National Library of Energy BETA

Sample records for butyl alcohol alkylate

  1. 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.

  2. Alkylate

    U.S. Energy Information Administration (EIA) Indexed Site

    Day) Product: Alkylate Aromatics Asphalt & Road Oil Isomers Isobutane Isopentane & Isohexane Isooctane Lubricants Marketable Petroleum Coke Hydrogen Sulfur Period: Annual (as of January 1) Download Series History Download Series History Definitions, Sources & Notes Definitions, Sources & Notes Show Data By: Product Area 2010 2011 2012 2013 2014 2015 View History U.S. 1,248,514 1,262,443 1,246,875 1,269,361 1,266,352 1,267,246 1982-2015 PAD District 1 95,500 108,629 79,429 91,429

  3. PREPARATION OF ALKYL PYROPHOSPHATE EXTRACTANTS

    DOE Patents [OSTI]

    Levine, C.A.; Skiens, W.E.; Moore, G.R.

    1960-08-01

    A process for providing superior solvent extractants for metal recovery processes is given wherein the extractant comprises an alkyl pyrophosphoric acid ester dissolved in an organic solvent diluent. Finely divided solid P/sub 2/O/ sub 5/ is slurried in an organic solvent-diluent selected from organic solvents such as kerosene, benzene, chlorobenzene, toluene, etc. An alcohol selected from the higher alcohols having 4 to 17 carbon atoms. e.g.. hexanol-1. heptanol-3, octanol-1. 2.6-dimethyl-heptanol-4, and decanol-1, is rapidly added to the P/sub 2/O/sub 5/ slurry in the amount of about 2 moles of alcohol to 1 mole of P/sub 2/ O/sub 5/. The temperature is maintained below about 110 deg C during the course of the P/sub 2/O/sub 5/-alcohol reaction. An alkyl pyrophosphate extractant compound is formed as a consequence of the reaction process. The alkyl pyrophosphate solvent-diluent extractant phase is useful in solvent extraction metal recovery processes.

  4. The photodissociation dynamics of alkyl radicals

    SciTech Connect (OSTI)

    Giegerich, Jens; Fischer, Ingo

    2015-01-28

    The photodisscociation dynamics of the alkyl radicals i-propyl (CH(CH{sub 3}){sub 2}) and t-butyl (C(CH{sub 3}){sub 3}) are investigated by H-atom photofragment imaging. While i-propyl is excited at 250 nm, the photodynamics of t-butyl are explored over a large energy range using excitation wavelengths between 347 nm and 233 nm. The results are compared to those obtained previously for ethyl, CH{sub 3}CH{sub 2}, and to those reported for t-butyl using 248 nm excitation. The translational energy (E{sub T}) distribution of the H-atom photofragments is bimodal and appears rather similar for all three radicals. The low E{sub T} part of the distribution shows an isotropic photofragment angular distribution, while the high E{sub T} part is associated with a considerable anisotropy. Thus, for t-butyl, two H-atom loss channels of roughly equal importance have been identified in addition to the CH{sub 3}-loss channel reported previously. A mechanism for the photodissociation of alkyl radicals is suggested that is based on interactions between Rydberg- and valence states.

  5. Methods of making alkyl esters

    DOE Patents [OSTI]

    Elliott, Brian

    2010-08-03

    A method comprising contacting an alcohol, a feed comprising one or more glycerides and equal to or greater than 2 wt % of one or more free fatty acids, and a solid acid catalyst, a nanostructured polymer catalyst, or a sulfated zirconia catalyst in one or more reactors, and recovering from the one or more reactors an effluent comprising equal to or greater than about 75 wt % alkyl ester and equal to or less than about 5 wt % glyceride.

  6. PROCESS FOR PRODUCING ALKYL ORTHOPHOSPHORIC ACID EXTRACTANTS

    DOE Patents [OSTI]

    Grinstead, R.R.

    1962-01-23

    A process is given for producing superior alkyl orthophosphoric acid extractants for use in solvent extraction methods to recover and purify various metals such as uranium and vanadium. The process comprises slurrying P/sub 2/O/ sub 5/ in a solvent diluent such as kerosene, benzene, isopropyl ether, and the like. An alipbatic alcohol having from nine to seventeen carbon atoms, and w- hcrein ihc OH group is situated inward of the terminal carbon atoms, is added to the slurry while the reaction temperature is mainiained below 60 deg C. The alcohol is added in the mole ratio of about 2 to l, alcohol to P/sub 2/O/sub 5/. A pyrophosphate reaotion product is formed in the slurry-alcohol mixture. Subsequently, the pyrophosphate reaction product is hydrolyzed with dilute mineral acid to produce the desired alkyl orthophosphoric aeid extractant. The extraetant may then be separated and utilized in metal-recovery, solvent- extraction processes. (AEC)

  7. Method of making alkyl esters

    DOE Patents [OSTI]

    Elliott, Brian (Wheat Ridge, CO)

    2010-09-14

    Methods of making alkyl esters are described herein. The methods are capable of using raw, unprocessed, low-cost feedstocks and waste grease. Generally, the method involves converting a glyceride source to a fatty acid composition and esterifying the fatty acid composition to make alkyl esters. In an embodiment, a method of making alkyl esters comprises providing a glyceride source. The method further comprises converting the glyceride source to a fatty acid composition comprising free fatty acids and less than about 1% glyceride by mass. Moreover, the method comprises esterifying the fatty acid composition in the presence of a solid acid catalyst at a temperature ranging firm about 70.degree. C. to about 120.degree. C. to produce alkyl esters, such that at least 85% of the free fatty acids are converted to alkyl esters. The method also incorporates the use of packed bed reactors for glyceride conversion and/or fatty acid esterification to make alkyl esters.

  8. Catalytic conversion of alcohols to hydrocarbons with low benzene content

    DOE Patents [OSTI]

    Narula, Chaitanya K.; Davison, Brian H.; Keller, Martin

    2016-03-08

    A method for converting an alcohol to a hydrocarbon fraction having a lowered benzene content, the method comprising: converting said alcohol to a hydrocarbon fraction by contacting said alcohol, under conditions suitable for converting said alcohol to said hydrocarbon fraction, with a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon fraction, and contacting said hydrocarbon fraction with a benzene alkylation catalyst, under conditions suitable for alkylating benzene, to form alkylated benzene product in said hydrocarbon fraction. Also described is a catalyst composition useful in the method, comprising a mixture of (i) a metal-loaded zeolite catalyst catalytically active for converting said alcohol to said hydrocarbon, and (ii) a benzene alkylation catalyst, in which (i) and (ii) may be in a mixed or separated state. A reactor for housing the catalyst and conducting the reaction is also described.

  9. Butyl Fuel LLC formerly Environmental Energy Inc | Open Energy...

    Open Energy Info (EERE)

    Butyl Fuel LLC formerly Environmental Energy Inc Jump to: navigation, search Name: Butyl Fuel LLC (formerly Environmental Energy Inc) Place: Ohio Zip: 43004 Product:...

  10. Mild Catalytic methods for Alkyl-Alkyl Bond Formation

    SciTech Connect (OSTI)

    Vicic, David A

    2009-08-10

    Overview of Research Goals and Accomplishments for the Period 07/01/06 06/30/07: Our overall research goal is to transform the rapidly emerging synthetic chemistry involving alkyl-alkyl cross-couplings into more of a mechanism-based field so that that new, rationally-designed catalysts can be performed under energy efficient conditions. Our specific objectives for the previous year were 1) to obtain a proper electronic description of an active catalyst for alkyl-alkyl cross-coupling reactions and 2) to determine the effect of ligand structure on the rate, scope, selectivity, and functional group compatibility of C(sp3)-C(sp3) cross-coupling catalysis. We have completed both of these initial objectives and established a firm base for further studies. The specific significant achievements of the current grant period include: 1) we have performed magnetic and computational studies on (terpyridine)NiMe, an active catalyst for alkyl-alkyl cross couplings, and have discovered that the unpaired electron resides heavily on the terpyridine ligand and that the proper electronic description of this nickel complex is a Ni(II)-methyl cation bound to a reduced terpyridine ligand; 2) we have for the first time shown that alkyl halide reduction by terpyridyl nickel catalysts is substantially ligand based; 3) we have shown by isotopic labeling studies that the active catalyst (terpyridine)NiMe is not produced via a mechanism that involves the formation of methyl radicals when (TMEDA)NiMe2 is used as the catalyst precursor; 4) we have performed an extensive ligand survey for the alkyl-alkyl cross-coupling reactions and have found that electronic factors only moderately influence reactivity in the terpyridine-based catalysis and that the most dramatic effects arise from steric and solubility factors; 5) we have found that the use of bis(dialkylphosphino)methanes as ligands for nickel does not produce active catalysts for cross-coupling but rather leads to bridging hydride complexes of varying geometries; 6) we have determined that the geometry of aforementioned bridging hydride complexes is largely determined by external forces such as hydrogen bonding interactions and crystal packing forces; 7) we have found that the rate of reductive elimination of alkane from a (pyridyl-2-pyrrolide)AuMe2 complex is severely inhibited due to the rigid geometry of the pyridyl-2-pyrrolide ligand; 8) we have prepared, structurally characterized, and explored the reactivity of 1-adamantylzinc reagents as model nucleophiles for sterically challenging alkyl-alkyl cross-coupling reactions. The continued success of this work will lead to alkyl-alkyl cross-coupling catalysts with broad scope and selectivities. The work has potential to significantly impact science and technologies of interest to the DOE as the chemistry is focused on developing useful reactions using reagents that can be directly prepared from petroleum and natural gas feedstocks. Moreover, the developing synthetic chemistry can profoundly affect the way materials, fine chemicals, and drugs are made. Since the methodology we are developing can shorten existing synthetic protocols, proceed at room temperature, and operate under environmentally benign conditions, it can greatly reduce energy expenditures, especially considering the contribution of the chemical manufacturing field to the gross domestic product.

  11. Theory Of Alkyl Terminated Silicon Quantum Dots

    SciTech Connect (OSTI)

    Reboredo, F; Galli, G

    2004-08-19

    We have carried out a series of ab-initio calculations to investigate changes in the optical properties of Si quantum dots as a function of surface passivation. In particular, we have compared hydrogen passivated dots with those having alkyl groups at the surface. We find that, while on clusters with reconstructed surfaces a complete alkyl passivation is possible, steric repulsion prevents full passivation of Si dots with unreconstructed surfaces. In addition, our calculations show that steric repulsion may have a dominant effect in determining the surface structure, and eventually the stability of alkyl passivated clusters, with results dependent on the length of the carbon chain. Alkyl passivation weakly affects optical gaps of silicon quantum dots, while it substantially decreases ionization potentials and electron affinities and affect their excited state properties. On the basis of our results we propose that alkyl terminated quantum dots may be size selected taking advantage of the change in ionization potential as a function of the cluster size.

  12. Pseudo-hydroxide extraction in the separation of sodium hydroxide from aqueous solutions using alkyl phenols

    SciTech Connect (OSTI)

    Kang, Hyun Ah; Moyer, Bruce A

    2006-01-01

    Pseudo-hydroxide extraction of sodium hydroxide from aqueous solution using four alkyl phenols of nearly identical molecular weight in 1-octanol at 25 degrees C was examined to understand the effect of alkyl substituents. The order of extraction strength among the four alkyl phenols tested was 4-tert-octylphenol. 3,5-di-tertbutylphenol. 2,4-di-tert-butylphenol. 2,6-di-tert-butyl-4-methylphenol. A good correlation with phenol pK(a) was observed, indicating that extraction strength is determined by phenol acidity, as modified by steric effects in proximity to the phenol - OH group. The effective partition ratios (P-eff) of two phenols from 1 M NaOH solution were determined, showing that the phenols remain predominantly in the 1-octanol phase even when converted to their sodium salts. However, the hydrophobicity of the tested phenols may not be sufficient for process purposes. The equilibrium constants for the governing extraction equilibria were determined by modeling the data using the program SXLSQI, supporting the cation-exchange extraction mechanism. The proposed mechanism consists of two simple sets of equilibria for a. Ion-pair extraction to give Na+OH- ion pairs and corresponding free ions in 1-octanol the phase and b. Cation exchange by monomeric phenol molecules (HAs) to form monomeric organic-phase Na(+)A(-) ion pairs and corresponding free organic-phase ions.

  13. Alkylation of organic aromatic compounds

    DOE Patents [OSTI]

    Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

    1993-09-07

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a molecular sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene to about the mid point of the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 figures.

  14. Alkylation of organic aromatic compounds

    DOE Patents [OSTI]

    Smith, Jr., Lawrence A.

    1989-01-01

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

  15. Alkylation of organic aromatic compounds

    DOE Patents [OSTI]

    Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

    1993-01-01

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene to about the mid point of the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

  16. Alkylation of organic aromatic compounds

    DOE Patents [OSTI]

    Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

    1994-06-14

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a molecular sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 fig.

  17. Alkylation of organic aromatic compounds

    DOE Patents [OSTI]

    Smith, L.A. Jr.; Arganbright, R.P.; Hearn, D.

    1993-01-05

    Aromatic compounds are alkylated in a combination reactor/distillation column comprising a vessel suitable for operating between 70 C and 500 C and from 0.5 to 20 atmospheres pressure; an inert distillation packing in the lower one-third of said vessel; solid acidic catalytic material such as zeolites or an acidic cation exchange resin supported in the middle one-third of said vessel; and inert distillation packing in the upper one-third of said vessel. A benzene inlet is located near the upper end of the vessel; an olefin inlet is juxtaposed with said solid acidic catalytic material; a bottoms outlet is positioned near the bottom of said vessel for removing said cumene and ethyl benzene; and an overhead outlet is placed at the top of said vessel for removing any unreacted benzene and olefin.

  18. Alkylation of organic aromatic compounds

    DOE Patents [OSTI]

    Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

    1993-01-01

    Aromatic compounds are alkylated in a combination reactor/distillation column comprising a vessel suitable for operating between 70.degree. C. and 500.degree. C. and from 0.5 to 20 atmospheres pressure; an inert distillation packing in the lower one-third of said vessel; solid acidic catalytic material such as zeolites or an acidic cation exchange resin supported in the middle one-third of said vessel; and inert distillation packing in the upper one-third of said vessel. A benzene inlet is located near the upper end of the vessel; an olefin inlet is juxtaposed with said solid acidic catalytic material; a bottoms outlet is positioned near the bottom of said vessel for removing said cumene and ethyl benzene; and an overhead outlet is placed at the top of said vessel for removing any unreacted benzene and olefin.

  19. Alkylation of organic aromatic compounds

    DOE Patents [OSTI]

    Smith, Jr., Lawrence A.; Arganbright, Robert P.; Hearn, Dennis

    1994-01-01

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C.sub.2 to C.sub.10 olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80.degree. C. to 500.degree. C., using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms.

  20. Alkylation of organic aromatic compounds

    DOE Patents [OSTI]

    Smith, L.A. Jr.

    1989-07-18

    Aromatic compounds are alkylated in a catalytic distillation, wherein the catalyst structure also serves as a distillation component by contacting the aromatic compound with a C[sub 2] to C[sub 10] olefin in the catalyst bed under 0.25 to 50 atmospheres of pressure and at temperatures in the range of 80 C to 500 C, using as the catalyst a mole sieve characterized as acidic or an acidic cation exchange resin. For example, ethyl benzene is produced by feeding ethylene below the catalyst bed while benzene is conveniently added through the reflux in molar excess to that required to react with ethylene, thereby reacting substantially all of the ethylene and recovering benzene as the principal overhead and ethyl benzene in the bottoms. 1 fig.

  1. Solid Catalyst - Alkylation - Energy Innovation Portal

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

    Vehicles and Fuels Vehicles and Fuels Find More Like This Return to Search Solid Catalyst - Alkylation Idaho National Laboratory Contact INL About This Technology Technology Marketing Summary This is a method used to reactivate solid/liquid catalysts used in INL's super critical process to produce alkylates. The method brings the catalyst into contact with the designated fluid that serves as the reactivating agent and has the density to dissolve the impurities. The process reactivates the

  2. Molecular dynamics study of the effect of alkyl chain length on melting points of [CnMIM][PF6] ionic liquids

    SciTech Connect (OSTI)

    Zhang, Y; Maginn, EJ

    2014-01-01

    Based on molecular dynamics simulations, the melting points T-m of a series of 1-alkyl-3-methylimidazolium hexafluorophosphate ionic liquids [CnMIM][PF6] with n = 2, 4, 10, 12, and 14 were studied using the free energy-based pseudosupercritical path (PSCP) method. The experimental trend that the Tm decreases with increasing alkyl chain length for ILs with short alkyl chains and increases for the ones with long alkyl chains was correctly captured. Further analysis revealed that the different trends are the results of the balance between fusion enthalpy and fusion entropy. For the ILs with short alkyl chains (ethyl and butyl groups), fusion entropy plays the dominant role so that [C4MIM][PF6], which has a larger fusion entropy due to its higher liquid phase entropy has the lower melting temperature. As for the ILs with long alkyl chains, due to the enhanced van der Waals interactions brought about by the long non-polar alkyl chains, enthalpy becomes the deciding factor and the melting points increase when the alkyl chain goes from C10 to C14. While the melting points for [C2MIM][PF6] and [C4MIM][PF6] were quantitatively predicted and the trends for the long chain ILs were captured correctly, the absolute melting points for [C10MIM][PF6], [C12MIM][PF6] and [C14MIM][PF6] were systematically overestimated in the simulations. Three possible reasons for the overestimation were studied but all ruled out. Further simulation or experimental studies are needed to explain the difference.

  3. Enhancement of alkylation catalysts for improved supercritical fluid regeneration

    DOE Patents [OSTI]

    Ginosar, Daniel M. (Idaho Falls, ID); Petkovic, Lucia (Idaho Falls, ID)

    2009-09-22

    A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

  4. Enhancement of alkylation catalysts for improved supercritical fluid regeneration

    DOE Patents [OSTI]

    Ginosar, Daniel M. (Idaho Falls, ID); Petkovic, Lucia M. (Idaho Falls, ID)

    2010-12-28

    A method of modifying an alkylation catalyst to reduce the formation of condensed hydrocarbon species thereon. The method comprises providing an alkylation catalyst comprising a plurality of active sites. The plurality of active sites on the alkylation catalyst may include a plurality of weakly acidic active sites, intermediate acidity active sites, and strongly acidic active sites. A base is adsorbed to a portion of the plurality of active sites, such as the strongly acidic active sites, selectively poisoning the strongly acidic active sites. A method of modifying the alkylation catalyst by providing an alkylation catalyst comprising a pore size distribution that sterically constrains formation of the condensed hydrocarbon species on the alkylation catalyst or by synthesizing the alkylation catalyst to comprise a decreased number of strongly acidic active sites is also disclosed, as is a method of improving a regeneration efficiency of the alkylation catalyst.

  5. Poly(ethyleneoxide) functionalization through alkylation

    DOE Patents [OSTI]

    Sivanandan, Kulandaivelu; Eitouni, Hany Basam; Li, Yan; Pratt, Russell Clayton

    2015-04-21

    A new and efficient method of functionalizing high molecular weight polymers through alkylation using a metal amide base is described. This novel procedure can also be used to synthesize polymer-based macro-initiators containing radical initiating groups at the chain-ends for synthesis of block copolymers.

  6. Alcohol conversion

    DOE Patents [OSTI]

    Wachs, Israel E. (Bridgewater, NJ); Cai, Yeping (Louisville, KY)

    2002-01-01

    Preparing an aldehyde from an alcohol by contacting the alcohol in the presence of oxygen with a catalyst prepared by contacting an intimate mixture containing metal oxide support particles and particles of a catalytically active metal oxide from Groups VA, VIA, or VIIA, with a gaseous stream containing an alcohol to cause metal oxide from the discrete catalytically active metal oxide particles to migrate to the metal oxide support particles and to form a monolayer of catalytically active metal oxide on said metal oxide support particles.

  7. Poly(ethyleneoxide) functionalization through alkylation (Patent) | SciTech

    Office of Scientific and Technical Information (OSTI)

    Connect Poly(ethyleneoxide) functionalization through alkylation Citation Details In-Document Search Title: Poly(ethyleneoxide) functionalization through alkylation A new and efficient method of functionalizing high molecular weight polymers through alkylation using a metal amide base is described. This novel procedure can also be used to synthesize polymer-based macro-initiators containing radical initiating groups at the chain-ends for synthesis of block copolymers. Authors: Sivanandan,

  8. Electrophilic Metal Alkyl Chemistry in New Ligand Environments (Technical

    Office of Scientific and Technical Information (OSTI)

    Report) | SciTech Connect Technical Report: Electrophilic Metal Alkyl Chemistry in New Ligand Environments Citation Details In-Document Search Title: Electrophilic Metal Alkyl Chemistry in New Ligand Environments The goals of this project were to design new electrophilic metal alkyl complexes and to exploit these systems in fundamental studies of olefin polymerization and other important and new catalytic reactions. A key target reaction is insertion copolymerization of olefins and polar

  9. Electrophilic Metal Alkyl Chemistry in New Ligand Environments...

    Office of Scientific and Technical Information (OSTI)

    The goals of this project were to design new electrophilic metal alkyl complexes and to ... Pd catalysts that produce high molecular weight linear polyethylene and ...

  10. Conversion of Lignocellulosic Biomass to Ethanol Butyl Acrylate

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Conversion of Lignocellulosic Biomass to Ethanol and Butyl Acrylate March 25, 2015 Principal Investigator Thomas P. Binder ARCHER DANIELS MIDLAND COMPANY 2 Where does ADM fit with the IBR? * Ensuring a supply of technology for future growth is a priority for ADM Research * Corn stover utilization may enable continued growth in starch supply while starting a new industry around a currently underutilized material James R Randall Research Center Decatur, IL ARCHER DANIELS MIDLAND COMPANY 3 Quad

  11. Identification of volatile butyl rubber thermal-oxidative degradation products by cryofocusing gas chromatography/mass spectrometry (cryo-GC/MS).

    SciTech Connect (OSTI)

    Smith, Jonell Nicole; White, Michael Irvin; Bernstein, Robert; Hochrein, James Michael

    2013-02-01

    Chemical structure and physical properties of materials, such as polymers, can be altered as aging progresses, which may result in a material that is ineffective for its envisioned intent. Butyl rubber formulations, starting material, and additives were aged under thermal-oxidative conditions for up to 413 total days at up to 124 %C2%B0C. Samples included: two formulations developed at Kansas City Plant (KCP) (%236 and %2310), one commercially available formulation (%2321), Laxness bromobutyl 2030 starting material, and two additives (polyethylene AC-617 and Vanax MBM). The low-molecular weight volatile thermal-oxidative degradation products that collected in the headspace over the samples were preconcentrated, separated, and detected using cryofocusing gas chromatography mass spectrometry (cryo-GC/MS). The majority of identified degradation species were alkanes, alkenes, alcohols, ketones, and aldehydes. Observations for Butyl %2310 aged in an oxygen-18 enriched atmosphere (18O2) were used to verify when the source of oxygen in the applicable degradation products was from the gaseous environment rather than the polymeric mixture. For comparison purposes, Butyl %2310 was also aged under non-oxidative thermal conditions using an argon atmosphere.

  12. Solid Catalyzed Isoparaffin Alkylation at Supercritical Fluid and

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

    Near-Supercritical Fluid Conditions - Energy Innovation Portal Startup America Startup America Find More Like This Return to Search Solid Catalyzed Isoparaffin Alkylation at Supercritical Fluid and Near-Supercritical Fluid Conditions Idaho National Laboratory Contact INL About This Technology Technology Marketing Summary INL has developed a solid catalyst process for the alkylation reaction of isoparaffins with olefins over solid catalysts. The process includes contacting a mixture of an

  13. Poly(ethyleneoxide) functionalization through alkylation (Patent) | SciTech

    Office of Scientific and Technical Information (OSTI)

    Connect Poly(ethyleneoxide) functionalization through alkylation Citation Details In-Document Search Title: Poly(ethyleneoxide) functionalization through alkylation × You are accessing a document from the Department of Energy's (DOE) SciTech Connect. This site is a product of DOE's Office of Scientific and Technical Information (OSTI) and is provided as a public service. Visit OSTI to utilize additional information resources in energy science and technology. A paper copy of this document is

  14. Final Technical Report [Development of Catalytic Alkylation and Fluoroalkylation Methods

    SciTech Connect (OSTI)

    Vicic, David A.

    2014-05-01

    In the early stages of this DOE-funded research project, we sought to prepare and study a well-defined nickel-alkyl complex containing tridentate nitrogen donor ligands. We found that reaction of (TMEDA)NiMe2 (1) with terpyridine ligand cleanly led to the formation of (terpyridyl)NiMe (2), which we also determined to be an active alkylation catalyst. The thermal stability of 2 was unlike that seen for any of the active pybox ligands, and enabled a number of key studies on alkyl transfer reactions to be performed, providing new insights into the mechanism of nickel-mediated alkyl-alkyl cross-coupling reactions. In addition to the mechanistic studies, we showed that the terpyridyl nickel compounds can catalytically cross-couple alkyl iodides in yields up to 98% and bromides in yields up to 46 %. The yields for the bromides can be increased up to 67 % when the new palladium catalyst [(tpy)Pd-Ph]I is used. The best route to the targeted [(tpy)NiBr] (1) was found to involve the comproportionation reaction of [(dme)NiBr{sub 2}] and [Ni(COD){sub 2}] in the presence of two equivalents of terpyridine. This reaction was driven to high yields of product formation (72 % isolated) by the precipitation of 1 from THF solvent.

  15. Preparation and reactivity of macrocyclic rhodium(III) alkyl complexes

    SciTech Connect (OSTI)

    Carraher, Jack M.; Ellern, Arkady; Bakac, Andreja

    2013-09-21

    Macrocyclic rhodium(II) complexes LRh(H2O)(2+) (L = L-1 = cyclam and L-2 = meso-Me-6-cyclam) react with alkyl hydroperoxides RC(CH3)(2)OOH to generate the corresponding rhodium(III) alkyls L(H2O)RhR2+ (R = CH3, C2H5, PhCH2). Methyl and benzyl complexes can also be prepared by bimolecular group transfer from alkyl cobaloximes (dmgH)(2)(H2O) CoR and (dmgBF(2))(2)(H2O) CoR (R = CH3, PhCH2) to LRh(H2O)(2+). The new complexes were characterized by solution NMR and by crystal structure analysis. They exhibit great stability in aqueous solution at room temperature, but undergo efficient Rh-C bond cleavage upon photolysis. (C) 2013 Elsevier B.V. All rights reserved.

  16. Alkyl phospholipid antihypertensive agents in method of lowering blood pressure

    DOE Patents [OSTI]

    Snyder, Fred L.; Blank, Merle L.; Muirhead, Ernest E.; Leach, deceased, Byron E.; Byers, Lawrence W.

    1988-01-01

    The composition of this invention is 1-O-alkyl-2-acetoyl-sn-glycero-3-phosphocholine, having the ionic structural formula; ##STR1## wherein R is saturated alkyl having 9-21 carbon atoms, or salts or hydrates of the composition. Preferably R has 13-19 carbon atoms and most preferably R has 15 carbon atoms. The composition of this invention is useful for reducing hypertension in warm-blooded animals, including humans, when administered either orally or by injection or innoculation, e.g., intravenous injection. The composition can be prepared from naturally occurring lipids or synthetically from commercially available material.

  17. Weekly Petroleum Status Report

    Gasoline and Diesel Fuel Update (EIA)

    5 Alcohol. The family name of a group of organic chemical compounds composed of carbon, hydrogen, and oxygen. The series of molecules vary in chain length and are composed of a hydrocarbon plus a hydroxyl group; CH3-(CH2)n-OH (e.g., methanol, ethanol, and tertiary butyl alcohol). Alkylate. The product of an alkylation reaction. It usually refers to the high octane product from alkylation units. This alkylate is used in blending high octane gasoline. Alkylation. A refning process for chemically

  18. Petroleum Supply Monthly

    Gasoline and Diesel Fuel Update (EIA)

    December 2015 Alcohol. The family name of a group of organic chemical compounds composed of carbon, hydrogen, and oxygen. The series of molecules vary in chain length and are composed of a hydrocarbon plus a hydroxyl group; CH3-(CH2)n-OH (e.g., methanol, ethanol, and tertiary butyl alcohol). Alkylate. The product of an alkylation reaction. It usually refers to the high octane product from alkylation units. This alkylate is used in blending high octane gasoline. Alkylation. A refning process for

  19. Glossary - U.S. Energy Information Administration (EIA)

    U.S. Energy Information Administration (EIA) Indexed Site

    petroleum Alcohol: The family name of a group of organic chemical compounds composed of carbon, hydrogen, and oxygen. The series of molecules vary in chain length and are composed of a hydrocarbon plus a hydroxyl group; CH(3)-(CH(2))n-OH (e.g., methanol, ethanol, and tertiary butyl alcohol). Alkylate: The product of an alkylation reaction. It usually refers to the high-octane product from alkylation units. This alkylate is used in blending high octane gasoline. Alkylation: A refining process for

  20. Petroleum Supply Monthly

    U.S. Energy Information Administration (EIA) Indexed Site

    June 2015 Alcohol. The family name of a group of organic chemical compounds composed of carbon, hydrogen, and oxygen. The series of molecules vary in chain length and are composed of a hydrocarbon plus a hydroxyl group; CH3-(CH2)n-OH (e.g., methanol, ethanol, and tertiary butyl alcohol). Alkylate. The product of an alkylation reaction. It usually refers to the high octane product from alkylation units. This alkylate is used in blending high octane gasoline. Alkylation. A refning process for

  1. Mild and selective vanadium-catalyzed oxidation of benzylic, allylic, and propargylic alcohols using air

    DOE Patents [OSTI]

    Hanson, Susan Kloek; Silks, Louis A; Wu, Ruilian

    2013-08-27

    The invention concerns processes for oxidizing an alcohol to produce a carbonyl compound. The processes comprise contacting the alcohol with (i) a gaseous mixture comprising oxygen; and (ii) an amine compound in the presence of a catalyst, having the formula: ##STR00001## where each of R.sup.1-R.sup.12 are independently H, alkyl, aryl, CF.sub.3, halogen, OR.sup.13, SO.sub.3R.sup.14, C(O)R.sup.15, CONR.sup.16R.sup.17 or CO.sub.2R.sup.18; each of R.sup.13-R.sup.18 is independently alkyl or aryl; and Z is alkl or aryl.

  2. Fluoro-alcohol phase modifiers and process for cesium solvent extraction

    DOE Patents [OSTI]

    Bonnesen, Peter V.; Moyer, Bruce A.; Sachleben, Richard A.

    2003-05-20

    The invention relates to a class of phenoxy fluoro-alcohols, their preparation, and their use as phase modifiers and solvating agents in a solvent composition for the extraction of cesium from alkaline solutions. These phenoxy fluoro-alcohols comply with the formula: ##STR1## in which n=2 to 4; X represents a hydrogen or a fluorine atom, and R.sup.2 -R.sup.6 are hydrogen or alkyl substituents. These phenoxy fluoro-alcohol phase modifiers are a necessary component to a robust solvent composition and process useful for the removal of radioactive cesium from alkaline nuclear waste streams. The fluoro-alcohols can also be used in solvents designed to extract other cesium from acidic or neutral solutions.

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

    Reports and Publications (EIA)

    2006-01-01

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

  4. Novel Fluorescent Cationic Phospholipid, O-4-Napthylimido-1-Butyl-DOPC,

    Office of Scientific and Technical Information (OSTI)

    Exhibits Unusual Foam Morphology, Forms Hexagonal and Cubic Phases in Mixtures, and Transfects DNA (Journal Article) | SciTech Connect Novel Fluorescent Cationic Phospholipid, O-4-Napthylimido-1-Butyl-DOPC, Exhibits Unusual Foam Morphology, Forms Hexagonal and Cubic Phases in Mixtures, and Transfects DNA Citation Details In-Document Search Title: Novel Fluorescent Cationic Phospholipid, O-4-Napthylimido-1-Butyl-DOPC, Exhibits Unusual Foam Morphology, Forms Hexagonal and Cubic Phases in

  5. Method for reactivating solid catalysts used in alkylation reactions

    DOE Patents [OSTI]

    Ginosar, Daniel M.; Thompson, David N.; Coates, Kyle; Zalewski, David J.; Fox, Robert V.

    2003-06-17

    A method for reactivating a solid alkylation catalyst is provided which can be performed within a reactor that contains the alkylation catalyst or outside the reactor. Effective catalyst reactivation is achieved whether the catalyst is completely deactivated or partially deactivated. A fluid reactivating agent is employed to dissolve catalyst fouling agents and also to react with such agents and carry away the reaction products. The deactivated catalyst is contacted with the fluid reactivating agent under pressure and temperature conditions such that the fluid reactivating agent is dense enough to effectively dissolve the fouling agents and any reaction products of the fouling agents and the reactivating agent. Useful pressures and temperatures for reactivation include near-critical, critical, and supercritical pressures and temperatures for the reactivating agent. The fluid reactivating agent can include, for example, a branched paraffin containing at least one tertiary carbon atom, or a compound that can be isomerized to a molecule containing at least one tertiary carbon atom.

  6. Furfuryl alcohol cellular product

    DOE Patents [OSTI]

    Sugama, T.; Kukacka, L.E.

    1982-05-26

    Self-extinguishing rigid foam products are formed by polymerization of furfuryl alcohol in the presence of a lightweight, particulate, filler, zinc chloride and selected catalysts.

  7. PSADEFS.CHP:Corel VENTURA

    Annual Energy Outlook [U.S. Energy Information Administration (EIA)]

    Definitions of Petroleum Products and Other Terms Alcohol. The family name of a group of organic chemical compounds composed of carbon, hydrogen, and oxygen. The series of molecules vary in chain length and are composed of a hydrocarbon plus a hydroxyl group; CH 3 - (CH 2 )n-OH (e.g., methanol, ethanol, and tertiary butyl alcohol). Alkylate. The product of an alkylation reaction. It usu- ally refers to the high octane product from alkylation units. This alkylate is used in blending high octane

  8. Methods of producing alkylated hydrocarbons from an in situ heat treatment process liquid

    DOE Patents [OSTI]

    Roes, Augustinus Wilhelmus Maria (Houston, TX); Mo, Weijian (Sugar Land, TX); Muylle, Michel Serge Marie (Houston, TX); Mandema, Remco Hugo (Houston, TX); Nair, Vijay (Katy, TX)

    2009-09-01

    A method for producing alkylated hydrocarbons is disclosed. Formation fluid is produced from a subsurface in situ heat treatment process. The formation fluid is separated to produce a liquid stream and a first gas stream. The first gas stream includes olefins. The liquid stream is fractionated to produce at least a second gas stream including hydrocarbons having a carbon number of at least 3. The first gas stream and the second gas stream are introduced into an alkylation unit to produce alkylated hydrocarbons. At least a portion of the olefins in the first gas stream enhance alkylation.

  9. Extracting alcohols from aqueous solutions

    DOE Patents [OSTI]

    Compere, Alicia L.; Googin, John M.; Griffith, William L.

    1984-01-01

    Hydrocarbon and surfactants are contacted with a solution of alcohol and water to extract the alcohol into the hydrocarbon-surfactant mixture.

  10. Supported metal catalysts for alcohol/sugar alcohol steam reforming

    SciTech Connect (OSTI)

    Davidson, Stephen; Zhang, He; Sun, Junming; Wang, Yong

    2014-08-21

    Despite extensive studies on hydrogen production via steam reforming of alcohols and sugar alcohols, catalysts typically suffer a variety of issues from poor hydrogen selectivity to rapid deactivation. Here, we summarize recent advances in fundamental understanding of functionality and structure of catalysts for alcohol/sugar alcohol steam reforming, and provide perspectives on further development required to design highly efficient steam reforming catalysts.

  11. Process to convert biomass and refuse derived fuel to ethers and/or alcohols

    DOE Patents [OSTI]

    Diebold, J.P.; Scahill, J.W.; Chum, H.L.; Evans, R.J.; Rejai, B.; Bain, R.L.; Overend, R.P.

    1996-04-02

    A process is described for conversion of a feedstock selected from the group consisting of biomass and refuse derived fuel (RDF) to provide reformulated gasoline components comprising a substantial amount of materials selected from the group consisting of ethers, alcohols, or mixtures thereof, comprising: drying said feedstock; subjecting said dried feedstock to fast pyrolysis using a vortex reactor or other means; catalytically cracking vapors resulting from said pyrolysis using a zeolite catalyst; condensing any aromatic byproduct fraction; catalytically alkylating any benzene present in said vapors after condensation; catalytically oligomerizing any remaining ethylene and propylene to higher olefins; isomerizing said olefins to reactive iso-olefins; and catalytically reacting said iso-olefins with an alcohol to form ethers or with water to form alcohols. 35 figs.

  12. Process to convert biomass and refuse derived fuel to ethers and/or alcohols

    DOE Patents [OSTI]

    Diebold, James P.; Scahill, John W.; Chum, Helena L.; Evans, Robert J.; Rejai, Bahman; Bain, Richard L.; Overend, Ralph P.

    1996-01-01

    A process for conversion of a feedstock selected from the group consisting of biomass and refuse derived fuel (RDF) to provide reformulated gasoline components comprising a substantial amount of materials selected from the group consisting of ethers, alcohols, or mixtures thereof, comprising: drying said feedstock; subjecting said dried feedstock to fast pyrolysis using a vortex reactor or other means; catalytically cracking vapors resulting from said pyrolysis using a zeolite catalyst; condensing any aromatic byproduct fraction; catalytically alkylating any benzene present in said vapors after condensation; catalytically oligomerizing any remaining ethylene and propylene to higher olefins; isomerizing said olefins to reactive iso-olefins; and catalytically reacting said iso-olefins with an alcohol to form ethers or with water to form alcohols.

  13. Computational Studies of [Bmim][PF6]/n-Alcohol Interfaces with Many-Body Potentials

    SciTech Connect (OSTI)

    Chang, Tsun-Mei; Dang, Liem X.

    2014-09-04

    In this paper, we present the results from molecular-dynamics simulations of the equilibrium properties of liquid/liquid interfaces of room temperature ionic liquid [bmim][PF6] and simple alcohols (i.e., methanol, 1-butanol, and 1-hexanol) at room temperature. Polarizable potential models are employed to describe the interactions among species. Results from our simulations show stable interfaces between the ionic liquid and n-alcohols, and we found that the interfacial widths decrease from methanol to 1-butanol systems, and then increase for 1-hexanol interfaces. Angular distribution analysis reveals that the interface induces a strong orientational order of [bmim] and n-alcohol molecules near the interface, with [bmim] extending its butyl group into the alcohol phase while the alcohol has the OH group pointing into the ion liquid region, which is consistent with the recent sum-frequency-generation experiments. We found the interface to have a significant influence on the dynamics of ionic liquids and n-alcohols. The orientational autocorrelation functions illustrate that [bmim] rotate more freely near the interface than in the bulk, while the rotation of n-alcohol is hindered at the interface. Additionally, the time scale associated with the diffusion along the interfacial direction is found to be faster for [bmim] but slowed down for n-alcohols approaching the interface. We also calculate the dipole moment of n-alcohols as a function of the distance normal to the interface. We found that, even though methanol and 1-butanol have different dipole moments in bulk phase, they reach a similar value at the interface. This work was supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Pacific Northwest National Laboratory is a multiprogram national laboratory operated for the Department of Energy by Battelle. The calculations were carried out using computer resources provided by the Office of Basic Energy Sciences.

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

    DOE Patents [OSTI]

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

    1983-01-01

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

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

    DOE Patents [OSTI]

    Smith, L.A. Jr.

    1983-03-01

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

  16. Effect of hydrotropic salts on phase relationships involving hydrocarbons, water, and alcohols

    SciTech Connect (OSTI)

    Ho, P.C.; Kraus, K.A.

    1980-01-01

    Hydrotropic salts, which can increase the solubility of organic materials in aqueous solutions, are useful to tertiary oil recovery. We have examined effects on solubility of hydrocarbons in water (with and without alcohols) through addition of inorganic hydrotropic salts, such as perchlorates, thiocyanates, and iodides - high in the usual Hofmeister series - and of organic salts such as short chain alkyl benzene sulfonates and other salts based on substituted benzene derivatives. Although the inorganic salts are relatively ineffective in increasing solubility of hydrocarbons in water, many of the organic salts are excellent hydrotropic agents for hydrocarbons. We have examined the phase relationships for several series of aromatic salts such as sulfonates, carboxylates and hydroxycarboxylates, as a function of alkyl-carbon substitution in three-component (hydrocarbon, salt, water) and in four-component (hydrocarbon, salt, alcohol, water) systems. We have also examined miscibility relationships for a given hydrotropic salt as the chain length of alkanes and alkyl benzenes is systematically varied. While miscibilities decrease with increase in chain length of the hydrocarbon, the hydrotropic properties in these systems increase rapidly with the number of alkyl carbons on the benzene ring of the salts and they are relatively insensitive to the type of charged group (sulfonate vs carboxylate) attached to the benzene ring. However, there were significant increases in hydrotropy as one goes from equally substituted sulfonates or carboxylates to salicylates. A number of salts have been identified which have much greater hydrotropic properties for hydrocarbons than such well-known hydrotropic materials as toluene and xylene sulfonates.

  17. Portal Vein Embolization before Right Hepatectomy: Improved Results Using n-Butyl-Cyanoacrylate Compared to Microparticles Plus Coils

    SciTech Connect (OSTI)

    Guiu, Boris Bize, Pierre; Gunthern, Daniel; Demartines, Nicolas; Halkic, Nermin; Denys, Alban

    2013-10-15

    Background: There is currently no consensus in the literature on which embolic agent induces the greatest degree of liver hypertrophy after portal vein embolization (PVE). Only experimental results in a pig model have demonstrated an advantage of n-butyl-cyanoacrylate (NBCA) over 3 other embolic materials (hydrophilic gel, small and large polyvinyl alcohol particles) for PVE. Therefore, the aim of this human study was to retrospectively compare the results of PVE using NBCA with those using spherical microparticles plus coils. Methods: A total of 34 patients underwent PVE using either NBCA (n = 20), or spherical microparticles plus coils (n = 14). PVE was decided according to preoperative volumetry on the basis of contrast-enhanced CT. Groups were compared for age, sex, volume of the left lobe before PVE and future remnant liver ratio (FRL) (volume of the left lobe/total liver volume - tumor volume). The primary end point was the increase in left lobe volume 1 month after PVE. Secondary end points were procedure complications and biological tolerance. Results: Both groups were similar in terms of age, sex ratio, left lobe volume, and FRL before PVE. NBCA induced a greater increase in volume after PVE than did microparticles plus coils (respectively, +74 {+-} 69 % and +23 {+-} 14 %, p < 0.05). The amount of contrast medium used for the procedure was significantly larger when microparticles and coils rather than NBCA were used (respectively, 264 {+-} 43 ml and 162 {+-} 34 ml, p < 0.01). The rate of PVE complications as well as the biological tolerance was similar in both groups. Conclusion: NBCA seems more effective than spherical microparticles plus coils to induce left-lobe hypertrophy.

  18. Fermentative alcohol production

    DOE Patents [OSTI]

    Wilke, Charles R. (El Cerrito, CA); Maiorella, Brian L. (Berkeley, CA); Blanch, Harvey W. (Berkeley, CA); Cysewski, Gerald R. (Kennewick, WA)

    1982-01-01

    An improved fermentation process for producing alcohol which includes the combination of vacuum fermentation and vacuum distillation. Preferably, the vacuum distillation is carried out in two phases, one a fermentor proper operated at atmospheric pressure and a flash phase operated at reduced pressure with recycle of fermentation brew having a reduced alcohol content to the fermentor, using vapor recompression heating of the flash-pot recycle stream to heat the flash-pot or the distillation step, and using "water load balancing" (i.e., the molar ratio of water in the fermentor feed is the same as the molar ratio of water in the distillation overhead).

  19. ESE Alcohol | Open Energy Information

    Open Energy Info (EERE)

    ESE Alcohol Jump to: navigation, search Name: ESE Alcohol Place: Leoti, Kansas Zip: 67861 Product: Owner of a 6.6m litre per year ethanol plant Coordinates: 38.481425,...

  20. Production of hydrogen from alcohols

    DOE Patents [OSTI]

    Deluga, Gregg A. (St. Paul, MN); Schmidt, Lanny D. (Minneapolis, MN)

    2007-08-14

    A process for producing hydrogen from ethanol or other alcohols. The alcohol, optionally in combination with water, is contacted with a catalyst comprising rhodium. The overall process is preferably carried out under autothermal conditions.

  1. Alcoholes Biocarburantes de Extremadura Albiex | Open Energy...

    Open Energy Info (EERE)

    search Name: Alcoholes Biocarburantes de Extremadura (Albiex) Place: Spain Product: Spanish bioethanol producer building a plant in Extremadura. References: Alcoholes...

  2. PROCESS OF RECOVERING ZIRCONIUM VALUES FROM HAFNIUM VALUES BY SOLVENT EXTRACTION WITH AN ALKYL PHOSPHATE

    DOE Patents [OSTI]

    Peppard, D.F.

    1960-02-01

    A process of separating hafnium nitrate from zirconium nitrate contained in a nitric acid solution by selectively. extracting the zirconium nitrate with a water-immiscible alkyl phosphate is reported.

  3. Fuel alcohol opportunities for Indiana

    SciTech Connect (OSTI)

    Greenglass, Bert

    1980-08-01

    Prepared at the request of US Senator Birch Bayh, Chairman of the National Alcohol Fuels Commission, this study may be best utilized as a guidebook and resource manual to foster the development of a statewide fuel alcohol plan. It examines sectors in Indiana which will impact or be impacted upon by the fuel alcohol industry. The study describes fuel alcohol technologies that could be pertinent to Indiana and also looks closely at how such a fuel alcohol industry may affect the economic and policy development of the State. Finally, the study presents options for Indiana, taking into account the national context of the developing fuel alcohol industry which, unlike many others, will be highly decentralized and more under the control of the lifeblood of our society - the agricultural community.

  4. Exchange Reactions Between a Molten Salt and a Solution of Tri-Butyl

    Office of Scientific and Technical Information (OSTI)

    Phosphate in a Liquid Silicone; REACTIONS D'ECHANGE ENTRE UN SEL FONDU ET UNE SOLUTION DE PHOSPHATE DE TRIBUTYLE DANS UN SILICONE LIQUIDE (Technical Report) | SciTech Connect Technical Report: Exchange Reactions Between a Molten Salt and a Solution of Tri-Butyl Phosphate in a Liquid Silicone; REACTIONS D'ECHANGE ENTRE UN SEL FONDU ET UNE SOLUTION DE PHOSPHATE DE TRIBUTYLE DANS UN SILICONE LIQUIDE Citation Details In-Document Search Title: Exchange Reactions Between a Molten Salt and a

  5. Suppression of alkylating agent induced cell transformation and gastric ulceration by low-dose alkylating agent pretreatment

    SciTech Connect (OSTI)

    Onodera, Akira; Department of Pharmaceutical Sciences, Kobegakuin University, 1-1-3 Minatojima, Chuo-ku, Kobe 650-8586 ; Kawai, Yuichi; Kashimura, Asako; Ogita, Fumiya; Tsutsumi, Yasuo; Itoh, Norio

    2013-06-14

    Highlights: Low-dose MNNG pretreatment suppresses high-dose MNNG induced in vitro transformation. Gastric ulcers induced by high-dose MNNG decreased after low-dose MNNG pretreatment. Efficacy of low-dose MNNG related to resistance of mutation and oxidative stress. -- Abstract: Exposure to mild stress by chemicals and radiation causes DNA damage and leads to acquired stress resistance. Although the linear no-threshold (LNT) model of safety assessment assumes risk from any dose, evidence from radiological research demonstrates a conflicting hormetic phenomenon known as the hormesis effect. However, the mechanisms underlying radiation hormesis have not yet been clarified, and little is known about the effects of low doses of chemical carcinogens. We analyzed the efficacy of pretreatment with low doses of the alkylating agent N-methyl-N?-nitro-N-nitrosoguanidine (MNNG) on the subsequent induction of cell transformation and gastric ulceration by high-dose MNNG. We used an in vitro Balb/3T3 A31-1-1 cell transformation test and monitored the formation of gastric ulcers in 5-week-old male ICR mice that were administered MNNG in drinking water. The treatment concentrations of MNNG were determined by the cell survival rate and past reports. For low-dose in vitro and in vivo experiments, MNNG was used at 0.028 ?M, and 2.8 ?g/mL, respectively. The frequency of cell transformation induced by 10 ?m MNNG was decreased by low-dose MNNG pretreatment to levels similar to that of spontaneous transformation. In addition, reactive oxygen species (ROS) and mutation frequencies induced by 10 ?m MNNG were decreased by low-dose MNNG pretreatment. Importantly, low-dose MNNG pretreatment had no effect on cell proliferation. In vivo studies showed that the number of gastric ulcers induced by 1 mg/mL MNNG decreased after low-dose MNNG pretreatment. These data indicate that low-dose pretreatment with carcinogens may play a beneficial role in the prevention of chemical toxicity under specified conditions.

  6. Oligonucleoside alkyl or arylphosphonate derivatives capable of crosslinking with or cleaving nucleic acids

    DOE Patents [OSTI]

    Miller, P.S.; Ts'o, P.O.P.

    1999-06-15

    A composition for inactivating a target nucleic acid which comprises an oligonucleoside alkyl or arylphosphonate analogue which is complementary to the sequence of the target nucleic acid is provided. It includes a functional group which reacts with the target nucleic acid to render the target nucleic acid inactive or nonfunctional. 16 figs.

  7. Oligonucleoside alkyl or arylphosphonate derivatives capable of crosslinking with or cleaving nucleic acids

    DOE Patents [OSTI]

    Miller, Paul S. (Baltimore, MD); Ts'o, Paul O.P. (Lutherville, MD)

    1999-06-15

    A composition for inactivating a target nucleic acid which comprises an oligonucleoside alkyl or arylphosphonate analogue which is complementary to the sequence of the target nucleic acid and includes a functional group which reacts with the target nucleic acid to render the target nucleic acid inactive or nonfunctional.

  8. Alcohol fuels program technical review

    SciTech Connect (OSTI)

    1981-07-01

    The last issue of the Alcohol Fuels Process R/D Newsletter contained a work breakdown structure (WBS) of the SERI Alcohol Fuels Program that stressed the subcontracted portion of the program and discussed the SERI biotechnology in-house program. This issue shows the WBS for the in-house programs and contains highlights for the remaining in-house tasks, that is, methanol production research, alcohol utilization research, and membrane research. The methanol production research activity consists of two elements: development of a pressurized oxygen gasifier and synthesis of catalytic materials to more efficiently convert synthesis gas to methanol and higher alcohols. A report is included (Finegold et al. 1981) that details the experimental apparatus and recent results obtained from the gasifier. The catalysis research is principally directed toward producing novel organometallic compounds for use as a homogeneous catalyst. The utilization research is directed toward the development of novel engine systems that use pure alcohol for fuel. Reforming methanol and ethanol catalytically to produce H/sub 2/ and CO gas for use as a fuel offers performance and efficiency advantages over burning alcohol directly as fuel in an engine. An application of this approach is also detailed at the end of this section. Another area of utilization is the use of fuel cells in transportation. In-house researchers investigating alternate electrolyte systems are exploring the direct and indirect use of alcohols in fuel cells. A workshop is being organized to explore potential applications of fuel cells in the transportation sector. The membrane research group is equipping to evaluate alcohol/water separation membranes and is also establishing cost estimation and energy utilization figures for use in alcohol plant design.

  9. Green polymer electrolytes based on chitosan and 1-butyl-3-methylimidazolium acetate

    SciTech Connect (OSTI)

    Shamsudin, Intan Juliana [Chemistry Department, Centre for Defence Foundation Studies, National Defence University of Malaysia, 57000 Kuala Lumpur (Malaysia); Ahmad, Azizan; Hassan, Nur Hasyareeda [School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600, Bangi, Selangor Darul Ehsan (Malaysia)

    2014-09-03

    Green polymer electrolytes based on chitosan as the polymer matrix and ionic liquid 1-butyl-3-methylimidazolium acetate [Bmim][OAc] as charge carriers were prepared by solution casting technique. Complexes with various amount of ionic liquid loading were investigated as possible ionic conducting polymers. The ionic conductivity was found to increase with increasing weight percent of ionic liquid. The highest ionic conductivity of the charged chitosan-[Bmim][OAc] was 2.44 10{sup ?3} S cm{sup ?1} at 90 wt.% of [Bmim][OAc] content at ambient temperature. Attenuated Total Reflection Fourier Transform infrared (ATR-FTIR) spectroscopy has proven the interaction between chitosan and [Bmim][OAc]. X-ray Diffraction (XRD) has shown that the amorphosity of the complexes increase as the amount of [Bmim][OAc] increase.

  10. Mixed Alcohol Synthesis Catalyst Screening

    SciTech Connect (OSTI)

    Gerber, Mark A.; White, James F.; Stevens, Don J.

    2007-09-03

    National Renewable Energy Laboratory (NREL) and Pacific Northwest National Laboratory (PNNL) are conducting research to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas (syngas). PNNL is tasked with obtaining commercially available or preparing promising mixed-alcohol catalysts and screening them in a laboratory-scale reactor system. Commercially available catalysts and the most promising experimental catalysts are provided to NREL for testing using a slipstream from a pilot-scale biomass gasifier. From the standpoint of producing C2+ alcohols as the major product, it appears that the rhodium catalyst is the best choice in terms of both selectivity and space-time yield (STY). However, unless the rhodium catalyst can be improved to provide minimally acceptable STYs for commercial operation, mixed alcohol synthesis will involve significant production of other liquid coproducts. The modified Fischer-Tropsch catalyst shows the most promise for providing both an acceptable selectivity to C2+ alcohols and total liquid STY. However, further optimization of the Fischer-Tropsch catalysts to improve selectivity to higher alcohols is highly desired. Selection of a preferred catalyst will likely entail a decision on the preferred coproduct slate. No other catalysts tested appear amenable to the significant improvements needed for acceptable STYs.

  11. Solid catalyzed isoparaffin alkylation at supercritical fluid and near-supercritical fluid conditions

    DOE Patents [OSTI]

    Ginosar, Daniel M. (Idaho Falls, ID); Fox, Robert V. (Idaho Falls, ID); Kong, Peter C. (Idaho Falls, ID)

    2000-01-01

    This invention relates to an improved method for the alkylation reaction of isoparaffins with olefins over solid catalysts including contacting a mixture of an isoparaffin, an olefin and a phase-modifying material with a solid acid catalyst member under alkylation conversion conditions at either supercritical fluid, or near-supercritical fluid conditions, at a temperature and a pressure relative to the critical temperature(T.sub.c) and the critical pressure(P.sub.c) of the reaction mixture. The phase-modifying phase-modifying material is employed to promote the reaction's achievement of either a supercritical fluid state or a near-supercritical state while simultaneously allowing for decreased reaction temperature and longer catalyst life.

  12. Features of the spectral dependences of transmittance of organic semiconductors based on tert-butyl substituted lutetium phthalocyanine molecules

    SciTech Connect (OSTI)

    Belogorokhov, I. A.; Tikhonov, E. V.; Dronov, M. A.; Belogorokhova, L. I.; Ryabchikov, Yu. V.; Tomilova, L. G.; Khokhlov, D. R.

    2011-11-15

    Vibronic properties of organic semiconductors based on tert-butyl substituted phthalocyanine lutetium diphthalocyanine molecules are studied by IR and Raman spectroscopy. It is shown that substitution of several carbon atoms in initial phthalocyanine (Pc) ligands with {sup 13}C isotope atoms causes a spectral shift in the main absorption lines attributed to benzene, isoindol, and peripheral C-H groups. A comparison of spectral characteristics showed that the shift can vary from 3 to 1 cm{sup -1}.

  13. Method for photochemical reduction of uranyl nitrate by tri-N-butyl phosphate and application of this method to nuclear fuel reprocessing

    DOE Patents [OSTI]

    De Poorter, Gerald L. (Los Alamos, NM); Rofer-De Poorter, Cheryl K. (Los Alamos, NM)

    1978-01-01

    Uranyl ion in solution in tri-n-butyl phosphate is readily photochemically reduced to U(IV). The product U(IV) may effectively be used in the Purex process for treating spent nuclear fuels to reduce Pu(IV) to Pu(III). The Pu(III) is readily separated from uranium in solution in the tri-n-butyl phosphate by an aqueous strip.

  14. Alcohol Fuels - Combustion Energy Frontier Research Center

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

    Alcohol Fuels Alcohol Fuels Goals Advance a multiscale approach to collaborative reaction kinetic model development and validation, by focusing team efforts on particular alcohol fuels. The team's initial focus has been on n-butanol. This has recently broadened to include detailed kinetic modeling of other isomeric butanols, plus some comparisons with smaller alcohols and the corresponding ketones, aldehydes, and enols. In the future we expect to use what we have learned from the butanol study

  15. N-butyl Cyanoacrylate Glue Embolization of Arterial Networks to Facilitate Hepatic Arterial Skeletonization before Radioembolization

    SciTech Connect (OSTI)

    Samuelson, Shaun D.; Louie, John D.; Sze, Daniel Y.

    2013-06-15

    Purpose. Avoidance of nontarget microsphere deposition via hepatoenteric anastomoses is essential to the safety of yttrium-90 radioembolization (RE). The hepatic hilar arterial network may remain partially patent after coil embolization of major arteries, resulting in persistent risk. We retrospectively reviewed cases where n-butyl cyanoacrylate (n-BCA) glue embolization was used to facilitate endovascular hepatic arterial skeletonization before RE. Methods. A total of 543 RE procedures performed between June 2004 and March 2012 were reviewed, and 10 were identified where n-BCA was used to embolize hepatoenteric anastomoses. Arterial anatomy, prior coil embolization, and technical details were recorded. Outcomes were reviewed to identify subsequent complications of n-BCA embolization or nontarget RE. Results. The rate of complete technical success was 80 % and partial success 20 %, with one nontarget embolization complication resulting in a minor change in treatment plan. No evidence of gastrointestinal or biliary ischemia or infarction was identified, and no microsphere-related gastroduodenal ulcerations or other evidence of nontarget RE were seen. Median volume of n-BCA used was <0.1 ml. Conclusion. n-BCA glue embolization is useful to eliminate hepatoenteric networks that may result in nontarget RE, especially in those that persist after coil embolization of major vessels such as the gastroduodenal and right gastric arteries.

  16. A Stable Fluorinated and Alkylated Lithium Malonatoborate Salt for Lithium Ion Battery Application

    SciTech Connect (OSTI)

    Wan, Shun; Jiang, Xueguang; Guo, Bingkun; Dai, Sheng; Sun, Xiao-Guang

    2015-01-01

    A new fluorinated and alkylated lithium malonatoborate salt, lithium bis(2-methyl-2-fluoromalonato)borate (LiBMFMB), has been synthesized for lithium ion battery application. A 0.8 M LiBMFMB solution is obtained in a mixture of ethylene carbonate (EC) and ethyl methyl carbonate (EMC) (1:2 by wt.). The new LiBMFMB based electrolyte exhibits good cycling stability and rate capability in LiNi0.5Mn1.5O4 and graphite based half-cells.

  17. Catalyst for producing lower alcohols

    DOE Patents [OSTI]

    Rathke, Jerome W. (Bolingbrook, IL); Klingler, Robert J. (Woodridge, IL); Heiberger, John J. (Glen Ellyn, IL)

    1987-01-01

    A process and system for the production of the lower alcohols such as methanol, ethanol and propanol involves the reaction of carbon monoxide and water in the presence of a lead salt and an alkali metal formate catalyst combination. The lead salt is present as solid particles such as lead titanate, lead molybdate, lead vanadate, lead zirconate, lead tantalate and lead silicates coated or in slurry within molten alkali metal formate. The reactants, carbon monoxide and steam are provided in gas form at relatively low pressures below 100 atmospheres and at temperatures of 200-400.degree. C. The resulted lower alcohols can be separated into boiling point fractions and recovered from the excess reactants by distillation.

  18. Syngas Mixed Alcohol Cost Validation

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    1, 2013 DOE Bioenergy Technologies Office: Project Peer Review Syngas Mixed Alcohol Cost Validation Abhijit Dutta, NREL This presentation does not contain any proprietary, confidential, or otherwise restricted information Goal Statement Enable research and development of cost-competitive biomass to liquid fuels by providing: - Techno-economic analysis (TEA) - Feedback to the research efforts Specific objective in 2012: Provide TEA and validate DOE BETO's goal to demonstrate technologies capable

  19. High-Octane Fuel from Refinery Exhaust Gas: Upgrading Refinery Off-Gas to High-Octane Alkylate

    SciTech Connect (OSTI)

    2009-12-01

    Broad Funding Opportunity Announcement Project: Exelus is developing a method to convert olefins from oil refinery exhaust gas into alkylate, a clean-burning, high-octane component of gasoline. Traditionally, olefins must be separated from exhaust before they can be converted into another source of useful fuel. Exelus process uses catalysts that convert the olefin to alkylate without first separating it from the exhaust. The ability to turn up to 50% of exhaust directly into gasoline blends could result in an additional 46 million gallons of gasoline in the U.S. each year.

  20. 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...

  1. 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...

  2. Distribution of 1-Butyl-3-methylimidazolium Bistrifluoromethylsulfonimide in Mesoporous Silica as a Function of Pore Filling

    SciTech Connect (OSTI)

    Han, Kee Sung; Wang, Xiqing; Hagaman, Edward {Ed} W; Dai, Sheng

    2013-01-01

    Rotational dynamics of the ionic liquid (IL) 1-butyl-3-methlyimidazolium bistrifluoromethylsulfonimide, [C4mim][Tf2N], 1, as a neat liquid and confined in mesoporous silica were investigated by 1H spin-spin (T2) and spin-lattice (T1) relaxation measurements and 13C NMR spectroscopy. Translational dynamics (self-diffusion) were monitored via the diffusion coefficient, D, obtained with 1H pulsed field gradient NMR measurements. These data were used to determine the distribution of 1 in the pores of KIT-6, a mesoporous silica with a bicontinuous gyroid pore structure, as a function of filling fraction. Relaxation studies performed as a function of filling factor and temperature, reveal a dynamic heterogeneity in both translational and rotational motions for 1 at filling factors, f, = 0.2-1.0 (f = 1 corresponds to fully filled pores). Spin-lattice and spin-spin relaxation times reveal the motion of 1 in silica mesopores conform to that expected for a two-dimensional relaxation model. The relaxation dynamics are interpreted using a two-state, fast exchange model for all motions; a slow rotation (and translation) of molecules in contact with the surface and a faster motion approximated by the values for bulk relaxation and diffusion. 1 retains liquid like behavior at all filling factors and temperatures that extend to ca. 50 degrees below the bulk melting point. Translational motion in these systems, interpreted with MD-simulated diffusivity limits, confirms the high propensity of 1 to form a monolayer film on the silica surface at low filling factors.. The attractive interaction of 1 with the surface is greater than that for self-association of 1. The trends in diffusion data at short and long diffusion time suggest that the population of surface-bound 1 is in intimate contact with 1 in the pores. This condition is most easily met at higher filling fractions with successive additions of 1 increasing the layer thickness built up on the surface layer.

  3. Formation of alcohol conversion catalysts

    DOE Patents [OSTI]

    Wachs, Israel E. (Bridgewater, NJ); Cai, Yeping (Louisville, KY)

    2001-01-01

    The method of the present invention involves a composition containing an intimate mixture of (a) metal oxide support particles and (b) a catalytically active metal oxide from Groups VA, VIA, or VIIA, its method of manufacture, and its method of use for converting alcohols to aldehydes. During the conversion process, catalytically active metal oxide from the discrete catalytic metal oxide particles migrates to the oxide support particles and forms a monolayer of catalytically active metal oxide on the oxide support particle to form a catalyst composition having a higher specific activity than the admixed particle composition.

  4. Pressure dispensable gelled alcohol fuel

    SciTech Connect (OSTI)

    Monick, J.A.

    1982-12-28

    A pressurized fuel gel composition particularly suitable for igniting wood and charcoal consisting essentially of, by weight, 42-90% of at least one c1-c6 monohydric alcohol, 0.5-6% of water-soluble gelling agent, up to about 24% water and a correlated amount of propellant from 0.5% to 30% characterized by a gel structure which forms a shape retaining mass upon contact with wood or charcoal that is maintained during the burning of said composition. Also within the scope of the invention is an aerosol product comprising said pressurized composition enclosed within a pressure-tight container having valve means for expelling the composition.

  5. Alkyl-bis(imidazolium) salts: a new amphiphile platform that forms thermotropic and non-aqueous lyotropic bicontinuous cubic phases

    SciTech Connect (OSTI)

    Robertson, LA; Schenkel, MR; Wiesenauer, BR; Gin, DL

    2013-01-01

    New ionic amphiphiles with a hexyl-bridged bis(imidazolium) headgroup; Br-, BF4-, or Tf2N- anions; and a long n-alkyl tail can form thermotropic bicontinuous cubic liquid crystal phases in neat form and/or lyotropic bicontinuous cubic phases with several non-aqueous solvents or water.

  6. Alkyl group substitution by oxime-bound palladium(II) (the Shaw reaction): Alkly group selectivity and deuterium isotope effects

    SciTech Connect (OSTI)

    Wells, A.P.; Kitching, W.

    1992-08-01

    This report provides information regarding the selectivity of alkyl groups and the nature of the transition state for C-H palladation by oxime-bound palladium(II) (the Shaw reaction). The kinetic deuterium isotope effects are also presented. 21 refs.

  7. Vapor pressures of 1,3-dialkylimidazolium bis(trifluoromethylsulfonyl)imide ionic liquids with long alkyl chains

    SciTech Connect (OSTI)

    Rocha, Marisa A. A. E-mail: marisa.alexandra.rocha@gmail.com; Coutinho, João A. P.; Santos, Luís M. N. B. F. E-mail: marisa.alexandra.rocha@gmail.com

    2014-10-07

    This work presents the vapor pressure at several temperatures for the 1,3-dialkylimidazolium bis(trifluoromethylsulfonyl)imide series, [C{sub N/2}C{sub N/2}im][NTf{sub 2}] (N = 14, 16, 18, and 20), measured by a Knudsen effusion method combined with a quartz crystal microbalance. The thermodynamic properties of vaporization of the ionic liquids under study are analysed together with the results obtained previously for the shorter alkyl chain length [C{sub N/2}C{sub N/2}im][NTf{sub 2}] (N = 2, 4, 6, 8, 10, and 12), in order to evaluate the effect of the alkyl side chains of the cation and to get additional insights concerning the nanostructuration of ionic liquids. The symmetry effect is explored, based on the comparison with the asymmetric imidazolium based ionic liquids, [C{sub N-1}C{sub 1}im][NTf{sub 2}]. A trend shift on the thermodynamic properties of vaporization along the alkyl side chains of the extended symmetric ionic liquids, around [C{sub 6}C{sub 6}im][NTf{sub 2}], was detected. An intensification of the odd-even effect was observed starting from [C{sub 6}C{sub 6}im][NTf{sub 2}], with higher enthalpies and entropies of vaporization for the odd numbered ionic liquids, [C{sub 7}C{sub 7}im][NTf{sub 2}] and [C{sub 9}C{sub 9}im][NTf{sub 2}]. Similar, but less pronounced, odd-even effect was found for the symmetric ionic liquids with lower alkyl side chains length, [C{sub N/2}C{sub N/2}im][NTf{sub 2}] (with N = 4, 6, 8, 10, and 12). This effect is related with the predominant orientation of the terminal methyl group of the alkyl chain to the imidazolium ring and their influence in the cation-anion interaction. The same Critical Alkyl length at the hexyl, (C{sub 6}C{sub 1}and C{sub 6}C{sub 6}) was found for both asymmetric and symmetric series indicating that the nanostructuration of the ionic liquids is related with alkyl chain length.

  8. Raman Scattering Sensor for Control of the Acid Alkylation Process in Gasoline Production

    SciTech Connect (OSTI)

    Uibel, Rory, H.; Smith, Lee M.; Benner, Robert, E.

    2006-04-19

    Gasoline refineries utilize a process called acid alkylation to increase the octane rating of blended gasoline, and this is the single most expensive process in the refinery. For process efficiency and safety reasons, the sulfuric acid can only be used while it is in the concentration range of 98 to 86 %. The conventional technique to monitor the acid concentration is time consuming and is typically conducted only a few times per day. This results in running higher acid concentrations than they would like to ensure that the process proceeds uninterrupted. Maintaining an excessively high acid concentration costs the refineries millions of dollars each year. Using SBIR funding, Process Instruments Inc. has developed an inline sensor for real time monitoring of acid concentrations in gasoline refinery alkylation units. Real time data was then collected over time from the instrument and its responses were matched up with the laboratory analysis. A model was then developed to correlate the laboratory acid values to the Raman signal that is transmitted back to the instrument from the process stream. The instrument was then used to demonstrate that it could create real-time predictions of the acid concentrations. The results from this test showed that the instrument could accurately predict the acid concentrations to within ~0.15% acid strength, and this level of prediction proved to be similar or better then the laboratory analysis. By utilizing a sensor for process monitoring the most economic acid concentrations can be maintained. A single smaller refinery (50,000 barrels/day) estimates that they should save over $120,000/year, with larger refineries saving considerably more.

  9. Production of alcohol from apple pomace

    SciTech Connect (OSTI)

    Hang, Y.D.; Lee, C.Y.; Woodams, E.E.; Cooley, H.J.

    1981-12-01

    Production of ethyl alcohol from apple pomace with a Montrachet strain of Saccharomyces cerevisiae is described. More than 43 grams of the ethyl alcohol could be produced per kg of apple pomace fermented at 30 degrees Celcius in 24 hours. The fermentation efficiency of this process was approximately 89%. (Refs. 9).

  10. Dosimetric measurements of an n-butyl cyanoacrylate embolization material for arteriovenous malformations

    SciTech Connect (OSTI)

    Labby, Zacariah E.; Chaudhary, Neeraj; Gemmete, Joseph J.; Pandey, Aditya S.; Roberts, Donald A.

    2015-04-15

    Purpose: The therapeutic regimen for cranial arteriovenous malformations often involves both stereotactic radiosurgery and endovascular embolization. Embolization agents may contain tantalum or other contrast agents to assist the neurointerventionalists, leading to concerns regarding the dosimetric effects of these agents. This study investigated dosimetric properties of n-butyl cyanoacrylate (n-BCA) plus lipiodol with and without tantalum powder. Methods: The embolization agents were provided cured from the manufacturer with and without added tantalum. Attenuation measurements were made for the samples and compared to the attenuation of a solid water substitute using a 6 MV photon beam. Effective linear attenuation coefficients (ELAC) were derived from attenuation measurements made using a portal imager and derived sample thickness maps projected in an identical geometry. Probable dosimetric errors for calculations in which the embolized regions are overridden with the properties of water were calculated using the ELAC values. Interface effects were investigated using a parallel plate ion chamber placed at set distances below fixed samples. Finally, Hounsfield units (HU) were measured using a stereotactic radiosurgery CT protocol, and more appropriate HU values were derived from the ELAC results and the CT scanners HU calibration curve. Results: The ELAC was 0.0516 0.0063 cm{sup ?1} and 0.0580 0.0091 cm{sup ?1} for n-BCA without and with tantalum, respectively, compared to 0.0487 0.0009 cm{sup ?1} for the water substitute. Dose calculations with the embolized region set to be water equivalent in the treatment planning system would result in errors of ?0.29% and ?0.93% per cm thickness of n-BCA without and with tantalum, respectively. Interface effects compared to water were small in magnitude and limited in distance for both embolization materials. CT values at 120 kVp were 2082 and 2358 HU for n-BCA without and with tantalum, respectively; dosimetrically appropriate HU values were estimated to be 79 and 199 HU, respectively. Conclusions: The dosimetric properties of the embolization agents are very close to those of water for a 6 MV beam. Therefore, treating the entire intracranial space as uniform in composition will result in less than 1% dosimetric error for n-BCA emboli smaller than 3.4 cm without added tantalum and n-BCA emboli smaller than 1.1 cm with added tantalum. Furthermore, when effective embolization can be achieved by the neurointerventionalist using n-BCA without tantalum, the dosimetric impact of overriding material properties will be lessened. However, due to the high attenuation of embolization agents with and without added tantalum for diagnostic energies, artifacts may occur that necessitate additional imaging to accurately identify the spatial extent of the region to be treated.

  11. Process for the synthesis of unsaturated alcohols

    DOE Patents [OSTI]

    Maughon, Bob R.; Burdett, Kenneth A.; Lysenko, Zenon

    2007-02-13

    A process of preparing an unsaturated alcohol (olefin alcohol), such as, a homo-allylic mono-alcohol or homo-allylic polyol, involving protecting a hydroxy-substituted unsaturated fatty acid or fatty acid ester, such as methyl ricinoleate, derived from a seed oil, to form a hydroxy-protected unsaturated fatty acid or fatty acid ester; homo-metathesizing or cross-metathesizing the hydroxy-protected unsaturated fatty acid or fatty acid ester to produce a product mixture containing a hydroxy-protected unsaturated metathesis product; and deprotecting the hydroxy-protected unsaturated metathesis product under conditions sufficient to prepare the unsaturated alcohol. Preferably, methyl ricinoleate is converted by cross-metathesis or homo-metathesis into the homo-allylic mono-alcohol 1-decene-4-ol or the homo-allylic polyol 9-octadecene-7,12-diol, respectively.

  12. HD Applications of Significantly Downsized SI Engines Using Alcohol...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Applications of Significantly Downsized SI Engines Using Alcohol DI for Knock Avoidance HD Applications of Significantly Downsized SI Engines Using Alcohol DI for Knock Avoidance ...

  13. Design Case Summary: Production of Mixed Alcohols from Municipal...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Design Case Summary: Production of Mixed Alcohols from Municipal Solid Waste via Gasification Design Case Summary: Production of Mixed Alcohols from Municipal Solid Waste via ...

  14. Thermochemical Ethanol via Indirect Gasification and Mixed Alcohol...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Thermochemical Ethanol via Indirect Gasification and Mixed Alcohol Synthesis of Lignocellulosic Biomass Thermochemical Ethanol via Indirect Gasification and Mixed Alcohol Synthesis ...

  15. Jilin Fuel Alcohol Company Ltd | Open Energy Information

    Open Energy Info (EERE)

    Alcohol Company Ltd Jump to: navigation, search Name: Jilin Fuel Alcohol Company Ltd Place: Jilin, Jilin Province, China Zip: 132011 Product: One of the four Chinese government...

  16. Effect of alcohols on aqueous lysozyme-lysozyme interactions...

    Office of Scientific and Technical Information (OSTI)

    Effect of alcohols on aqueous lysozyme-lysozyme interactions from static light-scattering measurements Citation Details In-Document Search Title: Effect of alcohols on aqueous...

  17. Transition metal ion-assisted photochemical generation of alkyl halides and hydrocarbons from carboxylic acids

    SciTech Connect (OSTI)

    Carraher, Jack; Pestovsky, Oleg; Bakac, Andreja

    2012-03-14

    Near-UV photolysis of aqueous solutions of propionic acid and aqueous Fe3+ in the absence of oxygen generates a mixture of hydrocarbons (ethane, ethylene and butane), carbon dioxide, and Fe2+. The reaction becomes mildly catalytic (about five turnovers) in the presence of oxygen which converts a portion of alkyl radicals to oxidizing intermediates that reoxidize Fe2+. The photochemistry in the presence of halide ions (X? = Cl?, Br?) generates ethyl halides via halogen atom abstraction from FeXn3?n by ethyl radicals. Near-quantitative yields of C2H5X are obtained at ?0.05 M X?. Competition experiments with Co(NH3)5Br2+ provided kinetic data for the reaction of ethyl radicals with FeCl2+ (k = (4.0 0.5) 106 M?1 s?1) and with FeBr2+ (k = (3.0 0.5) 107 M?1 s?1). Photochemical decarboxylation of propionic acid in the presence of Cu2+ generates ethylene and Cu+. Longer-chain acids also yield alpha olefins as exclusive products. These reactions become catalytic under constant purge with oxygen which plays a dual role. It reoxidizes Cu+ to Cu2+, and removes gaseous olefins to prevent accumulation of Cu+(olefin) complexes and depletion of Cu2+. The results underscore the profound effect that the choice of metal ions, the medium, and reaction conditions exert on the photochemistry of carboxylic acids.

  18. Preparation and use of tetra-alkyl cobalt dicarbollide for extraction of cesium and strontium into hydrocarbon solvents

    DOE Patents [OSTI]

    Miller, R.L.; Pinkerton, A.B.; Abney, K.D.; Kinkead, S.A.

    1997-02-11

    Preparation and use of tetra-C-alkyl cobalt dicarbollide for extraction of cesium and strontium into hydrocarbon solvents. Tetra-C-alkyl derivatives of cobalt dicarbollide, Co(C{sub 2}R{sub 2}B{sub 9}H{sub 9}){sub 2}{sup {minus}}(CoB{sub 2}R{sub 4}{sup {minus}}; R=CH{sub 3} and C{sub 6}H{sub 13}) are demonstrated to be significant cesium and strontium extractants from acidic and alkaline solutions into non-toxic organic solvent systems. Extractions using mesitylene and diethylbenzene are compared to those with nitrobenzene as the organic phase. CoB{sub 2}-hexyl{sub 4}{sup {minus}} in diethylbenzene shows improved selectivity (10{sup 4}) for Cs over Na in acidic solution. In dilute alkaline solution, CoB{sub 2}-hexyl{sub 4}{sup {minus}} extracts Cs less efficiently, but more effectively removes Sr from higher base concentrations. A general synthesis of tetra-C-alkyl cobalt dicarbollides is described. 6 figs.

  19. Preparation and use of tetra-alkyl cobalt dicarbollide for extraction of cesium and strontium into hydrocarbon solvents

    DOE Patents [OSTI]

    Miller, Rebecca L. (Los Alamos, NM); Pinkerton, Anthony B. (Santa Fe, NM); Abney, Kent D. (Los Alamos, NM); Kinkead, Scott A. (Los Alamos, NM)

    1997-01-01

    Preparation and use of tetra-C-alkyl cobalt dicarbollide for extraction of cesium and strontium into hydrocarbon solvents. Tetra-C-alkyl derivatives of cobalt dicarbollide, Co(C.sub.2 R.sub.2 B.sub.9 H.sub.9).sub.2.sup.- (CoB.sub.2 R.sub.4.sup.- ; R=CH.sub.3 and C.sub.6 H.sub.13) are demonstrated to be significant cesium and strontium extractants from acidic and alkaline solutions into non-toxic organic solvent systems. Extractions using mesitylene and diethylbenzene are compared to those with nitrobenzene as the organic phase. CoB.sub.2 -hexyl.sub.4.sup.- in diethylbenzene shows improved selectivity (10.sup.4) for Cs over Na in acidic solution. In dilute alkaline solution, CoB.sub.2 -hexyl.sub.4.sup.- extracts Cs less efficiently, but more effectively removes Sr from higher base concentrations. A general synthesis of tetra-C-alkyl cobalt dicarbollides is described.

  20. Alcohol injection cuts diesel consumption on turbocharged tractors

    SciTech Connect (OSTI)

    Edson, D.V.

    1980-07-21

    M and W Gear Co. of Gibson City, IL, are marketing a new alcohol- injection system that permits turbocharged diesel engines to burn alcohol and claims to cut diesel consumption by 30% and more. The alcohol fuel, a blend of alcohol and water, does not meet the diesel fuel until the alcohol has been atomized and sprayed through the intake manifold into the cylinders. It permits farmers to use home- still-produced ethanol without the added expense of refining to anhydrous composition.

  1. Third international symposium on alcohol fuels technology

    SciTech Connect (OSTI)

    1980-04-01

    At the opening of the Symposium, Dr. Sharrah, Senior Vice President of Continental Oil Company, addressed the attendees, and his remarks are included in this volume. The Symposium was concluded by workshops which addressed specific topics. The topical titles are as follows: alcohol uses; production; environment and safety; and socio-economic. The workshops reflected a growing confidence among the attendees that the alcohols from coal, remote natural gas and biomass do offer alternatives to petroleum fuels. Further, they may, in the long run, prove to be equal or superior to the petroleum fuels when the aspects of performance, environment, health and safety are combined with the renewable aspect of the biomass derived alcohols. Although considerable activity in the production and use of alcohols is now appearing in many parts of the world, the absence of strong, broad scale assessment and support for these fuels by the United States Federal Government was a noted point of concern by the attendees. The environmental consequence of using alcohols continues to be more benign in general than the petroleum based fuels. The exception is the family of aldehydes. Although the aldehydes are easily suppressed by catalysts, it is important to understand their production in the combustion process. Progress is being made in this regard. Of course, the goal is to burn the alcohols so cleanly that catalytic equipment can be eliminated. Separate abstracts are prepared for the Energy Data Base for individual presentations.

  2. Terrestrial fate of coal-liquid constituents: behavior of alkyl anilines in soil

    SciTech Connect (OSTI)

    Felice, L.J.; Zachara, J.M.; Rogers, J.E.

    1982-07-01

    The low molecular weight aromatic amines (anilines) are important water soluble constituents of coal liquids. The impact of anilines released to the terrestrial environment will largely depend on their mobility and persistence. Studies were conducted to investigate those processes governing the mobility and persistence of the alkylanilines, namely, soil sorption and chemical/microbial degradation. Soil sorption measurements were conducted on aniline and several methyl substituted anilines on A and B horizons of a soil profile collected from Davies County, Kentucky. The magnitude of sorption was large in all horizons. Sorption in the B horizons was larger than in the A horizon for many of the anilines studied, indicating the importance of both the mineral matrix and organic carbon content of the soil in determining the magnitude of sorption. Results of these measurements indicate that movement of the anilines through the soil would be significantly attenuated by sorption reactions. Aniline sorption measurement in the A horizon after removal of the organic matter and in the B/sub 22/ horizon after removal of amorphous iron oxides and crystalline iron oxides indicate that organic matter largely controls aniline sorption in the A horizon, while crystalline iron oxides and phyllosilicates are important in the B horizons. The effects of pH on aniline sorption was also examined and shown to have significant effects on the magnitude of sorption in both A and B horizons. Soil degradation studies using /sup 14/C-3-methylaniline as a model for alkyl aniline degradation show that 3-methylaniline is readily metabolized by soil microorganisms during the 32-day period examined.

  3. Hydrogen bond dynamics in bulk alcohols

    SciTech Connect (OSTI)

    Shinokita, Keisuke; Cunha, Ana V.; Jansen, Thomas L. C.; Pshenichnikov, Maxim S.

    2015-06-07

    Hydrogen-bonded liquids play a significant role in numerous chemical and biological phenomena. In the past decade, impressive developments in multidimensional vibrational spectroscopy and combined molecular dynamicsquantum mechanical simulation have established many intriguing features of hydrogen bond dynamics in one of the fundamental solvents in nature, water. The next class of a hydrogen-bonded liquidalcoholshas attracted much less attention. This is surprising given such important differences between water and alcohols as the imbalance between the number of hydrogen bonds, each molecule can accept (two) and donate (one) and the very presence of the hydrophobic group in alcohols. Here, we use polarization-resolved pump-probe and 2D infrared spectroscopy supported by extensive theoretical modeling to investigate hydrogen bond dynamics in methanol, ethanol, and isopropanol employing the OH stretching mode as a reporter. The sub-ps dynamics in alcohols are similar to those in water as they are determined by similar librational and hydrogen-bond stretch motions. However, lower density of hydrogen bond acceptors and donors in alcohols leads to the appearance of slow diffusion-controlled hydrogen bond exchange dynamics, which are essentially absent in water. We anticipate that the findings herein would have a potential impact on fundamental chemistry and biology as many processes in nature involve the interplay of hydrophobic and hydrophilic groups.

  4. Computational Study of Molecular Structure and Self-Association of Tri-n-butyl Phosphates in n-Dodecane

    SciTech Connect (OSTI)

    Vo, Quynh N.; Hawkins, Cory; Dang, Liem X.; Nilsson, Mikael; Nguyen, Hung D.

    2015-01-29

    Tri-n-butyl phosphate is an important extractant used in solvent extraction process for the recovery of uranium and plutonium from spent nuclear fuel. To understand the fundamental molecular level behavior of extracting agents in solution, an atomistic parameterization study was carried out using the AMBER force field to model TBP molecule and n-dodecane molecule, a commonly used organic solvent, for molecular dynamics simulations. For validation of the optimized force field, various thermophysical properties of pure TBP and pure n-dodecane in the bulk liquid phase such as mass density, dipole moment, self-diffusion coefficient and heat of vaporization were calculated and compared favorably with experimental values. The molecular structure of TBPs in n-dodecane at various TBP concentrations was examined based on radial distribution functions and 2D potential mean force, which was used as criteria for identifying TBP aggregates. The dimerization constant of TBP in n-dodecane was also obtained and matches the experimental value. The U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences funded the work performed by LXD.

  5. Molecular Dynamics Simulations of Tri-n-butyl-phosphate/n-Dodecane Mixture: Thermophysical Properties and Molecular Structure

    SciTech Connect (OSTI)

    de Almeida, Valmor F; Cui, Shengting; Khomami, Bamin

    2014-01-01

    Molecular dynamics simulations of tri-n-butyl-phosphate (TBP)/n-dodecane mixture in the liquid phase have been carried out using two recently developed TBP force field models (J. Phys. Chem. B 2012, 116, 305) in combination with the all-atom optimized potentials for liquid simulations (OPLS-AA) force field model for n-dodecane. Specifically, the electric dipole moment of TBP, mass density of the mixture, and the excess volume of mixing were computed with TBP mole fraction ranging from 0 to 1. It is found that the aforementioned force field models accurately predict the mass density of the mixture in the entire mole fraction range. Commensurate with experimental measurements, the electric dipole moment of the TBP was found to slightly increase with the mole fraction of TBP in the mixture. Also, in accord with experimental data, the excess volume of mixing is positive in the entire mole fraction range, peaking at TBP mole fraction range 0.3 0.5. Finally, a close examination of the spatial pair correlation functions between TBP molecules, and between TBP and n-dodecane molecules, revealed formation of TBP dimers through self-association at close distance, a phenomenon with ample experimental evidence.

  6. Alcohol Fuels Program technical review, Spring 1984

    SciTech Connect (OSTI)

    Not Available

    1984-10-01

    The alcohol fuels program consists of in-house and subcontracted research for the conversion of lignocellulosic biomass into fuel alcohols via thermoconversion and bioconversion technologies. In the thermoconversion area, the SERI gasifier has been operated on a one-ton per day scale and produces a clean, medium-Btu gas that can be used to manufacture methanol with a relatively small gas-water shift reaction requirement. Recent research has produced catalysts that make methanol and a mixture of higher alcohols from the biomass-derived synthetic gas. Three hydrolysis processes have emerged as candidates for more focused research. They are: a high-temperature, dilute-acid, plug-flow approach based on the Dartmouth reactor; steam explosion pretreatment followed by hydrolysis using the RUT-C30 fungal organism; and direct microbial conversion of the cellulose to ethanol using bacteria in a single or mixed culture. Modeling studies, including parametric and sensitivity analyses, have recently been completed. The results of these studies will lead to a better definition of the present state-of-the-art for these processes and provide a framework for establishing the research and process engineering issues that still need resolution. In addition to these modeling studies, economic feasibility studies are being carried out by commercial engineering firms. Their results will supplement and add commercial validity to the program results. The feasibility contractors will provide input at two levels: Technical and economic assessment of the current state-of-the-art in alcohol production from lignocellulosic biomass via thermoconversion to produce methanol and higher alcohol mixtures and bioconversion to produce ethanol; and identification of research areas having the potential to significantly reduce the cost of production of alcohols.

  7. Improved fermentative alcohol production. [Patent application

    DOE Patents [OSTI]

    Wilke, C.R.; Maiorella, B.L.; Blanch, H.W.; Cysewski, G.R.

    1980-11-26

    An improved fermentation process is described for producing alcohol which includes the combination of vacuum fermentation and vacuum distillation. Preferably, the vacuum distillation is carried out in two phases, one a fermentor proper operated at atmospheric pressure and a flash phase operated at reduced pressure with recycle of fermentation brew having a reduced alcohol content to the fermentor, using vapor recompression heating of the flash-pot recycle stream to heat the flash-pot or the distillation step, and using water load balancing (i.e., the molar ratio of water in the fermentor feed is the same as the molar ratio of water in the distillation overhead).

  8. Electrochemical method for producing a biodiesel mixture comprising fatty acid alkyl esters and glycerol

    DOE Patents [OSTI]

    Lin, YuPo J; St. Martin, Edward J

    2013-08-13

    The present invention relates to an integrated method and system for the simultaneous production of biodiesel from free fatty acids (via esterification) and from triglycerides (via transesterification) within the same reaction chamber. More specifically, one preferred embodiment of the invention relates to a method and system for the production of biodiesel using an electrodeionization stack, wherein an ion exchange resin matrix acts as a heterogeneous catalyst for simultaneous esterification and transesterification reactions between a feedstock and a lower alcohol to produce biodiesel, wherein the feedstock contains significant levels of free fatty acid. In addition, because of the use of a heterogeneous catalyst, the glycerol and biodiesel have much lower salt concentrations than raw biodiesel produced by conventional transesterification processes. The present invention makes it much easier to purify glycerol and biodiesel.

  9. Alcohols as hydrogen-donor solvents for treatment of coal

    DOE Patents [OSTI]

    Ross, David S. (Palo Alto, CA); Blessing, James E. (Menlo Park, CA)

    1981-01-01

    A method for the hydroconversion of coal by solvent treatment at elevated temperatures and pressure wherein an alcohol having an .alpha.-hydrogen atom, particularly a secondary alcohol such as isopropanol, is utilized as a hydrogen donor solvent. In a particular embodiment, a base capable of providing a catalytically effective amount of the corresponding alcoholate anion under the solvent treatment conditions is added to catalyze the alcohol-coal reaction.

  10. Microbes Produce High Yields of Fatty Alcohols From Glucose - Energy

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

    Innovation Portal Microbes Produce High Yields of Fatty Alcohols From Glucose Great Lakes Bioenergy Research Center Contact GLBRC About This Technology Technology Marketing Summary Fatty alcohols are used in detergents, emulsifiers, lubricants and personal care items. More than 1.3 million tons of fatty alcohols are used worldwide each year, representing a $3 billion market. Currently, fatty alcohols are produced either through the processing of natural fats and oils or from petrochemicals.

  11. Alcohol synthesis from CO or CO.sub.2

    DOE Patents [OSTI]

    Hu, Jianli [Kennewick, WA; Dagle, Robert A [Richland, WA; Holladay, Jamelyn D [Kennewick, WA; Cao, Chunshe [Houston, TX; Wang, Yong [Richland, WA; White, James F [Richland, WA; Elliott, Douglas C [Richland, WA; Stevens, Don J [Richland, WA

    2010-12-28

    Methods for producing alcohols from CO or CO.sub.2 and H.sub.2 utilizing a palladium-zinc on alumina catalyst are described. Methods of synthesizing alcohols over various catalysts in microchannels are also described. Ethanol, higher alcohols, and other C.sub.2+ oxygenates can produced utilizing Rh--Mn or a Fisher-Tropsch catalyst.

  12. Communication: Spectroscopic characterization of an alkyl substituted Criegee intermediate syn-CH{sub 3}CHOO through pure rotational transitions

    SciTech Connect (OSTI)

    Nakajima, Masakazu; Endo, Yasuki

    2014-01-07

    An alkyl-substituted Criegee intermediate syn-CH{sub 3}CHOO was detected in the gas phase through Fourier-transform microwave spectroscopy. Observed pure rotational transitions show a small splitting corresponding to the A/E components due to the threefold methyl internal rotation. The rotational constants and the barrier height of the hindered methyl rotation were determined to be A = 17?586.5295(15) MHz, B = 7133.4799(41) MHz, C = 5229.1704(40) MHz, and V{sub 3} = 837.1(17)cm{sup ?1}. High-level ab initio calculations which reproduce the experimentally determined values well indicate that the in-plane CH bond in the methyl moiety is trans to the CO bond, and other two protons are directed to the terminal oxygen atom for the most stable structure of syn-CH{sub 3}CHOO. The torsional barrier of the methyl top is fairly large in syn-CH{sub 3}CHOO, implying a significant interaction between the terminal oxygen and the protons of the methyl moiety, which may be responsible for the high production yields of the OH radical from energized alkyl-substituted Criegee intermediates.

  13. UV-visible spectroscopy of macrocyclic alkyl, nitrosyl and halide complexes of cobalt and rhodium. Experiment and calculation

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

    Hull, Emily A.; West, Aaron C.; Pestovsky, Oleg; Kristian, Kathleen E.; Ellern, Arkady; Dunne, James F.; Carraher, Jack M.; Bakac, Andreja; Windus, Theresa L.

    2015-01-22

    In this paper, transition metal complexes (NH3)5CoX2+ (X = CH3, Cl) and L(H2O)MX2+, where M = Rh or Co, X = CH3, NO, or Cl, and L is a macrocyclic N4 ligand are examined by both experiment and computation to better understand their electronic spectra and associated photochemistry. Specifically, irradiation into weak visible bands of nitrosyl and alkyl complexes (NH3)5CoCH32+ and L(H2O)MIIIX2+ (X = CH3 or NO) leads to photohomolysis that generates the divalent metal complex and ˙CH3 or ˙NO, respectively. On the other hand, when X = halide or NO2, visible light photolysis leads to dissociation of X– and/ormore » cis/trans isomerization. Computations show that visible bands for alkyl and nitrosyl complexes involve transitions from M–X bonding orbitals and/or metal d orbitals to M–X antibonding orbitals. In contrast, complexes with X = Cl or NO2 exhibit only d–d bands in the visible, so that homolytic cleavage of the M–X bond requires UV photolysis. UV-Vis spectra are not significantly dependent on the structure of the equatorial ligands, as shown by similar spectral features for (NH3)5CoCH32+ and L1(H2O)CoCH32+.« less

  14. Process for producing high purity isoolefins and dimers thereof by dissociation of ethers

    DOE Patents [OSTI]

    Smith, L.A. Jr.; Jones, E.M. Jr.; Hearn, D.

    1984-05-08

    Alkyl tertiary butyl ether or alkyl tertiary amyl ether is dissociated by vapor phase contact with a cation acidic exchange resin at temperatures in the range of 150 to 250 F at LHSV of 0.1 to 20 to produce a stream consisting of unreacted ether, isobutene or isoamylene and an alcohol corresponding to the alkyl radical. After the alcohol is removed, the ether/isoolefin stream may be fractionated to obtain a high purity isoolefin (99+%) or the ether/isoolefin stream can be contacted in liquid phase with a cation acidic exchange resin to selectively dimerize the isoolefin in a highly exothermic reaction, followed by fractionation of the dimerization product to produce high purity diisoolefin (97+%). In the case where the alkyl is C[sub 3] to C[sub 6] and the corresponding alcohol is produced on dissociation of the ether, combined dissociation-distillation may be carried out such that isoolefin is the overhead product and alcohol the bottom. 2 figs.

  15. Process for producing high purity isoolefins and dimers thereof by dissociation of ethers

    DOE Patents [OSTI]

    Smith, Jr., Lawrence A. (Bellaire, TX); Jones, Jr., Edward M. (Friendswood, TX); Hearn, Dennis (Houston, TX)

    1984-01-01

    Alkyl tertiary butyl ether or alkyl tertiary amyl ether is dissociated by vapor phase contact with a cation acidic exchange resin at temperatures in the range of 150.degree. to 250.degree. F. at LHSV of 0.1 to 20 to produce a stream consisting of unreacted ether, isobutene or isoamylene and an alcohol corresponding to the alkyl radical. After the alcohol is removed, the ether/isoolefin stream may be fractionated to obtain a high purity isoolefin (99+%) or the ether/isoolefin stream can be contacted in liquid phase with a cation acidic exchange resin to selectively dimerize the isoolefin in a highly exothermic reaction, followed by fractionation of the dimerization product to produce high purity diisoolefin (97+%). In the case where the alkyl is C.sub.3 to C.sub.6 and the corresponding alcohol is produced on dissociation of the ether, combined dissociation-distillation may be carried out such that isoolefin is the overhead product and alcohol the bottom.

  16. Limonene and tetrahydrofurfuryl alcohol cleaning agent

    DOE Patents [OSTI]

    Bohnert, G.W.; Carter, R.D.; Hand, T.E.; Powers, M.T.

    1997-10-21

    The present invention is a tetrahydrofurfuryl alcohol and limonene cleaning agent and method for formulating and/or using the cleaning agent. This cleaning agent effectively removes both polar and nonpolar contaminants from various electrical and mechanical parts and is readily used without surfactants, thereby reducing the need for additional cleaning operations. The cleaning agent is warm water rinsable without the use of surfactants. The cleaning agent can be azeotropic, enhancing ease of use in cleaning operations and ease of recycling.

  17. Limonene and tetrahydrofurfurly alcohol cleaning agent

    DOE Patents [OSTI]

    Bohnert, George W. (Harrisonville, MO); Carter, Richard D. (Lee's Summit, MO); Hand, Thomas E. (Lee's Summit, MO); Powers, Michael T. (Santa Rosa, CA)

    1997-10-21

    The present invention is a tetrahydrofurfuryl alcohol and limonene cleaning agent and method for formulating and/or using the cleaning agent. This cleaning agent effectively removes both polar and nonpolar contaminants from various electrical and mechanical parts and is readily used without surfactants, thereby reducing the need for additional cleaning operations. The cleaning agent is warm water rinsable without the use of surfactants. The cleaning agent can be azeotropic, enhancing ease of use in cleaning operations and ease of recycling.

  18. Limonene and tetrahydrofurfuryl alcohol cleaning agent

    DOE Patents [OSTI]

    Bohnert, George W. (Harrisonville, MO); Carter, Richard D. (Lee's Summit, MO); Hand, Thomas E. (Lee's Summit, MO); Powers, Michael T. (Santa Rosa, CA)

    1996-05-07

    The present invention is a tetrahydrofurfuryl alcohol and limonene or terpineol cleaning agent and method for formulating and/or using the cleaning agent. This cleaning agent effectively removes both polar and nonpolar contaminants from various electrical and mechanical parts and is readily used without surfactants, thereby reducing the need for additional cleaning operations. The cleaning agent is warm water rinsable without the use of surfactants. The cleaning agent can be azeotropic, enhancing ease of use in cleaning operations and ease of recycling.

  19. A model system for QTL analysis: Effects of alcohol dehydrogenase genotype on alcohol pharmacokinetics

    SciTech Connect (OSTI)

    Martin, N.G.; Nightingale, B.; Whitfield, J.B.

    1994-09-01

    There is much interest in the detection of quantitative trait loci (QTL) - major genes which affect quantitative phenotypes. The relationship of polymorphism at known alcohol metabolizing enzyme loci to alcohol pharmacokinetics is a good model system. The three class I alcohol dehydrogenase genes are clustered on chromosome 4 and protein electrophoresis has revealed polymorphisms at the ADH2 and ADH3 loci. While different activities of the isozymes have been demonstrated in vitro, little work has been done in trying to relate ADH polymorphism to variation in ethanol metabolism in vivo. We previously measured ethanol metabolism and psychomotor reactivity in 206 twin pairs and demonstrated that most of the repeatable variation was genetic. We have now recontacted the twins to obtain DNA samples and used PCR with allele specific primers to type the ADH2 and ADH3 polymorphisms in 337 individual twins. FISHER has been used to estimate fixed effects of typed polymorphisms simultaneously with remaining linked and unlinked genetic variance. The ADH2*1-2 genotypes metabolize ethanol faster and attain a lower peak blood alcohol concentration than the more common ADH2*1-1 genotypes, although less than 3% of the variance is accounted for. There is no effect of ADH3 genotype. However, sib-pair linkage analysis suggests that there is a linked polymorphism which has a much greater effect on alcohol metabolism that those typed here.

  20. Catalyst Activity Comparison of Alcohols over Zeolites

    SciTech Connect (OSTI)

    Ramasamy, Karthikeyan K.; Wang, Yong

    2013-01-01

    Alcohol transformation to transportation fuel range hydrocarbon on HZSM-5 (SiO2 / Al2O3 = 30) catalyst was studied at 360oC and 300psig. Product distributions and catalyst life were compared using methanol, ethanol, 1-propanol or 1-butanol as a feed. The catalyst life for 1-propanol and 1-butanol was more than double compared to that for methanol and ethanol. For all the alcohols studied, the product distributions (classified to paraffin, olefin, napthene, aromatic and naphthalene compounds) varied with time on stream (TOS). At 24 hours TOS, liquid product from 1-propanol and 1-butanol transformation primarily contains higher olefin compounds. The alcohol transformation process to higher hydrocarbon involves a complex set of reaction pathways such as dehydration, oligomerization, dehydrocyclization, and hydrogenation. Compared to ethylene generated from methanol and ethanol, oligomerization of propylene and butylene has a lower activation energy and can readily take place on weaker acidic sites. On the other hand, dehydrocyclization of propylene and butylene to form the cyclic compounds requires the sits with stronger acid strength. Combination of the above mentioned reasons are the primary reasons for olefin rich product generated in the later stage of the time on stream and for the extended catalyst life time for 1 propanol and 1 butanol compared to methanol and ethanol conversion over HZSM-5.

  1. Manipulation of the HIFVegf pathway rescues methyl tert-butyl ether (MTBE)-induced vascular lesions

    SciTech Connect (OSTI)

    Bonventre, Josephine A.; Kung, Tiffany S.; White, Lori A.; Cooper, Keith R.

    2013-12-15

    Methyl tert-butyl ether (MTBE) has been shown to be specifically anti-angiogenic in piscine and mammalian model systems at concentrations that appear non-toxic in other organ systems. The mechanism by which MTBE targets developing vascular structures is unknown. A global transcriptome analysis of zebrafish embryos developmentally exposed to 0.006255 mM MTBE suggested that hypoxia inducible factor (HIF)-regulated pathways were affected. HIF-driven angiogenesis via vascular endothelial growth factor (vegf) is essential to the developing vasculature of an embryo. Three rescue studies were designed to rescue MTBE-induced vascular lesions: pooled blood in the common cardinal vein (CCV), cranial hemorrhages (CH), and abnormal intersegmental vessels (ISV), and test the hypothesis that MTBE toxicity was HIFVegf dependent. First, zebrafish vegf-a over-expression via plasmid injection, resulted in significantly fewer CH and ISV lesions, 46 and 35% respectively, in embryos exposed to 10 mM MTBE. Then HIF degradation was inhibited in two ways. Chemical rescue by N-oxaloylglycine significantly reduced CCV and CH lesions by 30 and 32% in 10 mM exposed embryos, and ISV lesions were reduced 24% in 5 mM exposed zebrafish. Finally, a morpholino designed to knock-down ubiquitin associated von HippelLindau protein, significantly reduced CCV lesions by 35% in 10 mM exposed embryos. In addition, expression of some angiogenesis related genes altered by MTBE exposure were rescued. These studies demonstrated that MTBE vascular toxicity is mediated by a down regulation of HIFVegf driven angiogenesis. The selective toxicity of MTBE toward developing vasculature makes it a potentially useful chemical in the designing of new drugs or in elucidating roles for specific angiogenic proteins in future studies of vascular development. - Highlights: Global gene expression of MTBE exposed zebrafish suggested altered HIF1 signaling. Over expression of zebrafish vegf-a rescues MTBE-induced vascular lesions. Inhibiting PHD or knocking down VHL rescues MTBE-induced vascular lesions. HIF1-Vegf driven angiogenesis is a target for MTBE vascular toxicity.

  2. Separation and concentration of lower alcohols from dilute aqueous solutions

    DOE Patents [OSTI]

    Moore, Raymond H. (Richland, WA); Eakin, David E. (Kennewick, WA); Baker, Eddie G. (Richland, WA); Hallen, Richard T. (Richland, WA)

    1991-01-01

    A process for producing, from a dilute aqueous solution of a lower (C.sub.1 -C.sub.5) alcohol, a concentrated liquid solution of the alcohol in an aromatic organic solvent is disclosed. Most of the water is removed from the dilute aqueous solution of alcohol by chilling sufficiently to form ice crystals. Simultaneously, the remaining liquid is extracted at substantially the same low temperature with a liquid organic solvent that is substantially immiscible in aqueous liquids and has an affinity for the alcohol at that temperature, causing the alcohol to transfer to the organic phase. After separating the organic liquid from the ice crystals, the organic liquid can be distilled to enrich the concentration of alcohol therein. Ethanol so separated from water and concentrated in an organic solvent such as toluene is useful as an anti-knock additive for gasoline.

  3. Autothermal Partial Oxidation of Ethanol and Alcohols - Energy Innovation

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

    Portal Biomass and Biofuels Biomass and Biofuels Find More Like This Return to Search Autothermal Partial Oxidation of Ethanol and Alcohols Syngas from Autothermal Reforming of Ethanol DOE Grant Recipients University of Minnesota Contact University of Minnesota About This Technology Technology Marketing Summary Autothermal Reforming of Ethanol and Alcohols into Syngas Ethanol and alcohols can be converted into syngas using a robust autothermal reforming process. Syngas is a mixture of carbon

  4. Heavy Alcohols as a Fuel Blending Agent for Compression Ignition...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    More Documents & Publications HD Applications of Significantly Downsized SI Engines Using Alcohol DI for Knock Avoidance Characterization of Dual-Fuel Reactivity Controlled ...

  5. Renewable Hydrogen Production Using Sugars and Sugar Alcohols...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Hydrogen Production Using Sugars and Sugar Alcohols (Presentation) Presented at the 2007 Bio-Derived Liquids to Hydrogen Distributed Reforming Working Group held November 6, 2007...

  6. Improving Ethanol-Gasoline Blends by Addition of Higher Alcohols

    Broader source: Energy.gov [DOE]

    Mixtures of ethanol, gasoline, and higher alcohols were evaluated to determine if they offer superior performance to ethanol/gasoline blends in meeting the Renewal Fuels Standard II.

  7. Electrocatalyst for alcohol oxidation in fuel cells

    DOE Patents [OSTI]

    Adzic, Radoslav R. (Setauket, NY); Marinkovic, Nebojsa S. (Coram, NY)

    2001-01-01

    Binary and ternary electrocatalysts are provided for oxidizing alcohol in a fuel cell. The binary electrocatalyst includes 1) a substrate selected from the group consisting of NiWO.sub.4 or CoWO.sub.4 or a combination thereof, and 2) Group VIII noble metal catalyst supported on the substrate. The ternary electrocatalyst includes 1) a substrate as described above, and 2) a catalyst comprising Group VIII noble metal, and ruthenium oxide or molybdenum oxide or a combination thereof, said catalyst being supported on said substrate.

  8. Liver proteomics in progressive alcoholic steatosis

    SciTech Connect (OSTI)

    Fernando, Harshica; Wiktorowicz, John E.; Soman, Kizhake V.; Kaphalia, Bhupendra S.; Khan, M. Firoze; Shakeel Ansari, G.A.

    2013-02-01

    Fatty liver is an early stage of alcoholic and nonalcoholic liver disease (ALD and NALD) that progresses to steatohepatitis and other irreversible conditions. In this study, we identified proteins that were differentially expressed in the livers of rats fed 5% ethanol in a LieberDeCarli diet daily for 1 and 3 months by discovery proteomics (two-dimensional gel electrophoresis and mass spectrometry) and non-parametric modeling (Multivariate Adaptive Regression Splines). Hepatic fatty infiltration was significantly higher in ethanol-fed animals as compared to controls, and more pronounced at 3 months of ethanol feeding. Discovery proteomics identified changes in the expression of proteins involved in alcohol, lipid, and amino acid metabolism after ethanol feeding. At 1 and 3 months, 12 and 15 different proteins were differentially expressed. Of the identified proteins, down regulation of alcohol dehydrogenase (? 1.6) at 1 month and up regulation of aldehyde dehydrogenase (2.1) at 3 months could be a protective/adaptive mechanism against ethanol toxicity. In addition, betaine-homocysteine S-methyltransferase 2 a protein responsible for methionine metabolism and previously implicated in fatty liver development was significantly up regulated (1.4) at ethanol-induced fatty liver stage (1 month) while peroxiredoxin-1 was down regulated (? 1.5) at late fatty liver stage (3 months). Nonparametric analysis of the protein spots yielded fewer proteins and narrowed the list of possible markers and identified D-dopachrome tautomerase (? 1.7, at 3 months) as a possible marker for ethanol-induced early steatohepatitis. The observed differential regulation of proteins have potential to serve as biomarker signature for the detection of steatosis and its progression to steatohepatitis once validated in plasma/serum. -- Graphical abstract: The figure shows the Hierarchial cluster analysis of differentially expressed protein spots obtained after ethanol feeding for 1 (13) and 3 (46) months. C and E represent pair-fed control and ethanol-fed rats, respectively. Highlights: ? Proteins related to ethanol-induced steatosis and mild steatohepatitis are identified. ? ADH1C and ALDH2 involved in alcohol metabolism are differentially expressed at 1 and 3 months. ? Discovery proteomics identified a group of proteins to serve as potential biomarkers. ? Using nonparametric analysis DDT is identified as a possible marker for liver damage.

  9. Office of Alcohol Fuels Program plan, FY 1981

    SciTech Connect (OSTI)

    1980-10-01

    The goal of the Office of Alcohol Fuels is to promote the production, distribution, and use of alcohol fuels. The program objectives are defined and the strategy for implementation is described. An organizational model of the operation is included. The roles of the 3 program offices and various field offices are described. (DMC)

  10. STEP 1: TO BE COMPLETED BY ALCOHOL TECHNICIAN

    Energy Savers [EERE]

    7 (07/03) OMB Control No. 1910-5122 U.S. Department of Energy (DOE) Human Reliability Program (HRP) Alcohol Testing Form (Instructions for completing this form are attached.) STEP 1: TO BE COMPLETED BY ALCOHOL TECHNICIAN A. Employee Name __________________________________________________________________ (Print) First M.I. Last B. Employee ID No. __________________________________________________________ C. Employer Name __________________________________________________________

  11. Process for producing fuel grade ethanol by continuous fermentation, solvent extraction and alcohol separation

    DOE Patents [OSTI]

    Tedder, Daniel W. (Marietta, GA)

    1985-05-14

    Alcohol substantially free of water is prepared by continuously fermenting a fermentable biomass feedstock in a fermentation unit, thereby forming an aqueous fermentation liquor containing alcohol and microorganisms. Continuously extracting a portion of alcohol from said fermentation liquor with an organic solvent system containing an extractant for said alcohol, thereby forming an alcohol-organic solvent extract phase and an aqueous raffinate. Said alcohol is separated from said alcohol-organic solvent phase. A raffinate comprising microorganisms and unextracted alcohol is returned to the fermentation unit.

  12. Quantifying the Sigma and Pi interactions between U(V) f orbitals and halide, alkyl, alkoxide, amide and ketimide ligands

    SciTech Connect (OSTI)

    University of California, Berkeley; Lukens, Wayne W.; Edelstein, Norman M.; Magnani, Nicola; Hayton, Trevor W.; Fortier, Skye; Seaman, Lani A.

    2013-06-20

    f Orbital bonding in actinide and lanthanide complexes is critical to their behavior in a variety of areas from separations to magnetic properties. Octahedral f1 hexahalide complexes have been extensively used to study f orbital bonding due to their simple electronic structure and extensive spectroscopic characterization. The recent expansion of this family to include alkyl, alkoxide, amide, and ketimide ligands presents the opportunity to extend this study to a wider variety of ligands. To better understand f orbital bonding in these complexes, the existing molecular orbital (MO) model was refined to include the effect of covalency on spin orbit coupling in addition to its effect on orbital angular momentum (orbital reduction). The new MO model as well as the existing MO model and the crystal field (CF) model were applied to the octahedral f1 complexes to determine the covalency and strengths of the ? and ? bonds formed by the f orbitals. When covalency is significant, MO models more precisely determined the strengths of the bonds derived from the f orbitals; however, when covalency was small, the CF model was better than either MO model. The covalency determined using the new MO model is in better agreement with both experiment and theory than that predicted by the existing MO model. The results emphasize the role played by the orbital energy in determining the strength and covalency of bonds formed by the f orbitals.

  13. Cyclization of N-alkyl azinium cations with bifunctional nucleophiles. 21. Regioisomeric 1,3,4-thiadiazino(5,6-b)quinoxalines

    SciTech Connect (OSTI)

    Baklykov, V.G.; Charushin, V.N.; Chupakhin, O.N.; Drozd, V.N.

    1987-10-01

    Thiobenzyhydrazides undergo cyclization with N-alkyl-quinoxalinium salts to give 5-alkyl-substituted 1,4,4a,5,10,10a-hexahydro-1,3,4-thiadiazino(5,6-b)quinoxalines, which undergo isomerization to 10-alkyl-substituted thiadiazinoquinoxalines when they are heated in ethanol or in the presence of acids. The IR spectra of suspensions of the compounds in mineral oil were recorded with a UR-20 spectrometer. The PMR spectra of solutions in d/sub 6/-DMSO were recorded with Perkin-Elmer R-12B (60 MHz) and Brucker WP-80 (80 MHz) spectrometers with tetramethylsilane (TMS) and hexamethyldisiloxane (HMDS) as the internal standards. The /sup 13/C NMR spectra of solutions in d/sub 6/-DMSO were recorded with Brucker WH-90 (22.62 MHz) and Varian FT-80A (20.13 MHz) spectrometers. The chemical shifts were measured with respect to the signal of the solvent (d/sub 6/-DMSO, 39.6 ppm).

  14. Electro-autotrophic synthesis of higher alcohols

    DOE Patents [OSTI]

    Liao, James C.; Cho, Kwang Myung

    2015-10-06

    The disclosure provides a process that converts CO.sub.2 to higher alcohols (e.g. isobutanol) using electricity as the energy source. This process stores electricity (e.g. from solar energy, nuclear energy, and the like) in liquid fuels that can be used as high octane number gasoline substitutes. Instead of deriving reducing power from photosynthesis, this process derives reducing power from electrically generated mediators, either H.sub.2 or formate. H.sub.2 can be derived from electrolysis of water. Formate can be generated by electrochemical reduction of CO.sub.2. After delivering the reducing power in the cell, formate becomes CO.sub.2 and recycles back. Therefore, the biological CO.sub.2 fixation process can occur in the dark.

  15. Extracting alcohols from aqueous solutions. [USDOE patent application

    DOE Patents [OSTI]

    Compere, A.L.; Googin, J.M.; Griffith, W.L.

    1981-12-02

    The objective is to provide an efficient process for extracting alcohols in aqueous solutions into hydrocarbon fuel mixtures, such as gasoline, diesel fuel and fuel oil. This is done by contacting an aqueous fermentation liquor with a hydrocarbon or hydrocarbon mixture containing carbon compounds having 5-18 carbon atoms, which may include gasoline, diesel fuel or fuel oil. The hydrocarbon-aqueous alcohol solution is then mixed with one or more of a group of polyoxyalkylene polymers to extract the alcohol into the hydrocarbon fuel-polyoxyalkylene polymer mixture.

  16. Method for producing hydrocarbon and alcohol mixtures. [Patent application

    DOE Patents [OSTI]

    Compere, A.L.; Googin, J.M.; Griffith, W.L.

    1980-12-01

    It is an object of this invention to provide an efficient process for extracting alcohols and ketones from an aqueous solution containing the same into hydrocarbon fuel mixtures, such as gasoline, diesel fuel and fuel oil. Another object of the invention is to provide a mixture consisting of hydrocarbon, alcohols or ketones, polyoxyalkylene polymer and water which can be directly added to fuels or further purified. The above stated objects are achieved in accordance with a preferred embodiment of the invention by contacting an aqueous fermentation liquor with a hydrocarbon or hydrocarbon mixture containing carbon compounds having 5 to 18 carbon atoms, which may include gasoline, diesel fuel or fuel oil. The hydrocarbon-aqueous alcohol solution is mixed in the presence or one or more of a group of polyoxyalkylene polymers described in detail hereinafter; the fermentation alcohol being extracted into the hydrocarbon fuel-polyoxyalkylene polymer mixture.

  17. Cold-Start Performance and Emissions Behavior of Alcohol Fuels...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Discusses results of cold- and hot-start transient tests using gasoline and 3 alcohol-gasoline blends (50% and 85% ethanol, and 83% iso-butanol) PDF icon deer11ickes.pdf More ...

  18. 1

    Office of Environmental Management (EM)

    Tetrachloroethylene, Trichloroethylene, Trichloroflouromethane, Acetone, Ethyl ether, Methanol, Methyl isobutyl ketone, n-Butyl alcohol, Xylene, Cresols, Cresylic acid,...

  19. 1

    Office of Environmental Management (EM)

    Tetrachloroethylene; Trichloroethylene; Trichloroflouromethane; Acetone; Ethyl ether; Methanol; Methyl isobutyl ketone; n-Butyl alcohol; Xylene; Cresols; Cresylic acid;...

  20. 1

    Office of Environmental Management (EM)

    Tetrachloroethylene; Trichloroethylene; Trichloroflouromethane; Acetone; Ethyl ether; Methanol; Methyl isobutyl ketone; n-Butyl alcohol; Xylene; 2- Ethoxyethanol; 2-Nitropropane;...

  1. Downregulation of Cinnamyl Alcohol Dehydrogenase (CAD) Leads to Improved

    Office of Scientific and Technical Information (OSTI)

    Saccharification Efficiency in Switchgrass (Journal Article) | SciTech Connect Downregulation of Cinnamyl Alcohol Dehydrogenase (CAD) Leads to Improved Saccharification Efficiency in Switchgrass Citation Details In-Document Search Title: Downregulation of Cinnamyl Alcohol Dehydrogenase (CAD) Leads to Improved Saccharification Efficiency in Switchgrass Authors: Chunxiang,Fu ; Xirong,Xiao ; Yajun,Xi ; Yaxin,Ge ; Fang,Chen ; Joseph,Bouton ; Richard A.,Dixon ; Zeng-Yu,Wang ; , Publication Date:

  2. Pyrochlore-Based Catalysts for Syngas-Derived Alcohol Synthesis

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

    Pyrochlore-Based Catalysts for Syngas-Derived Alcohol Synthesis Contact NETL Technology Transfer Group techtransfer@netl.doe.gov May 2013 Opportunity This technology provides an advantageous means to convert syngas into a class of chemicals known as higher oxygenates as well as other long-chain hydrocarbons. Research is currently active on this patent-pending technology "Synthesis, Characterization, and Catalytic Activity of Rh-based Lanthanum Zirconate Pyrochlores for Higher Alcohol

  3. Catalysts for Syngas-Derived Alcohol Synthesis - Energy Innovation Portal

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

    Vehicles and Fuels Vehicles and Fuels Biomass and Biofuels Biomass and Biofuels Find More Like This Return to Search Catalysts for Syngas-Derived Alcohol Synthesis Improves the conversion of syngas from natural gas, coal, or biomass National Energy Technology Laboratory Contact NETL About This Technology Publications: PDF Document Publication Pyrochlore-Based Catalysts for Syngas-Derived Alcohol Synthesis (294 KB) Technology Marketing Summary This technology provides an advantageous means to

  4. Converting sugars to sugar alcohols by aqueous phase catalytic hydrogenation

    DOE Patents [OSTI]

    Elliott, Douglas C. (Richland, WA); Werpy, Todd A. (West Richland, WA); Wang, Yong (Richland, WA); Frye, Jr., John G. (Richland, WA)

    2003-05-27

    The present invention provides a method of converting sugars to their corresponding sugar alcohols by catalytic hydrogenation in the aqueous phase. It has been found that surprisingly superior results can be obtained by utilizing a relatively low temperature (less than 120.degree. C.), selected hydrogenation conditions, and a hydrothermally stable catalyst. These results include excellent sugar conversion to the desired sugar alcohol, in combination with long life under hydrothermal conditions.

  5. Thermochemical Ethanol via Indirect Gasification and Mixed Alcohol

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Synthesis of Lignocellulosic Biomass | Department of Energy Thermochemical Ethanol via Indirect Gasification and Mixed Alcohol Synthesis of Lignocellulosic Biomass Thermochemical Ethanol via Indirect Gasification and Mixed Alcohol Synthesis of Lignocellulosic Biomass This process design and technoeconomic evaluation addresses the conversion of biomass to ethanol via thermochemical pathways that are expected to be demonstrated at the pilot level by 2012. PDF icon Thermochemical Ethanol via

  6. Design Case Summary: Production of Mixed Alcohols from Municipal Solid

    Office of Environmental Management (EM)

    Waste via Gasification | Department of Energy Design Case Summary: Production of Mixed Alcohols from Municipal Solid Waste via Gasification Design Case Summary: Production of Mixed Alcohols from Municipal Solid Waste via Gasification The Bioenergy Technologies Office develops design cases to understand the current state of conversion technologies and to determine where improvements need to take place in the future. This design case establishes cost targets for converting MSW to ethanol and

  7. Method of forming a dianhydrosugar alcohol

    DOE Patents [OSTI]

    Holladay, Johnathan E. (Kennewick, WA); Hu, Jianli (Kennewick, WA); Wang, Yong (Richland, WA); Werpy, Todd A. (West Richland, WA); Zhang, Xinjie (Burlington, MA)

    2010-01-19

    The invention includes methods of producing dianhydrosugars. A polyol is reacted in the presence of a first catalyst to form a monocyclic sugar. The monocyclic sugar is transferred to a second reactor where it is converted to a dianhydrosugar alcohol in the presence of a second catalyst. The invention includes a process of forming isosorbide. An initial reaction is conducted at a first temperature in the presence of a solid acid catalyst. The initial reaction involves reacting sorbitol to produce 1,4-sorbitan, 3,6-sorbitan, 2,5-mannitan and 2,5-iditan. Utilizing a second temperature, the 1,4-sorbitan and 3,6-sorbitan are converted to isosorbide. The invention includes a method of purifying isosorbide from a mixture containing isosorbide and at least one additional component. A first distillation removes a first portion of the isosorbide from the mixture. A second distillation is then conducted at a higher temperature to remove a second portion of isosorbide from the mixture.

  8. Alcohol production from agricultural and forestry residues

    SciTech Connect (OSTI)

    Opilla, R.; Dale, L.; Surles, T.

    1980-05-01

    A variety of carbohydrate sources can be used as raw material for the production of ethanol. Section 1 is a review of technologies available for the production of ethanol from whole corn. Particular emphasis is placed on the environmental aspects of the process, including land utilization and possible air and water pollutants. Suggestions are made for technological changes intended to improve the economics of the process as well as to reduce some of the pollution from by-product disposal. Ethanol may be derived from renewable cellulosic substances by either enzymatic or acid hydrolysis of cellulose to sugar, followed by conventional fermentation and distillation. Section 2 is a review of the use of two agricultural residues - corn stover (field stalks remaining after harvest) and straw from wheat crops - as a cellulosic feedstock. Two processes have been evaluated with regard to environmental impact - a two-stage acid process developed by G.T. Tsao of Purdue University and an enzymatic process based on the laboratory findings of C.R. Wilke of the University of California, Berkeley. Section 3 deals with the environmental residuals expected from the manufacture of methyl and ethyl alcohols from woody biomass. The methanol is produced in a gasification process, whereas ethanol is produced by hydrolysis and fermentation processes similar to those used to derive ethanol from cellulosic materials.

  9. Alcohol production from agricultural and forestry residues

    SciTech Connect (OSTI)

    Dale, L; Opilla, R; Surles, T

    1980-09-01

    Technologies available for the production of ethanol from whole corn are reviewed. Particular emphasis is placed on the environmental aspects of the process, including land utilization and possible air and water pollutants. Suggestions are made for technological changes intended to improve the economics of the process as well as to reduce some of the pollution from by-product disposal. Ethanol may be derived from renewable cellulosic substances by either enzymatic or acid hydrolysis of cellulose to sugar, followed by conventional fermentation and distillation. The use of two agricultural residues - corn stover (field stalks remaining after harvest) and straw from wheat crops - is reviewed as a cellulosic feedstock. Two processes have been evaluated with regard to environmental impact - a two-stage acid process developed by G.T. Tsao of Purdue University and an enzymatic process based on the laboratory findings of C.R. Wilke of the University of California, Berkeley. The environmental residuals expected from the manufacture of methyl and ethyl alcohols from woody biomass are covered. The methanol is produced in a gasification process, whereas ethanol is produced by hydrolysis and fermentation processes similar to those used to derive ethanol from cellulosic materials.

  10. Use of alcohol in farming applications: alternative fuels utilization program

    SciTech Connect (OSTI)

    Borman, G.L.; Foster, D.E.; Uyehara, O.A.; McCallum, P.W.; Timbario, T.J.

    1980-11-01

    The use of alcohol with diesel fuel has been investigated as a means of extending diesel fuel supplies. The ability to use ethanol in diesel-powered farm equipment could provide the means for increasing the near-term fuels self-sufficiency of the American farmer. In the longer term, the potential availability of methanol (from coal) in large quantities could serve to further decrease the dependency on diesel fuel. This document gives two separate overviews of the use of alcohols in farm equipment. Part I of this document compares alcohol with No. 1 and No. 2 diesel fuels and describes several techniques for using alcohol in farm diesels. Part II of this document discusses the use of aqueous ethanol in diesel engines, spark ignition engines and provides some information on safety and fuel handling of both methanol and ethanol. This document is not intended as a guide for converting equipment to utilize alcohol, but rather to provide information such that the reader can gain insight on the advantages and disadvantages of using alcohol in existing engines currently used in farming applications.

  11. Hige Compression Ratio Turbo Gasoline Engine Operation Using Alcohol Enhancement

    SciTech Connect (OSTI)

    Heywood, John; Jo, Young Suk; Lewis, Raymond; Bromberg, Leslie; Heywood, John

    2015-10-31

    The overall objective of this project was to quantify the potential for improving the performance and efficiency of gasoline engine technology by use of alcohols to suppress knock. Knock-free operation is obtained by direct injection of a second “anti-knock” fuel such as ethanol, which suppresses knock when, with gasoline fuel, knock would occur. Suppressing knock enables increased turbocharging, engine downsizing, and use of higher compression ratios throughout the engine’s operating map. This project combined engine testing and simulation to define knock onset conditions, with different mixtures of gasoline and alcohol, and with this information quantify the potential for improving the efficiency of turbocharged gasoline spark-ignition engines, and the on-vehicle fuel consumption reductions that could then be realized. The more focused objectives of this project were therefore to: Determine engine efficiency with aggressive turbocharging and downsizing and high compression ratio (up to a compression ratio of 13.5:1) over the engine’s operating range; Determine the knock limits of a turbocharged and downsized engine as a function of engine speed and load; Determine the amount of the knock-suppressing alcohol fuel consumed, through the use of various alcohol-gasoline and alcohol-water gasoline blends, for different driving cycles, relative to the gasoline consumed; Determine implications of using alcohol-boosted engines, with their higher efficiency operation, in both light-duty and medium-duty vehicle sectors.

  12. Chemistry of enol ethers. LXXXIV. Condensation of acetals of saturated aldehydes with 2-trimethylsilyloxy-1,3-dienes. Synthesis of /beta/-alkoxy-alkyl vinyl and divinyl ketones

    SciTech Connect (OSTI)

    Makin, S.M.; Nazarova, O.N.; Dymshakova, G.M.; Kundryutskova, L.A.

    1988-11-10

    The addition of the acetals of saturated aldehydes (formaldehyde, acetaldehyde, propionaldehyde, butyraldehyde, and isobutyraldehyde) to 2-trimethylsilyloxy-4-methyl-1,3-pentadiene in the presence of aprotic acids (ZnCl/sub 2/, ZnBr/sub 2/, FeCl/sub 3/, SnCl/sub 4/, BF/sub 3/ /times/ OEt/sub 2/) takes place at positions 1, 2 of the diene system with the formation of /beta/-alkoxyalkyl vinyl ketones. The most effective catalysts of this reaction were stannic chloride and zinc bromide. The alkyl derivatives of divinyl ketones are formed when the obtained /beta/-alkoxyalkyl vinyl ketones are heated with p-toluenesulfonic acid.

  13. Low-temperature CVD of iron, cobalt, and nickel nitride thin films from bis[di(tert-butyl)amido]metal(II) precursors and ammonia

    SciTech Connect (OSTI)

    Cloud, Andrew N.; Abelson, John R., E-mail: abelson@illinois.edu [Department of Materials Science and Engineering, University of Illinois at Urbana-Champaign, 201 Materials Science and Engineering Building, 1304 W. Green St., Urbana, Illinois 61801 (United States); Davis, Luke M.; Girolami, Gregory S., E-mail: girolami@scs.illinois.edu [School of Chemical Sciences, University of Illinois at Urbana-Champaign, 600 S. Mathews Ave., Urbana, Illinois 61801 (United States)

    2014-03-15

    Thin films of late transition metal nitrides (where the metal is iron, cobalt, or nickel) are grown by low-pressure metalorganic chemical vapor deposition from bis[di(tert-butyl)amido]metal(II) precursors and ammonia. These metal nitrides are known to have useful mechanical and magnetic properties, but there are few thin film growth techniques to produce them based on a single precursor family. The authors report the deposition of metal nitride thin films below 300?C from three recently synthesized M[N(t-Bu){sub 2}]{sub 2} precursors, where M?=?Fe, Co, and Ni, with growth onset as low as room temperature. Metal-rich phases are obtained with constant nitrogen content from growth onset to 200?C over a range of feedstock partial pressures. Carbon contamination in the films is minimal for iron and cobalt nitride, but similar to the nitrogen concentration for nickel nitride. X-ray photoelectron spectroscopy indicates that the incorporated nitrogen is present as metal nitride, even for films grown at the reaction onset temperature. Deposition rates of up to 18?nm/min are observed. The film morphologies, growth rates, and compositions are consistent with a gas-phase transamination reaction that produces precursor species with high sticking coefficients and low surface mobilities.

  14. Geothermal source potential and utilization for alcohol production

    SciTech Connect (OSTI)

    Austin, J.C.

    1981-11-01

    A study was conducted to assess the technical and economic feasibility of using a potential geothermal source to drive a fuel grade alcohol plant. Test data from the well at the site indicated that the water temperature at approximately 8500 feet should approach 275/sup 0/F. However, no flow data was available, and so the volume of hot water that can be expected from a well at this site is unknown. Using the available data, numerous fuel alcohol production processes and various heat utilization schemes were investigated to determine the most cost effective system for using the geothermal resource. The study found the direct application of hot water for alcohol production based on atmospheric processes using low pressure steam to be most cost effective. The geothermal flow rates were determined for various sizes of alcohol production facility using 275/sup 0/F water, 235/sup 0/F maximum processing temperature, 31,000 and 53,000 Btu per gallon energy requirements, and appropriate process approach temperatures. It was determined that a 3 million gpy alcohol plant is the largest facility that can practically be powered by the flow from one large geothermal well. An order-of-magnitude cost estimate was prepared, operating costs were calculated, the economic feasibility of the propsed project was examined, and a sensitivity analysis was performed.

  15. Modeling and cold start in alcohol-fueled engines

    SciTech Connect (OSTI)

    Markel, A.J.; Bailey, B.K.

    1998-05-01

    Neat alcohol fuels offer several benefits over conventional gasoline in automotive applications. However, their low vapor pressure and high heat of vaporization make it difficult to produce a flammable vapor composition from a neat alcohol fuel during a start under cold ambient conditions. Various methods have been introduced to compensate for this deficiency. In this study, the authors applied computer modeling and simulation to evaluate the potential of four cold-start technologies for engines fueled by near-neat alcohol. The four technologies were a rich combustor device, a partial oxidation reactor, a catalytic reformer, and an enhanced ignition system. The authors ranked the competing technologies by their ability to meet two primary criteria for cold starting an engine at {minus}25 deg C and also by several secondary parameters related to commercialization. Their analysis results suggest that of the four technologies evaluated, the enhanced ignition system is the best option for further development.

  16. Ag-Al2O3 Catalyst HC-SCR: Performance with Light Alcohols and...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Ag-Al2O3 Catalyst HC-SCR: Performance with Light Alcohols and Other Reductants Ag-Al2O3 Catalyst HC-SCR: Performance with Light Alcohols and Other Reductants 2004 Diesel Engine...

  17. Methods for sequestering carbon dioxide into alcohols via gasification fermentation

    DOE Patents [OSTI]

    Gaddy, James L; Ko, Ching-Whan; Phillips, J. Randy; Slape, M. Sean

    2013-11-26

    The present invention is directed to improvements in gasification for use with synthesis gas fermentation. Further, the present invention is directed to improvements in gasification for the production of alcohols from a gaseous substrate containing at least one reducing gas containing at least one microorganism.

  18. Electrocatalyst for alcohol oxidation at fuel cell anodes

    DOE Patents [OSTI]

    Adzic, Radoslav (East Setauket, NY); Kowal, Andrzej (Cracow, PL)

    2011-11-02

    In some embodiments a ternary electrocatalyst is provided. The electrocatalyst can be used in an anode for oxidizing alcohol in a fuel cell. In some embodiments, the ternary electrocatalyst may include a noble metal particle having a surface decorated with clusters of SnO.sub.2 and Rh. The noble metal particles may include platinum, palladium, ruthenium, iridium, gold, and combinations thereof. In some embodiments, the ternary electrocatalyst includes SnO.sub.2 particles having a surface decorated with clusters of a noble metal and Rh. Some ternary electrocatalysts include noble metal particles with clusters of SnO.sub.2 and Rh at their surfaces. In some embodiments the electrocatalyst particle cores are nanoparticles. Some embodiments of the invention provide a fuel cell including an anode incorporating the ternary electrocatalyst. In some aspects a method of using ternary electrocatalysts of Pt, Rh, and SnO.sub.2 to oxidize an alcohol in a fuel cell is described.

  19. Alcohol-free alkoxide process for containing nuclear waste

    DOE Patents [OSTI]

    Pope, James M.; Lahoda, Edward J.

    1984-01-01

    Disclosed is a method of containing nuclear waste. A composition is first prepared of about 25 to about 80%, calculated as SiO.sub.2, of a partially hydrolyzed silicon compound, up to about 30%, calculated as metal oxide, of a partially hydrolyzed aluminum or calcium compound, about 5 to about 20%, calculated as metal oxide, of a partially hydrolyzed boron or calcium compound, about 3 to about 25%, calculated as metal oxide, of a partially hydrolyzed sodium, potassium or lithium compound, an alcohol in a weight ratio to hydrolyzed alkoxide of about 1.5 to about 3% and sufficient water to remove at least 99% of the alcohol as an azeotrope. The azeotrope is boiled off and up to about 40%, based on solids in the product, of the nuclear waste, is mixed into the composition. The mixture is evaporated to about 25 to about 45% solids and is melted and cooled.

  20. 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.

  1. 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.

  2. Electrocatalyst for Alcohol Oxidation at Fuel Cell Anodes - Energy

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

    Innovation Portal Alcohol Oxidation at Fuel Cell Anodes Brookhaven National Laboratory Contact BNL About This Technology Publications: PDF Document Publication Ternary Pt/Rh/SnO2 electrocatalysts for oxidizing ethanol to CO2 (2,641 KB) <p> Scanning transmission electron micrograph showing uniform dispersion of the catalyst particles (bright spots) on the carbon support (dark background). The average particle size is about 1.5&nbsp;nm.</p> Scanning transmission electron

  3. Electrocatalysts for Alcohol Oxidation in Fuel Cells - Energy Innovation

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

    Portal Electrocatalysts for Alcohol Oxidation in Fuel Cells Brookhaven National Laboratory Contact BNL About This Technology <p> Higher current indicates higher activity for catalyzing methanol oxidation in a fuel cell. Here the ternary electrocatalyst is comparable to the best commercially available catalyst for methanol oxidation.</p> Higher current indicates higher activity for catalyzing methanol oxidation in a fuel cell. Here the ternary electrocatalyst is comparable to the

  4. On-farm anaerobic digester and fuel alcohol plant

    SciTech Connect (OSTI)

    Not Available

    1985-01-01

    An anaerobic digestion system was constructed and set up on a southern Illinois farm. The anaerobic digestion system was designed to be coupled with a fuel alcohol plant constructed by the farm family as part of an integrated farm energy system. The digester heating can be done using waste hot water from the alcohol plant and biogas from the digester can be used as fuel for the alcohol production. The anaerobic digestion system is made up of the following components. A hog finishing house, which already had a slotted floor and manure pit beneath it, was fitted with a system to scrape the manure into a feed slurry pit constructed at one end of the hog house. A solids handling pump feeds the manure from the feed slurry pit into the digester, a 13,000 gallon tank car body which has been insulated with styrofoam and buried underground. Another pump transfers effluent (digested manure) from the digester to a 150,000 gallon storage tank. The digested manure is then applied to cropland at appropriate times of the year. The digester temperature is maintained at the required level by automated hot water circulation through an internal heat exchanger. The biogas produced in the digester is pumped into a 32,000 gallon gas storage tank.

  5. Syngas Conversion to Hydrocarbon Fuels through Mixed Alcohol Intermediates

    SciTech Connect (OSTI)

    Dagle, Robert A.; Lebarbier, Vanessa M.; Albrecht, Karl O.; Li, Jinjing; Taylor, Charles E.; Bao, Xinhe; Wang, Yong

    2013-05-13

    Synthesis gas (syngas) can be used to synthesize a variety of fuels and chemicals. Domestic transportation and military operational interests have driven continued focus on domestic syngas-based fuels production. Liquid transportation fuels may be made from syngas via four basic processes: 1) higher alcohols, 2) Fischer-Tropsch (FT), 3) methanol-to-gasoline (MTG), and 4) methanol-to-olefins (MTO) and olefins-to-gasoline/distillate (MOGD). Compared to FT and higher alcohols, MTG and MTO-MOGD have received less attention in recent years. Due to the high capital cost of these synthetic fuel plants, the production cost of the finished fuel cannot compete with petroleum-derived fuel. Pacific Northwest National Laboratory has recently evaluated one way to potentially reduce capital cost and overall production cost for MTG by combining the methanol and MTG syntheses in a single reactor. The concept consists of mixing the conventional MTG catalyst (i.e. HZSM-5) with an alcohol synthesis catalyst. It was found that a methanol synthesis catalyst, stable at high temperature (i.e. Pd/ZnO/Al2O3) [1], when mixed with ZSM-5, was active for syngas conversion. Relatively high syngas conversion can be achieved as the equilibrium-driven conversion limitations for methanol and dimethyl ether are removed as they are intermediates to the final hydrocarbon product. However, selectivity control was difficult to achieve as formation of undesirable durene and light hydrocarbons was problematic [2]. The objective of the present study was thus to evaluate other potential composite catalyst systems and optimize the reactions conditions for the conversion of syngas to hydrocarbon fuels, through the use of mixed alcohol intermediates. Mixed alcohols are of interest as they have recently been reported to produce higher yields of gasoline compared to methanol [3]. 1. Lebarbier, V.M., Dagle, R.A., Kovarik, L., Lizarazo-Adarme, J.A., King, D.L., Palo, D.R., Catalyst Science & Technology, 2012, 2, 2116-2127. 2. Zhu, Y., Jones, S.B., Biddy, M.J., Dagle, R.A., Palo, D.P., Bioresource Technology, 2012, 117, 341-351. 3. Gujar, A.C., Guda, V.K., Nolan, M., Yan W., Toghiani, H., White, M.G., Applied Catalysis A: General, 2009, 363, 115-121.

  6. Electrolytic method to make alkali alcoholates using ion conducting alkali electrolyte/separator

    DOE Patents [OSTI]

    Joshi, Ashok V. (Salt Lake City, UT); Balagopal, Shekar (Sandy, UT); Pendelton, Justin (Salt Lake City, UT)

    2011-12-13

    Alkali alcoholates, also called alkali alkoxides, are produced from alkali metal salt solutions and alcohol using a three-compartment electrolytic cell. The electrolytic cell includes an anolyte compartment configured with an anode, a buffer compartment, and a catholyte compartment configured with a cathode. An alkali ion conducting solid electrolyte configured to selectively transport alkali ions is positioned between the anolyte compartment and the buffer compartment. An alkali ion permeable separator is positioned between the buffer compartment and the catholyte compartment. The catholyte solution may include an alkali alcoholate and alcohol. The anolyte solution may include at least one alkali salt. The buffer compartment solution may include a soluble alkali salt and an alkali alcoholate in alcohol.

  7. Exploring Hydrogen Generation from Biomass-Derived Sugar and Sugar Alcohols

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    to Reduce Costs | Department of Energy Exploring Hydrogen Generation from Biomass-Derived Sugar and Sugar Alcohols to Reduce Costs Exploring Hydrogen Generation from Biomass-Derived Sugar and Sugar Alcohols to Reduce Costs April 15, 2013 - 12:00am Addthis With support from EERE, researchers at Virent, Inc. in Madison developed new cost-effective methods to produce hydrogen from renewable resources like biomass-derived sugar and sugar alcohols. Hydrogen can be used with fuel cells to produce

  8. 01-12-1998 - Bench Top FIre Involving Use of Alcohol and Burner...

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

    1998 - Bench Top FIre Involving Use of Alcohol and Burner Document Number: NA Effective Date: 011998 File (public): PDF icon 01-12-1998...

  9. Internal combustion engines for alcohol motor fuels: a compilation of background technical information

    SciTech Connect (OSTI)

    Blaser, Richard

    1980-11-01

    This compilation, a draft training manual containing technical background information on internal combustion engines and alcohol motor fuel technologies, is presented in 3 parts. The first is a compilation of facts from the state of the art on internal combustion engine fuels and their characteristics and requisites and provides an overview of fuel sources, fuels technology and future projections for availability and alternatives. Part two compiles facts about alcohol chemistry, alcohol identification, production, and use, examines ethanol as spirit and as fuel, and provides an overview of modern evaluation of alcohols as motor fuels and of the characteristics of alcohol fuels. The final section compiles cross references on the handling and combustion of fuels for I.C. engines, presents basic evaluations of events leading to the use of alcohols as motor fuels, reviews current applications of alcohols as motor fuels, describes the formulation of alcohol fuels for engines and engine and fuel handling hardware modifications for using alcohol fuels, and introduces the multifuel engines concept. (LCL)

  10. Quick setting water-compatible furfuryl alcohol polymer concretes

    DOE Patents [OSTI]

    Sugama, Toshifumi (Ridge, NY); Kukacka, Lawrence E. (Port Jefferson, NY); Horn, William H. (Brookhaven, NY)

    1982-11-30

    A novel quick setting polymer concrete composite comprising a furfuryl alcohol monomer, an aggregate containing a maximum of 8% by weight water, and about 1-10% trichlorotoluene initiator and about 20-80% powdered metal salt promoter, such as zinc chloride, based on the weight of said monomer, to initiate and promote polymerization of said monomer in the presence of said aggregate, within 1 hour after mixing at a temperature of -20.degree. C. to 40.degree. C., to produce a polymer concrete having a 1 hour compressive strength greater than 2000 psi.

  11. Understanding chemical reactions of CO{sub 2} and its isoelectronic molecules with 1-butyl-3-methylimidazolium acetate by changing the nature of the cation: The case of CS{sub 2} in 1-butyl-1-methylpyrrolidinium acetate studied by NMR spectroscopy and density functional theory calculations

    SciTech Connect (OSTI)

    Cabao, M. Isabel, E-mail: isabelcabaco@ist.utl.pt [Departamento de Fsica, Instituto Superior Tcnico, UTL, Av. Rovisco Pais 1049-001 Lisboa (Portugal); Centro de Fsica Atmica da UL, Av. Prof. Gama Pinto 2, 1649-003 Lisboa (Portugal); Besnard, Marcel; Danten, Yann [GSM Institut des Sciences Molculaires, CNRS (UMR 5255), Universit de Bordeaux, 351, Cours de la Libration 33405 Talence Cedex (France); Chvez, Fabin Vaca [Centro de Fsica da Matria Condensada da UL, Av. Prof. Gama Pinto 2, 1694-003 Lisboa (Portugal); Pinaud, Nol [CESAMO Institut des Sciences Molculaires, CNRS (UMR 5255), Universit de Bordeaux, 351, Cours de la Libration 33405 Talence Cedex (France); Sebastio, Pedro J. [Departamento de Fsica, Instituto Superior Tcnico, UTL, Av. Rovisco Pais 1049-001 Lisboa (Portugal); Centro de Fsica da Matria Condensada da UL, Av. Prof. Gama Pinto 2, 1694-003 Lisboa (Portugal); Coutinho, Joo A. P. [CICECO, Departamento de Qumica, Universidade de Aveiro 3810-193 Aveiro (Portugal)

    2014-06-28

    NMR spectroscopy ({sup 1}H, {sup 13}C, {sup 15}N) shows that carbon disulfide reacts spontaneously with 1-butyl-1-methylpyrrolidinium acetate ([BmPyrro][Ac]) in the liquid phase. It is found that the acetate anions play an important role in conditioning chemical reactions with CS{sub 2} leading, via coupled complex reactions, to the degradation of this molecule to form thioacetate anion (CH{sub 3}COS{sup ?}), CO{sub 2}, OCS, and trithiocarbonate (CS{sub 3}{sup 2?}). In marked contrast, the cation does not lead to the formation of any adducts allowing to conclude that, at most, its role consists in assisting indirectly these reactions. The choice of the [BmPyrro]{sup +} cation in the present study allows disentangling the role of the anion and the cation in the reactions. As a consequence, the ensemble of results already reported on CS{sub 2}-[Bmim][Ac] (1), OCS-[Bmim][Ac] (2), and CO{sub 2}-[Bmim][Ac] (3) systems can be consistently rationalized. It is argued that in system (1) both anion and cation play a role. The CS{sub 2} reacts with the acetate anion leading to the formation of CH{sub 3}COS{sup ?}, CO{sub 2}, and OCS. After these reactions have proceeded the nascent CO{sub 2} and OCS interact with the cation to form imidazolium-carboxylate ([Bmim] CO{sub 2}) and imidazolium-thiocarboxylate ([Bmim] COS). The same scenario also applies to system (2). In contrast, in the CO{sub 2}-[Bmim] [Ac] system a concerted cooperative process between the cation, the anion, and the CO{sub 2} molecule takes place. A carbene issued from the cation reacts to form the [Bmim] CO{sub 2}, whereas the proton released by the ring interacts with the anion to produce acetic acid. In all these systems, the formation of adduct resulting from the reaction between the solute molecule and the carbene species originating from the cation is expected. However, this species was only observed in systems (2) and (3). The absence of such an adduct in system (1) has been theoretically investigated using DFT calculations. The values of the energetic barrier of the reactions show that the formation of [Bmim] CS{sub 2} is unfavoured and that the anion offers a competitive reactive channel via an oxygen-sulphur exchange mechanism with the solute in systems (1) and (2)

  12. Structure and thermodynamics of core-softened models for alcohols

    SciTech Connect (OSTI)

    Muna, Gianmarco; Urbic, Tomaz

    2015-06-07

    The phase behavior and the fluid structure of coarse-grain models for alcohols are studied by means of reference interaction site model (RISM) theory and Monte Carlo simulations. Specifically, we model ethanol and 1-propanol as linear rigid chains constituted by three (trimers) and four (tetramers) partially fused spheres, respectively. Thermodynamic properties of these models are examined in the RISM context, by employing closed formul for the calculation of free energy and pressure. Gas-liquid coexistence curves for trimers and tetramers are reported and compared with already existing data for a dimer model of methanol. Critical temperatures slightly increase with the number of CH{sub 2} groups in the chain, while critical pressures and densities decrease. Such a behavior qualitatively reproduces the trend observed in experiments on methanol, ethanol, and 1-propanol and suggests that our coarse-grain models, despite their simplicity, can reproduce the essential features of the phase behavior of such alcohols. The fluid structure of these models is investigated by computing radial distribution function g{sub ij}(r) and static structure factor S{sub ij}(k); the latter shows the presence of a low?k peak at intermediate-high packing fractions and low temperatures, suggesting the presence of aggregates for both trimers and tetramers.

  13. Addendum: Tenth International Symposium on Alcohol Fuels, The road to commercialization

    SciTech Connect (OSTI)

    Not Available

    1994-05-01

    The Tenth International Symposium on ALCOHOL FUELS ``THE ROAD TO COMMERCIALIZATION`` was held at the Broadmoor Hotel, Colorado Springs, Colorado, USA November 7--10, 1993. Twenty-seven papers on the production of alcohol fuels, specifications, their use in automobiles, buses and trucks, emission control, and government policies were presented. Individual papers have been processed separately for entry into the data base.

  14. Novel Vertimass Catalyst for Conversion of Ethanol and Other Alcohols into Fungible Gasoline, Jet, and Diesel Fuel Blend Stocks

    Broader source: Energy.gov [DOE]

    Novel Vertimass Catalyst for Conversion of Ethanol and Other Alcohols into Fungible Gasoline, Jet, and Diesel Fuel Blend Stocks

  15. Production of branched-chain alcohols by recombinant Ralstonia eutropha in fed-batch cultivation

    SciTech Connect (OSTI)

    Fei, Q; Brigham, CJ; Lu, JN; Fu, RZ; Sinskey, AJ

    2013-09-01

    Branched-chain alcohols are considered promising green energy sources due to their compatibility with existing infrastructure and their high energy density. We utilized a strain of Ralstonia eutropha capable of producing branched-chain alcohols and examined its production in flask cultures. In order to increase isobutanol and 3-methyl-1-butanol (isoamyl alcohol) productivity in the engineered strain, batch, fed-batch, and two-stage fed-batch cultures were carried out in this work. The effects of nitrogen source concentration on branched-chain alcohol production were investigated under four different initial concentrations in fermenters. A maximum 380 g m(-3) of branched-chain alcohol production was observed with 2 kg m(-3) initial NH4Cl concentration in batch cultures. A pH-stat control strategy was utilized to investigate the optimum carbon source amount fed during fed-batch cultures for higher cell density. In cultures of R. eutropha strains that did not produce polyhydroxyalkanoate or branched-chain alcohols, a maximum cell dry weight of 36 kg m(-3) was observed using a fed-batch strategy, when 10 kg m(-3) carbon source was fed into culture medium. Finally, a total branched-chain alcohol titer of 790 g m(-3), the highest branched-chain alcohol yield of 0.03 g g(-1), and the maximum branched-chain alcohol productivity of 8.23 g m(-3) h(-1) were obtained from the engineered strain Re2410/pJL26 in a two-stage fed-batch culture system with pH-stat control. Isobutanol made up over 95% (mass fraction) of the total branched-chain alcohols titer produced in this study. (C) 2013 Published by Elsevier Ltd.

  16. Catalysts and process for hydrogenolysis of sugar alcohols to polyols

    DOE Patents [OSTI]

    Chopade, Shubham P. (East Lansing, MI) [East Lansing, MI; Miller, Dennis J. (Okemos, MI) [Okemos, MI; Jackson, James E. (Haslett, MI) [Haslett, MI; Werpy, Todd A. (West Richland, WA) [West Richland, WA; Frye, Jr., John G [Richland, WA; Zacher, Alan H. (Richland, WA) [Richland, WA

    2001-09-18

    The present invention provides a process for preparation of low molecular weight polyols from high molecular weight polyols in a hydrogenolysis reaction under elevated temperature and hydrogen pressure. The process comprises providing in a reaction mixture the polyols, a base, and a metal catalyst prepared by depositing a transition metal salt on an inert support, reducing the metal salt to the metal with hydrogen, and passivating the metal with oxygen, and wherein the catalyst is reduced with hydrogen prior to the reaction. In particular, the process provides for the preparation of glycerol, propylene glycol, and ethylene glycol from sugar alcohols such as sorbitol or xylitol. In a preferred process, the metal catalyst comprises ruthenium which is deposited on an alumina, titania, or carbon support, and the dispersion of the ruthenium on the support increases during the hydrogenolysis reaction.

  17. Cold-Start Performance and Emissions Behavior of Alcohol Fuels in an SIDI

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Engine Using Transient Hardware-In-Loop Test Meth | Department of Energy Performance and Emissions Behavior of Alcohol Fuels in an SIDI Engine Using Transient Hardware-In-Loop Test Meth Cold-Start Performance and Emissions Behavior of Alcohol Fuels in an SIDI Engine Using Transient Hardware-In-Loop Test Meth Discusses results of cold- and hot-start transient tests using gasoline and 3 alcohol-gasoline blends (50% and 85% ethanol, and 83% iso-butanol) PDF icon deer11_ickes.pdf More Documents

  18. 1

    Office of Environmental Management (EM)

    Xylene, Ethyl acetate, Ethyl benzene, Ethyl ether, n-butyl alcohol, Cyclohexanone, Methanol, Cresols, Cresylic acid, Nitrobenzene, Carbon disulfide, Isobutanol, Pyridine,...

  19. 1

    Office of Environmental Management (EM)

    Ethyl benzene, Ethyl ether, Methyl Isobutyl Ketone, n-Butyl alcohol, Cyclohexanone, Methanol, Cresols, Cresylic acid, Nitrobenzene, Toluene, Carbon disulfide, Isobutanol,...

  20. 1

    Office of Environmental Management (EM)

    Xylene, Ethyl acetate, Ethyl benzene, Ethyl ether, n-Butyl alcohol, Cyclohexanone, Methanol, Cresols, Cresylic acid, Nitroobenzene, Carbon disulfide, Isobutanol, Pyridine, 2-...

  1. 1

    Office of Environmental Management (EM)

    Xylene, Ethyl acetate, Ethyl benzene, Ethyl ether, n-butyl alcohol, Cyclohexanone, Methanol, Cresols, Cresylic acid, Nitroobenzene, Carbon disulfide, Isobutanol, Pyridine, 2-...

  2. Cloning and sequencing of the alcohol dehydrogenase II gene from Zymomonas mobilis

    DOE Patents [OSTI]

    Ingram, Lonnie O. (Gainesville, FL); Conway, Tyrrell (Gainesville, FL)

    1992-01-01

    The alcohol dehydrogenase II gene from Zymomonas mobilis has been cloned and sequenced. This gene can be expressed at high levels in other organisms to produce acetaldehyde or to convert acetaldehyde to ethanol.

  3. 01-12-1998 - Bench Top FIre Involving Use of Alcohol and Burner | The Ames

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

    Laboratory 1998 - Bench Top FIre Involving Use of Alcohol and Burner Document Number: NA Effective Date: 01/1998 File (public): PDF icon 01-12-1998

  4. Photochemical dimerization and functionalization of alkanes, ethers, primary alcohols and silanes

    DOE Patents [OSTI]

    Crabtree, R.H.; Brown, S.H.

    1988-02-16

    The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary alcohols and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

  5. 5-Carbon Alcohols for Drop-in Gasoline Replacement - Energy Innovation

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

    Portal Vehicles and Fuels Vehicles and Fuels Biomass and Biofuels Biomass and Biofuels Find More Like This Return to Search 5-Carbon Alcohols for Drop-in Gasoline Replacement Lawrence Berkeley National Laboratory Contact LBL About This Technology Technology Marketing SummaryJay Keasling and Howard Chou of Berkeley Lab and the Joint BioEnergy Institute (JBEI) have invented a fermentation process to produce 5-carbon alcohols from genetically modified E. coli host cells regardless of the

  6. HD Applications of Significantly Downsized SI Engines Using Alcohol DI for

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Knock Avoidance | Department of Energy Applications of Significantly Downsized SI Engines Using Alcohol DI for Knock Avoidance HD Applications of Significantly Downsized SI Engines Using Alcohol DI for Knock Avoidance Direct injection of a second fuel (ethanol or methanol) is explored as a means of avoiding knock in turbocharged, high-compression ratio spark-ignited engines that could replace diesels in certain vocational applications. PDF icon deer08_blumberg.pdf More Documents &

  7. Thermochemical Ethanol via Indirect Gasification and Mixed Alcohol Synthesis of Lignocellulosic Biomass

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Thermochemical Ethanol via Indirect Gasification and Mixed Alcohol Synthesis of Lignocellulosic Biomass S. Phillips, A. Aden, J. Jechura, and D. Dayton National Renewable Energy Laboratory T. Eggeman Neoterics International, Inc. Technical Report NREL/TP-510-41168 April 2007 NREL is operated by Midwest Research Institute ● Battelle Contract No. DE-AC36-99-GO10337 Thermochemical Ethanol via Indirect Gasification and Mixed Alcohol Synthesis of Lignocellulosic Biomass S. Phillips, A. Aden, J.

  8. Process for the conversion of alcohols and oxygenates to hydrocarbons in a turbulent fluid bed reactor

    SciTech Connect (OSTI)

    Avidan, A. A.; Kam, A. Y.

    1985-04-23

    Improvements in converting C/sub 1/-C/sub 3/ monohydric alcohols, particularly methanol, related oxygenates of said alcohols and/or oxygenates produced by Fischer-Tropsch synthesis to light olefins, gasoline boiling range hydrocarbons and/or distillate boiling range hydrocarbons are obtained in a fluidized bed of ZSM-5 type zeolite catalyst operating under conditions effective to provide fluidization in the turbulent regime.

  9. Microbial Reduction of Furfurals to Furan Alcohols by a Microbial Species -

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

    Energy Innovation Portal Microbial Reduction of Furfurals to Furan Alcohols by a Microbial Species Oak Ridge National Laboratory Contact ORNL About This Technology Technology Marketing SummaryAn ORNL researcher developed a method for producing furfuryl alcohol (FA) through bioprocessing using a thermophilic microorganism. This organism has been shown to be highly resistant to the toxic effects of furfural and hydroxymethylfurfural (HMF) and can propagate in the presence of over 48 g/L (500

  10. Photochemical dimerization and functionalization of alkanes, ethers, primary alcohols and silanes

    DOE Patents [OSTI]

    Crabtree, Robert H. (Bethany, CT); Brown, Stephen H. (East Haven, CT)

    1988-01-01

    The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary alcohols and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

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

    DOE Patents [OSTI]

    Greene, Marvin I. (Oradell, NJ); Gelbein, Abraham P. (Morristown, NJ)

    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.

  12. 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.

  13. Geothermal source potential and utilization for methane generation and alcohol production

    SciTech Connect (OSTI)

    Austin, J.C.

    1981-11-01

    A study was conducted to assess the technical and economic feasibility of integrating a geothermally heated anaerobic digester with a fuel alcohol plant and cattle feedlot. Thin stillage produced from the alcohol production process and manure collected from the cattle feedlot would be digested in anaerobic digesters to produce biogas, a mixture of methane and carbon dioxide, and residue. The energy requirements to maintain proper digester temperatures would be provided by geothermal water. The biogas produced in the digesters would be burned in a boiler to produce low-pressure steam which would be used in the alcohol production process. The alcohol plant would be sized so that the distiller's grains byproduct resulting from the alcohol production would be adequate to supply the daily cattle feed requirements. A portion of the digester residue would substitute for alfalfa hay in the cattle feedlot ration. The major design criterion for the integrated facilty was the production of adequate distiller's grain to supply the daily requirements of 1700 head of cattle. It was determined that, for a ration of 7 pounds of distiller's grain per head per day, a 1 million gpy alcohol facility would be required. An order-of-magnitude cost estimate was prepared for the proposed project, operating costs were calculated for a facility based on a corn feedstock, the economic feasibility of the proposed project was examined by calculating its simple payback, and an analysis was performed to examine the sensitivity of the project's economic viability to variations in feedstock costs and alcohol and distiller's grain prices.

  14. On-farm anaerobic digester and fuel-alcohol plant. Final report

    SciTech Connect (OSTI)

    Bengtson, H.H.

    1985-12-01

    An anaerobic-digestion system, coupled with a fuel-alcohol plant, was constructed and set up on a southern Illinois farm as part of an integrated farm-energy system. The digester heating can be done using waste hot water from the alcohol plant and biogas from the digester can be used as fuel for the alcohol production. The anaerobic digestion system is made up of the following components; a hog finishing house with a manure pit; a solids handling pump to feed the manure; and a 13,000-gallon railroad tank car as the main digester vessel and pump to transfer effluent from the digester to a 150,000 gallon storage tank. The digester was operated for sufficient time to demonstrate the use of hot water in an automated digester temperature control system. Sufficient biogas was produced to demonstrate the use of biogas in a converted propane boiler.

  15. Photochemical dimerization and functionalization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and silanes

    DOE Patents [OSTI]

    Crabtree, R.H.; Brown, S.H.

    1989-10-17

    The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and primary, secondary and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

  16. Process for the conversion of lower alcohols to higher branched oxygenates

    DOE Patents [OSTI]

    Barger, P.T.

    1996-09-24

    A process is provided for the production of branched C{sub x} oxygenates from lower alcohols such as methanol, ethanol, propanol and mixtures thereof. The process comprises contacting the lower alcohols with a solid catalyst comprising a mixed metal oxide support having components selected from the group consisting of oxides of zinc, magnesium, zirconia, titanium, manganese, chromium, and lanthanides, and an activation metal selected from the group consisting of Group VIII metal, Group IB metals, and mixtures thereof. The advantage of the process is improved yields and selectivity to isobutanol which can subsequently be employed in the production of high octane motor gasoline.

  17. Process for the conversion of lower alcohols to higher branched oxygenates

    DOE Patents [OSTI]

    Barger, Paul T. (Arlington Heights, IL)

    1996-01-01

    A process is provided for the production of branched C.sub.4+ oxygenates from lower alcohols such as methanol, ethanol, propanol and mixtures thereof. The process comprises contacting the lower alcohols with a solid catalyst comprising a mixed metal oxide support having components selected from the group consisting of oxides of zinc, magnesium, zirconia, titanium, manganese, chromium, and lanthanides, and an activation metal selected from the group consisting of Group VIII metal, Group IB metals, and mixtures thereof. The advantage of the process is improved yields and selectivity to isobutanol which can subsequently be employed in the production of high octane motor gasoline.

  18. Design Case Summary: Production of Mixed Alcohols from Municipal Solid Waste via Gasification

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Mixed Alcohols from Municipal Solid Waste via Gasification March 2010 Adapted from reports prepared by: C Valkenburg Y Zhu CW Walton BL Thompson MA Gerber SB Jones DJ Stevens of the Pacifc Northwest National Laboratory A two volume report "Municipal Solid Waste (MSW) to Liquid Fuels, Volume 1: Availability of Feedstock and Technology" & "Municipal Solid Waste (MSW) to Liquid Fuels, Volume 2: A Techno-economic Evalua- tion of the Production of Mixed Alcohols" is available

  19. 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.

  20. Photochemical dimerization and functionalization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and silanes

    DOE Patents [OSTI]

    Crabtree, Robert H. (Bethany, CT); Brown, Stephen H. (East Haven, CT)

    1989-01-01

    The space-time yield and/or the selectivity of the photochemical dimerization of alkanes, ethers, primary and secondary alcohols, phosphine oxides and primary, secondary and tertiary silanes with Hg and U.V. light is enhanced by refluxing the substrate in the irradiated reaction zone at a temperature at which the dimer product condenses and remains condensed promptly upon its formation. Cross-dimerization of the alkanes, ethers and silanes with primary alcohols is disclosed, as is the functionalization to aldehydes of the alkanes with carbon monoxide.

  1. Design Case Summary. Production of Mixed Alcohols from Municipal Solid Waste via Gasification

    SciTech Connect (OSTI)

    Valkenburg, C.; Zhu, Y.; Walton, C. W.; Thompson, B. L.; Gerber, M. A.; Jones, S. B.; Stevens, D. J.

    2010-03-01

    The Biomass Program develops design cases to understand the current state of conversion technologies and to determine where improvements need to take place in the future. This design case establishes cost targets for converting MSW to ethanol and other mixed alcohols via gasification.

  2. Heterogeneous catalytic process for alcohol fuels from syngas. Final technical report

    SciTech Connect (OSTI)

    Dombek, B.D.

    1996-03-01

    The primary objective of this project has been the pursuit of a catalyst system which would allow the selective production from syngas of methanol and isobutanol. It is desirable to develop a process in which the methanol to isobutanol weight ratio could be varied from 70/30 to 30/70. The 70/30 mixture could be used directly as a fuel additive, while, with the appropriate downstream processing, the 30/70 mixture could be utilized for methyl tertiary-butyl ether (MTBE) synthesis. The indirect manufacture of MTBE from a coal derived syngas to methanol and isobutanol process would appear to be a viable solution to MTBE feedstock limitations. To become economically attractive, a process fro producing oxygenates from coal-derived syngas must form these products with high selectivity and good rates, and must be capable of operating with a low-hydrogen-content syngas. This was to be accomplished through extensions of known catalyst systems and by the rational design of novel catalyst systems.

  3. Controlled etching of hexagonal ZnO architectures in an alcohol thermal process

    SciTech Connect (OSTI)

    Wu, Junshu [State Key Laboratory of Fine Chemicals, Department of Materials Science and Chemical Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116012 (China)] [State Key Laboratory of Fine Chemicals, Department of Materials Science and Chemical Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116012 (China); Xue, Dongfeng, E-mail: dfxue@chem.dlut.edu.cn [State Key Laboratory of Fine Chemicals, Department of Materials Science and Chemical Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116012 (China)] [State Key Laboratory of Fine Chemicals, Department of Materials Science and Chemical Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116012 (China)

    2010-03-15

    An alcohol thermal technique was applied to the controlled growth of hexagonal ZnO architectures via selective chemical etching. ZnO microdisks were produced first under mild alcohol thermal conditions in presence of formamide. Due to a higher surface energy/atomic density of Zn{sup 2+} {l_brace}0 0 0 1{r_brace} than that of the other faces, hexagonal ZnO microring was obtained by selectively etching positive polar surface of disk-like precursor with a high density of planar defects at the center. The selective etching of ZnO is related to its crystallographic characteristics of surface polarity and chemical activities, which opens a new opportunity for the shape-controlled synthesis of wurtzite-structured materials.

  4. Nickel Phosphine Catalysts with Pendant Amines for Electrocatalytic Oxidation of Alcohols

    SciTech Connect (OSTI)

    Weiss, Charles J.; Wiedner, Eric S.; Roberts, John A.; Appel, Aaron M.

    2015-01-01

    Nickel phosphine complexes with pendant amines have been found to be electrocatalysts for the oxidation of primary and secondary alcohols, with turnover frequencies as high as 3.3 s-1. These complexes are the first electrocatalysts for alcohol oxidation based on non-precious metals, which will be critical for use in fuel cells. The research by CJW, ESW, and AMA was supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. The research by JASR was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  5. Catalytic oxidation of hydrocarbons and alcohols by carbon dioxide on oxide catalysts

    SciTech Connect (OSTI)

    Krylov, O.V. . N.N. Semenov Inst. of Chemical Physics); Mamedov, A.Kh.; Mirzabekova, S.R. . Yu.G. Mamedaliev Inst. of Petrochemical Processes)

    1995-02-01

    The great interest displayed lately in heterogeneous catalytic reactions of carbon dioxide is caused by two reasons: (1) the necessity to fight the greenhouse effect and (2) the exhaust of carbon raw material sources. Reactions of oxidative transformation of organic compounds of different classes (alkanes, alkenes, and alcohols) with a nontraditional oxidant, carbon dioxide, were studied on oxide catalysts Fe-O, Cr-O, Mn-O and on multicomponent systems based on manganese oxide. The supported manganese oxide catalysts are active, selective, and stable in conversion of the CH[sub 4] + CO[sub 2] mixture into synthesis gas and in oxidative dehydrogenation of C[sub 2] [minus] C[sub 7] hydrocarbons and the lower alcohols. Unlike metal catalysts manganese oxide based catalysts do not form a carbon layer during the reaction.

  6. Correlation between speciated hydrocarbon emissions and flame ionization detector response for gasoline/alcohol blends .

    SciTech Connect (OSTI)

    Wallner, T.

    2011-08-01

    The U.S. renewable fuel standard has made it a requirement to increase the production of ethanol and advanced biofuels to 36 billion by 2022. Ethanol will be capped at 15 billion, which leaves 21 billion to come from other sources such as butanol. Butanol has a higher energy density and lower affinity for water than ethanol. Moreover, alcohol fueled engines in general have been shown to positively affect engine-out emissions of oxides of nitrogen and carbon monoxide compared with their gasoline fueled counterparts. In light of these developments, the variety and blend levels of oxygenated constituents is likely to increase in the foreseeable future. The effect on engine-out emissions for total hydrocarbons is less clear due to the relative insensitivity of the flame ionization detector (FID) toward alcohols and aldehydes. It is well documented that hydrocarbon (HC) measurement using a conventional FID in the presence of oxygenates in the engine exhaust stream can lead to a misinterpretation of HC emissions trends for alcohol fuel blends. Characterization of the exhaust stream for all expected hydrocarbon constituents is required to accurately determine the actual concentration of unburned fuel components in the exhaust. In addition to a conventional exhaust emissions bench, this characterization requires supplementary instrumentation capable of hydrocarbon speciation and response factor independent quantification. Although required for certification testing, this sort of instrumentation is not yet widely available in engine development facilities. Therefore, an attempt is made to empirically determine FID correction factors for oxygenate fuels. Exhaust emissions of an engine fueled with several blends of gasoline and ethanol, n-butanol and iso-Butanol were characterized using both a conventional FID and a Fourier transform infrared. Based on these results, a response factor predicting the actual hydrocarbon emissions based solely on FID results as a function of alcohol type and content is presented. Finally, the correlation derived from data presented in this study is compared with equations and results found in the literature.

  7. Hydrogenolysis Of 5-Carbon Sugars, Sugar Alcohols And Compositions For Reactions Involving Hydrogen

    DOE Patents [OSTI]

    Werpy, Todd A. (West Richland, WA); Frye, Jr., John G. (Richland, WA); Zacher, Alan H. (Kennewick, WA); Miller, Dennis J. (Okemos, MI)

    2004-01-13

    Methods and compositions for reactions of hydrogen over a Re-containing catalyst with compositions containing a 5-carbon sugar, sugar alcohol, or lactic acid are described. It has been surprisingly discovered that reaction with hydrogen over a Re-containing multimetallic catalyst resulted in superior conversion and selectivity to desired products such as propylene glycol. A process for the synthesis of PG from lactate or lactic acid is also described.

  8. Hydrogenolysis of 5-carbon sugars, sugar alcohols, and methods of making propylene glycol

    DOE Patents [OSTI]

    Werpy, Todd A [West Richland, WA; Zacher, Alan H [Kennewick, WA

    2006-05-02

    Methods and compositions for reactions of hydrogen over a Re-containing catalyst with compositions containing a 5-carbon sugar, sugar alcohol, or lactic acid are described. It has been surprisingly discovered that reaction with hydrogen over a Re-containing multimetallic catalyst resulted in superior conversion and selectivity to desired products such as propylene glycol. A process for the synthesis of PG from lactate or lactic acid is also described.

  9. Hydrogenolysis of 5-carbon sugars, sugar alcohols, and other methods and compositions for reactions involving hydrogen

    DOE Patents [OSTI]

    Werpy, Todd A [West Richland, WA; Zacher, Alan H [Kennewick, WA

    2002-11-12

    Methods and compositions for reactions of hydrogen over a Re-containing catalyst with compositions containing a 5-carbon sugar, sugar alcohol, or lactic acid are described. It has been surprisingly discovered that reaction with hydrogen over a Re-containing multimetallic catalyst resulted in superior conversion and selectivity to desired products such as propylene glycol. A process for the synthesis of PG from lactate or lactic acid is also described.

  10. miR-339-5p inhibits alcohol-induced brain inflammation through regulating NF-κB pathway

    SciTech Connect (OSTI)

    Zhang, Yu; Wei, Guangkuan; Di, Zhiyong; Zhao, Qingjie

    2014-09-26

    Graphical abstract: - Highlights: • Alcohol upregulates miR-339-5p expression. • miR-339-5p inhibits the NF-kB pathway. • miR-339-5p interacts with and blocks activity of IKK-beat and IKK-epsilon. • miR-339-5p modulates IL-1β, IL-6 and TNF-α. - Abstract: Alcohol-induced neuroinflammation is mediated by the innate immunesystem. Pro-inflammatory responses to alcohol are modulated by miRNAs. The miRNA miR-339-5p has previously been found to be upregulated in alcohol-induced neuroinflammation. However, little has been elucidated on the regulatory functions of this miRNA in alcohol-induced neuroinflammation. We investigated the function of miR-339-5p in alcohol exposed brain tissue and isolated microglial cells using ex vivo and in vitro techniques. Our results show that alcohol induces transcription of miR 339-5p, IL-6, IL-1β and TNF-α in mouse brain tissue and isolated microglial cells by activating NF-κB. Alcohol activation of NF-κB allows for nuclear translocation of the NF-κB subunit p65 and expression of pro-inflammatory mediators. miR-339-5p inhibited expression of these pro-inflammatory factors through the NF-κB pathway by abolishing IKK-β and IKK-ε activity.

  11. Intermediate Alcohol-Gasoline Blends, Fuels for Enabling Increased Engine Efficiency and Powertrain Possibilities

    SciTech Connect (OSTI)

    Splitter, Derek A; Szybist, James P

    2014-01-01

    The present study experimentally investigates spark-ignited combustion with 87 AKI E0 gasoline in its neat form and in mid-level alcohol-gasoline blends with 24% vol./vol. iso-butanol-gasoline (IB24) and 30% vol./vol. ethanol-gasoline (E30). A single-cylinder research engine is used with a low and high compression ratio of 9.2:1 and 11.85:1 respectively. The engine is equipped with hydraulically actuated valves, laboratory intake air, and is capable of external exhaust gas recirculation (EGR). All fuels are operated to full-load conditions with =1, using both 0% and 15% external cooled EGR. The results demonstrate that higher octane number bio-fuels better utilize higher compression ratios with high stoichiometric torque capability. Specifically, the unique properties of ethanol enabled a doubling of the stoichiometric torque capability with the 11.85:1 compression ratio using E30 as compared to 87 AKI, up to 20 bar IMEPg at =1 (with 15% EGR, 18.5 bar with 0% EGR). EGR was shown to provide thermodynamic advantages with all fuels. The results demonstrate that E30 may further the downsizing and downspeeding of engines by achieving increased low speed torque, even with high compression ratios. The results suggest that at mid-level alcohol-gasoline blends, engine and vehicle optimization can offset the reduced fuel energy content of alcohol-gasoline blends, and likely reduce vehicle fuel consumption and tailpipe CO2 emissions.

  12. Method and system for producing lower alcohols. [Heteropolyatomic lead salt coated with alkali metal formate

    DOE Patents [OSTI]

    Rathke, J.W.; Klingler, R.J.; Heiberger, J.J.

    1983-09-26

    It is an object of the present invention to provide an improved catalyst for the reaction of carbon monoxide with water to produce methanol and other lower alcohols. It is a further object to provide a process for the production of methanol from carbon monoxide and water in which a relatively inexpensive catalyst permits the reaction at low pressures. It is also an object to provide a process for the production of methanol from carbon monoxide and water in which a relatively inexpensive catalyst permits the reaction at low pressures. It is also an object to provide a process for the production of methanol in which ethanol is also directly produced. It is another object to provide a process for the production of mixtures of methanol with ethanol and propanol from the reaction of carbon monoxide and water at moderate pressure with inexpensive catalysts. It is likewise an object to provide a system for the catalytic production of lower alcohols from the reaction of carbon monoxide and water at moderate pressure with inexpensive catalysts. In accordance with the present invention, a catalyst is provided for the reaction of carbon monoxide and water to produce lower alcohols. The catalyst includes a lead heteropolyatomic salt in mixture with a metal formate or a precursor to a metal formate.

  13. Activation of farnesoid X receptor attenuates hepatic injury in a murine model of alcoholic liver disease

    SciTech Connect (OSTI)

    Wu, Weibin; Institutes of Biomedical Science, Fudan University, Shanghai 200032 ; Zhu, Bo; Peng, Xiaomin; Zhou, Meiling; Jia, Dongwei; Gu, Jianxin; Institutes of Biomedical Science, Fudan University, Shanghai 200032

    2014-01-03

    Highlights: FXR activity was impaired by chronic ethanol ingestion in a murine model of ALD. Activation of FXR attenuated alcohol-induced liver injury and steatosis. Activation of FXR attenuated cholestasis and oxidative stress in mouse liver. -- Abstract: Alcoholic liver disease (ALD) is a common cause of advanced liver disease, and considered as a major risk factor of morbidity and mortality worldwide. Hepatic cholestasis is a pathophysiological feature observed in all stages of ALD. The farnesoid X receptor (FXR) is a member of the nuclear hormone receptor superfamily, and plays an essential role in the regulation of bile acid, lipid and glucose homeostasis. However, the role of FXR in the pathogenesis and progression of ALD remains largely unknown. Mice were fed Lieber-DeCarli ethanol diet or an isocaloric control diet. We used a specific agonist of FXR WAY-362450 to study the effect of pharmacological activation of FXR in alcoholic liver disease. In this study, we demonstrated that FXR activity was impaired by chronic ethanol ingestion in a murine model of ALD. Activation of FXR by specific agonist WAY-362450 protected mice from the development of ALD. We also found that WAY-362450 treatment rescued FXR activity, suppressed ethanol-induced Cyp2e1 up-regulation and attenuated oxidative stress in liver. Our results highlight a key role of FXR in the modulation of ALD development, and propose specific FXR agonists for the treatment of ALD patients.

  14. Oxidation, Reduction, and Condensation of Alcohols over (MO3)3 (M=Mo, W) Nanoclusters

    SciTech Connect (OSTI)

    Fang, Zongtang; Li, Zhenjun; Kelley, Matthew S.; Kay, Bruce D.; Li, Shenggang; Hennigan, Jamie M.; Rousseau, Roger J.; Dohnalek, Zdenek; Dixon, David A.

    2014-10-02

    The reactions of deuterated methanol, ethanol, 1-propanol, 1-butanol, 2-propanol, 2-butanol and t-butanol over cyclic (MO3)3 (M = Mo, W) clusters were studied experimentally with temperature programmed desorption (TPD) and theoretically with coupled cluster CCSD(T) theory and density functional theory. The reactions of two alcohols per M3O9 cluster are required to provide agreement with experiment for D2O release, dehydrogenation and dehydration. The reaction begins with the elimination of water by proton transfers and forms an intermediate dialkoxy species which can undergo further reaction. Dehydration proceeds by a ? hydrogen transfer to a terminal M=O. Dehydrogenation takes place via an ? hydrogen transfer to an adjacent MoVI = O atom or a WVI metal center with redox involved for M = Mo and no redox for M = W. The two channels have comparable activation energies. H/D exchange to produce alcohols can take place after olefin is released or via the dialkoxy species depending on the alcohol and the cluster. The Lewis acidity of the metal center with WVI being larger than MoVI results in the increased reactivity of W3O9 over Mo3O9 for dehydrogenation and dehydration.

  15. Development of Effective Solvent Modifiers for the Solvent Extraction of Cesium from Alkaline High-Level Tank Waste.

    SciTech Connect (OSTI)

    Bonnesen, Peter V.; Delmau, Laetitia H.; Moyer, Bruce A.; Lumetta, Gregg J. )

    2003-01-01

    A series of novel alkylphenoxy fluorinated alcohols were prepared and investigated for their effectiveness as modifiers in solvents containing calix[4]arene-bis-(tert-octylbenzo)-crown-6 for extracting cesium from alkaline nitrate media. A modifier that contained a terminal 1,1,2,2-tetrafluoroethoxy group was found to decompose following long-term exposure to warm alkaline solutions. However, replacement of the tetrafluoroethoxy group with a 2,2,3,3-tetrafluoropropoxy group led to a series of modifiers that possessed the alkaline stability required for a solvent extraction process. Within this series of modifiers, the structure of the alkyl substituent (tert-octyl, tert-butyl, tert-amyl, and sec-butyl) of the alkylphenoxy moiety was found to have a profound impact on the phase behavior of the solvent in liquid-liquid contacting experiments, and hence on the overall suitability of the modifier for a solvent extraction process. The sec-butyl derivative[1-(2,2,3,3-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol] (Cs-7SB) was found to possess the best overall balance of properties with respect to third phase and coalescence behavior, cleanup following degradation, resistance to solids formation, and cesium distribution behavior. Accordingly, this modifier was selected for use as a component of the solvent employed in the Caustic-Side Solvent Extraction (CSSX) process for removing cesium from high level nuclear waste (HLW) at the U.S. Department of Energy?s (DOE) Savannah River Site. In batch equilibrium experiments, this solvent has also been successfully shown to extract cesium from both simulated and actual solutions generated from caustic leaching of HLW tank sludge stored in tank B-110 at the DOE?s Hanford Site.

  16. The role of acetate in alcohol-induced alterations of uterine glucose metabolism in the mouse during pregnancy

    SciTech Connect (OSTI)

    Simm, B. ); Murdoch, R.N. )

    1990-01-01

    The acute exposure of mice to ethanol during post-implantation pregnancy has been reported to cause alterations in the levels of several glycolytic intermediates in the uterus, suggesting a possible indirect mechanism of alcohol embryo-toxicity. The present study was undertaken to assess whether the ethanol metabolite, acetate is implicated in this phenomenon. Blood and uterine alcohol concentrations in day 9 - pregnant Quackenbush Swiss mice were maximal 15 minutes after the intraperitoneal injection of ethanol, and fell to almost negligible levels 6 hours later. In response to this treatment, the levels of blood and uterine acetate increased, liver glycogen decreased, plasma glucose increased, and uterine glucose, glucose-6-phosphate (G-6-P), fructose-6-phosphate (F-6-P), and citrate increased. When acetate was administered to pregnant mice in amounts approximating those generated by exposure to alcohol, the levels of uterine F-6-P and citrate increased while other metabolic parameters remained unaffected. The administration of 4-methylpyrazole to mice subsequently treated with alcohol produced conditions of alcohol exposure in the absence of ethanol-derived acetate and depressed the ethanol-induced rise in uterine G-6-P and citrate.

  17. Coupling of alcohols to ethers: The dominance of the surface S{sub N}2 reaction pathway

    SciTech Connect (OSTI)

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

    1996-12-31

    Coupling of alcohols to ethers, important high value oxygenates, proceeds on acid catalysts via general pathways that uniquely control product composition, oxygen retention, chirality inversion, and kinetics. The dominant pathway is the S{sub N}2 reaction with competition of the alcohols for the surface acid sites. This is exemplified by formation of methyl(ethyl) isobutylether (M(E)IBE) from methanol(ethanol)/isobutanol mixtures, retention of oxygen ({sup 18}O) of the heavier alcohol, and optimum rate as a function of concentration of either reactant alcohol. The S{sub N}2 pathway in the confinement of zeolite pores exhibits additional features of a near-100% selectivity to dimethylether (DME) in H-mordenite and a near-100% selectivity to chiral inversion in 2-pentanol/ethanol coupling to 2-ethoxypentane in HZSM-5. A minor reaction pathway entails olefin or carbenium intermediates, as exemplified by the formation of methyl tertiarybutyl ether (MTBE) from methanol/isobutanol mixtures with oxygen retention of the lighter alcohol. Calculations of transition state and molecular modeling of the oxonium-involving pathways dramatically demonstrate how the reaction path selects the products.

  18. Global warming impact of gasoline and alcohol use in light-duty highway vehicles in Brazil

    SciTech Connect (OSTI)

    Uria, L.A.B.; Schaeffer, R.

    1997-12-31

    This paper examines the direct and indirect global warming impact of gasoline and alcohol use in light-duty highway vehicles in Brazil. In order to do that, it quantifies emissions of CO{sub 2}, CO{sub 2} HC and NO{sub x} in terms of CO{sub 2}-equivalent units for time spans of 20, 100 and 500 years. It shows that the consideration of CO{sub 2} HC and NO{sub x} emissions in addition to CO{sub 2} provides an important contribution for better understanding the total warming impact of transportation fuels in Brazil.

  19. Alcohol homologation

    DOE Patents [OSTI]

    Wegman, R.W.; Moloy, K.G.

    1988-02-23

    A process is described for the homologation of an alkanol by reaction with synthesis gas in contact with a system containing rhodium atom, ruthenium atom, iodine atom and a bis(diorganophosphino) alkane to selectivity produce the next higher homologue.

  20. Alcohol homologation

    DOE Patents [OSTI]

    Wegman, Richard W.; Moloy, Kenneth G.

    1988-01-01

    A process for the homologation of an alkanol by reaction with synthesis gas in contact with a system containing rhodium atom, ruthenium atom, iodine atom and a bis(diorganophosphino) alkane to selectivity produce the next higher homologue.

  1. High octane ethers from synthesis gas-derived alcohols. Quarterly technical progress report, April--June 1993

    SciTech Connect (OSTI)

    Klier, K.; Herman, R.G.; Menszak, J.; Johansson, M.A.; Feeley, O.C.; Kim, D.

    1993-07-01

    The results shown in Figures 10 and 11 demonstrate that the formation of butenes was very sensitive to the alcohol partial pressure. A small elevation of the alcohol pressure suppressed the formation of butenes rather drastically at both 90 and 117{degree}C. The synthesis rates of DME, MIBE, and MTBE ethers were not significantly affected at 90{degree}C, although there was a trend to increase the space time yield of DME as the alcohol pressure was increased. At the reaction temperature of 117{degree}C, all of the ethers showed increasing productivities as the pressure of the reactants was increased (Figure 11). An isotope labelling experiment was carried out to provide mechanistic insight into the manner in which methanol and isobutanol react together to form DME, MIBE, and MTBE ethers and to determine if MTBE were derived from MIBE.

  2. The potential for alcohols and related ethers to displace conventional gasoline components

    SciTech Connect (OSTI)

    Hadder, G.R.; McNutt, B.D.

    1996-02-01

    The United States Department of Energy is required by law to determine the feasibility of producing sufficient replacement fuels to replace 30 percent of the projected United States consumption of motor fuels by light duty vehicles in the year 2010. A replacement fuel is a non-petroleum portion of gasoline, including alcohols, natural gas and certain other components. A linear program has been used to study refinery impacts for production of ``low petroleum`` gasolines, which contain replacement fuels. The analysis suggests that high oxygenation is the key to meeting the replacement fuel target, and major contributors to cost increase can include investment in processes to produce olefins for etherification with alcohols. High oxygenation can increase the costs of control of vapor pressure, distillation properties, and pollutant emissions of gasolines. Year-round low petroleum gasoline with near-30 percent non-petroleum might be produced with cost increases of 23 to 37 cents per gallon, with substantial decreases in greenhouse gas emissions in some cases. Cost estimates are sensitive to assumptions about extrapolation of a national model for pollutant emissions, availability of raw materials and other issues. Reduction in crude oil use, a major objective of the low petroleum gasoline program, is 10 to 17 percent in the analysis.

  3. Polymer Growth Rate in a Wire Chamber with Oxygen,Water, or Alcohol Gas Additives

    SciTech Connect (OSTI)

    Boyarski, Adam; /SLAC

    2008-07-02

    The rate of polymer growth on wires was measured in a wire chamber while the chamber was aged initially with helium-isobutane (80:20) gas, and then with either oxygen, water, or alcohol added to the gas. At the completion of the aging process for each gas mixture, the carbon content on the wires was measured in a SEM/EDX instrument. The same physical wires were used in all the gas mixtures, allowing measurement of polymer build up or polymer depletion by each gas additive. It is found that the rate of polymer growth is not changed by the presence of oxygen, water or alcohol. Conjecture that oxygen reduces breakdown by removing polymer deposits on field wires is negated by these measurements. Instead, it appears that the reduced breakdown is due to lower resistance in the polymer from oxygen ions being transported into the polymer. It is also observed that field wires bombarded by the electrons in the SEM and then placed back into the chamber show an abundance of single electrons being emitted, indicating that electron charge is stored in the polymer layer and that a high electric field is necessary to remove the charge.

  4. Ascorbic acid suppresses endotoxemia and NF-?B signaling cascade in alcoholic liver fibrosis in guinea pigs: A mechanistic approach

    SciTech Connect (OSTI)

    Abhilash, P.A.; Harikrishnan, R.; Indira, M.

    2014-01-15

    Alcohol consumption increases the small intestinal bacterial overgrowth (SIBO) and intestinal permeability of endotoxin. The endotoxin mediated inflammatory signaling plays a major role in alcoholic liver fibrosis. We evaluated the effect of ascorbic acid (AA), silymarin and alcohol abstention on the alcohol induced endotoxemia and NF-?B activation cascade pathway in guinea pigs (Cavia porcellus). Guinea pigs were administered ethanol at a daily dose of 4 g/kg b.wt for 90 days. After 90 days, ethanol administration was stopped. The ethanol treated animals were divided into abstention, silymarin (250 mg/kg b.wt) and AA (250 mg/kg b.wt) supplemented groups and maintained for 30 days. The SIBO, intestinal permeability and endotoxin were significantly increased in the ethanol group. The mRNA expressions of intestinal proteins claudin, occludin and zona occludens-1 were significantly decreased in ethanol group. The mRNA levels of inflammatory receptors, activity of IKK? and the protein expressions of phospho-I?B?, NF-?B, TNF-?, TGF-?{sub 1} and IL-6 were also altered in ethanol group. The expressions of fibrosis markers ?-SMA, ?{sub 1} (I) collagen and sirius red staining in the liver revealed the induction of fibrosis. But the supplementation of AA could induce greater reduction of ethanol induced SIBO, intestinal barrier defects, NF-?B activation and liver fibrosis than silymarin. The possible mechanism may be the inhibitory effect of AA on SIBO, intestinal barrier defect and IKK?, which decreased the activation of NF-?B and synthesis of cytokines. This might have led to suppression of HSCs activation and liver fibrosis. - Highlights: Alcohol increases intestinal bacterial overgrowth and permeability of endotoxin. Endotoxin mediated inflammation plays a major role in alcoholic liver fibrosis. Ascorbic acid reduces endotoxemia, NF-?B activation and proinflammatory cytokines. AA's action is by inhibition of SIBO, IKK? and alteration of intestinal permeability. This might have led to suppression of HSCs activation and liver fibrosis.

  5. Structural and phase transition changes of sodium dodecyl sulfate micellar solution in alcohols probed by small-angle neutron scattering (SANS)

    SciTech Connect (OSTI)

    Putra, Edy Giri Rachman; Patriati, Arum

    2015-04-16

    Small-angle neutron scattering (SANS) measurements on 0.3M sodium dodecyl sulfate (SDS) micellar solutions have been performed in the presence of n-alcohols, from ethanol to decanol at different alcohol concentrations, 210 wt%. The ellipsoid micellar structure which occurred in the 0.3M SDS in aqueous solution with the size range of 3050 has different behavior at various hydrocarbon chain length and concentration of alcohols. At low concentration and short chain-length of alcohols, such as ethanol, propanol, and butanol, the size of micelles reduced and had a spherical-like structure. The opposite effect occurred as medium to long chain alcohols, such as hexanol, octanol and decanol was added into the 0.3M SDS micellar solutions. The micelles structure changed to be more elongated in major axis and then crossed the critical phase transition from micellar solution into liquid crystal phase as lamellar structure emerged by further addition of alcohols. The inter-lamellar distances were also depending on the hydrocarbon chain length and concentration of alcohols. In the meantime, the persistent micellar structures occurred in addition of medium chain of n-alcohol, pentanol at all concentrations.

  6. Alkylation damage repair in mammalian genomes

    SciTech Connect (OSTI)

    Mitra, S.; Roy, R.; Kim, N.K. |; Tano, K. |; Ibeanu, G.C. |; Dunn, W.C.; Natarajan, A.T.; Hartenstein, B.; Kaina, B.

    1992-11-01

    The repair of O{sup 6} -alkylguanine in DNA involves only O{sup 6} -methyltransferase (MGMT) while the repair of N-alkylpurines requires multiple proteins including N-methylpurine-DNA glycosylase (MPG). While the biochemical properties human and mouse MGMTs are very similar, the mouse MPG removes 7-methylguanine more efficiently than the human protein. An increased level of MGMT, without a change in the level of MPG associated with gene amplification, was observed in a mouse cell line resistant to 2-chloroethyl-N-nitrosourea. In contrast, no correlation was observed between MPG level and resistance to methyl methanesulfonate in Chinese hamster ovary (CHO) cells. This result suggests a protein other than MPG limits the repair rate of N-alkylpurine in CHO cells.

  7. Alkylation damage repair in mammalian genomes

    SciTech Connect (OSTI)

    Mitra, S.; Roy, R.; Kim, N.K. . Sealy Center for Molecular Science Oak Ridge National Lab., TN ); Tano, K. Oak Ridge National Lab., TN ); Ibeanu, G.C. Oak Ridge National Lab., TN ); Dunn, W.C. (

    1992-01-01

    The repair of O{sup 6} -alkylguanine in DNA involves only O{sup 6} -methyltransferase (MGMT) while the repair of N-alkylpurines requires multiple proteins including N-methylpurine-DNA glycosylase (MPG). While the biochemical properties human and mouse MGMTs are very similar, the mouse MPG removes 7-methylguanine more efficiently than the human protein. An increased level of MGMT, without a change in the level of MPG associated with gene amplification, was observed in a mouse cell line resistant to 2-chloroethyl-N-nitrosourea. In contrast, no correlation was observed between MPG level and resistance to methyl methanesulfonate in Chinese hamster ovary (CHO) cells. This result suggests a protein other than MPG limits the repair rate of N-alkylpurine in CHO cells.

  8. Synergistic interaction between oxides of copper and iron for production of fatty alcohols from fatty acids

    SciTech Connect (OSTI)

    Kandel, Kapil; Chaudhary, Umesh; Nelson, Nicholas C.; Slowing, Igor I.

    2015-10-08

    In this study, the selective hydrogenation of fatty acids to fatty alcohols can be achieved under moderate conditions (180 °C, 30 bar H2) by simultaneously supporting copper and iron oxides on mesoporous silica nanoparticles. The activity of the cosupported oxides is significantly higher than that of each supported metal oxide and of a physical mixture of both individually supported metal oxides. A strong interaction between both metal oxides is evident from dispersion, XRD, TPR, and acetic acid TPD measurements, which is likely responsible for the synergistic behavior of the catalyst. Copper oxide is reduced in situ to its metallic form and thereby activates hydrogen.

  9. Adsorption of various alcohols on Illinois No. 6 coal in aqueous solutions

    SciTech Connect (OSTI)

    Kwon, K.C.; Rigby, R.R.

    1993-07-01

    Hydrophilicity, hydrophobicity and aromacity of Illinois {number_sign}6 coal in water are relatively determined by evaluating equilibrium physical/chemical adsorption of probe compounds on the coal. Experiments on equilibrium adsorption loadings of various additives on 60--200 mesh Illinois {number_sign}6 coal (DECS-2; Randolph county) were performed to investigate relatively surface properties of the coal at 25{degree}C. The additives include various alcohols, alkanes and aromatic compounds. The main objectives of this research are to evaluate relatively surface properties of raw coals, treated coals and coal minerals with the inverse liquid chromatography technique, using various probe compounds, to analyze flotation recoveries of coals with a micro-flotation apparatus in order to relate coal floatability to evaluated coal surface properties, and to delineate roles of coal-cleaning/handling additives with the inverse liquid chromatography technique.

  10. Optimization of Rhodium-Based Catalysts for Mixed Alcohol Synthesis -- 2011 Progress Report

    SciTech Connect (OSTI)

    Gerber, Mark A.; Gray, Michel J.; Albrecht, Karl O.; Rummel, Becky L.

    2011-10-01

    Pacific Northwest National Laboratory has been conducting research to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas (syngas). In recent years, this research has primarily involved the further development of catalysts containing rhodium and manganese based on the results of earlier catalyst screening tests. Research during FY 2011 continued to examine the performance of RhMn catalysts on alternative supports including selected zeolite, silica, and carbon supports. Catalyst optimization continued using both the Davisil 645 and Merck Grade 7734 silica supports. Research also was initiated in FY 2011, using the both Davisil 645 silica and Hyperion CS-02C-063 carbon supports, to evaluate the potential for further improving catalyst performance, through the addition of one or two additional metals as promoters to the catalysts containing Rh, Mn, and Ir.

  11. Liquid Fuel From Renewable Electricity and Bacteria: Electro-Autotrophic Synthesis of Higher Alcohols

    SciTech Connect (OSTI)

    2010-07-01

    Electrofuels Project: UCLA is utilizing renewable electricity to power direct liquid fuel production in genetically engineered Ralstonia eutropha bacteria. UCLA is using renewable electricity to convert carbon dioxide into formic acid, a liquid soluble compound that delivers both carbon and energy to the bacteria. The bacteriaare genetically engineered to convert the formic acid into liquid fuelin this case alcohols such as butanol. The electricity required for the process can be generated from sunlight, wind, or other renewable energy sources. In fact, UCLAs electricity-to-fuel system could be a more efficient way to utilize these renewable energy sources considering the energy density of liquid fuel is much higher than the energy density of other renewable energy storage options, such as batteries.

  12. Optimization of Rhodium-Based Catalysts for Mixed Alcohol Synthesis 2012 Progress Report

    SciTech Connect (OSTI)

    Gerber, Mark A.; Gray, Michel J.; Albrecht, Karl O.; Thompson, Becky L.

    2012-11-01

    Pacific Northwest National Laboratory has been conducting research to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas (syngas). In recent years, this research has primarily involved the further development of catalysts containing rhodium and manganese based on the results of earlier catalyst screening tests. Testing continued in FY 2012 to further improve the Ir-promoted RhMn catalysts on both silica and carbon supports for producing mixed oxygenates from synthesis gas. This testing re-examined selected alternative silica and carbon supports to follow up on some uncertainties in the results with previous test results. Additional tests were conducted to further optimize the total and relative concentrations of Rh, Mn, and Ir, and to examine selected promoters and promoter combinations based on earlier results. To establish optimum operating conditions, the effects of the process pressure and the feed gas composition also were evaluated.

  13. Optimization of Rhodium-Based Catalysts for Mixed Alcohol Synthesis -- 2010 Progress Report

    SciTech Connect (OSTI)

    Gerber, Mark A.; Gray, Michel J.; Albrecht, Karl O.; White, J. F.; Rummel, Becky L.; Stevens, Don J.

    2010-10-01

    Pacific Northwest National Laboratory has been conducting research for the U.S. Department of Energy, Energy Efficiency Renewable Energy, Biomass Program to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas. In recent years this research has primarily involved the further development of a silica-supported catalyst containing rhodium and manganese that was selected from earlier catalyst screening tests. A major effort during 2010 was to examine alternative catalyst supports to determine whether other supports, besides the Davisil 645 silica, would improve performance. Optimization of the Davisil 645 silica-supported catalyst also was continued with respect to candidate promoters iridium, platinum, and gallium, and examination of selected catalyst preparation and activation alternatives for the baseline RhMn/SiO2 catalyst.

  14. Synergistic interaction between oxides of copper and iron for production of fatty alcohols from fatty acids

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

    Kandel, Kapil; Chaudhary, Umesh; Nelson, Nicholas C.; Slowing, Igor I.

    2015-10-08

    In this study, the selective hydrogenation of fatty acids to fatty alcohols can be achieved under moderate conditions (180 °C, 30 bar H2) by simultaneously supporting copper and iron oxides on mesoporous silica nanoparticles. The activity of the cosupported oxides is significantly higher than that of each supported metal oxide and of a physical mixture of both individually supported metal oxides. A strong interaction between both metal oxides is evident from dispersion, XRD, TPR, and acetic acid TPD measurements, which is likely responsible for the synergistic behavior of the catalyst. Copper oxide is reduced in situ to its metallic formmore » and thereby activates hydrogen.« less

  15. Feasibility study of fuel grade ethanol plant for Alcohol Fuels of Mississippi, Inc. , Vicksburg, Mississippi

    SciTech Connect (OSTI)

    None

    1981-01-01

    The results are presented of a feasibility study performed to determine the technical and economic viability of constructing an alcohol plant utilizing the N.Y.U. continuous acid hydrolysis process to convert wood wastes to fuel grade alcohol. The following is a summary of the results: (1) The proposed site in the Vicksburg Industrial Foundation Corporation Industrial Park is adequate from all standpoints, for all plant capacities envisioned. (2) Local hardwood sawmills can provide adequate feedstock for the facility. The price per dry ton varies between $5 and $15. (3) Sale of fuel ethanol would be made primarily through local distributors and an adequate market exists for the plant output. (4) With minor modifications to the preparation facilities, other waste cellulose materials can also be utilized. (5) There are no anticipated major environmental, health, safety or socioeconomic risks related to the construction and operation of the proposed facility. (6) The discounted cash flow and rate of return analysis indicated that the smallest capacity unit which should be built is the 16 million gallon per year plant, utilizing cogeneration. This facility has a 3.24 year payback. (7) The 25 million gallon per year plant utilizing cogeneration is an extremely attractive venture, with a zero interest break-even point of 1.87 years, and with a discounted rate of return of 73.6%. (8) While the smaller plant capacities are unattractive from a budgetary viewpoint, a prudent policy would dictate that a one million gallon per year plant be built first, as a demonstration facility. This volume contains process flowsheets and maps of the proposed site.

  16. Evaluation of Promoters for Rhodium-Based Catalysts for Mixed Alcohol Synthesis

    SciTech Connect (OSTI)

    Gerber, Mark A.; White, James F.; Gray, Michel J.; Stevens, Don J.

    2008-12-08

    Pacific Northwest National Laboratory (PNNL) and National Renewable Energy Laboratory (NREL) are conducting research to investigate the feasibility of producing mixed alcohols from biomass-derived synthesis gas (syngas). PNNL is tasked with obtaining commercially-available catalysts or preparing promising mixed-alcohol catalysts and screening them in a laboratory-scale reactor system. Commercially-available catalysts and the most promising experimental catalysts are provided to NREL for testing using a slipstream from a pilot-scale biomass gasifier. A total of 28 tests were conducted to evaluate 22 different promoters as well as an unpromoted catalyst. The following general trends were observed for the test results: The highest carbon selectivity to C2+ oxygenates occurred at the lowest reaction temperatures and accompanying lowest space time yields (STYs). The lowest carbon selectivity to C2+ oxygenates occurred at the highest reaction temperatures because of high carbon conversion to hydrocarbons. The highest C2+-oxygenate STYs occurred between 300C and 325C, with the gas hourly space velocity (GHSV) adjusted when necessary to maintain carbon conversion ranges between ~ 30 and 40 percent. Higher carbon selectivity to hydrocarbons at higher temperatures resulted in lower C2+-oxygenate STYs. When catalysts were heated to between 300C and 325C the catalysts showed evidence of some deactivation with respect to C2+ oxygenate productivity, accompanied by reduced chain growth for the hydrocarbon products. The degree of deactivation and the temperature at which it occurred varied between the different catalysts tested. Of all of the catalysts evaluated, the Li-promoted catalysts had the highest carbon selectivity to C2+ oxygenates (47 percent) under the conditions at which the maximum C2+-oxygenate STYs were obtained.

  17. H.R. 5299: A Bill to amend the Internal Revenue Code of 1986 to phase out the tax subsidies for alcohol fuels involving alcohol produced from feedstocks eligible to receive Federal agricultural subsidies. Introduced in the House of Representatives, One Hundred Third Congress, Second Session, November 29, 1994

    SciTech Connect (OSTI)

    1994-12-31

    The report H.R. 5299 is a bill to amend the Internal Revenue Code of 1986 to phase out the tax subsidies of alcohol fuels involving alcohol produced from feedstocks eligible to receive Federal agriculture subsidies. The proposed legislative text is included.

  18. Direct Conversion of Syngas-to-Hydrocarbons over Higher Alcohols Synthesis Catalysts Mixed with HZSM-5

    SciTech Connect (OSTI)

    Lebarbier Dagel, Vanessa M.; Dagle, Robert A.; Li, Jinjing; Deshmane, Chinmay A.; Taylor, Charles E.; Bao, Xinhe; Wang, Yong

    2014-09-10

    The synthesis of hydrocarbon fuels directly from synthesis gas (i.e. one step process) was investigated with a catalytic system comprised of HZSM-5 physically mixed with either a methanol synthesis catalyst or a higher alcohols synthesis (HAS) catalyst. The metal sites of the methanol or HAS synthesis catalyst enable the conversion of syngas to alcohols, whereas HZSM-5 provides acid sites required for methanol dehydration, and dimethyl ether-to-hydrocarbons reactions. Catalytic performance for HZSM-5 when mixed with either a 5 wt.% Pd/ZnO/Al2O3 methanol synthesis catalyst or a HAS catalyst was evaluated at 300C, 70 bars, GHSV=700 h-1 and H2/CO=1 using a HZSM-5: alcohols synthesis catalyst weight ratio of 3:1. The major difference observed between the methanol synthesis and HAS catalyst mixtures was found in the production of durene which is an undesirable byproduct. While durene formation is negligible with any of the HAS catalysts mixed with the HZSM-5 evaluated in this study, it represents almost 50% of the C5+ fraction for the methanol synthesis catalyst (5 wt.% Pd/ZnO/Al2O3 ) mixed with HZSM-5. This presents an advantage for using HAS catalysts over the methanol synthesis catalyst to minimize the durene by-product. The yield toward the desired C5+ hydrocarbons is thus twice higher with selected HAS catalysts as compared to when HZSM-5 is mixed with 5 wt.% Pd/ZnO/Al2O3. Among all the HAS catalysts evaluated in this study, a catalyst with 0.5 wt.% Pd/FeCoCu catalyst was found the most promising due to higher production of C5+ hydrocarbons and low durene formation. The efficiency of the one-step process was thus further evaluated using the HZSM-5: 0.5 wt.% Pd/FeCoCu catalyst mixture under a number of process conditions to maximize liquid hydrocarbons product yield. At 300oC, 70 bars, GHSV = 700 h-1 and HZSM-5: 0.5 wt.% Pd/FeCoCu = 3:1 (wt.), the C5+ fraction represents 48.5% of the hydrocarbons. Unfortunately, it is more difficult to achieve higher selectivity to desired C5+ hydrocarbons as the formation of CO2, CH4, and other light hydrocarbons is challenging to suppress in the presence of mixed metal and acid sites. When the 0.5 wt.% Pd/FeCoCu and HZSM-5 are operated sequentially by way of a two-step process the C5+ hydrocarbons fraction is lower and represents 30.4% of the hydrocarbons under comparable conditions. The yield toward the C5+ hydrocarbons is twice higher for the one-step process due to an improved CO conversion and higher C5+ hydrocarbons fraction. The main advantage of the one-step process is that higher syngas conversion can be achieved as the equilibrium-driven conversion limitations for methanol and dimethyl ether are removed since they are intermediates to the final hydrocarbons product.

  19. Gel electrophoretic analysis of Zymomonas mobilis glycolytic and fermentative enzymes: Identification of alcohol dehydrogenase II as a stress protein

    SciTech Connect (OSTI)

    Haejung An; Keshav, K.F.; Ingram, L.O. ); Scopes, R.K.; Rodriguez, M. )

    1991-10-01

    The 13 major enzymes which compose the glycolytic and fermentative pathways in Zymomonas mobilis are particularly abundant and represent one-half of the soluble protein in exponential-phase cells. One- and two-dimensional polyacrylamide gel electrophoresis maps were developed for 12 of these enzymes. Assignments were made by comigration with purified proteins, comparison with overexpressed genes in recombinant strains, and Western blots (immunoblots). Although most glycolytic enzymes appeared resistant to turnover and accumulated in stationary-phase cells, the protein levels of pyruvate kinase, alcohol dehydrogenase I, and glucokinase declined. Alcohol dehydrogenase II was identified as a major stress protein and was induced both by exposure to ethanol and by elevated temperature (45C). This enzyme, encoded by the adhB gene, is expressed from tandem promoters which share partial sequence identity with Escherichia coli consensus sequence for heat shock proteins.

  20. Alcohol decreases baseline brain glucose metabolism more in heavy drinkers than controls but has no effect on stimulation-induced metabolic increases

    SciTech Connect (OSTI)

    Volkow, Nora D.; Fowler, Joanna S.; Wang, Gene-Jack; Kojori, Eshan Shokri; Benveniste, Helene; Tomasi, Dardo

    2015-02-18

    During alcohol intoxication the human brain increases metabolism of acetate and decreases metabolism of glucose as energy substrate. Here we hypothesized that chronic heavy drinking facilitates this energy substrate shift both for baseline and stimulation conditions. To test this hypothesis we compared the effects of alcohol intoxication (0.75g/kg alcohol versus placebo) on brain glucose metabolism during video-stimulation (VS) versus when given with no-stimulation (NS), in 25 heavy drinkers (HD) and 23 healthy controls each of whom underwent four PET-?FDG scans. We showed that resting whole-brain glucose metabolism (placebo-NS) was lower in HD than controls (13%, p=0.04); that alcohol (compared to placebo) decreased metabolism more in HD (2013%) than controls (911%, p=0.005) and in proportion to daily alcohol consumption (r=0.36, p=0.01) but found that alcohol did not reduce the metabolic increases in visual cortex from VS in either group. Instead, VS reduced alcohol-induced decreases in whole-brain glucose metabolism (1012%) compared to NS in both groups (1513%, p=0.04), consistent with stimulation-related glucose metabolism enhancement. These findings corroborate our hypothesis that heavy alcohol consumption facilitates use of alternative energy substrates (i.e. acetate) for resting activity during intoxication, which might persist through early sobriety, but indicate that glucose is still favored as energy substrate during brain stimulation. Our findings are consistent with reduced reliance on glucose as the main energy substrate for resting brain metabolism during intoxication (presumably shifting to acetate or other ketones) and a priming of this shift in heavy drinkers, which might make them vulnerable to energy deficits during withdrawal.

  1. Alcohol decreases baseline brain glucose metabolism more in heavy drinkers than controls but has no effect on stimulation-induced metabolic increases

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

    Volkow, Nora D.; Fowler, Joanna S.; Wang, Gene-Jack; Kojori, Eshan Shokri; Benveniste, Helene; Tomasi, Dardo

    2015-02-18

    During alcohol intoxication the human brain increases metabolism of acetate and decreases metabolism of glucose as energy substrate. Here we hypothesized that chronic heavy drinking facilitates this energy substrate shift both for baseline and stimulation conditions. To test this hypothesis we compared the effects of alcohol intoxication (0.75g/kg alcohol versus placebo) on brain glucose metabolism during video-stimulation (VS) versus when given with no-stimulation (NS), in 25 heavy drinkers (HD) and 23 healthy controls each of whom underwent four PET-¹⁸FDG scans. We showed that resting whole-brain glucose metabolism (placebo-NS) was lower in HD than controls (13%, p=0.04); that alcohol (compared tomore » placebo) decreased metabolism more in HD (20±13%) than controls (9±11%, p=0.005) and in proportion to daily alcohol consumption (r=0.36, p=0.01) but found that alcohol did not reduce the metabolic increases in visual cortex from VS in either group. Instead, VS reduced alcohol-induced decreases in whole-brain glucose metabolism (10±12%) compared to NS in both groups (15±13%, p=0.04), consistent with stimulation-related glucose metabolism enhancement. These findings corroborate our hypothesis that heavy alcohol consumption facilitates use of alternative energy substrates (i.e. acetate) for resting activity during intoxication, which might persist through early sobriety, but indicate that glucose is still favored as energy substrate during brain stimulation. Our findings are consistent with reduced reliance on glucose as the main energy substrate for resting brain metabolism during intoxication (presumably shifting to acetate or other ketones) and a priming of this shift in heavy drinkers, which might make them vulnerable to energy deficits during withdrawal.« less

  2. Alcohol decreases baseline brain glucose metabolism more in heavy drinkers than controls but has no effect on stimulation-induced metabolic increases

    SciTech Connect (OSTI)

    Volkow, Nora D.; Fowler, Joanna S.; Wang, Gene-Jack; Kojori, Eshan Shokri; Benveniste, Helene; Tomasi, Dardo

    2015-02-18

    During alcohol intoxication the human brain increases metabolism of acetate and decreases metabolism of glucose as energy substrate. Here we hypothesized that chronic heavy drinking facilitates this energy substrate shift both for baseline and stimulation conditions. To test this hypothesis we compared the effects of alcohol intoxication (0.75g/kg alcohol versus placebo) on brain glucose metabolism during video-stimulation (VS) versus when given with no-stimulation (NS), in 25 heavy drinkers (HD) and 23 healthy controls each of whom underwent four PET-¹⁸FDG scans. We showed that resting whole-brain glucose metabolism (placebo-NS) was lower in HD than controls (13%, p=0.04); that alcohol (compared to placebo) decreased metabolism more in HD (20±13%) than controls (9±11%, p=0.005) and in proportion to daily alcohol consumption (r=0.36, p=0.01) but found that alcohol did not reduce the metabolic increases in visual cortex from VS in either group. Instead, VS reduced alcohol-induced decreases in whole-brain glucose metabolism (10±12%) compared to NS in both groups (15±13%, p=0.04), consistent with stimulation-related glucose metabolism enhancement. These findings corroborate our hypothesis that heavy alcohol consumption facilitates use of alternative energy substrates (i.e. acetate) for resting activity during intoxication, which might persist through early sobriety, but indicate that glucose is still favored as energy substrate during brain stimulation. Our findings are consistent with reduced reliance on glucose as the main energy substrate for resting brain metabolism during intoxication (presumably shifting to acetate or other ketones) and a priming of this shift in heavy drinkers, which might make them vulnerable to energy deficits during withdrawal.

  3. Sterically shielded diboron-containing metallocene olefin polymerization catalysts

    DOE Patents [OSTI]

    Marks, Tobin J. (Evanston, IL); Ja, Li (Chicago, IL); Yang, Xinmin (Evanston, IL)

    1995-09-05

    A non-coordinating anion, preferably containing a sterically shielded diboron hydride, if combined with a cyclopenta-dienyl-substituted metallocene cation component, such as a zirconocene metallocene, is a useful olefin polymerization catalyst component. The anion preferably has the formula ##STR1## where R is branched lower alkyl, such as t-butyl.

  4. Room temperature alcohol sensing by oxygen vacancy controlled TiO{sub 2} nanotube array

    SciTech Connect (OSTI)

    Hazra, A.; Dutta, K.; Bhowmik, B.; Bhattacharyya, P.; Chattopadhyay, P. P.

    2014-08-25

    Oxygen vacancy (OV) controlled TiO{sub 2} nanotubes, having diameters of 5070?nm and lengths of 200250?nm, were synthesized by electrochemical anodization in the mixed electrolyte comprising NH{sub 4}F and ethylene glycol with selective H{sub 2}O content. The structural evolution of TiO{sub 2} nanoforms has been studied by field emission scanning electron microscopy. Variation in the formation of OVs with the variation of the structure of TiO{sub 2} nanoforms has been evaluated by photoluminescence and X-ray photoelectron spectroscopy. The sensor characteristics were correlated to the variation of the amount of induced OVs in the nanotubes. The efficient room temperature sensing achieved by the control of OVs of TiO{sub 2} nanotube array has paved the way for developing fast responding alcohol sensor with corresponding response magnitude of 60.2%, 45.3%, and 36.5% towards methanol, ethanol, and 2-propanol, respectively.

  5. Transsinusoidal Portal Vein Embolization with Ethylene Vinyl Alcohol Copolymer (Onyx): A Feasibility Study in Pigs

    SciTech Connect (OSTI)

    Smits, Maarten L. J.; Vanlangenhove, Peter Sturm, Emiel J. C.; Bosch, Maurice A. A. J. van den; Hav, Monirath Praet, Marleen; Vente, Maarten A. D.; Snaps, Frederic R.; Defreyne, Luc

    2012-10-15

    Purpose: Portal vein embolization is performed to increase the future liver remnant before liver surgery in patients with liver malignancies. This study assesses the feasibility of a transsinusoidal approach for portal vein embolization (PVE) with the ethylene vinyl alcohol copolymer, Onyx. Methods: Indirect portography through contrast injection in the cranial mesenteric artery was performed in eight healthy pigs. Onyx was slowly injected through a microcatheter from a wedged position in the hepatic vein and advanced through the liver lobules into the portal system. The progression of Onyx was followed under fluoroscopy, and the extent of embolization was monitored by indirect portography. The pigs were euthanized immediately (n = 2), at 7 days (n = 4), or at 21 days postprocedure (n = 2). All pigs underwent necropsy and the ex vivo livers were grossly and histopathologically analyzed. Results: Transsinusoidal PVE was successfully performed in five of eight pigs (63%). In 14 of 21 injections (67%), a segmental portal vein could be filled completely. A mean of 1.6 liver lobes per pig was embolized (range 1-2 lobes). There were no periprocedural adverse events. Focal capsular scarring was visible on the surface of two resected livers, yet the capsules remained intact. Histopathological examination showed no signs of recanalization or abscess formation. Mild inflammatory reaction to Onyx was observed in the perivascular parenchyma. Conclusions: The porcine portal vein can be embolized through injection of Onyx from a wedged position in the hepatic vein. Possible complications of transsinusoidal PVE and the effect on contralateral hypertrophy need further study.

  6. Molecular control of the induction of alcohol dehydrogenase by ethanol in Drosophila melanogaster larvae

    SciTech Connect (OSTI)

    Kapoun, A.M.; Geer, B.W.; Heinstra, P.W.H. ); Corbin, V. ); McKechnie, S.W. )

    1990-04-01

    The activity of alcohol dehydrogenase, the initial enzyme in the major pathway for ethanol degradation, is induced in Drosophila melanogaster larvae by low concentrations of dietary ethanol. Two lines of evidence indicate that the metabolic products of the ADH pathway for ethanol degradation are not directly involved in the induction of Adh. First, the accumulation of the proximal transcript in Adh{sup n2} larvae was increased when the intracellular level of ethanol was elevated. In addition, the ADH activity, the proximal Adh mRNA, and the intracellular concentration of ethanol were elevated coordinately in wild-type larvae fed hexadeuterated-ethanol, which is metabolized more slowly than normal ethanol.l An examination of P element transformant lines with specific deletions in the 5{prime} regulatory DNA of the Adh gene showed that the DNA sequence between +604 and +634 of the start site of transcription from the distal promoter was essential for this induction. The DNA sequence between {minus}660 and about {minus}5,000 of the distal transcript start site was important for the down-regulation of the induction response.

  7. Oxidative Mineralization and Characterization of Polyvinyl Alcohol Solutions for Wastewater Treatment

    SciTech Connect (OSTI)

    Oji, L.N.

    2003-08-07

    Photochemical and ultrasonic treatment of polyvinyl alcohol (PVA), derived from PVA fabric material, with hydrogen peroxide was evaluated as a primary method for PVA mineralization into simpler organic molecules. PVA-based waste streams have been found to be compatible with nuclear process wastewater treatment facilities only when solubilized PVA is more than 90 percent mineralized with hydrogen peroxide. No undesirable solid particles are formed with other nuclear process liquid waste when they are mixed, pH adjusted, evaporated and blended with this type of oxidized PVA waste streams. The presence of oxidized PVA in a typical nuclear process wastewater has been found to have no detrimental effect on the efficiency of ion exchange resins, inorganic, and precipitation agents used for the removal of radionuclides from nuclear waste streams. The disappearance of PVA solution in hydrogen peroxide with ultrasonic/ ultraviolet irradiation treatment was characterized by pseudo-first-order reaction kinetics. Radioactive waste contaminated PVA fabric can be solubilized and mineralized to produce processible liquid waste, hence, no bulky solid waste disposal cost can be incurred and the radionuclides can be effectively recovered. Therefore, PVA fabric materials can be considered as an effective substitute for cellulose fabrics that are currently used in radioactive waste decontamination processes.

  8. CHARACTERIZATION OF PHASE AND EMULSION BEHAVIOR, SURFACTANT RETENTION, AND OIL RECOVERY FOR NOVEL ALCOHOL ETHOXYCARBOXYLATE SURFACTANTS

    SciTech Connect (OSTI)

    LEBONE MOETI; RAMANATHAN SAMPATH

    1998-11-01

    This semi-annual technical progress report describes work performed at Clark Atlanta University under DOE Grant No. DE-FG26-97FT97278 during the period April 01, 1998 to October 01, 1998 which covers the second six months of the project. Presently work is in progress at the EOR Laboratory, Clark Atlanta University (CAU), to characterize phase and emulsion behavior for a novel, hybrid (ionic/non-ionic), alcohol ethoxycarboxylate surfactant (NEODOX 23-4 from Shell Chemical Company). During this reporting period, salinity scans were completed for 0, 5, 10, 20, 50, 100, 250, 500, 1000, 2000, 3000, 4000, 5000, and 6000 mM salt concentrations at 20, 25, and 30 C to identify optimal salinity intervals in which all three phases coexist for this surfactant. Temperature scans were also performed at 20 mM salt concentration for various surfactant concentrations ranging from 0 to 60 weight percent at temperatures ranging from 5 to 50 C to identify optimal surfactant concentration and temperature intervals in which all three phases coexist. This resulted in an "alpha" curve with an interval of temperature in which all three phases coexisted. Presently, temperature scans are being repeated at 100, 250, 500, 1000, and 5000 mM salt concentrations to see whether increase in salt concentration has any effect on the temperature interval. This will provide us better understanding and experimental control of the many variables involved in this research in the future. Following completion of the temperature scans, phase studies will be conducted at CAU, and coreflooding experiments at the facility of our industrial partner, Surtek, Golden, CO.

  9. Novel Characterization of GDI Engine Exhaust for Gasoline and Mid-Level Gasoline-Alcohol Blends

    SciTech Connect (OSTI)

    Storey, John Morse; Lewis Sr, Samuel Arthur; Szybist, James P; Thomas, John F; Barone, Teresa L; Eibl, Mary A; Nafziger, Eric J; Kaul, Brian C

    2014-01-01

    Gasoline direct injection (GDI) engines can offer improved fuel economy and higher performance over their port fuel-injected (PFI) counterparts, and are now appearing in increasingly more U.S. and European vehicles. Small displacement, turbocharged GDI engines are replacing large displacement engines, particularly in light-duty trucks and sport utility vehicles, in order for manufacturers to meet more stringent fuel economy standards. GDI engines typically emit the most particulate matter (PM) during periods of rich operation such as start-up and acceleration, and emissions of air toxics are also more likely during this condition. A 2.0 L GDI engine was operated at lambda of 0.91 at typical loads for acceleration (2600 rpm, 8 bar BMEP) on three different fuels; an 87 anti-knock index (AKI) gasoline (E0), 30% ethanol blended with the 87 AKI fuel (E30), and 48% isobutanol blended with the 87 AKI fuel. E30 was chosen to maximize octane enhancement while minimizing ethanol-blend level and iBu48 was chosen to match the same fuel oxygen level as E30. Particle size and number, organic carbon and elemental carbon (OC/EC), soot HC speciation, and aldehydes and ketones were all analyzed during the experiment. A new method for soot HC speciation is introduced using a direct, thermal desorption/pyrolysis inlet for the gas chromatograph (GC). Results showed high levels of aromatic compounds were present in the PM, including downstream of the catalyst, and the aldehydes were dominated by the alcohol blending.

  10. Pregnancy Following Uterine Artery Embolization with Polyvinyl Alcohol Particles for Patients with Uterine Fibroid or Adenomyosis

    SciTech Connect (OSTI)

    Kim, Man Deuk Kim, Nahk Keun; Kim, Hee Jin; Lee, Mee Hwa

    2005-06-15

    Purpose:To determine whether uterine fibroid embolization (UFE) with polyvinyl alcohol (PVA) particles affects fertility in women desiring future pregnancy.Methods:Of 288 patients managed with UFE with PVA particles for uterine myoma or adenomyosis between 1998 and 2001, 94 patients were enrolled in this study. The age range of participants was 20-40 years. The data were collected through review of medical records and telephone interviews. Mean duration of follow-up duration was 35 months (range 22-60 months). Patients using contraception and single women were excluded, and the chance of infertility caused by possible spousal infertility or other factors was disregarded. Contrast-enhanced magnetic resonance imaging was performed in all patients before and after UFE, and the size of PVA particles used was 255-700 {mu}m.Results:Among 94 patients who underwent UFE with PVA, 74 were on contraceptives, 6 had been single until the point of interview, and 8 were lost to follow-up. Of the remaining 6 patients who desired future pregnancy, 5 (83%) succeeded in becoming pregnant (1 patient became pregnant twice). Of a total of 8 pregnancies, 6 were planned pregnancies and 2 occurred after contraception failed. Five deliveries were vaginal, and 2 were by elective cesarean. Artificial abortion was performed in 1 case of unplanned pregnancy. There was 1 case of premature rupture of membrane (PROM) followed by preterm labor and delivery of an infant who was small-for-gestational-age. After UFE, mean volume reduction rates of the uterus and fibroid were 36.6% (range 0 to 62.6%) and 69.3% (range 36.3% to 93.3%), respectively.Conclusion:Although the absolute number of cases was small, UFE with PVA particles ultimately did not affect fertility in the women who underwent the procedure.

  11. Vicarious nucleophilic substitution to prepare 1,3-diamino-2,4,6-trinitrobenzene or 1,3,5-triamino-2,4,6-trinitrobenzene

    DOE Patents [OSTI]

    Mitchell, Alexander R. (Livermore, CA); Pagoria, Philip F. (Livermore, CA); Schmidt, Robert D. (Livermore, CA)

    1996-01-01

    The present invention relates to a process to produce 1,3-diamino-2,4,6-trinitrobenzene (DATB) or 1,3,5-triamino-2,4,6,-trinitrobenzene (TATB) by: (a) reacting at ambient pressure and a temperature of between about 0.degree. and 50.degree. C. for between about 0.1 and 24 hr, a trinitroaromatic compound of structure V: ##STR1## wherein X, Y, and Z are each independently selected from --H, or --NH.sub.2, with the proviso that at least 1 or 2 of X, Y, and Z are hydrogen, with an amount effective to produce DATB or TATB of 1,1,1-trialkylhydrazinium halide wherein alkyl is selected from methyl, ethyl, propyl or butyl and halide is selected from chloride, bromide or iodide. in the presence of a strong base selected from sodium butoxide, potassium butoxide, potassium propoxide, sodium propoxide, sodium ethoxide, potassium ethoxide, sodium methoxide, potassium methoxide, and combinations thereof; in a solvent selected from the group consisting of methanol, ethanol, propanol, butanol, dimethylsulphoxide, N-methylpyrrolidone, hexamethylphosphoramide, dimethylformide, dimethylacetamide and mixtures thereof, provided that when alcohols are present primarily DATB and picramide is formed; and (b) isolating the DATB or TATB produced. DATB and TATB are useful specialty explosives. TATB is also used for the preparation of benzenehexamine, a starting material for the synthesis of novel materials (optical imaging devices, liquid crystals, ferromagnetic compounds).

  12. Vicarious nucleophilic substitution to prepare 1,3-diamino-2,4,6-trinitrobenzene or 1,3,5-triamino-2,4,6-trinitrobenzene

    DOE Patents [OSTI]

    Mitchell, A.R.; Pagoria, P.F.; Schmidt, R.D.

    1996-10-29

    The present invention relates to a process to produce 1,3-diamino-2,4,6-trinitrobenzene (DATB) or 1,3,5-triamino-2,4,6,trinitrobenzene (TATB) by: (a) reacting at ambient pressure and a temperature of between about 0 and 50 C for between about 0.1 and 24 hr, a trinitroaromatic compound of the structure shown within where X, Y, and Z are each independently selected from --H, or --NH{sub 2}, with the proviso that at least 1 or 2 of X, Y, and Z are hydrogen, with an amount effective to produce DATB or TATB, or 1,1,1-trialkylhydrazinium halide wherein alkyl is selected from methyl, ethyl, propyl or butyl and halide is selected from chloride, bromide or iodide, in the presence of a strong base selected from sodium butoxide, potassium butoxide, potassium propoxide, sodium propoxide, sodium ethoxide, potassium ethoxide, sodium methoxide, potassium methoxide, and combinations thereof; in a solvent selected from the group consisting of methanol, ethanol, propanol, butanol, dimethylsulfoxide, N-methylpyrrolidone, hexamethylphosphoramide, dimethylformide, dimethylacetamide and mixtures thereof, provided that when alcohols are present primarily DATB and picramide is formed; and (b) isolating the DATB or TATB produced. DATB and TATB are useful specialty explosives. TATB is also used for the preparation of benzenehexamine, a starting material for the synthesis of novel materials (optical imaging devices, liquid crystals, ferromagnetic compounds).

  13. CHARACTERIZATION OF PHASE AND EMULSION BEHAVIOR, SURFACTANT RETENTION, AND OIL RECOVERY FOR NOVEL ALCOHOL ETHOXYCARBOXYLATE SURFACTANTS

    SciTech Connect (OSTI)

    Lebone T. Moeti; Ramanathan Sampath

    2001-09-28

    This final technical report describes work performed under DOE Grant No. DE-FG26-97FT97278 during the period October 01, 1997 to August 31, 2001 which covers the total performance period of the project. During this period, detailed information on optimal salinity, temperature, emulsion morphologies, effectiveness for surfactant retention and oil recovery was obtained for an Alcohol Ethoxycarboxylate (AEC) surfactant to evaluate its performance in flooding processes. Tests were conducted on several AEC surfactants and NEODOX (23-4) was identified as the most suitable hybrid surfactant that yielded the best proportion in volume for top, middle, and bottom phases when mixed with oil and water. Following the selection of this surfactant, temperature and salinity scans were performed to identify the optimal salinity and temperature, and the temperature and salinity intervals in which all three phases coexisted. NEODOX 23-4 formed three phases between 4 and 52.5 C. It formed an aqueous rich microemulsion phase at high temperatures and an oleic rich microemulsion phase at low temperatures--a characteristic of the ionic part of the surfactant. The morphology measurement system was set-up successfully at CAU. The best oil/water/surfactant system defined by the above phase work was then studied for emulsion morphologies. Electrical conductivities were measured for middle and bottom phases of the NEODOX 23-4/dodecane/10mM water system and by mixing measured volumes of the middle phase into a fixed volume of the bottom phase and vice versa at room temperature. Electrical conductivity of the mixture decreased as the fraction of volume of the middle phase was increased and vice versa. Also inversion phenomena was observed. These experiments were then repeated for bottom/middle (B/M) and middle/bottom (M/B) conjugate pair phases at 10, 15, 25, 30, 35, 40, and 45 C. Electrical conductivity measurements were then compared with the predictions of the conductivity model developed in this project. The M/B and B/M morphologies and their inversion hysteresis lines conformed to the previously postulated dispersion morphology diagram; that is, within experimental uncertainties, the two emulsion inversion lines in phase volume-temperature space met at a critical point that coincided with the upper critical end point for the phases. Coreflooding measurements were performed by our industrial partner in this project, Surtek, Golden, CO which showed poor hydrocarbon recovery (38.1%) for NEODOX 23-4. It was also found that NEODOX 23-4 surfactant adsorbed too much to the rock (97.1% surfactant loss to the core), a characteristic of the non-ionic part of the surfactant.

  14. 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

  15. Novel Fluorescent Cationic Phospholipid, O-4-Napthylimido-1-Butyl...

    Office of Scientific and Technical Information (OSTI)

    Research Org: Advanced Photon Source (APS), Argonne National Laboratory (ANL), Argonne, IL ... LIFE SCIENCES; ANHYDRIDES; CARDIOLIPIN; DNA; ENCAPSULATION; HYDRATION; LECITHINS; ...

  16. Solvent Extraction of Sodium Hydroxide Using Alkylphenols and Fluorinated Alcohols: Understanding the Extraction Mechanism by Equilibrium Modeling

    SciTech Connect (OSTI)

    Kang, Hyun-Ah; Engle, Nancy L.; Bonnesen Peter V.; Delmau, Laetitia H.; Haverlock, Tamara J.; Moyer, Bruce A.

    2004-03-29

    In the present work, it has been the aim to examine extraction efficiencies of nine proton-ionizable alcohols (HAs) in 1-octanol and to identify both the controlling equilibria and predominant species involved in the extraction process within a thermochemical model. Distribution ratios for sodium (DNa) extraction were measured as a function of organic-phase HA and aqueous-phase NaOH molarity at 25 C. Extraction efficiency follows the expected order of acidity of the HAs, 4-(tert-octyl) phenol (HA 1a) and 4-noctyl- a,a-bis-(trifluoromethyl)benzyl alcohol (HA 2a) being the most efficient extractants among the compounds tested. By use of the equilibrium-modeling program SXLSQI, a model for the extraction of NaOH has been advanced based on an ion-pair extraction by the diluent to give organic-phase Na+OH- and corresponding free ions and cation exchange by the weak acids to form monomeric organic-phase Na+A- and corresponding free organic-phase ions.

  17. Chlorine atom-initiated low-temperature oxidation of prenol and isoprenol: The effect of C=C double bonds on the peroxy radical chemistry in alcohol oxidation

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

    Welz, Oliver; Savee, John D.; Osborn, David L.; Taatjes, Craig A.

    2014-07-04

    The chlorine atom-initiated oxidation of two unsaturated primary C5 alcohols, prenol (3-methyl-2-buten-1-ol, (CH3)2CCHCH2OH) and isoprenol (3-methyl-3-buten-1-ol, CH2C(CH3)CH2CH2OH), is studied at 550 K and low pressure (8 Torr). The time- and isomer-resolved formation of products is probed with multiplexed photoionization mass spectrometry (MPIMS) using tunable vacuum ultraviolet ionizing synchrotron radiation. The peroxy radical chemistry of the unsaturated alcohols appears much less rich than that of saturated C4 and C5 alcohols. The main products observed are the corresponding unsaturated aldehydes – prenal (3-methyl-2-butenal) from prenol oxidation and isoprenal (3-methyl-3-butenal) from isoprenol oxidation. No significant products arising from QOOH chemistry are observed. Thesemore » results can be qualitatively explained by the formation of resonance stabilized allylic radicals via H-abstraction in the Cl + prenol and Cl + isoprenol initiation reactions. The loss of resonance stabilization upon O2 addition causes the energies of the intermediate wells, saddle points, and products to increase relative to the energy of the initial radicals and O2. These energetic shifts make most product channels observed in the peroxy radical chemistry of saturated alcohols inaccessible for these unsaturated alcohols. The experimental findings are underpinned by quantum-chemical calculations for stationary points on the potential energy surfaces for the reactions of the initial radicals with O2. Under our conditions, the dominant channels in prenol and isoprenol oxidation are the chain-terminating HO2-forming channels arising from radicals, in which the unpaired electron and the –OH group are on the same carbon atom, with stable prenal and isoprenal co-products, respectively. These results suggest that the presence of C=C double bonds in alcohols will reduce low-temperature reactivity during autoignition.« less

  18. Equipment Design and Cost Estimation for Small Modular Biomass Systems, Synthesis Gas Cleanup, and Oxygen Separation Equipment; Task 9: Mixed Alcohols From Syngas -- State of Technology

    SciTech Connect (OSTI)

    Nexant Inc.

    2006-05-01

    This deliverable is for Task 9, Mixed Alcohols from Syngas: State of Technology, as part of National Renewable Energy Laboratory (NREL) Award ACO-5-44027, ''Equipment Design and Cost Estimation for Small Modular Biomass Systems, Synthesis Gas Cleanup and Oxygen Separation Equipment''. Task 9 supplements the work previously done by NREL in the mixed alcohols section of the 2003 technical report Preliminary Screening--Technical and Economic Assessment of Synthesis Gas to Fuels and Chemicals with Emphasis on the Potential for Biomass-Derived Syngas.

  19. Rh-Based Mixed Alcohol Synthesis Catalysts: Characterization and Computational Report

    SciTech Connect (OSTI)

    Albrecht, Karl O.; Glezakou, Vassiliki Alexandra; Rousseau, Roger J.; Engelhard, Mark H.; Varga, Tamas; Colby, Robert J.; Jaffe, John E.; Li, Xiaohong S.; Mei, Donghai; Windisch, Charles F.; Kathmann, Shawn M.; Lemmon, Teresa L.; Gray, Michel J.; Hart, Todd R.; Thompson, Becky L.; Gerber, Mark A.

    2013-08-01

    The U.S. Department of Energy is conducting a program focused on developing a process for the conversion of biomass to bio-based fuels and co-products. Biomass-derived syngas is converted thermochemically within a temperature range of 240 to 330C and at elevated pressure (e.g., 1200 psig) over a catalyst. Ethanol is the desired reaction product, although other side compounds are produced, including C3 to C5 alcohols; higher (i.e., greater than C1) oxygenates such as methyl acetate, ethyl acetate, acetic acid and acetaldehyde; and higher hydrocarbon gases such as methane, ethane/ethene, propane/propene, etc. Saturated hydrocarbon gases (especially methane) are undesirable because they represent a diminished yield of carbon to the desired ethanol product and represent compounds that must be steam reformed at high energy cost to reproduce CO and H2. Ethanol produced by the thermochemical reaction of syngas could be separated and blended directly with gasoline to produce a liquid transportation fuel. Additionally, higher oxygenates and unsaturated hydrocarbon side products such as olefins also could be further processed to liquid fuels. The goal of the current project is the development of a Rh-based catalyst with high activity and selectivity to C2+ oxygenates. This report chronicles an effort to characterize numerous supports and catalysts to identify particular traits that could be correlated with the most active and/or selective catalysts. Carbon and silica supports and catalysts were analyzed. Generally, analyses provided guidance in the selection of acceptable catalyst supports. For example, supports with high surface areas due to a high number of micropores were generally found to be poor at producing oxygenates, possibly because of mass transfer limitations of the products formed out of the micropores. To probe fundamental aspects of the complicated reaction network of CO with H2, a computational/ theoretical investigation using quantum mechanical and ab initio molecular dynamics calculations was initiated in 2009. Computational investigations were performed first to elucidate understanding of the nature of the catalytically active site. Thermodynamic calculations revealed that Mn likely exists as a metallic alloy with Rh in Rh-rich environments under reducing conditions at the temperatures of interest. After determining that reduced Rh-Mn alloy metal clusters were in a reduced state, the activation energy barriers of numerous transition state species on the catalytically active metal particles were calculated to compute the activation barriers of several reaction pathways that are possible on the catalyst surface. Comparison of calculations with a Rh nanoparticle versus a Rh-Mn nanoparticle revealed that the presence of Mn enabled the reaction pathway of CH with CO to form an adsorbed CHCO species, which was a precursor to C2+ oxygenates. The presence of Mn did not have a significant effect on the rate of CH4 production. Ir was observed during empirical catalyst screening experiments to improve the activity and selectivity of Rh-Mn catalysts. Thus, the addition of Ir to the Rh-Mn nanoparticles also was probed computationally. Simulations of Rh-Mn-Ir nanoparticles revealed that, with sufficient Ir concentrations, the Rh, Mn and Ir presumably would be well mixed within a nanoparticle. Activation barriers were calculated for Rh-Mn-Ir nanoparticles for several C-, H-, and O-containing transitional species on the nanoparticle surface. It was found that the presence of Ir opened yet another reactive pathway whereby HCO is formed and may undergo insertion with CHx surface moieties. The reaction pathway opened by the presence of Ir is in addition to the CO + CH pathway opened by the presence of Mn. Similar to Mn, the presence of Ir was not found to not affect the rate of CH4 production.

  20. Methyl tert-butyl ether and ethyl tert-butyl ether: A comparison of properties, synthesis techniques, and operating conditions

    SciTech Connect (OSTI)

    Sneesby, M.G.; Tade, M.O.; Datta, R.

    1996-12-31

    MTBE is currently the most industrially significant oxygenate but some of the properties of ETBE and the EPA ethanol mandate suggest that ETBE could become a viable competitor. Similar synthesis techniques are used for both ethers but the phase behaviour of the ETBE system requires slightly different operating conditions and creates some alternatives for product recovery. The process control strategy for both systems must address some unusual challenges. 9 refs., 1 tab.

  1. THE ECONOMICAL PRODUCTION OF ALCOHOL FUELS FROM COAL-DERIVED SYNTHESIS GAS. Includes quarterly technical progress report No.25 from 10/01/1997-12/31/1997, and quarterly technical progress report No.26 from 01/01/1998-03/31/1998

    SciTech Connect (OSTI)

    1999-03-01

    This project was divided into two parts. One part evaluated possible catalysts for producing higher-alcohols (C{sub 2} to C{sub 5+}) as fuel additives. The other part provided guidance by looking both at the economics of mixed-alcohol production from coal-derived syngas and the effect of higher alcohol addition on gasoline octane and engine performance. The catalysts studied for higher-alcohol synthesis were molybdenum sulfides promoted with potassium. The best catalysts produced alcohols at a rate of 200 g/kg of catalyst/h. Higher-alcohol selectivity was over 40%. The hydrocarbon by-product was less than 20%. These catalysts met established success criteria. The economics for mixed alcohols produced from coal were poor compared to mixed alcohols produced from natural gas. Syngas from natural gas was always less expensive than syngas from coal. Engine tests showed that mixed alcohols added to gasoline significantly improved fuel quality. Mixed-alcohols as produced by our catalysts enhanced gasoline octane and decreased engine emissions. Mixed-alcohol addition gave better results than adding individual alcohols as had been done in the 1980's when some refiners added methanol or ethanol to gasoline.

  2. Energy balances in the production and end use of alcohols derived from biomass. A fuels-specific comparative analysis of alternate ethanol production cycles

    SciTech Connect (OSTI)

    Not Available

    1980-10-01

    Considerable public interest and debate have been focused on the so-called energy balance issue involved in the conversion of biomass materials into ethanol for fuel use. This report addresses questions of net gains in premium fuels that can be derived from the production and use of ethanol from biomass, and shows that for the US alcohol fuel program, energy balance need not be a concern. Three categories of fuel gain are discussed in the report: (1) Net petroleum gain; (2) Net premium fuel gain (petroleum and natural gas); and (3) Net energy gain (for all fuels). In this study the investment of energy (in the form of premium fuels) in alcohol production includes all investment from cultivating, harvesting, or gathering the feedstock and raw materials, through conversion of the feedstock to alcohol, to the delivery to the end-user. To determine the fuel gains in ethanol production, six cases, encompassing three feedstocks, five process fuels, and three process variations, have been examined. For each case, two end-uses (automotive fuel use and replacement of petrochemical feedstocks) were scrutinized. The end-uses were further divided into three variations in fuel economy and two different routes for production of ethanol from petrochemicals. Energy requirements calculated for the six process cycles accounted for fuels used directly and indirectly in all stages of alcohol production, from agriculture through distribution of product to the end-user. Energy credits were computed for byproducts according to the most appropriate current use.

  3. Expression of a heat-stable NADPH-dependent alcohol dehydrogenase in Caldicellulosiruptor bescii results in furan aldehyde detoxification

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

    Chung, Daehwan; Verbeke, Tobin J.; Cross, Karissa L.; Westpheling, Janet; Elkins, James G.

    2015-07-22

    Compounds such as furfural and 5-hydroxymethylfurfural (5-HMF) are generated through the dehydration of xylose and glucose, respectively, during dilute-acid pretreatment of lignocellulosic biomass and are also potent microbial growth and fermentation inhibitors. The enzymatic reduction of these furan aldehydes to their corresponding, and less toxic, alcohols is an engineering approach that has been successfully implemented in both Saccharomyces cerevisiae and ethanologenicEscherichia coli, but has not yet been investigated in thermophiles relevant to biofuel production through consolidated bioprocessing (CBP). Developing CBP-relevant biocatalysts that are either naturally resistant to such inhibitors, or are amenable to engineered resistance, is therefore, an important componentmore » in making biofuels production from lignocellulosic biomass feasible.« less

  4. High-throughput behavioral phenotyping of drug and alcohol susceptibility traits in the expanded panel of BXD recombinant inbred strains

    SciTech Connect (OSTI)

    Philip, Vivek M [ORNL; Ansah, T [University of Tennessee Health Science Center, Memphis; Blaha, C, [University of Tennessee Health Science Center, Memphis; Cook, Melloni N. [University of Memphis; Hamre, Kristin M. [University of Tennessee Health Science Center, Memphis; Lariviere, William R [University of Pittsburgh; Matthews, Douglas B [Baylor University; Goldowitz, Daniel [University of British Columbia, Vancouver; Chesler, Elissa J [ORNL

    2010-01-01

    Genetic reference populations, particularly the BXD recombinant inbred strains, are a valuable resource for the discovery of the bio-molecular substrates and genetic drivers responsible for trait variation and co- ariation. This approach can be profitably applied in the analysis of susceptibility and mechanisms of drug and alcohol use disorders for which many predisposing behaviors may predict occurrence and manifestation of increased preference for these substances. Many of these traits are modeled by common mouse behavioral assays, facilitating the detection of patterns and sources of genetic co-regulation of predisposing phenotypes and substance consumption. Members of the Tennessee Mouse Genome Consortium have obtained behavioral phenotype data from 260 measures related to multiple behavioral assays across several domains: self-administration, response to, and withdrawal from cocaine, MDMA, morphine and alcohol; novelty seeking; behavioral despair and related neurological phenomena; pain sensitivity; stress sensitivity; anxiety; hyperactivity; and sleep/wake cycles. All traits have been measured in both sexes and the recently expanded panel of 69 additional BXD recombinant inbred strains (N=69). Sex differences and heritability estimates were obtained for each trait, and a comparison of early (N = 32) and recent BXD RI lines was performed. Primary data is publicly available for heritability, sex difference and genetic analyses using www.GeneNetwork.org. These analyses include QTL detection and genetic analysis of gene expression. Stored results from these analyses are available at http://ontologicaldiscovery.org for comparison to other genomic analysis results. Together with the results of related studies, these data form a public resource for integrative systems genetic analysis of neurobehavioral traits.

  5. FCC LPG olefinicity and branching enhanced by octane catalysts

    SciTech Connect (OSTI)

    Keyworth, D.A.; Reid, T.A.; Kreider, K.R.; Yatsu, C.A.

    1989-05-29

    Refiners are increasingly recognizing the downstream opportunities for fluid catalytic cracking LPG olefins for the production of methyl tertiary butyl ether (MTBE), ethyl tertiary butyl ether (ETBE, if the ethanol subsidy is extended to the production of ETBE), and as petrochemical feedstocks. Some of new gasoline FCC octane-enhancing catalysts can support those opportunities because their low non-framework alumina (low NFA) preserve both LPG olefinicity and promote branching of the LPG streams from the FCCU. The combined effect results in more isobutane for alkylate feed, more propylene in the propane/propylene stream, and more isobutene - which makes the addition of an MTBE unit very enticing.

  6. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    Ethanol Plant Production Definitions Key Terms Definition Barrel A unit of volume equal to 42 U.S. gallons. Fuel Ethanol An anhydrous alcohol (ethanol with less than 1% water) intended for gasoline blending as described in the Oxygenates definition. Oxygenates Substances which, when added to gasoline, increase the amount of oxygen in that gasoline blend. Ethanol, Methyl Tertiary Butyl Ether (MTBE), Ethyl Tertiary Butyl Ether (ETBE), and methanol are common oxygenates. Fuel Ethanol: Blends of up

  7. Ethanol-induced impairment of polyamine homeostasis A potential cause of neural tube defect and intrauterine growth restriction in fetal alcohol syndrome

    SciTech Connect (OSTI)

    Haghighi Poodeh, Saeid; Alhonen, Leena; Salonurmi, Tuire; Savolainen, Markku J.

    2014-03-28

    Highlights: Polyamine pools in embryonic and extraembryonic tissues are developmentally regulated. Alcohol administration perturbs polyamine levels in the tissues with various patterns. Total absence of polyamines in the embryo head at 9.5 dpc is critical for development. The deficiency is associated with reduction in endothelial cell sprouting in the head. Retarded migration of neural crest cells may cause development of neural tube defect. - Abstract: Introduction: Polyamines play a fundamental role during embryogenesis by regulating cell growth and proliferation and by interacting with RNA, DNA and protein. The polyamine pools are regulated by metabolism and uptake from exogenous sources. The use of certain inhibitors of polyamine synthesis causes similar defects to those seen in alcohol exposure e.g. retarded embryo growth and endothelial cell sprouting. Methods: CD-1 mice received two intraperitoneal injections of 3 g/kg ethanol at 4 h intervals 8.75 days post coitum (dpc). The fetal head, trunk, yolk sac and placenta were collected at 9.5 and 12.5 dpc and polyamine concentrations were determined. Results: No measurable quantity of polyamines could be detected in the embryo head at 9.5 dpc, 12 h after ethanol exposure. Putrescine was not detectable in the trunk of the embryo at that time, whereas polyamines in yolk sac and placenta were at control level. Polyamine deficiency was associated with slow cell growth, reduction in endothelial cell sprouting, an altered pattern of blood vessel network formation and consequently retarded migration of neural crest cells and growth restriction. Discussion: Our results indicate that the polyamine pools in embryonic and extraembryonic tissues are developmentally regulated. Alcohol administration, at the critical stage, perturbs polyamine levels with various patterns, depending on the tissue and its developmental stage. The total absence of polyamines in the embryo head at 9.5 dpc may explain why this stage is so vulnerable to the development of neural tube defect, and growth restriction, the findings previously observed in fetal alcohol syndrome.

  8. Direct Catalytic Upgrading of Current Dilute Alcohol Fermentation Streams to Hydrocarbons for Fungible Fuels Presentation for BETO 2015 Project Peer Review

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Direct Catalytic Upgrading of Current Dilute Alcohol Fermentation Streams to Hydrocarbons for Fungible Fuels [2.3.1.100] Chaitanya Narula, 1 Zhenglong Li, 1 E. Casbeer, 1 Robert A. Geiger, 1 James P. Szybist, 2 Martin Keller, 2 Brian H. Davison, 2 and Tim Theiss 2 (PI) Oak Ridge National Laboratory 1 Materials Science and Technology Division 2 Energy and Environmental Sciences Directorate Technology Area Review: Biochemical Conversion 2015 DOE Bioenergy Technologies Office (BETO) Project Peer

  9. Catalysis for Mixed Alcohol Synthesis from Biomass Derived Syngas: Cooperative Research and Development Final Report, CRADA Number CRD-08-292

    SciTech Connect (OSTI)

    Hensley, J.

    2013-04-01

    The Dow Chemical Company (Dow) developed and tested catalysts for production of mixed alcohols from synthesis gas (syngas), under research and development (R&D) projects that were discontinued a number of years ago. Dow possesses detailed laboratory notebooks, catalyst samples, and technical expertise related to this past work. The National Renewable Energy Laboratory (NREL) is conducting R&D in support of the United States Department of Energy (DOE) to develop methods for economically producing ethanol from gasified biomass. NREL is currently conducting biomass gasification research at an existing 1/2 ton/day thermochemical test platform. Both Dow and NREL believe that the ability to economically produce ethanol from biomass-derived syngas can be enhanced through collaborative testing, refinement, and development of Dow's mixed-alcohol catalysts at NREL's and/or Dow's bench- and pilot-scale facilities. Dow and NREL further agree that collaboration on improvements in catalysts as well as gasifier operating conditions (e.g., time, temperature, upstream gas treatment) will be necessary to achieve technical and economic goals for production of ethanol and other alcohols.

  10. The economical production of alcohol fuels from coal-derived synthesis gas. Seventh quarterly technical progress report, April 1, 1993--June 30, 1993

    SciTech Connect (OSTI)

    Not Available

    1993-07-01

    An analysis of the current base cases has been undertaken to determine if the economic status of the proposed alcohol fuels may benefit from economies of scale. This analysis was based on a literature review which suggested that plants of capacities substantially below 5000 metric tons/day are unlikely to be competitive for the bulk production of alcohols for fuel consumption or chemicals manufacture. The preliminary results of this scale up procedure would indicate that the capacity of the current base cases be increased by a factor of eight. This would yield annual production of 4.1 million metric tons and essentially reduce the plant gate cost by approximately 41 percent in both cases. A facility of this size would be the equivalent of a medium sized oil refinery and would be capable of sustaining local market demands for fuel oxygenates. The actual competitiveness of this product with current oxygenates such as MTBE remains to be determined. The alcohol synthesis loop is being used to evaluate optimization procedures which will eventually be used to optimize the entire process. A more detailed design of the synthesis reactor is required, and a preliminary design of this reactor has been completed.

  11. Ethanol metabolism, oxidative stress, and endoplasmic reticulum stress responses in the lungs of hepatic alcohol dehydrogenase deficient deer mice after chronic ethanol feeding

    SciTech Connect (OSTI)

    Kaphalia, Lata; Boroumand, Nahal; Hyunsu, Ju; Kaphalia, Bhupendra S.; Calhoun, William J.

    2014-06-01

    Consumption and over-consumption of alcoholic beverages are well-recognized contributors to a variety of pulmonary disorders, even in the absence of intoxication. The mechanisms by which alcohol (ethanol) may produce disease include oxidative stress and prolonged endoplasmic reticulum (ER) stress. Many aspects of these processes remain incompletely understood due to a lack of a suitable animal model. Chronic alcohol over-consumption reduces hepatic alcohol dehydrogenase (ADH), the principal canonical metabolic pathway of ethanol oxidation. We therefore modeled this situation using hepatic ADH-deficient deer mice fed 3.5% ethanol daily for 3 months. Blood ethanol concentration was 180 mg% in ethanol fed mice, compared to < 1.0% in the controls. Acetaldehyde (oxidative metabolite of ethanol) was minimally, but significantly increased in ethanol-fed vs. pair-fed control mice. Total fatty acid ethyl esters (FAEEs, nonoxidative metabolites of ethanol) were 47.6 ?g/g in the lungs of ethanol-fed mice as compared to 1.5 ?g/g in pair-fed controls. Histological and immunohistological evaluation showed perivascular and peribronchiolar lymphocytic infiltration, and significant oxidative injury, in the lungs of ethanol-fed mice compared to pair-fed controls. Several fold increases for cytochrome P450 2E1, caspase 8 and caspase 3 found in the lungs of ethanol-fed mice as compared to pair-fed controls suggest role of oxidative stress in ethanol-induced lung injury. ER stress and unfolded protein response signaling were also significantly increased in the lungs of ethanol-fed mice. Surprisingly, no significant activation of inositol-requiring enzyme-1? and spliced XBP1 was observed indicating a lack of activation of corrective mechanisms to reinstate ER homeostasis. The data suggest that oxidative stress and prolonged ER stress, coupled with formation and accumulation of cytotoxic FAEEs may contribute to the pathogenesis of alcoholic lung disease. - Highlights: Chronic ethanol feeding causes oxidative stress, ER stress and inflammation in lungs of ADH deer mice. Chronic ethanol feeding generates FAEEs (nonoxidative metabolites of ethanol) in lungs of ADH deer mice. Chronic ethanol feeding induces CYP2E1 in the lungs of ADH deer mice. Lack of ER homeostasis due to a prolonged ethanol feeding could trigger inflammation.

  12. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

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

  13. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

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

  14. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

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

  15. Bile acids override steatosis in farnesoid X receptor deficient mice in a model of non-alcoholic steatohepatitis

    SciTech Connect (OSTI)

    Wu, Weibin; Liu, Xijun; Peng, Xiaomin; Xue, Ruyi; Ji, Lingling; Shen, Xizhong; Chen, She; Gu, Jianxin; Zhang, Si

    2014-05-23

    Highlights: FXR deficiency enhanced MCD diet-induced hepatic fibrosis. FXR deficiency attenuated MCD diet-induced hepatic steatosis. FXR deficiency repressed genes involved in fatty acid uptake and triglyceride accumulation. - Abstract: Non-alcoholic fatty liver disease (NAFLD) is one of the most common liver diseases, and the pathogenesis is still not well known. The farnesoid X receptor (FXR) is a member of the nuclear hormone receptor superfamily and plays an essential role in maintaining bile acid and lipid homeostasis. In this study, we study the role of FXR in the pathogenesis of NFALD. We found that FXR deficient (FXR{sup ?/?}) mice fed methionine- and choline-deficient (MCD) diet had higher serum ALT and AST activities and lower hepatic triglyceride levels than wild-type (WT) mice fed MCD diet. Expression of genes involved in inflammation (VCAM-1) and fibrosis (?-SMA) was increased in FXR{sup ?/?} mice fed MCD diet (FXR{sup ?/?}/MCD) compared to WT mice fed MCD diet (WT/MCD). Although MCD diet significantly induced hepatic fibrosis in terms of liver histology, FXR{sup ?/?}/MCD mice showed less degree of hepatic steatosis than WT/MCD mice. Moreover, FXR deficiency synergistically potentiated the elevation effects of MCD diet on serum and hepatic bile acids levels. The super-physiological concentrations of hepatic bile acids in FXR{sup ?/?}/MCD mice inhibited the expression of genes involved in fatty acid uptake and triglyceride accumulation, which may be an explanation for less steatosis in FXR{sup ?/?}/MCD mice in contrast to WT/MCD mice. These results suggest that hepatic bile acids accumulation could override simple steatosis in hepatic injury during the progression of NAFLD and further emphasize the role of FXR in maintaining hepatic bile acid homeostasis in liver disorders and in hepatic protection.

  16. Prenatal ethanol exposure programs an increased susceptibility of non-alcoholic fatty liver disease in female adult offspring rats

    SciTech Connect (OSTI)

    Shen, Lang; Liu, Zhongfen; Gong, Jun; Zhang, Li; Wang, Linlong; Magdalou, Jacques; Chen, Liaobin; Wang, Hui

    2014-01-15

    Prenatal ethanol exposure (PEE) induces dyslipidemia and hyperglycemia in fetus and adult offspring. However, whether PEE increases the susceptibility to non-alcoholic fatty liver disease (NAFLD) in offspring and its underlying mechanism remain unknown. This study aimed to demonstrate an increased susceptibility to high-fat diet (HFD)-induced NAFLD and its intrauterine programming mechanisms in female rat offspring with PEE. Rat model of intrauterine growth retardation (IUGR) was established by PEE, the female fetus and adult offspring that fed normal diet (ND) or HFD were sacrificed. The results showed that, in PEE + ND group, serum corticosterone (CORT) slightly decreased and insulin-like growth factor-1 (IGF-1) and glucose increased with partial catch-up growth; In PEE + HFD group, serum CORT decreased, while serum IGF-1, glucose and triglyceride (TG) increased, with notable catch-up growth, higher metabolic status and NAFLD formation. Enhanced liver expression of the IGF-1 pathway, gluconeogenesis, and lipid synthesis as well as reduced expression of lipid output were accompanied in PEE + HFD group. In PEE fetus, serum CORT increased while IGF-1 decreased, with low body weight, hyperglycemia, and hepatocyte ultrastructural changes. Hepatic IGF-1 expression as well as lipid output was down-regulated, while lipid synthesis significantly increased. Based on these findings, we propose a two-programming hypothesis for an increased susceptibility to HFD-induced NAFLD in female offspring of PEE. That is, the intrauterine programming of liver glucose and lipid metabolic function is the first programming, and postnatal adaptive catch-up growth triggered by intrauterine programming of GC-IGF1 axis acts as the second programming. - Highlights: Prenatal ethanol exposure increase the susceptibility of NAFLD in female offspring. Prenatal ethanol exposure reprograms fetal livers glucose and lipid metabolism . Prenatal ethanol exposure cause the adaptive change of glucocorticoid-IGF1 axis.

  17. Dehydrogenation links LPG to more octanes

    SciTech Connect (OSTI)

    Gussow, S.; Spence, D.C.; White, E.A.

    1980-01-01

    Air Products and Chemicals Inc.'s Houdry Catofin process, a new application of well-known Houdry catalytic dehydrogenation technology, is an adiabatic, fixed-bed, multireactor catalytic process which produces propylene, isobutylene, and mixed n-butylenes by dehydrogenation of the corresponding saturates. The process is very flexible in that propylene, isobutylene, and mixed n-butylenes can be produced either separately or simultaneously from the corresponding saturates. The process will be used to prepare purity propylene at a Morelos, Mex., plant, which is now in the engineering stage. Five variations of the procedure for producing propylene; methyl tert.-butyl ether; propylene and alkylate; methyl tert.-butyl ether and alkylate; and methyl tert.-butyl ether, alkylate, and 1-butylene are compared with respect to typical product yields, costs and values for process economics, the dehydrogenation route to the three products, manufacturing costs, the sensitivity of return on investment to feedstock costs, and the return on investment, which varies from a low of 11.5% for the third case to a high of 14.4% for the fourth case. The Catofin process is discussed.

  18. Municipal Solid Waste (MSW) to Liquid Fuels Synthesis, Volume 2: A Techno-economic Evaluation of the Production of Mixed Alcohols

    SciTech Connect (OSTI)

    Jones, Susanne B.; Zhu, Yunhua; Valkenburt, Corinne

    2009-05-01

    Biomass is a renewable energy resource that can be converted into liquid fuel suitable for transportation applications and thus help meet the Energy Independence and Security Act renewable energy goals (U.S. Congress 2007). However, biomass is not always available in sufficient quantity at a price compatible with fuels production. Municipal solid waste (MSW) on the other hand is readily available in large quantities in some communities and is considered a partially renewable feedstock. Furthermore, MSW may be available for little or no cost. This report provides a techno-economic analysis of the production of mixed alcohols from MSW and compares it to the costs for a wood based plant. In this analysis, MSW is processed into refuse derived fuel (RDF) and then gasified in a plant co-located with a landfill. The resulting syngas is then catalytically converted to mixed alcohols. At a scale of 2000 metric tons per day of RDF, and using current technology, the minimum ethanol selling price at a 10% rate of return is approximately $1.85/gallon ethanol (early 2008 $). However, favorable economics are dependent upon the toxicity characteristics of the waste streams and that a market exists for the by-product scrap metal recovered from the RDF process.

  19. Biogas and alcohol fuels production. Proceedings of the Seminar on Biomass, Energy for City, Farm, and Industry, Chicago, IL, October 25, 26, 1979

    SciTech Connect (OSTI)

    Goldstein, J.

    1980-01-01

    Basic principles of anaerobic digestion are considered along with the status of the Imperial Valley Biogas Project, the Department of Energy program for the recovery of energy and materials from urban waste, the principles of alcohol production from wastes, the mechanical recovery of a refuse-derived cellulosic feedstock for ethanol production, and the production of ethanol from cellulosic biomass. Attention is given to on-farm alcohol fuel production, the current status and future role of gasohol production, methane generation from small scale farms, farmsite installations of energy harvester anaerobic digesters, biogas/composting and landfill recovery, farm-scale composting as an option to anaerobic digestion, designing a high-quality biogas system, and methane as fuel of the future. A description is presented of subjects which are related to landfill gas recovery, biogas purification with permselective membranes, and anaerobic digestion of marine biomass. Other topics studied include the application of biogas technology in India, biogas production in China, biogasification of organic wastes in the Republic of the Philippines, and economics and operational experience of full-scale anaerobic dairy manure digester.

  20. SU-E-T-58: Calculation of Dose Distribution of Accuboost Brachytherapy in Deformable Polyvinil Alcohol Breast Phantom Using Biomechanical Modeling and Monte Carlo Simulation

    SciTech Connect (OSTI)

    Mohammadyari, P; Faghihi, R; Shirazi, M Mosleh; Lotfi, M; Meigooni, A

    2014-06-01

    Purpose: the accuboost is the most modern method of breast brachytherapy that is a boost method in compressed tissue by a mammography unit. the dose distribution in uncompressed tissue, as compressed tissue is important that should be characterized. Methods: In this study, the mechanical behavior of breast in mammography loading, the displacement of breast tissue and the dose distribution in compressed and uncompressed tissue, are investigated. Dosimetry was performed by two dosimeter methods of Monte Carlo simulations using MCNP5 code and thermoluminescence dosimeters. For Monte Carlo simulations, the dose values in cubical lattice were calculated using tally F6. The displacement of the breast elements was simulated by Finite element model and calculated using ABAQUS software, from which the 3D dose distribution in uncompressed tissue was determined. The geometry of the model is constructed from MR images of 6 volunteers. Experimental dosimetery was performed by placing the thermoluminescence dosimeters into the polyvinyl alcohol breast equivalent phantom and on the proximal edge of compression plates to the chest. Results: The results indicate that using the cone applicators would deliver more than 95% of dose to the depth of 5 to 17mm, while round applicator will increase the skin dose. Nodal displacement, in presence of gravity and 60N forces, i.e. in mammography compression, was determined with 43% contraction in the loading direction and 37% expansion in orthogonal orientation. Finally, in comparison of the acquired from thermoluminescence dosimeters with MCNP5, they are consistent with each other in breast phantom and in chest's skin with average different percentage of 13.7±5.7 and 7.7±2.3, respectively. Conclusion: The major advantage of this kind of dosimetry is the ability of 3D dose calculation by FE Modeling. Finally, polyvinyl alcohol is a reliable material as a breast tissue equivalent dosimetric phantom that provides the ability of TLD dosimetry for validation.

  1. Transition metal complexes of oxazolinylboranes and cyclopentadienyl-bis(oxazolinyl)borates: Catalysts for asymmetric olefin hydroamination and acceptorless alcohol decarbonylation

    SciTech Connect (OSTI)

    Manna, Kuntal [Ames Laboratory

    2012-12-17

    The research presented and discussed in this dissertation involves the synthesis of transition metal complexes of oxazolinylboranes and cyclopentadienyl-bis(oxazolinyl)borates, and their application in catalytic enantioselective olefin hydroamination and acceptorless alcohol decarbonylation. Neutral oxazolinylboranes are excellent synthetic intermediates for preparing new borate ligands and also developing organometallic complexes. Achiral and optically active bis(oxazolinyl)phenylboranes are synthesized by reaction of 2-lithio-2-oxazolide and 0.50 equiv of dichlorophenylborane. These bis(oxazolinyl)phenylboranes are oligomeric species in solid state resulting from the coordination of an oxazoline to the boron center of another borane monomer. The treatment of chiral bis(oxazolinyl)phenylboranes with sodium cyclopentadienide provide optically active cyclopentadienyl-bis(oxazolinyl)borates H[PhB(C{sub 5}H{sub 5})(Ox{sup R}){sub 2}] [Ox{sup R} = Ox{sup 4S-iPr,Me2}, Ox{sup 4R-iPr,Me2}, Ox{sup 4S-tBu]}. These optically active proligands react with an equivalent of M(NMe{sub 2}){sub 4} (M = Ti, Zr, Hf) to afford corresponding cyclopentadienyl-bis(oxazolinyl)borato group 4 complexes {PhB(C{sub 5}H{sub 4})(Ox{sup R}){sub 2}}M(NMe{sub 2}){sub 2} in high yields. These group 4 compounds catalyze cyclization of aminoalkenes at room temperature or below, providing pyrrolidine, piperidine, and azepane with enantiomeric excesses up to 99%. Our mechanistic investigations suggest a non-insertive mechanism involving concerted C?N/C?H bond formation in the turnover limiting step of the catalytic cycle. Among cyclopentadienyl-bis(oxazolinyl)borato group 4 catalysts, the zirconium complex {PhB(C{sub 5}H{sub 4})(Ox{sup 4S-iPr,Me2}){sub 2}}Zr(NMe{sub 2}){sub 2} ({S-2}Zr(NMe{sub 2}){sub 2}) displays highest activity and enantioselectivity. Interestingly, {S-2}Zr(NMe{sub 2}){sub 2} also desymmetrizes olefin moieties of achiral non-conjugated aminodienes and aminodiynes during cyclization. The cyclization of aminodienes catalyzed by {S-2}Zr(NMe{sub 2}){sub 2} affords diastereomeric mixture of cis and trans cylic amines with high diasteromeric ratios and excellent enantiomeric excesses. Similarly, the desymmetrization of alkyne moieties in {S-2}Zr(NMe{sub 2}){sub 2}-catalyzed cyclization of aminodiynes provides corresponding cyclic imines bearing quaternary stereocenters with enantiomeric excesses up to 93%. These stereoselective desymmetrization reactions are significantly affected by concentration of the substrate, temperature, and the presence of a noncyclizable primary amine. In addition, both the diastereomeric ratios and enantiomeric excesses of the products are markedly enhanced by N-deuteration of the substrates. Notably, the cationic zirconium-monoamide complex [{S-2}Zr(NMe{sub 2})][B(C{sub 6}F{sub 5}){sub 4}] obtained from neutral {S-2}Zr(NMe{sub 2}){sub 2} cyclizes primary aminopentenes providing pyrrolidines with S-configuration; whereas {S-2}Zr(NMe{sub 2}){sub 2} provides R-configured pyrrolidines. The yttrium complex {S-2}YCH{sub 2}SiMe{sub 3} also affords S-configured pyrrolidines by cyclization of aminopentenes, however the enantiomeric excesses of products are low. An alternative optically active yttrium complex {PhB(C{sub 5}H{sub 4})(Ox{sup 4S-tBu}){sub 2}}YCH{sub 2}SiMe{sub 3} ({S-3}YCH{sub 2}SiMe{sub 3}) is synthesized, which displays highly enantioselective in the cyclization of aminoalkenes at room temperature affording S-configured cyclic amines with enantiomeric excesses up to 96%. A noninsertive mechanism involving a six-membered transition state by a concerted C?N bond formation and N?H bond cleavage is proposed for {S-3}YCH{sub 2}SiMe{sub 3} system based on the kinetic, spectroscopic, and stereochemical features. In the end, a series of bis- and tris(oxazolinyl)borato iridium and rhodium complexes are synthesized with bis(oxazolinyl)phenylborane [PhB(Ox{sup Me2}){sub 2}]{sub n}, tris(oxazolinyl)borane [B(Ox{sup Me2}){sub 3}]n, and tris(4,4-dimethyl-2-oxazolinyl)phenylborate [To{sup M}]{sup ?}. All these new an

  2. Production of biodiesel using expanded gas solvents

    SciTech Connect (OSTI)

    Ginosar, Daniel M; Fox, Robert V; Petkovic, Lucia M

    2009-04-07

    A method of producing an alkyl ester. The method comprises providing an alcohol and a triglyceride or fatty acid. An expanding gas is dissolved into the alcohol to form a gas expanded solvent. The alcohol is reacted with the triglyceride or fatty acid in a single phase to produce the alkyl ester. The expanding gas may be a nonpolar expanding gas, such as carbon dioxide, methane, ethane, propane, butane, pentane, ethylene, propylene, butylene, pentene, isomers thereof, and mixtures thereof, which is dissolved into the alcohol. The gas expanded solvent may be maintained at a temperature below, at, or above a critical temperature of the expanding gas and at a pressure below, at, or above a critical pressure of the expanding gas.

  3. Characterizing HfXZr1-XO2 by EXAFS: Relationship Between Bulk and Surface Composition, and Impact on Catalytic Selectivity for Alcohol Conversion

    SciTech Connect (OSTI)

    Jacobs, G.; Milling, M; Ji, Y; Patterson, P; Sparks, D; Davis, B

    2009-01-01

    A series of mixed Hf{sub X}Zr{sub 1-X}O{sub 2} oxide catalysts was prepared according to a recipe that yields the monoclinic structure. The samples were examined by EXAFS spectroscopy at the Zr K and Hf L{sub III} edges. A fitting model was used that simultaneously fits data from both edges, and makes use of an interdependent mixing parameter X mix to take into account substitution of the complementary atom in the nearest metal-metal shell. For XPS analysis, Scofield factors were applied to estimate the relative atomic surface concentrations of Zr and Hf. EXAFS results suggested that a solid bulk solution was formed over a wide range of X for Hf{sub X}Zr{sub 1-X}O{sub 2} binary oxides, and that the relative ratio was retained in the surface shell (i.e., including some subsurface layers by XPS) and the surface (e.g., by ISS). The increase in selectivity for the 1-alkene from dehydration of alcohols at high Zr content does not correlate smoothly with the tuned relative atomic concentration of Hf to Zr. The step change at high Zr content appears to be due to other indirect factors (e.g., surface defects, oxygen vacancies).

  4. An Organometallic Future in Green and Energy Chemistry?

    SciTech Connect (OSTI)

    Crabtree, Robert H

    2011-01-10

    The title topic is reviewed with selected examples taken from recent work, such as: the 'hydrogen borrowing' amine alkylation by alcohols; the dehydrogenative coupling of amine and alcohol to give amide; Ru complexes as solar cell photosensitizers; Ir organometallics as water oxidation catalyst precursors and as OLED emitters; as well as recent hydrogen storage strategies involving catalytic dehydrogenation of ammonia-borane and of organic heterocycles.

  5. Process for selective production of di- and tri-alkylamines

    DOE Patents [OSTI]

    Klier, Kamil (Bethlehem, PA); Herman, Richard G. (Whitehall, PA); Vedage, Gamini A. (Bethlehem, PA)

    1984-01-01

    A primary alkyl amine and an alcohol of up to 12 carbon atoms are reacted at low temperature (50.degree.-250.degree. C.) over specific catalysts (alkali-treated catalysts generally or binary Cu/ZnO and Pd/SiO.sub.2 systems, with or without alkali treatment) to produce, with good selectivity, secondary and tertiary alkylamines of the general formula, R.sub.1 N(R.sub.2).sub.2, wherein R.sub.1 is a lower alkyl or an aryl group, and R.sub.2 is hydrogen or another lower alkyl or aryl group, with at least one of R.sub.2 's being an alkyl or aryl group.

  6. Portal Vein Embolization with Radiolabeled Polyvinyl Alcohol Particles in a Swine Model: Hepatic Distribution and Implications for Pancreatic Islet Cell Transplantation

    SciTech Connect (OSTI)

    Owen, Richard J.; Mercer, John R.; Al-Saif, Faisal; Molinari, Michele; Ashforth, Robert A.; Rajotte, Ray V.; Conner-Spady, Barbara; Shapiro, A. M. James

    2009-05-15

    The distribution of radiolabeled polyvinyl alcohol microspheres (PVAMs) when infused into the portal vein of domestic swine was investigated, with the purpose of assessing implications for pancreatic islet cell transplantation. PVAMs measuring 100-300 {mu}m (Contour SE) and labeled with {sup 99m}Tc were infused into the main portal vein of 12 swine, with intermittent portal venous pressure measurements. The infusion catheter was introduced antegradely via direct or indirect cannulation of the portal vein. The liver was subsequently divided into anatomical segments. Radioactivity (decay corrected) was measured for {sup 99m}Tc microsphere synthesis, dose preparation, gross organ activities, tissue samples, and blood. Particulate labeling, catheter positioning, and infusion were successful in all cases. The number of particles used was (185,000 {+-} 24,000) with a volume of 1 ml. Mean portal pressure at 5 min was significantly higher than baseline, but without a significant difference at 15 min. Extrahepatic tissue and serum radioactivity was negligible. A significant difference in number of radioactive particles per gram was detected between segments 6/7 and segments 5/8. Intrasegmental activity was analyzed, and for segments 2/3 a significant difference in the percentage dose per gram across samples was demonstrated (P = 0.001). Effective and stable radiolabeling of PVAMs with {sup 99m}Tc-sulfur colloid was demonstrated. Portal venous infusion of 100- to 300-{mu}m particles showed entrapment in the sinusoidal hepatic system with transient portal pressure elevation. Preferential embolization into the right lateral and posterior segments occurs, suggesting that flow dynamics/catheter tip position plays a role in particle distribution.

  7. Metal-free g-C{sub 3}N{sub 4} photocatalyst by sulfuric acid activation for selective aerobic oxidation of benzyl alcohol under visible light

    SciTech Connect (OSTI)

    Zhang, Ligang; Liu, Di; Guan, Jing; Chen, Xiufang; Guo, Xingcui; Zhao, Fuhua; Hou, Tonggang; Mu, Xindong

    2014-11-15

    Highlights: A novel visible-light-driven acid-modified g-C{sub 3}N{sub 4} was prepared. The texture, electronic and surface property were tuned by acid modification. Acid-modified g-C{sub 3}N{sub 4} shows much higher activity for photocatalytic activity. Acid sites on the surface of g-C{sub 3}N{sub 4} favor efficient charge separation. - Abstract: In this work, modification of graphitic carbon nitride photocatalyst with acid was accomplished with a facile method through reflux in different acidic substances. The g-C{sub 3}N{sub 4}-based material was found to be a metal-free photocatalyst useful for the selective oxidation of benzyl alcohol with dioxygen as the oxidant under visible light irradiation. Acid modification had a significant influence on the photocatalytic performance of g-C{sub 3}N{sub 4}. Among all acid tested, sulfuric acid-modified g-C{sub 3}N{sub 4} showed the highest catalytic activity and gave benzaldehyde in 23% yield for 4 h under visible light irradiation, which was about 2.5 times higher than that of g-C{sub 3}N{sub 4}. The acid modification effectively improved surface area, reduced structural size, enlarged band gap, enhanced surface chemical state, and facilitated photoinduced charge separation, contributing to the enhanced photocatalytic activity. It is hoped that our work can open promising prospects for the utilization of metal free g-C{sub 3}N{sub 4}-based semiconductor as visible-light photocatalyst for selective organic transformation.

  8. 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.

  9. Homologation process making higher alcohols

    DOE Patents [OSTI]

    Leung, Tak W. (Charleston, WV); Dombek, Bernard D. (Charleston, WV)

    1990-01-01

    A liquid phase process for the manufacture of C.sub.2+ alkanols by the reaction of hydrogen with carbon monoxide in the presence of a catalyst containing ruthenium, cobalt, a halide-containing compound, and an aromatic compound substituted in adjacent ring positions by nitrogen atoms. The process embraces the use of rhodium as an additive to the catalyst system.

  10. Production of long chain alcohols and alkanes upon coexpression of an acyl-ACP reductase and aldehyde-deformylating oxgenase with a bacterial type-I fatty acid synthase in E. coli

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

    Coursolle, Dan; Shanklin, John; Lian, Jiazhang; Zhao, Huimin

    2015-06-23

    Microbial long chain alcohols and alkanes are renewable biofuels that could one day replace petroleum-derived fuels. Here we report a novel pathway for high efficiency production of these products in Escherichia coli strain BL21(DE3). We first identified the acyl-ACP reductase/aldehyde deformylase combinations with the highest activity in this strain. Next, we used catalase coexpression to remove toxic byproducts and increase the overall titer. Finally, by introducing the type-I fatty acid synthase from Corynebacterium ammoniagenes, we were able to bypass host regulatory mechanisms of fatty acid synthesis that have thus far hampered efforts to optimize the yield of acyl-ACP-derived products inmore » BL21(DE3). When all these engineering strategies were combined with subsequent optimization of fermentation conditions, we were able to achieve a final titer around 100 mg/L long chain alcohol/alkane products including a 57 mg/L titer of pentadecane, the highest titer reported in E. coli BL21(DE3) to date. The expression of prokaryotic type-I fatty acid synthases offer a unique strategy to produce fatty acid-derived products in E. coli that does not rely exclusively on the endogenous type-II fatty acid synthase system.« less

  11. Production of long chain alcohols and alkanes upon coexpression of an acyl-ACP reductase and aldehyde-deformylating oxgenase with a bacterial type-I fatty acid synthase in E. coli

    SciTech Connect (OSTI)

    Coursolle, Dan; Shanklin, John; Lian, Jiazhang; Zhao, Huimin

    2015-06-23

    Microbial long chain alcohols and alkanes are renewable biofuels that could one day replace petroleum-derived fuels. Here we report a novel pathway for high efficiency production of these products in Escherichia coli strain BL21(DE3). We first identified the acyl-ACP reductase/aldehyde deformylase combinations with the highest activity in this strain. Next, we used catalase coexpression to remove toxic byproducts and increase the overall titer. Finally, by introducing the type-I fatty acid synthase from Corynebacterium ammoniagenes, we were able to bypass host regulatory mechanisms of fatty acid synthesis that have thus far hampered efforts to optimize the yield of acyl-ACP-derived products in BL21(DE3). When all these engineering strategies were combined with subsequent optimization of fermentation conditions, we were able to achieve a final titer around 100 mg/L long chain alcohol/alkane products including a 57 mg/L titer of pentadecane, the highest titer reported in E. coli BL21(DE3) to date. The expression of prokaryotic type-I fatty acid synthases offer a unique strategy to produce fatty acid-derived products in E. coli that does not rely exclusively on the endogenous type-II fatty acid synthase system.

  12. The Structure and Phase Diagram of Chiral Alkyl-Serine Monolayers on Mercury

    SciTech Connect (OSTI)

    L Tamam; D Medina; T Menahem; Y Mastai; E Sloutskin; S Yefet; M Deutsch

    2011-12-31

    The structure of liquid-mercury-supported Langmuir films (LFs) of chiral serine-modified fatty acid molecules was studied as a function of length, n = 8-22 carbons, temperature, T = 5-25 C, and surface coverage, A {approx} 40-200 {angstrom}{sup 2} per molecule, for both homochiral and heterochiral compounds. Using surface pressure {pi}-area A isotherms and surface-specific synchrotron X-ray diffraction methods the phase diagram was determined in detail. No lateral order was found for phases comprising surface-parallel molecules, in contrast with unmodified fatty acid LFs on mercury. For phases comprising standing-up molecules, long range lateral order was found for n {>=} 12, but no order for n = 8. The molecules in the ordered phases are extended, and tilt rigidly by {approx}40{sup o} from the surface normal. The homochiral LFs pack in an oblique, single-molecule, unit cell. The heterochiral LFs pack in a body-centered rectangular unit cell, containing two molecules. Unlike unmodified fatty acid LFs, the structure of the standing-up phase does not vary with n, T or A. The interactions underlying these characteristics, and the role of chirality, are discussed.

  13. Growth and stability of oxidation resistant Si nanocrystals formed by decomposition of alkyl silanes

    SciTech Connect (OSTI)

    Zaitseva, N; Hamel, S; Dai, Z R; Saw, C; Williamson, A J; Galli, G

    2007-01-12

    The synthesis and characterization of 1-10 nm Si nanocrystals highly resistant to oxidation is described. The nanocrystals were prepared by thermal decomposition of tetramethylsilane at 680 C, or in a gold- induced catalytic process at lower temperatures down to 400-450 C using trioctylamine as an initial solvent. Transmission electron microscopic analysis of samples obtained in the presence of gold show that the nanocrystals form via solid-phase epitaxial attachment of Si to the gold crystal lattice. The results of computational modeling performed using first principles density functional theory (DFT) calculations predict that the enhanced stability of nanocrystals to oxidation is due to the presence of N or N-containing groups on the surface of nanocrystals.

  14. I. The synthesis and characterization of annulated uranocenes. II. The variable temperature /sup 1/H NMR of uranocenes

    SciTech Connect (OSTI)

    Luke, W.D.

    1980-01-01

    A general synthetic route to alkyl annulated cyclooctatetraene dianions and the corresponding annulated uranocenes has been developed. Dideprotonation of bicyclooctatrienes, resulting from reaction of cyclooctatetraene dianion with l,n-dialkylbromides or methanesulfonates, affords alkyl annulated cyclooctatetraene dianions in moderate yields. Dicyclopenteno-, bisdimethylcyclopenteno- and dicyclohexenouranocene were prepared from the corresponding cyclooctatetraene dianions and UCl/sub 4/. The structures of dicyclobuteno- and dicyclopentenouranocene were elucidated by single crystal X-ray diffraction, and the effects of annulation on the uranocene skeleton are discussed. Attempted synthesis of benzocyclooctatetraene and a benzannulated uranocene is reported. The variable temperature /sup 1/H NMR spectrum of uranocene has been reinvestigated from -100 to 100/sup 0/C. The isotropic shift was found to be linear in T/sup -1/ with an extrapolated intercept of 0 at T/sup -1/ = 0. Variable temperature /sup 1/H NMR spectra, from -80 to 70/sup 0/C, of 17 substituted uranocenes are reported. The energy barrier to ring rotation in 1,1', 4,4'-tetra-t-butyl-uranocene was determined to be 8.24 +- 0.5 kcal/mole while the barrier in the corresponding 1,1', 3,3'-tetra-t-butylferrocene was determined to be 13.1 kcal/mole. Alkyl substitution is shown to have little effect on the electronic and magnetic properties of the uranocene skeleton, and thus alkyl substituted uranocenes are treated as having effective axial symmetry in analysis of the observed isotropic shifts. Using diannulated uranocenes as model systems an analysis of the contact and pseudocontact components of the observed isotropic shifts in uranocene and alkyl substituted uranocenes is presented.

  15. Process for recycling components of a PEM fuel cell membrane electrode assembly

    DOE Patents [OSTI]

    Shore, Lawrence (Edison, NJ)

    2012-02-28

    The membrane electrode assembly (MEA) of a PEM fuel cell can be recycled by contacting the MEA with a lower alkyl alcohol solvent which separates the membrane from the anode and cathode layers of the assembly. The resulting solution containing both the polymer membrane and supported noble metal catalysts can be heated under mild conditions to disperse the polymer membrane as particles and the supported noble metal catalysts and polymer membrane particles separated by known filtration means.

  16. Biodiesel - SSC Process - Energy Innovation Portal

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

    Biodiesel - SSC Process Idaho National Laboratory Contact INL About This Technology Publications: PDF Document Publication Fact Sheet (1,290 KB) Technology Marketing Summary INL's biodiesel-SSC uses solid catalyst under super-critical fluid conditions to produce biodiesel from a full range of lipid feedstock. This invention provides in a single-phase process for producing alkyl esters from triglycerides or fatty acid material feedstock. The material is mixed with an alcohol and a solvent

  17. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    Processing Area Definitions Key Terms Definition Aviation Gasoline Blending Components Naphthas which will be used for blending or compounding into finished aviation gasoline (e.g., straight-run gasoline, alkylate, reformate, benzene, toluene, and xylene). Excludes oxygenates (alcohols, ethers), butane, and pentanes plus. Oxygenates are reported as other hydrocarbons, hydrogen, and oxygenates. Barrel A unit of volume equal to 42 U.S. gallons. Conventional Blendstock for Oxygenate Blending (CBOB)

  18. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    Input Definitions Key Terms Definition Aviation Gasoline Blending Components Naphthas which will be used for blending or compounding into finished aviation gasoline (e.g., straight-run gasoline, alkylate, reformate, benzene, toluene, and xylene). Excludes oxygenates (alcohols, ethers), butane, and pentanes plus. Oxygenates are reported as other hydrocarbons, hydrogen, and oxygenates. Barrel A unit of volume equal to 42 U.S. gallons. Conventional Blendstock for Oxygenate Blending (CBOB) Motor

  19. Table Definitions, Sources, and Explanatory Notes

    Gasoline and Diesel Fuel Update (EIA)

    and Blender Net Inputs Definitions Key Terms Definition Aviation Gasoline Blending Components Naphthas which will be used for blending or compounding into finished aviation gasoline (e.g., straight-run gasoline, alkylate, reformate, benzene, toluene, and xylene). Excludes oxygenates (alcohols, ethers), butane, and pentanes plus. Oxygenates are reported as other hydrocarbons, hydrogen, and oxygenates. Barrel A unit of volume equal to 42 U.S. gallons. Blending Plant A facility which has no

  20. Preparation of titanium oxide ceramic membranes

    DOE Patents [OSTI]

    Anderson, Marc A. (Madison, WI); Xu, Qunyin (Madison, WI)

    1992-01-01

    A procedure is disclosed for the reliable production of either particulate or polymeric titanium ceramic membranes by a highly constrained sol-gel procedure. The critical constraints in the procedure include the choice of alkyl alcohol solvent, the amount of water and its rate of addition, the pH of the solution during hydrolysis, and the limit of sintering temperature applied to the resulting gels.

  1. Preparation of titanium oxide ceramic membranes

    DOE Patents [OSTI]

    Anderson, M.A.; Xu, Q.

    1992-03-17

    A procedure is disclosed for the reliable production of either particulate or polymeric titanium ceramic membranes by a highly constrained sol-gel procedure. The critical constraints in the procedure include the choice of alkyl alcohol solvent, the amount of water and its rate of addition, the pH of the solution during hydrolysis, and the limit of sintering temperature applied to the resulting gels.

  2. ARTIFACT FORMATION DURING NEUTRALIZATION OF TANK 50 SAMPLES

    SciTech Connect (OSTI)

    Crump, S.; Young, J.

    2014-08-01

    Degradation products have been identified in the extracts of Tank 50 samples analyzed by semivolatile organic compound analysis (SVOA) using gas chromatography/mass spectrometry (GC/MS). These materials, identified as short chain alkyl alcohols, were formed by acidification during sample preparation. A number of questions were raised about the formation of these and other materials reported in Tank 50 surface samples, and this report serves to address these questions.

  3. Downregulation of Cinnamyl Alcohol Dehydrogenase (CAD) Leads...

    Office of Scientific and Technical Information (OSTI)

    Sponsoring Org: USDOE Office of Science (SC), Biological and Environmental Research (BER) Country of Publication: United States Language: English Word Cloud More Like This Full ...

  4. Demonstration of alcohol as an aviation fuel

    SciTech Connect (OSTI)

    1996-07-01

    A recently funded Southeastern Regional Biomass Energy Program (SERBEP) project with Baylor University will demonstrate the effectiveness of ethanols as an aviation fuel while providing several environmental and economic benefits. Part of this concern is caused by the petroleum industry. The basis for the petroleum industry to find an alternative aviation fuel will be dictated mainly by economic considerations. Three other facts compound the problem. First is the disposal of oil used in engines burning leaded fuel. This oil will contain too much lead to be burned in incinerators and will have to be treated as a toxic waste with relatively high disposal fees. Second, as a result of a greater demand for alkalites to be used in the automotive reformulated fuel, the costs of these components are likely to increase. Third, the Montreal Protocol will ban in 1998 the use of Ethyl-Di-Bromide, a lead scavenger used in leaded aviation fuel. Without a lead scavenger, leaded fuels cannot be used. The search for alternatives to leaded aviation fuels has been underway by different organizations for some time. As part of the search for alternatives, the Renewable Aviation Fuels Development Center (RAFDC) at Baylor University in Waco, Texas, has received a grant from the Federal Aviation Administration (FAA) to improve the efficiencies of ethanol powered aircraft engines and to test other non-petroleum alternatives to aviation fuel.

  5. Fuel alcohol production from agricultural lignocellulosic feedstocks

    SciTech Connect (OSTI)

    Farina, G.E.; Barrier, J.W.; Forsythe, M.L. )

    1988-01-01

    A two-stage, low-temperature, ambient pressure, acid hydrolysis process that utilizes separate unit operations to convert hemicellulose and cellulose in agricultural residues and crops to fermentable sugars is being developed and tested. Based on the results of the bench-scale tests, an acid hydrolysis experimental plant to demonstrate the concepts of low-temperature acid hydrolysis on a much larger scale was built. Plant tests using corn stover have been conducted for more that a year and conversion efficiences have equaled those achieved in the laboratory. Laboratory tests to determine the potential for low-temperature acid hydrolysis of other feedstocks - including red clover, alfalfa, kobe lespedeza, winter rape, and rye grass - are being conducted. Where applicable, process modifications to include extraction before or after hydrolysis also are being studied. This paper describes the experimental plant and process, results obtained in the plant, results of alternative feedstocks testing in the laboratory, and a plan for an integrated system that will produce other fuels, feed, and food from crops grown on marginal land.

  6. Alcohol fuels bibliography, 1901-March 1980

    SciTech Connect (OSTI)

    Not Available

    1981-04-01

    This annotated bibliography is subdivided by subjects, as follows: general; feedstocks-general; feedstocks-sugar; feedstocks-starch; feedstocks-cellulose crops and residues; production; coproducts; economics; use as vehicle fuel; government policies; and environmental effects and safety. (MHR)

  7. Task 4.9 -- Value-added products from syngas. Semi-annual report, July 1--December 31, 1996

    SciTech Connect (OSTI)

    Olson, E.S.; Sharma, R.K.

    1997-08-01

    The work on advanced fuel forms in 1996 focused on the synthesis of higher alcohols from mixtures of hydrogen and carbon dioxide (syngas) from coal gasification. Initial work in this project utilized a novel molybdenum sulfide catalyst previously shown to be active for hydrodesulfurization reactions of coal liquids. A pressurized fixed-bed flow-through reactor was constructed, and the MoS{sub 2} catalysts were tested with syngas under a variety of conditions. Unfortunately, the catalysts, even with higher molybdenum loading and addition of promoters, failed to give alcohol products. A batch reactor test of the catalyst was also conducted, but did not produce alcohol products. Group VIII metals have been used previously in catalysts for syngas reactions. Ruthenium and rhodium catalysts were prepared by impregnation of a hydrotalcite support. Tests with these catalysts in flow-through reactors also did not produce the desired alcohol products. The formation of higher alcohols from smaller ones, such as methanol and ethanol, could be commercially important if high selectivity could be achieved. The methanol and ethanol would be derived from syngas and fermentation, respectively. Based on previous work in other laboratories, it was hypothesized that the hydrotalcite-supported MoS{sub 2} or Ru or Rh catalysts could catalyze the formation of butyl alcohols. Although the desired 1-butanol was obtained in batch reactions with the promoted ruthenium catalyst, the reaction was not as selective as desired. Product suitable for a lower-vapor-pressure gasoline oxygenate additive was obtained, but it may not be economical to market such products in competition with methyl tertiary-butyl ether (MTBE). Flow-through catalytic bed reactions were not successful.

  8. Delayed cure bismaleimide resins

    DOE Patents [OSTI]

    Adams, Johnnie E. (Grandview, MO); Jamieson, Donald R. (Merriam, KS)

    1984-08-07

    Polybismaleimides prepared by delayed curing of bis-imides having the formula ##STR1## wherein R.sub.1 and R.sub.2 each independently is H, C.sub.1-4 -alkyl, C.sub.1-4 -alkoxy, Cl or Br, or R.sub.1 and R.sub.2 together form a fused 6-membered hydrocarbon aromatic ring, with the proviso that R.sub.1 and R.sub.2 are not t-butyl or t-butoxy; X is O, S or Se; n is 1-3; and the --(CH.sub.2).sub.n -- group, optionally, is substituted by 1-3 methyl groups or by fluorine.

  9. Bismaleimide compounds

    DOE Patents [OSTI]

    Adams, Johnnie E. (Grandview, MO); Jamieson, Donald R. (Merriam, KS)

    1986-01-14

    Bismaleimides of the formula ##STR1## wherein R.sub.1 and R.sub.2 each independently is H, C.sub.1-4 -alkyl, C.sub.1-4 -alkoxy, C1 or Br, or R.sub.1 and R.sub.2 together form a fused 6-membered hydrocarbon aromatic ring, with the proviso that R.sub.1 and R.sub.2 are not t-butyl or t-butoxy; X is O, S or Se; n is 1-3; and the alkylene bridging group, optionally, is substituted by 1-3 methyl groups or by fluorine, form polybismaleimide resins which have valuable physical properties. Uniquely, these compounds permit extended cure times, i.e., they remain fluid for a time sufficient to permit the formation of a homogeneous melt prior to curing.

  10. Synthesis and characterization of new class of ionic liquids containing phenolate anion

    SciTech Connect (OSTI)

    Lethesh, Kallidanthiyil Chellappan; Wilfred, Cecilia Devi; Taha, M. F.; Thanabalan, M.

    2014-10-24

    In these manuscript novel ionic liquids containing a new class of 'phenolate' anions was synthesized and characterized. 1-methylmidazole with different alkyl chains such as butyl, hexyl and octyl groups was used as the cationic part. All the ionic liquids were obtained as liquids at room temperature. The synthesized ionic liquids were characterized using {sup 1}H NMR and {sup 13}C NMR spectroscopy. The thermal stability of the ionic liquids was studied using thermo gravimetric analysis (TGA). The effect of temperature on the density and viscosity of the ionic liquids were studied over a temperature range from 293.15 K to 373.15K at atmospheric pressure. From the experimental values of density, the molecular volume, standard molar entropy and the lattice energy of the ionic liquids were calculated.

  11. Separation of actinides(III) from lanthanides(III) by extraction chromatography using new n,n'-dialkyl-n,n'-diphenyl-pyridine-2,6-di-carboxy-amides

    SciTech Connect (OSTI)

    Arisaka, Makoto; Watanabe, Masayuki; Kimura, Takaumi

    2007-07-01

    Four N,N'-dialkyl-N,N'-diphenyl-pyridine-2,6- di-carboxy-amides (R-PDA; R butyl, octyl, decyl, dodecyl) were newly synthesized and were applied to extraction chromatography as extractant to attain the separation of actinides(III) from high level radioactive waste containing lanthanides(III). R-PDA was successfully impregnated into XAD-4 resin. It was found that (i) the leakage of R-PDA from XAD-4 resin was suppressed with an increase of the length of the alkyl groups in R-PDA, while the leakage for each adsorbent resin was promoted with an increase of HNO{sub 3} concentration in the aqueous phase and (ii) Oc-PDA or De-PDA/XAD-4 resin exhibits moderate separation ability of actinides(III) from lanthanides(III) at relatively high HNO{sub 3} concentration. (authors)

  12. Bismaleimide compounds

    DOE Patents [OSTI]

    Adams, J.E.; Jamieson, D.R.

    1986-01-14

    Bismaleimides of the formula shown in the diagram wherein R[sub 1] and R[sub 2] each independently is H, C[sub 1-4]-alkyl, C[sub 1-4]-alkoxy, Cl or Br, or R[sub 1] and R[sub 2] together form a fused 6-membered hydrocarbon aromatic ring, with the proviso that R[sub 1] and R[sub 2] are not t-butyl or t-butoxy; X is O, S or Se; n is 1--3; and the alkylene bridging group, optionally, is substituted by 1--3 methyl groups or by fluorine, form polybismaleimide resins which have valuable physical properties. Uniquely, these compounds permit extended cure times, i.e., they remain fluid for a time sufficient to permit the formation of a homogeneous melt prior to curing.

  13. The efficient use of natural gas in transportation

    SciTech Connect (OSTI)

    Stodolsky, F.; Santini, D.J.

    1992-04-01

    Concerns over air quality and greenhouse gas emissions have prompted discussion as well as action on alternative fuels and energy efficiency. Natural gas and natural gas derived fuels and fuel additives are prime alternative fuel candidates for the transportation sector. In this study, we reexamine and add to past work on energy efficiency and greenhouse gas emissions of natural gas fuels for transportation (DeLuchi 1991, Santini et a. 1989, Ho and Renner 1990, Unnasch et al. 1989). We add to past work by looking at Methyl tertiary butyl ether (from natural gas and butane component of natural gas), alkylate (from natural gas butanes), and gasoline from natural gas. We also reexamine compressed natural gas, liquified natural gas, liquified petroleum gas, and methanol based on our analysis of vehicle efficiency potential. We compare the results against nonoxygenated gasoline.

  14. The efficient use of natural gas in transportation

    SciTech Connect (OSTI)

    Stodolsky, F.; Santini, D.J.

    1992-01-01

    Concerns over air quality and greenhouse gas emissions have prompted discussion as well as action on alternative fuels and energy efficiency. Natural gas and natural gas derived fuels and fuel additives are prime alternative fuel candidates for the transportation sector. In this study, we reexamine and add to past work on energy efficiency and greenhouse gas emissions of natural gas fuels for transportation (DeLuchi 1991, Santini et a. 1989, Ho and Renner 1990, Unnasch et al. 1989). We add to past work by looking at Methyl tertiary butyl ether (from natural gas and butane component of natural gas), alkylate (from natural gas butanes), and gasoline from natural gas. We also reexamine compressed natural gas, liquified natural gas, liquified petroleum gas, and methanol based on our analysis of vehicle efficiency potential. We compare the results against nonoxygenated gasoline.

  15. Ordered, microphase-separated, noncharged-charged diblock copolymers via the sequential ATRP of styrene and styrenic imidazolium monomers

    SciTech Connect (OSTI)

    Shi, ZX; Newell, BS; Bailey, TS; Gin, DL

    2014-12-15

    A series of imidazolium-based noncharged-charged diblock copolymers (1) was synthesized by the direct, sequential ATRP of styrene and styrenic imidazolium bis(trifluoromethyl)sulfonamide monomers with methyl, n-butyl, and n-decyl side-chains. Small-angle X-ray scattering studies on initial examples of 1 with a total of 50 repeat units and styrene:imidazolium-styrene repeat unit ratios of 25:25, 20:30, and 15:35 showed that their ability to form ordered nanostructures (i.e., sphere and cylinder phases) in their neat states depends on both the block ratio and the length of the alkyl side-chain on the imidazolium monomer. To our knowledge, the synthesis of imidazolium-based BCPs that form ordered, phase-separated nanostructures via direct ATRP of immiscible co-monomers is unprecedented. (C) 2014 Elsevier Ltd. All rights reserved.

  16. Synthesis of triazole-based and imidazole-based zinc catalysts

    DOE Patents [OSTI]

    Valdez, Carlos A.; Satcher, Jr., Joe H.; Aines, Roger D.; Baker, Sarah E.

    2013-03-12

    Various methods and structures of complexes and molecules are described herein related to a zinc-centered catalyst for removing carbon dioxide from atmospheric or aqueous environments. According to one embodiment, a method for creating a tris(triazolyl)pentaerythritol molecule includes contacting a pentaerythritol molecule with a propargyl halide molecule to create a trialkyne molecule, and contacting the trialkyne molecule with an azide molecule to create the tris(triazolyl)pentaerythritol molecule. In another embodiment, a method for creating a tris(imidazolyl)pentaerythritol molecule includes alkylating an imidazole 2-carbaldehyde molecule to create a monoalkylated aldehyde molecule, reducing the monoalkylated aldehyde molecule to create an alcohol molecule, converting the alcohol molecule to create an alkyl halide molecule using thionyl halide, and reacting the alkyl halide molecule with a pentaerythritol molecule to create a tris(imidazolyl)pentaerythritol molecule. In another embodiment, zinc is bound to the tris(triazolyl)pentaerythritol molecule to create a zinc-centered tris(triazolyl)pentaerythritol catalyst for removing carbon dioxide from atmospheric or aqueous environments.

  17. Chain architecture and micellization: A mean-field coarse-grained model for poly(ethylene oxide) alkyl ether surfactants

    SciTech Connect (OSTI)

    García Daza, Fabián A.; Mackie, Allan D.; Colville, Alexander J.

    2015-03-21

    Microscopic modeling of surfactant systems is expected to be an important tool to describe, understand, and take full advantage of the micellization process for different molecular architectures. Here, we implement a single chain mean field theory to study the relevant equilibrium properties such as the critical micelle concentration (CMC) and aggregation number for three sets of surfactants with different geometries maintaining constant the number of hydrophobic and hydrophilic monomers. The results demonstrate the direct effect of the block organization for the surfactants under study by means of an analysis of the excess energy and entropy which can be accurately determined from the mean-field scheme. Our analysis reveals that the CMC values are sensitive to branching in the hydrophilic head part of the surfactant and can be observed in the entropy-enthalpy balance, while aggregation numbers are also affected by splitting the hydrophobic tail of the surfactant and are manifested by slight changes in the packing entropy.

  18. Deetherification process

    DOE Patents [OSTI]

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

    1985-01-01

    Ethers such as isobutyl tertiary butyl ether are dissociated into their component alcohols and isolefins by heat stabilized catalyst compositions prepared from nuclear sulfonic acid, for example, macroporous crosslinked polyvinyl aromatic compounds containing sulfonic acid groups are neutralized with a metal of Al, Fe, Zn, Cu, Ni, ions or mixtures and alkali, alkaline earth metals or ammonium ions by contacting the resin containing the sulfonic acid with aqueous solutions of the metals salts and alkali, alkaline earth metal or ammonium salts. The catalysts have at least 50% of the sulfonic acid groups neutralized with metal ions and the balance of the sulfonic acid groups neutralized with alkali, alkaline earth ions or ammonium ions.

  19. Deetherification process

    DOE Patents [OSTI]

    Smith, L.A. Jr.

    1985-11-05

    Ethers such as isobutyl tertiary butyl ether are dissociated into their component alcohols and isoolefins by heat stabilized catalyst compositions prepared from nuclear sulfonic acid, for example, macroporous crosslinked polyvinyl aromatic compounds containing sulfonic acid groups are neutralized with a metal of Al, Fe, Zn, Cu, Ni, ions or mixtures and alkali, alkaline earth metals or ammonium ions by contacting the resin containing the sulfonic acid with aqueous solutions of the metals salts and alkali, alkaline earth metal or ammonium salts. The catalysts have at least 50% of the sulfonic acid groups neutralized with metal ions and the balance of the sulfonic acid groups neutralized with alkali, alkaline earth ions or ammonium ions.

  20. Selective flotation of phosphate minerals with hydroxamate collectors

    DOE Patents [OSTI]

    Miller, Jan D.; Wang, Xuming; Li, Minhua

    2002-01-01

    A method is disclosed for separating phosphate minerals from a mineral mixture, particularly from high-dolomite containing phosphate ores. The method involves conditioning the mineral mixture by contacting in an aqueous in environment with a collector in an amount sufficient for promoting flotation of phosphate minerals. The collector is a hydroxamate compound of the formula; ##STR1## wherein R is generally hydrophobic and chosen such that the collector has solubility or dispersion properties it can be distributed in the mineral mixture, typically an alkyl, aryl, or alkylaryl group having 6 to 18 carbon atoms. M is a cation, typically hydrogen, an alkali metal or an alkaline earth metal. Preferably, the collector also comprises an alcohol of the formula, R'--OH wherein R' is generally hydrophobic and chosen such that the collector has solubility or dispersion properties so that it can be distributed in the mineral mixture, typically an alkyl, aryl, or alkylaryl group having 6 to 18 carbon atoms.

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

    SciTech Connect (OSTI)

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

    1991-03-01

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

  2. Synthesis of high specific activity (1- sup 3 H)-Farnesyl pyrophosphate

    SciTech Connect (OSTI)

    Saljoughian, M.; Morimoto, H.; Williams, P.G. . Chemical Biodynamics Div.)

    1992-03-01

    In this paper, the synthesis of tritiated farnesyl pyrophosphate with high specific activity is reported. E, E-Farnesol was oxidized to the corresponding aldehyde followed by reduction with lithium aluminum tritide (5% {sup 3}H) to give (1-{sup 3}H)-E, E-Farnesol. The specific radioactivity of the alcohol was determined from its triphenylsilane derivative, prepared under very mild conditions. The tritiated alcohol was phosphorylated by initial conversion to an allylic halide, and subsequent treatment of the halide with tris (tetra-n-butyl) ammonium hydrogen pyrophosphate. The hydride procedure followed in this work has advantages over existing methods for the synthesis of tritiated farnesyl pyrophosphate, giving a much higher radiochemical yield and offering the possibility of achieving theoretical specific activity levels when fully tritiated LiAlT{sub 4} is employed.

  3. Task 4.9 -- Value-added products from syngas

    SciTech Connect (OSTI)

    Olson, E.S.; Sharma, R.K.

    1997-02-01

    The work on advanced fuel forms in 1996 focused on the synthesis of higher alcohols from mixtures of hydrogen and carbon dioxide (syngas) from coal gasification. The conversion of coal gasification products to commercially valuable alcohols will provide an important new market for current and future gasification plants. Initial work in this project utilized a novel molybdenum sulfide catalyst previously shown to be active for hydrodesulfurization reactions of coal liquids. The support for the active metal sulfide is a layered mixed oxide (hydrotalcite) capable of interaction with the metal sites for catalysis of carbon monoxide reductions. These catalysts have a high surface area, are highly porous, and have basic and acidic functionality. A pressurized fixed-bed flow-through reactor was constructed, and the MoS{sub 2} catalysts were tested with syngas under a variety of conditions. Unfortunately, the catalysts, even with higher molybdenum loading and addition of promoters, failed to give alcohol products. A batch reactor test of the catalyst was also conducted, but did not produce alcohol products. Group 8 metals have been used previously in catalysts for syngas reactions. Ruthenium and rhodium catalysts were prepared by impregnation of a hydrotalcite support. Tests with these catalysts in flow-through reactors also did not produce the desired alcohol products. The formation of higher alcohols from smaller ones, such as methanol and ethanol, could be commercially important if high selectivity could be achieved. The methanol and ethanol would be derived from syngas and fermentation, respectively. Based on previous work in other laboratories, it was hypothesized that the hydrotalcite supported MoS{sub 2} or Ru or Rh catalysts could catalyze the formation of butyl alcohols. Although the desired 1-butanol was obtained in batch reactions with the promoted Ru catalyst, the reaction was not as selective as desired. Product suitable for a lower-vapor-pressure gasoline oxygenate additive was obtained, but it may not be economical to market such products in competition with methyl tertiary-butyl-ether. Flow-through catalytic bed reactions were not successful.

  4. Removal of arsenic compounds from spent catecholated polymer

    DOE Patents [OSTI]

    Fish, Richard H.

    1985-01-01

    Described is a process for removing arsenic from petroliferous derived liquids by contacting said liquid at an elevated temperature with a divinylbenzene-crosslinked polystyrene having catechol ligands anchored thereon. Also, described is a process for regenerating spent catecholated polystyrene by removal of the arsenic bound to it from contacting petroliferous liquid as described above and involves: a. treating said spent catecholated polystyrene, at a temperature in the range of about 20.degree. to 100.degree. C. with an aqueous solution of at least one carbonate and/or bicarbonate of ammonium, alkali and alkaline earth metals, said solution having a pH between about 8 and 10 and, b. separating the solids and liquids from each other. Preferably the regeneration treatment is in two steps wherein step (a) is carried out with an aqueous alcoholic carbonate solution containing lower alkyl alcohol, and, steps (a) and (b) are repeated using a bicarbonate.

  5. Removal of arsenic compounds from petroliferous liquids

    DOE Patents [OSTI]

    Fish, Richard H.

    1985-01-01

    Described is a process for removing arsenic from petroliferous derived liquids by contacting said liquid at an elevated temperature with a divinylbenzene-crosslinked polystyrene having catechol ligands anchored thereon. Also, described is a process for regenerating spent catecholated polystyrene by removal of the arsenic bound to it from contacting petroliferous liquid as described above and involves: a. treating said spent catecholated polystyrene, at a temperature in the range of about 20.degree. to 100.degree. C. with an aqueous solution of at least one carbonate and/or bicarbonate of ammonium, alkali and alkaline earth metals, said solution having a pH between about 8 and 10 and, b. separating the solids and liquids from each other. Preferably the regeneration treatment is in two steps wherein step (a) is carried out with an aqueous alcoholic carbonate solution containing lower alkyl alcohol, and, steps (a) and (b) are repeated using a bicarbonate.

  6. Catalytic conversion of light alkanes, Phase 3. Topical report, January 1990--December 1992

    SciTech Connect (OSTI)

    1992-12-31

    The mission of this work is to devise a new catalyst which can be used in the first simple, economic process to convert the light alkanes in natural gas to an alcohol-rich oxygenated product which can either be used as an environmentally friendly, high-performance liquid fuel, or a precursor to a liquid hydrocarbon transportation fuel. The authors have entered the proof-of-concept stage for converting isobutane to tert butyl alcohol in a practical process and are preparing to enter proof-of-concept of a propane to isopropyl alcohol process in the near future. Methane and ethane are more refractory and thus more difficult to oxidize than the C{sub 3} and C{sub 4} hydrocarbons. Nonetheless, advances made in this area indicate that further research progress could achieve the goal of their direct conversion to alcohols. Progress in Phase 3 catalytic vapor phase methane and ethane oxidation over metals in regular oxidic lattices are the subject of this topical report.

  7. Catalytic ionic hydrogenation of ketones using tungsten or molybdenum organometallic species

    DOE Patents [OSTI]

    Voges, Mark; Bullock, R. Morris

    2000-01-01

    The present invention is a process for the catalytic hydrogenation of ketones and aldehydes to alcohols at low temperatures and pressures using organometallic molybdenum and tungsten complexes. The functional group is selected from groups represented by the formulas R(C.dbd.O)R' and R(C.dbd.O)H, wherein R and R' are selected from hydrogen or any alkyl or aryl group. The active catalyst for the process has the form: [CpM(CO).sub.2 (PR*.sub.3) L].sup.+ A.sup.-, where Cp=.eta..sup.5 -R.sup..tangle-solidup..sub.m C.sub.5 H.sub.5-m and R.sup..tangle-solidup. represents an alkyl group or a halogen (F, Cl, Br, I) or R.sup..tangle-solidup. =OR' (where R'=H, an alkyl group or an aryl group) or R.sup..tangle-solidup. =CO.sub.2 R' (where R'=H, an alkyl group or an aryl group) and m=0 to 5; M represents a molybdenum atom or a tungsten atom; R*.sub.3 represents three hydrocarbon groups selected from a cyclohexyl group (C.sub.6 H.sub.11), a methyl group (CH.sub.3), and a phenyl group (C.sub.6 H.sub.5) and all three R* groups can be the same or different or two of the three groups can be the same; L represents a ligand; and A.sup.- represents an anion. In another embodiment, one, two or three of the R* groups can be an OR*.

  8. Alcohol as a fuel for farm and construction equipment

    SciTech Connect (OSTI)

    Borman, G L; Foster, D E; Meyers, P S; Uyehara, O A

    1982-06-01

    Work in three areas dealing with the utilization of ethanol as fuel for farm and construction diesels is summarized. The first part is a review of what is known about the retrofitting of diesels for use of ethanol and the combustion problems involved. The second part is a discussion of the work that has been done under the contract on the performance of a single-cylinder, open-chamber diesel using solutions and emulsions of diesel fuel with ethanol. Data taken include performance, emissions and cylinder pressure-time for diesel fuel with zero to forty percent ethanol by volume. Analysis of the data includes calculation of heat release rates using a single zone model. The third part is a discussion of work done retrofitting a multicylinder turbocharged farm tractor diesel to use ethanol by fumigation. Three methods of ethanol introduction are discussed; spraying ethanol upstream and downstream of the compressor and prevaporization of the ethanol. Data on performance and emissions are given for the last two methods. A three zone heat release model is described and results from the model are given. A correlation of the ignition delay using prevaporized ethanol fumigation data is also given. Comparisons are made between fumigation in DI and IDI engines.

  9. 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.

  10. Methods for dehydration of sugars and sugar alcohols

    DOE Patents [OSTI]

    Holladay, Johnathan E [Kennewick, WA; Hu, Jianli [Kennewick, WA; Zhang, Xinjie [Burlington, MA; Wang, Yong [Richland, WA

    2010-08-10

    The invention includes a method of dehydration of a sugar using a dehydration catalyst and a co-catalyst within a reactor. A sugar is introduced and H.sub.2 is flowed through the reactor at a pressure of less than or equal to about 300 psig to convert at least some of the sugar into an anhydrosugar product. The invention includes a process for producing isosorbide. A starting material comprising sorbitol is flowed into a reactor. H.sub.2 is counter flowed through the reactor. The starting material is exposed to a catalyst in the presence of a co-catalyst which comprises at least one metal. The exposing is conducted at a hydrogen pressure of less than or equal to 300 psig within the reactor and the hydrogen removes at least some of any water present during the exposing and inhibits formation of colored byproducts.

  11. Renewable Hydrogen Production Using Sugars and Sugar Alcohols (Presentation)

    Broader source: Energy.gov [DOE]

    Presented at the 2007 Bio-Derived Liquids to Hydrogen Distributed Reforming Working Group held November 6, 2007 in Laurel, Maryland.

  12. Supply Impacts of an MTBE Ban

    Reports and Publications (EIA)

    2002-01-01

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

  13. Development of candidate chemical simulant list: the evaluation of candidate chemical simulants which may be used in chemically hazardous operations. Final report 15 Jun-15 Dec 82

    SciTech Connect (OSTI)

    Not Available

    1982-12-01

    The objectives of this task were threefold: (1) to provide additional data for the proposed candidate simulates dipentene, methyl benzoate and benzyl alcohol by means of in-depth literature searches encompassing both computerized data bases and a manual search of the older literature; (2) to fully evaluate twelve possible candidate simulants under more flexible simulant criteria; and (3) to develop a list of candidate simulants in the low and non-volatile categories. Computerized literature searches were conducted for the twelve possible candidate simulants under more flexible intake simulant criteria as well as for dimethyl methylphosphonate, a compound selected for evaluation by the USAF. The twelve possible candidates included: cyclohexanone, n-dodecanethiol, methyl salicylate, dihexyl ether, dypnone, n-aminopropyl morpholine, n-(2-hydroxyethyl) morpholine, butyl salicylate, di(2-ethyl hexyl) ether, 2-undecanol, 2-hydroxyethyl-n-octyl sulfide and n,n-diethyl-m-toluamide. Full assessments of the potential health hazards associated with exposure to n-dodecanethiol, methyl salicylate, butyl salicylate and n,n-diethyl-m-toluamide were completed. All of these compounds meet the majority of USAF criteria for candidate simulants. Cyclohexanone was disqualified for reasons of toxicity, while the available toxicological data for the seven remaining candidates were considered inadequate for full assessment of hazard.

  14. Low emissions diesel fuel

    DOE Patents [OSTI]

    Compere, A.L.; Griffith, W.L.; Dorsey, G.F.; West, B.H.

    1998-05-05

    A method and matter of composition for controlling NO{sub x} emissions from existing diesel engines. The method is achieved by adding a small amount of material to the diesel fuel to decrease the amount of NO{sub x} produced during combustion. Specifically, small amounts, less than about 1%, of urea or a triazine compound (methylol melamines) are added to diesel fuel. Because urea and triazine compounds are generally insoluble in diesel fuel, microemulsion technology is used to suspend or dissolve the urea or triazine compound in the diesel fuel. A typical fuel formulation includes 5% t-butyl alcohol, 4.5% water, 0.5% urea or triazine compound, 9% oleic acid, and 1% ethanolamine. The subject invention provides improved emissions in heavy diesel engines without the need for major modifications.

  15. Argentina set for privatization

    SciTech Connect (OSTI)

    Chynoweth, E.

    1992-12-09

    Buyers are lining up for Argentina's two big state-controlled petrochemical groups, Buenos Aires-based Petroquimica General Mosconi (PGM) and Petroquimica Bahia Blance (PBB). However, feedstock supply contracts with government-owned oil group Yacientos Petroliferos Fiscales (YPG) and gas group Gas del Estado hold the key to both sales. Shell Compania Argentina Petroleo SA (CAPSA), Perez Companc, and Global Petroleum have already bought PGM tender documentation. Shell says it will bid for PGM if the feedstock contract with YPF is acceptable. In addition to price and volume, Shell says the length is critical; it wants a 15-year deal, but would settle for 11. YPF initially sought a five-year contract. PGM, which produces 300,000 m.t./year of aromatics, plus oxo alcohols, methanol, and methyl tert-butyl ether, has sales of $150 million/year.

  16. Low emissions diesel fuel

    DOE Patents [OSTI]

    Compere, Alicia L.; Griffith, William L.; Dorsey, George F.; West, Brian H.

    1998-01-01

    A method and matter of composition for controlling NO.sub.x emissions from existing diesel engines. The method is achieved by adding a small amount of material to the diesel fuel to decrease the amount of NO.sub.x produced during combustion. Specifically, small amounts, less than about 1%, of urea or a triazine compound (methylol melamines) are added to diesel fuel. Because urea and triazine compounds are generally insoluble in diesel fuel, microemulsion technology is used to suspend or dissolve the urea or triazine compound in the diesel fuel. A typical fuel formulation includes 5% t-butyl alcohol, 4.5% water, 0.5% urea or triazine compound, 9% oleic acid, and 1% ethanolamine. The subject invention provides improved emissions in heavy diesel engines without the need for major modifications.

  17. Polarizability effects on the structure and dynamics of ionic liquids

    SciTech Connect (OSTI)

    Cavalcante, Ary de Oliveira; Ribeiro, Mauro C. C.; Skaf, Munir S.

    2014-04-14

    Polarization effects on the structure and dynamics of ionic liquids are investigated using molecular dynamics simulations. Four different ionic liquids were simulated, formed by the anions Cl{sup ?} and PF{sub 6}{sup ?}, treated as single fixed charge sites, and the 1-n-alkyl-3-methylimidazolium cations (1-ethyl and 1-butyl-), which are polarizable. The partial charge fluctuation of the cations is provided by the electronegativity equalization model (EEM) and a complete parameter set for the cations electronegativity (?) and hardness (J) is presented. Results obtained from a non-polarizable model for the cations are also reported for comparison. Relative to the fixed charged model, the equilibrium structure of the first solvation shell around the imidazolium cations shows that inclusion of EEM polarization forces brings cations closer to each other and that anions are preferentially distributed above and below the plane of the imidazolium ring. The polarizable model yields faster translational and reorientational dynamics than the fixed charges model in the rotational-diffusion regime. In this sense, the polarizable model dynamics is in better agreement with the experimental data.

  18. Non-strinking siloxane polymers

    DOE Patents [OSTI]

    Loy, Douglas A.; Rahimian, Kamyar

    2001-01-01

    Cross-linked polymers formed by ring-opening polymerization of a precursor monomer of the general formula R[CH.sub.2 CH(Si(CH.sub.3).sub.2).sub.2 O].sub.2, where R is a phenyl group or an alkyl group having at least two carbon atoms. A cross-linked polymer is synthesized by mixing the monomer with a co-monomer of the general formula CH.sub.2 CHR.sup.2 (SiMe.sub.2).sub.2 O in the presence of an anionic base to form a cross-linked polymer of recurring units of the general formula R(Me.sub.2 SiOCH.sub.2 CHSiMe.sub.2).sub.2 [CH.sub.2 CHR.sup.2 (SiMe.sub.2).sub.2 O].sub.n, where R.sup.2 is hydrogen, phenyl, ethyl, propyl or butyl. If the precursor monomer is a liquid, the polymer can be directly synthesized in the presence of an anionic base to a cross-linked polymer containing recurring units of the general formula R(Me.sub.2 SiOCH.sub.2 CHSiMe.sub.2).sub.2. The polymers have approximately less than 1% porosity and are thermally stable at temperatures up to approximately 500.degree. C. The conversion to the cross-linked polymer occurs by ring opening polymerization and results in shrinkage of less than approximately 5% by volume.

  19. Transition metal-free olefin polymerization catalyst

    DOE Patents [OSTI]

    Sen, Ayusman (State College, PA); Wojcinski, II, Louis M. (State College, PA); Liu, Shengsheng (State College, PA)

    2001-01-01

    Ethylene and/or propylene are polymerized to form high molecular weight, linear polymers by contacting ethylene and/or propylene monomer, in the presence of an inert reaction medium, with a catalyst system which consists essentially of (1) an aluminum alkyl component, such as trimethylaluminum, triethylaluminum, triisobutylaluminum, tri-n-octylaluminum and diethylaluminum hydride and (2) a Lewis acid or Lewis acid derivative component, such as B (C.sub.6 F.sub.5).sub.3, [(CH.sub.3).sub.2 N (H) (C.sub.6 H.sub.5)].sup.+ [B (C.sub.6 F.sub.5)4].sup.-, [(C.sub.2 H.sub.5).sub.3 NH].sup.+ [B C.sub.6 F.sub.5).sub.4 ],.sup.-, [C(C.sub.6 F.sub.5).sub.3 ].sup.+ [B(C.sub.6 F.sub.5).sub.4 ].sup.-, (C.sub.2 H.sub.5).sub.2 Al(OCH.sub.3), (C.sub.2 H.sub.5).sub.2 Al(2,6-di-t-butyl-4-methylphenoxide), (C.sub.2 H.sub.5)Al(2,6 -di-t-butylphenoxide).sub.2, (C.sub.2 H.sub.5).sub.2 Al(2,6-di-t-butylphonoxide) , 2,6 -di-t-butylphenol.multidot.methylaluminoxane or an alkylaluminoxane, and which may be completely free any transition metal component(s).

  20. Conformations of organophosphine oxides

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

    De Silva, Nuwan; Zahariev, Federico; Hay, Benjamin P.; Gordon, Mark S.; Windus, Theresa L.

    2015-07-17

    The conformations of a series of organophosphine oxides, OP(CH3)2R, where R = methyl, ethyl, isopropyl, tert-butyl, vinyl, and phenyl, are predicted using the MP2/cc-pVTZ level of theory. Comparison of potential energy surfaces for rotation about P–C bonds with crystal structure data reveals a strong correlation between predicted location and energetics of minima and histograms of dihedral angle distributions observed in the solid state. In addition, the most stable conformers are those that minimize the extent of steric repulsion between adjacent rotor substituents, and the torsional barriers tend to increase with the steric bulk of the rotating alkyl group. MM3 forcemore » field parameters were adjusted to fit the MP2 results, providing a fast and accurate model for predicting organophosphine oxides shapes—an essential part of understanding the chemistry of these compounds. As a result, the predictive power of the modified MM3 model was tested against MP2/cc-pVTZ conformations for triethylphosphine oxide, OP(CH2CH3)3, and triphenylphosphine oxide, OP(Ph)3.« less

  1. Carbocation Stability in H-ZSM5 at High Temperature

    SciTech Connect (OSTI)

    Ferguson, Glen A.; Cheng, Lei; Bu, Lintao; Kim, Seonah; Robichaud, David J.; Nimlos, Mark R.; Curtiss, Larry A.; Beckham, Gregg T.

    2015-10-26

    Zeolites are common catalysts for multiple industrial applications, including alcohol dehydration to produce olefins, and given their commercial importance, reaction mechanisms in zeolites have long been proposed and studied. Some proposed reaction mechanisms for alcohol dehydration exhibit noncyclic carbocation intermediates or transition states that resemble carbocations, and several previous studies suggest that the tert-butyl cation is the only noncyclic cation more stable than the corresponding chemisorbed species with the hydrocarbon bound to the framework oxygen (i.e., an alkoxide). To determine if carbocations can exist at high temperatures in zeolites, where these catalysts are finding new applications for biomass vapor-phase upgrading (~500 C), the stability of carbocations and the corresponding alkoxides were calculated with two ONIOM embedding methods (M06-2X/6-311G(d,p):M06-2X/3-21G) and (PBE-D3/6-311G(d,p):PBE-D3/3-21G) and plane-wave density functional theory (DFT) using the PBE functional corrected with entropic and TkatchenkoScheffler van der Waals corrections. Additionally, the embedding methods tested are unreliable at finding minima for primary carbocations, and only secondary or higher carbocations can be described with embedding methods consistent with the periodic DFT results. The relative energy between the carbocations and alkoxides differs significantly between the embedding and the periodic DFT methods. The difference is between ~0.23 and 14.30 kcal/mol depending on the molecule, the model, and the functional chosen for the embedding method. At high temperatures, the pw-DFT calculations predict that the allyl, isopropyl, and sec-butyl cations exhibit negligible populations while acetyl and tert-butyl cations exhibit significant populations (>10%). Furthermore, the periodic DFT results indicate that mechanisms including secondary and tertiary carbocations intermediates or carbocations stabilized by adjacent oxygen or double bonds are possible at high temperatures relevant to some industrial uses of zeolite catalysts, although as the minority species in most cases.

  2. Removal of arsenic compounds from petroliferous liquids

    DOE Patents [OSTI]

    Fish, R.H.

    1984-04-06

    The present invention in one aspect comprises a process for removing arsenic from petroliferous-derived liquids by contacting said liquid with a divinylbenzene-crosslinked polystyrene polymer (i.e. PS-DVB) having catechol ligands anchored to said polymer, said contacting being at an elevated temperature. In another aspect, the invention is a process for regenerating spent catecholated polystyrene polymer by removal of the arsenic bound to it from contacting petroliferous liquid in accordance with the aspect described above which regenerating process comprises: (a) treating said spent catecholated polystyrene polymer with an aqueous solution of at least one member selected from the group consisting of carbonates and bicarbonates of ammonium, alkali metals, and alkaline earth metals, said solution having a pH between about 8 and 10, and said treating being at a temperature in the range of about 20/sup 0/ to 100/sup 0/C; (b) separating the solids and liquids from each other. In a preferred embodiment the regeneration treatment is in two steps wherein step: (a) is carried out with an aqueous alcoholic carbonate solution which includes at least one lower alkyl alcohol, and, steps (c) and (d) are added. Steps (c) and (d) comprise: (c) treating the solids with an aqueous alcoholic solution of at least one ammonium, alkali or alkaline earth metal bicarbonate at a temperature in the range of about 20 to 100/sup 0/C; and (d) separating the solids from the liquids.

  3. Microbial process for the preparation of acetic acid as well as solvent for its extraction from the fermentation broth

    DOE Patents [OSTI]

    Gaddy, James L.; Clausen, Edgar C.; Ko, Ching-Whan; Wade, Leslie E.; Wikstrom, Carl V.

    2002-01-01

    A modified water-immiscible solvent useful in the extraction of acetic acid from aqueous streams is a substantially pure mixture of isomers of highly branched di-alkyl amines. This solvent is substantially devoid of mono-alkyl amines and alcohols. Solvent mixtures formed of such a modified solvent with a desired cosolvent, preferably a low boiling hydrocarbon which forms an azeotrope with water are useful in the extraction of acetic acid from aqueous gaseous streams. An anaerobic microbial fermentation process for the production of acetic acid employs such solvents, under conditions which limit amide formation by the solvent and thus increase the efficiency of acetic acid recovery. Methods for the direct extraction of acetic acid and the extractive fermentation of acetic acid also employ the modified solvents and increase efficiency of acetic acid production. Such increases in efficiency are also obtained where the energy source for the microbial fermentation contains carbon dioxide and the method includes a carbon dioxide stripping step prior to extraction of acetic acid in solvent.

  4. Microbial process for the preparation of acetic acid as well as solvent for its extraction from the fermentation broth

    DOE Patents [OSTI]

    Gaddy, James L.; Clausen, Edgar C.; Ko, Ching-Whan; Wade, Leslie E.; Wikstrom, Carl V.

    2006-07-11

    A modified water-immiscible solvent useful in the extraction of acetic acid from aqueous streams is a substantially pure mixture of isomers of highly branched di-alkyl amines. This solvent is substantially devoid of mono-alkyl amines and alcohols. Solvent mixtures formed of such a modified solvent with a desired cosolvent, preferably a low boiling hydrocarbon which forms an azeotrope with water are useful in the extraction of acetic acid from aqueous gaseous streams. An anaerobic microbial fermentation process for the production of acetic acid employs such solvents, under conditions which limit amide formation by the solvent and thus increase the efficiency of acetic acid recovery. Methods for the direct extraction of acetic acid and the extractive fermentation of acetic acid also employ the modified solvents and increase efficiency of acetic acid production. Such increases in efficiency are also obtained where the energy source for the microbial fermentation contains carbon dioxide and the method includes a carbon dioxide stripping step prior to extraction of acetic acid in solvent.

  5. Process for removal of ammonia and acid gases from contaminated waters

    DOE Patents [OSTI]

    King, C.J.; Mackenzie, P.D.

    1982-09-03

    Contaminating basic gases, i.e., ammonia and acid gases, e.g., carbon dioxide, are removed from process waters or waste waters in a combined extraction and stripping process. Ammonia in the form of ammonium ion is extracted by an immiscible organic phase comprising a liquid cation exchange component, especially an organic phosphoric acid derivative, and preferably di-2-ethyl hexyl phosphoric acid, dissolved in an alkyl hydrocarbon, aryl hydrocarbon, higher alcohol, oxygenated hydrocarbon, halogenated hydrocarbon, and mixtures thereof. Concurrently, the acidic gaseous contaminants are stripped from the process or waste waters by stripping with stream, air, nitrogen, or the like. The liquid cation exchange component has the ammonia stripped therefrom by heating, and the component may be recycled to extract additional amounts of ammonia.

  6. Process for removal of ammonia and acid gases from contaminated waters

    DOE Patents [OSTI]

    King, C. Judson (Kensington, CA); MacKenzie, Patricia D. (Berkeley, CA)

    1985-01-01

    Contaminating basic gases, i.e., ammonia, and acid gases, e.g., carbon dioxide, are removed from process waters or waste waters in a combined extraction and stripping process. Ammonia in the form of ammonium ion is extracted by an immiscible organic phase comprising a liquid cation exchange component, especially an organic phosphoric acid derivative, and preferably di-2-ethyl hexyl phosphoric acid, dissolved in an alkyl hydrocarbon, aryl hydrocarbon, higher alcohol, oxygenated hydrocarbon, halogenated hydrocarbon, and mixtures thereof. Concurrently, the acidic gaseous contaminants are stripped from the process or waste waters by stripping with steam, air, nitrogen, or the like. The liquid cation exchange component has the ammonia stripped therefrom by heating, and the component may be recycled to extract additional amounts of ammonia.

  7. Phase change compositions

    DOE Patents [OSTI]

    Salyer, Ival O. (Dayton, OH); Griffen, Charles W. (Mason, OH)

    1986-01-01

    Compositions containing crystalline, long chain, alkyl hydrocarbons as phase change materials including cementitious compositions containing the alkyl hydrocarbons neat or in pellets or granules formed by incorporating the alkyl hydrocarbons in polymers or rubbers; and polymeric or elastomeric compositions containing alkyl hydrocarbons.

  8. Phase change compositions

    DOE Patents [OSTI]

    Salyer, Ival O. (Dayton, OH)

    1989-01-01

    Compositions containing crystalline, straight chain, alkyl hydrocarbons as phase change materials including cementitious compositions containing the alkyl hydrocarbons neat or in pellets or granules formed by incorporating the alkyl hydrocarbons in polymers or rubbers; and polymeric or elastomeric compositions containing alkyl hydrocarbons.

  9. N-(N-[2-(3,5-Difluorophenyl)acetyl]-(S)-alanyl)-(S)-phenylglycine tert-butyl ester (DAPT): an inhibitor of ?-secretase, revealing fine electronic and hydrogen-bonding features

    SciTech Connect (OSTI)

    Czerwinski, Andrzej; Valenzuela, Francisco; Afonine, Pavel; Dauter, Miroslawa; Dauter, Zbigniew

    2010-12-01

    The title compound, C{sub 23}H{sub 26}F{sub 2}N{sub 2}O{sub 4}, is a dipeptidic inhibitor of ?-secretase, one of the enzymes involved in Alzheimers dis@@ease. The mol@@ecule adopts a compact conformation, without intra@@molecular hydrogen bonds. In the crystal structure, one of the amide N atoms forms the only inter@@molecular NH?O hydrogen bond; the second amide N atom does not form hydrogen bonds. High-resolution synchrotron diffraction data permitted the unequivocal location and refinement without restraints of all H atoms, and the identification of the characteristic shift of the amide H atom engaged in the hydrogen bond from its ideal position, resulting in a more linear hydrogen bond. Significant residual densities for bonding electrons were revealed after the usual SHELXL refinement, and modeling of these features as additional inter@@atomic scatterers (IAS) using the program PHENIX led to a significant decrease in the R factor from 0.0411 to 0.0325 and diminished the r.m.s. deviation level of noise in the final difference Fourier map from 0.063 to 0.037 e {sup ?3}.

  10. Reductive deconstruction of organosolv lignin catalyzed by zeolite supported nickel nanoparticles

    SciTech Connect (OSTI)

    Kasakov, Stanislav; Shi, Hui; Camaioni, Donald M.; Zhao, Chen; Barath, Eszter; Jentys, Andreas; Lercher, Johannes A.

    2015-11-01

    Mechanistic aspects of deconstruction and hydrodeoxygenation of organosolv lignin using supported Ni catalysts with (Ni/HZSM-5 and Ni/HBEA) and without Brønsted acid sites (Ni/SiO2) are reported. Lignin was deconstructed and converted to saturated cyclic hydrocarbons ranging from C5 to C14. In the one-stage reaction, full conversion with total yield of 70 ± 5 wt.% saturated hydrocarbons was achieved at 593 K and 20 bar H2. The organosolv lignin used consists of seven to eight monolignol subunits and has an average molecular weight of ca. 1200 g mol-1. The monolignols were mainly guaiacyl, syringyl and phenylcoumaran, randomly interconnected through β-O-4, 4-O-5, β-1, 5-5’ and β-β ether bonds. In situ IR spectroscopy was used to follow the changes in lignin constituents during reaction. The proposed reaction pathways for the catalytic transformation of this organosolv lignin to alkanes start with the hydrogenolysis of aryl alkyl ether bonds, followed by hydrogenation of the aromatic compounds on Ni to cyclic alcohols. Oxygen is removed from the alcohols via dehydration on Brønsted acid sites to yield cyclic alkenes that are further hydrogenated to alkanes. Formation of condensation products may occur via intermolecular recombination of aromatic monomers or alkylation of aromatic compounds by alkenes. The financial support from TUM-PNNL cooperation project “Development of new methods for in situ characterization in liquid phase reactions” (CN-177939) is highly appreciated. The work by S.K., H.S., and J.A.L was partially supported by the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences.

  11. Advanced quadrupole ion trap instrumentation for low level vehicle emissions measurements. CRADA final report for number ORNL93-0238

    SciTech Connect (OSTI)

    McLuckey, S.A.; Buchanan, M.V.; Asano, K.G.; Hart, K.J.; Goeringer, D.E.; Dearth, M.A.

    1997-09-01

    Quadrupole ion trap mass spectrometry has been evaluated for its potential use in vehicle emissions measurements in vehicle test facilities as an analyzer for the top 15 compounds contributing to smog generation. A variety of ionization methods were explored including ion trap in situ chemical ionization, atmospheric sampling glow discharge ionization, and nitric oxide chemical ionization in a glow discharge ionization source coupled with anion trap mass spectrometer. Emphasis was placed on the determination of hydrocarbons and oxygenated hydrocarbons at parts per million to parts per billion levels. Ion trap in situ water chemical ionization and atmospheric sampling glow discharge ionization were both shown to be amenable to the analysis of arenes, alcohols, aldehydes and, to some degree, alkenes. Atmospheric sampling glow discharge also generated molecular ions of methyl-t-butyl ether (MTBE). Neither of these ionization methods, however, were found to generate diagnostic ions for the alkanes. Nitric oxide chemical ionization, on the other hand, was found to yield diagnostic ions for alkanes, alkenes, arenes, alcohols, aldehydes, and MTBE. The ability to measure a variety of hydrocarbons present at roughly 15 parts per billion at measurement rates of 3 Hz was demonstrated. These results have demonstrated that the ion trap has an excellent combination of sensitivity, specificity, speed, and flexibility with respect to the technical requirements of the top 15 analyzer.

  12. Catalytic conversion of light alkanes. Final report, January 1, 1990--October 31, 1994

    SciTech Connect (OSTI)

    1998-12-31

    During the course of the first three years of the Cooperative Agreement (Phase I-III), we uncovered a family of metal perhaloporphyrin complexes which had unprecedented activity for the selective air-oxidation of fight alkanes to alcohols. The reactivity of fight hydrocarbon substrates with air or oxygen was in the order: isobutane>propane>ethane>methane, in accord with their homolytic bond dissociation energies. Isobutane was so reactive that the proof-of concept stage of a process for producing tert-butyl alcohol from isobutane was begun (Phase V). It was proposed that as more active catalytic systems were developed (Phases IV, VI), propane, then ethane and finally methane oxidations will move into this stage (Phases VII through IX). As of this writing, however, the program has been terminated during the later stages of Phases V and VI so that further work is not anticipated. We made excellent progress during 1994 in generating a class of less costly new materials which have the potential for high catalytic activity. New routes were developed for replacing costly perfluorophenyl groups in the meso-position of metalloporphyrin catalysts with far less expensive and lower molecular weight perfluoromethyl groups.

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

    Reports and Publications (EIA)

    2001-01-01

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

  14. Process for producing biodiesel, lubricants, and fuel and lubricant additives in a critical fluid medium

    DOE Patents [OSTI]

    Ginosar, Daniel M.; Fox, Robert V.

    2005-05-03

    A process for producing alkyl esters useful in biofuels and lubricants by transesterifying glyceride- or esterifying free fatty acid-containing substances in a single critical phase medium is disclosed. The critical phase medium provides increased reaction rates, decreases the loss of catalyst or catalyst activity and improves the overall yield of desired product. The process involves the steps of dissolving an input glyceride- or free fatty acid-containing substance with an alcohol or water into a critical fluid medium; reacting the glyceride- or free fatty acid-containing substance with the alcohol or water input over either a solid or liquid acidic or basic catalyst and sequentially separating the products from each other and from the critical fluid medium, which critical fluid medium can then be recycled back in the process. The process significantly reduces the cost of producing additives or alternatives to automotive fuels and lubricants utilizing inexpensive glyceride- or free fatty acid-containing substances, such as animal fats, vegetable oils, rendered fats, and restaurant grease.

  15. Removal of arsenic, vanadium, and/or nickel compounds from petroliferous liquids

    DOE Patents [OSTI]

    Fish, Richard H.

    1986-01-01

    Described is a process for removing arsenic, vanadium, and/or nickel from petroliferous derived liquids by contacting said liquid at an elevated temperature with a divinylbenzene-crosslinked polystyrene having catechol ligands anchored thereon. For vanadium and nickel removal an amine, preferably a diamine is included. Also, described is a process for regenerating spent catecholated polystyrene by removal of the arsenic, vanadium, and/or nickel bound to it from contacting petroliferous liquid as described above and involves: treating the spent polymer containing any vanadium and/or nickel with an aqueous acid to achieve an acid pH; and, separating the solids from the liquid; and then treating said spent catecholated polystyrene, at a temperature in the range of about 20.degree. to 100.degree. C. with an aqueous solution of at least one carbonate and/or bicarbonate of ammonium, alkali and alkaline earth metals, said solution having a pH between about 8 and 10; and, separating the solids and liquids from each other. Preferably the regeneration treatment of arsenic containing catecholated polymer is in two steps wherein the first step is carried out with an aqueous alcoholic carbonate solution containing lower alkyl alcohol, and, the steps are repeated using a bicarbonate.

  16. Removal of arsenic, vanadium and/or nickel compounds from spent catecholated polymer

    DOE Patents [OSTI]

    Fish, R.H.

    1987-04-21

    Described is a process for removing arsenic, vanadium, and/or nickel from petroliferous derived liquids by contacting said liquid at an elevated temperature with a divinylbenzene-crosslinked polystyrene having catechol ligands anchored thereon. For vanadium and nickel removal an amine, preferably a diamine is included. Also, described is a process for regenerating spent catecholated polystyrene by removal of the arsenic, vanadium, and/or nickel bound to it from contacting petroliferous liquid as described above and involves: treating the spent polymer containing any vanadium and/or nickel with an aqueous acid to achieve an acid pH; and, separating the solids from the liquid; and then treating said spent catecholated polystyrene, at a temperature in the range of about 20 to 100 C with an aqueous solution of at least one carbonate and/or bicarbonate of ammonium, alkali and alkaline earth metals, said solution having a pH between about 8 and 10; and, separating the solids and liquids from each other. Preferably the regeneration treatment of arsenic containing catecholated polymer is in two steps wherein the first step is carried out with an aqueous alcoholic carbonate solution containing lower alkyl alcohol, and, the steps are repeated using a bicarbonate.

  17. Removal of arsenic, vanadium, and/or nickel compounds from petroliferous liquids

    DOE Patents [OSTI]

    Fish, R.H.

    1985-05-17

    Described is a process for removing arsenic, vanadium, and/or nickel from petroliferous derived liquids (shale oil, SRC, etc.) by contacting said liquid at an elevated temperature with a divinylbenzene-crosslinked polystyrene having catechol ligands anchored thereon. For vanadium and nickel removal an amine, preferably a diamine is included. Also, described is a process for regenerating spent catecholated polystyrene by removal of the arsenic, vanadium, and/or nickel bound to it from contacting petroliferous liquid as described above and involves: treating the spent polymer containing any vanadium and/or nickel with an aqueous acid to achieve an acid pH; and, separating the solids from the liquid; and then treating said spent catecholated polystyrene, at a temperature in the range of about 20/sup 0/ to 100/sup 0/C with an aqueous solution of at least one carbonate and/or bicarbonate of ammonium, alkali and alkaline earth metals, said solution having a pH between about 8 and 10; and, separating the solids and liquids from each other. Preferably the regeneration treatment of arsenic containing catecholated polymer is in two steps wherein the first step is carried out with an aqueous alcoholic carbonate solution containing lower alkyl alcohol, and, the steps are repeated using a bicarbonate.

  18. Removal of arsenic, vanadium and/or nickel compounds from spent catecholated polymer

    DOE Patents [OSTI]

    Fish, Richard H.

    1987-01-01

    Described is a process for removing arsenic, vanadium, and/or nickel from petroliferous derived liquids by contacting said liquid at an elevated temperature with a divinylbenzene-crosslinked polystyrene having catechol ligands anchored thereon. For vanadium and nickel removal an amine, preferably a diamine is included. Also, described is a process for regenerating spent catecholated polystyrene by removal of the arsenic, vanadium, and/or nickel bound to it from contacting petroliferous liquid as described above and involves: treating the spent polymer containing any vanadium and/or nickel with an aqueous acid to achieve an acid pH; and, separating the solids from the liquid; and then treating said spent catecholated polystyrene, at a temperature in the range of about 20.degree. to 100.degree. C. with an aqueous solution of at least one carbonate and/or bicarbonate of ammonium, alkali and alkaline earth metals, said solution having a pH between about 8 and 10; and, separating the solids and liquids from each other. Preferably the regeneration treatment of arsenic containing catecholated polymer is in two steps wherein the first step is carried out with an aqueous alcoholic carbonate solution containing lower alkyl alcohol, and, the steps are repeated using a bicarbonate.

  19. Characterization of Phase and Emulsion Behavior, Surfactant Retention, and Oil Recovery for Novel Alcohol Ethoxycarboxylate Surfactants

    SciTech Connect (OSTI)

    Lebone T. Moeti; Ramanathan Sampath

    1998-05-01

    This semi-annual technical progress report describes work performed at Clark Atlanta University under DOE Grant No. DE-FG26-97FT97278 during the period October 01, 1997 to April 01, 1998 which covers the first six months of the project. During this reporting period, laboratory space to set up the surfactant characterization measurement system in the Research Science Center was made available. A Ph.D. student in Chemistry was identified and is supported as a Graduate Research Assistant in this project. Her contribution towards this project will form her Ph.D. thesis. The test matrix to perform salinity and temperature scans was established. Supply requests to obtain refined hydrocarbon, surfactant, and crude were processed and supplies obtained. A temperature bath with a control unit to perform temperature scans was obtained on loan from Federal Energy Technology Center, Morgantown, WV. The setting up of the temperature control unit, and associated chiller with water circulation lines is in progress. Tests were conducted on several hybrid surfactants to identify the best surfactants for future experimental work that yield almost equal volumes of top, middle, and bottom phases when mixed with oil and water. The student reviewed the current literature in the subject area, and modeling efforts that were established in previous studies to predict electrical conductivities and inversion phenomena. These activities resulted in one published conference paper, and one student poster paper during this reporting period.

  20. Characterization of Phase and Emulsion Behavior, Surfactant Retention, and Oil Recovery for Novel Alcohol Ethoxycarboxylate Surfactant

    SciTech Connect (OSTI)

    Moeti, Lebone T.; Sampath, Ramanathan

    2002-03-13

    Electrical conductivity measurements for middle, bottom, and top phases, as well as bottom/middle, and middle/bottom conjugate pair phases of the NEODOX 23-4/dodecane/10mM water system were continued from the previous reporting period. Electrical conductivity of the mixture decreased as the fraction of volume of the middle phase was increased and vice versa. Also inversion phenomena was observed. Following this, more emulsion studies at various temperatures were progresses. A theoretical model to predict the conductivity measurements using Maxwell equations was developed and sensitivity analyses to test the performance of the model was completed. Surtek, Golden, CO, our industrial partner in this project, investigated the suitability of the surfactant for enhanced oil recovery employing coreflooding techniques and observed lower surfactant and hydrocarbon recovery for NEODOX 23-4.

  1. Sampling for Beryllium Surface Contamination using Wet, Dry and Alcohol Wipe Sampling

    SciTech Connect (OSTI)

    Kerr, Kent

    2004-12-17

    This research project was conducted at the National Nuclear Security Administration's Kansas City Plant, operated by Honeywell Federal Manufacturing and Technologies, in conjunction with the Safety Sciences Department of Central Missouri State University, to compare relative removal efficiencies of three wipe sampling techniques currently used at Department of Energy facilities. Efficiencies of removal of beryllium contamination from typical painted surfaces were tested by wipe sampling with dry Whatman 42 filter paper, with water-moistened (Ghost Wipe) materials, and by methanol-moistened wipes. Test plates were prepared using 100 mm X 15 mm Pyrex Petri dishes with interior surfaces spray painted with a bond coat primer. To achieve uniform deposition over the test plate surface, 10 ml aliquots of solution containing 1 beryllium and 0.1 ml of metal working fluid were transferred to the test plates and subsequently evaporated. Metal working fluid was added to simulate the slight oiliness common on surfaces in metal working shops where fugitive oil mist accumulates over time. Sixteen test plates for each wipe method (dry, water, and methanol) were processed and sampled using a modification of wiping patterns recommended by OSHA Method 125G. Laboratory and statistical analysis showed that methanol-moistened wipe sampling removed significantly more (about twice as much) beryllium/oil-film surface contamination as water-moistened wipes (p< 0.001), which removed significantly more (about twice as much) residue as dry wipes (p <0.001). Evidence for beryllium sensitization via skin exposure argues in favor of wipe sampling with wetting agents that provide enhanced residue removal efficiency.

  2. Tantalum-containing catalyst useful for producing alcohols from synthesis gas

    DOE Patents [OSTI]

    Kinkade, N.E.

    1992-04-07

    A catalyst is described which is useful for selectively converting a mixture of carbon monoxide and hydrogen to a mixture of lower alkanols. The catalyst consists essentially of a mixture of molybdenum sulfide, an alkali metal compound and a tantalum compound.

  3. Method for the synthesis of chiral allylic alcohols utilizing selone based chiral derivatizing agents

    DOE Patents [OSTI]

    Silks, III, Louis A. (White Rock, NM)

    2002-01-01

    Molecules containing a chiral 1,2-diol unit are synthesized from reactions between aldehydes and N-acyl selones. A chilled N-acyl selone is reacted with a Lewis acid such as TiCl.sub.4 and mixed with a tertiary amine such as diisopropylethylamine to generate an enolate solution. Upon further chilling of the enolate solution a desired aldehyde is added and after an acceptable reaction period a quencher is introduced and the product isolated.

  4. Synthesis of PD particles by alcohols-assisted photoreduction for use in supported catalysts

    DOE Patents [OSTI]

    Burton, Patrick David; Boyle, Timothy J; Datye, Abhaya

    2015-02-24

    The present disclosure provides a novel synthesis method for palladium nanoparticles and palladium nanoparticles made using the method. The nanoparticles resulting from the method are highly reactive and, when deposited on a support, are highly suitable for use as catalytic material.

  5. Thermochemical Design Report: Thermochemical Ethanol via Indirect Gasification and Mixed Alcohol Synthesis of Lignocellulosic Biomass

    SciTech Connect (OSTI)

    Phillips, S.; Aden, A.; Jechura, J.; Dayton, D.; Eggeman, T.

    2007-04-01

    This process design and technoeconomic evaluation addresses the conversion of biomass to ethanol via thermochemical pathways that are expected to be demonstrated at the pilot-unit level by 2012.

  6. Thermochemical ethanol via indirect gasification and mixed alcohol synthesis of lignocellulosic biomass

    SciTech Connect (OSTI)

    Phillips, S.; Aden, A.; Jechura, J.; Dayton, D.; Eggeman, T.

    2007-04-01

    This process design and technoeconomic evaluation addresses the conversion of biomass to ethanol via thermochemical pathways that are expected to be demonstrated at the pilot level by 2012.

  7. Thermochemical Ethanol via Indirect Gasification and Mixed Alcohol Synthesis of Lignocellulosic Biomass

    SciTech Connect (OSTI)

    Phillips, S.; Aden, A.; Jechura, J.; Dayton, D.; Eggeman, T.

    2007-04-01

    This process design and technoeconomic evaluation addresses the conversion of biomass to ethanol via thermochemical pathways that are expected to be demonstrated at the pilot level by 2012.

  8. Hydrogen transfer from alcohols to carbonyl compounds catalyzed by aluminum porphyrins. Stereochemical aspects

    SciTech Connect (OSTI)

    Konishi, Katsuaki; Aida, Takuzo; Inoue, Shohei (Univ. of Tokyo (Japan))

    1990-02-02

    There is interest in synthesizing molecules containing di- or tri-sulfide linkages together with sulfinate functions because of their potential as antiradiation agents. In the process of synthesizing such compounds, formation of monothioquinone S,S-dioxides presented a mechanistic problem which had to be overcome. This paper focuses on the formation of these dioxides and routes around them.

  9. Thermochemical Ethanol via Direct Gasification and Mixed Alcohol Synthesis of Lignocellulosic Biomass

    SciTech Connect (OSTI)

    Dutta, A.; Phillips, S. D.

    2009-07-01

    This report evaluates process design and technoeconomic criteria for a direct gasification process for conversion of biomass to ethanol. Follow-up to NREL/TP-510-41168.

  10. Tantalum-containing catalyst useful for producing alcohols from synthesis gas

    DOE Patents [OSTI]

    Kinkade, Nancy E. (Charleston, WV)

    1992-01-01

    A catalyst useful for selectively converting a mixture of carbon monoxide and hydrogen to a mixture of lower alkanols consisting essentially of a mixture of molybdenum sulfide, an alkali metal compound and a tantalum compound.

  11. Tantalum-containing catalyst useful for producing alcohols from synthesis gas

    DOE Patents [OSTI]

    Kinkade, Nancy E. (Charleston, WV)

    1991-01-01

    A catalyst useful for selectively converting a mixture of carbon monoxide and hydrogen to a mixture of lower alkanols consisting essentially of a mixture of molybdenum sulfide, an alkali metal compound and a tantalum compound.

  12. Heavy Alcohols as a Fuel Blending Agent for Compression Ignition Engine Applications

    Broader source: Energy.gov [DOE]

    Blends of Phytol and diesel (by volume) were compared against baseline diesel experiments and simulations

  13. Vehicle Technologies Office Merit Review 2014: High Compression Ratio Turbo Gasoline Engine Operation Using Alcohol Enhancement

    Broader source: Energy.gov [DOE]

    Presentation given by Massachusetts Institute of Technology at 2014 DOE Hydrogen and Fuel Cells Program and Vehicle Technologies Office Annual Merit Review and Peer Evaluation Meeting about high...

  14. Alcohol-fueled vehicles: An alternative fuels vehicle, emissions, and refueling infrastructure technology assessment

    SciTech Connect (OSTI)

    McCoy, G.A.; Kerstetter, J.; Lyons, J.K.

    1993-06-01

    Interest in alternative motor vehicle fuels has grown tremendously over the last few years. The 1990 Clean Air Act Amendments, the National Energy Policy Act of 1992 and the California Clean Air Act are primarily responsible for this resurgence and have spurred both the motor fuels and vehicle manufacturing industries into action. For the first time, all three U.S. auto manufacturers are offering alternative fuel vehicles to the motoring public. At the same time, a small but growing alternative fuels refueling infrastructure is beginning to develop across the country. Although the recent growth in alternative motor fuels use is impressive, their market niche is still being defined. Environmental regulations, a key driver behind alternative fuel use, is forcing both car makers and the petroleum industry to clean up their products. As a result, alternative fuels no longer have a lock on the clean air market and will have to compete with conventional vehicles in meeting stringent future vehicle emission standards. The development of cleaner burning gasoline powered vehicles has signaled a shift in the marketing of alternative fuels. While they will continue to play a major part in the clean vehicle market, alternative fuels are increasingly recognized as a means to reduce oil imports. This new role is clearly defined in the National Energy Policy Act of 1992. The Act identifies alternative fuels as a key strategy for reducing imports of foreign oil and mandates their use for federal and state fleets, while reserving the right to require private and municipal fleet use as well.

  15. The processing of alcohols, hydrocarbons and ethers to produce hydrogen for a PEMFC for transportation applications

    SciTech Connect (OSTI)

    Dams, R.A.J.; Hayter, P.R.; Moore, S.C.

    1997-12-31

    Wellman CJB Limited is involved in a number of projects to develop fuel processors to provide a hydrogen-rich fuel in Proton Exchange Membrane Fuel Cells (PEMFC) systems for transportation applications. This work started in 1990 which resulted in the demonstration of 10kW PEMFC system incorporating a methanol reformer and catalytic gas clean-up system. Current projects include: The development of a compact fast response methanol reformer and gas clean-up system for a motor vehicle; Reforming of infrastructure fuels including gasoline, diesel, reformulated fuel gas and LPG to produce a hydrogen rich gas for PEMFC; Investigating the potential of dimethylether (DME) as source of hydrogen rich gas for PEMFCs; The use of thin film palladium diffusers to produce a pure hydrogen stream from the hydrogen rich gas from a reformer; and Processing of naval logistic fuels to produce a hydrogen rich gas stream for PEMFC power system to replace diesel generators in surface ships. This paper outlines the background to these projects and reports their current status.

  16. Catalytic ionic hydrogenation of ketones using tungsten or molybdenum catalysts with increased lifetimes

    DOE Patents [OSTI]

    Bullock, R. Morris; Kimmich, Barbara F. M.; Fagan, Paul J.; Hauptman, Elisabeth

    2003-09-02

    The present invention is a process for the catalytic hydrogenation of ketones and aldehydes to alcohols at low temperatures and pressures using organometallic molybdenum and tungsten complexes and the catalyst used in the process. The reactants include a functional group which is selected from groups represented by the formulas R*(C.dbd.O)R' and R*(C.dbd.O)H, wherein R* and R' are selected from hydrogen or any alkyl or aryl group. The process includes reacting the organic compound in the presence of hydrogen and a catalyst to form a reaction mixture. The catalyst is prepared by reacting Ph.sub.3 C.sup.+ A.sup.- with a metal hydride. A.sup.- represents an anion and can be BF.sub.4.sup.-, PF.sub.6.sup.-, CF.sub.3 SO.sub.3.sup.- or Bar'.sub.4.sup.-, wherein Ar'=3,5-bis(trifluoromethyl)phenyl. The metal hydride is represented by the formula: HM(CO).sub.2 [.eta..sup.5 :.eta..sup.1 --C.sub.5 H.sub.4 (XH.sub.2).sub.n PR.sub.2 ] wherein M represents a molybdenum (Mo) atom or a tungsten (W) atom; X is a carbon atom, a silicon atom or a combination of carbon (C) and silicon (Si) atoms; n is any positive integer; R represents two hydrocarbon groups selected from H, an aryl group and an alkyl group, wherein both R groups can be the same or different. The metal hydride is reacted with Ph.sub.3 C.sup.+ A.sup.- either before reacting with the organic compound or in the reaction mixture.

  17. A Literature Survey to Identify Potentially Volatile Iodine-Bearing Species Present in Off-Gas Streams

    SciTech Connect (OSTI)

    Bruffey, S. H.; Spencer, B. B.; Strachan, D. M.; Jubin, R. T.; Soelberg, N. R.; Riley, B. J.

    2015-06-30

    Four radionuclides have been identified as being sufficiently volatile in the reprocessing of nuclear fuel that their gaseous release needs to be controlled to meet regulatory requirements (Jubin et al. 2011, 2012). These radionuclides are 3H, 14C, 85Kr, and 129I. Of these, 129I has the longest half-life and potentially high biological impact. Accordingly, control of the release of 129I is most critical with respect to the regulations for the release of radioactive material in stack emissions. It is estimated that current EPA regulations (EPA 2010) would require any reprocessing plant in the United States to limit 129I release to less than 0.05 Ci/MTIHM for a typical fuel burnup of 55 gigawatt days per metric tonne (GWd/t) (Jubin 2011). The study of inorganic iodide in off-gas systems has been almost exclusively limited to I2 and the focus of organic iodide studies has been CH3I. In this document, we provide the results of an examination of publically available literature that is relevant to the presence and sources of both inorganic and organic iodine-bearing species in reprocessing plants. We especially focus on those that have the potential to be poorly sequestered with traditional capture methodologies. Based on the results of the literature survey and some limited thermodynamic modeling, the inorganic iodine species hypoiodous acid (HOI) and iodine monochloride (ICl) were identified as potentially low-sorbing iodine species that could present in off-gas systems. Organic species of interest included both short chain alkyl iodides such as methyl iodide (CH3I) and longer alkyl iodides up to iodododecane (C10H21I). It was found that fuel dissolution may provide conditions conducive to HOI formation and has been shown to result in volatile long-chain alkyl iodides, though these may not volatilize until later in the reprocessing sequence. Solvent extraction processes were found to be significant sources of various organic iodine-bearing species; formation of these was facilitated by the presence of radiolytic decomposition products resulting from radiolysis of tri-n-butyl phosphate and dodecane. Primarily inorganic iodine compounds were expected from waste management processes, including chlorinated species such as ICl. Critical knowledge gaps that must still be addressed include confirmation of the existence and quantification of low-sorbing species in the off-gas of reprocessing facilities. The contributions from penetrating forms of iodine to the plant DF are largely unknown and highly dependent on the magnitude of their presence. These species are likely to be more difficult to remove and it is likely that their sequestration could be improved through the use of different sorbents, through design modifications of the off-gas capture system, or through chemical conversion prior to iodine abatement that would produce more easily captured forms.

  18. Decontamination of water using nitrate selective ion exchange resin

    DOE Patents [OSTI]

    Lockridge, J.E.; Fritz, J.S.

    1990-07-31

    A method for nitrate decontamination of water which involves passing the water through a bed of alkyl phosphonium anion exchange resin which has pendant alkyl groups of C[sub 3] or larger.

  19. Decontamination of water using nitrate selective ion exchange resin

    DOE Patents [OSTI]

    Lockridge, James E. (Ames, IA); Fritz, James S. (Ames, IA)

    1990-07-31

    A method for nitrate decontamination of water which involves passing the water through a bed of alkyl phosphonium anion exchange resin which has pendant alkyl groups of C.sub.3 or larger.

  20. New iodocuprates(I) with N-heterocyclic molecules as the cations

    SciTech Connect (OSTI)

    Zhao, Jin-Jing; Zhang, Xiao; Wang, Yan-Ning; Jia, Hong-Li; Yu, Jie-Hui; Xu, Ji-Qing

    2013-11-15

    Under the hydrothermal conditions, the reactions between CuI, KI and bp/bpp (bp=4,4?-bipiperidine, bpp=1,3-bis(4-piperidyl)propane) in an acidic alcohol solution produced three new organically templated iodocuprates(I) as [H{sub 2}bp]{sub 2}[Cu{sub 2}I{sub 6}] 1, [tmbp][Cu{sub 2}I{sub 4}] 2 and [tmbpp] 2 [Cu{sub 4}I{sub 8}]2H{sub 2}O 3 (tmbp{sup 2+}=N,N,N?,N?-tetramethyl-4,4?-bipiperidinium; tmbpp{sup 2+}=N,N,N?,N?-tetramethyl-1,3-bis(4-piperidyl)propane dication). X-ray analysis revealed that (i) tmbp{sup 2+} and tmbpp{sup 2+} in compounds 2 and 3 originated from the complete N-alklation of bp/bpp with CH{sub 3}OH; (ii) templated by H{sub 2}bp{sup 2+}, the inorganic anion [Cu{sub 2}I{sub 6}]{sup 2?} of 1 possesses a dinuclear structure, whereas templated by tmbp{sup 2+}, the inorganic anion [Cu{sub 2}I{sub 4}]{sup 2?} of 2 exhibits a one-dimensional (1D) chain structure; (iii) templated by tmbpp{sup 2+}, the inorganic anion [Cu{sub 4}I{sub 8}]{sup 4?} of 3 shows a cubane-like structure modified by four terminal I{sup ?} ions. The photoluminescence analysis indicates that compounds 1 and 2 emit blue light, while compound 3 emits green light. - Graphical abstract: By employing hydrothermal in situ N-alkylation of bp/bpp with CH{sub 3}OH, three new organically templated iodocuprates(I) were obtained. Display Omitted - Highlights: Three new organically templated iodocuprates(I) were reported. Cations tmbp{sup 2+} and tmbpp{sup 2+} originated from in situ alkylation of bp/bpp with CH{sub 3}OH. H{sup +} and I{sup ?} play a key role in alkylation of bp/bpp with CH{sub 3}OH. Photoluminescence emission for iodocuprates(I) is related to CuCu interaction.

  1. Too Crowded to Exit! | The Ames Laboratory

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

    Too Crowded to Exit! Crowding controls whether carbon chains or a hydrogen atom will transfer from transition metal molecular complexes to acceptor molecules. To gain this new insight into the factors governing the onset of hydrogen abstraction from metal alkyls, researchers carefully designed experiments involving series of cobalt and chromium alkyls. The results show that when the alkyl chain is only one carbon long, the alkyl group will transfer to a rhodium acceptor molecule. But, if the

  2. Method of producing polyalkylated oligoalkylenepolyamines

    DOE Patents [OSTI]

    Elangovan, Arumugasamy

    2014-02-25

    A method of preparing polyalkylated oligoalkylenepolyamines is provided. The method includes contacting oligoalkylenepolyamine with a reagent composition comprising (a) alkyl bromide and/or alkyl chloride; (b) a basic agent; and (c) iodide salt. The alkylation reaction may be carried out in a polar, aprotic organic solvent.

  3. Proposed plant will turn wood residues into synfuel

    SciTech Connect (OSTI)

    Not Available

    1981-01-01

    A group of entrepreneurs plan to have a plant operating in Burney, CA. The projected facility will produce an estimated 21,000 gallons of oil per day, converting about 300 tons of raw material. Converting cellulose into synthetic fuel is superior to alcohol production. The process yields approximately 84 gallons of synthetic fuel per ton of raw material. The entire LHG (liquid hydrogen gas) patented facility is self-sufficient and releases only carbon dioxide into the atmosphere. Synfuel production is a three-phase process. First, butyl alcohol (butanol) and acetone are produced from a portion of the raw material. This is facilitated by adding to the raw material a bacteria culture. The planned facility in Burney will have thirty-five 2100 gallon fermentation tanks and will produce 1.25 million gallons of butanol. Next, organic material is blended with water and is pumped into patented LHG catalytic converters, charged with carbon monoxide gas as a catalyst and then heated to 350 degrees C at 2000 to 5000 psi. Here, the organic material is converted to No. 4 oil with bituminous tar as a residue. A patented gasifier system produces the carbon monoxide catalyst plus COH (carbon hydroxide) gas. The COH is used to power a gas turbine driving a 100 kW generator and a central hydraulic pump. The facility, which will be energy self-sufficient, will have approximately 50 kW of excess power to sell to the local utility power grid. Finally, the No. 4 oil, butanol and liquified COH gas are blended to produce any grade fuel oil or a gasoline substitute of very high octane.

  4. The photocatalysis of Bi{sub 2}MoO{sub 6} under the irradiation of blue LED

    SciTech Connect (OSTI)

    Sun, Yuanyuan; Wang, Wenzhong Zhang, Ling; Sun, Songmei

    2013-10-15

    Graphical abstract: - Highlights: • ·OH trap and hole sink were involved to investigate the active radicals. • Holes play a more important role in the degradation of RhB. • The ·OH were related to the decomposition of phenol. • The ·O{sub 2}-played a leading role in the photodegradation of phenol. • Blue LED is competitive and promising alternative for the future application. - Abstract: Bi{sub 2}MoO{sub 6} has been reported as a promising photocatalyst in wastewater treatment. The active radicals generated over the Bi{sub 2}MoO{sub 6} during the photocatalytic process were thought to be hydroxyl radical (·OH) but have not been proved. Herein, Bi{sub 2}MoO{sub 6} with nanoplate like morphology was synthesized and its photocatalytic performances in the degradation of rhodamine B (RhB) and phenol as colored and colorless model pollutants respectively were evaluated under the irradiation of blue light emitting diode (LED). The tert-butyl alcohol (TBA) as a ·OH trap and ethylene diamine tetraacetic acid (EDTA) as a hole sink were involved to investigate the main active groups that are generated on Bi{sub 2}MoO{sub 6} and function during the photodegradation of RhB and phenol. In addition, it is a competitive and promising alternative plan to use blue LED as light source for the future practical application in environmental remediation.

  5. Methods of making transportation fuel

    DOE Patents [OSTI]

    Roes, Augustinus Wilhelmus Maria (Houston, TX); Mo, Weijian (Sugar Land, TX); Muylle, Michel Serge Marie (Houston, TX); Mandema, Remco Hugo (Houston, TX); Nair, Vijay (Katy, TX)

    2012-04-10

    A method for producing alkylated hydrocarbons is disclosed. Formation fluid is produced from a subsurface in situ heat treatment process. The formation fluid is separated to produce a liquid stream and a first gas stream. The first gas stream includes olefins. The liquid stream is fractionated to produce at least a second gas stream including hydrocarbons having a carbon number of at least 3. The first gas stream and the second gas stream are introduced into an alkylation unit to produce alkylated hydrocarbons. At least a portion of the olefins in the first gas stream enhance alkylation. The alkylated hydrocarbons may be blended with one or more components to produce transportation fuel.

  6. Inhibitors of glycogen synthase 3 kinase

    DOE Patents [OSTI]

    Schultz, Peter; Ring, David B.; Harrison, Stephen D.; Bray, Andrew M.

    2000-01-01

    Compounds of formula 1: ##STR1## wherein R.sub.1 is alkyl, cycloalkyl, aryl, aralkyl, heteroaryl, or heteroaralkyl, substituted with 0-3 substituents selected from lower alkyl, halo, hydroxy, lower alkoxy, amino, lower alkyl-amino, and nitro; R.sub.2 is hydroxy, amino, or lower alkoxy; R.sub.3 is H, lower alkyl, lower acyl, lower alkoxy-acyl, or amnino-acyl; R.sub.4 is H or lower alkyl; and pharmaceutically acceptable salts and esters thereof; are effective inhibitors of GSK3.

  7. Inhibitors of glycogen synthase 3 kinase

    DOE Patents [OSTI]

    Schultz, Peter; Ring, David B.; Harrison, Stephen D.; Bray, Andrew M.

    2006-05-30

    Compounds of formula 1: ##STR00001## wherein R.sub.1 is alkyl, cycloalkyl, aryl, aralkyl, heteroaryl, or heteroaralkyl, substituted with 0 3 substituents selected from lower alkyl, halo, hydroxy, lower alkoxy, amino, lower alkyl-amino, and nitro; R.sub.2 is hydroxy, amino, or lower alkoxy; R.sub.3 is H, lower alkyl, lower acyl, lower alkoxy-acyl, or amino-acyl; R.sub.4 is H or lower alkyl; and pharmaceutically acceptable salts and esters thereof; are effective inhibitors of GSK3.

  8. Impact of Renewable Fuels Standard/MTBE Provisions of S. 517 Requested by Sens. Daschle & Murkowski

    Reports and Publications (EIA)

    2002-01-01

    Additional analysis of the impact of the Renewable Fuels Standard (RFS) and methyl tertiary butyl ether (MTBE) ban provisions of S. 517.

  9. Biomass IBR Fact Sheet: Archer Daniels Midland

    Broader source: Energy.gov [DOE]

    Archer Daniels Midland will develop a pilot plant to demonstrate the continuous production of cellulosic ethanol and butyl acrylate from densified corn stover.

  10. Improving Vehicle Fuel Efficiency Through Tire Design, Materials...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    ... Evaluate a light weight barrier film material as a replacement for standard halo-butyl inner liner. * Milestones - Status Conduct 2 nd tire program to further ...

  11. This Week In Petroleum Printer-Friendly Version

    Annual Energy Outlook [U.S. Energy Information Administration (EIA)]

    this transition from Methyl Tertiary Butyl Ether (MTBE) reformulated gasoline (RFG) to ethanol RFG, since ethanol is not blended into the gasoline mixture until just before the...

  12. untitled

    Gasoline and Diesel Fuel Update (EIA)

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

  13. Motor Gasoline Market Spring 2007 and Implications for Spring...

    Annual Energy Outlook [U.S. Energy Information Administration (EIA)]

    began to decline, and with the transition from methyl tertiary butyl ether (MTBE) to ethanol completed and the end of the summer driving season drawing near, gasoline prices...

  14. Platts 2nd Annual Renewable Chemicals Conference

    Annual Energy Outlook [U.S. Energy Information Administration (EIA)]

    Topsoe, INEOS Bio, Iogen, POET * Cane, Energy crops, Waste * Quality and standards * ... butyl rubber, PET Gevo, Butamax, Cathay, Green, Cobalt Adipic Acid nylon, polyurethane ...

  15. Synthesis metal nanoparticle

    DOE Patents [OSTI]

    Bunge, Scott D.; Boyle, Timothy J.

    2005-08-16

    A method for providing an anhydrous route for the synthesis of amine capped coinage-metal (copper, silver, and gold) nanoparticles (NPs) using the coinage-metal mesityl (mesityl=C.sub.6 H.sub.2 (CH.sub.3).sub.3 -2,4,6) derivatives. In this method, a solution of (Cu(C.sub.6 H.sub.2 (CH.sub.3).sub.3).sub.5, (Ag(C.sub.6 H.sub.2 (CH.sub.3).sub.3).sub.4, or (Au(C.sub.6 H.sub.2 (CH.sub.3).sub.3).sub.5 is dissolved in a coordinating solvent, such as a primary, secondary, or tertiary amine; primary, secondary, or tertiary phosphine, or alkyl thiol, to produce a mesityl precursor solution. This solution is subsequently injected into an organic solvent that is heated to a temperature greater than approximately 100.degree. C. After washing with an organic solvent, such as an alcohol (including methanol, ethanol, propanol, and higher molecular-weight alcohols), oxide free coinage NP are prepared that could be extracted with a solvent, such as an aromatic solvent (including, for example, toluene, benzene, and pyridine) or an alkane (including, for example, pentane, hexane, and heptane). Characterization by UV-Vis spectroscopy and transmission electron microscopy showed that the NPs were approximately 9.2.+-.2.3 nm in size for Cu.degree., (no surface oxide present), approximately 8.5.+-.1.1 nm Ag.degree. spheres, and approximately 8-80 nm for Au.degree..

  16. Novel pathways for fuels and lubricants from biomass optimized using life-cycle greenhouse gas assessment

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

    Balakrishnan, Madhesan; Sacia, Eric R.; Sreekumar, Sanil; Gunbas, Gorkem; Gokhale, Amit A.; Scown, Corinne D.; Toste, F. Dean; Bell, Alexis T.

    2015-06-08

    Decarbonizing the transportation sector is critical to achieving global climate change mitigation. Although biofuels will play an important role in conventional gasoline and diesel applications, bioderived solutions are particularly important in jet fuels and lubricants, for which no other viable renewable alternatives exist. Producing compounds for jet fuel and lubricant base oil applications often requires upgrading fermentation products, such as alcohols and ketones, to reach the appropriate molecular-weight range. Ketones possess both electrophilic and nucleophilic functionality, which allows them to be used as building blocks similar to alkenes and aromatics in a petroleum refining complex. Here, we develop a methodmore » for selectively upgrading biomass-derived alkyl methyl ketones with >95% yields into trimer condensates, which can then be hydrodeoxygenated in near-quantitative yields to give a new class of cycloalkane compounds. The basic chemistry developed here can be tailored for aviation fuels as well as lubricants by changing the production strategy. We demonstrate that a sugarcane biorefinery could use natural synergies between various routes to produce a mixture of lubricant base oils and jet fuels that achieve net life-cycle greenhouse gas savings of up to 80%.« less

  17. Calixarene crown ether solvent composition and use thereof for extraction of cesium from alkaline waste solutions

    DOE Patents [OSTI]

    Moyer, Bruce A. (Oak Ridge, TN); Sachleben, Richard A. (Knoxville, TN); Bonnesen, Peter V. (Knoxville, TN); Presley, Derek J. (Ooltewah, TN)

    2001-01-01

    A solvent composition and corresponding method for extracting cesium (Cs) from aqueous neutral and alkaline solutions containing Cs and perhaps other competing metal ions is described. The method entails contacting an aqueous Cs-containing solution with a solvent consisting of a specific class of lipophilic calix[4]arene-crown ether extractants dissolved in a hydrocarbon-based diluent containing a specific class of alkyl-aromatic ether alcohols as modifiers. The cesium values are subsequently recovered from the extractant, and the solvent subsequently recycled, by contacting the Cs-containing organic solution with an aqueous stripping solution. This combined extraction and stripping method is especially useful as a process for removal of the radionuclide cesium-137 from highly alkaline waste solutions which are also very concentrated in sodium and potassium. No pre-treatment of the waste solution is necessary, and the cesium can be recovered using a safe and inexpensive stripping process using water, dilute (millimolar) acid solutions, or dilute (millimolar) salt solutions. An important application for this invention would be treatment of alkaline nuclear tank wastes. Alternatively, the invention could be applied to decontamination of acidic reprocessing wastes containing cesium-137.

  18. Protonation of acyllithium reagents by acetonitrile: Synthesis of {beta}-hydroxy nitriles

    SciTech Connect (OSTI)

    Li, Nan-Sheng; Yu, Su; Kabalka, G.W. [Univ. of Tennessee, Knoxville, TN (United States)

    1995-09-08

    In recent years, the reaction of electrophiles with acyllithium (RCOLi) reagents has been extensively studied and has proven to be a convenient route to acylated products. For example, Seyferth reported that acyllithium reagents, generated in situ from an alkyllithium and carbon monoxide at -110 {degrees}C to -135 {degrees}C, would react with aldehydes, ketones, esters, lactones, isocyanates, isothiocyanates, carbodiimides, carbon disulfide, carbonyl sulfide, organic disulfides, iron pentacarbonyl, and trimethylchlorosilane to give acylated products. Nudelman found that the acyllithium generated from phenyllithium in the presence of alkyl bromides gave diphenylalkylcarbinols. The authors recently reported that trialkylboranes reacted with acyllithium reagents to afford ketones in modest yields. Although Seyferth predicted that acyl anion reagents might react with nitriles to afford addition products such as {alpha}-diketones, no report of a reaction of acyl anion reagents with nitriles has appeared in literature. Recently, the authors reported the first example of the protonation of acyllithium reagents by dichloromethane and dichloroarylmethane. The reaction affords the corresponding {alpha}, {alpha}-dichloro alcohols in excellent yields. The authors wish to report a new synthesis of {beta}-hydroxy nitriles which is based on the reaction of acyllithium with acetonitrile, Scheme 1. 1 tab.

  19. Vicarious nucleophilic substitution using 4-amino-1,2,4-triazole, hydroxylamine or O-alkylhydroxylamine to prepare 1,3-diamino-2,4,6-trinitrobenzene or 1,3,5-triamino-2,4,6-trinitrobenzene

    DOE Patents [OSTI]

    Mitchell, Alexander R. (Livermore, CA); Pagoria, Philip F. (Livermore, CA); Schmidt, Robert D. (Livermore, CA)

    1997-01-01

    The present invention relates to a process to produce 1,3-diamino-2,4,6-trinitrobenzene (DATB) or 1,3,5-triamino-2,4,6,-trinitrobenzene (TATB) by: (a) reacting at ambient pressure and a temperature of between about 0.degree. and 50.degree. C. for between about 0.1 and 24 hr, a trinitroaromatic compound of structure V: ##STR1## wherein X, Y, and Z are each independently selected from the group consisting of --H and --NH.sub.2, with the proviso that at least 1 or 2 of X, Y, and Z are hydrogen; with an effective amount of 1-amino-1,2,4-triazole, hydroxylamine or O-alkylhydroxamine to produce DATB or TATB; in the presence of a strong base selected from sodium butoxide, potassium butoxide, potassium propoxide, sodium propoxide, sodium ethoxide, potassium ethoxide, sodium methoxide, potassium methoxide, and combinations thereof; in a solvent selected from the group consisting of methanol, ethanol, propanol, butanol, dimethylsulphoxide, N-methylpyrrolidone, hexamethylphosphoramide, dimethylformide, dimethylacetamide and mixtures thereof, provided that when alcohols are present or when hydroxylamine or its O-alkyl derivatives replace ATA primarily DATB is formed; and (b) isolating the DATB or TATB produced. DATB and TATB are important and useful specialty explosives and intermediates for other materials.

  20. Vicarious nucleophilic substitution using 4-amino-1,2,4-triazole, hydroxylamine or O-alkylhydroxylamine to prepare 1,3-diamino-2,4,6-trinitrobenzene or 1,3,5-triamino-2,4,6-trinitrobenzene

    DOE Patents [OSTI]

    Mitchell, A.R.; Pagoria, P.F.; Schmidt, R.D.

    1997-05-27

    The present invention relates to a process to produce 1,3-diamino-2,4,6-trinitrobenzene (DATB) or 1,3,5-triamino-2,4,6,trinitrobenzene (TATB) by: (a) reacting at ambient pressure and a temperature of between about 0 and 50 C for between about 0.1 and 24 hr, a trinitroaromatic compound of the structure shown where X, Y, and Z are each independently selected from the group consisting of -H and -NH{sub 2}, with the proviso that at least 1 or 2 of X, Y, and Z are hydrogen; with an effective amount of 1-amino-1,2,4-triazole, hydroxylamine or O-alkylhydroxamine to produce DATB or TATB; in the presence of a strong base selected from sodium butoxide, potassium butoxide, potassium propoxide, sodium propoxide, sodium ethoxide, potassium ethoxide, sodium methoxide, potassium methoxide, and combinations thereof; in a solvent selected from the group consisting of methanol, ethanol, propanol, butanol, dimethylsulphoxide, N-methylpyrrolidone, hexamethylphosphoramide, dimethylformide, dimethylacetamide and mixtures thereof, provided that when alcohols are present or when hydroxylamine or its O-alkyl derivatives replace ATA primarily DATB is formed; and (b) isolating the DATB or TATB produced. DATB and TATB are important and useful specialty explosives and intermediates for other materials.

  1. Novel pathways for fuels and lubricants from biomass optimized using life-cycle greenhouse gas assessment

    SciTech Connect (OSTI)

    Balakrishnan, Madhesan; Sacia, Eric R.; Sreekumar, Sanil; Gunbas, Gorkem; Gokhale, Amit A.; Scown, Corinne D.; Toste, F. Dean; Bell, Alexis T.

    2015-06-08

    Decarbonizing the transportation sector is critical to achieving global climate change mitigation. Although biofuels will play an important role in conventional gasoline and diesel applications, bioderived solutions are particularly important in jet fuels and lubricants, for which no other viable renewable alternatives exist. Producing compounds for jet fuel and lubricant base oil applications often requires upgrading fermentation products, such as alcohols and ketones, to reach the appropriate molecular-weight range. Ketones possess both electrophilic and nucleophilic functionality, which allows them to be used as building blocks similar to alkenes and aromatics in a petroleum refining complex. Here, we develop a method for selectively upgrading biomass-derived alkyl methyl ketones with >95% yields into trimer condensates, which can then be hydrodeoxygenated in near-quantitative yields to give a new class of cycloalkane compounds. The basic chemistry developed here can be tailored for aviation fuels as well as lubricants by changing the production strategy. We demonstrate that a sugarcane biorefinery could use natural synergies between various routes to produce a mixture of lubricant base oils and jet fuels that achieve net life-cycle greenhouse gas savings of up to 80%.

  2. 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.

  3. Hydrogen storage composition and method

    DOE Patents [OSTI]

    Wicks, G.G.; Heung, L.K.

    1994-01-01

    A hydrogen storage composition based on a metal hydride dispersed in an aerogel prepared by a sol-gel process. The starting material for the aerogel is an organometallic compound, including the alkoxysilanes, organometals of the form M(OR){sub X} where R is an organic ligand of the form C{sub n}H{sub 2n+1}, and organometals of the form MO{sub x}Ry where R is an alkyl group, where M is an oxide-forming metal, n, x and y are integers and y is two less than the valence of M. A sol is prepared by combining the starting material, alcohol, water, and an acid. The sol is conditioned to the proper viscosity and a hydride in the form of a fine powder is added. The mixture is polymerized and dried under supercritical conditions. The final product is a composition having a hydride uniformly dispersed throughout an inert, stable and highly porous matrix. It is capable of absorbing up to 30 motes of hydrogen per kilogram at room temperature and pressure, rapidly and reversibly. Hydrogen absorbed by the composition can be readily be recovered by heat or evacuation.

  4. Hydrogen storage composition and method

    DOE Patents [OSTI]

    Heung, Leung K (Aiken, SC); Wicks, George G. (Aiken, SC)

    2003-01-01

    A hydrogen storage composition based on a metal hydride dispersed in an aerogel prepared by a sol-gel process. The starting material for the aerogel is an organometallic compound, including the alkoxysilanes, organometals of the form M(OR)x and MOxRy, where R is an alkyl group of the form C.sub.n H.sub.2n+1, M is an oxide-forming metal, n, x, and y are integers, and y is two less than the valence of M. A sol is prepared by combining the starting material, alcohol, water, and an acid. The sol is conditioned to the proper viscosity and a hydride in the form of a fine powder is added. The mixture is polymerized and dried under supercritical conditions. The final product is a composition having a hydride uniformly dispersed throughout an inert, stable and highly porous matrix. It is capable of absorbing up to 30 moles of hydrogen per kilogram at room temperature and pressure, rapidly and reversibly. Hydrogen absorbed by the composition can be readily be recovered by heat or evacuation.

  5. Summary of Decisions - April 15, 2013 - April 19, 2013 | Department...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    ... diagnosis of Alcohol Abuse and Major Depression, a history of binge alcohol drinking, ... related to his alcohol abuse and depression: though the individual is now taking ...

  6. Process Design and Economics for Conversion of Lignocellulosic Biomass to Ethanol: Thermochemical Pathway by Indirect Gasification and Mixed Alcohol Synthesis

    SciTech Connect (OSTI)

    Dutta, A.; Talmadge, M.; Hensley, J.; Worley, M.; Dudgeon, D.; Barton, D.; Groendijk, P.; Ferrari, D.; Stears, B.; Searcy, E. M.; Wright, C. T.; Hess, J. R.

    2011-05-01

    This design report describes an up-to-date benchmark thermochemical conversion process that incorporates the latest research from NREL and other sources. Building on a design report published in 2007, NREL and its subcontractor Harris Group Inc. performed a complete review of the process design and economic model for a biomass-to-ethanol process via indirect gasification. The conceptual design presented herein considers the economics of ethanol production, assuming the achievement of internal research targets for 2012 and nth-plant costs and financing. The design features a processing capacity of 2,205 U.S. tons (2,000 metric tonnes) of dry biomass per day and an ethanol yield of 83.8 gallons per dry U.S. ton of feedstock. The ethanol selling price corresponding to this design is $2.05 per gallon in 2007 dollars, assuming a 30-year plant life and 40% equity financing with a 10% internal rate of return and the remaining 60% debt financed at 8% interest. This ethanol selling price corresponds to a gasoline equivalent price of $3.11 per gallon based on the relative volumetric energy contents of ethanol and gasoline.

  7. Displacement of Hexanol by the Hexanoic Acid Overoxidation Product in Alcohol Oxidation on a Model Supported Palladium Nanoparticle Catalyst

    SciTech Connect (OSTI)

    Buchbinder, Avram M. [Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; Center for Catalysis and Surface Science; Inst. for Catalysis in Energy Processes; Ray, Natalie A. [Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; Center for Catalysis and Surface Science; Lu, Junling [Argonne National Lab. (ANL), Argonne, IL (United States). Energy System Division; Van Duyne, Richard P. [Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; Center for Catalysis and Surface Science; Inst. for Catalysis in Energy Processes; Stair, Peter C. [Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; Center for Catalysis and Surface Science; Inst. for Catalysis in Energy Processes; Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division; Weitz, Eric [Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; Center for Catalysis and Surface Science; Inst. for Catalysis in Energy Processes; Geiger, Franz M. [Northwestern Univ., Evanston, IL (United States). Dept. of Chemistry; Center for Catalysis and Surface Science; Inst. for Catalysis in Energy Processes

    2011-11-09

    This work characterizes the adsorption, structure, and binding mechanism of oxygenated organic species from cyclohexane solution at the liquid/solid interface of optically flat alumina-supported palladium nanoparticle surfaces prepared by atomic layer deposition (ALD). The surface-specific nonlinear optical vibrational spectroscopy, sum-frequency generation (SFG), was used as a probe for adsorption and interfacial molecular structure. 1-Hexanoic acid is an overoxidation product and possible catalyst poison for the aerobic heterogeneous oxidation of 1-hexanol at the liquid/solid interface of Pd/Al?O? catalysts. Single component and competitive adsorption experiments show that 1-hexanoic acid adsorbs to both ALD-prepared alumina surfaces and alumina surfaces with palladium nanoparticles, that were also prepared by ALD, more strongly than does 1-hexanol. Furthermore, 1-hexanoic acid adsorbs with conformational order on ALD-prepared alumina surfaces, but on surfaces with palladium particles the adsorbates exhibit relative disorder at low surface coverage and become more ordered, on average, at higher surface coverage. Although significant differences in binding constant were not observed between surfaces with and without palladium nanoparticles, the palladium particles play an apparent role in controlling adsorbate structures. The disordered adsorption of 1-hexanoic acid most likely occurs on the alumina support, and probably results from modification of binding sites on the alumina, adjacent to the particles. In addition to providing insight on the possibility of catalyst poisoning by the overoxidation product and characterizing changes in its structure that result in only small adsorption energy changes, this work represents a step toward using surface science techniques that bridge the complexity gap between fundamental studies and realistic catalyst models.

  8. Impact of zeolite aging in hot liquid water on activity for acid-catalyzed dehydration of alcohols

    SciTech Connect (OSTI)

    Vjunov, Aleksei; Derewinski, Miroslaw A.; Fulton, John L.; Camaioni, Donald M.; Lercher, Johannes A.

    2015-08-19

    The catalytic performance of zeolite in aqueous medium depends on a multitude of factors, such as the concentration and distribution of active sites and framework integrity. Al Kedge extended Xray absorption fine structure and 27Al MAS NMR spectroscopies in combination with DFT calculations are used to determine the distribution of tetrahedral Al sites both qualitatively and quantitatively for both parent and 48 h 160 C water treated HBEA catalysts. There is no evidence of Al coordination modification after aging in water. The distribution and concentration of Al Tsites, active centers for the dehydration of cyclohexanol, do not markedly impact the catalytic performance in water, because the Brnsted acidic protons are present in the form of hydrated hydronium ions and thus have very similar acid properties. The results suggest that all Brnsted acid sites are equally active in aqueous medium. The decrease of zeolite catalytic performance after water treatment is attributed to the reduced concentration of Brnsted acid sites. Increasing the stability of pore walls and decreasing the rate of SiOSi group hydrolysis may result in improved apparent zeolite catalytic performance in aqueous medium. Authors thank B. W. Arey (PNNL) for HIM measurements, T. Huthwelker for support during Al XAFS measurements at the Swiss Light Source (PSI, Switzerland), J. Z. Hu and S. D. Burton (PNNL) for support during NMR experiments. This work was supported by the U. S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. MD acknowledges support by the Materials Synthesis and Simulation Across Scales (MS3 Initiative) conducted under Laboratory Directed Research & Development Program at PNNL. HIM imaging and NMR experiments were performed at the Environmental Molecular Sciences Laboratory, a national scientific user facility sponsored by the DOE Office of Science, Office of Biological and Environmental Research, located at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated for the DOE by Battelle Memorial Institute under contract # DE-AC05-76RL0-1830

  9. Hydrogen Generation from Biomass-Derived Surgar Alcohols via the Aqueous-Phase Carbohydrate Reforming (ACR) Process

    SciTech Connect (OSTI)

    Randy Cortright

    2006-06-30

    This project involved the investigation and development of catalysts and reactor systems that will be cost-effective to generate hydrogen from potential sorbitol streams. The intention was to identify the required catalysts and reactors systems as well as the design, construction, and operation of a 300 grams per hour hydrogen system. Virent was able to accomplish this objective with a system that generates 2.2 kgs an hour of gas containing both hydrogen and alkanes that relied directly on the work performed under this grant. This system, funded in part by the local Madison utility, Madison, Gas & Electric (MGE), is described further in the report. The design and development of this system should provide the necessary scale-up information for the generation of hydrogen from corn-derived sorbitol.

  10. Ag-Al2O3 Catalyst HC-SCR: Performance with Light Alcohols and Other Reductants

    Broader source: Energy.gov [DOE]

    2004 Diesel Engine Emissions Reduction (DEER) Conference Presentation: Oak Ridge National Laboratory

  11. Novel Approaches to the Production of Higher Alcohols From Synthesis Gas. Quarterly report, January 1 - March 31, 1996

    SciTech Connect (OSTI)

    George W. Roberts

    1997-02-13

    Effort during this quarter was devoted to three areas: 1) analyzing the data from earlier runs with ?zinc chromite? catalyst and three different slurry liquids: decahydronaphthalene (Decalin, DHN), tetrahydronaphthalene (tetralin, THN) and tetrahydroquinoline (THQ); 2) analyzing newly-obtained data from earlier thermal stability tests on DHN and THN, and 3) carrying out a thermal stability test on THQ. Both the activity and selectivity of ?zinc chromite? catalyst depended on the slurry liquid that was used. The catalyst activity for methanol synthesis was in the order: THQ > DHN > THN. Despite the basic nature of THQ, it exhibited the highest dimethyl ether (DME) production rates of the three liquids. Gas chromatography/mass spectroscopy (GC/MS) analyses of samples of THN and DHN were taken at the end of standard thermal stability tests at 375C. With both liquids, the only measurable compositional change was a minor amount of isomerization. Analysis of a sample of THN after a thermal stability test at 425C showed a small reduction in molecular weight, and a significant amount of opening of the naphthenic ring. Preliminary data from the tehrmal stability test of THQ showed that this molecule is more stable than DHN, but less stable than THN.

  12. Novel Approaches to the Production of Higher Alcohols From Synthesis Gas. Quarterly report, January 1 - March 31, 1997

    SciTech Connect (OSTI)

    George W. Roberts

    1998-12-11

    A modified analytical system was assembled and calibrated, in preparation for a second run with cesium (Cs)-promoted ?zinc chromite? catalyst. A new column for the on-line gas chromatography (GC) was purchased for the analysis of various light olefin and paraffin isomers. A run was carried out in the continuous stirred autoclave using the Cs-promoted catalyst. Decahydronaphfialene was used as the slurry liquid. Reaction conditions were 375C, 2000 psig total pressure, 0.5 H&sub2;/CO ratio, and 5000 sL/Kg (cat.)-hr. Analysis of the data from this run is in progress. A manuscript on the thermal stability of potential slurry liquids was submitted to 'Industrial and Engineering Chemistry Research,' and a paper was presented at the 1997 Spring National Meeting of the American Institute of Chemical Engineers, Houston, Texas.

  13. Continuous wasteless ecologically safe technology of propylenecarbonate production in presence of phthalocyanine catalysts

    DOE Patents [OSTI]

    Afanasiev, Vladimir Vasilievich (Moscow, RU); Zefirov, Nikolai Serafimovich (Moscow, RU); Zalepugin, Dmitry Yurievich (Moscow, RU); Polyakov, Victor Stanislavovich (Moscow, RU); Tilkunova,Nataliya Alexandrovna (Moscow, RU); Tomilova, Larisa Godvigovna (Moscow, RU)

    2009-09-08

    A continuous method of producing propylenecarbonate includes carboxylation of propylene oxide with carbon dioxide in presence of phthalocyanine catalyst on an inert carrier, using as the phthalocyanine catalyst at least one catalyst selected from the group consisting of not-substituted, methyl, ethyl, butyl, and tret butyl-substituted phthalocyanines of metals, including those containing counterions, and using as the carrier a hydrophobic carrier.

  14. Henry's law constants for paint solvents and their implications on volatile organic compound emissions from automotive painting

    SciTech Connect (OSTI)

    Kim, B.R.; Kalis, E.M.; DeWulf, T.; Andrews, K.M.

    2000-02-01

    This paper describes experimental results of equilibrium partitioning of several significant paint solvents and formaldehyde between air and water to quantify the potential for capturing and retaining the constituents in spraybooth scrubber water during automotive painting. The compounds studied are toluene, n-butanol, methyl ethyl ketone methyl propyl ketone, methyl isobutyl ketone, methyl amyl ketone, butyl cellosolve, butyl cellosolve acetate, butyl carbitol, and n-methyl-2-pyrrolidinone. A set of field data collected at a Ford Motor Company assembly plant was also analyzed to determine whether data were consistent with the equilibrium phenomenon. The primary findings include: (a) There were more than six orders of magnitude difference in the Henry's law constants among the solvents studied. A solvent with a smaller constant is less easily stripped from water. The Henry's law constants decrease in the following order: toluene and xylenes > methyl ethyl ketone > n-butanol > butyl cellosolve acetate > butyl cellosolve > formaldehyde > butyl carbitol > n-methyl-2-pyrrolidinone. (b) Field data showed accumulation of n-methyl-2-pyrrolidinone and stable concentrations of butyl carbitol, butyl cellosolve, and n-butanol in the paint-sludge pit water during a 2-month period. Stable concentrations indicate a continuous, balanced capture and stripping of the solvents. Data were consistent with measured Henry's law constants. (c) The low Henry's law constant for formaldehyde is the result of the fact that it is hydrated when dissolved in water.

  15. Anti-cancer agents based on N-acyl-2, 3-dihydro-1H-pyrrolo[2,3-b] quinoline derivatives and a method of making

    DOE Patents [OSTI]

    Gakh, Andrei; Krasavin, Mikhail; Karapetian, Ruben; Rufanov, Konstantin A; Konstantinov, Igor; Godovykh, Elena; Soldatkina, Olga; Sosnov, Andrey V

    2013-04-16

    The present disclosure relates to novel compounds that can be used as anti-cancer agents in the prostate cancer therapy. In particular, the invention relates to N-acyl derivatives of 2,3-dihydro-1H-pyrrolo[2,3-b]quinolines having the structural Formula (I), ##STR00001## stereoisomers, tautomers, racemics, prodrugs, metabolites thereof, or pharmaceutically acceptable salt and/or solvate thereof. The meaning of R1 is independently selected from H; C1-C6 Alkyl, cyclo-Alkyl or iso-Alkyl substituents; R2 is selected from C1-C6 Alkyl, cyclo-Alkyl or iso-Alkyl; substituted or non-substituted, fused or non-fused to substituted or non-substituted aromatic ring, aryl or heteroaryl groups. The invention also relates to methods for preparing said compounds, and to pharmaceutical compositions comprising said compounds.

  16. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    ... F. The goals of this project were to design new electrophilic metal alkyl complexes ... Pd catalysts that produce high molecular weight linear polyethylene and ...

  17. Separation of gases through gas enrichment membrane composites

    DOE Patents [OSTI]

    Swedo, Raymond J. (Mt. Prospect, IL); Kurek, Paul R. (Schaumburg, IL)

    1988-01-01

    Thin film composite membranes having as a permselective layer a film of a homopolymer of certain vinyl alkyl ethers are useful in the separation of various gases. Such homopolymers have a molecular weight of greater than 30,000 and the alkyl group of the vinyl alkyl monomer has from 4 to 20 carbon atoms with branching within the alkyl moiety at least at the carbon atom bonded to the ether oxygen or at the next adjacent carbon atom. These membranes show excellent hydrolytic stability, especially in the presence of acidic or basic gaseous components.

  18. Light, Molecules, Action: Toward Cobalamin (Vitamin B12) Compounds...

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

    as a source for controlled release of reactive radicals including alkyl radicals and hydroxyl radicals. Here we will present time-resolved spectroscopic measurements of a variety...

  19. Separation of gases through gas enrichment membrane composites

    DOE Patents [OSTI]

    Swedo, R.J.; Kurek, P.R.

    1988-07-19

    Thin film composite membranes having as a permselective layer a film of a homopolymer of certain vinyl alkyl ethers are useful in the separation of various gases. Such homopolymers have a molecular weight of greater than 30,000 and the alkyl group of the vinyl alkyl monomer has from 4 to 20 carbon atoms with branching within the alkyl moiety at least at the carbon atom bonded to the ether oxygen or at the next adjacent carbon atom. These membranes show excellent hydrolytic stability, especially in the presence of acidic or basic gaseous components.

  20. Table Definitions, Sources, and Explanatory Notes

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

    Inputs & Utilization Definitions Key Terms Definition All Other Motor Gasoline Blending Components Naphthas (e.g. straight-run gasoline, alkylate, reformate, benzene, toluene,...

  1. Novel Fischer-Tropsch catalysts

    DOE Patents [OSTI]

    Vollhardt, Kurt P. C.; Perkins, Patrick

    1981-01-01

    Novel polymer-supported metal complexes of the formula PS -R Me(CO).sub.n H.sub.m where: PS represents a divinylbenzene crosslinked polystyrene in which the divinylbenzene crosslinking is greater than 1% and less than about 18%; R represents a cycloalkadienyl radical of 4 through 6 carbon atoms; Me represents a Group VIII metal; CO represents a carbonyl radical; H represents hydrogen; n represents an integer varying from 0 through 3; m represents an integer varying from 0 through 2 inclusively with the further provision that 2n+m must total 18 when added to the electrons in R and Me, or n+m must total 0; are prepared by: brominating PS -H by treating same with bromine in the presence of a thallium salt in a partially or fully halogenated solvent to form PS -Br; treating said PS -Br so produced with a lithium alkyl of 1 through 12 carbon atoms in an aromatic solvent to produce PS -Li; substituting said PS - Li so produced by reaction with a 2-cycloalkenone of 4 to 6 carbon atoms in the presence of an ether solvent and using a water work-up to form a cycloalkenylalcohol-substituted PS ; dehydrating said alcohol so produced by heating under a vacuum to produce a cycloalkadienyl-substituted PS ; reacting the cycloalkadienyl-substituted PS with metal carbonyl in the presence of a partially or fully halogenated hydrocarbon, aromatic hydrocarbon of 6 through 8 carbon atoms, ethers, or esters of 4 through 10 carbon atoms as a solvent to produce a polystyrene-supported cycloalkadienyl metal carbonyl. The novel compounds are used as improved Fischer-Tropsch catalysts particularly for the conversion of CO+H.sub.2 to gaseous and liquid hydrocarbons at milder conditions than with prior catalysts.

  2. Novel Fischer-Tropsch catalysts

    DOE Patents [OSTI]

    Vollhardt, Kurt P. C.; Perkins, Patrick

    1980-01-01

    Novel polymer-supported metal complexes of the formula: PS --R Me(CO).sub.n H.sub.m where: PS represents a divinylbenzene crosslinked polystyrene in which the divinylbenzene crosslinking is greater than 1% and less than about 18%; R represents a cycloalkadienyl radical of 4 through 6 carbon atoms; Me represents a Group VIII metal; CO represents a carbonyl radical; H represents hydrogen; n represents an integer varying from 0 through 3; m represents an integer varying from 0 through 2 inclusively with the further provision that 2n+m must total 18 when added to the electrons in R and Me, or n+m must total 0; are prepared by: brominating PS --H by treating same with bromine in the presence of a thallium salt in a partially or fully halogenated solvent to form PS --Br; treating said PS --Br so produced with a lithium alkyl of 1 through 12 carbon atoms in an aromatic solvent to produce PS --Li; substituting said PS-- Li so produced by reaction with a 2-cycloalkenone of 4 to 6 carbon atoms in the presence of an ether solvent and using a water work-up to form a cycloalkenylalcohol-substituted PS ; dehydrating said alcohol so produced by heating under a vacuum to produce a cycloalkadienyl-substituted PS ; reacting the cycloalkadienyl-substituted PS with metal carbonyl in the presence of a partially or fully halogenated hydrocarbon, aromatic hydrocarbon of 6 through 8 carbon atoms, ethers, or esters of 4 through 10 carbon atoms as a solvent to produce a polystyrene-supported cycloalkadienyl metal carbonyl. The novel compounds are used as improved Fischer-Tropsch catalysts particularly for the conversion of CO+H.sub.2 to gaseous and liquid hydrocarbons at milder conditions than with prior catalysts.

  3. Novel Fischer-Tropsch catalysts

    DOE Patents [OSTI]

    Vollhardt, Kurt P. C.; Perkins, Patrick

    1981-01-01

    Novel polymer-supported metal complexes of the formula: PS --R Me(CO).sub.n H.sub.m where: PS represents a divinylbenzene crosslinked polystyrene in which the divinylbenzene crosslinking is greater than 1% and less than about 18%; R represents a cycloalkadienyl radical of 4 through 6 carbon atoms; Me represents a Group VIII metal; CO represents a carbonyl radical; H represents hydrogen; n represents an integer varying from 0 through 3; m represents an integer varying from 0 through 2 inclusively with the further provision that 2n+m must total 18 when added to the electrons in R and Me, or n+m must total 0; are prepared by: brominating PS --H by treating same with bromine in the presence of a thallium salt in a partially or fully halogenated solvent to form PS --Br; treating said PS --Br so produced with a lithium alkyl of 1 through 12 carbon atoms in an aromatic solvent to produce PS --Li; substituting said PS-- Li so produced by reaction with a 2-cycloalkenone of 4 to 6 carbon atoms in the presence of an ether solvent and using a water work-up to form a cycloalkenylalcohol-substituted PS ; dehydrating said alcohol so produced by heating under a vacuum to produce a cycloalkadienyl-substituted PS ; reacting the cycloalkadienyl-substituted PS with metal carbonyl in the presence of a partially or fully halogenated hydrocarbon, aromatic hydrocarbon of 6 through 8 carbon atoms, ethers, or esters of 4 through 10 carbon atoms as a solvent to produce a polystyrene-supported cycloalkadienyl metal carbonyl. The novel compounds are used as improved Fischer-Tropsch catalysts particularly for the conversion of CO+H.sub.2 to gaseous and liquid hydrocarbons at milder conditions than with prior catalysts.

  4. Catalytic Upgrading of bio-oil using 1-octene and 1-butanol over sulfonic acid resin catalysts

    SciTech Connect (OSTI)

    Zhang, Zhijun; Wang, Qingwen; Tripathi, Prabhat; Pittman, Charles U.

    2011-02-04

    Raw bio-oil from fast pyrolysis of biomass must be refined before it can be used as a transporation fuel, a petroleum refinery feed or for many other fuel uses. Raw bio-oil was upgraded with the neat model olefin, 1-octene, and with 1-octene/1-butanol mixtures over sulfonic acid resin catalysts frin 80 to 150 degrees celisus in order to simultaneously lower water content and acidity and to increase hydrophobicity and heating value. Phase separation and coke formation were key factors limiting the reaction rate during upgrading with neat 1-octene although octanols were formed by 1-octene hydration along with small amounts of octyl acetates and ethers. GC-MS analysis confirmed that olefin hydration, carboxylic acid esterification, acetal formation from aldehydes and ketones and O- and C-alkylations of phenolic compounds occurred simultaneously during upgrading with 1-octene/1-butanol mixtures. Addition of 1-butanol increased olefin conversion dramatically be reducing mass transfer restraints and serving as a cosolvent or emulsifying agent. It also reacted with carboxylic acids and aldehydes/ketones to form esters, and acetals, respectively, while also serving to stabilize bio-oil during heating. 1-Butanol addition also protected the catalysts, increasing catalyst lifetime and reducing or eliminationg coking. Upgrading sharply increased ester content and decreased the amounts of levoglucosan, polyhydric alcohols and organic acids. Upgrading lowered acidity (pH value rise from 2.5 to >3.0), removed the uppleasant ordor and increased hydrocarbon solubility. Water content decreased from 37.2% to < 7.5% dramatically and calorific value increased from 12.6 MJ kg to about 30.0 MJ kg.

  5. Compositions for labeling .beta.-amyloid plaques and neurofibrillary tangles

    DOE Patents [OSTI]

    Barrio, Jorge R.; Petric, Andrej; Satyamurthy, Nagichettiar; Small, Gary W.; Cole, Gregory M.; Huang, Sung-Cheng

    2008-03-11

    Compositions useful for labeling .beta.-amyloid plaques and neurofibrillary tangles are provided. The compositions comprises compounds of formula (I): ##STR00001## wherein R.sub.1 is selected from the group consisting of --C(O)-alkyl, --C(O)-alkylenyl-R.sub.4, --C(O)O-alkyl, --C(O)O-alkylenyl-R.sub.4, --C.dbd.C(CN).sub.2-alkyl, --C.dbd.C(CN).sub.2-alkylenyl-R.sub.4, ##STR00002## wherein R.sub.4 is a radical selected from the group consisting of alkyl, substituted alkyl, aryl and substituted aryl; R.sub.5 is a radical selected from the group consisting of --NH.sub.2, --OH, --SH, --NH-alkyl, --NHR.sub.4, --NH-alkylenyl-R.sub.4, --O-alkyl, --O-alkylenyl-R.sub.4, --S-alkyl, and --S-alkylenyl-R.sub.4; R.sub.6 is a radical selected from the group consisting of --CN, --COOH, --C(O)O-alkyl, --C(O)O-alkylenyl-R.sub.4, --C(O)-alkyl, --C(O)-alkylenyl-R.sub.4, --C(O)-halogen, --C(O)NH-alkyl, --C(O)NH-alkylenyl-R.sub.4 and --C(O)NH.sub.2; R.sub.7 is a radical selected from the group consisting of O, NH, and S; and R.sub.8 is N, O or S; and R.sub.2 is selected from the group consisting of alkyl and alkylenyl-R.sub.10 and R.sub.3 is alkylenyl-R.sub.10, wherein R.sub.10 is selected from the group consisting of --OH, --OTs, halogen, spiperone, spiperone ketal, and spiperone-3-yl, or R.sub.2 and R.sub.3 together form a heterocyclic ring, optionally substituted with at least one radical selected from the group consisting of alkyl, alkoxy, OH, OTs, halogen, alkyl-R.sub.10, carbonyl, spiperone, spiperone ketal and spiperone-3-yl, and further wherein one or more of the hydrogen, halogen or carbon atoms are optionally replaced with a radiolabel.

  6. APPENDXD.CHP:Corel VENTURA

    Annual Energy Outlook [U.S. Energy Information Administration (EIA)]

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

  7. Preparations for Meeting New York and Connecticut MTBE Bans

    Reports and Publications (EIA)

    2003-01-01

    In response to a Congressional request, the Energy Information Administration examined the progress being made to meet the bans on the use of methyl tertiary butyl ether (MTBE) being implemented in New York and Connecticut at the end of 2003.

  8. Method for cleaning solution used in nuclear fuel reprocessing

    DOE Patents [OSTI]

    Tallent, O.K.; Crouse, D.J.; Mailen, J.C.

    1980-12-17

    Nuclear fuel processing solution consisting of tri-n-butyl phosphate and dodecane, with a complex of uranium, plutonium, or zirconium and with a solvent degradation product such as di-n-butyl phosphate therein, is contacted with an aqueous solution of a salt formed from hydrazine and either a dicarboxylic acid or a hydroxycarboxylic acid, thereby removing the aforesaid complex from the processing solution.

  9. Method for cleaning solution used in nuclear fuel reprocessing

    DOE Patents [OSTI]

    Tallent, Othar K. (Oak Ridge, TN); Crouse, David J. (Oak Ridge, TN); Mailen, James C. (Oak Ridge, TN)

    1982-01-01

    Nuclear fuel processing solution consisting of tri-n-butyl phosphate and dodecane, with a complex of uranium, plutonium, or zirconium and with a solvent degradation product such as di-n-butyl phosphate therein, is contacted with an aqueous solution of a salt formed from hydrazine and either a dicarboxylic acid or a hydroxycarboxylic acid, thereby removing the aforesaid complex from the processing solution.

  10. Methods for labeling .beta.-amyloid plaques and neurofibrillary tangles

    DOE Patents [OSTI]

    Barrio, Jorge R.; Petric, Andrej; Satyamurthy, Nagichettiar; Small, Gary W.; Cole, Gregory M.; Huang, Sung-Cheng

    2003-12-09

    A method for labeling .beta.-amyloid plaques and neurofibrillary tangles in vivo and in vitro, comprises contacting a compound of formula (I): ##STR1## with mammalian tissue. In formula (I), R.sub.1 is selected from the group consisting of --C(O)-alkyl, --C(O)-alkylenyl-R.sub.4, --C(O)O-alkyl, --C(O)O-alkylenyl-R.sub.4, --C.dbd.C(CN).sub.2 -alkyl, --C.dbd.C(CN).sub.2 -alkylenyl-R.sub.4, ##STR2## R.sub.4 is a radical selected from the group consisting of alkyl, substituted alkyl, aryl and substituted aryl; R.sub.5 is a radical selected from the group consisting of --NH.sub.2, --OH, --SH, --NH-alkyl, --NHR.sub.4, --NH-alkylenyl-R.sub.4, --O-alkyl, --O-alkylenyl-R.sub.4, --S-alkyl, and --S-alkylenyl-R.sub.4 ; R.sub.6 is a radical selected from the group consisting of --CN, --COOH, --C(O)O-alkyl, --C(O)O-alkylenyl-R.sub.4, --C(O)-alkyl, --C(O)-alkylenyl-R.sub.4, --C(O)-halogen, --C(O)NH, --C(O)NH-alkyl, --C(O)NH-alkylenyl-R.sub.4 ; R.sub.7 is a radical selected from the group consisting of O, NH, and S; and R.sub.8 is N, O or S. R.sub.2 and R.sub.3 are each independently selected from the group consisting of alkyl and alkylenyl-R.sub.10, wherein R.sub.10 is selected from the group consisting of --OH, --OTs, halogen, spiperone, spiperone ketal and spiperone-3-yl. Alternatively, R.sub.2 and R.sub.3 together form a heterocyclic ring, optionally substituted with at least one radical selected from the group consisting of alkyl, alkoxy, OH, OTs, halogen, alkylenyl-R.sub.10, carbonyl, spiperone, spiperone ketal and spiperone-3-yl. In the compounds of formula (I), one or more of the hydrogen, halogen or carbon atoms can, optionally, be replaced with a radiolabel.

  11. Methods for labeling .beta.-amyloid plaques and neurofibrillary tangles

    DOE Patents [OSTI]

    Barrio, Jorge R.; Petric, Andrej; Satyamurthy, Nagichettiar; Small, Gary W.; Cole, Gregory M.; Huang, Sung-Cheng

    2001-01-01

    A method for labeling .beta.-amyloid plaques and neurofibrillary tangles in vivo and in vitro, comprises contacting a compound of formula (I): ##STR1## with mammalian tissue. In formula (I), R.sub.1 is selected from the group consisting of --C(O)-alkyl, --C(O)-alkylenyl-R.sub.4, --C(O)O-alkyl, --C(O)O-alkylenyl-R.sub.4, --C.dbd.C(CN).sub.2 -alkyl, --C.dbd.C(CN).sub.2 -alkylenyl-R.sub.4 , ##STR2## R.sub.4 is a radical selected from the group consisting of alkyl, substituted alkyl, aryl and substituted aryl; R.sub.5, is a radical selected from the group consisting of --NH.sub.2, --OH, --SH, --NH-alkyl, --NHR.sub.4, --NH-alkylenyl-R.sub.4, --O-alkyl, --O-alkylenyl-R.sub.4, --S-alkyl, and --S-alkylenyl-R.sub.4 ; R.sub.6 is a radical selected from the group consisting of --CN, --COOH, --C(O)O-alkyl, --C(O)O-alkylenyl-R.sub.4, --C(O)-alkyl, --C(O)-alkylenyl-R.sub.4, --C(O)-halogen, --C(O)NH , --C(O)NH-alkyl, --C(O)NH-alkylenyl-R.sub.4 ; R.sub.7 is a radical selected from the group consisting of O, NH, and S; and R.sub.8 is N, O or S. R.sub.2 and R.sub.3 are each independently selected from the group consisting of alkyl and alkylenyl-R.sub.10, wherein R.sub.10 is selected from the group consisting of --OH, --OTs, halogen, spiperone, spiperone ketal and spiperone-3-yl. Alternatively, R.sub.2 and R.sub.3 together form a heterocyclic ring, optionally substituted with at least one radical selected from the group consisting of alkyl, alkoxy, OH, OTs, halogen, alkylenyl-R.sub.10, carbonyl, spiperone, spiperone ketal and spiperone-3-yl. In the compounds of formula (I), one or more of the hydrogen, halogen or carbon atoms can, optionally, be replaced with a radiolabel.

  12. Analysis of the Effects of Compositional and Configurational Assumptions on Product Costs for the Thermochemical Conversion of Lignocellulosic Biomass to Mixed Alcohols FY 2007 Progress Report

    SciTech Connect (OSTI)

    Zhu, Yunhua; Gerber, Mark A.; Jones, Susanne B.; Stevens, Don J.

    2009-02-01

    The purpose of this study was to examine alternative biomass-to-ethanol conversion process assumptions and configuration options to determine their relative effects on overall process economics. A process-flow-sheet computer model was used to determine the heat and material balance for each configuration that was studied. The heat and material balance was then fed to a costing spreadsheet to determine the impact on the ethanol selling price. By examining a number of operational and configuration alternatives and comparing the results to the base flow sheet, alternatives having the greatest impact the performance and cost of the overall system were identified and used to make decisions on research priorities. This report, which was originally published in December 2008, has been revised primarily to correct information presented in Appendix B -- Base Case Flow Sheets and Model Results. The corrections to Appendix B include replacement of several pages in Table B.1 that duplicated previous pages of the table. Other changes were made in Appendix B to correct inconsistencies between stream labels presented in the tables and the stream labels in the figures.

  13. Functionalized polyfluorenes for use in optoelectronic devices

    DOE Patents [OSTI]

    Chichak, Kelly Scott; Lewis, Larry Neil; Cella, James Anthony; Shiang, Joseph John

    2011-11-08

    The present invention relates to process comprising reacting a polyfluorenes comprising at least one structural group of formula I ##STR00001## with an iridium (III) compound of formula II ##STR00002## wherein R.sup.1 and R.sup.2 are independently alkyl, substituted alkyl, aryl, substituted aryl or a combination thereof; R.sup.5is H or CHO; R.sup.3 and R.sup.4 are independently hydrogen, alkyl, substituted alkyl, aryl, substituted aryl or a combination thereof; R.sup.11 and R.sup.12 taken together form a substituted or unsubstituted monocyclic or bicyclic heteroaromatic ring; R.sup.13 is independently at each occurrence halo, nitro, hydroxy, amino, alkyl, aryl, arylalkyl, alkoxy, substituted alkoxy, substituted alkyl, substituted aryl, or substituted arylalkyl; Ar is aryl, heteroaryl, substituted aryl, substituted heteroaryl, or a combination thereof; X is selected from a direct bond, alky, substituted alkyl, and combinations thereof; Y is CHO or NH.sub.2; Z is CHO or NH.sub.2 where Z does not equal Y; and p is 0, 1 or 2. The invention also relates to the polyfluorenes, which are products of the reaction, and the use of the polyfluorenes in optoelectronic devices.

  14. Synthesis of an acid addition salt of delta-aminolevulinic acid from 5-bromo levulinic acid esters

    DOE Patents [OSTI]

    Moens, L.

    1999-05-25

    A process is disclosed for preparing an acid addition salt of delta-aminolevulinic acid comprising. The process involves dissolving a lower alkyl 5-bromolevulinate and an alkali metal diformylamide in an organic solvent selected from the group consisting of acetonitrile, methanol, tetrahydrofuran, 2-methyltetrahydrofuran and methylformate or mixtures to form a suspension of an alkyl 5-(N,N-diformylamino) levulinate ester; and hydrolyzing the alkyl 5-(N,N-diformylamino) levulinate with an inorganic acid to form an acid addition salt of delta-amino levulinic acid.

  15. Low pour crude oil compositions

    SciTech Connect (OSTI)

    Motz, K.L.; Latham, R.A.; Statz, R.J.

    1990-05-22

    This patent describes and improvement in the process of transporting waxy crude oils through a pipeline. It comprises: incorporating into the crude oil an effective pour point depressant amount of an additive comprising a polymer selected from the group consisting of copolymers of ethylene and acrylonitrile, and terpolymers of ethylene, acrylonitrile and a third monomer selected from the group consisting of vinyl acetate, carbon monoxide, alkyl acrylates, alkyl methacrylates, alkyl vinyl ethers, vinyl chloride, vinyl fluoride, acrylic acid, and methacrylic acid, wherein the amount of third monomer in the terpolymer ranges from about 0.1 to about 10.0 percent by weight.

  16. Synthesis of an acid addition salt of delta-aminolevulinic acid from 5-bromo levulinic acid esters

    DOE Patents [OSTI]

    Moens, Luc (Lakewood, CO)

    1999-01-01

    A process of preparing an acid addition salt of delta-aminolevulinic acid comprising: dissolving a lower alkyl 5-bromolevulinate and an alkali metal diformylamide in an organic solvent selected from the group consisting of acetonitrile, methanol, tetrahydrofuran, 2-methyltetrahydrofuran and methylformate or mixtures thereof to form a suspension of an alkyl 5-(N,N-diformylamino) levulinate ester; and hydrolyzing said alkyl 5-(N,N-diformylamino) levulinate with an inorganic acid to form an acid addition salt of delta-amino levulinic acid.

  17. SOLVENT EXTRACTION PROCESS FOR THE RECOVERY OF METALS FROM PHOSPHORIC ACID

    DOE Patents [OSTI]

    Bailes, R.H.; Long, R.S.

    1958-11-01

    > A solvent extraction process is presented for recovering metal values including uranium, thorium, and other lanthanide and actinide elements from crude industrial phosphoric acid solutions. The process conslsts of contacting said solution with an immisclble organic solvent extractant containing a diluent and a material selected from the group consisting of mono and di alkyl phosphates, alkyl phosphonates and alkyl phosphites. The uranlum enters the extractant phase and is subsequently recovered by any of the methods known to the art. Recovery is improved if the phosphate solution is treated with a reducing agent such as iron or aluminum powder prior to the extraction step.

  18. Monthly Energy Review The Monthly Energy Review

    Gasoline and Diesel Fuel Update (EIA)

    finished motor gasoline (leaded or unleaded) and alcohol (generally ethanol but sometimes methanol) limited to 10 percent by volume of alcohol. Gasohol is included in finished...

  19. DOE F 470.7 | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Program) and the breath alcohol technician. Screening results are to be afixed to the form. PDF icon Human Reliability Program (HRP) Alcohol Testing Form More Documents & ...

  20. PSH-12-0043 - In the Matter of Personnel Security Hearing | Department...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    with her excessive consumption of alcohol in college and a determination from a ... the Individual suffered from Alcohol-Related Disorder, Not Otherwise ...

  1. PSH-12-0090 - In the Matter of Personnel Security Hearing | Department...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    had successfully addressed the DOE's security concerns regarding his alcohol consumption. ... and other factors, were sufficient to demonstrate rehabilitation from Alcohol Abuse. ...

  2. PIA - Savannah River Nuclear Solution (SRNS) MedGate Occupational...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    and Alcohol Testing System (Assistant)) PIA - Savannah River Nuclear Solution (SRNS) MedGate Occupational Health and Safety Medical System (OHS) (Includes the Drug and Alcohol ...

  3. Characterization of Particulate Emissions from GDI Engine Combustion...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Particulate Emissions from GDI Engine Combustion with Alcohol-blended Fuels Characterization of Particulate Emissions from GDI Engine Combustion with Alcohol-blended Fuels Analysis ...

  4. The original of this document contains information which is subject...

    Broader source: Energy.gov (indexed) [DOE]

    random breath alcohol test to the Individual. That test indicated that the Individual's blood alcohol level was .034 percent. This incident led the Local Security Office (LSO) to...

  5. Summary of Decisions - June 22, 2015 - June 26, 2015 | Department...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    had not successfully addressed the DOE's security concerns regarding his use of alcohol, which included frequent intoxication and had resulted in three alcohol-related...

  6. Summary of Decisions - May 26, 2014 - May 30, 2014 | Department...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    The individual has a history of four arrests for Driving Under the Influence of Alcohol (DUI). A DOE psychologist also found that the individual habitually used alcohol to...

  7. Security Cases | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    to administrative review citing as security concerns the individual's diagnosis of alcohol abuse and his alcohol-related arrests. After conducting a hearing, convened at the...

  8. Summary of Decisions - December 1, 2014 - December 5, 2014 |...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    found that the individual had not resolved the security concerns arising from his alcohol use and diagnosis by a DOE psychologist that he suffered from alcohol use disorder,...

  9. Water-enhanced solvation of organics

    SciTech Connect (OSTI)

    Lee, J.H.

    1993-07-01

    Water-enhanced solvation (WES) was explored for Lewis acid solutes in Lewis base organic solvents, to develop cheap extract regeneration processes. WES for solid solutes was determined from ratios of solubilities of solutes in water-sat. and low-water solvent; both were determined from solid-liquid equilibrium. Vapor-headspace analysis was used to determine solute activity coefficients as function of organic phase water concentration. WES magnitudes of volatile solutes were normalized, set equal to slope of log {gamma}{sub s} vs x{sub w}/x{sub s} curve. From graph shape {Delta}(log {gamma}{sub s}) represents relative change in solute activity coefficient. Solutes investigated by vapor-headspace analysis were acetic acid, propionic acid, ethanol, 1,2-propylene glycol, 2,3-butylene glycol. Monocarboxylic acids had largest decrease in activity coefficient with water addition followed by glycols and alcohols. Propionic acid in cyclohexanone showed greatest water-enhancement {Delta} (log {gamma}{sub acid})/{Delta}(x{sub w}/x{sub acid}) = {minus}0.25. In methylcyclohexanone, the decrease of the activity coefficient of propionic acid was {minus}0.19. Activity coefficient of propionic acid in methylcyclohexanone stopped decreasing once the water reached a 2:1 water to acid mole ratio, implying a stoichiometric relation between water, ketone, and acid. Except for 2,3-butanediol, activity coefficients of the solutes studied decreased monotonically with water content. Activity coefficient curves of ethanol, 1,2-propanediol and 2,3-butanediol did not level off at large water/solute mole ratio. Solutes investigated by solid-liquid equilibrium were citric acid, gallic acid, phenol, xylenols, 2-naphthol. Saturation concentration of citric acid in anhydrous butyl acetate increased from 0.0009 to 0.087 mol/L after 1.3 % (g/g) water co-dissolved into organic phase. Effect of water-enhanced solvation for citric acid is very large but very small for phenol and its derivatives.

  10. Extraction of actinides by multi-dentate diamides and their evaluation with computational molecular modeling

    SciTech Connect (OSTI)

    Sasaki, Y.; Kitatsuji, Y.; Hirata, M.; Kimura, T.; Yoshizuka, K.

    2008-07-01

    Multi-dentate diamides have been synthesized and examined for actinide (An) extractions. Bi- and tridentate extractants are the focus in this work. The extraction of actinides was performed from 0.1-6 M HNO{sub 3} to organic solvents. It was obvious that N,N,N',N'-tetra-alkyl-diglycolamide (DGA) derivatives, 2,2'-(methylimino)bis(N,N-dioctyl-acetamide) (MIDOA), and N,N'-dimethyl-N,N'-dioctyl-2-(3-oxa-pentadecane)-malonamide (DMDOOPDMA) have relatively high D values (D(Pu) > 70). The following notable results using DGA extractants were obtained: (1) DGAs with short alkyl chains give higher D values than those with long alkyl chain, (2) DGAs with long alkyl chain have high solubility in n-dodecane. Computational molecular modeling was also used to elucidate the effects of structural and electronic properties of the reagents on their different extractabilities. (authors)

  11. Poly(silylene)vinylenes from ethynylhydridosilanes

    DOE Patents [OSTI]

    Barton, T.J.; Ijadi-Maghsoodi, S.

    1992-11-10

    Catalytic polymerization of dialkyl-, alkyl aryl- or diaryl-diethynylhydridosilanes cleanly affords soluble poly(silylene)vinylenes which can be shaped as fibers, films and bulk objects and thermally converted to silicon carbide. No Drawings

  12. Lubricants or lubricant additives composed of ionic liquids containing ammonium cations

    DOE Patents [OSTI]

    Qu, Jun (Knoxville, TN) [Knoxville, TN; Truhan, Jr.,; John J. (Cookeville, TN) [Cookeville, TN; Dai, Sheng (Knoxville, TN) [Knoxville, TN; Luo, Huimin (Knoxville, TN) [Knoxville, TN; Blau, Peter J. (Knoxville, TN) [Knoxville, TN

    2010-07-13

    A lubricant or lubricant additive is an ionic liquid alkylammonium salt. The alkylammonium salt has the structure R.sub.xNH.sub.(4-x).sup.+,[F.sub.3C(CF.sub.2).sub.yS(O).sub.2].sub.2N.sup- .- where x is 1 to 3, R is independently C.sub.1 to C.sub.12 straight chain alkyl, branched chain alkyl, cycloalkyl, alkyl substituted cycloalkyl, cycloalkyl substituted alkyl, or, optionally, when x is greater than 1, two R groups comprise a cyclic structure including the nitrogen atom and 4 to 12 carbon atoms, and y is independently 0 to 11. The lubricant is effective for the lubrication of many surfaces including aluminum and ceramics surfaces.

  13. Novel anisole mixture and gasoline containing the same

    DOE Patents [OSTI]

    Singerman, Gary M. (Monroeville, PA)

    1982-01-26

    A novel anisole mixture containing anisole and a mixture of alkyl anisoles and liquid hydrocarbon fuels containing said novel anisole mixture in an amount sufficient to increase the octane number of said liquid fuel composition.

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

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

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

  15. Ion exchange materials, method of forming ion exchange materials, and methods of treating liquids

    DOE Patents [OSTI]

    Wertsching, Alan K. (Idaho Falls, ID); Peterson, Eric S. (Idaho Falls, ID); Wey, John E. (Idaho Falls, ID)

    2007-12-25

    The invention includes an ion affinity material having an organic component which is sulfonated and which is chemically bonded to an inorganic substrate component. The invention includes a method of forming a metal binding material. A solid support material comprising surface oxide groups is provided and an organic component having at least one alkyl halide is covalently linked to at least some of the surface oxide groups to form a modified support material. The at least one alkyl halide is subsequently converted into an alkyl sulfonate. The invention further includes a method and system for extracting ions from a liquid. An ion exchange material having a sulfonated alkyl silane component covalently bonded to a metal oxide support material is provided and a liquid is exposed to the ion exchange material.

  16. Surface functionalization of metal-organic polyhedron for homogeneous...

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

    reactions with linear alkyl anhydrides lead to new MOPs with enhanced solubility. As a result, the surface-modified MOP 4 was demonstrated as a homogeneous Lewis-acid catalyst...

  17. Advances in Process Intensification through Multifunctional Reactor Engineering

    SciTech Connect (OSTI)

    2004-07-01

    This factsheet describes a research project whose goal is to develop the knowledge and tools required to develop and scale a novel multiphase pulse-flow, catalytic reactor for acid catalyzed C4 paraffin/olefin alkylation, to industrial dimensions.

  18. Regeneration of polyborazylene

    DOE Patents [OSTI]

    Davis, Benjamin L.; Gordon, John C.

    2010-12-07

    Method of producing ammonia borane, comprising providing polyborazylene; digesting the polyborazylene with a dithiol-containing agent to produce a boro-sulfide compound and a byproduct; converting the byproduct to the boro-sulfide product of step (b) by reaction with a first alkyl-tin hydride; and, converting the boro-sulfide compound produced in steps (b) and (c) to ammonia borane by reaction with a second alkyl-tin hydride.

  19. Low toxicity method of inhibiting sickling of sickle erythrocytes

    DOE Patents [OSTI]

    Packer, Lester; Bymun, Edwin N.

    1977-01-01

    A low toxicity method of inhibiting sickling of sickle erythrocytes which comprises intermixing the erythrocytes with an effective anti-sickling amount of a water-soluble imidoester of the formula RC(=NH)OR' wherein R is an alkyl group of 1 - 8 carbon atoms, particularly 1 - 4 carbon atoms, and R' is an alkyl group of 1 - 4 carbon atoms, specifically methyl or ethyl acetimidate.

  20. Protein Bridges DNA Base and Nucleotide Excision Repair Pathways

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

    Protein Bridges DNA Base and Nucleotide Excision Repair Pathways Print Alkyltransferase proteins (AGT) protect cells from the biological effects of DNA damage caused by the addition of alkyl groups (alkylation). Alkyltransferase-like proteins (ATLs) can do the same, but they lack the reactive cysteine residue that allows the alkyltransferase function, and the mechanism for cell protection has remained unknown. To address this mystery, a British-American team lead by researchers at the Scripps

  1. Protein Bridges DNA Base and Nucleotide Excision Repair Pathways

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

    Protein Bridges DNA Base and Nucleotide Excision Repair Pathways Print Alkyltransferase proteins (AGT) protect cells from the biological effects of DNA damage caused by the addition of alkyl groups (alkylation). Alkyltransferase-like proteins (ATLs) can do the same, but they lack the reactive cysteine residue that allows the alkyltransferase function, and the mechanism for cell protection has remained unknown. To address this mystery, a British-American team lead by researchers at the Scripps

  2. Protein Bridges DNA Base and Nucleotide Excision Repair Pathways

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

    Protein Bridges DNA Base and Nucleotide Excision Repair Pathways Print Alkyltransferase proteins (AGT) protect cells from the biological effects of DNA damage caused by the addition of alkyl groups (alkylation). Alkyltransferase-like proteins (ATLs) can do the same, but they lack the reactive cysteine residue that allows the alkyltransferase function, and the mechanism for cell protection has remained unknown. To address this mystery, a British-American team lead by researchers at the Scripps

  3. Protein Bridges DNA Base and Nucleotide Excision Repair Pathways

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

    Protein Bridges DNA Base and Nucleotide Excision Repair Pathways Protein Bridges DNA Base and Nucleotide Excision Repair Pathways Print Wednesday, 28 October 2009 00:00 Alkyltransferase proteins (AGT) protect cells from the biological effects of DNA damage caused by the addition of alkyl groups (alkylation). Alkyltransferase-like proteins (ATLs) can do the same, but they lack the reactive cysteine residue that allows the alkyltransferase function, and the mechanism for cell protection has

  4. Method for producing hydrophobic aerogels

    DOE Patents [OSTI]

    Hrubesh, Lawrence W. (Pleasanton, CA); Poco, John F. (Livermore, CA); Coronado, Paul R. (Livermore, CA)

    1999-01-01

    A method for treating a dried monolithic aerogel containing non-dispersed particles, with an organometallic surface modifying agent to produce hydrophobic aerogels. The dried, porous hydrophobic aerogels contain a protective layer of alkyl groups, such as methyl groups, on the modified surfaces of the pores of the aerogel. The alkyl groups at the aerogel surface typically contain at least one carbon-metal bond per group.

  5. Protein Bridges DNA Base and Nucleotide Excision Repair Pathways

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

    Protein Bridges DNA Base and Nucleotide Excision Repair Pathways Print Alkyltransferase proteins (AGT) protect cells from the biological effects of DNA damage caused by the addition of alkyl groups (alkylation). Alkyltransferase-like proteins (ATLs) can do the same, but they lack the reactive cysteine residue that allows the alkyltransferase function, and the mechanism for cell protection has remained unknown. To address this mystery, a British-American team lead by researchers at the Scripps

  6. Polyethylene composites containing a phase change material having a C14 straight chain hydrocarbon

    DOE Patents [OSTI]

    Salyer, Ival O. (Dayton, OH)

    1987-01-01

    A composite useful in thermal energy storage, said composite being formed of a polyethylene matrix having a straight chain alkyl hydrocarbon incorporated therein, said polyethylene being crosslinked to such a degree that said polyethylene matrix is form stable and said polyethylene matrix is capable of absorbing at least 10% by weight of said straight chain alkyl hydrocarbon; the composite is useful in forming pellets or sheets having thermal energy storage characteristics.

  7. Method for producing hydrophobic aerogels

    SciTech Connect (OSTI)

    Hrubesh, L.W.; Poco, J.F.; Coronado, P.R.

    1999-12-21

    A method is described for treating a dried monolithic aerogel containing non-dispersed particles, with an organometallic surface modifying agent to produce hydrophobic aerogels. The dried, porous hydrophobic aerogels contain a protective layer of alkyl groups, such as methyl groups, on the modified surfaces of the pores of the aerogel. The alkyl groups at the aerogel surface typically contain at least one carbon-metal bond per group.

  8. RECOVERY OF TETRAVALENT CATIONS FROM AQUEOUS SOLUTIONS

    DOE Patents [OSTI]

    Moore, R.L.

    1958-05-01

    The recovery of plutonium, zirconium, and tetravalent cerium values from aqueous solutions is described. It consists of adding an alkyl phosphate to a nnineral acid aqueous solution containing the metal to be recovered, whereby a precipitate forms with the tetravalent values, and separating the precipitate from the solution. All alkyl phosphates, if water-soluble, are suitable for the process; however, monobutyl phosphate has been found best.

  9. Synthesis of acid addition salt of delta-aminolevulinic acid from 5-bromo levulinic acid esters

    DOE Patents [OSTI]

    Moens, Luc (Lakewood, CO)

    2003-06-24

    A process of preparing an acid addition salt of delta-aminolevulinc acid comprising: a) dissolving a lower alkyl 5-bromolevulinate and hexamethylenetetramine in a solvent selected from the group consisting of water, ethyl acetate, chloroform, acetone, ethanol, tetrahydrofuran and acetonitrile, to form a quaternary ammonium salt of the lower alkyl 5-bromolevulinate; and b) hydrolyzing the quaternary ammonium salt with an inorganic acid to form an acid addition salt of delta-aminolevulinic acid.

  10. Cytotoxicity, genotoxicity, and mutagenicity of 1-chloro-2-hydroxy-3-butene and 1-chloro-3-buten-2-one, two alternative metabolites of 1,3-butadiene

    SciTech Connect (OSTI)

    Liu, Xin-Jie; Zeng, Fang-Mao; An, Jing; Yu, Ying-Xin; Zhang, Xin-Yu; Elfarra, Adnan A.

    2013-08-15

    The cytotoxicity, genotoxicity, and mutagenicity of 1-chloro-2-hydroxy-3-butene (CHB), a known in vitro metabolite of the human carcinogen 1,3-butadiene, have not previously been investigated. Because CHB can be bioactivated by alcohol dehydrogenases to yield 1-chloro-3-buten-2-one (CBO), a bifunctional alkylating agent that caused globin-chain cross-links in erythrocytes, in the present study we investigated the cytotoxic and genotoxic potential of CHB and CBO in human normal hepatocyte L02 cells using the MTT assay, the relative cloning efficiency assay and the comet assay. We also investigated the mutagenic potential of these compounds with the Ames test using Salmonella strains TA1535 and TA1537. The results provide clear evidence for CHB and CBO being both cytotoxic and genotoxic with CBO being approximately 100-fold more potent than CHB. Interestingly, CHB generated both single-strand breaks and alkali-labile sites on DNA, whereas CBO produced only alkali-labile sites. CHB did not directly result in DNA breaks, whereas CBO was capable of directly generating breaks on DNA. Interestingly, both compounds did not induce DNA cross-links as examined by the comet assay. The Ames test results showed that CHB induced point mutation but not frameshift mutation, whereas the toxic effects of CBO made it difficult to reliably assess the mutagenic potential of CBO in the two strains. Collectively, the results suggest that CHB and CBO may play a role in the mutagenicity and carcinogenicity of 1,3-butadiene. - Highlights: 1-Chloro-2-hydroxy-3-butene (CHB) is cytotoxic and genotoxic in human liver cells. The CHB metabolite, 1-chloro-3-buten-2-one (CBO) is ? 100-fold more toxic than CHB. CHB and CBO cause DNA alkali-labile sites, but only CBO directly causes DNA breaks. CHB is mutagenic in the Ames test, but CBO is too toxic in the assay. The results suggest a role for CHB in 1,3-butadiene genotoxicity and mutagenicity.

  11. Synthesis and structural characterization of three copper coordination polymers with pyridine derivatives from hydro(solvo)thermal in situ decarboxylation reactions of 2,5-dicarboxylpyridine

    SciTech Connect (OSTI)

    Hou Qin; Xu Jianing; Yu Jiehui; Wang Tiegang; Yang Qingfeng; Xu Jiqing

    2010-07-15

    The hydro(solvo)thermal self-assembles of CuI, KI and 2,5-dicarboxylpyridine [2,5-(COOH){sub 2}py] in different molar ratios in H{sub 2}O/alcohol solutions produced three Cu coordination polymers as 2-D [N-C{sub 2}H{sub 5}py][Cu{sub 3}I{sub 4}] 1, 1-D [N-CH{sub 3}py][Cu{sub 2}I{sub 3}] 2 as well as 1-D [Cu(2-COOpy){sub 2}]{center_dot}H{sub 2}O 3 (N-C{sub 2}H{sub 5}py=N-ethylpyridine, N-CH{sub 3}py=N-methylpyridine, 2-COOpy=2-carboxylpyridine). N-C{sub 2}H{sub 5}py in 1 and N-CH{sub 3}py in 2 derived from the solvothermal in situ simultaneous decarboxylation and N-alkylation reactions of 2,5-(COOH){sub 2}py. The semi-decarboxylation reaction of 2,5-(COOH){sub 2}py into 2-COOpy occurred in the preparation of 3. X-ray single-crystal analysis revealed that CuI is transformed into a 2-D [Cu{sub 3}I{sub 4}]{sup -} layer in compound 1 and a 1-D chain in compound 2, templated by [N-C{sub 2}H{sub 5}py]{sup +} and [N-CH{sub 3}py]{sup +}, respectively. Compound 3 is a divalent Cu compound. The Cu(II) centers with a 4+2 geometry are coordinated by {mu}{sub 3}-mode 2-COOpy ligands. All of the title compounds were characterized by CHN analysis, IR spectrum analysis and TG analysis. Compounds 1 and 2 exhibit fluorescence properties with the maximum emissions at 581 nm for 1 and 537 nm for 2. - Graphical abstract: Three compounds were obtained via in situ metal-ligand hydro(solvo)thermal reactions of 2,5-(cooh){sub 2}py with cui. Three types of in situ reactions occurred for 2,5-(cooh){sub 2}py: decarboxylation n-ethylated in 1, n-methylated in 2 and semi-decarboxylation in 3.

  12. RECOVERY OF LACTIC ACID FROM AMERICAN CRYSTAL SUGAR COMPANY WASTEWATER

    SciTech Connect (OSTI)

    Daniel J. Stepan; Edwin S. Olson; Richard E. Shockey; Bradley G. Stevens; John R. Gallagher

    2001-04-30

    This project has shown that the recovery of several valuable lactic acid products is both technically feasible and economically viable. One of the original objectives of this project was to recover lactic acid. However, the presence of a variety of indigenous bacteria in the wastewater stream and technical issues related to recovery and purification have resulted in the production of lactic acid esters. These esters could by hydrolyzed to lactic acid, but only with unacceptable product losses that would be economically prohibitive. The developed process is projected to produce approximately 200,000 lb per day of lactate esters from wastewater at a single factory at costs that compete with conventional solvents. The lactate esters are good solvents for polymers and resins and could replace acetone, methyl ethyl ketone, MIBK, and other polar solvents used in the polymer industry. Because of their low volatility and viscosity-lowering properties, they will be especially useful for inks for jet printers, alkyl resins, and high-solid paints. Owing to their efficiency in dissolving salts and flux as well as oils and sealants, lactate esters can be used in cleaning circuit boards and machine and engine parts. Unlike conventional solvents, lactate esters exhibit low toxicity, are biodegradable, and are not hazardous air pollutants. Another application for lactate esters is in the production of plasticizers. Severe health problems have been attributed to widely used phthalate ester plasticizers. The U.S. Department of Agriculture showed that replacement of these with inexpensive lactate esters is feasible, owing to their superior polymer compatibility properties. A very large market is projected for polymers prepared from lactic acid. These are called polylactides and are a type of polyester. Thermoplastics of this type have a variety of uses, including moldings, fibers, films, and packaging of both manufactured goods and food products. Polylactides form tough, orientable, self-supporting thin films and have, therefore, been used for adhesives, safety glass, and finishes. If the bacterial culture produces the L-lactic acid enanatiomer form exclusively, the L-lactide prepared from this form can be used for making polymers with good fiber-forming properties. We have not currently achieved the exclusive production of L-lactate in our efforts. However, markets in films and structural shapes are available for polymers and copolymers prepared from the mixed D,L-lactide forms that result from processing the D,L-lactic acid obtained from fermentation such as that occurring naturally in sugar beet wastewater. These materials are slowly biodegraded to harmless compounds in the environment, and they burn with a clean blue flame when incinerated. These materials represent excellent opportunities for utilization of the D,L-lactic mixture produced from natural fermentation of the ACS flume water. Esters can be converted into a lactide, and the alcohol released from the ester can be recycled with no net consumption of the alcohol. Lactide intermediates could be produced locally and shipped to polymer producers elsewhere. The polymer and copolymer markets are extremely large, and the role of lactides in these markets is continuously expanding. The overall process can be readily integrated into existing factory wastewater operations. There are several environmental benefits that would be realized at the factories with incorporation of the lactate recovery process. The process reduces the organic loading to the existing wastewater treatment system that should result in enhanced operability with respect to both solids handling and treated-water quality. A higher-quality treated water will also help reduce odor levels from holding ponds. Several water reuse opportunities are probable, depending on the quality of treated water from the FT process.

  13. Emissive polymeric materials for optoelectronic devices

    DOE Patents [OSTI]

    Shiang, Joseph John; Chichak, Kelly Scott; Cella, James Anthony; Lewis, Larry Neil; Janora, Kevin Henry

    2011-07-05

    Polymers including at least one structural unit derived from a compound of formula I or including at least one pendant group of formula II may be used in optoelectronic devices ##STR00001## wherein R.sup.1, R.sup.3, R.sup.4 and R.sup.6 are independently hydrogen, alkyl, alkoxy, oxaalkyl, alkylaryl, aryl, arylalkyl, heteroaryl, substituted alkyl; substituted alkoxy, substituted oxaalkyl, substituted alkylaryl, substituted aryl, substituted arylalkyl, or substituted heteroaryl; R.sup.1a is hydrogen or alkyl; R.sup.2 is alkylene, substituted alkylene, oxaalkylene, CO, or CO.sub.2; R.sup.2a is alkylene; R.sup.5 is independently at each occurrence hydrogen, alkyl, alkylaryl, aryl, arylalkyl, alkoxy, carboxy, substituted alkyl; substituted alkylaryl, substituted aryl, substituted arylalkyl, or substituted alkoxy, X is halo, triflate, --B(OR.sup.1a).sub.2, or ##STR00002## located at the 2, 5- or 2, 7-positions; and L is derived from phenylpyridine, tolylpyridine, benzothienylpyridine, phenylisoquinoline, dibenzoquinozaline, fluorenylpyridine, ketopyrrole, 2-(1-naphthyl)benzoxazole)), 2-phenylbenzoxazole, 2-phenylbenzothiazole, coumarin, thienylpyridine, phenylpyridine, benzothienylpyridine, 3-methoxy-2-phenylpyridine, thienylpyridine, phenylimine, vinylpyridine, pyridylnaphthalene, pyridylpyrrole, pyridylimidazole, phenylindole, derivatives thereof or combinations thereof.

  14. Highly Stable, Anion Conductive, Comb-Shaped Copolymers for Alkaline Fuel Cells

    SciTech Connect (OSTI)

    Li, NW; Leng, YJ; Hickner, MA; Wang, CY

    2013-07-10

    To produce an anion-conductive and durable polymer electrolyte for alkaline fuel cell applications, a series of quaternized poly(2,6-dimethyl phenylene oxide)s containing long alkyl side chains pendant to the nitrogen-centered cation were synthesized using a Menshutkin reaction to form comb-shaped structures. The pendant alkyl chains were responsible for the development of highly conductive ionic domains, as confirmed by small-angle X-ray scattering (SAXS). The comb-shaped polymers having one alkyl side chain showed higher hydroxide conductivities than those with benzyltrimethyl ammonium moieties or structures with more than one alkyl side chain per cationic site. The highest conductivity was observed for comb-shaped polymers with benzyldimethylhexadecyl ammonium cations. The chemical stabilities of the comb-shaped membranes were evaluated under severe, accelerated-aging conditions, and degradation was observed by measuring IEC and ion conductivity changes during aging. The comb-shaped membranes retained their high ion conductivity in 1 M NaOH at 80 degrees C for 2000 h. These cationic polymers were employed as ionomers in catalyst layers for alkaline fuel cells. The results indicated that the C-16 alkyl side chain ionomer had a slightly better initial performance, despite its low IEC value, but very poor durability in the fuel cell. In contrast, 90% of the initial performance was retained for the alkaline fuel cell with electrodes containing the C-6 side chain after 60 h of fuel cell operation.

  15. Solubilities of toluene and n-octane in aqueous protosurfactant and surfactant solutions

    SciTech Connect (OSTI)

    Ho, P.C.

    1985-01-01

    The solubilities of toluene and n-octane in aqueous protosurfactant and surfactant solutins were determined at 25/sup 0/C. The protosurfactants studied are sodium salts of cyclohexanecarboxylic acid, 2,5-diisopropylbenzenesulfonic acid, and 3,5-diisopropyisalicylic acid. Each of them has six alkyl carbons (S /SUB AC/ =6) and does not form micelles in water. The two micelle-forming surfactants used are sodium n-hexanoate with six alkyl carbons (S /SUB AC/ =6) and sodium n-octanoate with eight alkyl carbons (S /SUB AC/ =8). In three-component systems of toluene or n-octane with water and organic salt (either protosurfactant or surfactant), the solubility of the hydrocarbon in the aqueous phase increases as the number of alkyl carbons of the organic salt and as the aqueous concentration of the organic salt increases. However, in this study we found that sodium 3,5-diisopropyisalicylate causes much more pronounced increases in hydrocarbon solubility than these two surfactants. Sodium 2,5-diisopropylbenzenesulfonate, although not as effective in solubilization as the salicylate, has much stronger hydrotropic properties for hydrocarbons than either of these two surfactants. Sodium cyclohexanoate, with a compact arrangement of the six alkyl carbons, shows a higher hydrotropic effect than sodium n-hexanoate.

  16. Electric current-producing device having sulfone-based electrolyte

    DOE Patents [OSTI]

    Angell, Charles Austen (Mesa, AZ); Sun, Xiao-Guang (Tempe, AZ)

    2010-11-16

    Electrolytic solvents and applications of such solvents including electric current-producing devices. For example, a solvent can include a sulfone compound of R1--SO2--R2, with R1 being an alkyl group and R2 a partially oxygenated alkyl group, to exhibit high chemical and thermal stability and high oxidation resistance. For another example, a battery can include, between an anode and a cathode, an electrolyte which includes ionic electrolyte salts and a non-aqueous electrolyte solvent which includes a non-symmetrical, non-cyclic sulfone. The sulfone has a formula of R1--SO2--R2, wherein R1 is a linear or branched alkyl or partially or fully fluorinated linear or branched alkyl group having 1 to 7 carbon atoms, and R2 is a linear or branched or partially or fully fluorinated linear or branched oxygen containing alkyl group having 1 to 7 carbon atoms. The electrolyte can include an electrolyte co-solvent and an electrolyte additive for protective layer formation.

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

    Reports and Publications (EIA)

    2002-01-01

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

  18. Eliminating MTBE in Gasoline in 2006

    Reports and Publications (EIA)

    2006-01-01

    A review of the market implications resulting from the rapid change from methyl tertiary butyl ether (MTBE) to ethanol-blended reformulated gasoline (RFG) on the East Coast and in Texas. Strains in ethanol supply and distribution will increase the potential for price volatility in these regions this summer.

  19. Status and Impacts of State MTBE Bans

    Reports and Publications (EIA)

    2003-01-01

    This paper describes legislation passed in 16 states banning or restricting the use of methyl tertiary butyl ether (MTBE) in gasoline. Analysis of the status and impact of these state MTBE bans is provided concerning the supply and potential price changes of gasoline.

  20. Motor Gasoline Outlook and State MTBE Bans

    Reports and Publications (EIA)

    2003-01-01

    The U.S. is beginning the summer 2003 driving season with lower gasoline inventories and higher prices than last year. Recovery from this tight gasoline market could be made more difficult by impending state bans on the blending of methyl tertiary butyl ether (MTBE) into gasoline that are scheduled to begin later this year.

  1. Electrolyte Materials Available for Sampling | Argonne National...

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

    ANL-1S1M3 2,2-dimethyl-4,7,10,13-tetraoxa-2-silatetradecane Properties ANL-RS2 1,4-di-tert-butyl-2,5-bis(2-methoxyethoxy)benzene Properties ANL-RS5 (2,5-dimethoxy-1,4-phenyle...

  2. CHARACTERIZATION OF GLOVEBOX GLOVES FOR THE SAVANNAH RIVER SITE

    SciTech Connect (OSTI)

    Korinko, P.

    2013-01-24

    A task was undertaken to characterize glovebox gloves that are currently used in the facilities at Savannah River Site (SRS) as well as some experimental and advanced compound gloves that have been proposed for use. Gloves from four manufacturers were tested for permeation in hydrogen and air, thermal stability, tensile properties, puncture resistance and dynamic mechanical response. The gloves were compared to each other within the type and also to the butyl rubber glove that is widely used at the SRS. The permeation testing demonstrated that the butyl compounds from three of the vendors behaved similarly and exhibited hydrogen permeabilities of .52‐.84 x10{sup ‐7} cc H{sub 2}*cm / (cm{sup 2}*atm). The Viton? glove performed at the lower edge of this bound, while the more advanced composite gloves exhibited permeabilities greater than a factor of two compared to butyl. Thermogravimetric analysis was used to determine the amount of material lost under slightly aggressive conditions. Glove losses are important since they can affect the life of glovebox stripper systems. During testing at 90, 120, and 150?C, the samples lost most of the mass in the initial 60 minutes of thermal exposure and as expected increasing the temperature increased the mass loss and shortened the time to achieve a steady state loss. The ranking from worst to best was Jung butyl‐Hypalon? with 12.9 %, Piercan Hypalon? with 11.4 %, and Jung butyl‐Viton? with 5.2% mass loss all at approximately 140?C. The smallest mass losses were experienced by the Jung Viton? and the Piercan polyurethane. Tensile properties were measured using a standard dog bone style test. The butyl rubber exhibited tensile strengths of 11‐15 MPa and elongations or 660‐843%. Gloves made from other compounds exhibited lower tensile strengths (5 MPa Viton) to much higher tensile strengths (49 MPa Urethane) with a comparable range of elongation. The puncture resistance of the gloves was measured in agreement with an ASTM standard. The Butyl gloves exhibited puncture resistance from 183 ? 296 lbs/in for samples of 0.020 ? 0.038? thick. Finally, the glass transition temperature and the elastic and viscoelastic properties as a function of temperature up to maximum use temperature were determined for each glove material using Dynamic Mechanical Analysis. The glass transition temperatures of the gloves were ‐60?C for butyl, ‐30?C for polyurethane, ‐ 16?C Hypalon?, ‐16?C for Viton?, and ‐24?C for polyurethane‐Hypalon?. The glass transition was too complex for the butyl‐Hypalon? and butyl‐Viton? composite gloves to be characterized by a single glass transition temperature. All of the glass transition temperatures exceed the vendor projected use temperatures.

  3. Rapid brain scanning radiopharmaceutical

    DOE Patents [OSTI]

    Sargent, T.W. III; Shulgin, A.T.; Mathis, C.A.

    1987-03-03

    A method for detecting the blood flow in animals, particularly in the brain, is provided wherein a detectable amount of a novel radioactive compound of the formula 1 is administered to one animal: as given in figure in patent wherein R[sub 1] and R[sub 2] are independently alkyl of 1 to 6 carbon atoms or benzyl; R[sub 3] is alkyl of 1 to 6 carbon atoms, benzyl, cyclopropylalkyl of 4 to 6 carbon atoms, or cyanoalkyl of 2 to 6 carbon atoms; R[sub 4] is hydrogen, benzyl or alkyl of 1 to 6 carbon atoms; with the provisos that R[sub 4] is not isopropyl and when R[sub 4] is methyl, R[sub 3] is not benzyl; and X is a radioactive halogen. 2 figs.

  4. Carboxy, carboalkoxy and carbamile substituted isonitrile radionuclide complexes

    DOE Patents [OSTI]

    Jones, Alun G.; Davison, Alan; Kronauge, James; Abrams, Michael J.

    1989-01-01

    A coordination complex comprising a radionuclide selected from the class consisting of radioactive isotopes of Tc, Ru, Co, Pt and Re and an isonitrile ligand of the formula: (CNX)R, where X is a lower alkyl group having 1 to 4 carbon atoms, wherein R is selected from the group consisting of COOR.sup.1 and CONR.sup.2 R.sup.3 where R.sup.1 can be H, a pharmaceutically acceptable cation, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. R.sup.2, and R.sup.3 can be H, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and R.sup.2 and R.sup.3 can be the same of different is disclosed. Kits that can be used to form these complexes are also disclosed.

  5. Carboxy, carboalkoxy and carbamile substituted isonitrile radionuclide complexes

    DOE Patents [OSTI]

    Jones, Alun G.; Davison, Alan; Kronauge, James; Abrams, Michael J.

    1988-04-05

    A coordination complex comprising a radionuclide selected from the class consisting of radioactive isotopes of Tc, Ru, Co, Pt and Re and an isonitrile ligand of the formula: (CNX)R, where X is a lower alkyl group having 1 to 4 carbon atoms, wherein R is selected from the group consisting of COOR.sup.1 and CONR.sup.2 R.sup.3 where R.sup.1 can be H, a pharmaceutically acceptable cation, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, R.sup.2, and R.sup.3 can be H, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms, and R.sup.2 and R.sup.3 can be the same or different is disclosed. Kits that can be used to form these complexes are also disclosed.

  6. No-carrier-added [.sup.18 F]-N-fluoroalkylspiroperidols

    DOE Patents [OSTI]

    Shiue, Chyng-Yann; Wolf, Alfred P.; Bai, Lan-Qin; Teng, Ren-Tui

    1989-01-01

    There is disclosed radioligands labeled with the position emitting radionuclide [.sup.18 F] suitable for dynamic study in living humans with position emission transaxial tomography. These new [.sup.18 F]-N-fluoroalkylspiroperidols, wherein the alkyl group contains from 2-6 carbon atoms, exhibit extremely high affinity for the dopamine receptors and provide enhanced uptake and retention in the brain concomitant with reduced radiation burden. These characteristics all combine to make these new radioligands useful for mapping dopamine receptors in normal and disease states in the living brain. Additionally, a new synthetic procedure for these radioligands as well as a new procedure for preparing the radiolabeled alkyl halide alkylating reagents are also disclosed.

  7. Rapid brain scanning radiopharmaceutical

    DOE Patents [OSTI]

    Sargent, III, Thornton W.; Shulgin, Alexander T.; Mathis, Chester A.

    1987-01-01

    A method for detecting the blood flow in animals, particularly in the brain, is provided wherein a detectable amount of a novel radioactive compound of the formula I is administered to one animal: ##STR1## wherein R.sub.1 and R.sub.2 are independently alkyl of 1 to 6 carbon atoms or benzyl; R.sub.3 is alkyl of 1 to 6 carbon atoms, benzyl, cyclopropylalkyl of 4 to 6 carbon atoms, or cyanoalkyl of 2 to 6 carbon atoms; R.sub.4 is hydrogen, benzyl or alkyl of 1 to 6 carbon atoms; with the provisos that R.sub.4 is not isopropyl and when R.sub.4 is methyl, R.sub.3 is not benzyl; and X is a radioactive halogen.

  8. Life cycle inventory of biodiesel and petroleum diesel for use...

    Office of Scientific and Technical Information (OSTI)

    Biodiesel is made by chemically combining any natural oil or fat with an alcohol such as methanol or ethanol. Methanol has been the most commonly used alcohol in the commercial ...

  9. Summary of Decisions - October 13, 2014 - October 17, 2014 |...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    that the individual had not mitigated the DOE's concerns regarding his use of alcohol, which had not led to any alcohol-related arrests or accidents but nevertheless was...

  10. Current State of the U S Ethanol Industry

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    ... for each gallon sold to an alcohol blender that is in excess of the producer's base ... to an alcohol blender may receive 0.075 for each gallon sold, up to 15,000,000 gallons. ...

  11. The original of this document contains information which is subject...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    ... habitually to excess, or has been diagnosed by a psychiatrist or licensed clinical psychologist as alcohol dependent or as suffering from alcohol abuse." 10 C.F.R. 710.8(j). ...

  12. Photoionization mass spectrometric measurements of initial reaction pathways in low-temperature oxidation of 2,5-dimethylhexane

    SciTech Connect (OSTI)

    Rotavera, Brandon; Zdor, Judit; Welz, Oliver; Sheps, Leonid; Scheer, Adam M.; Savee, John D.; Akbar Ali, Mohamad; Lee, Taek Soon; Simmons, Blake A.; Osborn, David L.; Violi, Angela; Taatjes, Craig A.

    2014-09-19

    The product formation from R + O2 reactions relevant to low-temperature autoignition chemistry was studied for 2,5-dimethylhexane, a symmetrically branched octane isomer, at 550 and 650 K using Cl-atom initiated oxidation and multiplexed photoionization mass spectrometry (MPIMS). The interpretation of time- and photon-energy-resolved mass spectra led to three specific results important to characterizing the initial oxidation steps: (1) quantified isomer-resolved branching ratios for HO2 + alkene channels; (2) 2,2,5,5-tetramethyltetrahydrofuran is formed in substantial yield from addition of O2 to tertiary 2,5-dimethylhex-2-yl followed by isomerization of the resulting ROO adduct to tertiary hydroperoxyalkyl (QOOH) and exhibits a positive dependence on temperature over the range covered leading to a higher flux relative to aggregate cyclic ether yield. The higher relative flux is explained by a 1,5-hydrogen atom shift reaction that converts the initial primary alkyl radical (2,5-dimethylhex-1-yl) to the tertiary alkyl radical 2,5-dimethylhex-2-yl, providing an additional source of tertiary alkyl radicals. Furthermore, quantum-chemical and master-equation calculations of the unimolecular decomposition of the primary alkyl radical reveal that isomerization to the tertiary alkyl radical is the most favorable pathway, and is favored over O2-addition at 650 K under the conditions herein. The isomerization pathway to tertiary alkyl radicals therefore contributes an additional mechanism to 2,2,5,5-tetramethyltetrahydrofuran formation; (3) carbonyl species (acetone, propanal, and methylpropanal) consistent with ?-scission of QOOH radicals were formed in significant yield, indicating unimolecular QOOH decomposition into carbonyl + alkene + OH.

  13. Photoionization mass spectrometric measurements of initial reaction pathways in low-temperature oxidation of 2,5-dimethylhexane

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

    Rotavera, Brandon; Zádor, Judit; Welz, Oliver; Sheps, Leonid; Scheer, Adam M.; Savee, John D.; Akbar Ali, Mohamad; Lee, Taek Soon; Simmons, Blake A.; Osborn, David L.; et al

    2014-09-19

    The product formation from R + O2 reactions relevant to low-temperature autoignition chemistry was studied for 2,5-dimethylhexane, a symmetrically branched octane isomer, at 550 and 650 K using Cl-atom initiated oxidation and multiplexed photoionization mass spectrometry (MPIMS). The interpretation of time- and photon-energy-resolved mass spectra led to three specific results important to characterizing the initial oxidation steps: (1) quantified isomer-resolved branching ratios for HO2 + alkene channels; (2) 2,2,5,5-tetramethyltetrahydrofuran is formed in substantial yield from addition of O2 to tertiary 2,5-dimethylhex-2-yl followed by isomerization of the resulting ROO adduct to tertiary hydroperoxyalkyl (QOOH) and exhibits a positive dependence on temperaturemore » over the range covered leading to a higher flux relative to aggregate cyclic ether yield. The higher relative flux is explained by a 1,5-hydrogen atom shift reaction that converts the initial primary alkyl radical (2,5-dimethylhex-1-yl) to the tertiary alkyl radical 2,5-dimethylhex-2-yl, providing an additional source of tertiary alkyl radicals. Furthermore, quantum-chemical and master-equation calculations of the unimolecular decomposition of the primary alkyl radical reveal that isomerization to the tertiary alkyl radical is the most favorable pathway, and is favored over O2-addition at 650 K under the conditions herein. The isomerization pathway to tertiary alkyl radicals therefore contributes an additional mechanism to 2,2,5,5-tetramethyltetrahydrofuran formation; (3) carbonyl species (acetone, propanal, and methylpropanal) consistent with β-scission of QOOH radicals were formed in significant yield, indicating unimolecular QOOH decomposition into carbonyl + alkene + OH.« less

  14. The role of polymer formation during vapor phase lubrication...

    Office of Scientific and Technical Information (OSTI)

    Subject: 32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION; ALCOHOLS; ALKENES; LUBRICATION; MASS SPECTROSCOPY; MOLECULAR WEIGHT; OXYGEN; PENTANOLS; POLYMERIZATION; POLYMERS; ...

  15. Peer Review 2013 Dutta Syngas | Department of Energy

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Demonstration Syngas Upgrading to Hydrocarbon Fuels Technology Pathway Thermochemical Ethanol via Indirect Gasification and Mixed Alcohol Synthesis of Lignocellulosic Biomass

  16. Enabling Small-Scale Biomass Gasification for Liquid Fuel Production...

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Biomass Indirect Liquefaction Strategy Workshop: Summary Report Thermochemical Ethanol via Indirect Gasification and Mixed Alcohol Synthesis of Lignocellulosic Biomass Gasification ...

  17. Characterization of Particulate Emissions from GDI Engine Combustion with

    Office of Energy Efficiency and Renewable Energy (EERE) Indexed Site

    Alcohol-blended Fuels | Department of Energy Particulate Emissions from GDI Engine Combustion with Alcohol-blended Fuels Characterization of Particulate Emissions from GDI Engine Combustion with Alcohol-blended Fuels Analysis showed that gasoline direct injection engine particulates from alcohol-blended fuels are significantly different in morphology and nanostructures PDF icon p-19_seong.pdf More Documents & Publications Vehicle Technologies Office Merit Review 2014: Fuel and Lubricant

  18. Abrasive slurry composition for machining boron carbide

    DOE Patents [OSTI]

    Duran, Edward L. (Santa Fe, NM)

    1985-01-01

    An abrasive slurry particularly suited for use in drilling or machining boron carbide consists essentially of a suspension of boron carbide and/or silicon carbide grit in a carrier solution consisting essentially of a dilute solution of alkylaryl polyether alcohol in octyl alcohol. The alkylaryl polyether alcohol functions as a wetting agent which improves the capacity of the octyl alcohol for carrying the grit in suspension, yet without substantially increasing the viscosity of the carrier solution.

  19. Abrasive slurry composition for machining boron carbide

    DOE Patents [OSTI]

    Duran, E.L.

    1984-11-29

    An abrasive slurry particularly suited for use in drilling or machining boron carbide consists essentially of a suspension of boron carbide and/or silicon carbide grit in a carrier solution consisting essentially of a dilute solution of alkylaryl polyether alcohol in octyl alcohol. The alkylaryl polyether alcohol functions as a wetting agent which improves the capacity of the octyl alcohol for carrying the grit in suspension, yet without substantially increasing the viscosity of the carrier solution.

  20. Alternative Fuels Data Center

    Alternative Fuels and Advanced Vehicles Data Center [Office of Energy Efficiency and Renewable Energy (EERE)]

    Ethanol and Methanol Tax Ethyl alcohol and methyl alcohol motor fuels are taxed at a rate of $0.14 per gallon when used as a motor fuel. Ethyl alcohol is defined as a motor fuel that is typically derived from agricultural products that have been denatured. Methyl alcohol is a motor fuel that is most commonly derived from wood products. (Reference Senate Bill 1, 2015, and South Dakota Statutes 10-47B-3 and 10-47B-4