can result in PCE and TCE destruction through conversion to cis-dichloroethene (cDCE) then to vinyl chloride (VC), and finally to ethene. Here, the chlorinated aliphatic hydrocarbons (CAHs) serve as electron acceptors in energy metabolism, requiring electron donors such as hydrogen from an external source. The purpose of this study was to learn more about the biochemistry of cDCE and VC conversion to ethene, to better understand the requirements for electron donors, and to determine factors affecting the rates of CAH degradation and organism growth. The biochemistry of reductive dehalogenation of VC was studied with an anaerobic mixed culture enriched on VC. In other studies on electron donor needs for dehalogenation of cDCE and VC, competition for hydrogen was found to occur between the dehalogenators and other microorganisms such as methanogens and homoacetogens in a benzoate-acclimated dehalogenating methanogenic mixed culture. Factors affecting the relative rates of destruction of the solvents and their intermediate products were evaluated. Studies using a mixed PCE-dehalogenating culture as well as the VC enrichment for biochemical studies suggested that the same species was involved in both cDCE and VC dechlorination, and that cDCE and VC competitively inhibited each other's dechlorination rate.

  14. Solid-state organometallic chemistry of molecular metal oxide clusters: C-H activation by an iridium polyoxometalate

    SciTech Connect (OSTI)

    Siedle, A.R.; Newmark, R.A.; Brown-Wensley, K.A.; Skarjune, R.P.; Haddad, L.C.; Hodgson, K.O.; Roe, A.L.

    1988-09-01

    Hydrogenation of ((Ph/sub 3/P)/sub 2/Ir(C/sub 8/H/sub 12/))/sub 3/PW/sub 12/O/sub 40/ in a solid-gas reaction produces ((Ph/sub 3/P)/sub 2/IrH/sub 2/)/sub 3/PW/sub 12/O/sub 40/. EXAFS studies of the molybdenum analogue indicate the presence of isolated, lattice-stabilized (Ph/sub 3/P)/sub 2/IrH/sub 2//sup +/ ions. H/emdash/D exchange with CD/sub 3/CH/double bond/CH/sub 2/ occurs via a reversible C/emdash/H addition reaction that also produces ((Ph/sub 3/P)/sub 2/IrH(/pi/-C/sub 3/H/sub 5/))/sub 3/PW/sub 12/O/sub 40/ and scrambles the C/sub 3/D/sub 3/H/sub 3/ deuterium label. Exchange with toluene is selective and involves activation of aromatic but not aliphatic C-H bonds. Slow exchange with c-C/sub 6/D/sub 12/ also occurs.

  15. Yellow phosphorus process to convert toxic chemicals to non-toxic products

    DOE Patents [OSTI]

    Chang, Shih-Ger

    1994-01-01

    The present invention relates to a process for generating reactive species for destroying toxic chemicals. This process first contacts air or oxygen with aqueous emulsions of molten yellow phosphorus. This contact results in rapid production of abundant reactive species such as O, O.sub.3, PO, PO.sub.2, etc. A gaseous or liquid aqueous solution organic or inorganic chemicals is next contacted by these reactive species to reduce the concentration of toxic chemical and result in a non-toxic product. The final oxidation product of yellow phosphorus is phosphoric acid of a quality which can be recovered for commercial use. A process is developed such that the byproduct, phosphoric acid, is obtained without contamination of toxic species in liquids treated. A gas stream containing ozone without contamination of phosphorus containing species is also obtained in a simple and cost-effective manner. This process is demonstrated to be effective for destroying many types of toxic organic, or inorganic, compounds, including polychlorinated biphenyls (PCB), aromatic chlorides, amines, alcohols, acids, nitro aromatics, aliphatic chlorides, polynuclear aromatic compounds (PAH), dyes, pesticides, sulfides, hydroxyamines, ureas, dithionates and the like.

  16. Chemical tagging of chlorinated phenols for their facile detection and analysis by NMR spectroscopy

    SciTech Connect (OSTI)

    Valdez, Carlos A.; Leif, Roald N.

    2015-03-22

    A derivatization method that employs diethyl (bromodifluoromethyl) phosphonate (DBDFP) to efficiently tag the endocrine disruptor pentachlorophenol (PCP) and other chlorinated phenols (CPs) along with their reliable detection and analysis by NMR is presented. The method accomplishes the efficient alkylation of the hydroxyl group in CPs with the difluoromethyl (CF2H) moiety in extremely rapid fashion (5 min), at room temperature and in an environmentally benign manner. The approach proved successful in difluoromethylating a panel of 18 chlorinated phenols, yielding derivatives that displayed unique 1H, 19F NMR spectra allowing for the clear discrimination between isomerically related CPs. Due to its biphasic nature, the derivatization can be applied to both aqueous and organic mixtures where the analysis of CPs is required. Furthermore, the methodology demonstrates that PCP along with other CPs can be selectively derivatized in the presence of other various aliphatic alcohols, underscoring the superiority of the approach over other general derivatization methods that indiscriminately modify all analytes in a given sample. The present work demonstrates the first application of NMR on the qualitative analysis of these highly toxic and environmentally persistent species.

  17. Organic solution-processible electroluminescent molecular glasses for non-doped standard red OLEDs with electrically stable chromaticity

    SciTech Connect (OSTI)

    Bi, Xiaoman; Zuo, Weiwei; Liu, Yingliang Zhang, Zhenru; Zeng, Cen; Xu, Shengang; Cao, Shaokui

    2015-10-15

    Highlights: • The D–A–D electroluminescent molecular glasses are synthesized. • Non-doped red electroluminescent film is fabricated by spin-coating. • Red OLED shows stable wavelength, luminous efficiency and chromaticity. • CIE1931 coordinate is in accord with standard red light in PAL system. - Abstract: Organic light-emitting molecular glasses (OEMGs) are synthesized through the introduction of nonplanar donor and branched aliphatic chain into electroluminescent emitters. The target OEMGs are characterized by {sup 1}H NMR, {sup 13}C NMR, IR, UV–vis and fluorescent spectra as well as elemental analysis, TG and DSC. The results indicated that the optical, electrochemical and electroluminescent properties of OEMGs are adjusted successfully by the replacement of electron-donating group. The non-doped OLED device with a standard red electroluminescent emission is achieved by spin-coating the THF solution of OEMG with a triphenylamine moiety. This non-doped red OLED device takes on an electrically stable electroluminescent performance, including the stable maximum electroluminescent wavelength of 640 nm, the stable luminous efficiency of 2.4 cd/A and the stable CIE1931 coordinate of (x, y) = (0.64, 0.35), which is basically in accord with the CIE1931 coordinate (x, y) = (0.64, 0.33) of standard red light in PAL system.

  18. Ras-GTP dimers activate the mitogen-activated protein kinase (MAPK) pathway

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Nan, Xiaolin; Tamgüney, Tanja M.; Collisson, Eric A.; Lin, Li -Jung; Pitt, Cameron; Galeas, Jacqueline; Lewis, Sophia; Gray, Joe W.; McCormick, Frank; Chu, Steven

    2015-06-16

    Rat sarcoma (Ras) GTPases regulate cell proliferation and survival through effector pathways including Raf-MAPK, and are the most frequently mutated genes in human cancer. Although it is well established that Ras activity requires binding to both GTP and the membrane, details of how Ras operates on the cell membrane to activate its effectors remain elusive. Efforts to target mutant Ras in human cancers to therapeutic benefit have also been largely unsuccessful. Here we show that Ras-GTP forms dimers to activate MAPK. We used quantitative photoactivated localization microscopy (PALM) to analyze the nanoscale spatial organization of PAmCherry1-tagged KRas 4B (hereafter referredmore » to KRas) on the cell membrane under various signaling conditions. We found that at endogenous expression levels KRas forms dimers, and KRasG12D, a mutant that constitutively binds GTP, activates MAPK. Overexpression of KRas leads to formation of higher order Ras nanoclusters. Conversely, at lower expression levels, KRasG12D is monomeric and activates MAPK only when artificially dimerized. Moreover, dimerization and signaling of KRas are both dependent on an intact CAAX (C, cysteine; A, aliphatic; X, any amino acid) motif that is also known to mediate membrane localization. These results reveal a new, dimerization-dependent signaling mechanism of Ras, and suggest Ras dimers as a potential therapeutic target in mutant Ras-driven tumors.« less

  19. High resolution capillary column development for selective separations in gas chromatography

    SciTech Connect (OSTI)

    Przybyciel, M.

    1985-01-01

    A review of techniques for the preparation of high resolution capillary columns for gas chromatography is presented. Surface roughing, surface deactivation, stationary phase coating, and stationary phase crosslinking are discussed. Criteria for the selection of GC stationary phases and procedures for column evaluation are presented. A method is proposed for the isolation and determination of crude oil contamination in tropical plants and sediments. The method uses Florisil (TM) chromatography for the simultaneous clean-up and fractionation of aliphatic and aromatic hydrocarbons. Crosslinked SE-54 fused silica capillary columns prepared in our laboratory were employed for all GC separations. Mass spectrometry was used to help locate and identify specific oil components despite the intense background of the chromatogram. Crude oil components were identified in extracts of mangrove plant samples collected from the Peck Slip oil spill site at Media Munda, Puerto Rico. Crude oil components were also identified in sediment samples from controlled oil spill of Prudhoe Bay oil at Laguna de Chiriqui, Panama.

  20. Ab Initio Study of the Wolff Rearrangement of C6H40 Intermediate in the Gas Phase

    SciTech Connect (OSTI)

    Borisov, Yurii A.; Garrett, Bruce C.; Feller, David F.

    1999-09-30

    Ab initio calculations of the geometry and reactivity of 1,2-ketocarbene C6H4O as an intermediate in organic reactions were performed using the second-order Møller-Plesset (MP2) perturbation theory in the 6-311G* basis set. Only the singlet state of the intermediate was considered. An oxirene-like structure (6) with a six-membered ring and a ketene-like structure (5) with a five-membered ring were localized on the potential energy surface. Attempts to locate a quinone type structure characteristic of aliphatic ketocarbenes failed. The energy of structure5 is -70 kcal mol-1 lower than that of structure 6. Harmonic frequencies and intensities of normal vibrations in the IR spectra of6 and5 were calculated. The activation energy of the Wolff rearrangement 6→5 was estimated at 12.5 kcal mol-1. The geometry of the transition state of this reaction resembles the quinone-like structure.

  1. Complexation of N4-Tetradentate Ligands with Nd(III) and Am(III)

    SciTech Connect (OSTI)

    Ogden, Mark D.; Sinkov, Sergey I.; Meier, G. Patrick; Lumetta, Gregg J.; Nash, Kenneth L.

    2012-12-06

    To improve understanding of aza-complexants in trivalent actinidelanthanide separations, a series of tetradentate N-donor ligands have been synthesized and their complexation of americium(III) and neodymium(III) investigated by UVvisible spectrophotometry in methanolic solutions. The six pyridine/alkyl amine/imine ligands are N,N0-bis(2-methylpyridyl)-1,2-diaminoethane, N,N0-bis(2-methylpyridyl)-1,3-diaminopropane, trans-N,N-bis(2-pyridylmethyl)-1,2-diaminocyclohexane (BPMDAC), N,N-bis(2-pyridylmethyl)piperazine, N,N-bis-[pyridin-2-ylmethylene]ethane-1,2-diamine, and trans-N,Nbis-([pyridin-2-ylmethylene]-cyclohexane-1,2-diamine. Each ligand has two pyridine groups and two aliphatic amine/imine N-donor atoms arranged with different degrees of preorganization and structural backbone rigidity. Conditional stability constants for the complexes of Am(III) and Nd(III) by these ligands establish the selectivity patterns. The overall selectivity of Am(III) over Nd(III) is similar to that reported for the terdentate bis(dialkyltriazinyl)pyridine molecules. The cyclohexane amine derivative (BPMDAC) is the strongest complexant and shows the highest selectivity for Am(III) over Nd(III) while the imines appear to prefer a bridging arrangement between two cations. These results suggest that this series of ligands could be employed to develop an enhanced actinide(III) lanthanide(III) separation system.

  2. CHARACTERIZATION AND EVALUATION OF CAUSTIC WASH TANK AND SOLVENT HOLD TANK SAMPLES FROM MCU FROM AUGUST TO SEPTEMBER 2011

    SciTech Connect (OSTI)

    Fondeur, F.; Fink, S.

    2012-08-01

    During processing of Salt Batches 3 and 4 in the Modular Caustic-Side Solvent Extraction Unit (MCU), the decontamination efficiency for cesium declined from historical values and from expectations based on laboratory testing. This report documents efforts to analyze samples of solvent and process solutions from MCU in an attempt to understand the cause of the reduced performance and to recommend mitigations. CWT Solutions from MCU from the time period of variable decontamination factor (DF) performance which covers from April 2011 to September 2011 (during processing of Salt Batch 4) were examined for impurities using chromatography and spectroscopy. The results indicate that impurities were found to be of two types: aromatic containing impurities most likely from Modifier degradation and aliphatic type impurities most likely from Isopar{reg_sign} L and tri-n-octylamine (TOA) degradation. Caustic washing the Solvent Hold Tank (SHT) solution with 1M NaOH improved its extraction ability as determined from {sup 22}Na uptake tests. Evidence from this work showed that pH variance in the aqueous solutions within the range of 1M nitric acid to 1.91M NaOH that contacted the solvent samples does not influence the analytical determination of the TOA concentration by GC-MS.

  3. Superfund Record of Decision (EPA Region 7): Vogel Paint and Wax, Maurice, IA. (First remedial action), September 1989. Final report

    SciTech Connect (OSTI)

    Not Available

    1989-09-20

    The Vogel Paint and Wax (VPW) site is an approximately two-acre disposal area two miles southwest of the town of Maurice, in Sioux County, Iowa. Adjacent land uses are primarily agricultural; however, several private residences are within one-quarter mile of the site. A surficial sand and gravel aquifer underlies the site and supplies nearby private wells and the Southern Sioux County Rural Water System, located a mile and one half southeast of the site. Paint sludge, resins, solvents, and other paint-manufacturing wastes were disposed of at the site between 1971 and 1979. VPW records indicate that approximately 43,000 gallons of aliphatic and aromatic hydrocarbons and 6,000 pounds of metals waste were buried at the site. The primary contaminants of concern affecting the soil and ground water are VOCs including benzene, toluene, and xylenes; and metals including chromium and lead. The selected remedial action for this site includes excavation of contaminated soil and separation of solid and liquid wastes; onsite bioremediation of 3,000 cubic yards of the contaminated soil in a fully contained surface impoundment unit, or onsite thermal treatment if soil contains high metal content; and stabilization of treated soil, if necessary to prevent leaching of metals, followed by disposal in the excavated area.

  4. Identification of sulfur heterocycles in coal liquids and shale oils. Technical progress report, August 1, 1980-May 1, 1981

    SciTech Connect (OSTI)

    Lee, M. L.; Castle, R. N.

    1981-01-01

    The sulfur heterocycle separation scheme which was described in the last progress report was evaluated for quantitative recovery of individual components. The results indicate that recoveries can range from 10% to approx. 30% depending on the structure of the compound. During this period, 23 unsubstituted sulfur-containing heterocyclic ring systems were synthesized in oder to confirm GC/MS identifications and for biological testing. The four possible 3-ring heterocycles and the thirteen possible 4-ring heterocycles were tested for mutagenic activity in the histidine reversion (Ames assay) system. One of the 3-ring isomers, naphtho(1,2-b)-thiophene, and six of the 4-ring isomers induced mutations in Salmonella test strains. One of these compounds, phenanthro(3,4-b)thiophene, displayed approximately the same mutagenic activity as benzo(a)pyrene. A two-step adsorption chromatographic procedure was developed in order to fractionate synthetic fuels into various chemical-type classes for studying the relative concentrations and mutagenic activities of the various types. An SRC-II Heavy Distillate was fractionated into aliphatic hydrocarbons, polycyclic aromatic hydrocarbons, sulfur heterocycles, indoles and carbazoles, azaarenes, and amino polycyclic aromatic hydrocarbons. It was found that the amino-PAH fraction contained most of the mutagenic activity. A survey was made for compounds containing both nitrogen and sulfur heteroatoms in their structures. A number of these compounds were detected by GC using nitrogen- and sulfur-selective detection.

  5. Process for hydrocracking carbonaceous material in liquid carrier

    DOE Patents [OSTI]

    Duncan, Dennis A.

    1980-01-01

    Solid carbonaceous material is hydrocracked to provide aliphatic and aromatic hydrocarbons for use as gaseous and liquid fuels or chemical feed stock. Particulate carbonaceous material such as coal in slurry with recycled product oil is preheated in liquid state to a temperature of 600.degree.-1200.degree. F. in the presence of hydrogen gas. The product oil acts as a sorbing agent for the agglomerating bitumins to minimize caking within the process. In the hydrocracking reactor, the slurry of oil and carbonaceous particles is heated within a tubular passageway to vaporize the oil and form a gas-solid mixture which is further heated to a hydropyrolysis temperature in excess of 1200.degree. F. The gas-solid mixture is quenched by contact with additional oil to condense normally liquid hydrocarbons for separation from the gases. A fraction of the hydrocarbon liquid product is recycled for quenching and slurrying with the carbonaceous feed. Hydrogen is recovered from the gas for recycle and additional hydrogen is produced by gasification of residual char.

  6. Linkages and aromatic clusters in a bituminous coal: Final report, September 1, 1985--September 30, 1988

    SciTech Connect (OSTI)

    Chung, K.E.

    1988-10-01

    The distribution and arrangement of aromatic clusters, oxygen functional groups, and linkages in an Illinois No. 6 bituminous coal were determined by controlled solubilization of the coal, followed by solvent fractionation of the soluble product and detailed analyses of the product fractions. The solubilization was carried out in reactions with NaOH/ethanol/H/sub 2/O at temperatures of 260/degree/, 300/degree/ and 320/degree/C. Elemental balance and spectroscopic data revealed that the oxygen functional groups of the coal were attacked selectively in the solubilization process, resulting in an orderly definable diminution of the complex coal structure. Also aliphatic linkages present in selected solubilized product fractions were subjected to a transalkylation reaction. A molecular structural model specific to the Illinois coal was constructed, and the hydroliquefaction behavior of the coal was evaluated in terms of potential product distribution and hydrogen consumption. The structural characteristics are compared with those of a Wyoming subbituminous coal in our previous study. 9 refs., 16 figs., 11 tabs.

  7. Molecular and crystal structures of p-heptyloxyphenyl p-hexyloxybenzoate and p-butyloxyphenyl p-heptyloxybenzoate: Mesophase design

    SciTech Connect (OSTI)

    Kuz'mina, L. G. Gunina, M. A.; Churakov, A. V.; Pestov, S. M.

    2013-03-15

    Two aromatic esters with the formulas C{sub 6}H{sub 13}-O-C{sub 6}H{sub 4}-C(O)O-C{sub 6}H{sub 4}-O-C{sub 7}H{sub 15} (1) and C{sub 7}H{sub 15}-O-C{sub 6}H{sub 4}-C(O)O-C{sub 6}H{sub 4}-O-C{sub 4}H{sub 9} (2) belonging to nematic liquid-crystal compounds were studied by X-ray diffraction. Compound 1 crystallizes in two modifications: monoclinic (1-m) and triclinic (1-tr). The crystal packing of 1 and 2 is built from alternating loosely packed aliphatic regions and closely packed aromatic regions. In crystal structures 1-m and 2, the aromatic regions are linked into chains by hydrogen bonds with the participation of the carbonyl oxygen atom of the ester group and the C-H fragment of the benzene ring, but these hydrogen bonds in 1-m are much weaker than in 2. In 1-m there are {pi}-stacking interactions between the molecules, resulting in the formation of centrosymmetric dimers with an interplanar distance of 3.45 A. In 1-tr, the aromatic fragments form a herringbone packing motif favorable for a two-dimensional network of directional C-H...{pi}-system interactions.

  8. Structural Transformation of Isolated Poplar and Switchgrass Lignins from Dilute Acid Pretreatment

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Sun, Qining; Pu, Yunqiao; Meng, Xianzhi; Wells, Tyrone; Ragauskas, Arthur J.

    2015-08-27

    A key step in conversion of cellulosic biomass into sustainable fuels and chemicals is thermochemical pretreatment to reduce plant cell wall recalcitrance. Obtaining an improved understanding of the fundamental chemistry of lignin, the most recalcitrant component of biomass, during pretreatment is critical to the continued development of renewable biofuel production. To examine the intrinsic chemistry of lignin during dilute acid pretreatment (DAP), lignin was isolated from poplar and switchgrass using a cellulolytic enzyme system and then treated under DAP conditions. These results highlight that lignin is subjected to depolymerization reactions within the first 2 min of dilute acid pretreatment andmore » these changes are accompanied by increased generation of aliphatic and phenolic hydroxyl groups of lignin. This is followed by a competing set of depolymerization and repolymerization reactions that lead to a decrease in the content of guaiacyl lignin units and an increase in condensed lignin units as the reaction residence time is extended beyond 5 min. Finally, we showed that a detailed comparison of changes in functional groups and molecular weights of cellulolytic enzyme lignins with different structural parameters, related to the recalcitrant properties of lignin, could be successfully altered during DAP conditions.« less

  9. Carbonyl Emissions from Gasoline and Diesel Motor Vehicles

    SciTech Connect (OSTI)

    Destaillats, Hugo; Jakober, Chris A.; Robert, Michael A.; Riddle, Sarah G.; Destaillats, Hugo; Charles, M. Judith; Green, Peter G.; Kleeman, Michael J.

    2007-12-01

    Carbonyls from gasoline powered light-duty vehicles (LDVs) and heavy-duty diesel powered vehicles (HDDVs) operated on chassis dynamometers were measured using an annular denuder-quartz filter-polyurethane foam sampler with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine derivatization and chromatography-mass spectrometry analyses. Two internal standards were utilized based on carbonyl recovery, 4-fluorobenzaldehyde for_C8 compounds. Gas- and particle-phase emissions for 39 aliphatic and 20 aromatic carbonyls ranged from 0.1 ? 2000 ?g/L fuel for LDVs and 1.8 - 27000 mu g/L fuel for HDDVs. Gas-phase species accounted for 81-95percent of the total carbonyls from LDVs and 86-88percent from HDDVs. Particulate carbonyls emitted from a HDDV under realistic driving conditions were similar to concentrations measured in a diesel particulate matter (PM) standard reference material. Carbonyls accounted for 19percent of particulate organic carbon (POC) emissions from low-emission LDVs and 37percent of POC emissions from three-way catalyst equipped LDVs. This identifies carbonyls as one of the largest classes of compounds in LDV PM emissions. The carbonyl fraction of HDDV POC was lower, 3.3-3.9percent depending upon operational conditions. Partitioning analysis indicates the carbonyls had not achieved equilibrium between the gas- and particle-phase under the dilution factors of 126-584 used in the current study.

  10. Commercial-scale demonstration of the Liquid Phase Methanol (LPMEOH{trademark}) Process. Peroxide formation of dimethyl ether in methanol mixtures

    SciTech Connect (OSTI)

    Waller, F.J.

    1997-11-01

    Organic peroxides could form when dimethyl ether in methanol is stored for three to six months at a time. The objective of this work was to determine the level of peroxide formation from dimethyl ether in reagent grade methanol and raw methanol at room temperature under 3 atmospheres (45 psig) of air. Raw methanol is methanol made from syngas by the LPMEOH Process without distillation. Aliphatic ethers tend to react slowly with oxygen from the air to form unstable peroxides. However, there are no reports on peroxide formation from dimethyl ether. After 172 days of testing, dimethyl ether in either reagent methanol or raw methanol at room temperature and under 60--70 psig pressure of air does not form detectable peroxides. Lack of detectable peroxides suggests that dimethyl ether or dimethyl ether and methanol may be stored at ambient conditions. Since the compositions of {approximately} 1.3 mol% or {approximately} 4.5 mol% dimethyl ether in methanol do not form peroxides, these compositions can be considered for diesel fuel or an atmospheric turbine fuel, respectively.

  11. Improved resolution of hydrocarbon structures and constitutional isomers in complex mixtures using Gas Chromatography-Vacuum Ultraviolet-Mass Spectrometry (GC-VUV-MS)

    SciTech Connect (OSTI)

    Aerosol Dynamics Inc; Aerodyne Research, Inc.,; Tofwerk AG, Thun; Isaacman, Gabriel; Wilson, Kevin R.; Chan, Arthur W. H.; Worton, David R.; Kimmel, Joel R.; Nah, Theodora; Hohaus, Thorsten; Gonin, Marc; Kroll, Jesse H.; Worsnop, Doug R.; Goldstein, Allen H.

    2011-09-13

    Understanding the composition of complex hydrocarbon mixtures is important for environmental studies in a variety of fields, but many prevalent compounds cannot be confidently identified using traditional gas chromatography-mass spectrometry (GC-MS) techniques. This work uses vacuum-ultraviolet (VUV) ionization to elucidate the structures of a traditionally"unresolved complex mixture" by separating components by GC retention time, tR, and mass-to-charge ratio, m/Q, which are used to determine carbon number, NC, and the number of rings and double bonds, NDBE. Constitutional isomers are resolved based on tR, enabling the most complete quantitative analysis to date of structural isomers in an environmentally-relevant hydrocarbon mixture. Unknown compounds are classified in this work by carbon number, degree of saturation, presence of rings, and degree of branching, providing structural constraints. The capabilities of this analysis are explored using diesel fuel, in which constitutional isomer distribution patterns are shown to be reproducible between carbon numbers and follow predictable rules. Nearly half of the aliphatic hydrocarbon mass is shown to be branched, suggesting branching is more important in diesel fuel than previously shown. The classification of unknown hydrocarbons and the resolution of constitutional isomers significantly improves resolution capabilities for any complex hydrocarbon mixture.

  12. Biofiltration control of VOC and air toxic emissions: n-Butane and benzene

    SciTech Connect (OSTI)

    Allen, E.R.

    1996-12-31

    n-Butane and benzene vapors are routinely observed in urban atmospheres. Their presence in urban airsheds is of concern because of their ozone production potential as volatile organic compounds (VOCs) and/or potential toxicity. Also, these saturated hydrocarbons are representative of airborne aliphatic and aromatic compounds. Separate laboratory studies have been conducted on the biological elimination of n-butane (n-C{sub 4}H{sub 10}) and benzene (C{sub 6}H{sub 6}) from airstreams using treated compost biofilters. The removal efficiencies were found to exceed 90% for a conditioned biofilter medium and pollutant low concentrations (< 25 ppm) and zeroth order kinetics at higher concentrations (> 100 ppm), whereas benzene vapor elimination followed zeroth order kinetics at concentrations up to 200 ppm. The maximum n-butane and benzene elimination capacities observed for the compost biofilters and conditions employed were 25 and 70 g pollutant m{sup -3} h{sup -1}, respectively. 13 refs., 6 figs., 2 tabs.

  13. Chemical Characterization and Water Content Determination of Bio-Oils Obtained from Various Biomass Species using 31P NMR Spectroscopy

    SciTech Connect (OSTI)

    David, K.; Ben, H.; Muzzy, J.; Feik, C.; Iisa, K.; Ragauskas, A.

    2012-03-01

    Pyrolysis is a promising approach to utilize biomass for biofuels. One of the key challenges for this conversion is how to analyze complicated components in the pyrolysis oils. Water contents of pyrolysis oils are normally analyzed by Karl Fischer titration. The use of 2-chloro-4,4,5,5,-tetramethyl-1,3,2-dioxaphospholane followed by {sup 31}P NMR analysis has been used to quantitatively analyze the structure of hydroxyl groups in lignin and whole biomass. Results: {sup 31}P NMR analysis of pyrolysis oils is a novel technique to simultaneously characterize components and analyze water contents in pyrolysis oils produced from various biomasses. The water contents of various pyrolysis oils range from 16 to 40 wt%. The pyrolysis oils obtained from Loblolly pine had higher guaiacyl content, while that from oak had a higher syringyl content. Conclusion: The comparison with Karl Fischer titration shows that {sup 31}P NMR could also reliably be used to measure the water content of pyrolysis oils. Simultaneously with analysis of water content, quantitative characterization of hydroxyl groups, including aliphatic, C-5 substituted/syringyl, guaiacyl, p-hydroxyl phenyl and carboxylic hydroxyl groups, could also be provided by {sup 31}P NMR analysis.

  14. Molecular Characterization of Organosulfates in Organic Aerosols from Shanghai and Los Angeles Urban Areas by Nanospray-Desorption Electrospray Ionization High-Resolution Mass Spectrometry

    SciTech Connect (OSTI)

    Tao, Shikang; Lu, Xiaohui; Levac, Nicole A.; Bateman, Adam P.; Nguyen, Tran B.; Bones, David L.; Nizkorodov, Sergey; Laskin, Julia; Laskin, Alexander; Yang, Xin

    2014-08-21

    Aerosol samples collected in the urban areas of Shanghai and Los Angeles were analyzed by nanospray-desorption electrospray ionization mass spectrometry (nano-DESI MS) with high mass resolution (m/?m=100,000). Solvent mixtures of acetonitrile/water and acetonitrile/toluene were used to extract and ionize polar and non-polar compounds, respectively. A diverse mixture of oxygenated hydrocarbons, organosulfates, organonitrates, and organics with reduced nitrogen were detected in the Los Angeles sample. Majority of the organics in the Shanghai sample were detected as organosulfates. The dominant organosulfates in the two samples have distinctly different molecular characteristics. Specifically, organosulfates in the Los Angeles sample were dominated by isoprene- or monoterpene-derived products, while organosulfates of yet unknown origin in the Shanghai sample had distinctive characteristics of long aliphatic carbon chains and low degree of oxidation and unsaturation. The use of acetonitrile/toluene solvent facilitated identification of this type of organosulfates, suggesting they could be missed in previous studies relying on sample extraction using common polar solvents. The high molecular weight and low degree of unsaturation and oxidization of the organosulfates detected in the Shanghai sample suggest that they may act as surfactants, and plausibly affect the surface tension and hygroscopicity of the atmospheric particulate matter. We propose that direct esterification of carbonyl or hydroxyl compounds by sulfates or sulfuric acid in liquid phase could be the formation pathway of these special organosulfates. Long-chain alkanes from vehicle emissions might be their precursors.

  15. Synthesis and characterization of interfacially polymerized films of tetraphenylporphyrin derivatives

    SciTech Connect (OSTI)

    Li, W.; Wamser, C.C.

    1995-10-01

    Thin films of polymeric porphyrins have been made by interfacial polymerization of derivatives of tetraphenyl porphyrins, in particular by condensation of a dichloromethane solution of the acid chloride derivative (TCCPP) with a buffered aqueous solution of either the amine derivative (TAPP) or the phenol derivative (THPP). Spectroscopic and other studies are consistent with cross-linked polyamide or polyester network structures. The polyamide and polyester films display a novel asymmetry of functional groups on opposite sides of the film; excess amine (or hydroxyl) groups appear on one side of the film and excess carboxyl groups on the other. Film thickness can be correlated with the intensity of the UV-visible absorption spectrum, x (in nm) = 120 A{sub max} (at the Soret peak), with typical thicknesses in the range 10-500 nm, easily controlled by reaction time and conditions. Significantly thicker films (up to several {mu}m) can be prepared using an aliphatic diamine orpolyamine as the comonomer with TCCPP. Addition of 2, 6-lutidine to the organic phase substantially increases the rate of polymerization, which is especially useful for TAPP reactions. In addition, control experiments show that TCCPP with lutidine in CH{sub 2}Cl{sub 2} reacts at the interface with an aqueous pH 3 buffer, giving a very thin, easily hydrolyzed film, apparently due to anhydride linkages formed by condensation reactions with partially hydrolyzed TCCPP. 56 refs., 11 figs., 4 tabs.

  16. Inhalation developmental toxicology studies: Teratology study of acetone in mice and rats: Final report

    SciTech Connect (OSTI)

    Mast, T.J.; Evanoff, J.J.; Rommereim, R.L.; Stoney, K.H.; Weigel, R.J.; Westerberg, R.B.

    1988-11-01

    Acetone, an aliphatic ketone, is a ubiquitous industrial solvent and chemical intermediate; consequently, the opportunity for human exposure is high. The potential for acetone to cause developmental toxicity was assessed in Sprague-Dawley rats exposed to 0, 440, 2200, or 11000 ppm, and in Swiss (CD-1) mice exposed to 0, 440, 2200, and 6600 ppm acetone vapors, 6 h/day, 7 days/week. Each of the four treatment groups consisted of 10 virgin females (for comparison), and approx.32 positively mated rats or mice. Positively mated mice were exposed on days 6-17 of gestation (dg), and rats on 6-19 dg. The day of plug or sperm detection was designated as 0 dg. Body weights were obtained throughout the study period, and uterine and fetal body weights were obtained at sacrifice (rats, 20 dg; mice, 18 dg). Implants were enumerated and their status recorded. Live fetuses were sexed and examined for gross, visceral, skeletal, and soft-tissue craniofacial defects. 46 refs., 6 figs., 27 tabs.

  17. Design, construction, operation, and evaluation of solar systems for industrial process-heat applications in the intermediate-temperature range (212/sup 0/F to 550/sup 0/F). Environmental assessment

    SciTech Connect (OSTI)

    1982-01-01

    The environmental impacts are assessed for a proposed 50,000 square foot field of single axis tracking, concentrating solar collectors along the Ohio River in southern Ohio. The facility is planned to produce process steam for use in the production of polystyrene. Absorbed solar energy would heat an aliphatic hydrocarbon synthetic heat transfer fluid to a maximum temperature of 500/sup 0/F. The existing environment is briefly described, particularly regarding air quality. The potential environmental impacts of the solar process heat system on the air, water, soil, endangered species and archaeological and historical resources are examined, including risks due to flood and glare and a comparison of alternatives. Also included are a Consent Judgment relating to two coal-fired boilers in violation of EPA regulations, property data of Gulf Synfluid 4CS (a candidate heat transfer fluid), piping and instrumentation diagrams and schematics, site grade and drainage plan, geological survey map, subsurface soil investigation, Ohio endangered species list, Ohio Archaeological Counsel certification list, and a study of heat transfer fluids and their properties. (LEW)

  18. Theoretical Study of the Thermal Decomposition of Carboxylic Acids at Pyrolysis Temperature

    SciTech Connect (OSTI)

    Clark, J. M.; Robichaud, D. J.; Nimlos, M. R.

    2013-01-01

    Carboxylic acids are important in the processing of biomass into renewable fuels and chemicals. They are formed from the pretreatment and pyrolysis of hemicellulose biopolymers and are released from the decomposition of sugars. They result from the deconstruction of polyhydroxyalkanoates (bacterial carbon storage polymers) from fatty acids derived from algae, bacteria, and oil crops. The thermal deoxygenation of carboxylic acids is an important step in the conversion of biomass into aliphatic hydrocarbons suitable for use in renewable biofuels and as petrochemical replacements. Decarboxylation, a primary decomposition pathway under pyrolysis conditions, represents an ideal conversion process, because it eliminates two atoms of oxygen for every carbon atom removed. Problematically, additional deoxygenation processes exist (e.g. dehydration) that are in direct competition with decarboxylation and result in the formation of reactive and more fragmented end products. To better understand the competition between decarboxylation and other deoxygenation processes and to gain insight into possible catalysts that would favor decarboxylation, we have investigated the mechanisms and thermochemistry of the various unimolecular and bimolecular deoxygenation pathways for a family of C1-C4 organic acids using electronic structure calculations at the M06-2X/6-311++G(2df,p) level of theory.

  19. Defective Pollen Wall is Required for Anther and Microspore Development in Rice and Encodes a Fatty Acyl Carrier Protein Reductase

    SciTech Connect (OSTI)

    Shi, J.; Shanklin, J.; Tan, H.; Yu, X.-H.; Liu, Y.; Liang, W.; Ranathunge, K.; Franke, R. B.; Schreiber, L.; Wang, Y.; Kai, G.; Ma, H.; Zhang, D.

    2011-06-01

    Aliphatic alcohols naturally exist in many organisms as important cellular components; however, their roles in extracellular polymer biosynthesis are poorly defined. We report here the isolation and characterization of a rice (Oryza sativa) male-sterile mutant, defective pollen wall (dpw), which displays defective anther development and degenerated pollen grains with an irregular exine. Chemical analysis revealed that dpw anthers had a dramatic reduction in cutin monomers and an altered composition of cuticular wax, as well as soluble fatty acids and alcohols. Using map-based cloning, we identified the DPW gene, which is expressed in both tapetal cells and microspores during anther development. Biochemical analysis of the recombinant DPW enzyme shows that it is a novel fatty acid reductase that produces 1-hexadecanol and exhibits >270-fold higher specificity for palmiltoyl-acyl carrier protein than for C16:0 CoA substrates. DPW was predominantly targeted to plastids mediated by its N-terminal transit peptide. Moreover, we demonstrate that the monocot DPW from rice complements the dicot Arabidopsis thaliana male sterile2 (ms2) mutant and is the probable ortholog of MS2. These data suggest that DPWs participate in a conserved step in primary fatty alcohol synthesis for anther cuticle and pollen sporopollenin biosynthesis in monocots and dicots.

  20. Peptide affinity labels for thrombin and other trypsin-like proteases

    DOE Patents [OSTI]

    Shaw, E.N.; Kettner, C.A.

    1982-03-09

    A peptide affinity label is disclosed of the formula (I): as given in the patent wherein X is a radical capable of acting as a leaving group in a nucleophilic substitution reaction; A is an aromatic amino acid residue; B is H, or a C[sub 1]--C[sub 4] alkyl group, or aryl; Y is selected from the group consisting of hydrogen, aroyl, C[sub 1]--C[sub 6] acyl, and Q--(A)--[sub n], wherein Q = hydrogen, aroyl, or C[sub 1]--C[sub 6] acyl, n = 1--10, A is an amino acid residue selected from the aliphatic, hydroxy-containing, carboxylic acid group, and amide-thereofcontaining, aromatic, sulfur-containing and imino-containing amino acids; and wherein J is selected from the group consisting of --CH[sub 2]--, --CH[sub 2]--CH[sub 2]--, --CH[sub 2]--CH[sub 2]--CH[sub 2]--, --CH[double bond]CH-- and --CH(OH)--CH[sub 2]. The affinity label is useful for irreversibly inactivating thrombin and trypsin-like enzymes and may be used as a potential anticlotting agent. 2 figs.

  1. BIOTIGER, A NATURAL MICROBIAL PRODUCT FOR ENHANCED HYDROCARBON RECOVERY FROM OIL SANDS.

    SciTech Connect (OSTI)

    Brigmon, R; Topher Berry, T; Whitney Jones, W; Charles Milliken, C

    2008-05-27

    BioTiger{trademark} is a unique microbial consortia that resulted from over 8 years of extensive microbiology screening and characterization of samples collected from a century-old Polish waste lagoon. BioTiger{trademark} shows rapid and complete degradation of aliphatic and aromatic hydrocarbons, produces novel surfactants, is tolerant of both chemical and metal toxicity and shows good activity at temperature and pH extremes. Although originally developed and used by the U.S. Department of Energy for bioremediation of oil-contaminated soils, recent efforts have proven that BioTiger{trademark} can also be used to increase hydrocarbon recovery from oil sands. This enhanced ex situ oil recovery process utilizes BioTiger{trademark} to optimize bitumen separation. A floatation test protocol with oil sands from Ft. McMurray, Canada was used for the BioTiger{trademark} evaluation. A comparison of hot water extraction/floatation test of the oil sands performed with BioTiger{trademark} demonstrated a 50% improvement in separation as measured by gravimetric analysis in 4 h and a five-fold increase at 25 hr. Since BioTiger{trademark} performs well at high temperatures and process engineering can enhance and sustain metabolic activity, it can be applied to enhance recovery of hydrocarbons from oil sands or other complex recalcitrant matrices.

  2. Application of /sup 13/C, /sup 2/H, /sup 1/H NMR and GPC to the study of structural evolution of subbituminous coal in tetralin at 427/sup 0/C

    SciTech Connect (OSTI)

    Franz, J.A.; Camaioni, D.M.; Skiens, W.E.

    1981-01-01

    The products from the treatment of subbituminous coal at 427/sup 0/C in tetralin or 1,1-d/sub 2/-tetralin for times varying from 2.5 to 120 min were examined by /sup 13/C, /sup 2/H, and /sup 1/H Fourier transform nuclear magnetic resonance (FTNMR), gel permeation chromatography (GPC), and elemental and hydroxyl group analysis. NMR and elemental analysis revealed that the flash hydroliquefaction products contained about 10% of aromatic ether carbon and phenolic carbon in roughly equal amounts, but no aliphatic ether, carboxyl, or quinine carbon. The combined asphaltenes and preasphaltenes from a 10-min reaction exhibited 68% carbon, 30% hydrogen, and 30% deuterium aromaticity, with aromaticity slowly increasing at longer reaction times. GPC analysis revealed that approximately 10% of the products were greater than 1500 mol wt, with number-average molecular weights reduced from 840 to 500 over a 2-hr reaction. Deuterium NMR revealed that the majority of deuterium transferred to coal appeared at benzylic carbons.

  3. Peptide affinity labels for thrombin and other trypsin-like proteases

    DOE Patents [OSTI]

    Shaw, Elliott N.; Kettner, Charles A.

    1982-03-09

    A peptide affinity label of the formula (I): ##STR1## wherein X is a radical capable of acting as a leaving group in a nucleophilic substitution reaction; A is an aromatic amino acid residue; B is H, or a C.sub.1 -C.sub.4 alkyl group, or aryl; Y is selected from the group consisting of hydrogen, aroyl, C.sub.1 -C.sub.6 acyl, and Q--(A)--.sub.n, wherein Q=hydrogen, aroyl, or C.sub.1 -C.sub.6 acyl, n=1-10, A is an amino acid residue selected from the aliphatic, hydroxy-containing, carboxylic acid group, and amide-thereof-containing, aromatic, sulfur-containing and imino-containing amino acids; and wherein J is selected from the group consisting of --CH.sub.2 --, --CH.sub.2 --CH.sub.2 --,--CH.sub.2 --CH.sub.2 --CH.sub.2 --, --CH.dbd.CH-- and --CH(OH)--CH.sub.2. The affinity label is useful for irreversibly inactivating thrombin and trypsin-like enzymes and may be used as a potential anticlotting agent.

  4. TALSPEAK CURVE: AN ILLUSTRATION OF A SEE-SAW EFFECT IN SEPARATIONS

    SciTech Connect (OSTI)

    Peter Zalupski; Leigh Martin

    2010-11-01

    A superbly balanced thermodynamic struggle for metal ion coordination by aqueous aminopolycarboxylate reagent, DTPA, and non-aqueous organophosphorous phase transfer reagent, HDEHP, affords the separation of trivalent actinides from trivalent lanthanides under the umbrella of the Talspeak liquid-liquid distribution process. This thermodynamic relationship has been linked to an analogous see-saw behavior, where the balance is distorted when either of the key complexing players is subject to adverse conditions that interfere with their optimal operation. The thermodynamic balance is tipped in favour of HDEHP whenever increased acidity of the aqueous solution out-competes the metal ion complexation by aqueous complexing agent. Also enhanced steric crowding may switch-off efficient coordination of the metal ion. When HDEHP is depolymerised due to the presence of aliphatic alcohol in the organic phase its phase transferring power is diminished. Such complication paves way for DTPA to establish its dominance on the distribution of trivalent metal ions in the 2-phase system. The illustrated sensitivity of the thermodynamic balance between DTPA and HDEHP in Talspeak-type systems may serve as informative tool when studying less-predictable realms of Talspeak chemistry.

  5. Composition and method for removing photoresist materials from electronic components

    DOE Patents [OSTI]

    Davenhall, Leisa B.; Rubin, James B.

    2002-01-01

    The invention is a combination of at least one dense phase fluid and at least one dense phase fluid modifier which can be used to contact substrates for electronic parts such as semiconductor wafers or chips to remove photoresist materials which are applied to the substrates during manufacture of the electronic parts. The dense phase fluid modifier is one selected from the group of cyclic, aliphatic or alicyclic compounds having the functional group: ##STR1## wherein Y is a carbon, oxygen, nitrogen, phosphorus or sulfur atom or a hydrocarbon group having from 1 to 10 carbon atoms, a halogen or halogenated hydrocarbon group having from 1 to 10 carbon atoms, silicon or a fluorinated silicon group; and wherein R.sub.1 and R.sub.2 can be the same or different substituents; and wherein, as in the case where X is nitrogen, R.sub.1 or R.sub.2 may not be present. The invention compositions generally are applied to the substrates in a pulsed fashion in order to remove the hard baked photoresist material remaining on the surface of the substrate after removal of soft baked photoresist material and etching of the barrier layer.

  6. Metal catalyzed synthesis of hyperbranched ethylene and/or .alpha.-olefin polymers

    DOE Patents [OSTI]

    Sen, Ayusman; Kim, Jang Sub; Pawlow, James H.; Murtuza, Shahid; Kacker, Smita; Wojcinski, III, Louis M.

    2001-01-01

    Oily hyperbranched polymers derived from ethylene, propylene, butene and/or a C.sub.5 -C.sub.24 .alpha.-olefin, and a method for their synthesis, are disclosed. The polymers have non-regular microstructures and are characterized by a ratio ({character pullout})of methyl hydrogens centered around 0.85 ppm on the 1H-NMR spectra of the polymers relative to total aliphatic hydrogens of from about 0.40 to about 0.65 for polymers derived from ethylene or butene, and a ratio ({character pullout})of from greater than 0.50 to about 0.65 for polymers derived from propylene. A method for grafting hyperbranched polymers derived from ethylene, propylene, butene and/or a C.sub.5 -C.sub.24 .alpha.-olefin onto aromatic rings in organic molecules and polymers, and the resulting grafted materials, are also disclosed. The hyperbranched polymers and grafted materials are useful, for example, as lubricants and lubricant additives.

  7. Low-temperature pyrolysis of coal to produce diesel-fuel blends

    SciTech Connect (OSTI)

    Shafer, T.B.; Jett, O.J.; Wu, J.S.

    1982-10-01

    Low-temperature (623 to 773/sup 0/K) coal pyrolysis was investigated in a bench-scale retort. Factorially designed experiments were conducted to determine the effects of temperature, coal-particle size, and nitrogen flow rate on the yield of liquid products. Yield of condensable organic products relative to the proximate coal volatile matter increased by 3.1 and 6.4 wt % after increasing nitrogen purge flow rate from 0.465 to 1.68 L/min and retort temperature from 623 to 723/sup 0/K, respectively. The liquid product may be suitable for blending with diesel fuel. The viscosity and density of coal liquids produced at 723/sup 0/K were compared with those of diesel fuel. The coal liquids had a higher carbon-to-hydrogen ratio and a lower aliphatic-to-aromatic ratio than premium quality No. 2 diesel fuel. It was recommended that liquids from coal pyrolysis be blended with diesel fuel to determine stability of the mixture and performance of the blend in internal combustion engines.

  8. Total internal reflection fluorescence spectrometer to study dynamic adsorption phenomena at liquid/liquid interfaces

    SciTech Connect (OSTI)

    Tupy, M.J.; Blanch, H.W.; Radke, C.J.

    1998-08-01

    Adsorption at oil/water interfaces affects the performance of many industrial systems including oil recovery, extraction processes, cosmetic products, and food technology. However, no technique currently available can monitor adsorption dynamics using molecularly sensitive methods. The authors have constructed a novel total internal reflection fluorescence spectrometer (TIRFS) to follow dynamic adsorption events at the oil/water interface. The TIRFS monitors changes in fluorescence intensity and fluorescence spectra over time by maintaining an optical focus on the fluid interface during adsorption and desorption processes. Kinetic adsorption phenomena are examined by altering the composition of the aqueous phase and recording surface fluorescence response without mechanically disturbing the fluid/fluid interface. The spectrometer captures changes in the fluorescence intensity over tenths of seconds and maintains optical focus for periods of days. Mass transport of fluorescing surface-active material to and from the oil/water interface is accurately modeled using the simple one-dimensional diffusion equation. The geometry designed for this apparatus can be applied to other light-based techniques studying adsorption at liquid/liquid interfaces. Here, the authors apply the TIRFS apparatus to the study of {beta}-casein adsorption and desorption at an aliphatic oil/water interface. The observed increase in interfacial fluorescence due to {beta}-casein adsorption is slower than the diffusive flux, and desorption is found to be very slow if not irreversible. The TIRF spectrum indicates interaction of sorbed {beta}-casein with the oil phase and subsequent rearrangement of the native structure.

  9. Time-resolved fluorometric determination of terbium in aqueous solution

    SciTech Connect (OSTI)

    Hemmilae, I.

    1985-07-01

    The fluorescent properties of water-soluble binary and ternary complexes of terbium(III) were studied and their applications in time-resolved fluorometric analysis were tested. Solutions composed of different ..beta..-diketones, tri-n-octylphosphine oxide as the synergistic agent, and Triton X-100 as the detergent were optimized to maximize fluorescence emission in Tb measurement. The results were then compared with seven published methods which included the use of the following respective solutions, ethylenediamine-N,N'-bis((o-hydroxy-phenyl)acetic acid), dipicolinic acid, iminodiacetic acid with Tiron, EDTA with Tiron, EDTA with 2,3-dihydroxynaphthalene, EDTA with sulfosalicylic acid, and EDTA with salicylate. Fluorinated aliphatic ..beta..-diketones showed the most promising properties in acidic solution. They were especially suitable for use in time-resolved fluorometric analyses where Tb was used as the label after being conjugated to the analyte via bifunctional complexones. An acidic pH is required for Tb release before conversion into a fluorescent chelate. The applicability of the developed measurement solutions to the measurement of Eu was also tested. 22 references, 3 figures, 7 tables.

  10. The Molecular Structure of a Phosphatidylserine Bilayer Determined by Scattering and Molecular Dynamics Simulations

    SciTech Connect (OSTI)

    Pan, Jianjun [University of South Florida, Tampa (USF)] [University of South Florida, Tampa (USF); Cheng, Xiaolin [ORNL] [ORNL; Monticelli, Luca [Institut National de la Sant et de la Recherche Mdicale (INSERM) and INTS, France] [Institut National de la Sant et de la Recherche Mdicale (INSERM) and INTS, France; Heberle, Frederick A [ORNL] [ORNL; Kucerka, Norbert [Atomic Energy of Canada Limited (AECL), Canadian Neutron Beam Centre (CNBC) and Comenius University,] [Atomic Energy of Canada Limited (AECL), Canadian Neutron Beam Centre (CNBC) and Comenius University,; Tieleman, D. Peter [University of Calgary, ALberta, Canada] [University of Calgary, ALberta, Canada; Katsaras, John [ORNL] [ORNL

    2014-01-01

    Phosphatidylserine (PS) lipids play essential roles in biological processes, including enzyme activation and apoptosis. We report on the molecular structure and atomic scale interactions of a fluid bilayer composed of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphatidylserine (POPS). A scattering density profile model, aided by molecular dynamics (MD) simulations, was developed to jointly refine different contrast small-angle neutron and X-ray scattering data, which yielded a lipid area of 62.7 A2 at 25 C. MD simulations with POPS lipid area constrained at different values were also performed using all-atom and aliphatic united-atom models. The optimal simulated bilayer was obtained using a model-free comparison approach. Examination of the simulated bilayer, which agrees best with the experimental scattering data, reveals a preferential interaction between Na+ ions and the terminal serine and phosphate moieties. Long-range inter-lipid interactions were identified, primarily between the positively charged ammonium, and the negatively charged carboxylic and phosphate oxygens. The area compressibility modulus KA of the POPS bilayer was derived by quantifying lipid area as a function of surface tension from area-constrained MD simulations. It was found that POPS bilayers possess a much larger KA than that of neutral phosphatidylcholine lipid bilayers. We propose that the unique molecular features of POPS bilayers may play an important role in certain physiological functions.

  11. Determination of organic acids (C/sub 1/-C/sub 10/) in the atmosphere, motor exhaust, and engine oils

    SciTech Connect (OSTI)

    Kawamura, K.; Ng, L.L.; Kaplan, I.R.

    1985-11-01

    A method is described for the determination of volatile organic acids in the atmosphere, motor exhausts, and engine oils. Atmospheric organic acids were collected on a KOH impregnated quartz filter and derivatized to p-bromophenacyl esters. The derivatives were analyzed by high-resolution capillary gas chromatography and gas chromatography-mass spectrometry. C/sub 1/-C/sub 10/ aliphatic organic acids and benzoic acid were detected in Los Angeles air. Acetic and formic acids are dominant followed by propionic acids. Total concentrations measured were 0.37-7.45 ppb. Organic acids (C/sub 1/-C/sub 10/) were also detected in the motor exhaust from a single automobile at idle conditions and showed that the distribution of individual acids was similar to that in the air, but the concentration was 17 times higher than for the average atmospheric content. Formic, acetic, and benzoic acids were detected as major species of used engine oil, but their content is negligible in new oil.

  12. Hydrogen Atom Reactivity toward Aqueous tert-Butyl Alcohol

    SciTech Connect (OSTI)

    Lymar S. V.; Schwarz, H.A.

    2012-02-09

    Through a combination of pulse radiolysis, purification, and analysis techniques, the rate constant for the H + (CH{sub 3}){sub 3}COH {yields} H{sub 2} + {sm_bullet}CH{sub 2}C(CH{sub 3}){sub 2}OH reaction in aqueous solution is definitively determined to be (1.0 {+-} 0.15) x 10{sup 5} M{sup -1} s{sup -1}, which is about half of the tabulated number and 10 times lower than the more recently suggested revision. Our value fits on the Polanyi-type, rate-enthalpy linear correlation ln(k/n) = (0.80 {+-} 0.05){Delta}H + (3.2 {+-} 0.8) that is found for the analogous reactions of other aqueous aliphatic alcohols with n equivalent abstractable H atoms. The existence of such a correlation and its large slope are interpreted as an indication of the mechanistic similarity of the H atom abstraction from {alpha}- and {beta}-carbon atoms in alcohols occurring through the late, product-like transition state. tert-Butyl alcohol is commonly contaminated by much more reactive secondary and primary alcohols (2-propanol, 2-butanol, ethanol, and methanol), whose content can be sufficient for nearly quantitative scavenging of the H atoms, skewing the H atom reactivity pattern, and explaining the disparity of the literature data on the H + (CH{sub 3}){sub 3}COH rate constant. The ubiquitous use of tert-butyl alcohol in pulse radiolysis for investigating H atom reactivity and the results of this work suggest that many other previously reported rate constants for the H atom, particularly the smaller ones, may be in jeopardy.

  13. Occupational hygiene in terms of volatile organic compounds (VOCs) and bioaerosols at two solid waste management plants in Finland

    SciTech Connect (OSTI)

    Lehtinen, Jenni; Tolvanen, Outi; Nivukoski, Ulla; Veijanen, Anja; Hnninen, Kari

    2013-04-15

    Highlights: ? Odorous VOCs: acetic acid, 2,3-butanedione, ethyl acetate, alpha-pinene and limonene. ? VOC concentrations did not exceed occupational exposure limit concentrations. ? 2,3-Butanedione as the health effecting compound is discussed. ? Endotoxin concentrations may cause health problems in waste treatment. - Abstract: Factors affecting occupational hygiene were measured at the solid waste transferring plant at Hyvink and at the optic separation plant in Hmeenlinna. Measurements consisted of volatile organic compounds (VOCs) and bioaerosols including microbes, dust and endotoxins. The most abundant compounds in both of the plants were aliphatic and aromatic hydrocarbons, esters of carboxylic acids, ketones and terpenes. In terms of odour generation, the most important emissions were acetic acid, 2,3-butanedione, ethyl acetate, alpha-pinene and limonene due to their low threshold odour concentrations. At the optic waste separation plant, limonene occurred at the highest concentration of all single compounds of identified VOCs. The concentration of any single volatile organic compound did not exceed the occupational exposure limit (OEL) concentration. However, 2,3-butanedione as a health risk compound is discussed based on recent scientific findings linking it to lung disease. Microbe and dust concentrations were low at the waste transferring plant. Only endotoxin concentrations may cause health problems; the average concentration inside the plant was 425 EU/m{sup 3} which clearly exceeded the threshold value of 90 EU/m{sup 3}. In the wheel loader cabin the endotoxin concentrations were below 1 EU/m{sup 3}. High microbial and endotoxin concentrations were measured in the processing hall at the optic waste separation plant. The average concentration of endotoxins was found to be 10,980 EU/m{sup 3}, a concentration which may cause health risks. Concentrations of viable fungi were quite high in few measurements in the control room. The most problematic

  14. Solvent extraction of thorium(IV), uranium(VI), and europium(III) with lipophilic alkyl-substituted pyridinium salts. Final report for subcontract 9-XZ2-1123E-1, June 1, 1992--December 1, 1995

    SciTech Connect (OSTI)

    Ensor, D.D.

    1997-01-01

    In the treatment of high level nuclear wastes, aromatic pyridinium salts which are radiation-resistant are desired for the extraction of actinides and lanthanides. The solvent extraction of Th{sup +4}, UO{sub 2}{sup +2}, and Eu{sup +3} by three aromatic extractants, 3,5-didodecylpyridinium nitrate (35PY), 2,6-didodecylpyridinium nitrate (26PY), and 1-methyl-3,5-didodecyl-pyridinium iodide (1M35PY) has been studied in nitric acid media. The general order of extractability of the three extractants in toluene was 1M35PY>> 26PY > 35PY. The overall extraction efficiency of the metal ions was Th{sup +4} >UO{sub 2}{sup +2} > Eu{sup +3}. The extraction of HNO{sub 3}, which was competitive with the extraction of metal ions, was quantitatively investigated by NaOH titration and UV spectrometry. The loading capacity suggested that the extracted species in the organic phase for thorium was (R{sub 4}N{sup +}){sub 2}Th(NO{sub 3}{sup -}){sub 6}, where R{sub 4}N{sup +} denotes 1M35PY. A comparison of 1M35PY to the well-characterized extractant, Aliquat-336, an aliphatic ammonium salt was made. At the same extractant concentration, 1M35PY extracted thorium more efficiently than Aliquat-336 at high acidity. Thorium could be readily stripped with dilute nitric acid from 1M35PY. After irradiation of 0.1M 1M35PY with {sup 60}Co at 40R/min for 48 hours, no change in the extraction efficiency of thorium was observed.

  15. SEPARATION OF FISCHER-TROPSCH WAX PRODUCTS FROM ULTRAFINE IRON CATALYST PARTICLES

    SciTech Connect (OSTI)

    James K. Neathery; Gary Jacobs; Burtron H. Davis

    2005-03-31

    In this reporting period, a fundamental filtration study was continued to investigate the separation of Fischer-Tropsch Synthesis (FTS) liquids from iron-based catalyst particles. The overall focus of the program is with slurry-phase FTS in slurry bubble column reactor systems. Hydrocarbon products must be separated from catalyst particles before being removed from the reactor system. An efficient wax product/catalyst separation system is a key factor for optimizing operating costs for iron-based slurry-phase FTS. Previous work has focused on catalyst particle attrition and the formation of ultra-fine iron carbide and/or carbon particles. With the current study, we are investigating how the filtration properties are affected by these chemical and physical changes of the catalyst slurry during activation/synthesis. In this reporting period, a series of crossflow filtration experiments were initiated to study the effect of olefins and oxygenates on the filtration flux and membrane performance. Iron-based FTS reactor waxes contain a significant amount of oxygenates, depending on the catalyst formulation and operating conditions. Mono-olefins and aliphatic alcohols were doped into an activated iron catalyst slurry (with Polywax) to test their influence on filtration properties. The olefins were varied from 5 to 25 wt% and oxygenates from 6 to 17 wt% to simulate a range of reactor slurries reported in the literature. The addition of an alcohol (1-dodecanol) was found to decrease the permeation rate while the olefin added (1-hexadecene) had no effect on the permeation rate. A passive flux maintenance technique was tested that can temporarily increase the permeate rate for 24 hours.

  16. Pyrolysis of waste tyres: A review

    SciTech Connect (OSTI)

    Williams, Paul T.

    2013-08-15

    Graphical abstract: - Highlights: Pyrolysis of waste tyres produces oil, gas and char, and recovered steel. Batch, screw kiln, rotary kiln, vacuum and fluidised-bed are main reactor types. Product yields are influenced by reactor type, temperature and heating rate. Pyrolysis oils are complex and can be used as chemical feedstock or fuel. Research into higher value products from the tyre pyrolysis process is reviewed. - Abstract: Approximately 1.5 billion tyres are produced each year which will eventually enter the waste stream representing a major potential waste and environmental problem. However, there is growing interest in pyrolysis as a technology to treat tyres to produce valuable oil, char and gas products. The most common reactors used are fixed-bed (batch), screw kiln, rotary kiln, vacuum and fluidised-bed. The key influence on the product yield, and gas and oil composition, is the type of reactor used which in turn determines the temperature and heating rate. Tyre pyrolysis oil is chemically very complex containing aliphatic, aromatic, hetero-atom and polar fractions. The fuel characteristics of the tyre oil shows that it is similar to a gas oil or light fuel oil and has been successfully combusted in test furnaces and engines. The main gases produced from the pyrolysis of waste tyres are H{sub 2}, C{sub 1}C{sub 4} hydrocarbons, CO{sub 2}, CO and H{sub 2}S. Upgrading tyre pyrolysis products to high value products has concentrated on char upgrading to higher quality carbon black and to activated carbon. The use of catalysts to upgrade the oil to a aromatic-rich chemical feedstock or the production of hydrogen from waste tyres has also been reported. Examples of commercial and semi-commercial scale tyre pyrolysis systems show that small scale batch reactors and continuous rotary kiln reactors have been developed to commercial scale.

  17. Self-Assembly, Molecular Ordering, and Charge Mobility in Solution-Processed Ultrathin Oligothiophene Films

    SciTech Connect (OSTI)

    Murphy,A.; Chang, P.; VanDyke, P.; Liu, J.; Frechet, J.; Subramanian, V.; Delongchamp, D.; Sambasivan, S.; Fischer, D.; Lin, E.

    2005-01-01

    Symmetrical {alpha}, {omega}-substituted quarter-(T4), penta-(T5), sexi-(T6), and heptathiophene (T7) oligomers containing thermally removable aliphatic ester solubilizing groups were synthesized, and their UV-vis and thermal characteristics were compared. Spun-cast thin films of each oligomer were examined with atomic force microscopy and near-edge X-ray absorption fine structure spectroscopy to evaluate the ability of the material to self-assemble from a solution-based process while maintaining complete surface coverage. Films of the T5-T7 oligomers self-assemble into crystalline terraces after thermal annealing with higher temperatures required to affect this transformation as the size of the oligomers increases. A symmetrical {alpha}, {omega}-substituted sexithiophene (T6-acid) that reveals carboxylic acids after thermolysis was also prepared to evaluate the effect of the presence of hydrogen-bonding moieties. The charge transport properties for these materials evaluated in top-contact thin film transistor devices were found to correlate with the observed morphology of the films. Therefore, the T4 and the T6-acid performed poorly because of incomplete surface coverage after thermolysis, while T5-T7 exhibited much higher performance as a result of molecular ordering. Increases in charge mobility correlated to increasing conjugation length with measured mobilities ranging from 0.02 to 0.06 cm2/(V{center_dot}s). The highest mobilities were measured when films of each oligomer had an average thickness between one and two monolayers, indicating that the molecules become exceptionally well-ordered during the thermolysis process. This unprecedented ordering of the solution-cast molecules results in efficient charge mobility rarely seen in such ultrathin films.

  18. Identification and characterization of conservative organic tracers for use as hydrologic tracers for the Yucca Mountain site characterization study. Final report

    SciTech Connect (OSTI)

    Stetzenbach, K.; Farnham, I.

    1996-06-01

    Extensive tracer testing is expected to take place at the C-well complex in the Nevada Test Site as part of the Yucca Mountain Site Characterization Project. The C-well complex consists of one pumping well, C3, and two injection wells, C1 and C2 into which tracer will be introduced. The goal of this research was to provide USGS with numerous tracers to completed these tests. Several classes of fluorinated organic acids have been evaluated. These include numerous isomers of fluorinated benzoic acids, cinnamic acids, and salicylic acids. Also several derivatives of 2-hydroxy nicotinic acid (pyridone) have been tested. The stability of these compounds was determined using batch and column tests. Ames testing (mutagenicity/carcinogenicity) was conducted on the fluorinated benzoic acids and a literature review of toxicity of the fluorobenzoates and three perfluoro aliphatic acids was prepared. Solubilities were measured and method development work was performed to optimize the detection of these compounds. A Quality Assurance (QA) Program was developed under existing DOE and USGS guidelines. The program includes QA procedures and technical standard operating procedures. A tracer test, using sodium iodide, was performed at the C-well complex. HRC chemists performed analyses on site, to provide real time data for the USGS hydrologists and in the laboratories at UNLV. Over 2,500 analyses were performed. This report provides the results of the laboratory experiments and literature reviews used to evaluate the potential tracers and reports on the results of the iodide C-well tracer test.

  19. Accurate and Reliable Quantification of Total Microalgal Fuel Potential as Fatty Acid Methyl Esters by in situ Transesterfication

    SciTech Connect (OSTI)

    Laurens, L. M. L.; Quinn, M.; Van Wychen, S.; Templeton, D. W.; Wolfrum, E. J.

    2012-04-01

    In the context of algal biofuels, lipids, or better aliphatic chains of the fatty acids, are perhaps the most important constituents of algal biomass. Accurate quantification of lipids and their respective fuel yield is crucial for comparison of algal strains and growth conditions and for process monitoring. As an alternative to traditional solvent-based lipid extraction procedures, we have developed a robust whole-biomass in situ transesterification procedure for quantification of algal lipids (as fatty acid methyl esters, FAMEs) that (a) can be carried out on a small scale (using 4-7 mg of biomass), (b) is applicable to a range of different species, (c) consists of a single-step reaction, (d) is robust over a range of different temperature and time combinations, and (e) tolerant to at least 50% water in the biomass. Unlike gravimetric lipid quantification, which can over- or underestimate the lipid content, whole biomass transesterification reflects the true potential fuel yield of algal biomass. We report here on the comparison of the yield of FAMEs by using different catalysts and catalyst combinations, with the acid catalyst HCl providing a consistently high level of conversion of fatty acids with a precision of 1.9% relative standard deviation. We investigate the influence of reaction time, temperature, and biomass water content on the measured FAME content and profile for 4 different samples of algae (replete and deplete Chlorella vulgaris, replete Phaeodactylum tricornutum, and replete Nannochloropsis sp.). We conclude by demonstrating a full mass balance closure of all fatty acids around a traditional lipid extraction process.

  20. Studies of Human 2,4-Dienoyl CoA Reductase Shed New Light on Peroxisomal ?-Oxidation of Unsaturated Fatty Acids

    SciTech Connect (OSTI)

    Hua, Tian; Wu, Dong; Ding, Wei; Wang, Jiangyun; Shaw, Neil; Liu, Zhi-Jie

    2012-10-15

    Peroxisomes play an essential role in maintaining fatty acid homeostasis. Although mitochondria are also known to participate in the catabolism of fatty acids via ?-oxidation, differences exist between the peroxisomal and mitochondrial ?-oxidation. Only peroxisomes, but not mitochondrion, can shorten very long chain fatty acids. Here, we describe the crystal structure of a ternary complex of peroxisomal 2,4-dienoyl CoA reductases (pDCR) with hexadienoyl CoA and NADP, as a prototype for comparison with the mitochondrial 2,4-dienoyl CoA reductase (mDCR) to shed light on the differences between the enzymes from the two organelles at the molecular level. Unexpectedly, the structure of pDCR refined to 1.84 resolution reveals the absence of the tyrosine-serine pair seen in the active site of mDCR, which together with a lysine and an asparagine have been deemed a hallmark of the SDR family of enzymes. Instead, aspartate hydrogen-bonded to the C? hydroxyl via a water molecule seems to perturb the water molecule for protonation of the substrate. Our studies provide the first structural evidence for participation of water in the DCR-catalyzed reactions. Biochemical studies and structural analysis suggest that pDCRs can catalyze the shortening of six-carbon-long substrates in vitro. However, the Km values of pDCR for short chain acyl CoAs are at least 6-fold higher than those for substrates with 10 or more aliphatic carbons. Unlike mDCR, hinge movements permit pDCR to process very long chain polyunsaturated fatty acids.

  1. Synthetic fuel aromaticity and staged combustion

    SciTech Connect (OSTI)

    Longanbach, J. R.; Chan, L. K.; Levy, A.

    1982-11-15

    Samples of middle and heavy SRC-II distillates were distilled into 50 C boiling point range fractions. These were characterized by measurements of their molecular weight, elemental analysis and basic nitrogen content and calculation of average molecular structures. The structures typically consisted of 1 to 3 aromatic rings fused to alicyclic rings with short, 1 to 3 carbon aliphatic side chains. The lower boiling fractions contained significant amounts (1 atom/molecule) of oxygen while the heavier fractions contained so few heteroatoms that they were essentially hydrocarbons. Laboratory scale oxidative-pyrolysis experiments were carried out at pyrolysis temperatures of 500 to 1100 C and oxygen concentrations from 0 to 100 percent of stoichiometry. Analysis of liquid products, collected in condensers cooled with liquid nitrogen showed that aromatization is a major reaction in the absence of oxygen. The oxygen-containing materials (phenolics) seem to be more resistant to thermal pyrolysis than unsubstituted aromatics. Nitrogen converts from basic to nonbasic forms at about 500 C. The nonbasic nitrogen is more stable and survives up to 700 C after which it is slowly removed. A recently constructed 50,000 Btu/hr staged combustor was used to study the chemistry of the nitrogen and aromatics. SRC II combustion was studied under fuel-rich, first-stage conditions at air/fuel ratios from 0.6 to 1.0 times stoichiometric. The chemistry of the fuel during combustion calls for further investigation in order to examine the mechanism by which HCN is evolved as a common intermediate for the formation of the nitrogen-containing gaseous combustion products. 25 references, 45 figures, 25 tables.

  2. Carbon-Type Analysis and Comparison of Original and Reblended FACE Diesel Fuels (FACE 2, FACE 4, and FACE 7)

    SciTech Connect (OSTI)

    Bays, J. Timothy; King, David L.; O'Hagan, Molly J.

    2012-10-01

    This report summarizes the carbon-type analysis from 1H and 13C{1H} nuclear magnetic resonance spectroscopy (NMR) of Fuels for Advanced Combustion Engines (FACE) diesel blends, FD-2B, FD 4B, and FD-7B, and makes comparison of the new blends with the original FACE diesel blends, FD 2A, FD 4A, and FD-7A, respectively. Generally, FD-2A and FD-2B are more similar than the A and B blends of FD-4 and FD-7. The aromatic carbon content is roughly equivalent, although the new FACE blends have decreased monoaromatic content and increased di- and tri-cycloaromatic content, as well as a higher overall aromatic content, than the original FACE blends. The aromatic components of the new FACE blends generally have a higher alkyl substitution with longer alkyl substituents. The naphthenic and paraffinic contents remained relatively consistent. Based on aliphatic methyl and methylene carbon ratios, cetane numbers for FD-2A and -2B, and FD-7A and -7B are predicted to be consistent, while the cetane number for FD-4B is predicted to be higher than FD-4A. Overall, the new FACE fuel blends are fairly consistent with the original FACE fuel blends, but there are observable differences. In addition to providing important comparative compositional information on reformulated FACE diesel blends, this report also provides important information about the capabilities of the team at Pacific Northwest National Laboratory in the use of NMR spectroscopy for the detailed characterization and comparison of fuels and fuel blends.

  3. Standardization of chemical analytical techniques for pyrolysis bio-oil: history, challenges, and current status of methods

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Ferrell, Jack R.; Olarte, Mariefel V.; Christensen, Earl D.; Padmaperuma, Asanga B.; Connatser, Raynella M.; Stankovikj, Filip; Meier, Dietrich; Paasikallio, Ville

    2016-07-05

    Here, we discuss the standardization of analytical techniques for pyrolysis bio-oils, including the current status of methods, and our opinions on future directions. First, the history of past standardization efforts is summarized, and both successful and unsuccessful validation of analytical techniques highlighted. The majority of analytical standardization studies to-date has tested only physical characterization techniques. In this paper, we present results from an international round robin on the validation of chemical characterization techniques for bio-oils. Techniques tested included acid number, carbonyl titrations using two different methods (one at room temperature and one at 80 °C), 31P NMR for determination ofmore » hydroxyl groups, and a quantitative gas chromatography–mass spectrometry (GC-MS) method. Both carbonyl titration and acid number methods have yielded acceptable inter-laboratory variabilities. 31P NMR produced acceptable results for aliphatic and phenolic hydroxyl groups, but not for carboxylic hydroxyl groups. As shown in previous round robins, GC-MS results were more variable. Reliable chemical characterization of bio-oils will enable upgrading research and allow for detailed comparisons of bio-oils produced at different facilities. Reliable analytics are also needed to enable an emerging bioenergy industry, as processing facilities often have different analytical needs and capabilities than research facilities. We feel that correlations in reliable characterizations of bio-oils will help strike a balance between research and industry, and will ultimately help to -determine metrics for bio-oil quality. Lastly, the standardization of additional analytical methods is needed, particularly for upgraded bio-oils.« less

  4. Iron(II) catalysis in oxidation of hydrocarbons with ozone in acetonitrile

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja

    2015-02-11

    Oxidation of alcohols, ethers, and sulfoxides by ozone in acetonitrile is catalyzed by submillimolar concentrations of Fe(CH3CN)62+. The catalyst provides both rate acceleration and greater selectivity toward the less oxidized products. For example, Fe(CH3CN)62+-catalyzed oxidation of benzyl alcohol yields benzaldehyde almost exclusively (>95%), whereas the uncatalyzed reaction generates a 1:1 mixture of benzaldehyde and benzoic acid. Similarly, aliphatic alcohols are oxidized to aldehydes/ketones, cyclobutanol to cyclobutanone, and diethyl ether to a 1:1 mixture of ethanol and acetaldehyde. The kinetics of oxidation of alcohols and diethyl ether are first-order in [Fe(CH3CN)62+] and [O3] and independent of [substrate] at concentrations greater thanmore » ~5 mM. In this regime, the rate constant for all of the alcohols is approximately the same, kcat = (8 ± 1) × 104 M–1 s–1, and that for (C2H5)2O is (5 ± 0.5) × 104 M–1 s–1. In the absence of substrate, Fe(CH3CN)62+ reacts with O3 with kFe = (9.3 ± 0.3) × 104 M–1 s–1. The similarity between the rate constants kFe and kcat strongly argues for Fe(CH3CN)62+/O3 reaction as rate-determining in catalytic oxidation. The active oxidant produced in Fe(CH3CN)62+/O3 reaction is suggested to be an Fe(IV) species in analogy with a related intermediate in aqueous solutions. As a result, this assignment is supported by the similarity in kinetic isotope effects and relative reactivities of the two species toward substrates.« less

  5. Adhesive for solar control film

    SciTech Connect (OSTI)

    Penn, H.J.

    1984-01-31

    A water-activatable adhesive useful for adhering a solar film, polyester (polyethylene terephthalate) film, to glass or to metal substrates. The adhesive comprises the reacted product of (A) gamma-isocyanatopropyltriethoxy silane, containing a free isocyanate (NCO) group, and (B) a thermoplastic polyester formed by reacting (i) a dibasic acid selected from the group consisting of terephthalic acid, isophthalic acid and hexahydrophthalic acid, and mixtures thereof, with (ii) a polymethylene glycol of the formula HO(CH/sub 2/) /SUB x/ OH where x is an integer from 2 to 10, neopentyl glycol and glycerin, and mixtures thereof, and (iii) an aliphatic dibasic acid selected from the group consisting of those having the formula HOOC(CH/sub 2/) /SUB n/ COOH where n is an integer from 1 to 8, and mixtures of such acids, whereby substantially no free NCO remains in the adhesive. Solar film is used for absorbing and/or reflecting solar radiation. Solar film can be a single sheet of polyester dyed sufficiently to absorb the glare of bright sunlight, or it can be a single sheet of polyester, on one side of which a reflective metal (most often aluminum) is deposited in an amount which can be totally reflective or in an amount which still allows visible light transmission and over which a protective coating is deposited, or it can be a laminated structure of the reflective film adhered to a clear or dyed polyester film by which means the reflective metal is sandwiched between two layers of polyester film, or it can be a laminated structure of a reflective film to a polyolefin film.

  6. New organically templated photoluminescence iodocuprates(I)

    SciTech Connect (OSTI)

    Hou Qin; Zhao Jinjing; Zhao Tianqi; Jin Juan; Yu Jiehui; Xu Jiqing

    2011-07-15

    Two types of organic cyclic aliphatic diamine molecules piperazine (pip) and 1,3-bis(4-piperidyl)propane (bpp) were used, respectively, to react with an inorganic mixture of CuI and KI in the acidic CH{sub 3}OH solutions under the solvothermal conditions, generating finally three new organically templated iodocuprates as 2-D layered [(Hpip)Cu{sub 3}I{sub 4}] 1, 1-D chained [tmpip][Cu{sub 2}I{sub 4}] 2 (tmpip=N,N,N',N'-tetramethylpiperazinium) and dinuclear [H{sub 2}bpp]{sub 2}[Cu{sub 2}I{sub 5}] I.2H{sub 2}O 3. Note that the templating agent tmpip{sup 2+} in compound 2 originated from the in situ N-alkylation reaction between the pip molecule and the methanol solvent. The photoluminescence analysis indicates that the title compounds emit the different lights: yellow for 1, blue for 2 and yellow-green for 3, respectively. - Graphical abstract: The solvothermal self-assemblies of CuI, KI and pip/bpp in acidic CH{sub 3}OH solutions created three iodocuprates 2-D layered [(Hpip)Cu{sub 3}I{sub 4}] 1, 1-D chained [tmpip][Cu{sub 2}I{sub 4}] 2 and dinuclear [H{sub 2}bpp]{sub 2}[Cu{sub 2}I{sub 5}] I.2H{sub 2}O 3. Highlights: > A new layered iodocuprate(I) with 20-membered rings was hydrothermally prepared. > A simple approach to prepare the new organic templating agent was reported. > Photoluminescence analysis indicates the emission for iodocuprate(I) is associated with the Cu...Cu interactions.

  7. The Role of a Dipeptide Outer-Coordination Sphere on H2 -Production Catalysts: Influence on Catalytic Rates and Electron Transfer

    SciTech Connect (OSTI)

    Reback, Matthew L.; Ginovska-Pangovska, Bojana; Ho, Ming-Hsun; Jain, Avijita; Squier, Thomas C.; Raugei, Simone; Roberts, John A.; Shaw, Wendy J.

    2013-02-04

    The outer-coordination sphere of enzymes acts to fine-tune the active site reactivity and control catalytic rates, suggesting that incorporation of analogous structural elements into molecular catalysts may be necessary to achieve rates comparable to those observed in enzyme systems at low overpotentials. In this work, we evaluate the effect of an amino acid and dipeptide outer-coordination sphere on [Ni(PPh2NPh-R2)2]2+ hydrogen production catalysts. A series of 12 new complexes containing non-natural amino acids or dipeptides were prepared to test the effects of positioning, size, polarity and aromaticity on catalytic activity. The non-natural amino acid was either 3-(meta- or para-aminophenyl)propionic acid terminated as an acid, an ester or an amide. Dipeptides consisted of one of the non-natural amino acids coupled to one of four amino acid esters: alanine, serine, phenylalanine or tyrosine. All of the catalysts are active for hydrogen production, with rates averaging ~1000 s-1, 40% faster than the unmodified catalyst. Structure and polarity of the aliphatic or aromatic side chains of the C-terminal peptide do not strongly influence rates. However, the presence of an amide bond increases rates, suggesting a role for the amide in assisting catalysis. Overpotentials were lower with substituents at the N-phenyl meta position. This is consistent with slower electron transfer in the less compact, para-substituted complexes, as shown in digital simulations of catalyst cyclic voltammograms and computational modeling of the complexes. Combining the current results with insights from previous results, we propose a mechanism for the role of the amino acid and dipeptide based outer-coordination sphere in molecular hydrogen production catalysts.

  8. Acid-base properties, deactivation, and in situ regeneration of condensation catalysts for synthesis of methyl methacrylate

    SciTech Connect (OSTI)

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

    1996-12-31

    Condensation reaction of a propionate with formaldehyde is a novel route for synthesis of methyl methacrylate (MMA). The reaction mechanism involves a proton abstraction from the propionate on the basic sites and activation of the aliphatic aldehyde on the acidic sites of the catalyst. The acid-base properties of ternary V-Si-P oxide catalysts and their relation to the NWA yield in the vapor phase condensation of formaldehyde with propionic anhydride has been studied for the first time. Five different V-Si-P catalysts with different atomic ratios of vanadium, silicon, and phosphorous were synthesized, characterized, and tested in a fixed-bed microreactor system. A V-Si-P 1:10:2.8 catalyst gave the maximum condensation yield of 56% based on HCHO fed at 300{degrees}C and 2 atm and at a space velocity of 290 cc/g cat{center_dot}h. A parameter called the ``q-ratio`` has been defined to correlate the condensation yields to the acid-base properties. The correlation of q-ratio with the condensation yield shows that higher q-ratios are more desirable. The long-term deactivation studies on the V-Si-P 1: 10:2.8 catalyst at 300{degrees}C and 2 atm and at a space velocity of 290 cc/g cat{center_dot}h show that the catalyst activity drops by a factor of nearly 20 over a 180 h period. The activity can be restored to about 78% of the initial activity by a mild oxidative regeneration at 300{degrees}C and 2 atm. The performance of V-Si-P catalyst has been compared to a Ta/SiO{sub 2} catalyst. The Ta- catalyst is more stable and has a higher on-stream catalyst life.

  9. Development of a novel solvent for the simultaneous separation of strontium and cesium from dissolved Spent Nuclear Fuel solutions

    SciTech Connect (OSTI)

    Catherine L. Riddle; John D. Baker; Jack D. Law; Christopher A. McGrath; David H. Meikrantz; Bruce J. Mincher; Dean R. Peterman; Terry A. Todd

    2004-10-01

    The recovery of Cs and Sr from acidic solutions by solvent extraction has been investigated. The goal of this project was to develop an extraction process to remove Cs and Sr from high-level waste in an effort to reduce the heat loading in storage. Solvents for the extraction of Cs and Sr separately have been used on both caustic and acidic spent nuclear fuel waste in the past. The objective of this research was to find a suitable solvent for the extraction of both Cs and Sr simultaneously from acidic nitrate media. The solvents selected for this research possess good stability and extraction behavior when mixed together. The extraction experiments were performed with 4 ,4,(5 )-Di-(tbutyldicyclohexano)- 18-crown-6 {DtBuCH18C6}, Calix[4]arene-bis-(tert-octylbenzocrown-6) {BOBCalixC6} and 1-(2,2,3,3-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol {Cs-7SB modifier} in a branched aliphatic kerosene {Isopar L}. The BOBCalixC6 and Cs-7SB modifier were developed at Oak Ridge National Laboratory (ORNL) by Bonnesen et al. [1]. The values obtained from the SREX solvent for DSr in 1 M nitric acid ranged from 0.7 to 2.2 at 25oC and 10oC respectively. The values for DCs in 1 M nitric acid with the CSSX solvent ranged from 8.0 to 46.0 at 25oC and 10oC respectively. A new mixed solvent, developed at the Idaho National Engineering and Environmental Laboratory (INEEL) by Riddle et al. [2], showed distributions for Sr ranging from 8.8 to 17.4 in 1 M nitric acid at 25oC and 10oC respectively. The DCs for the mixed solvent ranged from 7.7 to 20.2 in 1 M nitric acid at 25oC to 10oC respectively. The unexpectedly high distributions for Sr at both 25oC and 10oC show a synergy in the mixed solvent. The DCs, although lower than with CSSX solvent, still showed good extraction behavior.

  10. Hydrotreating Pyrolytic Lignin to Produce a Refinery Feedstock (Poster)

    SciTech Connect (OSTI)

    French, R. J.

    2013-09-01

    Fast pyrolysis of biomass followed by water separation to produce pyrolytic lignin and hydrotreating of the lignin could be used to produce a stable volatile low-oxygen intermediate liquid. Such a liquid could be converted into a finished motor-fuel in a refinery, taking advantage of the existing infrastructure and economies of scale of refineries. Hydrotreating just the lignin would consume less hydrogen while preserving about half of the energy of the original oil. The aqueous by-products could be reformed to produce the needed hydrogen and would contain much of the unwanted acids and unstable oxygenates. To assess such intermediate liquids, several pyrolytic lignins were prepared by mixing pyrolysis oil with water at 1:1 and 3:1 ratios. The carboxylic acidity in the pyrolytic lignin was reduced to 24 and 10 mg-KOH/g-lignin compared to 81 in the whole oil. These lignins were hydrotreated using Ni-Mo(S)/alumina, Pt/char, or Pd/C(activated) in a semi-batch 1 L stirred autoclave. The oil was stabilized under hydrogen at 150-280 degrees C, then water and light organics were removed by partial depressurization. Hydrodeoxygenation was then performed at 340-400 degrees C. Total pressure was controlled at 70 or 170 bar with hydrogen gas. Organic liquid yields of 39-56% were obtained. For many experiments the organic oxygen content was <7%, acidity was < 7 mg-KOH/g-oil, the volatility was greater than or equal to 94% and, on a carbon basis, the total yield of organic products miscible in hydrocarbons at a 1:10 ratio was over 50%. These properties are probably acceptable to a refinery.The residual liquids left in the reactor at the end of the experiment comprised 60-85% of the organic-phase product while the rest was condensate. 13C-NMR of the residual liquids showed that they were 50-80% aliphatic. 13C-NMR coupled with GC-MS identified phenolic compounds as the main oxygenates in most residual liquids.

  11. Subtask 3.11 - Production of CBTL-Based Jet Fuels from Biomass-Based Feedstocks and Montana Coal

    SciTech Connect (OSTI)

    Sharma, Ramesh

    2014-06-01

    The Energy & Environmental Research Center (EERC), in partnership with the U.S. Department of Energy (DOE) and Accelergy Corporation, an advanced fuels developer with technologies exclusively licensed from Exxon Mobil, undertook Subtask 3.11 to use a recently installed bench-scale direct coal liquefaction (DCL) system capable of converting 45 pounds/hour of pulverized, dried coal to a liquid suitable for upgrading to fuels and/or chemicals. The process involves liquefaction of Rosebud mine coal (Montana coal) coupled with an upgrading scheme to produce a naphthenic fuel. The upgrading comprises catalytic hydrotreating and saturation to produce naphthenic fuel. A synthetic jet fuel was prepared by blending equal volumes of naphthenic fuel with similar aliphatic fuel derived from biomass and 11 volume % of aromatic hydrocarbons. The synthetic fuel was tested using standard ASTM International techniques to determine compliance with JP-8 fuel. The composite fuel thus produced not only meets but exceeds the military aviation fuel-screening criteria. A 500-milliliter synthetic jet fuel sample which met internal screening criteria was submitted to the Air Force Research Laboratory (AFRL) at Wright–Patterson Air Force Base, Dayton, Ohio, for evaluation. The sample was confirmed by AFRL to be in compliance with U.S. Air Force-prescribed alternative aviation fuel initial screening criteria. The results show that this fuel meets or exceeds the key specification parameters for JP-8, a petroleum-based jet fuel widely used by the U.S. military. JP-8 specifications include parameters such as freeze point, density, flash point, and others; all of which were met by the EERC fuel sample. The fuel also exceeds the thermal stability specification of JP-8 fuel as determined by the quartz crystalline microbalance (QCM) test also performed at an independent laboratory as well as AFRL. This means that the EERC fuel looks and acts identically to petroleum-derived jet fuel and can be used

  12. Development of Advanced Membranes Technology Platform for Hydrocarbon Separations

    SciTech Connect (OSTI)

    Kalthod, Dr Dilip

    2010-03-01

    selected for membrane development. A novel dope composition and spinning process were developed, which provide a new approach to controlling membrane porosity and wall and skin morphology. A hollow-fiber membrane with an external dense “skin” was produced that has a high water vapor permeation coefficient and selectivity, durability when in operation at 1000 psig and 70°C, and the ability to withstand aromatic and aliphatic hydrocarbon vapors for an extended period. The fiber meets the technical requirements for a commercial product offering in gas dehydration. It can be readily manufactured with some changes in process equipment and process conditions, and is an excellent candidate for scale-up to full-size membrane modules.

  13. Designer synthetic media for studying microbial-catalyzed biofuel production

    DOE Public Access Gateway for Energy & Science Beta (PAGES Beta)

    Tang, Xiaoyu; da Costa Sousa, Leonardo; Jin, Mingjie; Chundawat, Shishir; Chambliss, Charles; Lau, Ming W; Xiao, Zeyi; Dale, Bruce E; Balan, Venkatesh

    2015-01-01

    Background: The fermentation inhibition of yeast or bacteria by lignocellulose-derived degradation products, during hexose/pentose co-fermentation, is a major bottleneck for cost-effective lignocellulosic biorefineries. To engineer microbial strains for improved performance, it is critical to understand the mechanisms of inhibition that affect fermentative organisms in the presence of major components of a lignocellulosic hydrolysate. The development of a synthetic lignocellulosic hydrolysate (SH) media with a composition similar to the actual biomass hydrolysate will be an important advancement to facilitate these studies. In this work, we characterized the nutrients and plant-derived decomposition products present in AFEX™ pretreated corn stover hydrolysate (ACH). Themore » SH was formulated based on the ACH composition and was further used to evaluate the inhibitory effects of various families of decomposition products during Saccharomyces cerevisiae 424A (LNH-ST) fermentation. Results: The ACH contained high levels of nitrogenous compounds, notably amides, pyrazines, and imidazoles. In contrast, a relatively low content of furans and aromatic and aliphatic acids were found in the ACH. Though most of the families of decomposition products were inhibitory to xylose fermentation, due to their abundance, the nitrogenous compounds showed the most inhibition. From these compounds, amides (products of the ammonolysis reaction) contributed the most to the reduction of the fermentation performance. However, this result is associated to a concentration effect, as the corresponding carboxylic acids (products of hydrolysis) promoted greater inhibition when present at the same molar concentration as the amides. Due to its complexity, the formulated SH did not perfectly match the fermentation profile of the actual hydrolysate, especially the growth curve. However, the SH formulation was effective for studying the inhibitory effect of various compounds on yeast

  14. FY-2011 Status Report for Thermodynamics and Kinetics of Advanced Separations Systems

    SciTech Connect (OSTI)

    Leigh R. Martin; Peter R. Zalupski; Travis S. Grimes

    2011-09-01

    This report presents a summary of the work performed in the area of thermodynamics and kinetics of advanced separations systems under the Fuel Cycle Research and Development (FCR&D) program during FY 2011 at the INL. On the thermodynamic front, investigations of liquid-liquid distribution of lanthanides at TALSPEAK-related conditions continued in FY11. It has been determined that a classical ion-exchanging phase transfer mechanism, where three HDEHP dimers solvate the metal ion in the organic phase, dominates metal extraction for systems that contain up to 0.1 M free lactate in solution. The correct graphical interpretation of the observed data in those regions relied on incorporating corrections for non-ideal behavior of HDEHP dimer in aliphatic diluents as well as sodium extraction equilibria. When aqueous conditions enter the complex regions of high lactate concentrations, slope analysis is no longer possible. When normalized metal distribution ratios were studied along the increasing concentration of free lactate, a slope of -1 was apparent. Such dependency either indicates aqueous complexing competition from lactate, or, a more likely scenario, a participation of lactate in the extracted metal complex. This finding agrees with our initial assessment of postulated changes in the extraction mechanism as a source of the lactate-mediated loss of extraction efficiency. The observed shape in the lanthanide distribution curve in our studies of TALSPEAK systems was the same for solutions containing no lactate or 2.3 M lactate. As such we may conclude that the mechanism of phase transfer is not altered dramatically and remains similarly sensitive to effective charge density of the metal ion. In addition to these thermodynamics studies, this report also summarizes the first calorimetric determination of heat of extraction of 248Cm in a bi-phasic system. The heat of extraction measured by isothermal titration calorimetry is compared to that determined using van't Hoff

  15. Designer synthetic media for studying microbial-catalyzed biofuel production

    SciTech Connect (OSTI)

    Tang, Xiaoyu [Biogas Inst. of Ministry of Agriculture, Chengdu (China); da Costa Sousa, Leonardo [Michigan State Univ., East Lansing, MI (United States); Jin, Mingjie [Michigan State Univ., East Lansing, MI (United States); Chundawat, Shishir [Michigan State Univ., East Lansing, MI (United States); State Univ. of New Jersey, Piscataway, NJ (United States); Chambliss, Charles [Baylor Univ., Waco, TX (United States); Lau, Ming W [Michigan State Univ., East Lansing, MI (United States); Xiao, Zeyi [Sichuan Univ., Chengdu (China); Dale, Bruce E [Michigan State Univ., East Lansing, MI (United States); Balan, Venkatesh [Michigan State Univ., East Lansing, MI (United States)

    2015-01-01

    Background: The fermentation inhibition of yeast or bacteria by lignocellulose-derived degradation products, during hexose/pentose co-fermentation, is a major bottleneck for cost-effective lignocellulosic biorefineries. To engineer microbial strains for improved performance, it is critical to understand the mechanisms of inhibition that affect fermentative organisms in the presence of major components of a lignocellulosic hydrolysate. The development of a synthetic lignocellulosic hydrolysate (SH) media with a composition similar to the actual biomass hydrolysate will be an important advancement to facilitate these studies. In this work, we characterized the nutrients and plant-derived decomposition products present in AFEX pretreated corn stover hydrolysate (ACH). The SH was formulated based on the ACH composition and was further used to evaluate the inhibitory effects of various families of decomposition products during Saccharomyces cerevisiae 424A (LNH-ST) fermentation. Results: The ACH contained high levels of nitrogenous compounds, notably amides, pyrazines, and imidazoles. In contrast, a relatively low content of furans and aromatic and aliphatic acids were found in the ACH. Though most of the families of decomposition products were inhibitory to xylose fermentation, due to their abundance, the nitrogenous compounds showed the most inhibition. From these compounds, amides (products of the ammonolysis reaction) contributed the most to the reduction of the fermentation performance. However, this result is associated to a concentration effect, as the corresponding carboxylic acids (products of hydrolysis) promoted greater inhibition when present at the same molar concentration as the amides. Due to its complexity, the formulated SH did not perfectly match the fermentation profile of the actual hydrolysate, especially the growth curve. However, the SH formulation was effective for studying the inhibitory effect of various compounds on yeast fermentation

  16. Use of thermal analysis techniques (TG-DSC) for the characterization of diverse organic municipal waste streams to predict biological stability prior to land application

    SciTech Connect (OSTI)

    Fernandez, Jose M.; Plaza, Cesar; Polo, Alfredo; Plante, Alain F.

    2012-01-15

    ) techniques. Total amounts of CO{sub 2} respired indicated that the organic matter in the TS was the least stable, while that in the CS was the most stable. This was confirmed by changes detected with the spectroscopic methods in the composition of the organic wastes due to C mineralization. Differences were especially pronounced for TS, which showed a remarkable loss of aliphatic and proteinaceous compounds during the incubation process. TG, and especially DSC analysis, clearly reflected these differences between the three organic wastes before and after the incubation. Furthermore, the calculated energy density, which represents the energy available per unit of organic matter, showed a strong correlation with cumulative respiration. Results obtained support the hypothesis of a potential link between the thermal and biological stability of the studied organic materials, and consequently the ability of thermal analysis to characterize the maturity of municipal organic wastes and composts.

  17. Iron(II) catalysis in oxidation of hydrocarbons with ozone in acetonitrile

    SciTech Connect (OSTI)

    Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja

    2015-02-11

    Oxidation of alcohols, ethers, and sulfoxides by ozone in acetonitrile is catalyzed by submillimolar concentrations of Fe(CH3CN)62+. The catalyst provides both rate acceleration and greater selectivity toward the less oxidized products. For example, Fe(CH3CN)62+-catalyzed oxidation of benzyl alcohol yields benzaldehyde almost exclusively (>95%), whereas the uncatalyzed reaction generates a 1:1 mixture of benzaldehyde and benzoic acid. Similarly, aliphatic alcohols are oxidized to aldehydes/ketones, cyclobutanol to cyclobutanone, and diethyl ether to a 1:1 mixture of ethanol and acetaldehyde. The kinetics of oxidation of alcohols and diethyl ether are first-order in [Fe(CH3CN)62+] and [O3] and independent of [substrate] at concentrations greater than ~5 mM. In this regime, the rate constant for all of the alcohols is approximately the same, kcat = (8 ± 1) × 104 M–1 s–1, and that for (C2H5)2O is (5 ± 0.5) × 104 M–1 s–1. In the absence of substrate, Fe(CH3CN)62+ reacts with O3 with kFe = (9.3 ± 0.3) × 104 M–1 s–1. The similarity between the rate constants kFe and kcat strongly argues for Fe(CH3CN)62+/O3 reaction as rate-determining in catalytic oxidation. The active oxidant produced in Fe(CH3CN)62+/O3 reaction is suggested to be an Fe(IV) species in analogy with a related intermediate in aqueous solutions. As a result, this assignment is supported by the similarity in kinetic isotope effects and relative reactivities of the two species toward substrates.

  18. Systematic analysis of proteindetergent complexes applying dynamic light scattering to optimize solutions for crystallization trials

    SciTech Connect (OSTI)

    Meyer, Arne [University of Hamburg, c/o DESY, Building 22a, Notkestrasse 85, 22603 Hamburg (Germany); Dierks, Karsten [University of Hamburg, c/o DESY, Building 22a, Notkestrasse 85, 22603 Hamburg (Germany); XtalConcepts, Marlowring 19, 22525 Hamburg (Germany); Hussein, Rana [University of Hamburg, c/o DESY, Building 22a, Notkestrasse 85, 22603 Hamburg (Germany); Brillet, Karl [ESBS, Ple API, 300 Boulevard Sbastien Brant, CS10413, 67412 Illkirch CEDEX (France); Brognaro, Hevila [So Paulo State University, UNESP/IBILCE, Caixa Postal 136, So Jos do Rio Preto-SP, 15054 (Brazil); Betzel, Christian, E-mail: christian.betzel@uni-hamburg.de [University of Hamburg, c/o DESY, Building 22a, Notkestrasse 85, 22603 Hamburg (Germany)

    2015-01-01

    Application of in situ dynamic light scattering to solutions of proteindetergent complexes permits characterization of these complexes in samples as small as 2 l in volume. Detergents are widely used for the isolation and solubilization of membrane proteins to support crystallization and structure determination. Detergents are amphiphilic molecules that form micelles once the characteristic critical micelle concentration (CMC) is achieved and can solubilize membrane proteins by the formation of micelles around them. The results are presented of a study of micelle formation observed by in situ dynamic light-scattering (DLS) analyses performed on selected detergent solutions using a newly designed advanced hardware device. DLS was initially applied in situ to detergent samples with a total volume of approximately 2 l. When measured with DLS, pure detergents show a monodisperse radial distribution in water at concentrations exceeding the CMC. A series of all-transn-alkyl-?-d-maltopyranosides, from n-hexyl to n-tetradecyl, were used in the investigations. The results obtained verify that the application of DLS in situ is capable of distinguishing differences in the hydrodynamic radii of micelles formed by detergents differing in length by only a single CH{sub 2} group in their aliphatic tails. Subsequently, DLS was applied to investigate the distribution of hydrodynamic radii of membrane proteins and selected water-insoluble proteins in presence of detergent micelles. The results confirm that stable proteindetergent complexes were prepared for (i) bacteriorhodopsin and (ii) FetA in complex with a ligand as examples of transmembrane proteins. A fusion of maltose-binding protein and the Duck hepatitis B virus X protein was added to this investigation as an example of a non-membrane-associated protein with low water solubility. The increased solubility of this protein in the presence of detergent could be monitored, as well as the progress of proteolytic cleavage to

  19. Selective Extraction of Uranium from Liquid or Supercritical Carbon Dioxide

    SciTech Connect (OSTI)

    Farawila, Anne F.; O'Hara, Matthew J.; Wai, Chien M.; Taylor, Harry Z.; Liao, Yu-Jung

    2012-07-31

    Current liquid-liquid extraction processes used in recycling irradiated nuclear fuel rely on (1) strong nitric acid to dissolve uranium oxide fuel, and (2) the use of aliphatic hydrocarbons as a diluent in formulating the solvent used to extract uranium. The nitric acid dissolution process is not selective. It dissolves virtually the entire fuel meat which complicates the uranium extraction process. In addition, a solvent washing process is used to remove TBP degradation products, which adds complexity to the recycling plant and increases the overall plant footprint and cost. A liquid or supercritical carbon dioxide (l/sc -CO2) system was designed to mitigate these problems. Indeed, TBP nitric acid complexes are highly soluble in l/sc -CO2 and are capable of extracting uranium directly from UO2, UO3 and U3O8 powders. This eliminates the need for total acid dissolution of the irradiated fuel. Furthermore, since CO2 is easily recycled by evaporation at room temperature and pressure, it eliminates the complex solvent washing process. In this report, we demonstrate: (1) A reprocessing scheme starting with the selective extraction of uranium from solid uranium oxides into a TBP-HNO3 loaded Sc-CO2 phase, (2) Back extraction of uranium into an aqueous phase, and (3) Conversion of recovered purified uranium into uranium oxide. The purified uranium product from step 3 can be disposed of as low level waste, or mixed with enriched uranium for use in a reactor for another fuel cycle. After an introduction on the concept and properties of supercritical fluids, we first report the characterization of the different oxides used for this project. Our extraction system and our online monitoring capability using UV-Vis absorbance spectroscopy directly in sc-CO2 is then presented. Next, the uranium extraction efficiencies and kinetics is demonstrated for different oxides and under different physical and chemical conditions: l/sc -CO2 pressure and temperature, TBP/HNO3 complex used

  20. Group 4 Metalloporphyrin diolato Complexes and Catalytic Application of Metalloporphyrins and Related Transition Metal Complexes

    SciTech Connect (OSTI)

    Guodong Du

    2004-12-19

    In this work, the first examples of group 4 metalloporphyrin 1,2-diolato complexes were synthesized through a number of strategies. In general, treatment of imido metalloporphyrin complexes, (TTP)M=NR, (M = Ti, Zr, Hf), with vicinal diols led to the formation of a series of diolato complexes. Alternatively, the chelating pinacolate complexes could be prepared by metathesis of (TTP)MCl{sub 2} (M = Ti, Hf) with disodium pinacolate. These complexes were found to undergo C-C cleavage reactions to produce organic carbonyl compounds. For titanium porphyrins, treatment of a titanium(II) alkyne adduct, (TTP)Ti({eta}{sup 2}-PhC{triple_bond}CPh), with aromatic aldehydes or aryl ketones resulted in reductive coupling of the carbonyl groups to produce the corresponding diolato complexes. Aliphatic aldehydes or ketones were not reactive towards (TTP)Ti({eta}{sup 2}-PhC{triple_bond}CPh). However, these carbonyl compounds could be incorporated into a diolato complex on reaction with a reactive precursor, (TTP)Ti[O(Ph){sub 2}C(Ph){sub 2}O] to provide unsymmetrical diolato complexes via cross coupling reactions. In addition, an enediolato complex (TTP)Ti(OCPhCPhO) was obtained from the reaction of (TTP)Ti({eta}{sup 2}-PhC{triple_bond}CPh) with benzoin. Titanium porphyrin diolato complexes were found to be intermediates in the (TTP)Ti=O-catalyzed cleavage reactions of vicinal diols, in which atmospheric oxygen was the oxidant. Furthermore, (TTP)Ti=O was capable of catalyzing the oxidation of benzyl alcohol and {alpha}-hydroxy ketones to benzaldehyde and {alpha}-diketones, respectively. Other high valent metalloporphyrin complexes also can catalyze the oxidative diol cleavage and the benzyl alcohol oxidation reactions with dioxygen. A comparison of Ti(IV) and Sn(IV) porphyrin chemistry was undertaken. While chelated diolato complexes were invariably obtained for titanium porphyrins on treatment with 1,2-diols, the reaction of vicinal diols with tin porphyrins gave a number of

  1. Stable isotopic investigations of in-situ bioremediation of chlorinated organic solvents. 1998 annual progress report

    SciTech Connect (OSTI)

    Sturchio, N.C.

    1998-06-01

    'Contamination of soils and groundwaters with chlorinated aliphatic hydrocarbons (CAHs) is one of the most serious environmental problems in the DOE system and in the nation at large. These compounds are designated as priority pollutants by the US Environmental Protection Agency (EPA) and are known or suspected to be carcinogenic or mutagenic in humans. These compounds are readily transported by groundwater and are not reduced to acceptable concentrations for human consumption by most municipal water supply treatments; thus the compounds represent a significant hazard to a large portion of the human population. In situ bioremediation is an emerging technology that shows great promise for mitigation of CAH contamination at many sites. One of the most severe limitations of in-situ bioremediation is the difficulty of proving when it is working at a given site. The concentrations of CAHs and their degradation products in plumes may be difficult to relate to the efficiency of the remediation process because of dilution effects, but this problem is mitigated to a large extent by measuring isotope ratios. If there is a significant isotopic fractionation between CAHs and derivative chlorine-bearing products, then the fraction of CAH that is dechlorinated can be inferred from the {sup 37}Cl/{sup 35}Cl and {sup 13}C/{sup 12}C isotope ratios of the residual CAH. It is important to point out that there is currently no published information available on the magnitude of chlorine and carbon isotopic fractionation associated with biological degradation of CAHs. The authors plan to help eliminate this important gap in the knowledge with the work being performed here. This work is relevant to EMSP goals because it will provide a new and cost-effective means of evaluating and monitoring the effectiveness of in-situ bioremediation. It will employ newly developed techniques to characterize isotopic fractionation (of chlorine and carbon) associated with biotic and abiotic degradation

  2. Expedited Synthesis of Fluorine-18 Labeled Phenols. A Missing Link in PET Radiochemistry

    SciTech Connect (OSTI)

    Katzenellenbogen, John A.; Zhou, Dong

    2015-03-26

    Fluorine-18 (F-18) is arguably the most valuable radionuclide for positron emission tomographic (PET) imaging. However, while there are many methods for labeling small molecules with F-18 at aliphatic positions and on electron-deficient aromatic rings, there are essentially no reliable and practical methods to label electron-rich aromatic rings such as phenols, with F-18 at high specific activity. This is disappointing because fluorine-labeled phenols are found in many drugs; there are also many interesting plant metabolites and hormones that contain either phenols or other electron-rich aromatic systems such as indoles whose metabolism, transport, and distribution would be interesting to study if they could readily be labeled with F-18. Most approaches to label phenols with F-18 involve the labeling of electron-poor precursor arenes by nucleophilic aromatic substitution, followed by subsequent conversion to phenols by oxidation or other multi-step sequences that are often inefficient and time consuming. Thus, the lack of good methods for labeling phenols and other electron-rich aromatics with F-18 at high specific activity represents a significant methodological gap in F-18 radiochemistry that can be considered a “Missing Link in PET Radiochemistry”. The objective of this research project was to develop and optimize a series of unusual synthetic transformations that will enable phenols (and other electron-rich aromatic systems) to be labeled with F-18 at high specific activity, rapidly, reliably, and conveniently, thereby bridging this gap. Through the studies conducted with support of this project, we have substantially advanced synthetic methodology for the preparation of fluorophenols. Our progress is presented in detail in the sections below, and much has been published or presented publication; other components are being prepared for publication. In essence, we have developed a completely new method to prepare o-fluorophenols from non-aromatic precursors

  3. Mill Designed Bio bleaching Technologies

    SciTech Connect (OSTI)

    Institute of Paper Science Technology

    2004-01-30

    A key finding of this research program was that Laccase Mediator Systems (LMS) treatments on high-kappa kraft could be successfully accomplished providing substantial delignification (i.e., > 50%) without detrimental impact on viscosity and significantly improved yield properties. The efficiency of the LMS was evident since most of the lignin from the pulp was removed in less than one hour at 45 degrees C. Of the mediators investigated, violuric acid was the most effective vis-a-vis delignification. A comparative study between oxygen delignification and violuric acid revealed that under relatively mild conditions, a single or a double LMS{sub VA} treatment is comparable to a single or a double O stage. Of great notability was the retention of end viscosity of LMS{sub VA} treated pulps with respect to the end viscosity of oxygen treated pulps. These pulps could then be bleached to full brightness values employing conventional ECF bleaching technologies and the final pulp physical properties were equal and/or better than those bleached in a conventional ECF manner employing an aggressively O or OO stage initially. Spectral analyses of residual lignins isolated after LMS treated high-kappa kraft pulps revealed that similar to HBT, VA and NHA preferentially attack phenolic lignin moieties. In addition, a substantial decrease in aliphatic hydroxyl groups was also noted, suggesting side chain oxidation. In all cases, an increase in carboxylic acid was observed. Of notable importance was the different selectivity of NHA, VA and HBT towards lignin functional groups, despite the common N-OH moiety. C-5 condensed phenolic lignin groups were overall resistant to an LMS{sub NHA, HBT} treatments but to a lesser extent to an LMS{sub VA}. The inactiveness of these condensed lignin moieties was not observed when low-kappa kraft pulps were biobleached, suggesting that the LMS chemistry is influenced by the extent of delignification. We have also demonstrated that the current

  4. Bulk gold catalyzed oxidation reactions of amines and isocyanides and iron porphyrin catalyzed N-H and O-H bond insertion/cyclization reactions of diamines and aminoalcohols

    SciTech Connect (OSTI)

    Klobukowski, Erik

    2011-12-29

    conditions, it was found that the oxidative dehydrogenation of dibenzylamine to Nbenzylidenebenzylamine, with N-methylmorpholine N-oxide (NMMO), was nearly quantitative (96%) within 24 h. However, the reaction with oxygen was much slower, with only a 52% yield of imine product over the same time period. Moreover, the rate of reaction was found to be influenced by the nature of the amine N-oxide. For example, the use of the weakly basic pyridine N-oxide (PyNO) led to an imine yield of only 6% after 24 h. A comparison of amine N-oxide and O2 was also examined in the oxidation of PhCH{sub 2}OH to PhCHO catalyzed by bulk gold. In this reaction, a 52% yield of the aldehyde was achieved when NMMO was used, while only a 7% product yield was afforded when O{sub 2} was the oxidant after 48 h. The bulk gold-catalyzed oxidative dehydrogenation of cyclic amines generates amidines, which upon treatment with Aerosil and water were found to undergo hydrolysis to produce lactams. Moreover, 5-, 6-, and 7-membered lactams could be prepared through a one-pot reaction of cyclic amines by treatment with oxygen, water, bulk gold, and Aerosil. This method is much more atom economical than industrial processes, does not require corrosive acids, and does not generate undesired byproducts. Additionally, the gold and Aerosil catalysts can be readily separated from the reaction mixture. The second project involved studying iron(III) tetraphenylporphyrin chloride, Fe(TPP)Cl, as a homogeneous catalyst for the generation of carbenes from diazo reagents and their reaction with heteroatom compounds. Fe(TPP)Cl, efficiently catalyzed the insertion of carbenes derived from methyl 2-phenyldiazoacetates into O-H bonds of aliphatic and aromatic alcohols. Fe(TPP)Cl was also found to be an effective catalyst for tandem N-H and O-H insertion/cyclization reactions when 1,2-diamines and 1,2-alcoholamines were treated with diazo reagents. This approach provides a one-pot process for synthesizing piperazinones and