National Library of Energy BETA

Sample records for butyl ether mtbe

  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. 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.

  3. 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.

  4. 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.

  5. MTBE, Oxygenates, and Motor Gasoline

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

    MTBE, Oxygenates, and Motor Gasoline Contents * Introduction * Federal gasoline product quality regulations * What are oxygenates? * Who gets gasoline with oxygenates? * Which areas get MTBE? * How much has been invested in MTBE production capacity? * What does new Ethanol capacity cost? * What would an MTBE ban cost? * On-line information resources * Endnotes * Summary of revisions to this analysis Introduction The blending of methyl tertiary butyl ether (MTBE) into motor gasoline has increased

  6. MTBE Production Economics

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

    MTBE Production Economics Tancred C. M. Lidderdale Contents 1. Summary 2. MTBE Production Costs 3. Relationship between price of MTBE and Reformulated Gasoline 4. Influence of Natural Gas Prices on the Gasoline Market 5. Regression Results 6. Data Sources 7. End Notes 1. Summary Last year the price of MTBE (methyl tertiary butyl ether) increased dramatically on two occasions (Figure 1) (see Data Sources at end of article.): 1. Between April and June 2000, the price (U.S. Gulf Coast waterborne

  7. 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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).

  12. 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.

  13. 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.

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

    Reports and Publications (EIA)

    1999-01-01

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

  15. Ecofuel plans MTBE plant in Italy

    SciTech Connect (OSTI)

    Alperowicz, N.

    1992-04-29

    Ecofuel (Milan), an ENI company, is evaluating construction of a new methyl tert-butyl ether (MTBE) plant in Italy, but has shelved plans for a world-scale MTBE unit in Mexico. The Italian unit is tied to ethylene expansion now under way. Later this year EniChem (Milan), a sister company, is due to complete construction of a 360,000-m.t./year cracker at Brindisi. The C{sub 4} stream available there and from the existing cracker at Priolo in Sicily should provide enough feed for a unit of up to 100,000 m.t./year of MTBE capacity. Some of the feedstock could also come from the Ravenna cracker.

  16. 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.

  17. 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.

  18. Location of MTBE and toluene in the channel system of the zeolite mordenite: Adsorption and host-guest interactions

    SciTech Connect (OSTI)

    Arletti, Rossella; Martucci, Annalisa; Alberti, Alberto; Pasti, Luisa; Nassi, Marianna; Bagatin, Roberto

    2012-10-15

    This paper reports a study of the location of Methyl Tertiary Butyl Ether (MTBE) and toluene molecules adsorbed in the pores of the organophylic zeolite mordenite from an aqueous solution. The presence of these organic molecules in the zeolite channels was revealed by structure refinement performed by the Rietveld method. About 3 molecules of MTBE and 3.6 molecules of toluene per unit cell were incorporated into the cavities of mordenite, representing 75% and 80% of the total absorption capacity of this zeolite. In both cases a water molecule was localized inside the side pocket of mordenite. The saturation capacity determined by the adsorption isotherms, obtained by batch experiments, and the weight loss given by thermogravimetric (TG) analyses were in very good agreement with these values. The interatomic distances obtained after the structural refinements suggest MTBE could be connected to the framework through a water molecule, while toluene could be bonded to framework oxygen atoms. The rapid and high adsorption of these hydrocarbons into the organophylic mordenite zeolite makes this cheap and environmental friendly material a suitable candidate for the removal of these pollutants from water. - graphical abstract: Location of MTBE (a) and toluene (b) in mordenite channels (projection along the [001] direction). Highlights: Black-Right-Pointing-Pointer We investigated the MTBE and toluene adsorption process into an organophilic zeolite mordenite. Black-Right-Pointing-Pointer The presence of MTBE and toluene in mordenite was determined by X-ray diffraction studies. Black-Right-Pointing-Pointer About 3 molecules of MTBE and 3.6 molecules of toluene per unit cell were incorporated into the zeolite cavities. Black-Right-Pointing-Pointer MTBE is connected to the framework through a water molecule. Black-Right-Pointing-Pointer Toluene is directly bonded to framework oxygen atoms.

  19. Eliminating MTBE in Gasoline in 2006

    Gasoline and Diesel Fuel Update (EIA)

    in 2006. Companies' decisions to eliminate MTBE have been driven by State bans due to water contamination concerns, continuing liability exposure from adding MTBE to gasoline,...

  20. Shock tube ignition of ethanol, isobutene and MTBE: Experiments and modeling

    SciTech Connect (OSTI)

    Curran, H.J.; Dunphy, M.P.; Simmie, J.M.; Westbrook, C.K.; Pitz, W.J.

    1991-11-22

    The ignition of ethanol, isobutene and methyl tert-butyl ether (MTBE) has been studied experimentally in a shock tube and computationally with a detailed chemical kinetic model. Experimental results, consisting of ignition delay measurements, were obtained for a range of fuel/oxygen mixtures diluted in Argon, with temperatures varying over a range of 1100--1900 K. The numerical model consisted of a detailed kinetic reaction mechanism with more than 400 elementary reactions, chosen to describe reactions of each fuel and the smaller hydrocarbon and other species produced during their oxidation. The overall agreement between experimental and computed results was excellent, particularly for mixtures with greater than 0.3% fuel. The greatest sensitivity in the computed results was found to falloff parameters in the dissociation reactions of isobutene, ethane, methane, and ethyl and vinyl radicals, to the C{sub 3}H{sub 4} and C{sub 3}H{sub 5} reaction submechanisms in the model, and to the reactions in the H{sub 2}-O{sub 2}-Co submechanism.

  1. Motor Gasoline Outlook and State MTBE Bans

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

    Motor Gasoline Outlook and State MTBE Bans Tancred Lidderdale Contents 1. Summary 2. MTBE Supply and Demand 3. Ethanol Supply 4. Gasoline Supply 5. Gasoline Prices A. Long-Term Equilibrium Price Analysis B. Short-Term Price Volatility 6. Conclusion 7. Appendix A. Estimating MTBE Consumption by State 8. Appendix B. MTBE Imports and Exports 9. Appendix C. Glossary of Terms 10. End Notes 11. References 1. Summary The U.S. is beginning the summer 2003 driving season with lower gasoline inventories

  2. 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...

  3. 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...

  4. 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...

  5. 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.

  6. dimethyl ether

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

    dimethyl ether - Sandia Energy Energy Search Icon Sandia Home Locations Contact Us Employee Locator Energy & Climate Secure & Sustainable Energy Future Stationary Power Energy Conversion Efficiency Solar Energy Wind Energy Water Power Supercritical CO2 Geothermal Natural Gas Safety, Security & Resilience of the Energy Infrastructure Energy Storage Nuclear Power & Engineering Grid Modernization Battery Testing Nuclear Fuel Cycle Defense Waste Management Programs Advanced Nuclear

  7. 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...

  8. Crown ethers in graphene

    SciTech Connect (OSTI)

    Guo, Junjie; Lee, Jaekwang; Contescu, Cristian I; Gallego, Nidia C; Pantelides, Sokrates T.; Pennycook, Stephen J; Moyer, Bruce A; Chisholm, Matthew F

    2014-01-01

    Crown ethers, introduced by Pedersen1, are at their most basic level neutral rings constructed of oxygen atoms linked by two- or three-carbon chains. They have attracted special attention for their ability to selectively incorporate various atoms2 or molecules within the cavity formed by the ring3-6. This property has led to the use of crown ethers and their compounds in a wide range of chemical and biological applications7,8. However, crown ethers are typically highly flexible, frustrating efforts to rigidify them for many uses that demand higher binding affinity and selectivity9,10. In this Letter, we report atomic-resolution images of the same basic structures of the original crown ethers embedded in graphene. This arrangement constrains the crown ethers to be rigid and planar and thus uniquely suited for the many applications that crown ethers are known for. First-principles calculations show that the close similarity of the structures seen in graphene with those of crown ether molecules also extends to their selectivity towards specific metal cations depending on the ring size. Atoms (or molecules) incorporated within the crown ethers in graphene offer a simple environment that can be easily and systematically probed and modeled. Thus, we expect that this discovery will introduce a new wave of investigations and applications of chemically functionalized graphene.

  9. Crown ethers in graphene

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

    Guo, Junjie; Lee, Jaekwang; Contescu, Cristian I; Gallego, Nidia C; Pantelides, Sokrates T.; Pennycook, Stephen J; Moyer, Bruce A; Chisholm, Matthew F

    2014-01-01

    Crown ethers, introduced by Pedersen1, are at their most basic level neutral rings constructed of oxygen atoms linked by two- or three-carbon chains. They have attracted special attention for their ability to selectively incorporate various atoms2 or molecules within the cavity formed by the ring3-6. This property has led to the use of crown ethers and their compounds in a wide range of chemical and biological applications7,8. However, crown ethers are typically highly flexible, frustrating efforts to rigidify them for many uses that demand higher binding affinity and selectivity9,10. In this Letter, we report atomic-resolution images of the same basicmore » structures of the original crown ethers embedded in graphene. This arrangement constrains the crown ethers to be rigid and planar and thus uniquely suited for the many applications that crown ethers are known for. First-principles calculations show that the close similarity of the structures seen in graphene with those of crown ether molecules also extends to their selectivity towards specific metal cations depending on the ring size. Atoms (or molecules) incorporated within the crown ethers in graphene offer a simple environment that can be easily and systematically probed and modeled. Thus, we expect that this discovery will introduce a new wave of investigations and applications of chemically functionalized graphene.« less

  10. Automobile proximity and indoor residential concentrations of BTEX and MTBE

    SciTech Connect (OSTI)

    Corsi, Dr. Richard; Morandi, Dr. Maria; Siegel, Dr. Jeffrey; Hun, Diana E

    2011-01-01

    Attached garages have been identified as important sources of indoor residential air pollution. However, the literature lacks information on how the proximity of cars to the living area affects indoor concentrations of gasoline-related compounds, and the origin of these pollutants. We analyzed data from the Relationships of Indoor, Outdoor, and Personal Air (RIOPA) study and evaluated 114 residences with cars in an attached garage, detached garage or carport, or without cars. Results indicate that homes with cars in attached garages were affected the most. Concentrations in homes with cars in detached garages and residences without cars were similar. The contribution from gasoline-related sources to indoor benzene and MTBE concentrations appeared to be dominated by car exhaust, or a combination of tailpipe and gasoline vapor emissions. Residing in a home with an attached garage could lead to benzene exposures ten times higher than exposures from commuting in heavy traffic.

  11. Alternative Fuels Data Center: Dimethyl Ether

    Alternative Fuels and Advanced Vehicles Data Center [Office of Energy Efficiency and Renewable Energy (EERE)]

    Dimethyl Ether to someone by E-mail Share Alternative Fuels Data Center: Dimethyl Ether on Facebook Tweet about Alternative Fuels Data Center: Dimethyl Ether on Twitter Bookmark Alternative Fuels Data Center: Dimethyl Ether on Google Bookmark Alternative Fuels Data Center: Dimethyl Ether on Delicious Rank Alternative Fuels Data Center: Dimethyl Ether on Digg Find More places to share Alternative Fuels Data Center: Dimethyl Ether on AddThis.com... More in this section... Biobutanol Dimethyl Ether

  12. Propenyl ether monomers for photopolymerization

    DOE Patents [OSTI]

    Crivello, James V.

    1996-01-01

    Propenyl ether monomers of formula V A(OCH.dbd.CHCH.sub.3).sub.n wherein n is an integer from one to six and A is selected from cyclic ethers, polyether and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of formula V together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

  13. Propenyl ether monomers for photopolymerization

    DOE Patents [OSTI]

    Crivello, J.V.

    1996-10-22

    Propenyl ether monomers of formula A(OCH{double_bond}CHCH{sub 3}){sub n} wherein n is an integer from one to six and A is selected from cyclic ethers, polyether and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of the above formula together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

  14. 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:...

  15. 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

  16. 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.

  17. 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.

  18. 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.

  19. Sulfonimide-containing poly(arylene ether)s and poly(arylene ether sulfone)s, methods for producing the same, and uses thereof

    DOE Patents [OSTI]

    Hofmann, Michael A.

    2006-11-14

    The present invention is directed to sulfonimide-containing polymers, specifically sulfonimide-containing poly(arylene ether)s and sulfonimide-containing poly(arylene ether sulfone)s, and processes for making the sulfonimide-containing poly(arylene ether)s and sulfonimide-containing poly(arylene ether sulfone)s, for use conductive membranes and fuel cells.

  20. 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.

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

    SciTech Connect (OSTI)

    Hadder, G.R.

    2000-08-16

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

  2. Aza crown ether compounds as anion receptors

    DOE Patents [OSTI]

    Lee, Hung Sui (East Setauket, NY); Yang, Xiao-Oing (Port Jefferson Station, NY); McBreen, James (Bellport, NY)

    1998-08-04

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI.sup.+ ion in alkali metal batteries.

  3. Aza crown ether compounds as anion receptors

    DOE Patents [OSTI]

    Lee, H.S.; Yang, X.O.; McBreen, J.

    1998-08-04

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI{sup +} ion in alkali metal batteries. 3 figs.

  4. Alternative Fuels lDimethyl Ether Rheology and Materials Studies...

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

    Fuels lDimethyl Ether Rheology and Materials Studies Alternative Fuels lDimethyl Ether Rheology and Materials Studies 2004 Diesel Engine Emissions Reduction (DEER) Conference ...

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

    Reports and Publications (EIA)

    1998-01-01

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

  6. Update of Summer Reformulated Gasoline Supply Assessment for New York and Connecticut

    Reports and Publications (EIA)

    2004-01-01

    In October 2003, the Energy Information Administration (EIA) published a review of the status of the methyl tertiary butyl ether (MTBE) ban transition in New York (NY) and Connecticut (CT) that noted significant uncertainties in gasoline supply for those states for the summer of 2004. To obtain updated information, EIA spoke to major suppliers to the two states over the past several months as the petroleum industry began the switch from winter- to summer-grade gasoline.

  7. Total Crude Oil and Petroleum Products Exports

    Gasoline and Diesel Fuel Update (EIA)

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

  8. Refinery Stocks of Crude Oil and Petroleum Products

    Gasoline and Diesel Fuel Update (EIA)

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

  9. Refinery & Blenders Net Input of Crude Oil

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

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

  10. Process for making propenyl ethers and photopolymerizable compositions containing them

    DOE Patents [OSTI]

    Crivello, James V.

    1996-01-01

    Propenyl ether monomers of formula V A(OCH.dbd.CHCH.sub.3).sub.n wherein n is an integer from one to six and A is selected from cyclic ethers, polyether and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of formula V together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

  11. Process for making propenyl ethers and photopolymerizable compositions containing them

    DOE Patents [OSTI]

    Crivello, J.V.

    1996-01-23

    Propenyl ether monomers of formula A(OCH{double_bond}CHCH{sub 3}){sub n} (V) wherein n is an integer from one to six and A is selected from cyclic ethers, polyether, and alkanes are disclosed. The monomers are readily polymerized in the presence of cationic photoinitiators, when exposed to actinic radiation, to form poly(propenyl ethers) that are useful for coatings, sealants, varnishes and adhesives. Compositions for preparing polymeric coatings comprising the compounds of formula V together with particular cationic photoinitiators are also disclosed, as are processes for making the monomers from allyl halides and readily available alcohols. The process involves rearranging the resulting allyl ethers to propenyl ethers.

  12. 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

  13. Alternative Fuels lDimethyl Ether Rheology and Materials Studies |

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

    Department of Energy Fuels lDimethyl Ether Rheology and Materials Studies Alternative Fuels lDimethyl Ether Rheology and Materials Studies 2004 Diesel Engine Emissions Reduction (DEER) Conference Presentation: The Pennsylvania State University PDF icon 2004_deer_perez.pdf More Documents & Publications Research on Fuels & Lubricants Development of a Dimethyl Ether (DME)-Fueled Shuttle Bus Ionic Liquids as Multifunctional Ashless Additives for Engine Lubrication

  14. Divinyl ether synthase gene, and protein and uses thereof

    DOE Patents [OSTI]

    Howe, Gregg A.; Itoh, Aya

    2006-12-26

    The present invention relates to divinyl ether synthase genes, proteins, and methods of their use. The present invention encompasses both native and recombinant wild-type forms of the synthase, as well as mutants and variant forms, some of which possess altered characteristics relative to the wild-type synthase. The present invention also relates to methods of using divinyl ether synthase genes and proteins, including in their expression in transgenic organisms and in the production of divinyl ether fatty acids, and to methods of suing divinyl ether fatty acids, including in the protection of plants from pathogens.

  15. Divinyl ether synthase gene and protein, and uses thereof

    DOE Patents [OSTI]

    Howe, Gregg A. (East Lansing, MI); Itoh, Aya (Tsuruoka, JP)

    2011-09-13

    The present invention relates to divinyl ether synthase genes, proteins, and methods of their use. The present invention encompasses both native and recombinant wild-type forms of the synthase, as well as mutants and variant forms, some of which possess altered characteristics relative to the wild-type synthase. The present invention also relates to methods of using divinyl ether synthase genes and proteins, including in their expression in transgenic organisms and in the production of divinyl ether fatty acids, and to methods of suing divinyl ether fatty acids, including in the protection of plants from pathogens.

  16. 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.

  17. 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...

  18. 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...

  19. Arylations of coal model systems. [Benzyl phenyl ether and l-naphthylmethyl phenyl ether

    SciTech Connect (OSTI)

    Smith, B.F.; Venier, C.G.; Squires, T.G.

    1984-01-01

    Currently, coal is converted to clean liquids or low melting solids by processes which utilize high temperature, high pressure, or both. These processes occur by thermal bond cleavages and involve the intermediacy of free radicals. In a search for chemistry which could liquefy coal under milder conditions, the authors have focussed on thermally less demanding ionic reactions. Of the functional groups which commonly occur in coals, ethers are the easiest to cleave under acid conditions. Depending on the density of these linkages and their importance as crosslinks in the macromolecular structure of coals, solubilization might be greatly enhanced solely by cleaving and capping either bonds. Benzylic ethers are particularly reactive and have been implicated in the initiation of coal pyrolysis and hydropyrolysis. Arylation, the use of acids to cleave bonds in coals in the presence of aromatic rings to trap the consequent incipient carbonium ions, has a long history. This paper discusses the use of benzyl phenyl ether and l-naphthylmethyl phenyl ether and polymers related to them as models to develop and evaluate the chemistry involved in the arylations. 9 references, 1 figure, 4 tables.

  20. Process for producing dimethyl ether from synthesis gas

    DOE Patents [OSTI]

    Pierantozzi, R.

    1985-06-04

    This invention pertains to a Fischer Tropsch process for converting synthesis gas to an oxygenated hydrocarbon with particular emphasis on dimethyl ether. Synthesis gas comprising carbon monoxide and hydrogen are converted to dimethyl ether by carrying out the reaction in the presence of an alkali metal-manganese-iron carbonyl cluster incorporated onto a zirconia-alumina support.

  1. Process for producing dimethyl ether form synthesis gas

    DOE Patents [OSTI]

    Pierantozzi, Ronald (Macungie, PA)

    1985-01-01

    This invention pertains to a Fischer Tropsch process for converting synthesis gas to an oxygenated hydrocarbon with particular emphasis on dimethyl ether. Synthesis gas comprising carbon monoxide and hydrogen are converted to dimethyl ether by carrying out the reaction in the presence of an alkali metal-manganese-iron carbonyl cluster incorporated onto a zirconia-alumina support.

  2. Origin of mechanical modifications in poly (ether ether ketone)/carbon nanotube composite

    SciTech Connect (OSTI)

    Pavlenko, Ekaterina; Puech, Pascal; Bacsa, Wolfgang; Boyer, François; Olivier, Philippe; Sapelkin, Andrei; King, Stephen; Heenan, Richard; Pons, François; Gauthier, Bénédicte; Cadaux, Pierre-Henri

    2014-06-21

    Variations in the hardness of a poly (ether ether ketone) beam electrically modified with multi-walled carbon nanotubes (MWCNT, 0.5%-3%) are investigated. It is shown that both rupture and hardness variations correlate with the changes in carbon nanotube concentration when using micro indentation and extended Raman imaging. Statistical analysis of the relative spectral intensities in the Raman image is used to estimate local tube concentration and polymer crystallinity. We show that the histogram of the Raman D band across the image provides information about the amount of MWCNTs and the dispersion of MWCNTs in the composite. We speculate that we have observed a local modification of the ordering between pure and modified polymer. This is partially supported by small angle neutron scattering measurements, which indicate that the agglomeration state of the MWCNTs is the same at the concentrations studied.

  3. Development of specialty chemicals from dimethyl ether

    SciTech Connect (OSTI)

    Tartamella, T.L.; Lee, S.

    1996-12-31

    Dimethyl ether (DME) may be efficiently produced from coal-bases syngas in a high pressure, mechanically agitated slurry reactor. DME synthesis occurs in the liquid phase using a dual catalyst. By operating in a dual catalyst mode, DME may be converted from in-situ produced methanol resulting in higher methyl productivities and syngas conversions over methanol conversion alone. The feasibility of utilizing DME as a building block for more valuable specialty chemicals has been examined. A wide variety of petrochemicals may be produced from DME including light olefins, gasoline range hydrocarbons, oxygenates, and glycol precursors. These chemicals represent an important part of petroleum industries inventory of fine chemicals. Carbonylation, hydrocarbonylation, and oxidative dimerization are but a few of the reactions in which DME may undergo conversion. DME provides an additional route for the production of industrially important petrochemicals.

  4. High pressure injection of dimethyl ether

    SciTech Connect (OSTI)

    Glensvig, M.; Sorenson, S.C.; Abata, D.

    1996-12-31

    Partially oxygenated hydrocarbons produced from natural gas have been shown to be viable alternate fuels for the diesel engine, showing favorable combustion characteristics similar to that of diesel fuel but without exhaust particulates and with significantly reduced NO{sub x} emissions and lower engine noise. Further, engine studies have demonstrated that such compounds, like dimethyl ether (DME), can be injected at much lower pressures than conventional diesel fuel with better overall performance. This experimental study compares the injection of DME to that of conventional diesel fuel. Both fuels were injected into a quiescent high pressure chamber containing Nitrogen at pressures up to 25 atmospheres at room temperature with a pintle nozzle and jerk pump. Comparisons were obtained with high speed photography using a Hycam camera. Results indicate that there are significant differences in spray geometry and penetration which are not predictable with analytical models currently used for diesel fuels.

  5. 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.

  6. Atmospheric and combustion chemistry of dimethyl ether

    SciTech Connect (OSTI)

    Nielsen, O.J.; Egsgaard, H.; Larsen, E.; Sehested, J.; Wallington, T.J.

    1997-12-31

    It has been demonstrated that dimethyl ether (DME) is an ideal diesel fuel alternative. DME, CH{sub 3}OCH{sub 3}, combines good fuel properties with low exhaust emissions and low combustion noise. Large scale production of this fuel can take place using a single step catalytic process converting CH{sub 4} to DME. The fate of DME in the atmosphere has previously been studied. The atmospheric degradation is initiated by the reaction with hydroxyl radicals, which is also a common feature of combustion processes. Spectrokinetic investigations and product analysis were used to demonstrate that the intermediate oxy radical, CH{sub 3}OCH{sub 2}O, exhibits a novel reaction pathway of hydrogen atom ejection. The application of tandem mass spectrometry to chemi-ions based on supersonic molecular beam sampling has recently been demonstrated. The highly reactive ionic intermediates are sampled directly from the flame and identified by collision activation mass spectrometry and ion-molecule reactions. The mass spectrum reflects the distribution of the intermediates in the flame. The atmospheric degradation of DME as well as the unique fuel properties of a oxygen containing compound will be discussed.

  7. 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

  8. Development of a Dimethyl Ether (DME)-Fueled Shuttle Bus | Department of

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

    Energy a Dimethyl Ether (DME)-Fueled Shuttle Bus Development of a Dimethyl Ether (DME)-Fueled Shuttle Bus 2002 DEER Conference Presentation: The Pennsylvania State University PDF icon 2002_deer_boehman.pdf More Documents & Publications Development of a Dimethyl Ether (DME)-Fueled Shuttle Bus Chapter 7 - Advancing Systems and Technologies to Produce Cleaner Fuels Alternative Fuels lDimethyl Ether Rheology and Materials Studies Liquid Fuels from Biomass

  9. Li-air batteries having ether-based electrolytes

    DOE Patents [OSTI]

    Amine, Khalil; Curtiss, Larry A; Lu, Jun; Lau, Kah Chun; Zhang, Zhengcheng; Sun, Yang-Kook

    2015-03-03

    A lithium-air battery includes a cathode including a porous active carbon material, a separator, an anode including lithium, and an electrolyte including a lithium salt and polyalkylene glycol ether, where the porous active carbon material is free of a metal-based catalyst.

  10. Ether and ester derivatives of the perborate icosahedron

    DOE Patents [OSTI]

    Hawthorne, M. Frederick; Peymann, Toralf; Maderna, Andreas

    2003-12-16

    New boron icosahedral ethers and esters formed from Cs.sub.2 [closo-B.sub.12 (OH).sub.12 ],; Cs[closo-1-H-1-CB.sub.11 (OH).sub.11 ]; and closo-1,12-H.sub.2 -1,12-C.sub.2 B.sub.10 (OH).sub.10 are disclosed. Also set forth are their preparation by reacting the icosahedral boranes [closo-B.sub.12 H.sub.12 ].sup.2-, [closo-1-CB.sub.11 H.sub.12 ].sup.- and closo-1,12-(CH.sub.2 OH).sub.2 -1,12-C.sub.2 B.sub.10 H.sub.10 with an acid anhdride or acid chloride to form the ester or an alkylating agent to form the ether.

  11. CATALYSTS FOR HIGH CETANE ETHERS AS DIESEL FUELS

    SciTech Connect (OSTI)

    Kamil Klier; Richard G. Herman; James G.C. Shen; Qisheng Ma

    2000-08-31

    A novel 1,2-ethanediol, bis(hydrogen sulfate), disodium salt precursor-based solid acid catalyst with a zirconia substrate was synthesized and demonstrated to have significantly enhanced activity and high selectivity in producing methyl isobutyl ether (MIBE) or isobutene from methanol-isobutanol mixtures. The precursor salt was synthesized and provided by Dr. T. H. Kalantar of the M.E. Pruitt Research Center, Dow Chemical Co., Midland, MI 48674. Molecular modeling of the catalyst synthesis steps and of the alcohol coupling reaction is being carried out. A representation of the methyl transfer from the surface activated methanol molecule (left) to the activated oxygen of the isobutanol molecule (right) to form an ether linkage to yield MIBE is shown.

  12. 2' and 3' Carboranyl uridines and their diethyl ether adducts

    DOE Patents [OSTI]

    Soloway, Albert H. (Worthington, OH); Barth, Rolf F. (Columbus, OH); Anisuzzaman, Abul K. (Columbus, OH); Alam, Fazlul (Anaheim, CA); Tjarks, Werner (Columbus, OH)

    1992-01-01

    There is disclosed a process for preparing carboranyl uridine nucleoside compounds and their diethyl ether adducts, which exhibit a tenfold increase in boron content over prior art boron containing nucleoside compounds. Said carboranyl uridine nucleoside compounds exhibit enhanced lipophilicity and hydrophilic properties adequate to enable solvation in aqueous media for subsequent incorporation of said compounds in methods for boron neutron capture therapy in mammalian tumor cells.

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

    SciTech Connect (OSTI)

    Singerman, G.M.

    1980-11-01

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

  14. Thermodynamics of Hydrogen Production from Dimethyl Ether Steam Reforming and Hydrolysis

    SciTech Connect (OSTI)

    T.A. Semelsberger

    2004-10-01

    The thermodynamic analyses of producing a hydrogen-rich fuel-cell feed from the process of dimethyl ether (DME) steam reforming were investigated as a function of steam-to-carbon ratio (0-4), temperature (100 C-600 C), pressure (1-5 atm), and product species: acetylene, ethanol, methanol, ethylene, methyl-ethyl ether, formaldehyde, formic acid, acetone, n-propanol, ethane and isopropyl alcohol. Results of the thermodynamic processing of dimethyl ether with steam indicate the complete conversion of dimethyl ether to hydrogen, carbon monoxide and carbon dioxide for temperatures greater than 200 C and steam-to-carbon ratios greater than 1.25 at atmospheric pressure (P = 1 atm). Increasing the operating pressure was observed to shift the equilibrium toward the reactants; increasing the pressure from 1 atm to 5 atm decreased the conversion of dimethyl ether from 99.5% to 76.2%. The order of thermodynamically stable products in decreasing mole fraction was methane, ethane, isopropyl alcohol, acetone, n-propanol, ethylene, ethanol, methyl-ethyl ether and methanol--formaldehyde, formic acid, and acetylene were not observed. The optimal processing conditions for dimethyl ether steam reforming occurred at a steam-to-carbon ratio of 1.5, a pressure of 1 atm, and a temperature of 200 C. Modeling the thermodynamics of dimethyl ether hydrolysis (with methanol as the only product considered), the equilibrium conversion of dimethyl ether is limited. The equilibrium conversion was observed to increase with temperature and steam-to-carbon ratio, resulting in a maximum dimethyl ether conversion of approximately 68% at a steam-to-carbon ratio of 4.5 and a processing temperature of 600 C. Thermodynamically, dimethyl ether processed with steam can produce hydrogen-rich fuel-cell feeds--with hydrogen concentrations exceeding 70%. This substantiates dimethyl ether as a viable source of hydrogen for PEM fuel cells.

  15. Energy and crude oil input requirements for the production of reformulated gasolines

    SciTech Connect (OSTI)

    Singh, M.; McNutt, B.

    1993-10-01

    The energy and crude oil requirements for the production of reformulated gasoline (RFG) are estimated. The scope of the study includes both the energy and crude oil embodied in the final product and the process energy required to manufacture the RFG and its components. The effects on energy and crude oil use of employing various oxygenates to meet the minimum oxygen-content level required by the Clean Air Act Amendments are evaluated. The analysis shows that production of RFG requires more total energy, but uses less crude oil, than that of conventional gasoline. The energy and crude oil use requirements of the different RFGs vary considerably. For the same emissions performance level, RFG with ethanol requires substantially more total energy and crude oil than does RFG with methyl tertiary butyl ether (MTBE) or ethyl tertiary butyl ether. A specific proposal by the US Environmental Protection Agency, designed to allow the use of ethanol in RFG, would increase the total energy required to produce RFG by 2% and the total crude oil required by 2.0 to 2.5% over the corresponding values for the base RFG with MTBE.

  16. On the radiation stability of crown ethers in ionic liquids.

    SciTech Connect (OSTI)

    Shkrob, I.; Marin, T.; Dietz, M.

    2011-04-14

    Crown ethers (CEs) are macrocyclic ionophores used for the separation of strontium-90 from acidic nuclear waste streams. Room temperature ionic liquids (ILs) are presently being considered as replacements for traditional molecular solvents employed in such separations. It is desirable that the extraction efficacy obtained with such solvents should not deteriorate in the strong radiation fields generated by decaying radionuclides. This deterioration will depend on the extent of radiation damage to both the IL solvent and the CE solute. While radiation damage to ILs has been extensively studied, the issue of the radiation stability of crown ethers, particularly in an IL matrix, has not been adequately addressed. With this in mind, we have employed electron paramagnetic resonance (EPR) spectroscopy to study the formation of CE-related radicals in the radiolysis of selected CEs in ILs incorporating aromatic (imidazolium and pyridinium) cations. The crown ethers have been found to yield primarily hydrogen loss radicals, H atoms, and the formyl radical. In the low-dose regime, the relative yield of these radicals increases linearly with the mole fraction of the solute, suggesting negligible transfer of the excitation energy from the solvent to the solute; that is, the solvent has a 'radioprotective' effect. The damage to the CE in the loading region of practical interest is relatively low. Under such conditions, the main chemical pathway leading to decreased extraction performance is protonation of the macrocycle. At high radiation doses, sufficient to increase the acidity of the IL solvent significantly, such proton complexes compete with the solvent cations as electron traps. In this regime, the CEs will rapidly degrade as the result of H abstraction from the CE ring by the released H atoms. Thus, the radiation dose to which a CE/IL system is exposed must be maintained at a level sufficiently low to avoid this regime.

  17. Dimethyl ether production from methanol and/or syngas

    DOE Patents [OSTI]

    Dagle, Robert A; Wang, Yong; Baker, Eddie G; Hu, Jianli

    2015-02-17

    Disclosed are methods for producing dimethyl ether (DME) from methanol and for producing DME directly from syngas, such as syngas from biomass. Also disclosed are apparatus for DME production. The disclosed processes generally function at higher temperatures with lower contact times and at lower pressures than conventional processes so as to produce higher DME yields than do conventional processes. Certain embodiments of the processes are carried out in reactors providing greater surface to volume ratios than the presently used DME reactors. Certain embodiments of the processes are carried out in systems comprising multiple microchannel reactors.

  18. DIMETHYL ETHER (DME)-FUELED SHUTTLE BUS DEMONSTRATION PROJECT

    SciTech Connect (OSTI)

    Elana M. Chapman; Shirish Bhide; Andre L. Boehman; David Klinikowski

    2003-04-01

    The objectives of this research and demonstration program are to convert a campus shuttle bus to operation on dimethyl ether, a potential ultra-clean alternative diesel fuel. To accomplish this objective, this project includes laboratory evaluation of a fuel conversion strategy, as well as field demonstration of the DME-fueled shuttle bus. Since DME is a fuel with no lubricity (i.e., it does not possess the lubricating quality of diesel fuel), conventional fuel delivery and fuel injection systems are not compatible with dimethyl ether. Therefore, to operate a diesel engine on DME one must develop a fuel-tolerant injection system, or find a way to provide the necessary lubricity to the DME. In this project, they have chosen the latter strategy in order to achieve the objective with minimal need to modify the engine. The strategy is to blend DME with diesel fuel, to obtain the necessary lubricity to protect the fuel injection system and to achieve low emissions. Within the Combustion Laboratory of the Penn State Energy Institute, they have installed and equipped a Navistar V-8 direct-injection turbodiesel engine for measurement of gaseous and particulate emissions and examination of the impact of fuel composition on diesel combustion. They have also reconfigured a high-pressure viscometer for studies of the viscosity, bulk modulus (compressibility) and miscibility of blends of diesel fuel, dimethyl ether and lubricity additives. The results include baseline emissions, performance and combustion measurements on the Navistar engine for operation on a federal low sulfur diesel fuel (300 ppm S). Most recently, they have examined blends of an oxygenated fuel additive (a liquid fuel called CETANER{trademark}) produced by Air Products, for comparison with dimethyl ether blended at the same weight of oxygen addition, 2 wt.%. While they have not operated the engine on DME yet, they are now preparing to do so. A fuel system for delivery of DME/Diesel blends has been configured and initial investigations at low DME blend ratios (around 5-10 vol%) will begin shortly. They have also performed viscosity measurements on diesel fuel, DME and 50-50 blends of DME in diesel. These tests have verified that DME has a much lower viscosity than the diesel fuel and that the viscosity of the blended fuel is also much lower than the diesel base fuel. This has implications for the injection and atomization of the DME/diesel blends.

  19. Dimethyl ether synthesis from syngas in slurry phase

    SciTech Connect (OSTI)

    Han, Y.Z.; Fujimoto, K.; Shikata, T.

    1997-12-31

    Dimethyl ether (DME) is one of the important chemicals derived from synthesis gas. It can be widely used in syngas conversion, production of olefins, or MTG gasoline. Recently, is has been noticed as a substitute of LPG used as home fuel. In the present study, dimethyl ether was effectively synthesized from CO rich syngas (H{sub 2}/CO=1/1) over hybrid catalyst containing a Cu-Zn-Al(O) based methanol synthesis catalyst and {gamma}-alumina in an agitated slurry reactor under relatively mild reaction conditions: temperature 230--300 C, pressure 2.0--5.0 MPa, contact time 2.0--10 gram-cat.-h/mol. The catalysts used as the methanol active components were commercially available Cu-Zn-Al(O) based catalysts, BASF S385 and ICI 51-2. Two kinds of {gamma}-alumina ALO4 (standard catalyst of the Catalysis Society of Japan) and N612N (NIKKI Co., Japan) were used as the methanol dehydration components. The slurry was prepared by mixing the fine powder (<100 mesh) of catalyst components with purified n-hexadecane. The catalysts were reduced by a mixing gas containing 20% syngas and 80% nitrogen with a three-hour programmed temperature raising from room temperature to the final temperature. All products were analyzed by gas chromatographs. Results are given and discussed.

  20. Numerical study of the effect of oxygenated blending compounds on soot formation in shock tubes

    SciTech Connect (OSTI)

    Boehm, H.; Braun-Unkhoff, M.

    2008-04-15

    This numerical study deals with the influence of blends on the amount of soot formed in shock tubes, which were simulated by assuming a homogeneous plug flow reactor model. For this purpose, first, the reaction model used here was validated against experimental results previously obtained in the literature. Then, the soot volume fractions of various mixtures of methyl tert-butyl ether (MTBE)-benzene, isobutene-benzene, methanol-benzene, and ethanol-benzene diluted in argon were simulated and compared to the results of benzene-argon pyrolysis at 1721 K and 5.4 MPa. For MTBE, isobutene, methanol, and ethanol, small amounts of additives to benzene-argon mixtures promoted soot formation, for the shock tube model assumed, while higher concentrations of these additives led to smaller soot volume fractions in comparison to pure benzene-argon pyrolysis. The most significant soot promotion effect was found for the additives MTBE and isobutene. The channel for MTBE decomposition producing isobutene and methanol is very effective at temperatures beyond 1200 K. Thus, both MTBE-benzene and isobutene-benzene mixtures diluted in argon showed rather similar behavior in regard to soot formation. Special emphasis was directed toward the causes for the concentration-dependent influence of the blends on the amount of soot formed. Aromatic hydrocarbons and acetylene were identified as key gas-phase species that determine the trends in the formation of soot of various mixtures. From reaction flux analysis for phenanthrene, it was deduced that the combinative routes including phenyl species play a major role in forming PAHs, especially at early reaction times. It is found that the additives play an important role in providing material to grow side chains, such as by reaction channels including phenylacetylene or benzyl, which are confirmed to form aromatic hydrocarbons and thus to influence the amount of soot formed, particularly when the concentrations of the blends are increased. (author)

  1. Rational Design of Cesium-Selective Ionophores and Chemosensors: Dihydrocalix[4]arene Crown-6 Ethers

    SciTech Connect (OSTI)

    Sachleben, Richard A.; Bryan, Jeffrey C.; Brown, Gilbert M.; Engle, Nancy L.; Haverlock, Tamara J.; Hay, Benjamin P.; Urvoas, Agathe; Moyer, Bruce A.

    2003-12-15

    Molecular mechanics calculations performed on calix[4]arene crown-6 ethers predict that the 1,3-dihydro derivatives will exhibit greater complementarity for potassium and cesium ions than the parent 1,3-dialkoxy calix crowns. The X-ray crystal structures of 1,3-alt bis-octyloxycalix[4]arene benzocrown-6 ether, dihydrocalix[4]arene benzocrown-6 ether, and the cesium nitrate complex of dihydrocalix[4]arene benzocrown-6 ether were determined. The cesium complex structure corresponds closely to the structure predicted by molecular mechanics. The dihydrocalix[4]arene crown-6 ethers exhibit enhanced cesium selectivity in the extraction of alkali metal salts and provide a platform for a highly sensitive and selective cesium chemosensor.

  2. 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

  3. Dimethyl ether fuel proposed as an alternative to LNG

    SciTech Connect (OSTI)

    Kikkawa, Yoshitsugi; Aoki, Ichizo

    1998-04-06

    To cope with the emerging energy demand in Asia, alternative fuels to LNG must be considered. Alternative measures, which convert the natural gas to liquid fuel, include the Fischer-Tropsch conversion, methanol synthesis, and dimethyl ether (DME) synthesis. Comparisons are evaluated based on both transportation cost and feed-gas cost. The analysis will show that DME, one alternative to LNG as transportation fuel, will be more economical for longer distances between the natural-gas source and the consumer. LNG requires a costly tanker and receiving terminal. The break-even distance will be around 5,000--7,000 km and vary depending on the transported volume. There will be risk, however, since there has never been a DME plant the size of an LNG-equivalent plant [6 million metric tons/year (mty)].

  4. Role of acid catalysis in dimethyl ether conversion processes

    SciTech Connect (OSTI)

    Tartamella, T.L.; Lee, S.

    1996-12-31

    Acidity plays an important role in the conversion of methanol and dimethyl ether (DME) to hydrocarbons and oxygenates. In the conversion to hydrocarbons over zeolite catalyst, Broensted acidity is the main contributor to the first hydrocarbon formed. Here, acidity is also an important factor in determining olefin, paraffin, and aromatic content in the final product distribution. Catalyst life has also been found to be related to acidity content in zeolites. DME conversion to oxygenates is especially dependent on high acidity catalysts. Superacids like BF{sub 3}, HF-BF{sub 3}, and CF{sub 3}COOH have been used in the past for conversion of DME in carbonylation reactions to form methyl acetate and acetic acid at high pressures. Recently, heteropoly acids and their corresponding metal substituted salts have been used to convert DME to industrially important petrochemicals resulting in shorter reaction times and without the use of harsh operating conditions.

  5. DIMETHYL ETHER (DME)-FUELED SHUTTLE BUS DEMONSTRATION PROJECT

    SciTech Connect (OSTI)

    Elana M. Chapman; Shirish Bhide; Jennifer Stefanik; Andre L. Boehman; David Klinikowski

    2003-04-01

    The objectives of this research and demonstration program are to convert a campus shuttle bus to operation on dimethyl ether, a potential ultra-clean alternative diesel fuel. To accomplish this objective, this project includes laboratory evaluation of a fuel conversion strategy, as well as, field demonstration of the DME-fueled shuttle bus. Since DME is a fuel with no lubricity (i.e., it does not possess the lubricating quality of diesel fuel), conventional fuel delivery and fuel injection systems are not compatible with dimethyl ether. Therefore, to operate a diesel engine on DME one must develop a fuel-tolerant injection system, or find a way to provide the necessary lubricity to the DME. In this project, they have chosen the latter strategy in order to achieve the objective with minimal need to modify the engine. The strategy is to blend DME with diesel fuel, to obtain the necessary lubricity to protect the fuel injection system and to achieve low emissions. The laboratory studies have included work with a Navistar V-8 turbodiesel engine, demonstration of engine operation on DME-diesel blends and instrumentation for evaluating fuel properties. The field studies have involved performance, efficiency and emissions measurements with the Champion Motorcoach ''Defender'' shuttle bus which will be converted to DME-fueling. The results include baseline emissions, performance and combustion measurements on the Navistar engine for operation on a federal low sulfur diesel fuel (300 ppm S). Most recently, they have completed engine combustion studies on DME-diesel blends up to 30 wt% DME addition.

  6. 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.

  7. 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.

  8. Metal ion complexation by ionizable crown ethers. Final report, January 1, 1988--June 30, 1994

    SciTech Connect (OSTI)

    Bartsch, R.A.

    1994-12-31

    During the report period a variety of new lipophilic ionizable crown ethers with pendent proton-ionizable groups has been synthesized. The ligands possess one or more ionizable group (carboxylic acid, phosphonic acid monoethyl ester, para-nitrophenol, phosphonic acid) attached to crown ether, monoazacrown ether or diazacrown ether frameworks. These novel chelating agents have either pendent or inward-facing proton-ionizable groups. Such lipophilic proton-ionizable crown ethers are designed for use in multiphase metal ion separations (solvent extraction, liquid membrane transport). In addition a series of proton-ionizable crown ethers without lipophilic groups was prepared to study how structural variations within the ligand influence metal ion complexation in homogeneous media as assessed by NMR spectroscopy or titration calorimetry. A third class of new metal ion-complexing agents is a series of lipophilic acyclic polyether dicarboxylic acids. Competitive solvent extractions of alkali metal and alkaline earth cations and of the mixed species have been conducted to reveal the influence of ring size, nature and attachment site of the lipophilic group, sidearm length, and proton-ionizable group identity and location upon the selectivity and efficiency of metal ion complexation. In addition to such studies of structural variation within the lipophilic proton-ionizable crown ether, the effect of changing the organic solvent and variation of the stripping conditions have been assessed. The influence of structural variations within lipophilic acyclic polyether dicarboxylic acids upon competitive solvent extraction of alkaline earth cations has been probed. Also a new chromogenic, di-ionizable crown ether with extremely high selectivity for Hg{sup 2+} has been discovered.

  9. 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.

  10. 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.

  11. Wide range modeling study of dimethyl ether oxidation

    SciTech Connect (OSTI)

    Pitz, W.J.; Marinov, N.M.; Westbrook, C.K.; Dagaut, P.; Boettner, J-C; Cathonnet, M.

    1997-04-01

    A detailed chemical kinetic model has been used to study dimethyl ether (DME) oxidation over a wide range of conditions. Experimental results obtained in a jet-stirred reactor (JSR) at I and 10 atm, 0.2 < 0 < 2.5, and 800 < T < 1300 K were modeled, in addition to those generated in a shock tube at 13 and 40 bar, 0 = 1.0 and 650 :5 T :5 1300 K. The JSR results are particularly valuable as they include concentration profiles of reactants, intermediates and products pertinent to the oxidation of DME. These data test the Idnetic model severely, as it must be able to predict the correct distribution and concentrations of intermediate and final products formed in the oxidation process. Additionally, the shock tube results are very useful, as they were taken at low temperatures and at high pressures, and thus undergo negative temperature dependence (NTC) behavior. This behavior is characteristic of the oxidation of saturated hydrocarbon fuels, (e.g. the primary reference fuels, n-heptane and iso- octane) under similar conditions. The numerical model consists of 78 chemical species and 336 chemical reactions. The thermodynamic properties of unknown species pertaining to DME oxidation were calculated using THERM.

  12. DIMETHYL ETHER (DME)-FUELED SHUTTLE BUS DEMONSTRATION PROJECT

    SciTech Connect (OSTI)

    Elana M. Chapman; Shirish Bhide; Jennifer Stefanik; Howard Glunt; Andre L. Boehman; Allen Homan; David Klinikowski

    2003-04-01

    The objectives of this research and demonstration program are to convert a campus shuttle bus to operation on dimethyl ether, a potential ultra-clean alternative diesel fuel. To accomplish this objective, this project includes laboratory evaluation of a fuel conversion strategy, as well as, field demonstration of the DME-fueled shuttle bus. Since DME is a fuel with no lubricity (i.e., it does not possess the lubricating quality of diesel fuel), conventional fuel delivery and fuel injection systems are not compatible with dimethyl ether. Therefore, to operate a diesel engine on DME one must develop a fuel-tolerant injection system, or find a way to provide the necessary lubricity to the DME. In this project, they have chosen the latter strategy in order to achieve the objective with minimal need to modify the engine. Their strategy is to blend DME with diesel fuel, to obtain the necessary lubricity to protect the fuel injection system and to achieve low emissions. The bulk of the efforts over the past year were focused on the conversion of the campus shuttle bus. This process, started in August 2001, took until April 2002 to complete. The process culminated in an event to celebrate the launching of the shuttle bus on DME-diesel operation on April 19, 2002. The design of the system on the shuttle bus was patterned after the system developed in the engine laboratory, but also was subjected to a rigorous failure modes effects analysis (FMEA, referred to by Air Products as a ''HAZOP'' analysis) with help from Dr. James Hansel of Air Products. The result of this FMEA was the addition of layers of redundancy and over-pressure protection to the system on the shuttle bus. The system became operational in February 2002. Preliminary emissions tests and basic operation of the shuttle bus took place at the Pennsylvania Transportation Institute's test track facility near the University Park airport. After modification and optimization of the system on the bus, operation on the campus shuttle route began in early June 2002. However, the work and challenges continued as it has been difficult to maintain operability of the shuttle bus due to fuel and component difficulties. In late June 2002, the pump head itself developed operational problems (loss of smooth function) leading to excessive stress on the magnetic coupling and excessive current draw to operate. A new pump head was installed on the system to alleviate this problem and the shuttle bus operated successfully on DME blends from 10-25 vol% on the shuttle bus loop until September 30, 2002. During the period of operation on the campus loop, the bus was pulled from service, operated at the PTI test track and real-time emissions measurements were obtained using an on-board emissions analyzer from Clean Air Technologies International, Inc. Particulate emissions reductions of 60% and 80% were observed at DME blend ratios of 12 vol.% and 25 vol.%, respectively, as the bus was operated over the Orange County driving cycle. Increases in NOx, CO and HC emissions were observed, however. In summary, the conversion of the shuttle bus was successfully accomplished, particulate emissions reductions were observed, but there were operational challenges in the field. Nonetheless, they were able to demonstrate reliable operation of the shuttle bus on DME-diesel blends.

  13. 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}.

  14. DIMETHYL ETHER (DME)-FUELED SHUTTLE BUS DEMONSTRATION PROJECT

    SciTech Connect (OSTI)

    Elana M. Chapman; Shirish Bhide; Jennifer Stefanik; Howard Glunt; Andre L. Boehman; Allen Homan; David Klinikowski

    2003-04-01

    The objectives of this research and demonstration program are to convert a campus shuttle bus to operation on dimethyl ether, a potential ultra-clean alternative diesel fuel. To accomplish this objective, this project includes laboratory evaluation of a fuel conversion strategy, as well as, field demonstration of the DME-fueled shuttle bus. Since DME is a fuel with no lubricity (i.e., it does not possess the lubricating quality of diesel fuel), conventional fuel delivery and fuel injection systems are not compatible with dimethylether. Therefore, to operate a diesel engine on DME one must develop a fuel-tolerant injection system, or find a way to provide the necessary lubricity to the DME. In this project, they have chosen the latter strategy in order to achieve the objective with minimal need to modify the engine. The strategy is to blend DME with diesel fuel, to obtain the necessary lubricity to protect the fuel injection system and to achieve low emissions. The bulk of the efforts over the past year were focused on the conversion of the campus shuttle bus. This process, started in August 2001, took until April 2002 to complete. The process culminated in an event to celebrate the launching of the shuttle bus on DME-diesel operation on April 19, 2002. The design of the system on the shuttle bus was patterned after the system developed in the engine laboratory, but also was subjected to a rigorous failure modes effects analysis with help from Dr. James Hansel of Air Products. The result of this FMEA was the addition of layers of redundancy and over-pressure protection to the system on the shuttle bus. The system became operation in February 2002. Preliminary emissions tests and basic operation of the shuttle bus took place at the Pennsylvania Transportation institute's test track facility near the University Park airport. After modification and optimization of the system on the bus, operation on the campus shuttle route began in early June 2002. However, the work and challenges have continued as it has been difficult to maintain operability of the shuttle bus due to fuel and component difficulties. As of late June 2002, it appears that the pump head itself developed operational problems (loss of smooth function) leading to excessive stress on the magnetic coupling and excessive current draw to operate. A new pump head is being installed on the system to alleviate this problem and get the shuttle bus back in operation. In summary, the conversion is completed but there have been operational challenges in the field. They continue to work to make the shuttle bus as reliable to operate on DME-diesel blends as possible.

  15. MOF-based catalysts for selective hydrogenolysis of carbonoxygen ether bonds

    SciTech Connect (OSTI)

    Stavila, Vitalie; Parthasarathi, Ramakrishnan; Davis, Ryan W.; El Gabaly, Farid; Sale, Kenneth L.; Simmons, Blake A.; Singh, Seema; Allendorf, Mark D.

    2015-11-23

    We demonstrate that metalorganic frameworks (MOFs) can catalyze hydrogenolysis of aryl ether bonds under mild conditions. Mg-IRMOF-74(I) and Mg-IRMOF-74(II) are stable under reducing conditions and can cleave phenyl ethers containing ?-O-4, ?-O-4, and 4-O-5 linkages to the corresponding hydrocarbons and phenols. Reaction occurs at 10 bar H2 and 120 C without added base. DFT-optimized structures and charge transfer analysis suggest that the MOF orients the substrate near Mg2+ ions on the pore walls. Ti and Ni doping further increase conversions to as high as 82% with 96% selectivity for hydrogenolysis versus ring hydrogenation. Thus repeated cycling induces no loss of activity, making this a promising route for mild aryl-ether bond scission.

  16. MOF-based catalysts for selective hydrogenolysis of carbon–oxygen ether bonds

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

    Stavila, Vitalie; Parthasarathi, Ramakrishnan; Davis, Ryan W.; El Gabaly, Farid; Sale, Kenneth L.; Simmons, Blake A.; Singh, Seema; Allendorf, Mark D.

    2015-11-23

    We demonstrate that metal–organic frameworks (MOFs) can catalyze hydrogenolysis of aryl ether bonds under mild conditions. Mg-IRMOF-74(I) and Mg-IRMOF-74(II) are stable under reducing conditions and can cleave phenyl ethers containing β-O-4, α-O-4, and 4-O-5 linkages to the corresponding hydrocarbons and phenols. Reaction occurs at 10 bar H2 and 120 °C without added base. DFT-optimized structures and charge transfer analysis suggest that the MOF orients the substrate near Mg2+ ions on the pore walls. Ti and Ni doping further increase conversions to as high as 82% with 96% selectivity for hydrogenolysis versus ring hydrogenation. Thus repeated cycling induces no loss ofmore » activity, making this a promising route for mild aryl-ether bond scission.« less

  17. 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.

  18. 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.

  19. Catalyst system and process for benzyl ether fragmentation and coal liquefaction

    DOE Patents [OSTI]

    Zoeller, Joseph Robert (Kingsport, TN)

    1998-04-28

    Dibenzyl ether can be readily cleaved to form primarily benzaldehyde and toluene as products, along with minor amounts of bibenzyl and benzyl benzoate, in the presence of a catalyst system comprising a Group 6 metal, preferably molybdenum, a salt, and an organic halide. Although useful synthetically for the cleavage of benzyl ethers, this cleavage also represents a key model reaction for the liquefaction of coal; thus this catalyst system and process should be useful in coal liquefaction with the advantage of operating at significantly lower temperatures and pressures.

  20. 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.

  1. 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.

  2. APPLICATIONS OF LAYERED DOUBLE HYDROXIDES IN REMOVING OXYANIONS FROM OIL REFINING AND COAL MINING WASTEWATER

    SciTech Connect (OSTI)

    Song Jin; Paul Fallgren

    2006-03-01

    Western Research Institute (WRI), in conjunction with the U.S. Department of Energy (DOE), conducted a study of using the layered double hydroxides (LDH) as filter material to remove microorganisms, large biological molecules, certain anions and toxic oxyanions from various waste streams, including wastewater from refineries. Results demonstrate that LDH has a high adsorbing capability to those compounds with negative surface charge. Constituents studied include model bacteria, viruses, arsenic, selenium, vanadium, diesel range hydrocarbons, methyl tert-butyl ether (MTBE), mixed petroleum constituents, humic materials and anions. This project also attempted to modify the physical structure of LDH for the application as a filtration material. Flow characterizations of the modified LDH materials were also investigated. Results to date indicate that LDH is a cost-effective new material to be used for wastewater treatment, especially for the treatment of anions and oxyanions.

  3. 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.

  4. 1

    Office of Environmental Management (EM)

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

  5. 1

    Office of Environmental Management (EM)

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

  6. 1

    Office of Environmental Management (EM)

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

  7. 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.

  8. 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.

  9. Molecular modeling of the morphology and transport properties of two direct methanol fuel cell membranes: phenylated sulfonated poly(ether ether ketone ketone) versus Nafion

    SciTech Connect (OSTI)

    Devanathan, Ramaswami; Idupulapati, Nagesh B.; Dupuis, Michel

    2012-08-14

    We have used molecular dynamics simulations to examine membrane morphology and the transport of water, methanol and hydronium in phenylated sulfonated poly ether ether ketone ketone (Ph-SPEEKK) and Nafion membranes at 360 K for a range of hydration levels. At comparable hydration levels, the pore diameter is smaller, the sulfonate groups are more closely packed, the hydronium ions are more strongly bound to sulfonate groups, and the diffusion of water and hydronium is slower in Ph-SPEEKK relative to the corresponding properties in Nafion. The aromatic carbon backbone of Ph-SPEEKK is less hydrophobic than the fluorocarbon backbone of Nafion. Water network percolation occurs at a hydration level ({lambda}) of {approx}8 H{sub 2}O/SO{sub 3}{sup -}. At {lambda} = 20, water, methanol and hydronium diffusion coefficients were 1.4 x 10{sup -5}, 0.6 x 10{sup -5} and 0.2 x 10{sup -5} cm{sup 2}/s, respectively. The pore network in Ph-SPEEKK evolves dynamically and develops wide pores for {lambda} > 20, which leads to a jump in methanol crossover and ion transport. This study demonstrates the potential of aromatic membranes as low-cost challengers to Nafion for direct methanol fuel cell applications and the need to develop innovative strategies to combat methanol crossover at high hydration levels.

  10. 2[prime] and 3[prime] Carboranyl uridines and their diethyl ether adducts

    DOE Patents [OSTI]

    Soloway, A.H.; Barth, R.F.; Anisuzzaman, A.K.; Alam, F.; Tjarks, W.

    1992-12-15

    A process is described for preparing carboranyl uridine nucleoside compounds and their diethyl ether adducts, which exhibit a tenfold increase in boron content over prior art boron containing nucleoside compounds. The carboranyl uridine nucleoside compounds exhibit enhanced lipophilicity and hydrophilic properties adequate to enable solvation in aqueous media for subsequent incorporation of the compounds in methods for boron neutron capture therapy in mammalian tumor cells. No Drawings

  11. Barrierless proton transfer across weak CH?O hydrogen bonds in dimethyl ether dimer

    SciTech Connect (OSTI)

    Yoder, Bruce L. West, Adam H. C.; Signorell, Ruth; Bravaya, Ksenia B.; Bodi, Andras; Sztray, Blint

    2015-03-21

    We present a combined computational and threshold photoelectron photoion coincidence study of two isotopologues of dimethyl ether, (DME ? h{sub 6}){sub n} and (DME ? d{sub 6}){sub n}n = 1 and 2, in the 914 eV photon energy range. Multiple isomers of neutral dimethyl ether dimer were considered, all of which may be present, and exhibited varying CH?O interactions. Results from electronic structure calculations predict that all of them undergo barrierless proton transfer upon photoionization to the ground electronic state of the cation. In fact, all neutral isomers were found to relax to the same radical cation structure. The lowest energy dissociative photoionization channel of the dimer leads to CH{sub 3}OHCH{sub 3}{sup +} by the loss of CH{sub 2}OCH{sub 3} with a 0 K appearance energy of 9.71 0.03 eV and 9.73 0.03 eV for (DME ? h{sub 6}){sub 2} and deuterated (DME ? d{sub 6}){sub 2}, respectively. The ground state threshold photoelectron spectrum band of the dimethyl ether dimer is broad and exhibits no vibrational structure. Dimerization results in a 350 meV decrease of the valence band appearance energy, a 140 meV decrease of the band maximum, thus an almost twofold increase in the ground state band width, compared with DME ? d{sub 6} monomer.

  12. 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.

  13. 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.

  14. Improvement of performance and emissions of a compression ignition methanol engine with dimethyl ether

    SciTech Connect (OSTI)

    Guo, J.; Chikahisa, Takemi; Murayama, Tadashi; Miyano, Masaharu

    1994-10-01

    Dimethyl ether (DME) has very good compression ignition characteristics and can be converted from methanol using a {gamma}-alumina catalyst. In this study a torch ignition chamber (TIC) head with TIC close to the center of the main combustion chamber was designed for the TIC method. The possibility of improvements in reducing the quantities of DME and emission were investigated by optimizing the TIC position, methanol injection timing, DME injection timing, and intake and exhaust throttling. It was found that the necessary amount of DME was greatly reduced when optimizing methanol and DME injection timings. 2 refs., 16 figs., 1 tab.

  15. A laser and molecular beam mass spectrometer study of low-pressure dimethyl ether flames

    SciTech Connect (OSTI)

    Andrew McIlroy; Toby D. Hain; Hope A. Michelsen; Terrill A. Cool

    2000-12-15

    The oxidation of dimethyl ether (DME) is studied in low-pressure flames using new molecular beam mass spectrometer and laser diagnostics. Two 30.0-Torr, premixed DME/oxygen/argon flames are investigated with stoichiometries of 0.98 and 1.20. The height above burner profiles of nine stable species and two radicals are measured. These results are compared to the detailed chemical reaction mechanism of Curran and coworkers. Generally good agreement is found between the model and data. The largest discrepancies are found for the methyl radical profiles where the model predicts qualitatively different trends in the methyl concentration with stoichiometry than observed in the experiment.

  16. Assessing the toxic effects of ethylene glycol ethers using Quantitative Structure Toxicity Relationship models

    SciTech Connect (OSTI)

    Ruiz, Patricia; Mumtaz, Moiz; Gombar, Vijay

    2011-07-15

    Experimental determination of toxicity profiles consumes a great deal of time, money, and other resources. Consequently, businesses, societies, and regulators strive for reliable alternatives such as Quantitative Structure Toxicity Relationship (QSTR) models to fill gaps in toxicity profiles of compounds of concern to human health. The use of glycol ethers and their health effects have recently attracted the attention of international organizations such as the World Health Organization (WHO). The board members of Concise International Chemical Assessment Documents (CICAD) recently identified inadequate testing as well as gaps in toxicity profiles of ethylene glycol mono-n-alkyl ethers (EGEs). The CICAD board requested the ATSDR Computational Toxicology and Methods Development Laboratory to conduct QSTR assessments of certain specific toxicity endpoints for these chemicals. In order to evaluate the potential health effects of EGEs, CICAD proposed a critical QSTR analysis of the mutagenicity, carcinogenicity, and developmental effects of EGEs and other selected chemicals. We report here results of the application of QSTRs to assess rodent carcinogenicity, mutagenicity, and developmental toxicity of four EGEs: 2-methoxyethanol, 2-ethoxyethanol, 2-propoxyethanol, and 2-butoxyethanol and their metabolites. Neither mutagenicity nor carcinogenicity is indicated for the parent compounds, but these compounds are predicted to be developmental toxicants. The predicted toxicity effects were subjected to reverse QSTR (rQSTR) analysis to identify structural attributes that may be the main drivers of the developmental toxicity potential of these compounds.

  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. Catalyst activity maintenance study for the liquid phase dimethyl ether process

    SciTech Connect (OSTI)

    Peng, X.D.; Toseland, B.A.; Underwood, R.P.

    1995-12-31

    The co-production of dimethyl ether (DME) and methanol from syngas is a process of considerable commercial attractiveness. DME coproduction can double the productivity of a LPMEOH process when using coal-derived syngas. This in itself may offer chemical producers and power companies increased flexibility and more profitable operation. DME is also known as a clean burning liquid fuel; Amoco and Haldor-Topsoe have recently announced the use of DME as an alternative diesel fuel. Moreover, DME can be an interesting intermediate in the production of chemicals such as olefins and vinyl acetate. The current APCl liquid phase dimethyl ether (LPDME) process utilizes a physical mixture of a commercial methanol synthesis catalyst and a dehydration catalyst (e.g., {gamma}-alumina). While this arrangement provides a synergy that results in much higher syngas conversion per pass compared to the methanol-only process, the stability of the catalyst system suffers. The present project is aimed at reducing catalyst deactivation both by understanding the cause(s) of catalyst deactivation and by developing modified catalyst systems. This paper describes the current understanding of the deactivation mechanism.

  19. 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.

  20. 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.

  1. 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.

  2. Use of aluminum phosphate as the dehydration catalyst in single step dimethyl ether process

    DOE Patents [OSTI]

    Peng, Xiang-Dong (Allentown, PA); Parris, Gene E. (Coopersburg, PA); Toseland, Bernard A. (Allentown, PA); Battavio, Paula J. (Allentown, PA)

    1998-01-01

    The present invention pertains to a process for the coproduction of methanol and dimethyl ether (DME) directly from a synthesis gas in a single step (hereafter, the "single step DME process"). In this process, the synthesis gas comprising hydrogen and carbon oxides is contacted with a dual catalyst system comprising a physical mixture of a methanol synthesis catalyst and a methanol dehydration catalyst. The present invention is an improvement to this process for providing an active and stable catalyst system. The improvement comprises the use of an aluminum phosphate based catalyst as the methanol dehydration catalyst. Due to its moderate acidity, such a catalyst avoids the coke formation and catalyst interaction problems associated with the conventional dual catalyst systems taught for the single step DME process.

  3. Process for the production of ethylidene diacetate from dimethyl ether using a heterogeneous catalyst

    DOE Patents [OSTI]

    Ramprasad, D.; Waller, F.J.

    1998-04-28

    This invention relates to a process for producing ethylidene diacetate by the reaction of dimethyl ether, acetic acid, hydrogen and carbon monoxide at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that is stable to hydrogenation and comprises an insoluble polymer having pendant quaternized heteroatoms, some of which heteroatoms are ionically bonded to anionic Group VIII metal complexes, the remainder of the heteroatoms being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for 3 consecutive runs without loss in activity.

  4. Process for the production of ethylidene diacetate from dimethyl ether using a heterogeneous catalyst

    DOE Patents [OSTI]

    Ramprasad, Dorai (Allentown, PA); Waller, Francis Joseph (Allentown, PA)

    1998-01-01

    This invention relates to a process for producing ethylidene diacetate by the reaction of dimethyl ether, acetic acid, hydrogen and carbon monoxide at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that is stable to hydrogenation and comprises an insoluble polymer having pendant quaternized heteroatoms, some of which heteroatoms are ionically bonded to anionic Group VIII metal complexes, the remainder of the heteroatoms being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for 3 consecutive runs without loss in activity.

  5. Using Heteropolyacids in the Anode Catalyst Layer of Dimethyl Ether PEM Fuel Cells

    SciTech Connect (OSTI)

    Ferrell III, J. R.; Turner, J. A.; Herring, A. M.

    2008-01-01

    In this study, polarization experiments were performed on a direct dimethyl ether fuel cell (DMEFC). The experimental setup allowed for independent control of water and DME flow rates. Thus the DME flow rate, backpressure, and water flow rate were optimized. Three heteropoly acids, phosphomolybdic acid (PMA), phosphotungstic acid (PTA), and silicotungstic acid (STA) were incorporated into the anode catalyst layer in combination with Pt/C. Both PTA-Pt and STA-Pt showed higher performance than the Pt control at 30 psig of backpressure. Anodic polarizations were also performed, and Tafel slopes were extracted from the data. The trends in the Tafel slope values are in agreement with the polarization data. The addition of phosphotungstic acid more than doubled the power density of the fuel cell, compared to the Pt control.

  6. Methanol with dimethyl ether ignition promotor as fuel for compression ignition engines

    SciTech Connect (OSTI)

    Brook, D.L.; Cipolat, D.; Rallis, C.J.

    1984-08-01

    Reduction of the world dependence upon crude oil necessitates the use of long term alternative fuels for internal combustion engines. Alcohols appear to offer a solution as in the short term they can be manufactured from natural gas and coal, while ultimately they may be produced from agricultural products. A fair measure of success has been achieved in using alcohols in spark ignition engines. However the more widely used compression ignition engines cannot utilize unmodified pure alcohols. The current techniques for using alcohol fuels in compression ignition engines all have a number of shortcomings. This paper describes a novel technique where an ignition promotor, dimethyl ether (DME), is used to increase the cetane rating of methanol. The systems particular advantage is that the DME can be catalyzed from the methanol base fuel, in situ. This fuel system matches the performance characteristics of diesel oil fuel.

  7. Hydrogen production from the steam reforming of Dinethyl Ether and Methanol

    SciTech Connect (OSTI)

    Semelsberger, T. A.; Borup, R. L.

    2004-01-01

    This study investigates dimethyl ether (DME) steam reforming for the generation of hydrogen rich fuel cell feeds for fuel cell applications. Methanol has long been considered as a fuel for the generation of hydrogen rich fuel cell feeds due to its high energy density, low reforming temperature, and zero impurity content. However, it has not been accepted as the fuel of choice due its current limited availability, toxicity and corrosiveness. While methanol steam reforming for the generation of hydrogen rich fuel cell feeds has been extensively studied, the steam reforming of DME, CH{sub 3}OCH{sub 3} + 3H{sub 2}O = 2CO{sub 2} + 6H{sub 2}, has had limited research effort. DME is the simplest ether (CH{sub 3}OCH{sub 3}) and is a gas at ambient conditions. DME has physical properties similar to those of LPG fuels (i.e. propane and butane), resulting in similar storage and handling considerations. DME is currently used as an aerosol propellant and has been considercd as a diesel substitute due to the reduced NOx, SOx and particulate emissions. DME is also being considered as a substitute for LPG fuels, which is used extensively in Asia as a fuel for heating and cooking, and naptha, which is used for power generation. The potential advantages of both methanol and DME include low reforming temperature, decreased fuel proccssor startup energy, environmentally benign, visible flame, high heating value, and ease of storage and transportation. In addition, DME has the added advantages of low toxicity and being non-corrosive. Consequently, DME may be an ideal candidate for the generation of hydrogen rich fuel cell feeds for both automotive and portable power applications. The steam reforming of DME has been demonstrated to occur through a pair of reactions in series, where the first reaction is DME hydration followed by MeOH steam reforming to produce a hydrogen rich stream.

  8. 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.

  9. The use of dimethyl ether as a starting aid for methanol-fueled SI engines at low temperatures

    SciTech Connect (OSTI)

    Kozole, K.H.; Wallace, J.S

    1988-01-01

    Methanol-fueled SI engines have proven to be difficult to start at ambient temperatures below approximately 10/sup 0/C. The use of dimethyl ether (DME) is proposed to improve the cold starting performance of methanol-fueled SI engines. Tests to evaluate this idea were carried out with a modified single-cylinder CFR research engine having a compression ratio of 12:1. The engine was fueled with combinations of gaseous dimethyl ether and liquid methanol having DME mass fractions of 30%, 40%, 60% and 70%. For comparison, tests were also carried out with 100% methanol and with winter grade premium unleaded gasoline. Overall stoichiometric mixtures were used in all tests.

  10. Synthesis of dimethyl ether and alternative fuels in the liquid phase from coal-derived synthesis gas. Final technical report

    SciTech Connect (OSTI)

    Not Available

    1993-02-01

    Through the mid-1980s, Air Products has brought the liquid phase approach to a number of other synthesis gas reactions where effective heat management is a key issue. In 1989, in response to DOE`s PRDA No. DE-RA22-88PC88805, Air Products proposed a research and development program entitled ``Synthesis of Dimethyl Ether and Alternative Fuels in the Liquid Phase from Coal Derived Syngas.`` The proposal aimed at extending the LPMEOH experience to convert coal-derived synthesis gas to other useful fuels and chemicals. The work proposed included development of a novel one-step synthesis of dimethyl ether (DME) from syngas, and exploration of other liquid phase synthesis of alternative fuel directly from syngas. The one-step DME process, conceived in 1986 at Air Products as a means of increasing syngas conversion to liquid products, envisioned the concept of converting product methanol in situ to DME in a single reactor. The slurry reactor based liquid phase technology is ideally suited for such an application, since the second reaction (methanol to DME) can be accomplished by adding a second catalyst with dehydration activity to the methanol producing reactor. An area of exploration for other alternative fuels directly from syngas was single-step slurry phase synthesis of hydrocarbons via methanol and DME as intermediates. Other possibilities included the direct synthesis of mixed alcohols and mixed ethers in a slurry reactor.

  11. Direct Numerical Simulations of Autoignition in Stratified Dimethyl-ether (DME)/Air Turbulent Mixtures

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

    Bansal, Gaurav; Mascarenhas, Ajith; Chen, Jacqueline H.

    2014-10-01

    In our paper, two- and three-dimensional direct numerical simulations (DNS) of autoignition phenomena in stratified dimethyl-ether (DME)/air turbulent mixtures are performed. A reduced DME oxidation mechanism, which was obtained using rigorous mathematical reduction and stiffness removal procedure from a detailed DME mechanism with 55 species, is used in the present DNS. The reduced DME mechanism consists of 30 chemical species. This study investigates the fundamental aspects of turbulence-mixing-autoignition interaction occurring in homogeneous charge compression ignition (HCCI) engine environments. A homogeneous isotropic turbulence spectrum is used to initialize the velocity field in the domain. Moreover, the computational configuration corresponds to amore » constant volume combustion vessel with inert mass source terms added to the governing equations to mimic the pressure rise due to piston motion, as present in practical engines. DME autoignition is found to be a complex three-staged process; each stage corresponds to a distinct chemical kinetic pathway. The distinct role of turbulence and reaction in generating scalar gradients and hence promoting molecular transport processes are investigated. Then, by applying numerical diagnostic techniques, the different heat release modes present in the igniting mixture are identified. In particular, the contribution of homogeneous autoignition, spontaneous ignition front propagation, and premixed deflagration towards the total heat release are quantified.« less

  12. Direct Numerical Simulations of Autoignition in Stratified Dimethyl-ether (DME)/Air Turbulent Mixtures

    SciTech Connect (OSTI)

    Bansal, Gaurav; Mascarenhas, Ajith; Chen, Jacqueline H.

    2014-10-01

    In our paper, two- and three-dimensional direct numerical simulations (DNS) of autoignition phenomena in stratified dimethyl-ether (DME)/air turbulent mixtures are performed. A reduced DME oxidation mechanism, which was obtained using rigorous mathematical reduction and stiffness removal procedure from a detailed DME mechanism with 55 species, is used in the present DNS. The reduced DME mechanism consists of 30 chemical species. This study investigates the fundamental aspects of turbulence-mixing-autoignition interaction occurring in homogeneous charge compression ignition (HCCI) engine environments. A homogeneous isotropic turbulence spectrum is used to initialize the velocity field in the domain. Moreover, the computational configuration corresponds to a constant volume combustion vessel with inert mass source terms added to the governing equations to mimic the pressure rise due to piston motion, as present in practical engines. DME autoignition is found to be a complex three-staged process; each stage corresponds to a distinct chemical kinetic pathway. The distinct role of turbulence and reaction in generating scalar gradients and hence promoting molecular transport processes are investigated. Then, by applying numerical diagnostic techniques, the different heat release modes present in the igniting mixture are identified. In particular, the contribution of homogeneous autoignition, spontaneous ignition front propagation, and premixed deflagration towards the total heat release are quantified.

  13. A fluorescence-based method for rapid and direct determination of polybrominated diphenyl ethers in water

    SciTech Connect (OSTI)

    Shan, Huimei; Liu, Chongxuan; Wang, Zheming; Ma, Teng; Shang, Jianying; Pan, Duoqiang

    2015-01-01

    A new method was developed for rapid and direct measurement of polybrominated diphenyl ethers (PBDEs) in aqueous samples using fluorescence spectroscopy. The fluorescence spectra of tri- to deca-BDE (BDE 28, 47, 99, 153, 190, and 209) commonly found in environment were measured at variable emission and excitation wavelengths. The results revealed that the PBDEs have distinct fluorescence spectral profiles and peak positions that can be exploited to identify these species and determine their concentrations in aqueous solutions. The detection limits as determined in deionized water spiked with PBDEs are 1.71-5.82 ng/L for BDE 28, BDE 47, BDE 190, and BDE 209 and 45.5569.95 ng/L for BDE 99 and BDE 153. The effects of environmental variables including pH, humic substance, and groundwater chemical composition on PBDEs measurements were also investigated. These environmental variables affected fluorescence intensity, but their effect can be corrected through linear additivity and separation of spectral signal contribution. Compared with conventional GC-based analytical methods, the fluorescence spectroscopy method is more efficient as it only uses a small amount of samples (2-4 mL), avoids lengthy complicated concentration and extraction steps, and has a low detection limit of a few ng/L.

  14. Hydrogen-bonding interactions and protic equilibria in room-temperature ionic liquids containing crown ethers.

    SciTech Connect (OSTI)

    Marin, T.; Shkrob, I.; Dietz, M.

    2011-04-14

    Nuclear magnetic resonance (NMR) spectroscopy has been used to study hydrogen-bonding interactions between water, associated and dissociated acids (i.e., nitric and methanesulfonic acids), and the constituent ions of several water-immiscible room-temperature ionic liquids (ILs). In chloroform solutions also containing a crown ether (CE), water molecules strongly associate with the IL ions, and there is rapid proton exchange between these bound water molecules and hydronium associated with the CE. In neat ILs, the acids form clusters differing in their degree of association and ionization, and their interactions with the CEs are weak. The CE can either promote proton exchange between different clusters in IL solution when their association is weak or inhibit such exchange when the association is strong. Even strongly hydrophobic ILs are shown to readily extract nitric acid from aqueous solution, typically via the formation of a 1:1:1 {l_brace}H{sub 3}O{sup +} {center_dot} CE{r_brace}NO{sub 3}{sup -} complex. In contrast, the extraction of methanesulfonic acid is less extensive and proceeds mainly by IL cation-hydronium ion exchange. The relationship of these protic equilibria to the practical application of hydrophobic ILs (e.g., in spent nuclear fuel reprocessing) is discussed.

  15. A fluorescence-based method for rapid and direct determination of polybrominated diphenyl ethers in water

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

    Shan, Huimei; Liu, Chongxuan; Wang, Zheming; Ma, Teng; Shang, Jianying; Pan, Duoqiang

    2015-01-01

    A new method was developed for rapid and direct measurement of polybrominated diphenyl ethers (PBDEs) in aqueous samples using fluorescence spectroscopy. The fluorescence spectra of tri- to deca-BDE (BDE 28, 47, 99, 153, 190, and 209) commonly found in environment were measured at variable emission and excitation wavelengths. The results revealed that the PBDEs have distinct fluorescence spectral profiles and peak positions that can be exploited to identify these species and determine their concentrations in aqueous solutions. The detection limits as determined in deionized water spiked with PBDEs are 1.71-5.82 ng/L for BDE 28, BDE 47, BDE 190, and BDEmore » 209 and 45.55–69.95 ng/L for BDE 99 and BDE 153. The effects of environmental variables including pH, humic substance, and groundwater chemical composition on PBDEs measurements were also investigated. These environmental variables affected fluorescence intensity, but their effect can be corrected through linear additivity and separation of spectral signal contribution. Compared with conventional GC-based analytical methods, the fluorescence spectroscopy method is more efficient as it only uses a small amount of samples (2-4 mL), avoids lengthy complicated concentration and extraction steps, and has a low detection limit of a few ng/L.« less

  16. New clean fuel from coal -- Direct dimethyl ether synthesis from hydrogen and carbon monoxide

    SciTech Connect (OSTI)

    Ogawa, T.; Ono, M.; Mizuguchi, M.; Tomura, K.; Shikada, T.; Ohono, Y.; Fujimoto, K.

    1997-12-31

    Dimethyl ether (DME), which has similar physical properties to propane and is easily liquefied at low pressure, has a significant possibility as a clean and non-toxic fuel from coal or coal bed methane. Equilibrium calculation also shows a big advantage of high carbon monoxide conversion of DME synthesis compared to methanol synthesis. By using a 50 kg/day DME bench scale test plant, direct synthesis of DME from hydrogen and carbon monoxide has been studied with newly developed catalysts which are very fine particles. This test plant features a high pressure three-phase slurry reactor and low temperature DME separator. DME is synthesized at temperatures around 533--553 K and at pressures around 3--5 MPa. According to the reaction stoichiometry, the same amount of hydrogen and carbon monoxide react to DME and carbon dioxide. Carbon conversion to DME is one third and the rest of carbon is converted to carbon dioxide. As a result of the experiments, make-up CO conversion is 35--50% on an once-through basis, which is extremely high compared to that of methanol synthesis from hydrogen and carbon monoxide. DME selectivity is around 60 c-mol %. Most of the by-product is CO{sub 2} with a small amount of methanol and water. No heavy by-products have been recognized. Effluent from the reactor is finally cooled to 233--253 K in a DME separator and liquid DME is recovered as a product.

  17. Study on systems based on coal and natural gas for producing dimethyl ether

    SciTech Connect (OSTI)

    Zhou, L.; Hu, S.Y.; Chen, D.J.; Li, Y.R.; Zhu, B.; Jin, Y.

    2009-04-15

    China is a coal-dependent country and will remain so for a long time. Dimethyl ether (DME), a potential substitute for liquid fuel, is a kind of clean diesel motor fuel. The production of DME from coal is meaningful and is studied in this article. Considering the C/H ratios of coal and natural gas (NG), the cofeed (coal and NG) system (CFS), which does not contain the water gas shift process, is studied. It can reduce CO{sub 2} emission and increase the conversion rate of carbon, producing more DME. The CFS is simulated and compared with the coal-based and NG-based systems with different recycling ratios. The part of the exhaust gas that is not recycled is burned, producing electricity. On the basis of the simulation results, the thermal efficiency, economic index, and CO{sub 2} emission ratio are calculated separately. The CFS with a 100% recycling ratio has the best comprehensive evaluation index, while the energy, economy, and environment were considered at the same time.

  18. Experimental and Computational Study of Nonpremixed Ignition of Dimethyl Ether in Counterflow

    SciTech Connect (OSTI)

    Zheng, X L; Lu, T F; Law, C K; Westbrook, C K

    2003-12-19

    The ignition temperature of nitrogen-diluted dimethyl ether (DME) by heated air in counterflow was experimentally determined for DME concentration from 5.9 to 30%, system pressure from 1.5 to 3.0 atmospheres, and pressure-weighted strain rate from 110 to 170/s. These experimental data were compared with two mechanisms that were respectively available in 1998 and 2003, with the latter being a substantially updated version of the former. The comparison showed that while the 1998-mechanism uniformly over-predicted the ignition temperature, the 2003-mechanism yielded surprisingly close agreement for all experimental data. Sensitivity analysis for the near-ignition state based on both mechanisms identified the deficiencies of the 1998-mechanism, particularly the specifics of the low-temperature cool flame chemistry in effecting ignition at higher temperatures, as the fuel stream is being progressively heated from its cold boundary to the high-temperature ignition region around the hot-stream boundary. The 2003-mechanism, consisting of 79 species and 398 elementary reactions, was then systematically simplified by using the directed relation graph method to a skeletal mechanism of 49 species and 251 elementary reactions, which in turn was further simplified by using computational singular perturbation method and quasi-steady-state species assumption to a reduced mechanism consisting of 33 species and 28 lumped reactions. It was demonstrated that both the skeletal and reduced mechanisms mimicked the performance of the detailed mechanism with high accuracy.

  19. Slurry phase synthesis of dimethyl ether from syngas -- A reactor model simulation

    SciTech Connect (OSTI)

    Mizuguchi, Masatsugu; Ogawa, Takashi; Ono, Masami,; Tomura, Keiji; Shikada, Tsutomu; Ohno, Yotaro; Fujimoto, Kaoru

    1998-12-31

    Dimethyl ether (DME) would be an attractive alternative fuel for diesel, domestic use, and power generation, if it is economically synthesized directly from syngas (derived from coal gasification or natural gas reforming). DME, which is a colorless gas with a boiling point of {minus}25 C, is chemically stable and easily liquefied under pressure. Since the properties of DME are similar to LPG, it can be handled and stored with the same manner as LPG. The authors have performed the slurry phase DME synthesis by using the 50 kg/day bench-scale unit. DME was synthesized at high yield from syngas (H{sub 2}+CO) with the newly developed catalyst system. To establish the scale-up methodology, the reactor simulation technique is essential. The authors developed a mathematical model of the slurry phase bubble column reactor for DME synthesis, which is based on their experimental results. The performance of a commercial-scale DME reactor was simulated by this model, and the results were discussed.

  20. Mechanistic Investigation of Acid-Catalyzed Cleavage of Aryl-Ether Linkages: Implications for Lignin Depolymerization

    SciTech Connect (OSTI)

    Sturgeon, M. R.; Kim, S.; Chmely, S. C.; Foust, T. D.; Beckham, G. T.

    2013-01-01

    Carbon-oxygen bonds are the primary inter-monomer linkages lignin polymers in plant cell walls, and as such, catalyst development to cleave these linkages is of paramount importance to deconstruct biomass to its constituent monomers for the production of renewable fuels and chemicals. For many decades, acid catalysis has been used to depolymerize lignin. Lignin is a primary component of plant cell walls, which is connected primarily by aryl-ether linkages, and the mechanism of its deconstruction by acid is not well understood, likely due to its heterogeneous and complex nature compared to cellulose. For effective biomass conversion strategies, utilization of lignin is of significant relevance and as such understanding the mechanisms of catalytic lignin deconstruction to constituent monomers and oligomers is of keen interest. Here, we present a comprehensive experimental and theoretical study of the acid catalysis of a range of dimeric species exhibiting the b-O-4 linkage, the most common inter-monomer linkage in lignin. We demonstrate that the presence of a phenolic species dramatically increases the rate of cleavage in acid at 150 degrees C. Quantum mechanical calculations on dimers with the para-hydroxyl group demonstrate that this acid-catalyzed pathway differs from the nonphenolic dimmers. Importantly, this result implies that depolymerization of native lignin in the plant cell wall will proceed via an unzipping mechanism wherein b-O-4 linkages will be cleaved from the ends of the branched, polymer chains inwards toward the center of the polymer. To test this hypothesis further, we synthesized a homopolymer of b-O-4 with a phenolic hydroxyl group, and demonstrate that it is cleaved in acid from the end containing the phenolic hydroxyl group. This result suggests that genetic modifications to lignin biosynthesis pathways in plants that will enable lower severity processes to fractionate lignin for upgrading and for easier access to the carbohydrate fraction of the plant cell wall.

  1. ULEV potential of a DI/TCI diesel passenger car engine operated on dimethyl ether

    SciTech Connect (OSTI)

    Kapus, P.E.; Cartellieri, W.P.

    1995-12-31

    This paper describes a feasibility test program on a 2 liter, 4 cylinder DI/TCI passenger car engine operated on the new alternative fuel Dimethyl Ether (DME) with the aim of demonstrating its potential of meeting ULEV (ultra low emission vehicle) emissions (0.2 g/mi NOx in the FTP 75 test cycle) when installed in a full size passenger car. Special attention is drawn to the fuel injection equipment (FIE) as well as combustion system requirements towards the reduction of NOx and combustion noise while keeping energetic fuel consumption at the level of he baseline DI/TCI diesel engine. FIE and combustion system parameters were optimized on the steady state dynamometer by variation of a number of parameters, such as rate of injection, number of nozzle holes, compression ratio, piston bowl shape and exhaust gas recirculation. The paper presents engine test results achieved with DME under various operating conditions and compares these results to those achieved with the diesel version of the same engine.The FTP 75 cycle results were projected from steady state engine maps using a vehicle simulation program taking into account vehicle data and road resistance data of a given vehicle.The cycle results are also compared to actual chassis dynamometer results achieved with the diesel version of the same engine installed in the same vehicle.the passenger car DI/TCI engine adapted for and operated on DME shows very promising results with respect to meeting ULEV NOx emissions without any soot emissions and without the need for a DENOX catalyst. DME fuel consumption on energy basis can be kept very close to the DI diesel value. An oxidation catalyst will be necessary to meet the stringent CO and HC ULEV emission limits.

  2. Ligand-Thickness Effect Leads to Enhanced Preference for Large Anions in Alkali Metal Extraction by Crown Ethers

    SciTech Connect (OSTI)

    Haverlock, T.J.; Moyer, B.A.; Sachleben, R.A.

    1999-07-11

    Jean-Marie Lehn (Nobel laureate, 1987) suggested ligand thickness to be an important consideration in the design of host molecules for cation recognition. We have recently expanded the role of this simple ligand property by demonstrating a case in which ligand thickness contributes significantly to anion discrimination. It was found that in the extraction of sodium nitrate and perchlorate by a simple crown ether, bis(t-octylbenzo)-14-crown-4 (BOB 14C4), the normal preference for perchlorate is almost completely lost when the complex cation has the open-face sandwich vs. the sandwich structure.

  3. 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,...

  4. 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,...

  5. 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-...

  6. 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-...

  7. Single-Step Syngas-to-Distillates (S2D) Synthesis via Methanol and Dimethyl Ether Intermediates: Final Report

    SciTech Connect (OSTI)

    Dagle, Robert A.; Lebarbier, Vanessa MC; Lizarazo Adarme, Jair A.; King, David L.; Zhu, Yunhua; Gray, Michel J.; Jones, Susanne B.; Biddy, Mary J.; Hallen, Richard T.; Wang, Yong; White, James F.; Holladay, Johnathan E.; Palo, Daniel R.

    2013-11-26

    The objective of the work was to enhance price-competitive, synthesis gas (syngas)-based production of transportation fuels that are directly compatible with the existing vehicle fleet (i.e., vehicles fueled by gasoline, diesel, jet fuel, etc.). To accomplish this, modifications to the traditional methanol-to-gasoline (MTG) process were investigated. In this study, we investigated direct conversion of syngas to distillates using methanol and dimethyl ether intermediates. For this application, a Pd/ZnO/Al2O3 (PdZnAl) catalyst previously developed for methanol steam reforming was evaluated. The PdZnAl catalyst was shown to be far superior to a conventional copper-based methanol catalyst when operated at relatively high temperatures (i.e., >300°C), which is necessary for MTG-type applications. Catalytic performance was evaluated through parametric studies. Process conditions such as temperature, pressure, gas-hour-space velocity, and syngas feed ratio (i.e., hydrogen:carbon monoxide) were investigated. PdZnAl catalyst formulation also was optimized to maximize conversion and selectivity to methanol and dimethyl ether while suppressing methane formation. Thus, a PdZn/Al2O3 catalyst optimized for methanol and dimethyl ether formation was developed through combined catalytic material and process parameter exploration. However, even after compositional optimization, a significant amount of undesirable carbon dioxide was produced (formed via the water-gas-shift reaction), and some degree of methane formation could not be completely avoided. Pd/ZnO/Al2O3 used in combination with ZSM-5 was investigated for direct syngas-to-distillates conversion. High conversion was achieved as thermodynamic constraints are alleviated when methanol and dimethyl are intermediates for hydrocarbon formation. When methanol and/or dimethyl ether are products formed separately, equilibrium restrictions occur. Thermodynamic relaxation also enables the use of lower operating pressures than what would be allowed for methanol synthesis alone. Aromatic-rich hydrocarbon liquid (C5+), containing a significant amount of methylated benzenes, was produced under these conditions. However, selectivity control to liquid hydrocarbons was difficult to achieve. Carbon dioxide and methane formation was problematic. Furthermore, saturation of the olefinic intermediates formed in the zeolite, and necessary for gasoline production, occurred over PdZnAl. Thus, yield to desirable hydrocarbon liquid product was limited. Evaluation of other oxygenate-producing catalysts could possibly lead to future advances. Potential exists with discovery of other types of catalysts that suppress carbon dioxide and light hydrocarbon formation. Comparative techno-economics for a single-step syngas-to-distillates process and a more conventional MTG-type process were investigated. Results suggest operating and capital cost savings could only modestly be achieved, given future improvements to catalyst performance. Sensitivity analysis indicated that increased single-pass yield to hydrocarbon liquid is a primary need for this process to achieve cost competiveness.

  8. 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.

  9. Involvement of reactive oxygen species in brominated diphenyl ether-47-induced inflammatory cytokine release from human extravillous trophoblasts in vitro

    SciTech Connect (OSTI)

    Park, Hae-Ryung Kamau, Patricia W.; Loch-Caruso, Rita

    2014-01-15

    Polybrominated diphenyl ethers (PBDEs) are widely used flame retardant compounds. Brominated diphenyl ether (BDE)-47 is one of the most prevalent PBDE congeners found in human breast milk, serum and placenta. Despite the presence of PBDEs in human placenta, effects of PBDEs on placental cell function are poorly understood. The present study investigated BDE-47-induced reactive oxygen species (ROS) formation and its role in BDE-47-stimulated proinflammatory cytokine release in a first trimester human extravillous trophoblast cell line, HTR-8/SVneo. Exposure of HTR-8/SVneo cells for 4 h to 20 ?M BDE-47 increased ROS generation 1.7 fold as measured by the dichlorofluorescein (DCF) assay. Likewise, superoxide anion production increased approximately 5 fold at 10 and 15 ?M and 9 fold at 20 ?M BDE-47 with a 1-h exposure, as measured by cytochrome c reduction. BDE-47 (10, 15 and 20 ?M) decreased the mitochondrial membrane potential by 4764.5% at 4, 8 and 24 h as assessed with the fluorescent probe Rh123. Treatment with 15 and 20 ?M BDE-47 stimulated cellular release and mRNA expression of IL-6 and IL-8 after 12 and 24-h exposures: the greatest increases were a 35-fold increased mRNA expression at 12 h and a 12-fold increased protein concentration at 24 h for IL-6. Antioxidant treatments (deferoxamine mesylate, ()?-tocopherol, or tempol) suppressed BDE-47-stimulated IL-6 release by 54.1%, 56.3% and 37.7%, respectively, implicating a role for ROS in the regulation of inflammatory pathways in HTR-8/SVneo cells. Solvent (DMSO) controls exhibited statistically significantly decreased responses compared with non-treated controls for IL-6 release and IL-8 mRNA expression, but these responses were not consistent across experiments and times. Nonetheless, it is possible that DMSO (used to dissolve BDE-47) may have attenuated the stimulatory actions of BDE-47 on cytokine responses. Because abnormal activation of proinflammatory responses can disrupt trophoblast functions necessary for placental development and successful pregnancy, further investigation is warranted of the impact of ROS and BDE-47 on trophoblast cytokine responses. - Highlights: BDE-47 induced ROS overproduction and mitochondrial dysfunction. BDE-47 stimulated production of proinflammatory cytokines. Antioxidant treatment reduced BDE-47-stimulated ROS generation and cytokine release.

  10. 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.

  11. Calcitriol inhibits Ether-a go-go potassium channel expression and cell proliferation in human breast cancer cells

    SciTech Connect (OSTI)

    Garcia-Becerra, Rocio; Diaz, Lorenza; Camacho, Javier; Barrera, David; Ordaz-Rosado, David; Morales, Angelica; Ortiz, Cindy Sharon; Avila, Euclides; Bargallo, Enrique; Arrecillas, Myrna; Halhali, Ali; Larrea, Fernando

    2010-02-01

    Antiproliferative actions of calcitriol have been shown to occur in many cell types; however, little is known regarding the molecular basis of this process in breast carcinoma. Ether-a-go-go (Eag1) potassium channels promote oncogenesis and are implicated in breast cancer cell proliferation. Since calcitriol displays antineoplastic effects while Eag1 promotes tumorigenesis, and both factors antagonically regulate cell cycle progression, we investigated a possible regulatory effect of calcitriol upon Eag1 as a mean to uncover new molecular events involved in the antiproliferative activity of this hormone in human breast tumor-derived cells. RT real-time PCR and immunocytochemistry showed that calcitriol suppressed Eag1 expression by a vitamin D receptor (VDR)-dependent mechanism. This effect was accompanied by inhibition of cell proliferation, which was potentiated by astemizole, a nonspecific Eag1 inhibitor. Immunohistochemistry and Western blot demonstrated that Eag1 and VDR abundance was higher in invasive-ductal carcinoma than in fibroadenoma, and immunoreactivity of both proteins was located in ductal epithelial cells. Our results provide evidence of a novel mechanism involved in the antiproliferative effects of calcitriol and highlight VDR as a cancer therapeutic target for breast cancer treatment and prevention.

  12. Heat Capacity Uncertainty Calculation for the Eutectic Mixture of Biphenyl/Diphenyl Ether Used as Heat Transfer Fluid: Preprint

    SciTech Connect (OSTI)

    Gomez, J. C.; Glatzmaier, G. C.; Mehos, M.

    2012-09-01

    The main objective of this study was to calculate the uncertainty at 95% confidence for the experimental values of heat capacity of the eutectic mixture of biphenyl/diphenyl ether (Therminol VP-1) determined from 300 to 370 degrees C. Twenty-five samples were evaluated using differential scanning calorimetry (DSC) to obtain the sample heat flow as a function of temperature. The ASTM E-1269-05 standard was used to determine the heat capacity using DSC evaluations. High-pressure crucibles were employed to contain the sample in the liquid state without vaporizing. Sample handling has a significant impact on the random uncertainty. It was determined that the fluid is difficult to handle, and a high variability of the data was produced. The heat capacity of Therminol VP-1 between 300 and 370 degrees C was measured to be equal to 0.0025T+0.8672 with an uncertainty of +/- 0.074 J/g.K (3.09%) at 95% confidence with T (temperature) in Kelvin.

  13. Synergistic effect of mixing dimethyl ether with methane, ethane, propane, and ethylene fuels on polycyclic aromatic hydrocarbon and soot formation

    SciTech Connect (OSTI)

    Yoon, S.S.; Anh, D.H.; Chung, S.H.

    2008-08-15

    Characteristics of polycyclic aromatic hydrocarbon (PAH) and soot formation in counterflow diffusion flames of methane, ethane, propane, and ethylene fuels mixed with dimethyl ether (DME) have been investigated. Planar laser-induced incandescence and fluorescence techniques were employed to measure relative soot volume fractions and PAH concentrations, respectively. Results showed that even though DME is known to be a clean fuel in terms of soot formation, DME mixture with ethylene fuel increases PAH and soot formation significantly as compared to the pure ethylene case, while the mixture of DME with methane, ethane, and propane decreases PAH and soot formation. Numerical calculations adopting a detailed kinetics showed that DME can be decomposed to produce a relatively large number of methyl radicals in the low-temperature region where PAH forms and grows; thus the mixture of DME with ethylene increases CH{sub 3} radicals significantly in the PAH formation region. Considering that the increase in the concentration of O radicals is minimal in the PAH formation region with DME mixture, the enhancement of PAH and soot formation in the mixture flames of DME and ethylene can be explained based on the role of methyl radicals in PAH and soot formation. Methyl radicals can increase the concentration of propargyls, which could enhance incipient benzene ring formation through the propargyl recombination reaction and subsequent PAH growth. Thus, the result substantiates the importance of methyl radicals in PAH and soot formation, especially in the PAH formation region of diffusion flames. (author)

  14. On the competition between hydrogen abstraction versus C-O bond fission in initiating dimethyl ether combustion

    SciTech Connect (OSTI)

    Francisco, J.

    1999-07-01

    There has been a growing interest in the potential use of dimethyl ether (DME) as a diesel fuel in compression ignition engines. There are two initiation steps involved in the combustion of DME, one involving C-O bond fission and the other involving hydrogen abstraction by molecular oxygen. The kinetics and thermodynamics of C-O bond fission were explored computationally in a previous paper. The present paper addresses the competing process--hydrogen abstraction by molecular oxygen. Ab initio molecular orbital calculations are used to study the structures and energetics of the reactants, products, and the transition state for the CH{sub 3}OCH{sub 3} + O{sub 2} reaction. The calculations predict a barrier for hydrogen abstraction from CH{sub 3}OCH{sub 3} by O{sub 2} of 47.4 kcal/mol. This is lower than the barrier height for C-O bond fission previously calculated to be 81.1 kcal/mol. The results support values used in current models for the combustion of DME. Moreover, an examination of rates for C-O bond fission versus hydrogen abstraction by O{sub 2} suggests that the bimolecular process is the dominant pathway.

  15. Toxicity of polychlorinated diphenyl ethers in hydra attenuata and in rat whole-embryo culture. Master's thesis

    SciTech Connect (OSTI)

    Becker, M.C.

    1991-05-01

    Polychlorinated diphenyl ethers (PCDEs) are a class of biaryl compounds that have little commercial application, but appear to be widespread in the environment. They have been found in wood preservative waste dumpsites and in fly ash from municipal waste incinerators. They have been detected in bird eggs and tissues, fish, and other edible marine organisms in the United States, Canada, and Europe. There are limited reports in the extant literature on the toxicity of PCDEs. This study was designed to evaluate the toxicity of selected PCDEs in cultures of Hydra attenuata and post-implantation rat whole embryos. The toxicity of several closely related polychlorinated biphenyls (PCBs) was evaluated in both cultures and 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD) was evaluated in whole embryo culture. Embryonic growth and development parameters (yolk sac diameter, crown-rump length, somite count, and DNA and protein content) and gross morphology were determined. Findings indicated that these chemicals were neither embryotoxic nor teratogenic. Thus, the PCDEs, which elicit other diverse toxic and biochemical responses in rodents, are relatively inactive in these bioassays for developmental toxicity.

  16. Sorbents for High Temperature Removal of Arsenic from Coal-Derived Synthesis Gas

    SciTech Connect (OSTI)

    Alptekin, G.O.; Copeland, R.; Dubovik, M.; Gershanovich, Y.

    2002-09-20

    Gasification technologies convert coal and other heavy feedstocks into synthesis gas feed streams that can be used in the production of a wide variety of chemicals, ranging from hydrogen through methanol, ammonia, acetic anhydride, dimethyl ether (DME), methyl tertiary butyl ether (MTBE), high molecular weight liquid hydrocarbons and waxes. Syngas can also be burned directly as a fuel in advanced power cycles to generate electricity with very high efficiency. However, the coal-derived synthesis gas contains a myriad of trace contaminants that may poison the catalysts that are used in the downstream manufacturing processes and may also be regulated in power plant emissions. Particularly, the catalysts used in the conversion of synthesis gas to methanol and other liquid fuels (Fischer-Tropsch liquids) have been found to be very sensitive to the low levels of poisons, especially arsenic, that are present in the synthesis gas from coal. TDA Research, Inc. (TDA) is developing an expendable high capacity, low-cost chemical absorbent to remove arsenic from coal-derived syngas. Unlike most of the commercially available sorbents that physically adsorb arsenic, TDA's sorbent operates at elevated temperatures and removes the arsenic through chemical reaction. The arsenic content in the coal gas stream is reduced to ppb levels with the sorbent by capturing and stabilizing the arsenic gas (As4) and arsenic hydrides (referred to as arsine, AsH3) in the solid state. To demonstrate the concept of high temperature arsenic removal from coal-derived syngas, we carried out bench-scale experiments to test the absorption capacity of a variety of sorbent formulations under representative conditions. Using on-line analysis techniques, we monitored the pre- and post-breakthrough arsine concentrations over different sorbent samples. Some of these samples exhibited pre-breakthrough arsine absorption capacity over 40% wt. (capacity is defined as lb of arsenic absorbed/lb of sorbent), while maintaining an arsine outlet concentration at less than 10 ppb.

  17. Synthesis of dimethyl ether and alternative fuels in the liquid phase from coal-derived synthesis gas

    SciTech Connect (OSTI)

    Bhatt, B.L.

    1992-09-01

    As part of the DOE-sponsored contract for the Synthesis of Dimethyl Ether (DME) and Alternative Fuels in the Liquid Phase from Coal- Derived Syngas, the single-step, slurry phase DME synthesis process was developed. The development involved screening of catalyst systems, process variable studies, and catalyst life studies in two 300 ml stirred autoclaves. As a spin-off of the Liquid Phase Methanol (LPMEOH*) process, the new process significantly improves the syngas conversion efficiency of the LPMEOH process. This improvement can be achieved by replacing a portion of methanol catalyst with a dehydration catalyst in the reactor, resulting in the product methanol being converted to DME, thus avoiding the thermodynamic equilibrium constraint of the methanol reaction. Overall, this increases syngas conversion per-pass. The selectivity and productivity of DME and methanol are affected by the catalyst system employed as well as operating conditions. A preferred catalyst system, consisting of a physical mixture of a methanol catalyst and a gamma alumina, was identified. An improvement of about 50% in methanol equivalent productivity was achieved compared to the LPMEOH process. Results from the process variable study indicate that higher pressure and CO[sub 2] removal benefit the process significantly. Limited life studies performed on the preferred catalyst system suggest somewhat higher than expected deactivation rate for the methanol catalyst. Several DME/methanol mixtures were measured for their key properties as transportation fuels. With small amounts of DME added, significant improvements in both flash points and Reid Vapor Pressure (RVP) were observed over the corresponding values of methanol alone.

  18. Auto-ignition during instationary jet evolution of dimethyl ether (DME) in a high-pressure atmosphere

    SciTech Connect (OSTI)

    Fast, G.; Kuhn, D.; Class, A.G.; Maas, U.

    2009-01-15

    The auto-ignition process during transient injection of gaseous dimethyl ether (DME) in a constant high-pressure atmosphere is studied experimentally by laser-optical methods and compared with numerical calculations. With different non-intrusive measurement techniques jet properties and auto-ignition are investigated at high temporal and spatial resolution. The open jet penetrates a constant pressure oxidative atmosphere of up to 4 MPa. During the transient evolution, the fuel jet entrains air at up to 720 K. The subsequent auto-ignition of the ignitable part of the jet occurs simultaneously over a wide spatial extension. The ignition delay times are not affected by variation of the nozzle exit velocity. Thus, the low-temperature oxidation is slow compared with the shorter time scales of mixing, so that chemical kinetics is dominating the process. The typical two-stage ignition is resolved optically with high-speed shadowgraphy at a sampling rate of 10 kHz. The 2D fields of jet velocity and transient mixture fraction are measured phase-coupled with Particle Image Velocimetry (PIV) and Tracer Laser Induced Fluorescence (LIF) during the time-frame of ignition. The instationary Probability Density Functions (PDF) of mixture fraction are described very well by Beta functions within the complete area of the open jet. Additional 1D flamelet simulations of the auto-ignition process are computed with a detailed reaction mechanism for DME [S. Fischer, F. Dryer, H. Curran, Int. J. Chem. Kinet. 32 (12) (2000) 713-740; H. Curran, S. Fischer, F. Dryer, Int. J. Chem. Kinet. 32 (12) (2000) 741-759]. Calculated ignition delay times are in very good agreement with the measured mean ignition delay times of 3 ms. Supplemental flamelet simulations address the influence of DME and air temperature, pressure and strain. Underneath a critical strain rate the air temperature is identified to be the most sensitive factor on ignition delay time. (author)

  19. Microsoft Word - LBNL 53866_SPME-MTBE_Final_112103.doc

    Office of Scientific and Technical Information (OSTI)

    ... greater than 3 gL. TBA is classified as a "contaminant of current interest" and has a drinking water action level of 12 gL, based on a non-cancer endpoint assessment (5a). ...

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

    SciTech Connect (OSTI)

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

    1994-12-31

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

  1. Synthesis of methanol and dimethyl ether from syngas over Pd/ZnO/Al2O3 catalysts

    SciTech Connect (OSTI)

    Lebarbier, Vanessa M.; Dagle, Robert A.; Kovarik, Libor; Lizarazo-Adarme, Jair A.; King, David L.; Palo, Daniel R.

    2012-01-01

    A Pd/ZnO/Al2O3 catalyst was developed for the synthesis of methanol and dimethyl ether (DME) from syngas. Studied were temperatures of operation ranging from 250C to 380C. High temperatures (e.g. 380C) are necessary when combining methanol and DME synthesis with a methanol to gasoline (MTG) process in a single reactor bed. A commercial Cu/ZnO/Al2O3 catalyst, utilized industrially for the synthesis of methanol at 220-280C, suffers from a rapid deactivation when the reaction is conducted at high temperature (>320C). On the contrary, a Pd/ZnO/Al2O3 catalyst was found to be highly stable for methanol and DME synthesis at 380C. The Pd/ZnO/Al2O3 catalyst was thus further investigated for methanol and DME synthesis at P=34-69 bars, T= 250-380C, GHSV= 5 000-18 000 h-1, and molar feeds H2/CO= 1, 2, and 3. Selectivity to DME increased with decreasing operating temperature, and increasing operating pressure. Increased GHSVs and H2/CO syngas feed ratios also enhanced DME selectivity. Undesirable CH4 formation was observed, however, can be minimized through choice of process conditions and by catalyst design. By studying the effect of the Pd loading and the Pd:Zn molar ratio the formulation of the Pd/ZnO/Al2O3 catalyst was optimized. A catalyst with 5% Pd and a Pd:Zn molar ratio of 0.25:1 has been identified as the preferred catalyst. Results indicate that PdZn particles are more active than Pd particles for the synthesis of methanol and less active for CH4 formation. A correlation between DME selectivity and the concentration of acid sites of the catalysts has been established. Hence, two types of sites are required for the direct conversion of syngas to DME: 1) PdZn particles are active for the synthesis of methanol from syngas, and 2) acid sites which are active for the conversion of methanol to DME. Additionally, CO2 formation was problematic as PdZn was found to be active for the water-gas-shift (WGS) reaction, under all the conditions evaluated.

  2. 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)

  3. Synthesis of dimethyl ether and alternative fuels in the liquid phase from coal-derived syngas; Quarterly technical progress report No. 3, 1 July--30 September 1990

    SciTech Connect (OSTI)

    1991-01-25

    Contract objectives are: development of a one-step liquid phase dimethyl ether/methanol process; and investigation of the potential of liquid phase synthesis of alternative fuels from coal-derived synthesis gas. Definition of Preferred Catalyst System was completed after several commercial methanol catalysts and dehydration catalysts were tested. BASF S3-86 and Catapal gamma alumina is the preferred catalyst system of choice. Process Variable Scans on the Preferred Catalyst System was started with Shell gas. Data were obtained at various pressures (750 to 1400 psig), temperatures (250 to 280{degrees}C), and space velocities (5000 to 9000 sl/kg-hr). Increase in system pressure seems to have a very significant benefit to both DME and methanol formation. Both Texaco and Shell gases were evaluated. A ``stoichiometric`` feed composition (50% CO, 50% H{sub 2}) that yields maximum DME productivity at equilibrium was evaluated with a fresh batch of the optimum catalyst system. Productivities with the ``stoichiometric`` gas were much higher compared to Shell or Texaco gas. Following that test, Dow gas was evaluated (41% CO, 41% H{sub 2}, 16% CO{sub 2} and 2% N{sub 2}) using the same catalyst to study the effect of CO{sub 2}. Three DME/MEOH (1--4% DME) mixtures were evaluated by SWRI for their fuel properties. Results indicate that, with small amounts of DME added, significant improvements in both flash point and RVP are possible over the properties of LaPorte MEOH. the slurry-phase dehydration of alcohols to ethers was investigated by feeding 10 mol% mixed alcohols in N{sub 2} over an alumina catalyst suspended in mineral oil. Two alcohol mixture compositions were chosen for this study. One mixture contained methanol, ethanol, and 1-propanol in proportions representative of those in IFP Substifuel, while the other mixture contained methanol, ethanol, and isobutanol in proportions representative of those in Lurgi Octamix. 21 figs., 13 tabs.

  4. Fuel cycle evaluations of biomass-ethanol and reformulated gasoline. Volume 1

    SciTech Connect (OSTI)

    Tyson, K.S.

    1993-11-01

    The US Department of Energy (DOE) is using the total fuel cycle analysis (TFCA) methodology to evaluate energy choices. The National Energy Strategy (NES) identifies TFCA as a tool to describe and quantify the environmental, social, and economic costs and benefits associated with energy alternatives. A TFCA should quantify inputs and outputs, their impacts on society, and the value of those impacts that occur from each activity involved in producing and using fuels, cradle-to-grave. New fuels and energy technologies can be consistently evaluated and compared using TFCA, providing a sound basis for ranking policy options that expand the fuel choices available to consumers. This study is limited to creating an inventory of inputs and outputs for three transportation fuels: (1) reformulated gasoline (RFG) that meets the standards of the Clean Air Act Amendments of 1990 (CAAA) using methyl tertiary butyl ether (MTBE); (2) gasohol (E10), a mixture of 10% ethanol made from municipal solid waste (MSW) and 90% gasoline; and (3) E95, a mixture of 5% gasoline and 95% ethanol made from energy crops such as grasses and trees. The ethanol referred to in this study is produced from lignocellulosic material-trees, grass, and organic wastes -- called biomass. The biomass is converted to ethanol using an experimental technology described in more detail later. Corn-ethanol is not discussed in this report. This study is limited to estimating an inventory of inputs and outputs for each fuel cycle, similar to a mass balance study, for several reasons: (1) to manage the size of the project; (2) to provide the data required for others to conduct site-specific impact analysis on a case-by-case basis; (3) to reduce data requirements associated with projecting future environmental baselines and other variables that require an internally consistent scenario.

  5. Superacid catalysis of light hydrocarbon conversion. Final report, August 26, 1993--August 26, 1996

    SciTech Connect (OSTI)

    Gates, B.C.

    1996-12-31

    Motivated by the goal of finding improved catalysts for low- temperature conversion of light alkanes into fuel components or precursors of fuel components, the researchers have investigated sulfated zirconia and promoted sulfated zirconia for conversion of butane, propane, and ethane. Catalyst performance data for sulfated zirconia promoted with iron and manganese show that it is the most active noncorrosive, nonhalide catalyst known for n-butane isomerization, and it is an excellent candidate catalyst for new low- temperature n-butane isomerization processes to make isobutane, which can be converted by established technology into methyl t-butyl ether (MTBE). Various transition metals have been found to work as promoters of sulfated zirconia for n-butane isomerization. The combination of iron and manganese is the best known combination of promoters yet discovered. The iron- and manganese-promoted sulfated zirconia is also a catalyst for conversion of propane and of ethane. Ethane is converted into ethylene and butanes in the presence of the iron- and manganese-promoted sulfated zirconia; propane is also converted into butane, among other products. However, the activities of the catalyst for these reactions are orders of magnitude less than the activity for n-butane conversion, and there is no evidence that the catalyst would be of practical value for conversion of alkanes lighter than butane. The product distribution data for ethane and propane conversion provide new insights into the nature of the catalyst and its acidity. These data suggest the involvement of Olah superacid chemistry, whereby the catalyst protonates the alkane itself, giving carbonium ions (as transition states). The mechanism of protonation of the alkane may also pertain to the conversion of butane, but there is good evidence that the butane conversion also proceeds via alkene intermediates by conventional mechanisms of carbenium ion formation and rearrangement.

  6. Conceptual process design and economics for the production of high-octane gasoline blendstock via indirect liquefaction of biomass through methanol/dimethyl ether intermediates

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

    Tan, Eric C. D.; Talmadge, Michael; Dutta, Abhijit; Hensley, Jesse; Snowden-Swan, Lesley J.; Humbird, David; Schaidle, Joshua; Biddy, Mary

    2015-10-28

    This paper describes in detail one potential conversion process for the production of high-octane gasoline blendstock via indirect liquefaction of biomass. The processing steps of this pathway include the conversion of biomass to synthesis gas via indirect gasification, gas clean-up via reforming of tars and other hydrocarbons, catalytic conversion of syngas to methanol, methanol dehydration to dimethyl ether (DME), and the homologation of DME over a zeolite catalyst to high-octane gasoline-range hydrocarbon products. The current process configuration has similarities to conventional methanol-to-gasoline (MTG) technologies, but there are key distinctions, specifically regarding the product slate, catalysts, and reactor conditions. A techno-economicmore » analysis is performed to investigate the production of high-octane gasoline blendstock. The design features a processing daily capacity of 2000 tonnes (2205 short tons) of dry biomass. The process yields 271 liters of liquid fuel per dry tonne of biomass (65 gal/dry ton), for an annual fuel production rate of 178 million liters (47 MM gal) at 90% on-stream time. The estimated total capital investment for an nth-plant is $438 million. The resulting minimum fuel selling price (MFSP) is $0.86 per liter or $3.25 per gallon in 2011 US dollars. A rigorous sensitivity analysis captures uncertainties in costs and plant performance. Sustainability metrics for the conversion process are quantified and assessed. The potential premium value of the high-octane gasoline blendstock is examined and found to be at least as competitive as fossil-derived blendstocks. A simple blending strategy is proposed to demonstrate the potential for blending the biomass-derived blendstock with petroleum-derived intermediates. Published 2015. This article is a U.S. Government work and is in the public domain in the USA. Biofuels, Bioproducts and Biorefining published by Society of Industrial Chemistry and John Wiley & Sons Ltd.« less

  7. Conceptual process design and economics for the production of high-octane gasoline blendstock via indirect liquefaction of biomass through methanol/dimethyl ether intermediates

    SciTech Connect (OSTI)

    Tan, Eric C. D.; Talmadge, Michael; Dutta, Abhijit; Hensley, Jesse; Snowden-Swan, Lesley J.; Humbird, David; Schaidle, Joshua; Biddy, Mary

    2015-10-28

    This paper describes in detail one potential conversion process for the production of high-octane gasoline blendstock via indirect liquefaction of biomass. The processing steps of this pathway include the conversion of biomass to synthesis gas via indirect gasification, gas clean-up via reforming of tars and other hydrocarbons, catalytic conversion of syngas to methanol, methanol dehydration to dimethyl ether (DME), and the homologation of DME over a zeolite catalyst to high-octane gasoline-range hydrocarbon products. The current process configuration has similarities to conventional methanol-to-gasoline (MTG) technologies, but there are key distinctions, specifically regarding the product slate, catalysts, and reactor conditions. A techno-economic analysis is performed to investigate the production of high-octane gasoline blendstock. The design features a processing daily capacity of 2000 tonnes (2205 short tons) of dry biomass. The process yields 271 liters of liquid fuel per dry tonne of biomass (65 gal/dry ton), for an annual fuel production rate of 178 million liters (47 MM gal) at 90% on-stream time. The estimated total capital investment for an nth-plant is $438 million. The resulting minimum fuel selling price (MFSP) is $0.86 per liter or $3.25 per gallon in 2011 US dollars. A rigorous sensitivity analysis captures uncertainties in costs and plant performance. Sustainability metrics for the conversion process are quantified and assessed. The potential premium value of the high-octane gasoline blendstock is examined and found to be at least as competitive as fossil-derived blendstocks. A simple blending strategy is proposed to demonstrate the potential for blending the biomass-derived blendstock with petroleum-derived intermediates. Published 2015. This article is a U.S. Government work and is in the public domain in the USA. Biofuels, Bioproducts and Biorefining published by Society of Industrial Chemistry and John Wiley & Sons Ltd.

  8. Polybrominated diphenyl ethers in e-waste: Level and transfer in a typical e-waste recycling site in Shanghai, Eastern China

    SciTech Connect (OSTI)

    Li, Yue; Duan, Yan-Ping, E-mail: duanyanping@tongji.edu.cn; Huang, Fan; Yang, Jing; Xiang, Nan; Meng, Xiang-Zhou; Chen, Ling

    2014-06-01

    Highlights: PBDEs were detected in the majority of e-waste. PBDEs were found in TVs made in China after 1990. The levels of ?PBDEs in e-waste made in Japan far exceed the threshold limit of RoHS. The inappropriate recycling and disposal of e-waste is an important source of PBDEs. - Abstract: Very few data for polybrominated diphenyl ethers (PBDEs) were available in the electronic waste (e-waste) as one of the most PBDEs emission source. This study reported concentrations of PBDEs in e-waste including printer, rice cooker, computer monitor, TV, electric iron and water dispenser, as well as dust from e-waste, e-waste dismantling workshop and surface soil from inside and outside of an e-waste recycling plant in Shanghai, Eastern China. The results showed that PBDEs were detected in the majority of e-waste, and the concentrations of ?PBDEs ranged from not detected to 175 g/kg, with a mean value of 10.8 g/kg. PBDEs were found in TVs made in China after 1990. The mean concentrations of ?PBDEs in e-waste made in Korea, Japan, Singapore and China were 1.84 g/kg, 20.5 g/kg, 0.91 g/kg, 4.48 g/kg, respectively. The levels of ?PBDEs in e-waste made in Japan far exceed the threshold limit of RoHS (1.00 g/kg). BDE-209 dominated in e-waste, accounting for over 93%. The compositional patterns of PBDEs congeners resembled the profile of Saytex 102E, indicating the source of deca-BDE. Among the samples of dust and surface soil from a typical e-waste recycling site, the highest concentrations of ?{sub 18}PBDEs and BDE-209 were found in dust in e-waste, ranging from 1960 to 340,710 ng/g and from 910 to 320,400 ng/g, which were 12 orders of magnitude higher than other samples. It suggested that PBDEs released from e-waste via dust, and then transferred to surrounding environment.

  9. DME-to-oxygenates process studies

    SciTech Connect (OSTI)

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

    1994-12-31

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

  10. Process Design and Economics for the Conversion of Lignocellulosic Biomass to Hydrocarbons via Indirect Liquefaction. Thermochemical Research Pathway to High-Octane Gasoline Blendstock Through Methanol/Dimethyl Ether Intermediates

    SciTech Connect (OSTI)

    Tan, Eric C. D.; Talmadge, Michael; Dutta, Abhijit; Hensley, Jesse; Schaidle, Josh; Biddy, Mary; Humbird, David; Snowden-Swan, Lesley J.; Ross, Jeff; Sexton, Danielle; Yap, Raymond; Lukas, John

    2015-03-01

    This report was developed as part of the U.S. Department of Energy’s Bioenergy Technologies Office’s (BETO’s) efforts to enable the development of technologies for the production of infrastructure-compatible, cost-competitive liquid hydrocarbon fuels from lignocellulosic biomass feedstocks. The research funded by BETO is designed to advance the state of technology of biomass feedstock supply and logistics, conversion, and overall system sustainability. It is expected that these research improvements will be made within the 2022 timeframe. As part of their involvement in this research and development effort, the National Renewable Energy Laboratory and the Pacific Northwest National Laboratory investigate the economics of conversion pathways through the development of conceptual biorefinery process models and techno-economic analysis models. This report describes in detail one potential conversion process for the production of high-octane gasoline blendstock via indirect liquefaction of biomass. The processing steps of this pathway include the conversion of biomass to synthesis gas or syngas via indirect gasification, gas cleanup, catalytic conversion of syngas to methanol intermediate, methanol dehydration to dimethyl ether (DME), and catalytic conversion of DME to high-octane, gasoline-range hydrocarbon blendstock product. The conversion process configuration leverages technologies previously advanced by research funded by BETO and demonstrated in 2012 with the production of mixed alcohols from biomass. Biomass-derived syngas cleanup via reforming of tars and other hydrocarbons is one of the key technology advancements realized as part of this prior research and 2012 demonstrations. The process described in this report evaluates a new technology area for the downstream utilization of clean biomass-derived syngas for the production of high-octane hydrocarbon products through methanol and DME intermediates. In this process, methanol undergoes dehydration to DME, which is subsequently converted via homologation reactions to high-octane, gasoline-range hydrocarbon products.

  11. Development of alternative fuels from coal derived syngas. Topical report: Task 2.2, Demonstration of a one-step slurry-phase process for the production of dimethyl ether/methanol mixtures at the LaPorte Alternative Fuels Development Unit

    SciTech Connect (OSTI)

    Not Available

    1993-06-01

    This report documents engineering, modification, and operations efforts of demonstration of dimethyl-ether/methanol coproduction in a slurry-phase reactor, carried out in a 2-ft diameter bubble column reactor. Equipment modifications made it possible to remove the product DME and by-product CO{sub 2} from the reactor effluent. Coproduction of dimethyl-ether (DME) and methanol (MeOH) was accomplished in the slurry reactor by physically mixing two different catalysts. The catalyst used to produce MeOH from syngas was manufactured by BASF (type S3-86); the catalyst used to convert MeOH to DME was Catapal {gamma}-alumina. Ratio of MeOH to DME catalysts determined the selectivity towards DME. The demonstration sought to study effect of cocatalyst ratio on product selectivity. Three different proportions of DME catalyst were examined: 0, 6.6, and 19.3 wt % alumina. At each catalyst proportion, the plant was operated at two different gas space velocities. Some process variables were maintained at fixed conditions; most important variables included: reactor temperature (482F), reactor pressure (750 psig), and reactor feed gas composition (35% H{sub 2}, 51% CO,13% CO{sub 2} 1% other, nominal-molar basis).

  12. 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; ...

  13. This Week In Petroleum Printer-Friendly Version

    Gasoline and Diesel Fuel Update (EIA)

    this year. Companies decisions to eliminate MTBE have been driven by State bans due to water contamination concerns, continuing liability exposure from adding MTBE to gasoline,...

  14. 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.

  15. 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.

  16. 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),

  17. 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

  18. 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),

  19. 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.

  20. Synthesis of dimethyl ether and alternative fuels in the liquid phase from coal-derived synthesis gas. Task 2.2: Definition of preferred catalyst system; Task 2.3: Process variable scans on the preferred catalyst system; Task 2.4: Life-test on the preferred catalyst system

    SciTech Connect (OSTI)

    Bhatt, B.L.

    1992-09-01

    As part of the DOE-sponsored contract for the Synthesis of Dimethyl Ether (DME) and Alternative Fuels in the Liquid Phase from Coal- Derived Syngas, the single-step, slurry phase DME synthesis process was developed. The development involved screening of catalyst systems, process variable studies, and catalyst life studies in two 300 ml stirred autoclaves. As a spin-off of the Liquid Phase Methanol (LPMEOH*) process, the new process significantly improves the syngas conversion efficiency of the LPMEOH process. This improvement can be achieved by replacing a portion of methanol catalyst with a dehydration catalyst in the reactor, resulting in the product methanol being converted to DME, thus avoiding the thermodynamic equilibrium constraint of the methanol reaction. Overall, this increases syngas conversion per-pass. The selectivity and productivity of DME and methanol are affected by the catalyst system employed as well as operating conditions. A preferred catalyst system, consisting of a physical mixture of a methanol catalyst and a gamma alumina, was identified. An improvement of about 50% in methanol equivalent productivity was achieved compared to the LPMEOH process. Results from the process variable study indicate that higher pressure and CO{sub 2} removal benefit the process significantly. Limited life studies performed on the preferred catalyst system suggest somewhat higher than expected deactivation rate for the methanol catalyst. Several DME/methanol mixtures were measured for their key properties as transportation fuels. With small amounts of DME added, significant improvements in both flash points and Reid Vapor Pressure (RVP) were observed over the corresponding values of methanol alone.

  1. DEVELOPMENT OF ALTERNATIVE FUELS AND CHEMICALS FROM SYNTHESIS GAS

    SciTech Connect (OSTI)

    Peter J. Tijrn

    2003-05-31

    This Final Report for Cooperative Agreement No. DE-FC22-95PC93052, the ''Development of Alternative Fuels and Chemicals from Synthesis Gas,'' was prepared by Air Products and Chemicals, Inc. (Air Products), and covers activities from 29 December 1994 through 31 July 2002. The overall objectives of this program were to investigate potential technologies for the conversion of synthesis gas (syngas), a mixture primarily of hydrogen (H{sub 2}) and carbon monoxide (CO), to oxygenated and hydrocarbon fuels and industrial chemicals, and to demonstrate the most promising technologies at the LaPorte, Texas Alternative Fuels Development Unit (AFDU). Laboratory work was performed by Air Products and a variety of subcontractors, and focused on the study of the kinetics of production of methanol and dimethyl ether (DME) from syngas, the production of DME using the Liquid Phase Dimethyl Ether (LPDME{trademark}) Process, the conversion of DME to fuels and chemicals, and the production of other higher value products from syngas. Four operating campaigns were performed at the AFDU during the performance period. Tests of the Liquid Phase Methanol (LPMEOH{trademark}) Process and the LPDME{trademark} Process were made to confirm results from the laboratory program and to allow for the study of the hydrodynamics of the slurry bubble column reactor (SBCR) at a significant engineering scale. Two campaigns demonstrated the conversion of syngas to hydrocarbon products via the slurry-phase Fischer-Tropsch (F-T) process. Other topics that were studied within this program include the economics of production of methyl tert-butyl ether (MTBE), the identification of trace components in coal-derived syngas and the means to economically remove these species, and the study of systems for separation of wax from catalyst in the F-T process. The work performed under this Cooperative Agreement has continued to promote the development of technologies that use clean syngas produced from any one of a variety of sources (including coal) for the production of a spectrum of alternative fuels (hydrocarbons and oxygenate fuels), octane enhancers, and chemicals and chemical intermediates. In particular, the data from the 1995 LPMEOH{trademark} campaign provided confirmation of assumptions used in the design of the catalyst reduction system at the Kingsport LPMEOH{trademark} Commercial Demonstration Project, and the alternate methanol catalyst has been in use there since late 1998. The kinetic model was also expanded to allow for more accurate prediction of methanol production and carbon dioxide (CO{sub 2}) conversion, and more accurate modeling of by-product formation for the alternate methanol catalyst. The outstanding performance results of the LPMEOH{trademark} Process at Kingsport can be attributed in large part to the body of work performed since 1981 in collaboration between the U.S. Department of Energy (DOE) and Air Products. In addition, a pilot-plant-tested LPDME{trademark} Process has been demonstrated, and the product cost of DME from coal-derived syngas can be competitive in certain locations and applications. The need for liquid fuels will continue to be a critical concern for this nation in the 21st century. Efforts are needed to ensure the development and demonstration of economically competitive, efficient, environmentally responsible technologies that produce clean fuels and chemicals from coal under DOE's Vision 21 concept. These liquids will be a component of the fuel mix that will provide the transition from the current reliance on carbon-based fuels to the ultimate use of H{sub 2} as a means of energy transport. Indirect liquefaction, which converts the syngas (H{sub 2} and CO) produced by the gasification of coal to sulfur- and nitrogen-free liquid products, is a key component of the Vision 21 initiative. The results from this current program provide continued support to the objectives for the conversion of domestic coal to electric power and co-produced clean liquid fuels and chemicals in an environmentally superior manner.

  2. Characterization of DGEBA (diglycidyl ethers bisphenol-A) epoxy resins

    SciTech Connect (OSTI)

    Larsen, F.N.; Spieker, D.A.

    1987-04-01

    High-resolution gel permeation chromatography and high-performance liquid chromatography can be applied to commercially available DGEBA epoxy resins to elucidate small but significant differences in the oligomer and impurity compositions of these resins. The GPC profiles can be used to type or identify the various commercial grades of these DGEBA resins. Lot-to-lot consistency and aging characteristics can also be determined using GPC and HPLC. Quantitation of the various oligomers and impurities such as the ..cap alpha..-glycol, isomer, and chlorohydrin species is possible. Using 20% isoconversion predictive cure thermal analysis data, the relative resin reactivity of several liquid, low-molecular DGEBA resins has been measured. These data show that the higher viscosity, higher oligomer content resins, which have higher hydroxyl content, reacted faster with amine cure agents than the lower viscosity, higher purity - and consequently lower hydroxyl content - resins. Thus, a combination of liquid chromatography (GPC or HPLC) and DSC kinetics can be used to establish a correlation or equivalency beween the commercially available low-molecular-weight DGEBA epoxy resins.

  3. Extractant composition including crown ether and calixarene extractants

    DOE Patents [OSTI]

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

    2009-04-28

    An extractant composition comprising a mixed extractant solvent consisting of calix[4] arene-bis-(tert-octylbenzo)-crown-6 ("BOBCalixC6"), 4',4',(5')-di-(t-butyldicyclo-hexano)-18-crown-6 ("DtBu18C6"), and at least one modifier dissolved in a diluent. The DtBu18C6 may be present at from approximately 0.01M to approximately 0.4M, such as at from approximately 0.086 M to approximately 0.108 M. The modifier may be 1-(2,2,3,3-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol ("Cs-7SB") and may be present at from approximately 0.01M to approximately 0.8M. In one embodiment, the mixed extractant solvent includes approximately 0.15M DtBu18C6, approximately 0.007M BOBCalixC6, and approximately 0.75M Cs-7SB modifier dissolved in an isoparaffinic hydrocarbon diluent. The extractant composition further comprises an aqueous phase. The mixed extractant solvent may be used to remove cesium and strontium from the aqueous phase.

  4. 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.

  5. Word Pro - Untitled1

    Gasoline and Diesel Fuel Update (EIA)

    1 Table 10.5 Estimated Number of Alternative-Fueled Vehicles in Use and Fuel Consumption, 1992-2010 Year Alternative and Replacement Fuels 1 Liquefied Petroleum Gases Compressed Natural Gas Liquefied Natural Gas Methanol, 85 Percent (M85) 3 Methanol, Neat (M100) 4 Ethanol, 85 Percent (E85) 3,5 Ethanol, 95 Percent (E95) 3 Elec- tricity 6 Hydro- gen Other Fuels 7 Subtotal Oxygenates 2 Bio- diesel 10 Total Methyl Tertiary Butyl Ether 8 Ethanol in Gasohol 9 Total Alternative-Fueled Vehicles in Use

  6. Table 10.5 Estimated Number of Alternative-Fueled Vehicles in Use and Fuel Consumption, 1992-2010

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

    Estimated Number of Alternative-Fueled Vehicles in Use and Fuel Consumption, 1992-2010 Year Alternative and Replacement Fuels 1 Liquefied Petroleum Gases Compressed Natural Gas Liquefied Natural Gas Methanol, 85 Percent (M85) 3 Methanol, Neat (M100) 4 Ethanol, 85 Percent (E85) 3,5 Ethanol, 95 Percent (E95) 3 Elec- tricity 6 Hydro- gen Other Fuels 7 Subtotal Oxygenates 2 Bio- diesel 10 Total Methyl Tertiary Butyl Ether 8 Ethanol in Gasohol 9 Total Alternative-Fueled Vehicles in Use 11

  7. California's Move Toward E10 (released in AEO2009)

    Reports and Publications (EIA)

    2009-01-01

    In Annual Energy Outlook 2009, (AEO) E10a gasoline blend containing 10% ethanolis assumed to be the maximum ethanol blend allowed in California erformulated gasoline (RFG), as opposed to the 5.7% blend assumed in earlier AEOs. The 5.7% blend had reflected decisions made when California decided to phase out use of the additive methyl tertiary butyl ether in its RFG program in 2003, opting instead to use ethanol in the minimum amount that would meet the requirement for 2.0% oxygen content under the Clean Air Act provisions in effect at that time.

  8. Fuel Ethanol Oxygenate Production

    Gasoline and Diesel Fuel Update (EIA)

    Product: Fuel Ethanol Methyl Tertiary Butyl Ether Merchant Plants Captive Plants Period-Unit: Monthly-Thousand Barrels Monthly-Thousand Barrels per Day Annual-Thousand Barrels Annual-Thousand Barrels per Day Download Series History Download Series History Definitions, Sources & Notes Definitions, Sources & Notes Show Data By: Product Area Jul-15 Aug-15 Sep-15 Oct-15 Nov-15 Dec-15 View History U.S. 30,256 29,621 28,543 30,139 29,594 31,075 1981-2015 East Coast (PADD 1) 876 854 692 664 664

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

    SciTech Connect (OSTI)

    Czeskleba, H.M.

    1995-12-31

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

  10. Catalytic distillation process

    DOE Patents [OSTI]

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

    1982-01-01

    A method for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C.sub.4 feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

  11. Catalytic distillation process

    DOE Patents [OSTI]

    Smith, L.A. Jr.

    1982-06-22

    A method is described for conducting chemical reactions and fractionation of the reaction mixture comprising feeding reactants to a distillation column reactor into a feed zone and concurrently contacting the reactants with a fixed bed catalytic packing to concurrently carry out the reaction and fractionate the reaction mixture. For example, a method for preparing methyl tertiary butyl ether in high purity from a mixed feed stream of isobutene and normal butene comprising feeding the mixed feed stream to a distillation column reactor into a feed zone at the lower end of a distillation reaction zone, and methanol into the upper end of said distillation reaction zone, which is packed with a properly supported cationic ion exchange resin, contacting the C[sub 4] feed and methanol with the catalytic distillation packing to react methanol and isobutene, and concurrently fractionating the ether from the column below the catalytic zone and removing normal butene overhead above the catalytic zone.

  12. 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.

  13. untitled

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

    crude oil, natural gas plant liquids, and other liquids. Beginning in 1993, fuel ethanol blended into finished motor gasoline and oxygenate production from merchant MTBE...

  14. This Week In Petroleum Printer-Friendly Version

    Gasoline and Diesel Fuel Update (EIA)

    of domestic production and imports to meet demand; Additional transportation and blending costs related to the substitution of ethanol for MTBE in certain markets and the reduction...

  15. This Week In Petroleum Printer-Friendly Version

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

    Petroleum, companies decisions to eliminate MTBE have been driven by State bans due to water contamination concerns and the potential for increased liability exposure due to the...

  16. Extraction of protactinium-233 and separation from thermal neutron-irradiated thorium-232 using crown ethers

    SciTech Connect (OSTI)

    Jalhoom, Moayyed G.; Mohammed, Dawood A.; Khalaf, Jumah S.

    2008-07-01

    A new method was developed for the extraction and separation of {sup 233}Pa from thermal neutron-irradiated {sup 232}Th. Solutions of Pa{sup 233} were prepared in LiCI-HCl solutions from which appreciable extraction was obtained using dibenzo-18-crown-6 in 1,2-dichloroethane. The effects of cavity size, substitutions on the crown ring, type of the organic solvent, and temperature on extraction are discussed. Very high separation factors were obtained for the pairs {sup 233}Pa/{sup 232}Th (>105), {sup 233}Pa/{sup 233}U (> 1000), and {sup 232}U/{sup 232}Th (>60). (authors)

  17. 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.

  18. Cesium and strontium extraction using a mixed extractant solvent including crown ether and calixarene extractants

    DOE Patents [OSTI]

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

    2007-11-06

    A mixed extractant solvent including calix[4]arene-bis-(tert-octylbenzo)-crown-6 ("BOBCalixC6"), 4',4',(5')-di-(t-butyldicyclo-hexano)-18-crown-6 ("DtBu18C6"), and at least one modifier dissolved in a diluent. The mixed extractant solvent may be used to remove cesium and strontium from an acidic solution. The DtBu18C6 may be present from approximately 0.01 M to approximately 0.4M, such as from approximately 0.086 M to approximately 0.108 M. The modifier may be 1-(2,2,3,3-tetrafluoropropoxy)-3-(4-sec-butylphenoxy)-2-propanol ("Cs-7SB") and may be present from approximately 0.01M to approximately 0.8M. In one embodiment, the mixed extractant solvent includes approximately 0.15M DtBu18C6, approximately 0.007M BOBCalixC6, and approximately 0.75M Cs-7SB modifier dissolved in an isoparaffinic hydrocarbon diluent. The mixed extractant solvent may form an organic phase in an extraction system that also includes an aqueous phase. Methods of extracting cesium and strontium as well as strontium alone are also disclosed.

  19. Chlorine resistant desalination membranes based on directly sulfonated poly(arylene ether sulfone) copolymers

    DOE Patents [OSTI]

    McGrath, James E. (Blacksburg, VA); Park, Ho Bum (Austin, TX); Freeman, Benny D. (Austin, TX)

    2011-10-04

    The present invention provides a membrane, kit, and method of making a hydrophilic-hydrophobic random copolymer membrane. The hydrophilic-hydrophobic random copolymer membrane includes a hydrophilic-hydrophobic random copolymer. The hydrophilic-hydrophobic random copolymer includes one or more hydrophilic monomers having a sulfonated polyarylsulfone monomer and a second monomer and one or more hydrophobic monomers having a non-sulfonated third monomer and a fourth monomer. The sulfonated polyarylsulfone monomer introduces a sulfonate into the hydrophilic-hydrophobic random copolymer prior to polymerization.

  20. 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.

  1. Low-temperature superacid catalysis: Reactions of n-butane catalyzed by iron- and manganese-promoted sulfated zirconia

    SciTech Connect (OSTI)

    Cheung, T.K.; D`Itri, J.L.; Gates, B.C.

    1995-02-01

    Environmental concerns are leading to the replacement of aromatic hydrocarbons in gasoline with high-octane-number branched paraffins and oxygenated compounds such as methyl t-butyl ether, which is produced from methanol and isobutylene. The latter can be formed from n-butane by isomerization followed by dehydrogenation. To meet the need for improved catalysts for isomerization of n-butane and other paraffins, researchers identified solid acids that are noncorrosive and active at low temperatures. Sulfated zirconia catalyzes the isomerization of n-butane even at 25{degrees}C, and the addition of Fe and Mn promoters increases its activity by three orders of magnitude. Little is known about this new catalyst. Here the authors provide evidence of its performance for n-butane conversion, demonstrating that isomerization is accompanied by disproportionation and other, less well understood, acid-catalyzed reactions and undergoes rapid deactivation associated with deposition of carbonaceous material. 10 refs., 3 figs.

  2. Combined Extraction of Cesium and Strontium from Akaline Nitrate Solutions

    SciTech Connect (OSTI)

    Delmau, Laetitia Helene; Bonnesen, Peter V; Engle, Nancy L; Haverlock, Tamara; Sloop Jr, Frederick {Fred} V; Moyer, Bruce A

    2006-01-01

    The combined extraction of cesium and strontium from caustic wastes can be achieved by adding a crown ether and a carboxylic acid to the Caustic-Side Solvent Extraction (CSSX) solvent. The ligand 4,4'(5')-di(tert-butyl)cyclohexano-18-crown-6 and one of four different carboxylic acids were combined with the components of the CSSX solvent optimized for the extraction of cesium, allowing for the simultaneous extraction of cesium and strontium from alkaline nitrate media simulating alkaline high level wastes present at the U.S. Department of Energy Savannah River Site. Extraction and stripping experiments were conducted independently and exhibited adequate results for mimicking waste simulant processing through batch contacts. The promising results of these batch tests showed that the system could reasonably be tested on actual waste.

  3. 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.

  4. 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.

  5. 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.

  6. Eastman, AP start on coal unit

    SciTech Connect (OSTI)

    1995-10-25

    Eastman Chemical and Air Products and Chemicals (AP) have started construction of a $214-million, coal-to-methanol demonstration unit at Eastmans site in Kingsport, TN. The project is part of the Department of Energy`s clean coal technology program and is receiving $93 million in federal support. The demonstration unit-which will have a methanol capacity of 260 tons/day-will use novel catalyst technology for converting coal-derived synthesis gas (syngas) to methanol. Unlike conventional technology that processes syngas through a fixed bed of dry catalyst particles, the liquid-phase methanol process converts the syngas in a single vessel containing catalysts suspended in mineral oil. The companies say the innovation allows the process to better able handle the gases from coal gasifiers and is more stable and reliable than existing processes. Eastman says it will use the methanol produced by the plant as a chemical feedstock. It currently uses methanol as an intermediate in making acetic anhydride and dimethyl terephthalate. In addition, the companies say the methanol will be evaluated as a feedstock in making methyl tert-butyl ether for reformulated fuels. Eastman also says it will evaluate coproducing dimethyl ether (DME) with the methanol. DME can be used as a fuel additive or blended with methanol for a chemical feedstock, according to Eastman.

  7. DESIGN AND SYNTHESIS OF THE NEXT GENERATION OF CROWN ETHERS FOR WASTE SEPARATIONS: AN INTER-LABORATORY COMPREHENSIVE PROPOSAL

    SciTech Connect (OSTI)

    Moyer, Bruce A.

    2000-12-31

    The objectives of this project were to develop the techniques, materials, and fundamental understanding necessary to solve difficult separations problems of the USDOE in the 21st century. The specific goals included developing new, powerful molecular modeling tools for ligand design, performing computational and structural studies to reveal fundamental properties of ligand-metal ion interactions, studying solvent extraction behavior to provide basic understanding of solution speciation and equilibria, and preparing new ion-exchange resins for the separation of metal ions of environmental significance to the USDOE. Contaminants of special interest included alkali and alkaline-earth metal ions, especially, lithium, cesium, and strontium. For example, Li+ ions contaminate the groundwater at the Oak Ridge Y-12 Plant; Cs+ and Sr2+ represent fission products in groundwater (e.g., INEEL, Hanford), stored waste (e.g., Savannah River Site, Hanford tanks), and process-water streams (e. g., ORNL).

  8. Extraction of Cesium by a Calix[4]arene-Crown-6 Ether Bearing a Pendant amine Group

    SciTech Connect (OSTI)

    Harmon, Ben; Ensor, Dale; Delmau, Laetitia Helene; Moyer, Bruce A

    2007-01-01

    The goal of this work was to evaluate the role of the amino group of 5-aminomethylcalix[4]arene-[bis-4-(2-ethylhexyl)benzo-crown-6] (AMBEHB) in the extraction of cesium from acidic and basic mixtures of sodium nitrate and other concentrated salts. The extraction of cesium from nitrate media was measured as a function of extractant concentration, nitrate concentration, cesium concentration, and pH over the range 1-13. The initial studies showed a moderate decrease in the extraction of cesium in acidic media, which indicated the binding of cesium by the calixarene-crown was weakened by the protonation of the amine group. The results also indicated that a 1:1:1 Cs-ligand-nitrate complex is formed in the organic phase. To further evaluate AMBEHB, the empirical data were mathematically modeled to determine the formation constants of the complexes formed in the organic phase. The resulting formation constants showed that the attachment of the amine group to the calixarene-crown molecule reduced the binding stability for the cesium ion upon contact with an acidic solution. This supports the hypothesis of charge repulsion as the basis for more efficient stripping of cesium via pH-switching.

  9. 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.

  10. Aggregation behavior of hexaoxyethyleneglycol myristate and hexaoxyethyleneglycol mono (1-methyltridecane) ether and dynamics of their micelles in aqueous solution

    SciTech Connect (OSTI)

    Alami, E.; Zana, R. ); Van Os, N.M.; Jong, B. de; Kerkhof, F.J.M. ); Rupert, L.A.M. )

    1993-10-01

    The title surfactants have similar critical micelle concentrations and cloud temperatures. Their micellar solutions have been investigated by time resolved fluorescence quenching in the range 2--25 c. The micelle aggregation numbers of both surfactants do not differ much, and increase with temperature. Aggregation numbers are large, suggesting anisotropic micelles, and the results show that the micelles are polydisperse. Fast intermicellar exchange of material becomes detectable on the fluorescence timescale ([approximately]1 [mu]s) above T [approx] 10 C, i.e., some 35--40 C below the cloud temperature of the solution. This exchange probably occurs via micelle collisions with temporary merging. Overall the behavior of these two surfactants is very similar to that of the other ethoxylated nonionic surfactants previously examined.

  11. Superacid catalysis of light hydrocarbon conversion. DOE PETC third quarterly report, February 25, 1994--May 24, 1994

    SciTech Connect (OSTI)

    Gates, B.C.

    1995-12-31

    Environmental concerns are leading to the replacement of aromatic hydrocarbons in gasoline by high-octane-number branched paraffins and oxygenated compounds such as methyl t-butyl ether. The ether is produced from methanol and isobutylene, and the latter can be formed from n-butane by isomerization followed by dehydrogenation. Paraffin isomerization reactions are catalyzed by very strong acids such as aluminum chloride supported on alumina. The aluminum chloride-containing catalysts are corrosive, and their disposal is expensive. Alternatively, hydroisomerization is catalyzed by zeolite-supported metals at high temperatures, but high temperatures do not favor branched products at equilibrium. Thus there is a need for improved catalysts and processes for the isomerization of n-butane and other straight-chain paraffins. Consequently, researchers have sought for solid acids that are noncorrosive and active enough to catalyze isomerization of paraffins at low temperatures. For example, sulfated zirconia catalyzes isomerization of n-butane at temperatures as low as 25{degrees}C. The addition of iron and manganese promoters has been reported to increase the activity of sulfated zirconia for n-butane isomerization by three orders of magnitude. Although the high activity of this catalyst is now established, the reaction network is not known, and the mechanism has not been investigated. The goal of this work is to investigate low-temperature reactions of light paraffins catalyzed by solid superacids of the sulfated zirconia type. The present report is concerned with catalysis of n-butane conversion catalyzed by the Fe- and Mn- promoted sulfated zirconia described in the previous report in this series.

  12. Synthesis of new high performance lubricants and solid lubricants. Progress report, April 1992--March 1993

    SciTech Connect (OSTI)

    Lagow, R.J.

    1993-04-01

    Synthesis and testing was begun on a number of new classes of lubricants: perfluoropolyethers (branching effects), perfluoromethylene oxide ethers, chlorine-substituted fluorocarbon polyethers, fluorine-containing branched ether lubricants, glycerine- based perfluoropolyesters, perfluoro epoxy ether chains, etc.

  13. Synthesis of new high performance lubricants and solid lubricants

    SciTech Connect (OSTI)

    Lagow, R.J.

    1993-04-01

    Synthesis and testing was begun on a number of new classes of lubricants: perfluoropolyethers (branching effects), perfluoromethylene oxide ethers, chlorine-substituted fluorocarbon polyethers, fluorine-containing branched ether lubricants, glycerine- based perfluoropolyesters, perfluoro epoxy ether chains, etc.

  14. Selecting activated carbon for water and wastewater treatability studies

    SciTech Connect (OSTI)

    Zhang, W.; Chang, Q.G.; Liu, W.D.; Li, B.J.; Jiang, W.X.; Fu, L.J.; Ying, W.C.

    2007-10-15

    A series of follow-up investigations were performed to produce data for improving the four-indicator carbon selection method that we developed to identify high-potential activated carbons effective for removing specific organic water pollutants. The carbon's pore structure and surface chemistry are dependent on the raw material and the activation process. Coconut carbons have relatively more small pores than large pores; coal and apricot nutshell/walnut shell fruit carbons have the desirable pore structures for removing adsorbates of all sizes. Chemical activation, excessive activation, and/or thermal reactivation enlarge small pores, resulting in reduced phenol number and higher tannic acid number. Activated carbon's phenol, iodine, methylene blue, and tannic acid numbers are convenient indicators of its surface area and pore volume of pore diameters < 10, 10-15, 15-28, and > 28 angstrom, respectively. The phenol number of a carbon is also a good indicator of its surface acidity of oxygen-containing organic functional groups that affect the adsorptive capacity for aromatic and other small polar organics. The tannic acid number is an indicator of carbon's capacity for large, high-molecular-weight natural organic precursors of disinfection by-products in water treatment. The experimental results for removing nitrobenzene, methyl-tert-butyl ether, 4,4-bisphenol, humic acid, and the organic constituents of a biologically treated coking-plant effluent have demonstrated the effectiveness of this capacity-indicator-based method of carbon selection.

  15. 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.

  16. Zelenay named Electrochemical Society Fellow

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

    including non-precious metalprecious metal electrocatalysis of oxygen reduction and methanol and dimethyl ether oxidation; hydrogen, direct methanol, and direct dimethyl ether...

  17. 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}.

  18. Thermoset epoxy polymers from renewable resources

    DOE Patents [OSTI]

    East, Anthony; Jaffe, Michael; Zhang, Yi; Catalani, Luiz H

    2009-11-17

    Novel thermoset epoxy polymers using the bisglycidyl ethers of anhydrosugars, such as isosorbide, isomannide, and isoidide, are disclosed. The bisglycidyl ethers are useful as substitutes for bisphenol A in the manufacture of thermoset epoxy ethers. The anhydrosugars are derived from renewable sources and the bisglycidyl ethers are not xenoestrogenic and the thermoset curing agents are likewise derived form renewable resources.

  19. 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.

  20. Developing and Testing an Alkaline-Side Solvent Extraction Process for Technetium Separation from Tank Waste

    SciTech Connect (OSTI)

    Leonard, Ralph A.; Conner, Cliff; Liberatore, Matthew W.; Bonnesen, Peter V.; Presley, Derek J.; Moyer, Bruce A.; Lumetta, Gregg J. )

    1998-11-01

    Engineering development and testing of the SRTALK solvent extraction process are discussed in this paper. This process provides a way to carry out alkaline-side removal and recovery of technetium in the form of pertechnetate anion from nuclear waste tanks within the DOE complex. The SRTALK extractant consists of a crown ether, bis-4,4'(5')[(tert-butyl)cyclohexano]-18-crown-6, in a modifier, tributyl phosphate, and a diluent, Isopar-L. The SRTALK flowsheet given here separates technetium form the waste and concentrates it by a factor of ten to minimize the load on downstream evaporator for the technetium effluent. In this work, we initially generated and correlated the technetium extraction data, measured the dispersion number for various processing conditions, and determined hydraulic performance in a single-stage 2-cm centrifugal contactor. Then we used extraction-factor analysis, single-stage contactor tests, and stage-to-stage process calculations to develop a SRTALK flowsheet . Key features of the flowsheet are (1) a low organic-to-aqueous (O/A) flow ratio in the extraction section and a high O/A flow ratio in the strip section to concentrate the technetium and (2) the use of a scrub section to reduce the salt load in the concentrated technetium effluent. Finally, the SRTALK process was evaluated in a multistage test using a synthetic tank waste. This test was very successful. Initial batch tests with actual waste from the Hanford nuclear waste tanks show the same technetium extractability as determined with the synthetic waste feed. Therefore, technetium removal from actual tank wastes should also work well using the SRTALK process.

  1. The origin and fate of organic pollutants from the combustion of alternative fuels

    SciTech Connect (OSTI)

    1995-06-01

    The overall objective of this project is to determine the impact of alternative fuels on air quality, particularly ozone formation. The objective will be met through three steps: (1) qualitative identification of alternative fuel combustion products, (2) quantitative measurement of specific emission levels of these products, and (3) determination of the fate of the combustion products in the atmosphere. The alternative fuels of interest are methanol, ethanol, natural gas, and LP gas. The role of the University of Dayton Research Institute (UDRI) in this project is two-fold. First, fused silica flow reactor instrumentation is being used to obtain both qualitative identification and quantitative data on the thermal degradation products from the fuel-lean (oxidative), stoichiometric, and fuel-rich (pyrolytic) decomposition of methanol, ethanol, liquefied petroleum gas, and natural gas. Secondly, a laser photolysis/laser-induced fluorescence (LP/LIF) apparatus is being used to determine the rates and mechanisms of reaction of selected degradation products under atmospheric conditions. This draft final report contains the results of the second year of the study. The authors initially discuss the results of their flow reactor studies. This is followed by a discussion of the initial results from their LP/LIF studies of the reaction of hydroxyl (OH) radicals with methanol and ethanol. In the coming year, they plan to obtain quantitative data on the oxidation of methyl-t-butyl-ether and reformulated gasoline under fuel-lean, stoichiometric, and fuel-rich conditions. They also plan to conduct a mechanistic analysis of the reaction of OH with acetaldehyde and formaldehyde over an extended temperature range.

  2. CATALYST ACTIVITY MAINTENANCE FOR THE LIQUID PHASE SYNTHESIS GAS-TO-DIMETHYL ETHER PROCESS PART II: DEVELOPMENT OF ALUMINUM PHOSPHATE AS THE DEHYDRATION CATALYST FOR THE SINGLE-STEP LIQUID PHASE SYNGAS-TO-DME PROCESS

    SciTech Connect (OSTI)

    Xiang-Dong Peng

    2002-05-01

    At the heart of the single-step liquid phase syngas-to-DME process (LPDME{trademark}) is a catalyst system that can be active as well as stable. In the Alternative Fuels I program, a dual-catalyst system containing a Cu-based commercial methanol synthesis catalyst (BASF S3-86) and a commercial dehydration material ({gamma}-alumina) was demonstrated. It provided the productivity and selectivity expected from the LPDME process. However, the catalyst system deactivated too rapidly to warrant a viable commercial process [1]. The mechanistic investigation in the early part of the DOE's Alternative Fuels II program revealed that the accelerated catalyst deactivation under LPDME conditions is due to detrimental interaction between the methanol synthesis catalyst and methanol dehydration catalyst [2,3]. The interaction was attributed to migration of Cu- and/or Zn-containing species from the synthesis catalyst to the dehydration catalyst. Identification of a dehydration catalyst that did not lead to this detrimental interaction while retaining adequate dehydration activity was elusive. Twenty-nine different dehydration materials were tested, but none showed the desired performance [2]. The search came to a turning point when aluminum phosphate was tested. This amorphous material is prepared by precipitating a solution containing Al(NO{sub 3}){sub 3} and H{sub 3}PO{sub 4} with NH{sub 4}OH, followed by washing, drying and calcination. The aluminum phosphate catalyst has adequate dehydration activity and good stability. It can co-exist with the Cu-based methanol synthesis catalyst without negatively affecting the latter catalyst's stability. This report documents the details of the development of this catalyst. These include initial leads, efforts in improving activity and stability, investigation and development of the best preparation parameters and procedures, mechanistic understanding and resulting preparation guidelines, and the accomplishments of this work.

  3. Inquiring Minds - Questions About Physics

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

    Concept of ether in explaining forces You asked: Will there be any research carried out in the near or distant future to find a physical relationship between gravity, mass, light, matter/antimatter through something like the idea of ether hundred years ago? The concept of ether surfaced decades before scientists knew of quantum mechanics and some very fundamental symmetry principles of the microscopic world. Because of the huge change in knowledge, the historic word ether is not used anymore

  4. 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.

  5. 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 ...

  6. 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 ...

  7. U.S. Crude Oil and Petroleum Products Stocks by Type

    Gasoline and Diesel Fuel Update (EIA)

    Product: Crude Oil and Petroleum Products Crude Oil All Oils (Excluding Crude Oil) Pentanes Plus Liquefied Petroleum Gases Ethane/Ethylene Ethylene Propane/Propylene Propylene (Nonfuel Use) Normal Butane/Butylene Refinery Grade Butane Isobutane/Butylene Other Hydrocarbons Oxygenates (excluding Fuel Ethanol) MTBE Other Oxygenates Renewables (including Fuel Ethanol) Fuel Ethanol Renewable Diesel Fuel Other Renewable Fuels Unfinished Oils Unfinished Oils, Naphthas & Lighter Unfinished Oils,

  8. West Coast (PADD 5) Total Crude Oil and Products Imports

    Gasoline and Diesel Fuel Update (EIA)

    Reformulated Gasoline Blend. Comp. Conventional Gasoline Blend. Comp. MTBE (Oxygenate) Other Oxygenates Fuel Ethanol (Renewable) Biomass-Based Diesel (Renewable) Other Renewable Diesel Distillate Fuel Oil Distillate F.O., 15 ppm and under Distillate F.O., 15 to 500 ppm Distillate F.O., Greater than 500 ppm Distillate F.O., 501 to 2000 ppm Distillate F.O., Greater than 2000 ppm Kerosene Finished Aviation Gasoline Aviation Gasoline Blending Components Kerosene-Type Jet Fuel Special Naphthas

  9. Net Imports of Total Crude Oil and Products into the U.S. by Country

    Gasoline and Diesel Fuel Update (EIA)

    Product: Total Crude Oil and Products Crude Oil Products Pentanes Plus Liquefied Petroleum Gases Unfinished Oils Finished Motor Gasoline Reformulated Conventional Motor Gasoline Blending Components Reformulated Gasoline Blend. Comp. Conventional Gasoline Blend. Comp. MTBE (Oxygenate) Other Oxygenates Fuel Ethanol (Renewable) Biomass-Based Diesel Other Renewable Diesel Other Renewable Fuels Distillate Fuel Oil Distillate F.O., 15 ppm and under Distillate F.O., 15 to 500 ppm Distillate F.O., 500

  10. Total

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

    Product: Total Crude Oil Liquefied Petroleum Gases Propane/Propylene Normal Butane/Butylene Other Liquids Oxygenates Fuel Ethanol MTBE Other Oxygenates Biomass-based Diesel Fuel Other Renewable Diesel Fuel Other Renewable Fuels Gasoline Blending Components Petroleum Products Finished Motor Gasoline Reformulated Gasoline Conventional Gasoline Kerosene-Type Jet Fuel Kerosene Distillate Fuel Oil Distillate Fuel Oil, 15 ppm Sulfur and Under Distillate Fuel Oil, Greater than 15 ppm to 500 ppm Sulfur

  11. Total

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

    Product: Total Crude Oil Liquefied Petroleum Gases Propane/Propylene Normal Butane/Butylene Other Liquids Oxygenates Fuel Ethanol MTBE Other Oxygenates Biomass-based Diesel Other Renewable Diesel Fuel Other Renewable Fuels Gasoline Blending Components Petroleum Products Finished Motor Gasoline Reformulated Gasoline Conventional Gasoline Kerosene-Type Jet Fuel Kerosene Distillate Fuel Oil Distillate Fuel Oil, 15 ppm Sulfur and Under Distillate Fuel Oil, Greater than 15 ppm to 500 ppm Sulfur

  12. West Coast (PADD 5) Total Crude Oil and Products Imports

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

    Reformulated Gasoline Blend. Comp. Conventional Gasoline Blend. Comp. MTBE (Oxygenate) Other Oxygenates Fuel Ethanol (Renewable) Biomass-Based Diesel (Renewable) Other Renewable Diesel Distillate Fuel Oil Distillate F.O., 15 ppm and under Distillate F.O., 15 to 500 ppm Distillate F.O., Greater than 500 ppm Distillate F.O., 501 to 2000 ppm Distillate F.O., Greater than 2000 ppm Kerosene Finished Aviation Gasoline Aviation Gasoline Blending Components Kerosene-Type Jet Fuel Special Naphthas

  13. Composition and process for separating cesium ions from an acidic aqueous solution also containing other ions

    DOE Patents [OSTI]

    Dietz, M.L.; Horwitz, E.P.; Bartsch, R.A.; Barrans, R.E. Jr.; Rausch, D.

    1999-03-30

    A crown ether cesium ion extractant is disclosed as is its synthesis. The crown ether cesium ion extractant is useful for the selective purification of cesium ions from aqueous acidic media, and more particularly useful for the isolation of radioactive cesium-137 from nuclear waste streams. Processes for isolating cesium ions from aqueous acidic media using the crown ether cesium extractant are disclosed as are processes for recycling the crown ether cesium extractant and processes for recovering cesium from a crown ether cesium extractant solution. 4 figs.

  14. Composition and process for separating cesium ions from an acidic aqueous solution also containing other ions

    DOE Patents [OSTI]

    Dietz, Mark L.; Horwitz, E. Philip; Bartsch, Richard A.; Barrans, Jr., Richard E.; Rausch, David

    1999-01-01

    A crown ether cesium ion extractant is disclosed as is its synthesis. The crown ether cesium ion extractant is useful for the selective purification of cesium ions from aqueous acidic media, and more particularly useful for the isolation of radioactive cesium-137 from nuclear waste streams. Processes for isolating cesium ions from aqueous acidic media using the crown ether cesium extractant are disclosed as are processes for recycling the crown ether cesium extractant and processes for recovering cesium from a crown ether cesium extractant solution.

  15. 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.

  16. 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.

  17. [Research and workshop on alternative fuels for aviation. Final report

    SciTech Connect (OSTI)

    1999-09-01

    The Renewable Aviation Fuels Development Center (RAFDC) at Baylor University was granted U. S. Department of Energy (US DOE) and Federal Aviation Administration (FAA) funds for research and development to improve the efficiency in ethanol powered aircraft, measure performance and compare emissions of ethanol, Ethyl Tertiary Butyl Ether (ETBE) and 100 LL aviation gasoline. The premise of the initial proposal was to use a test stand owned by Engine Components Inc. (ECI) based in San Antonio, Texas. After the grant was awarded, ECI decided to close down its test stand facility. Since there were no other test stands available at that time, RAFDC was forced to find additional support to build its own test stand. Baylor University provided initial funds for the test stand building. Other obstacles had to be overcome in order to initiate the program. The price of the emission testing equipment had increased substantially beyond the initial quote. Rosemount Analytical Inc. gave RAFDC an estimate of $120,000.00 for a basic emission testing package. RAFDC had to find additional funding to purchase this equipment. The electronic ignition unit also presented a series of time consuming problems. Since at that time there were no off-the-shelf units of this type available, one had to be specially ordered and developed. FAA funds were used to purchase a Super Flow dynamometer. Due to the many unforeseen obstacles, much more time and effort than originally anticipated had to be dedicated to the project, with much of the work done on a volunteer basis. Many people contributed their time to the program. One person, mainly responsible for the initial design of the test stand, was a retired engineer from Allison with extensive aircraft engine test stand experience. Also, many Baylor students volunteered to assemble the. test stand and continue to be involved in the current test program. Although the program presented many challenges, which resulted in delays, the RAFDC's test stand is an asset which provides an ongoing research capability dedicated to the testing of alternative fuels for aircraft engines. The test stand is now entirely functional with the exception of the electronic ignition unit which still needs adjustments.

  18. Pressure Swing Absorption Device and Process for Separating CO{sub 2} from Shifted Syngas and its Capture for Subsequent Storage

    SciTech Connect (OSTI)

    Sirkar, Kamalesh; Jie, Xingming; Chau, John; Obuskovic, Gordana

    2013-03-31

    Using the ionic liquid (IL) 1-butyl-3-methylimidazolium dicyanamide ([bmim][DCA]) as the absorbent on the shell side of a membrane module containing either a porous hydrophobized ceramic tubule or porous hydrophobized polyether ether ketone (PEEK) hollow fiber membranes, studies for CO{sub 2} removal from hot simulated pre-combustion shifted syngas were carried out by a novel pressure swing membrane absorption (PSMAB) process. Helium was used as a surrogate for H{sub 2} in a simulated shifted syngas with CO{sub 2} around 40% (dry gas basis). In this cyclic separation process, the membrane module was used to achieve non-dispersive gas absorption from a high-pressure feed gas (689-1724 kPag; 100-250 psig) at temperatures between 25-1000C into a stationary absorbent liquid on the module shell side during a certain part of the cycle followed by among other cycle steps controlled desorption of the absorbed gases from the liquid in the rest of the cycle. Two product streams were obtained, one He-rich and the other CO{sub 2}-rich. Addition of polyamidoamine (PAMAM) dendrimer of generation 0 to IL [bmim][DCA] improved the system performance at higher temperatures. The solubilities of CO{sub 2} and He were determined in the ionic liquid with or without the dendrimer in solution as well as in the presence or absence of moisture; polyethylene glycol (PEG) 400 was also studied as a replacement for the IL. The solubility selectivity of the ionic liquid containing the dendrimer for CO{sub 2} over helium was considerably larger than that for the pure ionic liquid. The solubility of CO{sub 2} and CO{sub 2}-He solubility selectivity of PEG 400 and a solution of the dendrimer in PEG 400 were higher than the corresponding ones in the IL, [bmim][DCA]. A mathematical model was developed to describe the PSMAB process; a numerical solution of the governing equations described successfully the observed performance of the PSMAB process for the pure ionic liquid-based system.

  19. Radiation Stability of Benzyl Tributyl Ammonium Chloride Towards Technetium-99 Extraction

    SciTech Connect (OSTI)

    Jared Horkley; Audrey Roman; Keri Campbell; Ana Nunez; Amparo Espartero

    2013-02-01

    A closed nuclear fuel cycle combining new separation technologies along with generation III and generation IV reactors is a promising way to achieve a sustainable energy supply. But it is important to keep in mind that future recycling processes of used nuclear fuel (UNF) must minimize wastes, improve partitioning process, and integrate waste considerations into processes. New separation processes are being developed worldwide to complement the actual industrialized PUREX process which selectively separates U(VI) and Pu(IV) from the raffinate. As an example, low nitric acid concentration in the aqueous phase of a UREX based process will co-extract U(VI) and Tc(VII) by tri-n-butyl phosphate (TBP). Technetium (Tc-99) is recognized to be one of the most abundant, long-lived radiotoxic isotopes in UNF (half-life, t1/2 = 2.13 × 105 years), and as such, it is targeted in UNF separation strategies for isolation and encapsulation in solid waste forms for final disposal in a nuclear waste repository. Immobilization of Tc-99 by a durable solid waste form is a challenge, and its fate in new advanced technology processes is of importance. It is essential to be able to quantify and locate 1) its occurrence in any new developed flow sheets, 2) its chemical form in the individual phases of a process, 3) its potential quantitative transfer in any waste streams, and consequently, 4) its quantitative separation for either potential transmutation to Ru-100 or isolation and encapsulation in solid waste forms for ultimate disposal. Furthermore, as a result of an U(VI)-Tc(VII) co-extraction in a UREX-based process, Tc(VII) could be found in low level waste (LLW) streams. There is a need for the development of new extraction systems that would selectively extract Tc-99 from LLW streams and concentrate it for feed into high level waste (HLW) for either Tc-99 immobilization in metallic waste forms (Tc-Zr alloys), and/or borosilicate-based waste glass. Studies have been launched to investigate the suitability of new macrocompounds such as crown-ethers, aza-crown ethers, and resorcinarenes for the selective extraction of Tc-99 from nitric acid solutions. The selectivity of the ligand is important in evaluating potential separation processes and also the radiation stability of the molecule is essential for minimization of waste and radiolysis products. In this paper, we are reporting the extraction of TcO4- by benzyltributyl ammonium chloride (BTBA). Experimental efforts were focused on determining the best extraction conditions by varying the ligand’s matrix conditions and concentration, as well as varying the organic phase composition (i.e., diluent variation). Furthermore, the ligand has been investigated for radiation stability. The ?-irradiation was performed on the neat organic phases containing the ligand at different absorbed doses to a maximum of 200 kGy using external Co-60 source. Post-irradiation solvent extraction measurements will be discussed.

  20. Radiation Stability of Benzyl Tributyl Ammonium Chloride towards Technetium-99 Extraction - 13016

    SciTech Connect (OSTI)

    Paviet-Hartmann, Patricia; Horkley, Jared; Campbell, Keri; Roman, Audrey; Nunez, Ana; Espartero, Amparo

    2013-07-01

    A closed nuclear fuel cycle combining new separation technologies along with generation III and generation IV reactors is a promising way to achieve a sustainable energy supply. But it is important to keep in mind that future recycling processes of used nuclear fuel (UNF) must minimize wastes, improve partitioning processes, and integrate waste considerations into processes. New separation processes are being developed worldwide to complement the actual industrialized PUREX process which selectively separates U(VI) and Pu(IV) from the raffinate. As an example, the UREX process has been developed in the United States to co-extract hexavalent uranium (U) and hepta-valent technetium (Tc) by tri-n-butyl phosphate (TBP). Tc-99 is recognized to be one of the most abundant, long-lived radio-toxic isotopes in UNF (half-life, t{sub 1/2} = 2.13 x 10{sup 5} years), and as such, is targeted in UNF separation strategies for isolation and encapsulation in solid waste-forms for final disposal in a nuclear waste repository. Immobilization of Tc-99 by a durable solid waste-form is a challenge, and its fate in new advanced technology processes is of importance. It is essential to be able to quantify and locate 1) its occurrence in any new developed flowsheets, 2) its chemical form in the individual phases of a process, 3) its potential quantitative transfer in any waste streams, and consequently, 4) its quantitative separation for either potential transmutation to Ru-100 or isolation and encapsulation in solid waste-forms for ultimate disposal. In addition, as a result of an U(VI)-Tc(VII) co-extraction in a UREX-based process, Tc(VII) could be found in low level waste (LLW) streams. There is a need for the development of new extraction systems that would selectively extract Tc-99 from LLW streams and concentrate it for feed into high level waste (HLW) for either Tc-99 immobilization in metallic waste-forms (Tc-Zr alloys), and/or borosilicate-based waste glass. Studies have been launched to investigate the suitability of new macro-compounds such as crown-ethers, aza-crown ethers, quaternary ammonium salts, and resorcin-arenes for the selective extraction of Tc-99 from nitric acid solutions. The selectivity of the ligand is important in evaluating potential separation processes and also the radiation stability of the molecule is essential for minimization of waste and radiolysis products. In this paper, we are reporting the extraction of TcO{sub 4}{sup -} by benzyl tributyl ammonium chloride (BTBA). Experimental efforts were focused on determining the best extraction conditions by varying the ligand's matrix conditions and concentration, as well as varying the organic phase composition (i.e. diluent variation). Furthermore, the ligand has been investigated for radiation stability. The ?-irradiation was performed on the neat organic phases containing the ligand at different absorbed doses to a maximum of 200 kGy using an external Co-60 source. Post-irradiation solvent extraction measurements will be discussed. (authors)

  1. Radionuclide-binding compound, a radionuclide delivery system, a method of making a radium complexing compound, a method of extracting a radionuclide, and a method of delivering a radionuclide

    DOE Patents [OSTI]

    Fisher, Darrell R. (Richland, WA); Wai, Chien M. (Moscow, ID); Chen, Xiaoyuan (Moscow, ID)

    2000-01-01

    The invention pertains to compounds which specifically bind radionuclides, and to methods of making radionuclide complexing compounds. In one aspect, the invention includes a radionuclide delivery system comprising: a) a calix[n]arene-crown-[m]-ether compound, wherein n is an integer greater than 3, and wherein m is an integer greater than 3, the calix[n]arene-crown-[m]-ether compound comprising at least two ionizable groups; and b) an antibody attached to the calix[n]arene-crown-[m]-ether compound. In another aspect, the invention includes a method of making a radium complexing compound, comprising: a) providing a calix[n]arene compound, wherein n is an integer greater than 3, the calix[n]arene compound comprising n phenolic hydroxyl groups; b) providing a crown ether precursor, the crown ether precursor comprising a pair of tosylated ends; c) reacting the pair of tosylated ends with a pair of the phenolic hydroxyl groups to convert said pair of phenolic hydroxyl groups to ether linkages, the ether linkages connecting the crown ether precursor to the calix[n]arene to form a calix[n]arene-crown-[m]-ether compound, wherein m is an integer greater than 3; d) converting remaining phenolic hydroxyl groups to esters; e) converting the esters to acids, the acids being proximate a crown-[m]-ether portion of the calix[n]arene-crown-[m]-ether compound; and f) providing a Ra.sup.2+ ion within the crown-[m]-ether portion of the calix[n]arene-crown-[m]-ether compound.

  2. Aza compounds as anion receptors

    DOE Patents [OSTI]

    Lee, Hung Sui (East Setauket, NY); Yang, Xiao-Qing (Port Jefferson Station, NY); McBreen, James (Bellport, NY)

    1998-01-06

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of Li.sup.+ ion in alkali metal batteries.

  3. Anion receptor compounds for non-aqueous electrolytes

    DOE Patents [OSTI]

    Lee, Hung Sui (East Setauket, NY); Yang, Xiao-Oing (Port Jefferson Station, NY); McBreen, James (Bellport, NY)

    2000-09-19

    A new family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the new family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of LI.sup.+ ion in alkali metal batteries.

  4. Aza compounds as anion receptors

    DOE Patents [OSTI]

    Lee, H.S.; Yang, X.Q.; McBreen, J.

    1998-01-06

    A family of aza-ether based compounds including linear, multi-branched and aza-crown ethers is provided. When added to non-aqueous battery electrolytes, the family of aza-ether based compounds acts as neutral receptors to complex the anion moiety of the electrolyte salt thereby increasing the conductivity and the transference number of Li{sup +} ion in alkali metal batteries. 3 figs.

  5. Sandia Energy Research & Capabilities

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

    CRF Experiment Confirms Accepted Oxidation Scheme of Proposed Diesel Alternative: Dimethyl Ether http:energy.sandia.govcrf-experiment-confirms-accepted-oxidation-scheme-of-propo...

  6. DOE Selects 16 Transformational Carbon Capture Technologies Projects...

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

    Corporation (Woburn, MA), and Trimeric Corporation (Buda, TX) - will combine a graphene oxide (GO) membrane unit with the polyether ether ketone (PEEK) hollow fiber membrane...

  7. Nuclear Materials Research and Technology/Los Alamos National...

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

    Crown Ether Complex 6 "Excess" Nuclear Materials Hold Keys to Medicine, ... that culminates in plutonium. 2 Nuclear Materials Research and TechnologyLos ...

  8. Newsletter

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

    create expertly carved jack-o-lanterns, and enjoy this year's selection. Hear ethereal music performed by vibrating strings. Check out creepy, crawly critters like snakes,...

  9. Special Lecture:

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

    create expertly carved jack-o-lanterns, and enjoy this year's selection. Hear ethereal music performed by vibrating strings. Check out creepy, crawly critters like snakes,...

  10. Research on Fuels & Lubricants | Department of Energy

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

    PDF icon 2003deerperez.pdf More Documents & Publications Alternative Fuels lDimethyl Ether Rheology and Materials Studies Natural Oils - The Next Generation of Diesel Engine ...

  11. Scientific Achievement

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

    convert furans to alcohols via hydrogenation through the MPV mechanism and then to ethers. Combined with metal catalysts (RuC), synergetic hydrogenolysis occurs. Catalytic...

  12. ALSNews Vol. 319

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

    molecules mimic double slits Secrets of a Precision Protein Machine One "Cool Tool" That's Helping Repair Your DNA AFRD's Leemans Surfs the Ether in a Scientists' Soccer Match...

  13. Dr. Googin and his early days at Y-12, part 10 ? Googin, a valuable...

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

    first processing building for the Beta intermediate and final product cycles, where solvent extraction with diethyl ether was used to purify and recover the uranium instead of...

  14. Gulf Coast (PADD 3) Total Crude Oil and Products Imports

    Gasoline and Diesel Fuel Update (EIA)

    MTBE (Oxygenate) Other Oxygenates Fuel Ethanol (Renewable) Biomass-Based Diesel (Renewable) Other Renewable Diesel Distillate Fuel Oil Distillate F.O., 15 ppm and under Distillate F.O., 15 to 500 ppm Distillate F.O., Greater than 500 ppm Distillate F.O., 501 to 2000 ppm Distillate F.O., Greater than 2000 ppm Kerosene Finished Aviation Gasoline Aviation Gasoline Blending Components Kerosene-Type Jet Fuel Special Naphthas Residual Fuel Oil Residual F.O., Less than 0.31% Sulfur Residual F.O., 0.31

  15. Gulf Coast (PADD 3) Total Crude Oil and Products Imports

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

    MTBE (Oxygenate) Other Oxygenates Fuel Ethanol (Renewable) Biomass-Based Diesel (Renewable) Other Renewable Diesel Distillate Fuel Oil Distillate F.O., 15 ppm and under Distillate F.O., 15 to 500 ppm Distillate F.O., Greater than 500 ppm Distillate F.O., 501 to 2000 ppm Distillate F.O., Greater than 2000 ppm Kerosene Finished Aviation Gasoline Aviation Gasoline Blending Components Kerosene-Type Jet Fuel Special Naphthas Residual Fuel Oil Residual F.O., Less than 0.31% Sulfur Residual F.O., 0.31

  16. 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.

  17. 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.

  18. Water-soluble polymers and compositions thereof

    DOE Patents [OSTI]

    Smith, Barbara F. (Los Alamos, NM); Robison, Thomas W. (Los Alamos, NM); Gohdes, Joel W. (Los Alamos, NM)

    1999-01-01

    Water-soluble polymers including functionalization from the group of amino groups, carboxylic acid groups, phosphonic acid groups, phosphonic ester groups, acylpyrazolone groups, hydroxamic acid groups, aza crown ether groups, oxy crown ethers groups, guanidinium groups, amide groups, ester groups, aminodicarboxylic groups, permethylated polyvinylpyridine groups, permethylated amine groups, mercaptosuccinic acid groups, alkyl thiol groups, and N-alkylthiourea groups are disclosed.

  19. Water-soluble polymers and compositions thereof

    DOE Patents [OSTI]

    Smith, B.F.; Robison, T.W.; Gohdes, J.W.

    1999-04-06

    Water-soluble polymers including functionalization from the group of amino groups, carboxylic acid groups, phosphonic acid groups, phosphonic ester groups, acylpyrazolone groups, hydroxamic acid groups, aza crown ether groups, oxy crown ethers groups, guanidinium groups, amide groups, ester groups, aminodicarboxylic groups, permethylated polyvinylpyridine groups, permethylated amine groups, mercaptosuccinic acid groups, alkyl thiol groups, and N-alkylthiourea groups are disclosed.

  20. High energy electron beam curing of epoxy resin systems incorporating cationic photoinitiators

    DOE Patents [OSTI]

    Janke, C.J.; Lopata, V.J.; Havens, S.J.; Dorsey, G.F.; Moulton, R.J.

    1999-03-02

    A mixture of epoxy resins such as a semi-solid triglycidyl ether of tris (hydroxyphenyl) methane and a low viscosity bisphenol A glycidyl ether and a cationic photoinitiator such as a diaryliodonium salt is cured by irradiating with a dosage of electron beams from about 50 to about 150 kGy, forming a cross-linked epoxy resin polymer.

  1. High energy electron beam curing of epoxy resin systems incorporating cationic photoinitiators

    DOE Patents [OSTI]

    Janke, Christopher J. (Powell, TN); Lopata, Vincent J. (Manitoba, CA); Havens, Stephen J. (Knoxville, TN); Dorsey, George F. (Farragut, TN); Moulton, Richard J. (Lafayette, CA)

    1999-01-01

    A mixture of epoxy resins such as a semi-solid triglycidyl ether of tris (hydroxyphenyl) methane and a low viscosity bisphenol A glycidyl ether and a cationic photoinitiator such as a diaryliodonium salt is cured by irradiating with a dosage of electron beams from about 50 to about 150 kGy, forming a cross-linked epoxy resin polymer.

  2. Energy and crude oil input requirements for the production of reformulated gasolines

    SciTech Connect (OSTI)

    Singh, M.; McNutt, B.

    1993-11-01

    The energy and crude oil requirements for the production of reformulated gasolines (RFG) are estimated. Both the energy and crude oil embodied in the final product and the process energy required to manufacture the RFG and its components are included. The effects on energy and crude oil use of using various oxygenates to meet the minimum oxygen content level required by the Clean Air Act Amendments are evaluated. The analysis illustrates that production of RFG requires more total energy than that of conventional gasoline but uses less crude oil. The energy and crude oil use requirements of the different RFGs vary considerably. For the same emissions performance level, RFG with ethanol requires substantially more total energy and crude oil than RFG with MTBE or ETBE. A specific proposal by the EPA designed to allow the use of ethanol in RFG would increase the total energy required to produce RFG by 2% and the total crude oil required by 2.0 to 2.5% over that for the base RFG with MTBE.

  3. Sandia Corporate Overview - Core group

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

    Subsystem EtherCAT up to 1000 Hz All DAQ signals available for control Running on NI ... rotor preparation 1,000 sq. ft. machine shop Outline What is the SWiFT Facility? ...

  4. EA-1870: Mitigation Action Plan | Department of Energy

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

    could be suitable for production of clean fuels such as substitute natural gas, sulfur-free Fischer-Tropsch diesel, jet fuel, dimethyl ether, and methane. This MAP identifies...

  5. Transetherification method

    DOE Patents [OSTI]

    Hearn, Dennis (Houston, TX)

    1985-01-01

    Transetherification is carried out in a catalytic distillation reactor, wherein the catalytic structure also serves as a distillation structure, by feeding a first ether to the catalyst bed to at least partially dissociate it into a first olefin and a first alcohol while concurrently therewith feeding either a second olefin (preferably a tertiary olefin) having a higher boiling point than said first olefin or a second alcohol having a higher boiling point than said first alcohol to the catalyst whereby either the second olefin and the first alcohol or the first olefin and the second alcohol react to form a second ether which has a higher boiling point than the first ether, which second ether is concurrently removed as a bottoms in the concurrent reaction-distillation to force that reaction to completion, while the unreacted first olefin or first alcohol is removed in the overhead.

  6. Transetherification method

    DOE Patents [OSTI]

    Hearn, D.

    1985-04-09

    Transetherification is carried out in a catalytic distillation reactor, wherein the catalytic structure also serves as a distillation structure, by feeding a first ether to the catalyst bed to at least partially dissociate it into a first olefin and a first alcohol while concurrently therewith feeding either a second olefin (preferably a tertiary olefin) having a higher boiling point than said first olefin or a second alcohol having a higher boiling point than said first alcohol to the catalyst whereby either the second olefin and the first alcohol or the first olefin and the second alcohol react to form a second ether which has a higher boiling point than the first ether, which second ether is concurrently removed as a bottoms in the concurrent reaction-distillation to force that reaction to completion, while the unreacted first olefin or first alcohol is removed in the overhead. 1 fig.

  7. Poly(arylene)-based anion exchange polymer electrolytes

    DOE Patents [OSTI]

    Kim, Yu Seung; Bae, Chulsung

    2015-06-09

    Poly(arylene) electrolytes including copolymers lacking ether groups in the polymer may be used as membranes and binders for electrocatalysts in preparation of anodes for electrochemical cells such as solid alkaline fuel cells.

  8. Search for: All records | SciTech Connect

    Office of Scientific and Technical Information (OSTI)

    ... Polybrominated diphenyl ethers in e-waste: Level and transfer in a typical e-waste recycling site in Shanghai, Eastern China Li, Yue ; Duan, Yan-Ping, E-mail: duanyanping@tongji.ed...

  9. Qualitative assessment of the ignition of highly flammable fuels by primary explosives

    SciTech Connect (OSTI)

    Elischer, P.P.; De Yong, L.

    1983-06-01

    An assessment of the ignition of fuel/air mixtures and of fabrics soaked with different fuels (ethanol, n-hexane and diethyl ether) by primary explosives has been carried out.

  10. ALSNews Vol. 319

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

    Tool" That's Helping Repair Your DNA AFRD's Leemans Surfs the Ether in a Scientists' Soccer Match Subscribe to ALSNews Email: Go Email Us ALSNews Archive DOE Office of Science...

  11. Purifying contaminated water

    DOE Patents [OSTI]

    Daughton, Christian G. (San Pablo, CA)

    1983-01-01

    Process for removing biorefractory compounds from contaminated water (e.g., oil shale retort waste-water) by contacting same with fragmented raw oil shale. Biorefractory removal is enhanced by preactivating the oil shale with at least one member of the group of carboxylic, acids, alcohols, aldehydes, ketones, ethers, amines, amides, sulfoxides, mixed ether-esters and nitriles. Further purification is obtained by stripping, followed by biodegradation and removal of the cells.

  12. Quadrics Presentation for SC2001

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

    Finmeccanica Company April 2003 © Quadrics Ltd. Evolution of Interconnects for Supercomputing Moray McLaren Quadrics Ltd. A Finmeccanica Company April 2003 © Quadrics Ltd. EtherNet and EtherNot! Will standard interconnects solve all our problems? Whatever the volume interconnect of the future is, it will be called Ethernet. Incorporate ideas from specialised low latency interconnects into Ethernet? * RDMA is a start * Common DDI with high performance NICs? * Price advantage not so clear for

  13. Highly Active and Selective Metal-modified Zeolite Catalysts for Low

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

    Temperature Conversion of Methanol and Dimethyl Ether to Gasoline-range Branched Hydrocarbons - Energy Innovation Portal Biomass and Biofuels Biomass and Biofuels Find More Like This Return to Search Highly Active and Selective Metal-modified Zeolite Catalysts for Low Temperature Conversion of Methanol and Dimethyl Ether to Gasoline-range Branched Hydrocarbons National Renewable Energy Laboratory Contact NREL About This Technology Technology Marketing Summary Recent investigations by a

  14. CRF Experiment Confirms Accepted Oxidation Scheme of Proposed Diesel

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

    Alternative: Dimethyl Ether Experiment Confirms Accepted Oxidation Scheme of Proposed Diesel Alternative: Dimethyl Ether - Sandia Energy Energy Search Icon Sandia Home Locations Contact Us Employee Locator Energy & Climate Secure & Sustainable Energy Future Stationary Power Energy Conversion Efficiency Solar Energy Wind Energy Water Power Supercritical CO2 Geothermal Natural Gas Safety, Security & Resilience of the Energy Infrastructure Energy Storage Nuclear Power &

  15. New Catalyst Reduces Wasted Carbon in Biofuel Process, Lowers Cost (Fact Sheet), Highlights in Research & Development, NREL (National Renewable Energy Laboratory)

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

    researchers have shown that incorporating copper-modified catalysts into the dimethyl ether-to- fuels pathway increases carbon efficiency and decreases overall production costs. The biomass-to-liquid-fuel approach remains one of the most promising renewable fuel processes in terms of its immediate impact and compatibility with existing infrastructure. Methanol and dimethyl ether (DME) can be produced from biomass, and recent inves- tigations have shown that certain catalysts can convert these to

  16. Purifying contaminated water. [DOE patent application

    DOE Patents [OSTI]

    Daughton, C.G.

    1981-10-27

    Process is presented for removing biorefactory compounds from contaminated water (e.g., oil shale retort waste-water) by contacting same with fragmented raw oil shale. Biorefractory removal is enhanced by preactivating the oil shale with at least one member of the group of carboxylic acids, alcohols, aldehydes, ketones, ethers, amines, amides, sulfoxides, mixed ether-esters and nitriles. Further purification is obtained by stripping, followed by biodegradation and removal of the cells.

  17. Vehicular fuels and additives for the future

    SciTech Connect (OSTI)

    Not Available

    1988-01-01

    Interest in automotive fuel is resurging. Automobile fuels must increasingly deal with clean air regulations and ozone problems. Furthermore, feedstocks become heavier,as refinery production changes, as more unleaded is produced, and as an increasing number of pollution regulations must be satisfied greater attention will be paid to better mixtures, solvents, additives, and neat methanol. BCC report analyzes developments technologies, markets, players and the political/regulations aspects of this important market. Study also assesses the advantages and drawbacks of methanol, ethanol, MTBE and other additives which have their place as octane enhancers and fuel substitutes-all now deeply involved in the gasoline modification battle. Other issues addressed are subsidies, farm lobbying, imports, pricing, economics, Detroit's response, neat fuel testing projects, volatility problems vs. fewer ozone-forming hydrocarbon species, and emission ratings.

  18. Interaction between Titles 2 and 3 of the Clean Air Act as amended, 1990

    SciTech Connect (OSTI)

    Szpunar, C.B.

    1996-02-01

    This report examines Some issues that would I affect the refining industry if the requirements for hazardous air pollutants set out in Title III of the Clean Air Act Amendments were to impede the market entrance of oxygenated fuels, as me; required by Title II. It describes the mandate for reformulated gasoline; considers gasoline characteristics in light of component shifts in refining; examines the supply of, demand for, and cost of various feedstocks and blendstocks; and identifies the emissions and atmospheric impacts that might result from the production and use of reformulated gasoline. Attention is focused on methanol and MTBE, two potential blendstocks that are also hazardous air pollutants, and on maximum achievable control technology standards, which might be applied to the stationary sources that produce them.

  19. 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.

  20. 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.

  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. Synthesis of oxygenate products for high volume fuels applications. Quarterly status report No. 3 for the period April through June 1995

    SciTech Connect (OSTI)

    Not Available

    1995-09-26

    A rudimentary process variables study of the reaction of acetylene with methanol indicates high activity for the formation of ethanol, n- propanol, and i-butanol with a pure low temperature activated MgO catalyst. Initial results indicate that higher conversions and space- time yields may be obtainable by operation at higher temperatures and reactant feed rates, respectively. Also, ethanol formation was consistently observed to rise with decreasing reaction temperature between 454{degrees}C and 370{degrees}C. A 10% Al{sub 2}O{sub 3}/MgO catalyst exhibited high activity for methanol-dimethyl ether interconversion but was not very active for the condensation of these reactants to either the product alcohols or their methyl ethers. Neither catalyst exhibited significant activity for the condensation to dimethyl ether/water with acetylene to form such products. This lack of activity in the ether systems is attributed to insufficient hydrolysis of dimethyl ether to methanol, and it is expected that feeds containing additional water or methanol (which produces water via condensation) will exhibit higher activity. The aluminum- containing catalyst exhibited diminished condensation activity possibly as a result of deactivation of Mg sites by Al sites. The overall objective of this project is to develop catalyst and process technology for evaluation as potential routes for the production of high volume fuel oxygenates.

  4. Synthesis of oxygenate products for high volume fuels applications. Quarterly status report No. 4 for the period July through September 1995

    SciTech Connect (OSTI)

    Not Available

    1995-12-29

    A rudimentary process variables study of the reaction of acetylene with methanol indicates high activity for the formation of ethanol, n- propanol, and i-butanol with a pure low temperature activated MgO catalyst. Initial results indicate that higher conversions and space- time yields may be obtainable by operation at higher temperatures and reactant feed rates, respectively. Also, ethanol formation was consistently observed to rise with decreasing reaction temperature between 454{degrees}C and 370{degrees}C. A 10% Al{sub 2}O{sub 3}/MgO catalyst exhibited high activity for methanol-dimethyl ether interconversion but was not very active for the condensation of these reactants to either the product alcohols or their methyl ethers. Neither catalyst exhibited significant activity for the condensation of dimethyl ether/water with acetylene to form such products. This lack of activity in the ether systems us attributed to insufficient hydrolysis of dimethyl ether to methanol, and it is expected that feeds containing additional water or methanol (which produces water via condensation) will exhibit higher activity. The aluminum- containing catalyst exhibited diminished condensation activity possibly as the result of deactivation of Mg sites by Al sites. The overall objective of this project is to develop catalyst and process technology for evaluation as potential routes for the production of high volume fuel oxygenates.

  5. Solid sorbents for removal of carbon dioxide from gas streams at low temperatures

    DOE Patents [OSTI]

    Sirwardane, Ranjani V. (Morgantown, WV)

    2005-06-21

    New low-cost CO.sub.2 sorbents are provided that can be used in large-scale gas-solid processes. A new method is provided for making these sorbents that involves treating substrates with an amine and/or an ether so that the amine and/or ether comprise at least 50 wt. percent of the sorbent. The sorbent acts by capturing compounds contained in gaseous fluids via chemisorption and/or physisorption between the unit layers of the substrate's lattice where the polar amine liquids and solids and/or polar ether liquids and solids are located. The method eliminates the need for high surface area supports and polymeric materials for the preparation of CO.sub.2 capture systems, and provides sorbents with absorption capabilities that are independent of the sorbents' surface areas. The sorbents can be regenerated by heating at temperatures in excess of 35.degree. C.

  6. Solid Sorbents for Removal of Carbon Dioxide from Gas Streams at Low Temperatures

    SciTech Connect (OSTI)

    Sirwardane, Ranjani V.

    2005-06-21

    New low-cost CO2 sorbents are provided that can be used in large-scale gas-solid processes. A new method is provided for making these sorbents that involves treating substrates with an amine and/or an ether so that the amine and/or ether comprise at least 50 wt. percent of the sorbent. The sorbent acts by capturing compounds contained in gaseous fluids via chemisorption and/or physisorption between the unit layers of the substrate's lattice where the polar amine liquids and solids and/or polar ether liquids and solids are located. The method eliminates the need for high surface area supports and polymeric materials for the preparation of CO2 capture systems, and provides sorbents with absorption capabilities that are independent of the sorbents' surface areas. The sorbents can be regenerated by heating at temperatures in excess of 35 degrees C.

  7. High-energy metal air batteries

    DOE Patents [OSTI]

    Zhang, Ji-Guang; Xiao, Jie; Xu, Wu; Wang, Deyu; Williford, Ralph E.; Liu, Jun

    2013-07-09

    Disclosed herein are embodiments of lithium/air batteries and methods of making and using the same. Certain embodiments are pouch-cell batteries encased within an oxygen-permeable membrane packaging material that is less than 2% of the total battery weight. Some embodiments include a hybrid air electrode comprising carbon and an ion insertion material, wherein the mass ratio of ion insertion material to carbon is 0.2 to 0.8. The air electrode may include hydrophobic, porous fibers. In particular embodiments, the air electrode is soaked with an electrolyte comprising one or more solvents including dimethyl ether, and the dimethyl ether subsequently is evacuated from the soaked electrode. In other embodiments, the electrolyte comprises 10-20% crown ether by weight.

  8. High-energy metal air batteries

    DOE Patents [OSTI]

    Zhang, Ji-Guang; Xiao, Jie; Xu, Wu; Wang, Deyu; Williford, Ralph E.; Liu, Jun

    2014-07-01

    Disclosed herein are embodiments of lithium/air batteries and methods of making and using the same. Certain embodiments are pouch-cell batteries encased within an oxygen-permeable membrane packaging material that is less than 2% of the total battery weight. Some embodiments include a hybrid air electrode comprising carbon and an ion insertion material, wherein the mass ratio of ion insertion material to carbon is 0.2 to 0.8. The air electrode may include hydrophobic, porous fibers. In particular embodiments, the air electrode is soaked with an electrolyte comprising one or more solvents including dimethyl ether, and the dimethyl ether subsequently is evacuated from the soaked electrode. In other embodiments, the electrolyte comprises 10-20% crown ether by weight.

  9. Aromatic-Hydroxyl Interaction of a Lignin Model Compound on SBA-15, Present at Pyrolysis Temperatures

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

    Kandziolka, III, Michael V.; Kidder, Michelle; Gill, Lance W.; Wu, Zili; Savara, Aditya Ashi

    2014-07-14

    An aromatic alpha-aryl ether compound (a benzyl phenyl ether analogue) was covalently grafted to mesoporous silica SBA-15, to create BPEa-SBA-15. The BPEa-SBA-15 was subjected to successive heating cycles up to 600 °C, with in situ monitoring by DRIFTS. It was found that the toluene moiety coordinates to SBA-15 surface silanol hydroxyl groups via an aromatic–hydroxyl interaction. This interaction is evidenced by a red-shift of the aromatic C–H stretches, as well as a red-shift and broadening of the surface hydroxyl O–H stretches, which are features characteristic of a hydrogen bond. These features remain present during heating until ~400 °C whereupon themore » ether linkage of BPEa-SBA-15 is cleaved, accompanied by loss of the toluene moiety.« less

  10. 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.

  11. 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.

  12. Replacement solvents for use in chemical synthesis

    DOE Patents [OSTI]

    Molnar, Linda K. (Philadelphia, PA); Hatton, T. Alan (Sudbury, MA); Buchwald, Stephen L. (Newton, MA)

    2001-05-15

    Replacement solvents for use in chemical synthesis include polymer-immobilized solvents having a flexible polymer backbone and a plurality of pendant groups attached onto the polymer backbone, the pendant groups comprising a flexible linking unit bound to the polymer backbone and to a terminal solvating moiety. The polymer-immobilized solvent may be dissolved in a benign medium. Replacement solvents for chemical reactions for which tetrahydrofuran or diethyl may be a solvent include substituted tetrahydrofurfuryl ethers and substituted tetrahydro-3-furan ethers. The replacement solvents may be readily recovered from the reaction train using conventional methods.

  13. Inquiring Minds - Questions About Physics

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

    Particle theories Quantum fields, superstrings and all that Scattering matrix "Could you please help me by explaining what is actually meant by S-matrix?" Concept of ether in explaining forces? "Will there be any research carried out in the near or distant future to find a physical relationship between gravity, mass, light, matter/antimatter through something like the idea of ether hundred years ago?" Consequences of the success of superstring theory? "What will be the

  14. Solvate Structures and Computational/Spectroscopic Characterization of

    Office of Scientific and Technical Information (OSTI)

    LiBF4 Electrolytes (Journal Article) | SciTech Connect Solvate Structures and Computational/Spectroscopic Characterization of LiBF4 Electrolytes Citation Details In-Document Search Title: Solvate Structures and Computational/Spectroscopic Characterization of LiBF4 Electrolytes Crystal structures have been determined for both LiBF4 and HBF4 solvates-(acetonitrile)2:LiBF4, (ethylene glycol diethyl ether)1:LiBF4, (diethylene glycol diethyl ether)1:LiBF4, (tetrahydrofuran)1:LiBF4, (methyl

  15. Use of Advanced Oxidation and Aerobic Degradation for Remediation of Various Hydrocarbon Contaminates

    SciTech Connect (OSTI)

    Paul Fallgren

    2009-03-06

    Western Research Institute in conjunction with Sierra West Consultants, Inc., Tetra Tech, Inc., and the U.S. Department of Energy conducted laboratory and field studies to test different approaches to enhance degradation of hydrocarbons and associated contaminants. WRI in conjunction with Sierra West Consultants, Inc., conducted a laboratory and field study for using ozone to treat a site contaminated with MTBE and other hydrocarbons. Results from this study demonstrate that a TOD test can be used to resolve the O{sub 3} dosage problem by establishing a site-specific benchmark dosage for field ozone applications. The follow-up testing of the laboratory samples provided indications that intrinsic biodegradation could be stimulated by adding oxygen. Laboratory studies also suggests that O3 dosage in the full-scale field implementation could be dialed lower than stoichiometrically designed to eliminate the formation of Cr(VI). WRI conducted a study involving a series of different ISCO oxidant applications to diesel-contaminated soil and determined the effects on enhancing biodegradation to degrade the residual hydrocarbons. Soils treated with permanganate followed by nutrients and with persulfate followed by nutrients resulted in the largest decrease in TPH. The possible intermediates and conditions formed from NOM and TPH oxidation by permanganate and activated persulfate favors microbial TPH degrading activity. A 'passive-oxidation' method using microbial fuel cell (MFC) technology was conducted by WRI in conjunction with Tetra Tech, Inc., to degrade MTBE in groundwater. These experiments have demonstrated that a working MFC (i.e., one generating power) could be established in the laboratory using contaminated site water or buffered media inoculated with site water and spiked with MTBE, benzene, or toluene. Electrochemical methods were studied by WRI with goal of utilizing low voltage and amperage electrical sources for 'geo-oxidation' of organic contaminants. The results from a study with TCE contaminated-clay indicate that electrochemically inducing reductive dechlorination of TCE in a saturated matrix may offer an effective and viable alternative to remediation TCE and other contaminants with potential of being reduced. Another study focused on steel wool oxidation to electrochemically increase population of hydrocarbon-degrading denitrifying bacteria. Significantly larger denitrifying activity was observed in the cathode chamber of a treatment unit setup like an MFC with steel wool as the anode. This enhanced nitrate reduction could be due to direct electron utilization by denitrifying bacteria on the cathode, thereby stimulating microbial denitrification or a combination of electron transfer directly to NO{sub 3}{sup -} and electron transfer to nitrate reducing bacteria, which may serve as a type of bio-catalyst on the cathode for nitrate reduction. Overall, the studies conducted under Task 72 demonstrated different innovative methods to enhance petroleum hydrocarbon degradation and associated contaminants.

  16. Anion effects in the extraction of lanthanide 2-thenoyltrifluoroacetone complexes into an ionic liquid

    SciTech Connect (OSTI)

    Jensen, Mark P.; Beitz, James V.; Rickert, Paul G.; Borkowski, Marian; Laszak, Ivan; Dietz, Mark L.

    2012-07-01

    The extraction of trivalent lanthanides from an aqueous phase containing 1 M NaClO{sub 4} into the room temperature ionic liquid 1-butyl-3-methylimidazolium nonafluoro-1-butane sulfonate by the beta-diketone extractant 2-thenoyltrifluoroacetone (Htta) was studied. Radiotracer distribution, absorption spectroscopy, time-resolved laser-induced fluorescence spectroscopy, and X-ray absorption fine structure measurements point to the extraction of multiple lanthanide species. At low extractant concentrations, fully hydrated aqua cations of the lanthanides are present in the ionic liquid phase. As the extractant concentration is increased 1:2 and 1:3 lanthanide:tta species are observed. In contrast, 1:4 Ln:tta complexes were observed in the extraction of lanthanides by Htta into 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)imide. (authors)

  17. Composition and method for encapsulating photovoltaic devices

    DOE Patents [OSTI]

    Pern, Fu-Jann

    2000-01-01

    A composition and method for encapsulating a photovoltaic device which minimizes discoloration of the encapsulant. The composition includes an ethylene-vinyl acetate encapsulant, a curing agent, an optional ultraviolet light stabilizer, and/or an optional antioxidant. The curing agent is preferably 1,1-di-(t-butylperoxy)-3,3,5-trimethylcyclohexane; the ultraviolet light stabilizer is bis-(N-octyloxy-tetramethyl) piperidinyl sebacate and the antioxidant is selected from the group consisting of tris (2,4-di-tert-butylphenyl) phosphite, tetrakis methylene (3,5-di-tert-butyl-4-hydroxyhydrocinnamate) methane, octadecyl 3,5-di-tert-butyl-4-hydroxyhydrocinnamate, and 2,2'-ethylidene bis(4,6-di-t-butylphenyl) fluorophosponite. The composition is applied to a solar cell then cured. The cured product contains a minimal concentration of curing-generated chromophores and resists UV-induced degradation.

  18. Reactive formulations for a neutralization of toxic industrial chemicals

    DOE Patents [OSTI]

    Tucker, Mark D.; Betty, Rita G.

    2006-10-24

    Decontamination formulations for neutralization of toxic industrial chemicals, and methods of making and using same. The formulations are effective for neutralizing malathion, hydrogen cyanide, sodium cyanide, butyl isocyanate, carbon disulfide, phosgene gas, capsaicin in commercial pepper spray, chlorine gas, anhydrous ammonia gas; and may be effective at neutralizing hydrogen sulfide, sulfur dioxide, formaldehyde, ethylene oxide, methyl bromide, boron trichloride, fluorine, tetraethyl pyrophosphate, phosphorous trichloride, arsine, and tungsten hexafluoride.

  19. Electron Solvation Dynamics and Reactivity in Ionic Liquids Observed by Picosecond RadiolysisTechniques

    SciTech Connect (OSTI)

    Wishart J. F.; Funston, A.M.; Szreder, T.; Cook, A.R.; Gohdo, M.

    2012-01-01

    On time scales of a nanosecond or less, radiolytically-generated excess electrons in ionic liquids undergo solvation processes and reactions that determine all subsequent chemistry and the accumulation of radiolytic damage. Using picosecond pulse radiolysis detection methods, we observed and quantified the solvation response of the electron in 1-methyl-1-butyl-pyrrolidinium bis(trifluoromethylsulfonyl)amide and used it to understand electron scavenging by a typical solute, duroquinone.

  20. Electron impact and chemical ionization mass spectral analysis of a volatile uranyl derivative

    SciTech Connect (OSTI)

    Reutter, D.J.; Hardy, D.R.

    1981-01-01

    Quadrupole mass spectral analysis of the volatile uranium ligand complex bis (1,1,1,5,5,5-hexafluoro-2,4-pentanedionato) dioxouranium-di-n-butyl sulfoxide is described utilizing electron impact (EI) and methane chemical ionization (CI) ion sources. All major ions are tentatively identified and the potential usefulness of this complex for determining uranium isotope /sup 235/U//sup 238/U abundance is demonstrated.

  1. Method for the concentration and separation of actinides from biological and environmental samples

    DOE Patents [OSTI]

    Horwitz, E. Philip (Naperville, IL); Dietz, Mark L. (Tucson, AZ)

    1989-01-01

    A method and apparatus for the quantitative recover of actinide values from biological and environmental sample by passing appropriately prepared samples in a mineral acid solution through a separation column of a dialkyl(phenyl)-N,N-dialylcarbamoylmethylphosphine oxide dissolved in tri-n-butyl phosphate on an inert substrate which selectively extracts the actinide values. The actinide values can be eluted either as a group or individually and their presence quantitatively detected by alpha counting.

  2. Method for the concentration and separation of actinides from biological and environmental samples

    DOE Patents [OSTI]

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

    1989-05-30

    A method and apparatus for the quantitative recover of actinide values from biological and environmental sample by passing appropriately prepared samples in a mineral acid solution through a separation column of a dialkyl(phenyl)-N,N-dialylcarbamoylmethylphosphine oxide dissolved in tri-n-butyl phosphate on an inert substrate which selectively extracts the actinide values. The actinide values can be eluted either as a group or individually and their presence quantitatively detected by alpha counting. 3 figs.

  3. Process for synthesis of beryllium chloride dietherate

    DOE Patents [OSTI]

    Bergeron, Charles (Baton Rouge, LA); Bullard, John E. (Kendall Park, NJ); Morgan, Evan (Lynchburg, VA)

    1991-01-01

    A low temperature method of producing beryllium chloride dietherate through the addition of hydrogen chloride gas to a mixture of beryllium metal in ether in a reaction vessel is described. A reflux condenser provides an exit for hydrogen produced form the reaction. A distillation condenser later replaces the reflux condenser for purifying the resultant product.

  4. untitled

    Gasoline and Diesel Fuel Update (EIA)

    0 0 0 0 0 0 0 0 RBOB for Blending with Ether 0 0 0 0 0 0 0 0 0 RBOB for Blending with Alcohol 0 26 0 0 0 0 0 0 2,720 Conventional 0 50 0 266 199 0 0 145 1,487 CBOB for Blending...

  5. PSA Vol 1 Tables Revised Ver 2 Print.xls

    Gasoline and Diesel Fuel Update (EIA)

    0 0 0 0 576 128 RBOB for Blending with Ether 0 0 0 0 0 0 120 0 RBOB for Blending with Alcohol 22 26 0 24 0 0 394 0 Conventional 0 315 0 0 1,359 0 1,718 495 CBOB for Blending with...

  6. PSA Vol 1 Tables Revised Ver 2 Print.xls

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

    GTAB 0 0 0 0 0 0 0 RBOB for Blending with Ether 0 0 0 0 0 0 0 RBOB for Blending with Alcohol 0 0 0 0 0 3,223 29,499 Conventional 105 0 615 0 0 244 14,011 CBOB for Blending with...

  7. untitled

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

    GTAB 0 0 0 0 0 0 0 RBOB for Blending with Ether 0 0 0 0 0 0 0 RBOB for Blending with Alcohol 0 0 0 0 0 0 2,497 Conventional 0 0 266 0 0 0 1,099 CBOB for Blending with Alcohol 0 0...

  8. untitled

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

    GTAB 0 0 0 0 0 0 0 RBOB for Blending with Ether 0 0 0 0 0 0 0 RBOB for Blending with Alcohol 0 0 0 0 0 222 1,728 Conventional 25 0 0 0 0 0 817 CBOB for Blending with Alcohol 0 0...

  9. PSA Vol 1 Tables Revised Ver 2 Print.xls

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

    0 0 0 576 131 RBOB for Blending with Ether 0 0 0 0 0 0 0 120 0 RBOB for Blending with Alcohol 22 26 0 24 0 0 0 3,617 31,128 Conventional 105 315 0 615 1,359 0 0 1,962 17,808 CBOB...

  10. untitled

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

    0 0 0 0 0 0 0 0 RBOB for Blending with Ether 0 0 0 0 0 0 0 0 0 RBOB for Blending with Alcohol 0 0 0 0 0 0 0 248 1,899 Conventional 25 85 0 0 87 0 0 125 1,055 CBOB for Blending...

  11. Polymer nanocomposites for lithium battery applications

    DOE Patents [OSTI]

    Sandi-Tapia, Giselle; Gregar, Kathleen Carrado

    2006-07-18

    A single ion-conducting nanocomposite of a substantially amorphous polyethylene ether and a negatively charged synthetic smectite clay useful as an electrolyte. Excess SiO2 improves conductivity and when combined with synthetic hectorite forms superior membranes for batteries. A method of making membranes is also disclosed.

  12. untitled

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

    -109 -12 Isobutylene 7 0 7 0 0 0 0 Finished Motor Gasoline 21,280 1,066 22,346 25,478 3,607 12,672 41,757 Reformulated 11,460 0 11,460 0 0 0 0 Reformulated Blended with Ether...

  13. Ionic liquid-assisted sonochemical preparation of CeO2 nanoparticles for CO oxidation

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

    Alammar, Tarek; Noei, Heshmat; Wang, Yuemin; Grünert, Wolfgang; Mudring, Anja -Verena

    2014-10-10

    CeO2 nanoparticles were synthesized via a one-step ultrasound synthesis in different kinds of ionic liquids based on bis(trifluoromethanesulfonylamide, [Tf2N]–, in combination with various cations including 1-butyl-3-methylimidazolium ([C4mim]+), 1-ethyl-2,3-dimethylimidazolium ([Edimim]+), butyl-pyridinium([Py4]+), 1-butyl-1-methyl-pyrrolidinium ([Pyrr14]+), and 2-hydroxyethyl-trimethylammonium ([N1112OH]+). Depending on synthetic parameters, such as ionic liquid, Ce(IV) precursor, heating method, and precipitator, formed ceria exhibits different morphologies, varying from nanospheres, nanorods, nanoribbons, and nanoflowers. The morphology, crystallinity, and chemical composition of the obtained materials were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX), Raman spectroscopy, and N2 adsorption. The structural and electronic propertiesmore » of the as-prepared CeO2 samples were probed by CO adsorption using IR spectroscopy under ultrahigh vacuum conditions. The catalytic activities of CeO2 nanoparticles were investigated in the oxidation of CO. CeO2 nanospheres obtained sonochemically in [C4mim][Tf2N] exhibit the best performance for low-temperature CO oxidation. As a result, the superior catalytic performance of this material can be related to its mesoporous structure, small particle size, large surface area, and high number of surface oxygen vacancy sites.« less

  14. Advanced Materials for PEM-Based Fuel Cell Systems

    SciTech Connect (OSTI)

    James E. McGrath

    2005-10-26

    Proton exchange membrane fuel cells (PEMFCs) are quickly becoming attractive alternative energy sources for transportation, stationary power, and small electronics due to the increasing cost and environmental hazards of traditional fossil fuels. Two main classes of PEMFCs include hydrogen/air or hydrogen/oxygen fuel cells and direct methanol fuel cells (DMFCs). The current benchmark membrane for both types of PEMFCs is Nafion, a perfluorinated sulfonated copolymer made by DuPont. Nafion copolymers exhibit good thermal and chemical stability, as well as very high proton conductivity under hydrated conditions at temperatures below 80 ???????????????????????????????°C. However, application of these membranes is limited due to their high methanol permeability and loss of conductivity at high temperatures and low relative humidities. These deficiencies have led to the search for improved materials for proton exchange membranes. Potential PEMs should have good thermal, hydrolytic, and oxidative stability, high proton conductivity, selective permeability, and mechanical durability over long periods of time. Poly(arylene ether)s, polyimides, polybenzimidazoles, and polyphenylenes are among the most widely investigated candidates for PEMs. Poly(arylene ether)s are a promising class of proton exchange membranes due to their excellent thermal and chemical stability and high glass transition temperatures. High proton conductivity can be achieved through post-sulfonation of poly(arylene ether) materials, but this most often results in very high water sorption or even water solubility. Our research has shown that directly polymerized poly(arylene ether) copolymers show important advantages over traditional post-sulfonated systems and also address the concerns with Nafion membranes. These properties were evaluated and correlated with morphology, structure-property relationships, and states of water in the membranes. Further improvements in properties were achieved through incorporation of inorganic fillers, such as phosphotungstic acid and zirconium hydrogen phosphate. Block copolymers were also studied due to the possibility to achieve a desired combination of homopolymer properties as well as the unique morphologies that are possible with block copolymers. Bezoyl substituted poly(p-phenylene) blocks were combined with poly(arylene ether) blocks to merge the structural rigidity of the poly(p-phenylene) with the ductility and high protonic conductivity of the poly(arylene ether)s. As evidenced by our many refereed publications and preprints, the research that we have conducted over the past several years has made a valuable and significant contribution to the literature and to the state of understanding of proton exchange membranes. Our early efforts at scale-up have suggested that the directly polymerized disulfonated poly(arylene ether sulfone) copolymers are commercially viable alternatives for proton exchange membranes. A new process for bipolar plates was developed and is described. An important single domain PEMFC model was developed and is documented in this final report.

  15. Catalytic Synthesis of Oxygenates: Mechanisms, Catalysts and Controlling Characteristics

    SciTech Connect (OSTI)

    Kamil Klier; Richard G. Herman

    2005-11-30

    This research focused on catalytic synthesis of unsymmetrical ethers as a part of a larger program involving oxygenated products in general, including alcohols, ethers, esters, carboxylic acids and their derivatives that link together environmentally compliant fuels, monomers, and high-value chemicals. The catalysts studied here were solid acids possessing strong Br???????¸nsted acid functionalities. The design of these catalysts involved anchoring the acid groups onto inorganic oxides, e.g. surface-grafted acid groups on zirconia, and a new class of mesoporous solid acids, i.e. propylsulfonic acid-derivatized SBA-15. The former catalysts consisted of a high surface concentration of sulfate groups on stable zirconia catalysts. The latter catalyst consists of high surface area, large pore propylsulfonic acid-derivatized silicas, specifically SBA-15. In both cases, the catalyst design and synthesis yielded high concentrations of acid sites in close proximity to one another. These materials have been well-characterization in terms of physical and chemical properties, as well as in regard to surface and bulk characteristics. Both types of catalysts were shown to exhibit high catalytic performance with respect to both activity and selectivity for the bifunctional coupling of alcohols to form ethers, which proceeds via an efficient SN2 reaction mechanism on the proximal acid sites. This commonality of the dual-site SN2 reaction mechanism over acid catalysts provides for maximum reaction rates and control of selectivity by reaction conditions, i.e. pressure, temperature, and reactant concentrations. This research provides the scientific groundwork for synthesis of ethers for energy applications. The synthesized environmentally acceptable ethers, in part derived from natural gas via alcohol intermediates, exhibit high cetane properties, e.g. methylisobutylether with cetane No. of 53 and dimethylether with cetane No. of 55-60, or high octane properties, e.g. diisopropylether with blending octane No. of 105, and can replace aromatics in liquid fuels.

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

    SciTech Connect (OSTI)

    1995-03-08

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

  17. Development of a catalyst for conversion of syngas-derived materials to isobutylene. Quarterly report number 19, October 1--December 31, 1995

    SciTech Connect (OSTI)

    Spehlmann, B.C.

    1996-07-01

    The goals of this project are to develop a catalyst and process for the conversion of syngas to isobutanol. After identification and optimization of key catalyst and process characteristics, the commercial potential of the process is to be evaluated by an economic analysis. From independent process variable studies to investigate the conversion of a methanol/ethanol feed to isobutanol, the best performance to date has been achieved with the 2% Pt on Zn/Mn/Zr oxide catalyst. Using Hyprotech Hysim v2.5 process simulation software, and considering both gas and liquid recycle loops in the process flow diagram, the overall carbon conversion is 98% with 22% selectivity to isobutanol. The expected production of isobutanol is 92 MT/day from 500 MT/day of methanol and 172 MT/day of ethanol feed. An additional 13 MT/day of isobutryaldehyde intermediate is recovered in the liquid product and vent streams. Because of the low selectivity (22%) of the methanol conversion catalyst to isobutanol, the process is uneconomical, even if the isobutanol is valued as a solvent ($903/MT) and not as isobutylene for MTBE production ($352/MT).

  18. Cometabolic bioremediation

    SciTech Connect (OSTI)

    Hazen, Terry C.

    2009-02-15

    Cometabolic bioremediation is probably the most under appreciated bioremediation strategy currently available. Cometabolism strategies stimulate only indigenous microbes with the ability to degrade the contaminant and cosubstrate e.g. methane, propane, toluene and others. This highly targeted stimulation insures that only those microbes that can degrade the contaminant are targeted, thus reducing amendment costs, well and formation plugging, etc. Cometabolic bioremediation has been used on some of the most recalcitrant contaminants, e.g. PCE, TCE, MTBE, TNT, dioxane, atrazine, etc. Methanotrophs have been demonstrated to produce methane monooxygense, an oxidase that can degrade over 300 compounds. Cometabolic bioremediation also has the advantage of being able to degrade contaminants to trace concentrations, since the biodegrader is not dependent on the contaminant for carbon or energy. Increasingly we are finding that in order to protect human health and the environment that we must remediate to lower and lower concentrations, especially for compounds like endocrine disrupters, thus cometabolism may be the best and maybe the only possibility that we have to bioremediate some contaminants.

  19. 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.

  20. The importance of FCC catalyst selection on LPG profitability

    SciTech Connect (OSTI)

    Keyworth, D.A.; Gilman, R.; Pearce, J.R. )

    1989-01-01

    Recently the value of LPG in chemical operations downstream of the FCC unit has increased. Such downstream operations utilize propylene not only in alkylate, but also in rapid growth petrochemical applications such as for a raw material in the manufacture of polypropylene and propylene oxide. Isobutane and the butenes (particularly butene-2 in sulfuric acid catalyzed alkylation units) are prized for alkylate feed. The profit potential and incentives to use other LPG components such as isobutene to make MTBE is now increased because of legislative actions and increased octane performance demand; and because of the greater isobutene content in the LPG from the new FCC octane catalysts. A low non-framework alumina (NFA) zeolite studied made a more olefinic LPG with higher iso-to normal C4 ratio than the other zeolites. Pilot plant data has also shown the new low NFA zeolite gave not only outstanding motor octane (MON) performance, but produced an LPG with better propylene to propane ratio, more isobutene, more n-butenes and more C4 branching than other RE promoted zeolite catalysts. Commercial results have verified the improved performance and profitability for the new low-NFA type zeolite catalysts. Three commercial examples are described.

  1. Photoresponsive Release from Azobenzene-Modified Single Cubic Crystal NaCl/Silica Particles

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

    Jiang, Xingmao; Liu, Nanguo; Assink, Roger A.; Jiang, Yingbing; Brinker, C. Jeffrey

    2011-01-01

    Azobenzene ligands were uniformly anchored to the pore surfaces of nanoporous silica particles with single crystal NaCl using 4-(3-triethoxysilylpropylureido)azobenzene (TSUA). The functionalization delayed the release of NaCl significantly. The modified particles demonstrated a photocontrolled release by trans/cis isomerization of azobenzene moieties. The addition of amphiphilic solvents, propylene glycol (PG), propylene glycol propyl ether (PGPE), and dipropylene glycol propyl ether (DPGPE) delayed the release in water, although the wetting behavior was improved and the delay is the most for the block molecules with the longest carbon chain. The speedup by UV irradiation suggests a strong dependence of diffusion on the switchablemore » pore size. TGA, XRD, FTIR, and NMR techniques were used to characterize the structures.« less

  2. Homogeneous catalyst formulations for methanol production

    DOE Patents [OSTI]

    Mahajan, Devinder (Port Jefferson, NY); Sapienza, Richard S. (Shoreham, NY); Slegeir, William A. (Hampton Bays, NY); O'Hare, Thomas E. (Huntington Station, NY)

    1990-01-01

    There is disclosed synthesis of CH.sub.3 OH from carbon monoxide and hydrogen using an extremely active homogeneous catalyst for methanol synthesis directly from synthesis gas. The catalyst operates preferably between 100.degree.-150.degree. C. and preferably at 100-150 psia synthesis gas to produce methanol. Use can be made of syngas mixtures which contain considerable quantities of other gases, such as nitrogen, methane or excess hydrogen. The catalyst is composed of two components: (a) a transition metal carbonyl complex and (b) an alkoxide component. In the simplest formulation, component (a) is a complex of nickel tetracarbonyl and component (b) is methoxide (CH.sub.3 O.sup.13 ), both being dissolved in a methanol solvent system. The presence of a co-solvent such as p-dioxane, THF, polyalcohols, ethers, hydrocarbons, and crown ethers accelerates the methanol synthesis reaction.

  3. Homogeneous catalyst formulations for methanol production

    DOE Patents [OSTI]

    Mahajan, Devinder (Port Jefferson, NY); Sapienza, Richard S. (Shoreham, NY); Slegeir, William A. (Hampton Bays, NY); O'Hare, Thomas E. (Huntington Station, NY)

    1991-02-12

    There is disclosed synthesis of CH.sub.3 OH from carbon monoxide and hydrogen using an extremely active homogeneous catalyst for methanol synthesis directly from synthesis gas. The catalyst operates preferably between 100.degree.-150.degree. C. and preferably at 100-150 psia synthesis gas to produce methanol. Use can be made of syngas mixtures which contain considerable quantities of other gases, such as nitrogen, methane or excess hydrogen. The catalyst is composed of two components: (a) a transition metal carbonyl complex and (b) an alkoxide component. In the simplest formulation, component (a) is a complex of nickel tetracarbonyl and component (b) is methoxide (CH.sub.3 O.sup.-), both being dissolved in a methanol solvent system. The presence of a co-solvent such as p-dioxane, THF, polyalcohols, ethers, hydrocarbons, and crown ethers accelerates the methanol synthesis reaction.

  4. Extraction processes and solvents for recovery of cesium, strontium, rare earth elements, technetium and actinides from liquid radioactive waste

    DOE Patents [OSTI]

    Zaitsev, Boris N. (St. Petersburg, RU); Esimantovskiy, Vyacheslav M. (St. Petersburg, RU); Lazarev, Leonard N. (St. Petersburg, RU); Dzekun, Evgeniy G. (Ozersk, RU); Romanovskiy, Valeriy N. (St. Petersburg, RU); Todd, Terry A. (Aberdeen, ID); Brewer, Ken N. (Arco, ID); Herbst, Ronald S. (Idaho Falls, ID); Law, Jack D. (Pocatello, ID)

    2001-01-01

    Cesium and strontium are extracted from aqueous acidic radioactive waste containing rare earth elements, technetium and actinides, by contacting the waste with a composition of a complex organoboron compound and polyethylene glycol in an organofluorine diluent mixture. In a preferred embodiment the complex organoboron compound is chlorinated cobalt dicarbollide, the polyethylene glycol has the formula RC.sub.6 H.sub.4 (OCH.sub.2 CH.sub.2).sub.n OH, and the organofluorine diluent is a mixture of bis-tetrafluoropropyl ether of diethylene glycol with at least one of bis-tetrafluoropropyl ether of ethylene glycol and bis-tetrafluoropropyl formal. The rare earths, technetium and the actinides (especially uranium, plutonium and americium), are extracted from the aqueous phase using a phosphine oxide in a hydrocarbon diluent, and reextracted from the resulting organic phase into an aqueous phase by using a suitable strip reagent.

  5. Materials for use as proton conducting membranes for fuel cells

    DOE Patents [OSTI]

    Einsla, Brian R. (Blacksburg, VA); McGrath, James E. (Blacksburg, VA)

    2009-01-06

    A family of polymers having pendent sulfonate moieties connected to polymeric main chain phenyl groups are described. These polymers are prepared by the steps of polymerization (using a monomer with a phenyl with an alkoxy substitution), deportation by converting the alkoxy to a hydroxyl, and functionalization of the polymer with a pendant sulfonate group. As an example, sulfonated poly(arylene ether sulfone) copolymers with pendent sulfonic acid groups are synthesized by the direct copolymerization of methoxy-containing poly(arylene ether sulfone)s, then converting the methoxy groups to the reactive hydroxyl form, and finally functionalizing the hydroxyl form with proton-conducting sites through nucleophilic substitution. The family of polymers may have application in proton exchange membranes and in other applications.

  6. Local environment in poly(ethylene oxide)-zinc bromide complexes

    SciTech Connect (OSTI)

    Chintipalli, S.; Frech, R.; Grady, B.

    1996-12-31

    This study examines atomic-level local environments in Poly(ethylene oxide)-zinc bromide+lithium bromide (PEO){sub 20}[(ZnBr{sub 2}){sub 1-x} (LiBr){sub x}] complexes using Raman spectroscopy and x-ray absorption spectroscopy (XAS). Specific features in the Raman spectra were used to show that the zinc bromide species changes from ZnBr{sub 2} to ZnBr{sub 3}{sup -} to ZnBr{sub 4}{sup 2-} when x is varied from 0 to 0.8. XAS showed a similar change in oxygen coordination number from 4 to 0 when x is varied from 0 to 0.8. This study shows that lithium atoms displace zinc atoms from ether oxygen speciation indicating that lithium coordination to ether oxygens is thermodynamically favored. The effect of adding polar plasticizers is also discussed.

  7. Actinide extraction methods

    DOE Patents [OSTI]

    Peterman, Dean R. [Idaho Falls, ID; Klaehn, John R. [Idaho Falls, ID; Harrup, Mason K. [Idaho Falls, ID; Tillotson, Richard D. [Moore, ID; Law, Jack D. [Pocatello, ID

    2010-09-21

    Methods of separating actinides from lanthanides are disclosed. A regio-specific/stereo-specific dithiophosphinic acid having organic moieties is provided in an organic solvent that is then contacted with an acidic medium containing an actinide and a lanthanide. The method can extend to separating actinides from one another. Actinides are extracted as a complex with the dithiophosphinic acid. Separation compositions include an aqueous phase, an organic phase, dithiophosphinic acid, and at least one actinide. The compositions may include additional actinides and/or lanthanides. A method of producing a dithiophosphinic acid comprising at least two organic moieties selected from aromatics and alkyls, each moiety having at least one functional group is also disclosed. A source of sulfur is reacted with a halophosphine. An ammonium salt of the dithiophosphinic acid product is precipitated out of the reaction mixture. The precipitated salt is dissolved in ether. The ether is removed to yield the dithiophosphinic acid.

  8. Siloxane-grafted membranes

    DOE Patents [OSTI]

    Friesen, D.T.; Obligin, A.S.

    1989-10-31

    Composite cellulosic semipermeable membranes are disclosed which are the covalently bonded reaction product of an asymmetric cellulosic semipermeable membrane and a polysiloxane containing reactive functional group. The two reactants chemically bond by ether, ester, amide or acrylate linkages to form a siloxane-grafted cellulosic membrane having superior selectivity and flux stability. Selectivity may be enhanced by wetting the surface with a swelling agent such as water.

  9. Electron-donor dopant, method of improving conductivity of polymers by doping therewith, and a polymer so treated

    DOE Patents [OSTI]

    Liepins, Raimond (Los Alamos, NM); Aldissi, Mahmoud (Los Alamos, NM)

    1988-01-01

    Polymers with conjugated backbones, both polyacetylene and polyaromatic heterocyclic types, are doped with electron-donor agents to increase their electrical conductivity. The electron-donor agents are either electride dopants made in the presence of lithium or dopants derived from alkalides made in the presence of lithium. The dopants also contain a metal such as cesium and a trapping agent such as a crown ether.

  10. Radiolabelling and positron emission tomography of PT70, a time-dependent inhibitor of InhA, the Mycobacterium tuberculosis enoyl-ACP reductase

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

    Wang, Hui; Liu, Li; Lu, Yang; Pan, Pan; Hooker, Jacob M.; Fowler, Joanna S.; Tonge, Peter J.

    2015-07-14

    PT70 is a diaryl ether inhibitor of InhA, the enoyl-ACP reductase in the Mycobacterium tuberculosis fatty acid biosynthesis pathway. It has a residence time of 24 min on the target, and also shows antibacterial activity in a mouse model of tuberculosis infection. Due to the interest in studying target tissue pharmacokinetics of PT70, we developed a method to radiolabel PT70 with carbon-11 and have studied its pharmacokinetics in mice and baboons using positron emission tomography.

  11. Combined transuranic-strontium extraction process

    DOE Patents [OSTI]

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

    1992-12-08

    The transuranic (TRU) elements neptunium, plutonium and americium can be separated together with strontium from nitric acid waste solutions in a single process. An extractant solution of a crown ether and an alkyl(phenyl)-N,N-dialkylcarbanylmethylphosphine oxide in an appropriate diluent will extract the TRU's together with strontium, uranium and technetium. The TRU's and the strontium can then be selectively stripped from the extractant for disposal. 3 figs.

  12. Combined transuranic-strontium extraction process

    DOE Patents [OSTI]

    Horwitz, E. Philip; Dietz, Mark L.

    1992-01-01

    The transuranic (TRU) elements neptunium, plutonium and americium can be separated together with strontium from nitric acid waste solutions in a single process. An extractant solution of a crown ether and an alkyl(phenyl)-N,N-dialkylcarbanylmethylphosphine oxide in an appropriate diluent will extract the TRU's together with strontium, uranium and technetium. The TRU's and the strontium can then be selectively stripped from the extractant for disposal.

  13. Microsoft Word - TAMU abstract

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

    Extraction Chromatographic Studies of Rf (Z=104) Homologs Using Crown Ether Based Resins Megan E. Bennett University of Nevada - Las Vegas Studying the chemistry of transactinide elements, such as Rf (Z=104), allows not only for the element to be properly placed in the periodic table but also allows for extrapolation of the electronic structure based upon the position of the element in the Periodic Table. The chemical behavior of a transactinide element compared to its homologs allows for

  14. 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)

  15. 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

  16. 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

  17. East Coast (PADD 1) Total Crude Oil and Petroleum Products Net Receipts by

    Gasoline and Diesel Fuel Update (EIA)

    Pipeline, Tanker, Barge and Rail Product: Total Crude Oil and Products Crude Oil Petroleum Products Pentanes Plus Liquefied Petroleum Gases Ethane/Ethylene Propane/Propylene Normal Butane/Butylene Isobutane/Isobutylene Unfinished Oils Motor Gasoline Blend. Comp. (MGBC) MGBC - Reformulated MGBC - Reformulated RBOB MGBC - RBOB for Blending w/ Alcohol* MGBC - RBOB for Blending w/ Ether* MGBC - Reformulated GTAB* MGBC - Conventional MGBC - CBOB MGBC - Conventional GTAB MGBC - Conventional Other

  18. Joining of Advanced Thermoplastics

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

    3, 2012 Joining of Advanced Thermoplastics Ed Herderick, PhD George Ritter, PhD Applications Engineer Principal Engineer Materials Group EWI 614.688.5111 Sean Flowers eherderick@ewi.org Ultrasonics Group Thermoplastic Composites: Outline * Lighter than metals, tougher than thermosets, can be welded and recycled * Examples of joining approaches * Bio-based composites * Nano-reinforced composites * High temperature thermoplastics Joining of Engineering Thermoplastics MATERIAL * Polyether-ether

  19. Electron-donor dopant, method of improving conductivity of polymers by doping therewith, and a polymer so treated

    DOE Patents [OSTI]

    Liepins, R.; Aldissi, M.

    1984-07-27

    Polymers with conjugated backbones, both polyacetylene and polyaromatic heterocyclic types, are doped with electron-donor agents to increase their electrical conductivity. The electron-donor agents are either electride dopants made in the presence of lithium or dopants derived from alkalides made in the presence of lithium. The dopants also contain a metal such as cesium and a trapping agent such as a crown ether.

  20. Development of GREET Catalyst Module

    SciTech Connect (OSTI)

    Wang, Zhichao; Benavides, Pahola T.; Dunn, Jennifer B.; Cronauer, Donald C.

    2015-09-01

    In this report, we develop energy and material flows for the production of five different catalysts (tar reforming, alcohol synthesis, Zeolite Socony Mobil-5 [ZSM-5], Mo/Co/ ?-Al2O3, and Pt/ ?-Al2O3) and two chemicals (olivine, dimethyl ether of polyethylene glycol [DEPG]). These compounds and catalysts are now included in the Greenhouse Gases, Regulated Emissions and Energy Use in Transportation (GREET) catalyst module.

  1. Antihypertensive neutral lipid

    DOE Patents [OSTI]

    Snyder, Fred L. (Oak Ridge, TN); Blank, Merle L. (Oak Ridge, TN)

    1986-01-01

    The invention relates to the discovery of a class of neutral acetylated ether-linked glycerolipids having the capacity to lower blood pressure in warm-blooded animals. This physiological effect is structure sensitive requiring a long chain alkyl group at the sn-1 position and a short carbon chain acyl group (acetyl or propionyl) at the sn-2 position, and a hydroxyl group at the sn-3 position.

  2. Critical Oxidation Reactions Optimized with Solvent Swap | The Ames

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

    Laboratory Critical Oxidation Reactions Optimized with Solvent Swap By simply changing the solvent, organic reactions vital for producing the starting materials for many major industrial processes have been found to be faster and able to yield the desired product with close to 100% selectivity. In solution, the critical reaction between an iron(II) catalyst with ozone in the presence of one of a number of alcohols and ethers generates various useful products. Importantly, the active species

  3. Crude Oil Movements by Tanker, Pipeline, Barge and Rail between PAD

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

    Districts Product: Crude Oil and Petroleum Products Crude Oil Petroleum Products Pentanes Plus Liquefied Petroleum Gases Ethane/Ethylene Propane/Propylene Normal Butane/Butylene Isobutane/Isobutylene Unfinished Oils Motor Gasoline Blend. Components (MGBC) MGBC - Reformulated MGBC - Reformulated RBOB MGBC - RBOB for Blending w/ Alcohol* MGBC - RBOB for Blending w/ Ether* MGBC - Reformulated GTAB* MGBC - Conventional MGBC - CBOB MGBC - Conventional GTAB MGBC - Conventional Other Renewable

  4. Crude Oil Net Receipts by Pipeline, Tanker, Barge and Rail between PAD

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

    Districts Product: Total Crude Oil and Products Crude Oil Petroleum Products Pentanes Plus Liquefied Petroleum Gases Ethane/Ethylene Propane/Propylene Normal Butane/Butylene Isobutane/Isobutylene Unfinished Oils Motor Gasoline Blend. Comp. (MGBC) MGBC - Reformulated MGBC - Reformulated RBOB MGBC - RBOB for Blending w/ Alcohol* MGBC - RBOB for Blending w/ Ether* MGBC - Reformulated GTAB* MGBC - Conventional MGBC - CBOB MGBC - Conventional GTAB MGBC - Conventional Other Renewable Fuels Fuel

  5. Method for liquid chromatographic extraction of strontium from acid solutions

    DOE Patents [OSTI]

    Horwitz, E. Philip (Naperville, IL); Dietz, Mark L. (Evanston, IL)

    1992-01-01

    A method and apparatus for extracting strontium and technetium values from biological, industrial and environmental sample solutions using a chromatographic column is described. An extractant medium for the column is prepared by generating a solution of a diluent containing a Crown ether and dispersing the solution on a resin substrate material. The sample solution is highly acidic and is introduced directed to the chromatographic column and strontium or technetium is eluted using deionized water.

  6. Liquid chromatographic extraction medium

    DOE Patents [OSTI]

    Horwitz, E. Philip (Naperville, IL); Dietz, Mark L. (Evanston, IL)

    1994-01-01

    A method and apparatus for extracting strontium and technetium values from biological, industrial and environmental sample solutions using a chromatographic column is described. An extractant medium for the column is prepared by generating a solution of a diluent containing a Crown ether and dispersing the solution on a resin substrate material. The sample solution is highly acidic and is introduced directed to the chromatographic column and strontium or technetium is eluted using deionized water.

  7. Alkaline earth cation extraction from acid solution

    DOE Patents [OSTI]

    Dietz, Mark (Elmhurst, IL); Horwitz, E. Philip (Naperville, IL)

    2003-01-01

    An extractant medium for extracting alkaline earth cations from an aqueous acidic sample solution is described as are a method and apparatus for using the same. The separation medium is free of diluent, free-flowing and particulate, and comprises a Crown ether that is a 4,4'(5')[C.sub.4 -C.sub.8 -alkylcyclohexano]18-Crown-6 dispersed on an inert substrate material.

  8. Green Gasoline from Wood Using Carbona Gasification and Topsoe TIGAS Processes

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

    Green Gasoline from Wood Using Carbona Gasification and Topsoe TIGAS Processes March 24, 2015 Demonstration and Market Transformation Rick Knight Gas Technology Institute This presentation does not contain any proprietary, confidential, or otherwise restricted information Acronyms AGR Acid Gas Removal DME Dimethyl ether GTI Gas Technology Institute HGF Hot gas filter HTAS Haldor Topsoe A/S (Denmark) HTI Haldor Topsoe Inc. (Houston TX) TIGAS Topsoe Improved Gasoline Synthesis UHGF Ultra-hot gas

  9. Process for synthesis of ammonia borane for bulk hydrogen storage

    DOE Patents [OSTI]

    Autrey, S Thomas [West Richland, WA; Heldebrant, David J [Richland, WA; Linehan, John C [Richland, WA; Karkamkar, Abhijeet J [Richland, WA; Zheng, Feng [Richland, WA

    2011-03-01

    The present invention discloses new methods for synthesizing ammonia borane (NH.sub.3BH.sub.3, or AB). Ammonium borohydride (NH.sub.4BH.sub.4) is formed from the reaction of borohydride salts and ammonium salts in liquid ammonia. Ammonium borohydride is decomposed in an ether-based solvent that yields AB at a near quantitative yield. The AB product shows promise as a chemical hydrogen storage material for fuel cell powered applications.

  10. Liquid chromatographic extraction medium

    DOE Patents [OSTI]

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

    1994-09-13

    A method and apparatus are disclosed for extracting strontium and technetium values from biological, industrial and environmental sample solutions using a chromatographic column. An extractant medium for the column is prepared by generating a solution of a diluent containing a Crown ether and dispersing the solution on a resin substrate material. The sample solution is highly acidic and is introduced directed to the chromatographic column and strontium or technetium is eluted using deionized water. 1 fig.

  11. IMPACT OF DME-DIESEL FUEL BLEND PROPERTIES ON DIESEL FUEL INJECTION SYSTEMS

    SciTech Connect (OSTI)

    Elana M. Chapman; Andre L. Boehman; Kimberly Wain; Wallis Lloyd; Joseph M. Perez; Donald Stiver; Joseph Conway

    2002-07-01

    The objectives of this research program are to develop information on lubricity and viscosity improvers and their impact on the wear mechanisms in fuel injectors operating on blends of dimethyl ether (DME) and diesel fuel. This project complements another ongoing project titled ''Development of a Dimethyl Ether (DME)-Fueled Shuttle Bus Demonstration Project''. The objectives of that research and demonstration program are to convert a campus shuttle bus to operation on dimethyl ether, a potential ultra-clean alternative diesel fuel. To accomplish this objective, this project includes laboratory evaluation of a fuel conversion strategy, as well as, field demonstration of the DME-fueled shuttle bus. Since DME is a fuel with no lubricity (i.e., it does not possess the lubricating quality of diesel fuel), conventional fuel delivery and fuel injection systems are not compatible with dimethyl ether. Therefore, to operate a diesel engine on DME one must develop a fuel-tolerant injection system, or find a way to provide the necessary lubricity to the DME. In the shuttle bus project, they have chosen the latter strategy in order to achieve the objective with minimal need to modify the engine. The strategy is to blend DME with diesel fuel, to obtain the necessary lubricity to protect the fuel injection system and to achieve low emissions. In this project, they have sought to develop methods for extending the permissible DME content in the DME-diesel blends without experiencing rapid injector failure due to wear. To date, the activities have covered two areas: development of a high-pressure lubricity test apparatus for studies of lubricity and viscosity improvers and development of an injector durability stand for evaluation of wear rates in fuel injectors. This report provides summaries of the progress toward completion of both experimental systems and a summary of the plan for completion of the project objectives.

  12. Alternative Fuels Data Center: Biobutanol

    Alternative Fuels and Advanced Vehicles Data Center [Office of Energy Efficiency and Renewable Energy (EERE)]

    Biobutanol to someone by E-mail Share Alternative Fuels Data Center: Biobutanol on Facebook Tweet about Alternative Fuels Data Center: Biobutanol on Twitter Bookmark Alternative Fuels Data Center: Biobutanol on Google Bookmark Alternative Fuels Data Center: Biobutanol on Delicious Rank Alternative Fuels Data Center: Biobutanol on Digg Find More places to share Alternative Fuels Data Center: Biobutanol on AddThis.com... More in this section... Biobutanol Dimethyl Ether Methanol Renewable

  13. Alternative Fuels Data Center: Methanol

    Alternative Fuels and Advanced Vehicles Data Center [Office of Energy Efficiency and Renewable Energy (EERE)]

    Methanol to someone by E-mail Share Alternative Fuels Data Center: Methanol on Facebook Tweet about Alternative Fuels Data Center: Methanol on Twitter Bookmark Alternative Fuels Data Center: Methanol on Google Bookmark Alternative Fuels Data Center: Methanol on Delicious Rank Alternative Fuels Data Center: Methanol on Digg Find More places to share Alternative Fuels Data Center: Methanol on AddThis.com... More in this section... Biobutanol Dimethyl Ether Methanol Renewable Hydrocarbon Biofuels

  14. Alternative Fuels Data Center

    Alternative Fuels and Advanced Vehicles Data Center [Office of Energy Efficiency and Renewable Energy (EERE)]

    Alternative Fuel Commercial Vehicle Tax Credit Businesses are eligible to receive tax credits for purchasing new alternative fuel commercial vehicles. Qualified commercial vehicles must be powered primarily by natural gas, propane, hydrogen, dimethyl ether, or electricity. Tax credit amounts vary based on gross vehicle weight rating (GVWR) and are up to 50% of the incremental cost, with maximum credit values as follows: GVWR Maximum Credit Amount Per Vehicle Up to 14,000 pounds (lbs.) $5,000

  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. Ionic liquid-assisted sonochemical preparation of CeO2 nanoparticles for CO oxidation

    SciTech Connect (OSTI)

    Alammar, Tarek; Noei, Heshmat; Wang, Yuemin; Grnert, Wolfgang; Mudring, Anja -Verena

    2014-10-10

    CeO2 nanoparticles were synthesized via a one-step ultrasound synthesis in different kinds of ionic liquids based on bis(trifluoromethanesulfonylamide, [Tf2N], in combination with various cations including 1-butyl-3-methylimidazolium ([C4mim]+), 1-ethyl-2,3-dimethylimidazolium ([Edimim]+), butyl-pyridinium([Py4]+), 1-butyl-1-methyl-pyrrolidinium ([Pyrr14]+), and 2-hydroxyethyl-trimethylammonium ([N1112OH]+). Depending on synthetic parameters, such as ionic liquid, Ce(IV) precursor, heating method, and precipitator, formed ceria exhibits different morphologies, varying from nanospheres, nanorods, nanoribbons, and nanoflowers. The morphology, crystallinity, and chemical composition of the obtained materials were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy dispersive X-ray spectroscopy (EDX), Raman spectroscopy, and N2 adsorption. The structural and electronic properties of the as-prepared CeO2 samples were probed by CO adsorption using IR spectroscopy under ultrahigh vacuum conditions. The catalytic activities of CeO2 nanoparticles were investigated in the oxidation of CO. CeO2 nanospheres obtained sonochemically in [C4mim][Tf2N] exhibit the best performance for low-temperature CO oxidation. As a result, the superior catalytic performance of this material can be related to its mesoporous structure, small particle size, large surface area, and high number of surface oxygen vacancy sites.

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

    SciTech Connect (OSTI)

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

    2011-01-01

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

  18. Fluoroalkyl containing salts combined with fluorinated solvents for electrolytes

    DOE Patents [OSTI]

    Tikhonov, Konstantin; Yip, Ka Ki; Lin, Tzu-Yuan; Erickson, Michael Jason

    2015-04-21

    Provided are electrochemical cells and electrolytes used to build such cells. An electrolyte may include a fluoroalkyl-substituted LiPF.sub.6 salt or a fluoroalkyl-substituted LiBF.sub.4 salt. In some embodiments, at least one fluorinated alkyl of the salt has a chain length of from 1 to 8 or, more specifically, between about 2 and 8. These fluorinated alkyl groups, in particular, relatively large fluorinated alkyl groups improve solubility of these salts in fluorinated solvents that are less flammable than, for example, conventional carbonate solvents. At the same time, the size of fluoroalkyl-substituted salts should be limited to ensure adequate concentration of the salt in an electrolyte and low viscosity of the electrolyte. In some embodiments, the concentration of a fluoroalkyl-substituted salt is at least about 0.5M. Examples of fluorinated solvents include various fluorinated esters, fluorinated ethers, and fluorinated carbonates, such a 1-methoxyheptafluoropropane, methyl nonafluorobutyl ether, ethyl nonafluorobutyl ether, 1,1,1,2,2,3,4,5,5,5-decafluoro-3-methoxy-4-(trifluoromethyl)-pentane, 3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro-2-trifluoromethyl-hexane, and 1,1,1,2,3,3-hexafluoro-4-(1,1,2,3,3,3-hexafluoropropoxy)-pentane.

  19. Superacid Catalyzed Coal Conversion Chemistry. 1st and 2nd Quarterly Technical Progress Reports, September 1, 1983-March 30, 1984.

    DOE R&D Accomplishments [OSTI]

    Olah, G. A.

    1984-01-01

    In our laboratories we have previously developed a mild coal conversion process. This involves the use of a superacid system consisting of HF and BF{sub 3} in presence of hydrogen and/or a hydrogen donor solvent. In order to understand the chemistry involved in the process of depolymerization of coal by the HF:BF{sub 3}:H{sub 2} system we are carrying out a systematic study of a number of coal model compounds. The model compounds selected for present study have two benzene rings connected with various bridging units such as alkylidene, ether, sulfide etc. From studies so far carried out it appears that high pyridine extractibilities achieved by treating coal at temperature below 100 degrees C results from the cleavage of bridges such as present in bibenzyl, diphenyl methane, dibenzyl ether, dibenzyl sulfide etc. On the other hand the increased cyclohexane extractibility and distillability observed at relatively higher temperatures and hydrogen pressures reflects the hydrogenation and cleavage of the aromatic backbone in coal structure similar to what is seen in the conversion of model compounds such as biphenyl, diphenyl ether, diphenyl sulfide, anthracene, etc.

  20. Alkali metal cation complexation by 1,3-alternate, mono-ionisable calix[4]arene-benzocrown-6 compounds

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

    Surowiec, Malgorzata A.; Custelcean, Radu; Surowiec, Kazimierz; Bartsch, Richard A.

    2014-04-23

    Alkali metal cation extraction behavior for two series of 1,3-alternate, mono-ionizable calix[4]arene-benzocrown-6 compounds is examined. In Series 1, the proton-ionizable group is a substituent on the benzo group of the polyether ring that directs it away from the crown ether cavity. In Series 2, the proton-ionizable group is attached to one para position in the calixarene framework, thus positioning it over the crown ether ring. Competitive solvent extraction of alkali metal cations from aqueous solutions into chloroform shows high Cs+ efficiency and selectivity. Single-species extraction pH profiles of Cs+ for Series 1 and 2 ligands with the same proton-ionizable groupmore » are very similar. Thus, association of Cs+ with the calixcrown ring is more important than the the proton-ionizable group’s position in relation to the crown ether cavity. Solid-state structures are presented for two unionized ligands from Series 2, as is a crystal containing two different ionized ligand–Cs+ complexes.« less

  1. The use of CETANER{trademark} for the reduction of particulate matter emissions in a turbocharged direct injection (TDI) diesel engine

    SciTech Connect (OSTI)

    Hess, H.S.; Chiodo, J.A.; Boehman, A.L.; Tijim, P.J.A.; Waller, F.J.

    1999-07-01

    In this experimental study, the effects of the addition of CETANER{trademark} to a premium diesel fuel at various blend levels (5%, 10% and 15% by weight) were evaluated using a 1.9 liter turbocharged direct injection diesel engine. CETANER{trademark}, a product developed by Air Products and Chemicals, Inc., can be manufactured from coal-derived syngas through a two-stage process: (i) Liquid Phase DiMethyl Ether synthesis (LPDME); and (ii) oxidative coupling of DiMethyl Ether (DME) to form long chain linear ethers. When compared to other oxygenated components currently being researched, CETANER has several key advantages: (1) it is derived from a non-petroleum feedstock; (2) it has a cetane number greater than 100; and (3) it will have a cost comparable to diesel fuel. Particulate matter emissions and exhaust gas composition (NOx and CO), were determined at six steady-state engine operating conditions. In addition, fuel properties (viscosity, cloud point, pour point, density, flash point and calorific value) of the various blends were also determined. Engine test results indicate that CETANER is effective in reducing particulate matter emissions at all blend levels tested, without any modifications to engine operating parameters. At the highest blend level (15% CETANER by weight), particulate matter emissions were reduced by greater than 20% when compared to premium diesel fuel.

  2. Petrochemicals from coal-derived syngas

    SciTech Connect (OSTI)

    Sardesai, A.; Lee, S.

    1996-12-31

    The development of the Liquid Phase Dimethyl Ether (LPDME) process has established a means to effectively convert CO-rich syngas to dimethyl ether (DME) in a mechanically agitated slurry reactor. By operating in a dual catalyst mode, in-situ produced methanol may be converted to DME, thereby alleviating the chemical equilibrium limitation imposed on the methanol synthesis reaction. As a result, higher syngas conversions and methyl productivities are seen over methanol synthesis alone. This effective route to DME production over methanol has led to the development of conversion technologies based on a DME feedstock. Oxygenates, in particular, ethers and their precursors, are very important as potential clean fuel additives and have been postulated through vinylation/hydrogenation and oxidative coupling reactions. Specialty chemicals such as methyl acetate and acetic acid have widescale industrial importance in the conversion to ethanol from a non-agricultural feedstock. Vapor phase oxidative dimerization of DME over tin based catalysts produced precursors of ethylene glycol. Finally, DME has been extensively used as a feedstock for hydrocarbon synthesis including olefins, paraffins and gasoline range hydrocarbons, over zeolite based catalysts with a 46% increase in product selectivity over methanol. The efficient production of DME in the liquid phase has given it widescale industrial significance as a potential replacement for methanol and as a keystone for more important petrochemicals.

  3. A study of the kinetics and mechanism of the adsorption and anaerobic partial oxidation of n-butane over a vanadyl pyrophosphate catalyst

    SciTech Connect (OSTI)

    Sakakini, B.H.; Taufiq-Yap, Y.H.; Waugh, K.C.

    2000-01-25

    The interaction of n-butane with a ((VO){sub 2}P{sub 2}O{sub 7}) catalyst has been investigated by temperature-programmed desorption and anaerobic temperature-programmed reaction. n-Butane has been shown to adsorb on the (VO){sub 2}P{sub 2}O{sub 7} to as a butyl-hydroxyl pair. When adsorption is carried out at 223 K, upon temperature programming some of the butyl-hydroxyl species recombine resulting in butane desorption at 260 K. However, when adsorption is carried out at 423 K, the hydroxyl species of the butyl-hydroxyl pair migrate away from the butyl species during the adsorption, forming water which is detected in the gas phase. Butane therefore is not observed to desorb at 260 K after the authors lowered the temperature to 223 K under the butane/helium from the adsorption temperature of 423 K prior to temperature programming from that temperature to 1100 K under a helium stream. Anaerobic temperature-programmed oxidation of n-butane produces butene and butadiene at a peak maximum temperature of 1000 K; this is exactly the temperature at which, upon temperature programming, oxygen evolves from the lattice and desorbs as O{sub 2}. This, and the fact that the amount of oxygen desorbing from the (VO){sub 2}P{sub 2}O{sub 7} at {approximately}1000 K is the same as that required for the oxidation of the n-butane to butene and butadiene, strongly suggests (1) that lattice oxygen as it emerges at the surface is the selective oxidant and (2) that its appearance at the surface is the rate-determining step in the selective oxidation of n-butane. The surface of the (VO){sub 2}P{sub 2}O{sub 7} catalyst on which this selective oxidation takes place has had approximately two monolayers of oxygen removed from it by unselective oxidation of the n-butane to CO, CO{sub 2}, and H{sub 2}O between 550 and 950 K and has had approximately one monolayer of carbon deposited on it at {approximately}1000 K. It is apparent, therefore, that the original crystallography of the (VO){sub 2}P{sub 2}O{sub 7} catalyst will not exist during this selective oxidation and that theories that relate selectivity in partial oxidation to the (100) face of the (VO){sub 2}P{sub 2}O{sub 7} catalyst cannot apply in this case.

  4. 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

  5. Best Practices Case Study: Green Coast Enterprises - Project Home Again, New Orleans, LA

    SciTech Connect (OSTI)

    none,

    2011-04-01

    Case study about Green Coast Enterprises, who received design assistance and analysis from Building America team Building Science Corporation to build 100 homes for New Orleans families displaced by Hurricane Katrina. The homes incorporate a host of weather-resistant techniques: pier foundations, all borate pressure-treated lumber; hurricane strapping; moisture-resistant closed-cell spray foam insulation under the subfloor, in walls, and under the roof line to seal out moisture-laden air and glue the structure together to resist high winds; roof sheathing seams sealed with butyl-adhesive flashing tape; and a fully adhered roofing membrane over eaves and gable ends.

  6. War against water

    SciTech Connect (OSTI)

    Fitz-Hugh, S.

    1982-01-01

    It is stressed that waterproofing should be the most important concern in an earth-sheltered home, starting with the design and continuing throughout the construction. Damage which may be caused by water leakage is discussed. Proper site selection is most important and the need for outside professionals and consultants is emphasized. The ideal waterproofing system is discussed and illustrated. Waterproofing agents are discussed in detail. They are: (1) sodium bentonite; (2) elastomers, such as isobutylene isoprene (butyl rubber), EPDM (ethylene propylene diene monomer), and liquid elastomers (polyurethanes); and (3) rubberized asphalt. Availability, sheet sizes and application of these waterproofing agents are discussed. (MJJ)

  7. 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

  8. Metabolomics relative quantitation with mass spectrometry using chemical derivatization and isotope labeling

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

    O'Maille, Grace; Go, Eden P.; Hoang, Linh; Want, Elizabeth J.; Smith, Colin; O'Maille, Paul; NordstrÖm, Anders; Morita, Hirotoshi; Qin, Chuan; Uritboonthai, Wilasinee; et al

    2008-01-01

    Comprehensive detection and quantitation of metabolites from a biological source constitute the major challenges of current metabolomics research. Two chemical derivatization methodologies, butylation and amination, were applied to human serum for ionization enhancement of a broad spectrum of metabolite classes, including steroids and amino acids. LC-ESI-MS analysis of the derivatized serum samples provided a significant signal elevation across the total ion chromatogram to over a 100-fold increase in ionization efficiency. It was also demonstrated that derivatization combined with isotopically labeled reagents facilitated the relative quantitation of derivatized metabolites from individual as well as pooled samples.

  9. Fluorescent temperature sensor

    DOE Patents [OSTI]

    Baker, Gary A [Los Alamos, NM; Baker, Sheila N [Los Alamos, NM; McCleskey, T Mark [Los Alamos, NM

    2009-03-03

    The present invention is a fluorescent temperature sensor or optical thermometer. The sensor includes a solution of 1,3-bis(1-pyrenyl)propane within a 1-butyl-1-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquid solvent. The 1,3-bis(1-pyrenyl)propane remains unassociated when in the ground state while in solution. When subjected to UV light, an excited state is produced that exists in equilibrium with an excimer. The position of the equilibrium between the two excited states is temperature dependent.

  10. Method for measuring surface temperature

    DOE Patents [OSTI]

    Baker, Gary A. (Los Alamos, NM); Baker, Sheila N. (Los Alamos, NM); McCleskey, T. Mark (Los Alamos, NM)

    2009-07-28

    The present invention relates to a method for measuring a surface temperature using is a fluorescent temperature sensor or optical thermometer. The sensor includes a solution of 1,3-bis(1-pyrenyl)propane within a 1-butyl-1-1-methyl pyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquid solvent. The 1,3-bis(1-pyrenyl)propane remains unassociated when in the ground state while in solution. When subjected to UV light, an excited state is produced that exists in equilibrium with an excimer. The position of the equilibrium between the two excited states is temperature dependent.

  11. 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

  12. 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

  13. 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

  14. Lipid extraction from microalgae using a single ionic liquid

    DOE Patents [OSTI]

    Salvo, Roberto Di; Reich, Alton; Dykes, Jr., H. Waite H.; Teixeira, Rodrigo

    2013-05-28

    A one-step process for the lysis of microalgae cell walls and separation of the cellular lipids for use in biofuel production by utilizing a hydrophilic ionic liquid, 1-butyl-3-methylimidazolium. The hydrophilic ionic liquid both lyses the microalgae cell walls and forms two immiscible layers, one of which consists of the lipid contents of the lysed cells. After mixture of the hydrophilic ionic liquid with a suspension of microalgae cells, gravity causes a hydrophobic lipid phase to move to a top phase where it is removed from the mixture and purified. The hydrophilic ionic liquid is recycled to lyse new microalgae suspensions.

  15. Method for cleaning solution used in nuclear fuel reprocessing

    DOE Patents [OSTI]

    Tallent, Othar K. (Oak Ridge, TN); Dodson, Karen E. (Knoxville, TN); Mailen, James C. (Oak Ridge, TN)

    1983-01-01

    A nuclear fuel processing solution containing (1) hydrocarbon diluent, (2) tri-n-butyl phosphate or tri-2-ethylhexyl phosphate, and (3) monobutyl phosphate, dibutyl phosphate, mono-2-ethylhexyl phosphate, di-2-ethylhexyl phosphate, or a complex formed by plutonium, uranium, or a fission product thereof with monobutyl phosphate, dibutyl phosphate, mono-2-ethylhexyl phosphate, or di-2-ethylhexyl phosphate is contacted with silica gel having alkali ions absorbed thereon to remove any one of the degradation products named in section (3) above from said solution.

  16. Time-resolved energy transfer from single chloride-terminated nanocrystals to graphene

    SciTech Connect (OSTI)

    Ajayi, O. A. E-mail: cww2104@columbia.edu; Wong, C. W. E-mail: cww2104@columbia.edu; Anderson, N. C.; Wolcott, A.; Owen, J. S.; Cotlet, M.; Petrone, N.; Hone, J.; Gu, T.; Gesuele, F.

    2014-04-28

    We examine the time-resolved resonance energy transfer of excitons from single n-butyl amine-bound, chloride-terminated nanocrystals to two-dimensional graphene through time-correlated single photon counting. The radiative biexponential lifetime kinetics and blinking statistics of the individual surface-modified nanocrystal elucidate the non-radiative decay channels. Blinking modification as well as a 4 reduction in spontaneous emission were observed with the short chloride and n-butylamine ligands, probing the energy transfer pathways for the development of graphene-nanocrystal nanophotonic devices.

  17. Testing of a model to estimate vapor concentration of various organic chemicals. Master's thesis

    SciTech Connect (OSTI)

    Bakalyar, S.M.

    1990-01-01

    A model developed by Dr. Parker C. Reist to predict the build-up and decay rates of vapor concentrations following a chemical spill and clean-up was tested. The chemicals tested were: acetone, butyl acetate, ethyl acetate, hexane, methylene chloride, methyl ethyl ketone, and toluene. The evaporation rates of these chemicals were determined both by prediction, using a model developed by I. Kawamura and D. Mackay, and empirically and these rates were used in the Reist model. Chamber experiments were done to measure actual building-up and decay of vapor concentrations for simulated spills and simulated clean-up.

  18. Impacts of ethanol fuel level on emissions of regulated and unregulated pollutants from a fleet of gasoline light-duty vehicles

    SciTech Connect (OSTI)

    Karavalakis, Georgios; Durbin, Thomas; Shrivastava, ManishKumar B.; Zheng, Zhongqing; Villella, Phillip M.; Jung, Hee-Jung

    2012-03-30

    The study investigated the impact of ethanol blends on criteria emissions (THC, NMHC, CO, NOx), greenhouse gas (CO2), and a suite of unregulated pollutants in a fleet of gasoline-powered light-duty vehicles. The vehicles ranged in model year from 1984 to 2007 and included one Flexible Fuel Vehicle (FFV). Emission and fuel consumption measurements were performed in duplicate or triplicate over the Federal Test Procedure (FTP) driving cycle using a chassis dynamometer for four fuels in each of seven vehicles. The test fuels included a CARB phase 2 certification fuel with 11% MTBE content, a CARB phase 3 certification fuel with a 5.7% ethanol content, and E10, E20, E50, and E85 fuels. In most cases, THC and NMHC emissions were lower with the ethanol blends, while the use of E85 resulted in increases of THC and NMHC for the FFV. CO emissions were lower with ethanol blends for all vehicles and significantly decreased for earlier model vehicles. Results for NOx emissions were mixed, with some older vehicles showing increases with increasing ethanol level, while other vehicles showed either no impact or a slight, but not statistically significant, decrease. CO2 emissions did not show any significant trends. Fuel economy showed decreasing trends with increasing ethanol content in later model vehicles. There was also a consistent trend of increasing acetaldehyde emissions with increasing ethanol level, but other carbonyls did not show strong trends. The use of E85 resulted in significantly higher formaldehyde and acetaldehyde emissions than the specification fuels or other ethanol blends. BTEX and 1,3-butadiene emissions were lower with ethanol blends compared to the CARB 2 fuel, and were almost undetectable from the E85 fuel. The largest contribution to total carbonyls and other toxics was during the cold-start phase of FTP.

  19. Impact of California Phase 2 reformulated gasoline on atmospheric reactivity of exhaust and evaporative emissions

    SciTech Connect (OSTI)

    Kirchstetter, T.W.; Singer, B.C.; Harley, R.A.; Kendall, G.R.; Traverse, M.

    1997-12-31

    Phase 2 of California`s reformulated gasoline (RFG) program took effect statewide in the first half of 1996. Changes to gasoline composition required by Phase 2 specifications included: lower vapor pressure; lower olefin, aromatic, benzene, and sulfur content; lower T50 and T90; and a minimum oxygen content. In this paper, impacts of Phase 2 RFG on the atmospheric reactivity of motor vehicle exhaust and evaporative emissions are described. Volatile organic compounds in motor vehicle exhaust were measured at the Caldecott tunnel in summer 1995 and 1996. Aggregate emissions of greater than 8000 vehicles were measured each day. Regular and premium grade gasoline samples were collected from service stations in Berkeley concurrently with tunnel measurements both summers. Liquid gasoline samples and their headspace vapors were analyzed to determine detailed chemical composition. Normalized reactivity was calculated for exhaust and evaporative emissions by applying maximum incremental reactivity values to the detailed speciation profiles. Results indicate that the composition of gasoline in 1996 differed markedly from that of 1995. Changes in liquid gasoline composition led to corresponding changes in the speciation of vehicle exhaust and of gasoline headspace vapors. Benzene concentration in liquid gasoline decreased from 2.0 to 0.6 wt%, which contributed to a 70 and 37% reduction in benzene weight fraction in headspace vapors and vehicle exhaust, respectively. Addition of MTBE and reduction of olefins and aromatics in gasoline led to significant reductions in the atmospheric reactivity of unburned gasoline and gasoline headspace vapors. The normalized reactivity of liquid gasoline and headspace vapors decreased by 23 and 19%, respectively, between 1995 and 1996. The normalized reactivity of non-methane organic compounds in vehicle exhaust decreased by about 8%, but the uncertainty in this change was large.

  20. Anandamide and analogous endocannabinoids: a lipid self-assembly study

    SciTech Connect (OSTI)

    Sagnella, Sharon M.; Conn, Charlotte E.; Krodkiewska, Irena; Mulet, Xavier; Drummond, Calum J.

    2014-09-24

    Anandamide, the endogenous agonist of the cannabinoid receptors, has been widely studied for its interesting biological and medicinal properties and is recognized as a highly significant lipid signaling molecule within the nervous system. Few studies have, however, examined the effect of the physical conformation of anandamide on its function. The study presented herein has focused on characterizing the self-assembly behaviour of anandamide and four other endocannabinoid analogues of anandamide, viz., 2-arachidonyl glycerol, arachidonyl dopamine, 2-arachidonyl glycerol ether (noladin ether), and o-arachidonyl ethanolamide (virodhamine). Molecular modeling of the five endocannabinoid lipids indicates that the highly unsaturated arachidonyl chain has a preference for a U or J shaped conformation. Thermal phase studies of the neat amphiphiles showed that a glass transition was observed for all of the endocannabinoids at {approx} -110 C with the exception of anandamide, with a second glass transition occurring for 2-arachidonyl glycerol, 2-arachidonyl glycerol ether, and virodhamine (-86 C, -95 C, -46 C respectively). Both anandamide and arachidonyl dopamine displayed a crystal-isotropic melting point (-4.8 and -20.4 C respectively), while a liquid crystal-isotropic melting transition was seen for 2-arachidonyl glycerol (-40.7 C) and 2-arachidonyl glycerol ether (-71.2 C). No additional transitions were observed for virodhamine. Small angle X-ray scattering and cross polarized optical microscopy studies as a function of temperature indicated that in the presence of excess water, both 2-arachidonyl glycerol and anandamide form co-existing Q{sub II}{sup G} (gyroid) and Q{sub II}{sup D} (diamond) bicontinuous cubic phases from 0 C to 20 C, which are kinetically stable over a period of weeks but may not represent true thermodynamic equilibrium. Similarly, 2-arachidonyl glycerol ether acquired an inverse hexagonal (HII) phase in excess water from 0 C to 40 C, while virodhamine and arachidonyl dopamine exist as an isotropic L{sub 2} phase, even at very low temperatures. Due to their preferential conformation and lipid self-assembly behaviour, all five endocannabinoids constitute high curvature lipids that can impart membrane stress within a cell membrane which has been linked to a number of membrane and membrane protein associated processes.

  1. 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

  2. Physicochemical properties and toxicities of hydrophobicpiperidinium and pyrrolidinium ionic liquids

    SciTech Connect (OSTI)

    Salminen, Justin; Papaiconomou, Nicolas; Kumar, R. Anand; Lee,Jong-Min; Kerr, John; Newman, John; Prausnitz, John M.

    2007-06-25

    Some properties are reported for hydrophobic ionic liquids (IL) containing 1-methyl-1-propyl pyrrolidinium [MPPyrro]{sup +}, 1-methyl-1-butyl pyrrolidinium [MBPyrro]{sup +}, 1-methyl-1-propyl piperidinium [MPPip]{sup +}, 1-methyl-1-butyl piperidinium [MBPip]{sup +}, 1-methyl-1-octylpyrrolidinium [MOPyrro]{sup +} and 1-methyl-1-octylpiperidinium [MOPip]{sup +} cations. These liquids provide new alternatives to pyridinium and imidazolium ILs. High thermal stability of an ionic liquid increases safety in applications like rechargeable lithium-ion batteries and other electrochemical devices. Thermal properties, ionic conductivities, viscosities, and mutual solubilities with water are reported. In addition, toxicities of selected ionic liquids have been measured using a human cancer cell-line. The ILs studied here are sparingly soluble in water but hygroscopic. We show some structure-property relationships that may help to design green solvents for specific applications. While ionic liquids are claimed to be environmentally-benign solvents, as yet few data have been published to support these claims.

  3. Ion Recognition Approach to Volume Reduction of Alkaline Tank Waste by Separation of Sodium Salts

    SciTech Connect (OSTI)

    Moyer, Bruce A.; Marchand, Alan P.; Lumetta, Gregg J.

    2004-06-30

    In this project, now completing its third year of its second renewal period, a collaborative project involving Oak Ridge National Laboratory, Pacific Northwest National Laboratory, and the University of North Texas has been addressing outstanding questions regarding the separation of the bulk sodium constituents of alkaline tank waste. The principal potential benefit of this research is a major reduction in the volume of radioactive tank waste, obviating the building of expensive new tanks and reducing the costs of vitrification. As a general approach, principles of ion recognition are being explored toward discovery and basic understanding of liquid-liquid extraction systems that selectively separate sodium hydroxide and sodium salts from waste-like matrices. Questions being addressed pertain to applicable extraction equilibria and how extraction properties relate to extractant structure. Progress has included the elucidation of the promising concept of pseudo hydroxide extraction (PHE), demonstration of crown-ether synergized PHE, demonstration of combined sodium hydroxide/sodium nitrate separation, and synthesis of novel ditopic receptors for ditopic PHE. In future efforts (pending renewal), a thermochemical study of PHE relating extractant acidity to extraction strength is proposed, and this study will be extended to systems containing crown ethers, including proton-ionizable ones. A series of crown ethers will be synthesized for this purpose and to investigate the extraction of bulk sodium salts (e.g., nitrate, nitrite, and sulfate), possibly in combination with sodium hydroxide. Simple proof-of-principle tests with real tank waste at PNNL will provide feedback toward solvent designs that have desirable properties. In view of the upcoming milestone of completion of the second renewal period, this report will, in addition to providing a summary of the past year's progress, summarize all of the work completed since the start of this project.

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

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

    Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja

    2015-02-11

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

  5. Potentiometric Response Characteristics of Membrane-BasedCs+-Selective Electrodes Containing Ionophore-Functionalized Polymeric Microspheres

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

    Peper, Shane; Gonczy, Chad

    2011-01-01

    Cs+-selective solvent polymeric membrane-based ion-selective electrodes (ISEs) were developed by doping ethylene glycol-functionalized cross-linked polystyrene microspheres (P-EG) into a plasticized poly(vinyl chloride) (PVC) matrix containing sodium tetrakis-(3,5-bis(trifluoromethyl)phenyl) borate (TFPB) as the ion exchanger. A systematic study examining the effects of the membrane plasticizers bis(2-ethylhexyl) sebacate (DOS), 2-nitrophenyl octyl ether (NPOE), and 2-fluorophenyl nitrophenyl ether (FPNPE) on the potentiometric response and selectivity of the corresponding electrodes was performed. Under certain conditions, P-EG-based ion-selective electrodes (ISEs) containing TFPB and plasticized with NPOE exhibited a super-Nernstian response between110?3and110?4?M Cs+, a response characteristic not observed in analogous membranes plasticized with either DOS or FPNPE.moreAdditionally, the performance of P-EG-based ISEs was compared to electrodes based on two mobile ionophores, a neutral lipophilic ethylene glycol derivative (ethylene glycol monooctadecyl ether (U-EG)) and a charged metallacarborane ionophore, sodium bis(dicarbollyl)cobaltate(III) (CC). In general, P-EG-based electrodes plasticized with FPNPE yielded the best performance, with a linear range from 10-110-5?M Cs+, a conventional lower detection limit of8.110?6?M Cs+, and a response slope of 57.7?mV/decade. The pH response of P-EG ISEs containing TFPB was evaluated for membranes plasticized with either NPOE or FPNPE. In both cases, the electrodes remained stable throughout the pH range 312, with only slight proton interference observed below pH 3.less

  6. Potentiometric Response Characteristics of Membrane-Based Cs + -Selective Electrodes Containing Ionophore-Functionalized Polymeric Microspheres

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

    Peper, Shane; Gonczy, Chad

    2011-01-01

    Csmore » + -selective solvent polymeric membrane-based ion-selective electrodes (ISEs) were developed by doping ethylene glycol-functionalized cross-linked polystyrene microspheres (P-EG) into a plasticized poly(vinyl chloride) (PVC) matrix containing sodium tetrakis-(3,5-bis(trifluoromethyl)phenyl) borate (TFPB) as the ion exchanger. A systematic study examining the effects of the membrane plasticizers bis(2-ethylhexyl) sebacate (DOS), 2-nitrophenyl octyl ether (NPOE), and 2-fluorophenyl nitrophenyl ether (FPNPE) on the potentiometric response and selectivity of the corresponding electrodes was performed. Under certain conditions, P-EG-based ion-selective electrodes (ISEs) containing TFPB and plasticized with NPOE exhibited a super-Nernstian response between 1 × 10 − 3 and 1 × 10 − 4  M Cs + , a response characteristic not observed in analogous membranes plasticized with either DOS or FPNPE. Additionally, the performance of P-EG-based ISEs was compared to electrodes based on two mobile ionophores, a neutral lipophilic ethylene glycol derivative (ethylene glycol monooctadecyl ether (U-EG)) and a charged metallacarborane ionophore, sodium bis(dicarbollyl)cobaltate(III) (CC). In general, P-EG-based electrodes plasticized with FPNPE yielded the best performance, with a linear range from 10 -1 –10 -5  M Cs + , a conventional lower detection limit of 8.1 × 10 − 6  M Cs + , and a response slope of 57.7 mV/decade. The pH response of P-EG ISEs containing TFPB was evaluated for membranes plasticized with either NPOE or FPNPE. In both cases, the electrodes remained stable throughout the pH range 3–12, with only slight proton interference observed below pH 3.« less

  7. Process studies for a new method of removing H/sub 2/S from industrial gas streams

    SciTech Connect (OSTI)

    Neumann, D.W.; Lynn, S.

    1986-07-01

    A process for the removal of hydrogen sulfide from coal-derived gas streams has been developed. The basis for the process is the absorption of H/sub 2/S into a polar organic solvent where it is reacted with dissolved sulfur dioxide to form elemental sulfur. After sulfur is crystallized from solution, the solvent is stripped to remove dissolved gases and water formed by the reaction. The SO/sub 2/ is generated by burning a portion of the sulfur in a furnace where the heat of combustion is used to generate high pressure steam. The SO/sub 2/ is absorbed into part of the lean solvent to form the solution necessary for the first step. The kinetics of the reaction between H/sub 2/S and SO/sub 2/ dissolved in mixtures of N,N-Dimethylaniline (DMA)/ Diethylene Glycol Monomethyl Ether and DMA/Triethylene Glycol Dimethyl Ether was studied by following the temperature rise in an adiabatic calorimeter. This irreversible reaction was found to be first-order in both H/sub 2/S and SO/sub 2/, with an approximates heat of reaction of 28 kcal/mole of SO/sub 2/. The sole products of the reaction appear to be elemental sulfur and water. The presence of DMA increases the value of the second-order rate constant by an order of magnitude over that obtained in the glycol ethers alone. Addition of other tertiary aromatic amines enhances the observed kinetics; heterocyclic amines (e.g., pyridine derivatives) have been found to be 10 to 100 times more effective as catalysts when compared to DMA.

  8. Assessment of PNGV fuels infrastructure. Phase 1 report: Additional capital needs and fuel-cycle energy and emissions impacts

    SciTech Connect (OSTI)

    Wang, M.; Stork, K.; Vyas, A.; Mintz, M.; Singh, M.; Johnson, L.

    1997-01-01

    This report presents the methodologies and results of Argonne`s assessment of additional capital needs and the fuel-cycle energy and emissions impacts of using six different fuels in the vehicles with tripled fuel economy (3X vehicles) that the Partnership for a New Generation of Vehicles is currently investigating. The six fuels included in this study are reformulated gasoline, low-sulfur diesel, methanol, ethanol, dimethyl ether, and hydrogen. Reformulated gasoline, methanol, and ethanol are assumed to be burned in spark-ignition, direct-injection engines. Diesel and dimethyl ether are assumed to be burned in compression-ignition, direct-injection engines. Hydrogen and methanol are assumed to be used in fuel-cell vehicles. The authors have analyzed fuels infrastructure impacts under a 3X vehicle low market share scenario and a high market share scenario. The assessment shows that if 3X vehicles are mass-introduced, a considerable amount of capital investment will be needed to build new fuel production plants and to establish distribution infrastructure for methanol, ethanol, dimethyl ether, and hydrogen. Capital needs for production facilities will far exceed those for distribution infrastructure. Among the four fuels, hydrogen will bear the largest capital needs. The fuel efficiency gain by 3X vehicles translates directly into reductions in total energy demand, fossil energy demand, and CO{sub 2} emissions. The combination of fuel substitution and fuel efficiency results in substantial petroleum displacement and large reductions in emissions of nitrogen oxide, carbon monoxide, volatile organic compounds, sulfur oxide, and particulate matter of size smaller than 10 microns.

  9. Hybrid sol-gel optical materials

    DOE Patents [OSTI]

    Zeigler, John M. (Albuquerque, NM)

    1992-01-01

    Hybrid sol-gel materials comprise silicate sols cross-linked with linear polysilane, polygermane, or poly(silane-germane). The sol-gel materials are useful as optical identifiers in tagging and verification applications and, in a different aspect, as stable, visible light transparent non-linear optical materials. Methyl or phenyl silicones, polyaryl sulfides, polyaryl ethers, and rubbery polysilanes may be used in addition to the linear polysilane. The linear polymers cross-link with the sol to form a matrix having high optical transparency, resistance to thermooxidative aging, adherence to a variety of substrates, brittleness, and a resistance to cracking during thermal cycling.

  10. Hybrid sol-gel optical materials

    DOE Patents [OSTI]

    Zeigler, John M. (Albuquerque, NM)

    1993-01-01

    Hybrid sol-gel materials comprise silicate sols cross-linked with linear polysilane, polygermane, or poly(silane-germane). The sol-gel materials are useful as optical identifiers in tagging and verification applications and, in a different aspect, as stable, visible light transparent non-linear optical materials. Methyl or phenyl silicones, polyaryl sulfides, polyaryl ethers, and rubbery polysilanes may be used in addition to the linear polysilane. The linear polymers cross-link with the sol to form a matrix having high optical transparency, resistance to thermooxidative aging, adherence to a variety of substrates, brittleness, and a resistance to cracking during thermal cycling.

  11. Hydrogen-assisted catalytic ignition characteristics of different fuels

    SciTech Connect (OSTI)

    Zhong, Bei-Jing; Yang, Fan; Yang, Qing-Tao

    2010-10-15

    Hydrogen-assisted catalytic ignition characteristics of methane (CH{sub 4}), n-butane (n-C{sub 4}H{sub 10}) and dimethyl ether (DME) were studied experimentally in a Pt-coated monolith catalytic reactor. It is concluded that DME has the lowest catalytic ignition temperature and the least required H{sub 2} flow, while CH{sub 4} has the highest catalytic ignition temperature and the highest required H{sub 2} flow among the three fuels. (author)

  12. Next Generation Extractants for Cesium Separation from High-Level Waste: From Fundamental Concepts to Site Implementation

    SciTech Connect (OSTI)

    Bonnesen, Peter V.; Engle, Nancy L.; Gorbunova, Maryna G.; Haverlock, Tamara J.; Tomkins, Bruce A.; Bazelaire, Eve; Delamu, Laetitia H.; Moyer, Bruce A.

    2003-09-10

    The successful development of the Caustic-Side Solvent Extraction (CSSX) process at ORNL owes a great deal to basic scientific concepts uncovered and discoveries made through research programs funded both by the US DOE's Basic Energy Sciences and Environmental Management Science Programs. Under the EMSP, we have been designing, synthesizing and characterizing new calixarene-crown ethers for cesium extraction. Scientific issues we are addressing with the new extractants include increasing hydrocarbon solubility, and improving the efficiency of cesium ion binding and release. The fundamental chemistry and extraction behavior of these new calixarene crowns will be discussed.

  13. Supercritical fluid extraction

    DOE Patents [OSTI]

    Wai, Chien M.; Laintz, Kenneth

    1994-01-01

    A method of extracting metalloid and metal species from a solid or liquid material by exposing the material to a supercritical fluid solvent containing a chelating agent. The chelating agent forms chelates that are soluble in the supercritical fluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is a fluorinated or lipophilic crown ether or fluorinated dithiocarbamate. The method provides an environmentally benign process for removing contaminants from industrial waste without using acids or biologically harmful solvents. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process.

  14. Recent Advances in Catalytic Conversion of Ethanol to Chemicals

    SciTech Connect (OSTI)

    Sun, Junming; Wang, Yong

    2014-04-30

    With increased availability and decreased cost, ethanol is potentially a promising platform molecule for the production of a variety of value-added chemicals. In this review, we provide a detailed summary of recent advances in catalytic conversion of ethanol to a wide range of chemicals and fuels. We particularly focus on catalyst advances and fundamental understanding of reaction mechanisms involved in ethanol steam reforming (ESR) to produce hydrogen, ethanol conversion to hydrocarbons ranging from light olefins to longer chain alkenes/alkanes and aromatics, and ethanol conversion to other oxygenates including 1-butanol, acetaldehyde, acetone, diethyl ether, and ethyl acetate.

  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. Polystyrene-poly(vinylphenol) copolymers as compatibilzers for organic-inorganic composites

    SciTech Connect (OSTI)

    Landry, C.J.T.; Coltrain, B.K.; Teegarden, D.M.

    1996-12-31

    Random, graft, and block copolymers of polystyrene (PS) and poly(4-vinylphenol) (PVPh), and PVPh homopolymer are shown to act as compatibilizers for incompatible organic-inorganic composite materials. The VPh component reacts, or interacts strongly with the polymerizing inorganic (titanium or zirconium) alkoxide. The organic components studied were PS, poly(vinyl methyl ether), and poly(styrene-co-acrylonitrile). The use of such compatibilizers provides a means of combining in situ polymerized inorganic oxides and hydrophobic polymers. This is seen as a reduction in the size of the dispersed inorganic phase and results in improved optical and mechanical properties.

  17. Redox polymer electrodes for advanced batteries

    DOE Patents [OSTI]

    Gregg, Brian A. (Golden, CO); Taylor, A. Michael (Golden, CO)

    1998-01-01

    Advanced batteries having a long cycle lifetime are provided. More specifically, the present invention relates to electrodes made from redox polymer films and batteries in which either the positive electrode, the negative electrode, or both, comprise redox polymers. Suitable redox polymers for this purpose include pyridyl or polypyridyl complexes of transition metals like iron, ruthenium, osmium, chromium, tungsten and nickel; porphyrins (either free base or metallo derivatives); phthalocyanines (either free base or metallo derivatives); metal complexes of cyclams, such as tetraazacyclotetradecane; metal complexes of crown ethers and metallocenes such as ferrocene, cobaltocene and ruthenocene.

  18. Redox polymer electrodes for advanced batteries

    DOE Patents [OSTI]

    Gregg, B.A.; Taylor, A.M.

    1998-11-24

    Advanced batteries having a long cycle lifetime are provided. More specifically, the present invention relates to electrodes made from redox polymer films and batteries in which either the positive electrode, the negative electrode, or both, comprise redox polymers. Suitable redox polymers for this purpose include pyridyl or polypyridyl complexes of transition metals like iron, ruthenium, osmium, chromium, tungsten and nickel; porphyrins (either free base or metallo derivatives); phthalocyanines (either free base or metallo derivatives); metal complexes of cyclams, such as tetraazacyclotetradecane; metal complexes of crown ethers and metallocenes such as ferrocene, cobaltocene and ruthenocene. 2 figs.

  19. Influence of lithium salts on the discharge chemistry of Li-air cells

    SciTech Connect (OSTI)

    Veith, Gabriel M; Nanda, Jagjit; Delmau, Laetitia Helene; Dudney, Nancy J

    2012-01-01

    In this work we show that the use of a high boiling point ether solvent (tetraglyme) promotes the formation of Li2O2 in a lithium-air cell. In addition, another major constituent in the discharge product of a Li-air cell contains halides, from the lithium salt, and the tetraglyme used as the solvent. This information is critical to the development of Li-air electrolytes which are stable and promote the formation of the desired Li2O2 products.

  20. Injectible bodily prosthetics employing methacrylic copolymer gels

    DOE Patents [OSTI]

    Mallapragada, Surya K.; Anderson, Brian C.

    2007-02-27

    The present invention provides novel block copolymers as structural supplements for injectible bodily prosthetics employed in medical or cosmetic procedures. The invention also includes the use of such block copolymers as nucleus pulposus replacement materials for the treatment of degenerative disc disorders and spinal injuries. The copolymers are constructed by polymerization of a tertiary amine methacrylate with either a (poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) polymer, such as the commercially available Pluronic.RTM. polymers, or a poly(ethylene glycol) methyl ether polymer.

  1. pH-sensitive methacrylic copolymer gels and the production thereof

    DOE Patents [OSTI]

    Mallapragada, Surya K. (Ames, IA); Anderson, Brian C. (Lake Bluff, IA)

    2007-05-15

    The present invention provides novel gel forming methacrylic blocking copolymers that exhibit cationic pH-sensitive behavior as well as good water solubility. The copolymers are constructed by polymerization of a tertiary amine methacrylate with either a (poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) polymer, such as the commercially available Pluronic.RTM. polymers, or a poly(ethylene glycol)methyl ether polymer. The polymers may be used for drug and gene delivery, protein separation, as structural supplements, and more.

  2. Development of Extraction Techniques for the Detection of Signature Lipids from Oil

    SciTech Connect (OSTI)

    Borglin, Sharon; Geller, Jil; Chakraborty, Romy; Hazen, Terry; Mason, Olivia

    2010-05-17

    Pure cultures, including Desulfovibrio vulgaris and Methanococcus maripaludus, were combined with model oil samples and oil/diesel mixtures to optimize extraction techniques of signature lipids from oil in support of investigation of microbial communities in oil deposit samples targets for microbial enhanced hydrocarbon recovery. Several techniques were evaluated, including standard phospholipid extraction, ether linked lipid for Archaeal bacterial detection, and high pressure extractiontechniques. Recovery of lipids ranged from 50-80percent as compared to extraction of the pure culture. Extraction efficiency was evaluated by the use of internal standards. Field samples will also be tested for recovery of signature lipids with optimized extraction techniques.

  3. Process for extracting technetium from alkaline solutions

    DOE Patents [OSTI]

    Moyer, Bruce A. (Oak Ridge, TN); Sachleben, Richard A. (Knoxville, TN); Bonnesen, Peter V. (Knoxville, TN)

    1995-01-01

    A process for extracting technetium values from an aqueous alkaline solution containing at least one alkali metal hydroxide and at least one alkali metal nitrate, the at least one alkali metal nitrate having a concentration of from about 0.1 to 6 molar. The solution is contacted with a solvent consisting of a crown ether in a diluent for a period of time sufficient to selectively extract the technetium values from the aqueous alkaline solution. The solvent containing the technetium values is separated from the aqueous alkaline solution and the technetium values are stripped from the solvent.

  4. Proceedings of the 1995 SAE alternative fuels conference. P-294

    SciTech Connect (OSTI)

    1995-12-31

    This volume contains 32 papers and five panel discussions related to the fuel substitution of trucks, automobiles, buses, cargo handling equipment, diesel passenger cars, and pickup trucks. Fuels discussed include liquefied natural gas, natural gas, ethanol fuels, methanol fuels, dimethyl ether, methyl esters from various sources (rape oil, used cooking oils, soya, and canola oils), hydrogen fuels, and biodiesel. Other topics include fuel cell powered vehicles, infrastructure requirements for fuel substitution, and economics. Papers have been processed separately for inclusion on the data base.

  5. Molecular cobalt pentapyridine catalysts for generating hydrogen from water

    DOE Patents [OSTI]

    Long, Jeffrey R; Chang, Christopher J; Sun, Yujie

    2013-11-05

    A composition of matter suitable for the generation of hydrogen from water is described, the positively charged cation of the composition including the moiety of the general formula. [(PY5Me.sub.2)CoL].sup.2+, where L can be H.sub.2O, OH.sup.-, a halide, alcohol, ether, amine, and the like. In embodiments of the invention, water, such as tap water or sea water can be subject to low electric potentials, with the result being, among other things, the generation of hydrogen.

  6. Hybrid sol-gel optical materials

    DOE Patents [OSTI]

    Zeigler, J.M.

    1993-04-20

    Hybrid sol-gel materials comprise silicate sols cross-linked with linear polysilane, polygermane, or poly(silane-germane). The sol-gel materials are useful as optical identifiers in tagging and verification applications and, in a different aspect, as stable, visible light transparent non-linear optical materials. Methyl or phenyl silicones, polyaryl sulfides, polyaryl ethers, and rubbery polysilanes may be used in addition to the linear polysilane. The linear polymers cross-link with the sol to form a matrix having high optical transparency, resistance to thermooxidative aging, adherence to a variety of substrates, brittleness, and a resistance to cracking during thermal cycling.

  7. Preparation and use of polymeric materials containing hydrophobic anions and plasticizers for separation of cesium and strontium

    DOE Patents [OSTI]

    Abney, Kent D. (30 San Juan St., Los Alamos, NM 87544); Kinkead, Scott A. (70 Canada Cir., Los Alamos, NM 87544); Mason, Caroline F. V. (148 Piedra Loop, Los Alamos, NM 87544); Rais, Jiri (Fr. Krizka 11, 17000 Praha 7, CZ)

    1997-01-01

    Preparation and use of polymeric materials containing hydrophobic anions and plasticizers for extraction of cesium and strontium. The use of polymeric materials containing plasticizers which are solvents for hydrophobic anions such as derivatives of cobalt dicarbollide or tetraphenylborate which are capable of extracting cesium and strontium ions from aqueous solutions in contact with the polymeric materials, is described. The polymeric material may also include a synergistic agent for a given ion like polyethylene glycol or a crown ether, for removal of radioactive isotopes of cesium and strontium from solutions of diverse composition and, in particular, for solutions containing large excess of sodium nitrate.

  8. An integrated process for simultaneous desulfurization, dehydration, and recovery of hydrocarbon liquids from natural gas streams

    SciTech Connect (OSTI)

    Sciamanna, S.F. ); ))

    1988-01-01

    Conventional processing schemes for desulfurizing, drying, and separation of natural gas liquids from natural gas streams require treating the gas by a different process for each separation step. In a simpler process, based on the University of California, Berkeley Sulfur Recovery Process (UCBSRP) technology, hydrogen sulfide, propane and heavier hydrocarbons, and water are absorbed simultaneously by a polyglycol ether solvent containing a homogenous liquid phase catalyst. The catalyst promotes the subsequent reaction of hydrogen sulfide with added sulfur dioxide to produce a high quality sulfur product. Hydrocarbons are separated as two product streams with the split between propane and butane. This new process offers an overall reduction in both capital and energy costs.

  9. Oxidative decomposition of methanol on subnanometer palladium clusters : the effect of catalyst size and support composition.

    SciTech Connect (OSTI)

    Lee, S.; Lee, B.; Mehmood, F.; Seifert, S.; Libera, J. A.; Elam, J. W.; Greeley, J.; Zapol, P.; Curtiss, L. A.; Pellin, M. J.; Stair, P. C.; Winans, R. E; Vajda, S.; Northwestern Univ.

    2010-06-17

    Size and support effects in the oxidative decomposition of methanol on amorphous alumina supported subnanometer palladium clusters were studied under realistic reaction conditions of pressure and temperature. The smaller Pd{sub 8-12} clusters were found to promote the decomposition channel to CO and hydrogen, however with mediocre activity due to poisoning. The larger Pd{sub 15-18} clusters preferentially produce dimethyl ether and formaldehyde, without signs of posioning. A thin titania overcoat applied on the Pd{sub 15-18} improves the sintering-resistance of the catalyst. Accompanying density functional calculations confirm the posioning of small Pd clusters by CO.

  10. Oxidative Decomposition of Methanol on Subnanometer Palladium Clusters: The Effect of Catalyst Size and Support Composition

    SciTech Connect (OSTI)

    Lee, Sungsik; Lee, Byeongdu; Mehmood, Faisal; Seifert, Soenke; Libera, Joseph A.; Elam, J. W.; Greeley, Jeffrey P.; Zapol, Peter; Curtiss, Larry A.; Pellin, M. J.; Stair, Peter C.; Winans, R. E.; Vajda, S.

    2010-05-31

    Size and support effects in the oxidative decomposition of methanol on amorphous alumina supported subnanometer palladium clusters were studied under realistic reaction conditions of pressure and temperature. The smaller Pd8-12 clusters were found to promote the decomposition channel to CO and hydrogen, however with mediocre activity due to poisoning. The larger Pd15-18 clusters preferentially produce dimethyl ether and formaldehyde, without signs of posioning. A thin titania overcoat applied on the Pd15-18 improves the sintering-resistance of the catalyst. Accompanying density functional calculations confirm the posioning of small Pd clusters by CO.

  11. Preparation and use of polymeric materials containing hydrophobic anions and plasticizers for separation of cesium and strontium

    DOE Patents [OSTI]

    Abney, K.D.; Kinkead, S.A.; Mason, C.F.V.; Rais, J.

    1997-09-09

    Preparation and use is described for polymeric materials containing hydrophobic anions and plasticizers for extraction of cesium and strontium. The use of polymeric materials containing plasticizers which are solvents for hydrophobic anions such as derivatives of cobalt dicarbollide or tetraphenylborate which are capable of extracting cesium and strontium ions from aqueous solutions in contact with the polymeric materials, is described. The polymeric material may also include a synergistic agent for a given ion like polyethylene glycol or a crown ether, for removal of radioactive isotopes of cesium and strontium from solutions of diverse composition and, in particular, for solutions containing large excess of sodium nitrate.

  12. Production of chemicals and fuels from biomass

    DOE Patents [OSTI]

    Woods, Elizabeth M.; Qiao, Ming; Myren, Paul; Cortright, Randy D.; Kania, John

    2015-12-15

    Described are methods, reactor systems, and catalysts for converting biomass to fuels and chemicals in a batch and/or continuous process. The process generally involves the conversion of water insoluble components of biomass, such as hemicellulose, cellulose and lignin, to volatile C.sub.2+O.sub.1-2 oxygenates, such as alcohols, ketones, cyclic ethers, esters, carboxylic acids, aldehydes, and mixtures thereof. In certain applications, the volatile C.sub.2+O.sub.1-2 oxygenates can be collected and used as a final chemical product, or used in downstream processes to produce liquid fuels, chemicals and other products.

  13. Catalysts and process conditions favoring DME synthesis from CO, H{sub 2}, and CO{sub 2}

    SciTech Connect (OSTI)

    Stiles, A.B.

    1994-12-31

    Synthesis gas can be derived from many carbonaceous raw materials and by a large number of efficient processes. Synthesis gas can also be derived from many processes typified by the following reactions: partial oxidation; steam hydrocarbon reforming; and methanol dissociation. Because the foregoing processes are so efficient and low cost, the product gases are broadly used for hydrogenation, carbonylation, and organic synthesis. The authors will not go into further detail except in the case of synthesis gas to alcohols and dimethyl ether and methane for synthetic natural gas. The paper discusses historical aspects and more recent studies of the conversion of synthesis gas.

  14. ORNL/TM-2014/59

    Alternative Fuels and Advanced Vehicles Data Center [Office of Energy Efficiency and Renewable Energy (EERE)]

    ORNL/TM-2014/59 Emissions and Performance Benchmarking of a Prototype Dimethyl Ether-Fueled Heavy-Duty Truck February 2014 Prepared by James P. Szybist Oak Ridge National Laboratory Samuel McLaughlin Volvo North America Suresh Iyer The Pennsylvania State University DOCUMENT AVAILABILITY Reports produced after January 1, 1996, are generally available free via the U.S. Department of Energy (DOE) Information Bridge. Web site http://www.osti.gov/bridge Reports produced before January 1, 1996, may be

  15. 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.

  16. Radical Compatibility with Nonaqueous Electrolytes and Its Impact on an All-Organic Redox Flow Battery

    SciTech Connect (OSTI)

    Wei, Xiaoliang; Xu, Wu; Huang, Jinhua; Zhang, Lu; Walter, Eric D.; Lawrence, Chad W.; Vijayakumar, M.; Henderson, Wesley A.; Liu, Tianbiao L.; Cosimbescu, Lelia; Li, Bin; Sprenkle, Vincent L.; Wang, Wei

    2015-07-20

    Nonaqueous redox flow batteries hold the promise to achieve higher energy density ascribed to the broader voltage window than their aqueous counterparts, but their current performance is limited by low redox material concentration, poor cell efficiency, and inferior cycling stability. We report a new nonaqueous total-organic flow battery based on high concentrations of 9-fluorenone as negative and 2,5-di-tert-butyl-1-methoxy-4-[2’-methoxyethoxy]benzene as positive redox materials. The supporting electrolytes are found to greatly affect the cycling stability of flow cells through varying chemical stabilities of the charged radical species, especially the 9-fluorenone radical anions, as confirmed by electron spin resonance. Such an electrolyte optimization sheds light on mechanistic understandings of capacity fading in flow batteries employing organic radical-based redox materials and demonstrates that rational design of supporting electrolyte is vital for stable cyclability.

  17. High temperature concrete composites containing organosiloxane crosslinked copolymers

    DOE Patents [OSTI]

    Zeldin, Arkady; Carciello, Neal; Kukacka, Lawrence; Fontana, Jack

    1980-01-01

    This invention relates to high temperature polymer concrete composites comprising about 10-30% by weight of a liquid monomer mixture consisting essentially of an organosiloxane polymer crosslinked with an olefinically unsaturated monomer selected from the group consisting of styrene, methyl methacrylate, trimethylolpropane trimethacrylate, triallyl cyanurate, n-phenylmalimide, divinyl benzene and mixtures theroef; and about 70-90% by weight of an inert inorganic filler system containing silica sand and preferably a member selected from the group consisting of portland cement, Fe.sub.2 O.sub.3, carbon black and mixtures thereof; and optionally a free radical initiator such as di-tert-butyl peroxide, azobisisobutyronitrile, benzoyl peroxide, lauryl peroxide and other organic peroxides to initiate crosspolymerization of the monomer mixture in the presence of the inorganic filler.

  18. High temperature chemically resistant polymer concrete

    DOE Patents [OSTI]

    Sugama, T.; Kukacka, L.E.

    High temperature chemically resistant, non-aqueous polymer concrete composites consist of about 12 to 20% by weight of a water-insoluble polymer binder. The binder is polymerized in situ from a liquid vinyl-type monomer or mixture of vinyl containing monomers such as triallylcyanurate, styrene, acrylonitrile, acrylamide, methacrylamide, methyl-methacrylate, trimethylolpropane trimethacrylate and divinyl benzene. About 5 to 40% by weight of a reactive inorganic filler selected from the group consisting of tricalcium silicate and dicalcium silicate and mixtures containing less than 2% free lime, and about 48 to 83% by weight of silica sand/ and a free radical initiator such as di-tert-butyl peroxide, azobisisobutyronitrile, benzoyl peroxide, lauryl peroxide, other orgaic peroxides and combinations to initiate polymerization of the monomer in the presence of the inorganic filers are used.

  19. Polymer concrete composites for the production of high strength pipe and linings in high temperature corrosive environments

    DOE Patents [OSTI]

    Zeldin, A.; Carciello, N.; Fontana, J.; Kukacka, L.

    High temperature corrosive resistant, non-aqueous polymer concrete composites are described. They comprise about 12 to 20% by weight of a water-insoluble polymer binder polymerized in situ from a liquid monomer mixture consisting essentially of about 40 to 70% by weight of styrene, about 25 to 45% by weight acrylonitrile and about 2.5 to 7.5% by weight acrylamide or methacrylamide and about 1 to 10% by weight of a crosslinking agent. This agent is selected from the group consisting of trimethylolpropane trimethacrylate and divinyl benzene; and about 80 to 88% by weight of an inert inorganic filler system containing silica sand and portland cement, and optionally Fe/sub 2/O/sub 3/ or carbon black or mica. A free radical initiator such as di-tert-butyl peroxide, azobisisobutyronitrile, benzoyl peroxide, lauryl peroxide, other organic peroxides and combinations thereof to initiate crosspolymerization of the monomer mixture in the presence of said inorganic filler.

  20. PREPARATION OF HIGH PURITY UF$sub 4$

    DOE Patents [OSTI]

    Magner, J.E.; Long, R.S.; Ellis, D.A.; Grinstead, R.R.

    1962-04-17

    S>A process for preparing very highly pure uranous tetrafluoride from impure uranium laden solvent extraction strip solutions, ion exchange process and resin-inpulp process eluate solutions which are at least 8M in hydrochloric acid is described. The process first comprises treating any of the above-mentioned solutions with a reducing agent to reduce the uranium to the + 4 oxidation state, and then contacting the reduced solution with an extractant phase comprising about 10 to 70% of tri-butyl phosphate in an organic solvent-diluent selected from benzene, ethyl-benzene, chlorobenzene, xylene, kerosene, or the like. The uranium is extracted into the extractant phase and is subsequently precipitated by treating the extractant with an aqueous fluoride solution. The highly pure uranous tetrafluoride precipitate is separated from the phases and recovered for subsequent utilization. (AEC)

  1. High temperature concrete composites containing organosiloxane crosslinked copolymers

    DOE Patents [OSTI]

    Zeldin, A.; Carciello, N.; Kukacka, L.; Fontana, J.

    High temperature polymer concrete composites comprising about 10 to 30% by weight of a liquid monomer mixture is described. It consists essentially of an organosiloxane polymer crosslinked with an olefinically unsaturated monomer selected from the group consisting of styrene, methyl methacrylate, trimethylolpropane trimethacrylate, triallyl cyanurate, n-phenylmalimide, divinyl benzene and mixtures thereof. About 70 to 90% by weight of an inert inorganic filler system containing silica sand and portland cement, Fe/sub 2/O/sub 3/, carbon black or mixtures thereof. Optionally a free radical initiator such as di-tert-butyl peroxide, azobisisobyutyronitrile, benzoyl peroxide, lauryl peroxide and other organic peroxides are used to initiate crosspolymerization of the monomer mixture in the presence of the inorganic filler.

  2. 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.

  3. 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.

  4. 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.

  5. 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)

  6. 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.

  7. 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.

  8. High pressure chemistry of substituted acetylenes

    SciTech Connect (OSTI)

    Chellappa, Raja; Dattelbaum, Dana; Sheffield, Stephen; Robbins, David

    2011-01-25

    High pressure in situ synchrotron x-ray diffraction experiments were performed on substituted polyacetylenes: tert-butyl acetylene [TBA: (CH{sub 3}){sub 3}-C{triple_bond}CH] and ethynyl trimethylsilane [ETMS: (CH{sub 3}){sub 3}-Si{triple_bond}CH] to investigate pressure-induced chemical reactions. The starting samples were the low temperature crystalline phases which persisted metastably at room temperature and polymerized beyond 11 GPa and 26 GPa for TBA and ETMS respectively. These reaction onset pressures are considerably higher than what we observed in the shockwave studies (6.1 GPa for TBA and 6.6 GPa for ETMS). Interestingly, in the case of ETMS, it was observed with fluid ETMS as starting sample, reacts to form a semi-crystalline polymer (crystalline domains corresponding to the low-T phase) at pressures less than {approx}2 GPa. Further characterization using vibrational spectroscopy is in progress.

  9. Portal Vein Embolization: What Do We Know?

    SciTech Connect (OSTI)

    Denys, Alban; Prior, John; Bize, Pierre; Duran, Rafael; Baere, Thierry De; Halkic, Nermin; Demartines, Nicolas

    2012-10-15

    Portal vein embolization (PVE) has been developed to increase the size of the future remnant liver (FRL) left in place after major hepatectomy, thus reducing the risk of postoperative liver insufficiency. PVE consist in embolizing preoperatively portal branches of the segments that will be resected. Indication is based on preoperative measurements of the FRL by computed tomography and its ratio with either the theoretical liver volume or by direct measurement of the functional liver volume. After PVE, the volume and function of the FRL increases in 3 to 6 weeks, permitting extensive resections in patients otherwise contraindicated for liver resection. The PVE technique is variable from one center to another; however n-butyl-cyano-acrylate provides an interesting compromise between hypertrophy rate and procedure risk.

  10. Process for recovering actinide values

    DOE Patents [OSTI]

    Horwitz, E. Philip; Mason, George W.

    1980-01-01

    A process for rendering actinide values recoverable from sodium carbonate scrub waste solutions containing these and other values along with organic compounds resulting from the radiolytic and hydrolytic degradation of neutral organophosphorous extractants such as tri-n butyl phosphate (TBP) and dihexyl-N,N-diethyl carbamylmethylene phosphonate (DHDECAMP) which have been used in the reprocessing of irradiated nuclear reactor fuels. The scrub waste solution is preferably made acidic with mineral acid, to form a feed solution which is then contacted with a water-immiscible, highly polar organic extractant which selectively extracts the degradation products from the feed solution. The feed solution can then be processed to recover the actinides for storage or recycled back into the high-level waste process stream. The extractant is recycled after stripping the degradation products with a neutral sodium carbonate solution.

  11. 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.

  12. 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.

  13. 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.

  14. Disorder-to-order transitions induced by alkyne/azide click chemistry in diblock copolymer thin films.

    SciTech Connect (OSTI)

    Wei, X.; Gu, W.; Chen, W.; Shen, X.; Liu, F.; Strzalka, J. W.; Jiang, Z.; Russell, T. P.

    2012-01-01

    We investigated thin film morphologies of binary blends of alkyne-functionalized diblock copolymer poly(ethylene oxide)-block-poly(n-butyl methacrylate-random-propargyl methacrylate) (PEO-b-P(nBMA-r-PgMA)) and Rhodamine B azide, where the thermal alkyne/azide click reaction between the two components induced a disorder-to-order transition (DOT) of the copolymer. By controlling the composition of the neat copolymers and the mole ratio between the alkyne and azide groups, different microphase separated morphologies were achieved. At higher azide loading ratios, a perpendicular orientation of the microdomains was observed with wide accessible film thickness window. As less azide was incorporated, the microdomains have a stronger tendency to be parallel to the substrate, and the film thickness window for perpendicular orientation also became narrower.

  15. Modified cellulose synthase gene from Arabidopsis thaliana confers herbicide resistance to plants

    DOE Patents [OSTI]

    Somerville, Chris R. (Portola Valley, CA); Scheible, Wolf (Golm, DE)

    2007-07-10

    Cellulose synthase ("CS"), a key enzyme in the biosynthesis of cellulose in plants is inhibited by herbicides comprising thiazolidinones such as 5-tert-butyl-carbamoyloxy-3-(3-trifluromethyl)phenyl-4-thiazolidinone (TZ), isoxaben and 2,6-dichlorobenzonitrile (DCB). Two mutant genes encoding isoxaben and TZ-resistant cellulose synthase have been isolated from isoxaben and TZ-resistant Arabidopsis thaliana mutants. When compared with the gene coding for isoxaben or TZ-sensitive cellulose synthase, one of the resistant CS genes contains a point mutation, wherein glycine residue 998 is replaced by an aspartic acid. The other resistant mutation is due to a threonine to isoleucine change at amino acid residue 942. The mutant CS gene can be used to impart herbicide resistance to a plant; thereby permitting the utilization of the herbicide as a single application at a concentration which ensures the complete or substantially complete killing of weeds, while leaving the transgenic crop plant essentially undamaged.

  16. The importance of ion size and electrode curvature on electrical double layers in ionic liquids

    SciTech Connect (OSTI)

    Feng, G.; Qiao, R.; Huang, J; Dai, S.; Sumpter, B. G.; Meunier, V.

    2011-01-01

    Room-temperature ionic liquids (ILs) are an emerging class of electrolytes for supercapacitors. We investigate the effects of ion size and electrode curvature on the electrical double layers (EDLs) in two ILs 1-butyl-3-methylimidazolium chloride [BMIM][Cl] and 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF{sub 6}], using a combination of molecular dynamics (MD) and quantum density functional theory (DFT) simulations. The sizes of the counter-ion and co-ion affect the ion distribution and orientational structure of EDLs. The EDL capacitances near both planar and cylindrical electrodes were found to follow the order: [BMIM][Cl] (near the positive electrode) > [BMIM][PF{sub 6}] (near the positive electrode) ? [BMIM][Cl] (near the negative electrode) ? [BMIM][PF{sub 6}] (near the negative electrode). The EDL capacitance was also found to increase as the electrode curvature increases. These capacitance data can be fit to the Helmholtz model and the recently proposed exohedral electrical double-cylinder capacitor (xEDCC) model when the EDL thickness is properly parameterized, even though key features of the EDLs in ILs are not accounted for in these models. To remedy the shortcomings of existing models, we propose a Multiple Ion Layers with Overscreening (MILO) model for the EDLs in ILs that takes into account two critical features of such EDLs, i.e., alternating layering of counter-ions and co-ions and charge overscreening. The capacitance computed from the MILO model agrees well with the MD prediction. Although some input parameters of the MILO model must be obtained from MD simulations, the MILO model may provide a new framework for understanding many important aspects of EDLs in ILs (e.g., the variation of EDL capacitance with the electrode potential) that are difficult to interpret using classical EDL models and experiments.

  17. The Importance of Ion Size and Electrode Curvature on Electrical Double Layers in Ionic Liquids

    SciTech Connect (OSTI)

    Feng, Guang; Qiao, Rui; Huang, Jingsong; Dai, Sheng; Sumpter, Bobby G; Meunier, Vincent

    2010-01-01

    Room-temperature ionic liquids (ILs) are an emerging class of electrolytes for supercapacitors. We investigate the effects of ion size and electrode curvature on the electrical double layers (EDLs) in two ILs 1-butyl-3-methylimidazolium chloride [BMIM][Cl] and 1-butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF(6)], using a combination of molecular dynamics (MD) and quantum density functional theory (DFT) simulations. The sizes of the counter-ion and co-ion affect the ion distribution and orientational structure of EDLs. The EDL capacitances near both planar and cylindrical electrodes were found to follow the order: [BMIM][Cl] (near the positive electrode) > [BMIM][PF(6)] (near the positive electrode) {approx} [BMIM][Cl] (near the negative electrode) {approx} [BMIM][PF(6)] (near the negative electrode). The EDL capacitance was also found to increase as the electrode curvature increases. These capacitance data can be fit to the Helmholtz model and the recently proposed exohedral electrical double-cylinder capacitor (xEDCC) model when the EDL thickness is properly parameterized, even though key features of the EDLs in ILs are not accounted for in these models. To remedy the shortcomings of existing models, we propose a 'Multiple Ion Layers with Overscreening' (MILO) model for the EDLs in ILs that takes into account two critical features of such EDLs, i.e., alternating layering of counter-ions and co-ions and charge overscreening. The capacitance computed from the MILO model agrees well with the MD prediction. Although some input parameters of the MILO model must be obtained from MD simulations, the MILO model may provide a new framework for understanding many important aspects of EDLs in ILs (e.g., the variation of EDL capacitance with the electrode potential) that are difficult to interpret using classical EDL models and experiments.

  18. Economic contribution of lignins to ethanol production from biomass

    SciTech Connect (OSTI)

    Chum, H.L.; Parker, S.K.; Feinberg, D.A.; Wright, J.D.; Rice, P.A.; Sinclair, S.A.; Glasser, W.G.

    1985-05-01

    Lignin, one of the three major polymeric components of biomass (16% to 33% by weight in wood), has the highest specific heat content. Therefore, it can be burned for process fuel. Compared to coal, its fuel value is 2.2 cents/lb. This report investigates markets for lignin utilization of higher value. After lignin isolation from the process, purchase of replacement fuel (coal was analyzed), lignin sale for the manufacture of solid materials or higher value octane enhancers was evaluated. Polymeric applications evaluated were: surfactants, asphalt, carbon black, adhesives, and lignin plastics; agricultural applications were briefly reviewed. These lignins would generate coproduct credits of 25 cents to 150 cents/gallon of ethanol respectively for 7.5 cents to 60 cents/lb lignin value (isolation and eventual modification costs were taken into account). Overall markets for these polymeric applications were projected at 11 billion lb/year by the year 2000. These projections are intensities of demand and not actual shipments of lignins. In addition, this report investigates the possibility of converting lignins into mixtures of methyls aryl ethers and methyl substituted-aryl ethers which are high value octane enhancers, fully compatible with gasoline. The report intends to show that if fuel ethanol production in the billions of gallons scale occurs lignin markets would not be saturated. 10 refs., 14 figs., 36 tabs.

  19. Nano Structured Activated Carbon for Hydrogen Storge. Project Final Technical Report (May 2, 2005-Dec. 31, 2012)

    SciTech Connect (OSTI)

    Cabasso, Israel; Yuan, Youxin

    2013-02-27

    Development of a nanostructured synthetic carbons materials that have been synthesized by thermal-decomposition of aromatic rich polyether such as poly(ether ether ketone) (PEEK) is reported. These polymers based nanostructured carbons efficacious for gas adsorption and storage and have Brunauer-Emmett-Teller (BET) surface area of more than 3000 m2/g, and with average pore diameter of < 2nm. Surface-area, pore characteristics, and other critical variables for selecting porous materials of high gas adsorption capacities are presented. Analysis of the fragments evolved under various carbonization temperatures, and the correlation between the activation and carbonization temperatures provides a mechanistic perspective of the pore evolution during activation. Correlations between gas (N2 and H2) adsorption capacity and porous texture of the materials have been established. The materials possess excellent hydrogen storage properties, with hydrogen storage capacity up to 7.4 wt% (gravimetric) and ~ 45 g H2 L-1 (volumetric) at -196oC and 6.0 MPa.

  20. Arco to enter European PGE production with new Rotterdam plant

    SciTech Connect (OSTI)

    Young, I.

    1993-03-03

    Arco Chemical (Newtown Square, PA) will enter production of propylene glycol ethers (PGEs) in Europe by building a 70,000-m.t./year plant at its Rotterdam site. Arco's board has approved the project, with construction to begin this year and completion expected in mid-1995. This new plant supports the company's long-standing strategy to increase its downstream integration in value-added derivatives of propylene oxide,' says Jack Oppasser, president of Arco Chemical Europe (Maidenhead, U.K.). It allows the company to sustain its strong position in the growing European glycol ether market.' Arco's move represents a challenge to Dow Europe (Horgen, Switzerland), which dominates the European PGE market. Dow is Europe's biggest producer of PGEs, with its Dowanol brands commanding a share greater than 50% of the estimated 90,000-m.t./year methyl-based PGE market. This was recently boosted by completion of the expansion of its plant at Stade, Germany, from 60,000 m.t./year to 110,000 m.t./year. While Arco does not currently make PGEs in Europe, it is the second-largest supplier, with about 15,000 m.t.-20,000 m.t./year, via third-party manufacturing arrangements' with European producers, including BP Chemicals, and imports from its 90-million lbs/year plant at Bayport, TX. However, Arco refuses to comment on this because of antitrust aspects.'

  1. Ion Recognition Approach to Volume Reduction of Alkaline Tank Waste by Separation of Sodium Salts

    SciTech Connect (OSTI)

    Levitskaia, Tatiana G.; Lumetta, Gregg J.; Moyer, Bruce A.; Bonnesen, Peter V.

    2005-06-01

    The purpose of this research involving collaboration between Oak Ridge National Laboratory (ORNL) and Pacific Northwest National Laboratory (PNNL) is to explore new approaches to the separation of sodium hydroxide, sodium nitrate, and other sodium salts from high-level alkaline tank waste. The principal potential benefit is a major reduction in disposed waste volume, obviating the building of expensive new waste tanks and reducing the costs of low-activity waste immobilization. Principles of ion recognition are being researched toward discovery of liquid-liquid extraction systems that selectively separate sodium hydroxide and sodium nitrate from other waste components. The successful concept of pseudohydroxide extraction using fluorinated alcohols and phenols is being developed at ORNL and PNNL toward a greater understanding of the controlling equilibria, role of solvation, and of synergistic effects involving crown ethers. Synthesis efforts are being directed toward enhanced sodium binding by crown ethers, both neutral and proton-ionizable. Studies with real tank waste at PNNL will provide feedback toward solvent compositions that have promising properties.

  2. Ion Recognition Approach to Volume Reduction of Alkaline Tank Waste by Separation of Sodium Salts

    SciTech Connect (OSTI)

    Moyer, Bruce A.; Bonnesen, Peter V.; Custelcean, Radu; Delmau, Laetitia H.; Engle, Nancy L.; Kang, Hyun-Ah; Keever, Tamara J.; Marchand, Alan P.; Gadthula, Srinivas; Gore, Vinayak K.; Huang, Zilin; Sivappa, Rasapalli; Tirunahari, Pavan K.; Levitskaia, Tatiana G.; Lumetta, Gregg J.

    2005-09-26

    The purpose of this research involving collaboration between Oak Ridge National Laboratory (ORNL) and Pacific Northwest National Laboratory (PNNL) is to explore new approaches to the separation of sodium hydroxide, sodium nitrate, and other sodium salts from high-level alkaline tank waste. The principal potential benefit is a major reduction in disposed waste volume, obviating the building of expensive new waste tanks and reducing the costs of vitrification. Principles of ion recognition are being researched toward discovery of liquid-liquid extraction systems that selectively separate sodium hydroxide and sodium nitrate from other waste components. The successful concept of pseudo hydroxide extraction using fluorinated alcohols and phenols is being developed at ORNL and PNNL toward a greater understanding of the controlling equilibria, role of solvation, and of synergistic effects involving crown ethers. Synthesis efforts are being directed toward enhanced sodium binding by crown ethers, both neutral and proton-ionizable. Studies with real tank waste at PNNL will provide feedback toward solvent compositions that have promising properties.

  3. Combined Utilization of Cation Exchanger and Neutral Receptor to Volume Reduction of Alkaline Tank Waste by Separation of Sodium Salts

    SciTech Connect (OSTI)

    Levitskaia, Tatiana G.; Lumetta, Gregg J.; Moyer, Bruce A.

    2004-03-29

    In this report, novel approaches to the selective liquid-liquid extraction separation of sodium hydroxide and sodium nitrate from high-level alkaline tank waste will be discussed. Sodium hydroxide can be successfully separated from alkaline tank-waste supernatants by weakly acidic lipophilic hydroxy compounds via a cation-exchange mechanism referred to as pseudo hydroxide extraction. In a multi-cycle process, as sodium hydroxide in the aqueous phase becomes depleted, it is helpful to have a neutral sodium receptor in the extraction system to exploit the high nitrate concentration in the waste solution to promote sodium removal by an ion-pair extraction process. Simultaneous utilization of an ionizable organic hydroxy compound and a neutral extractant (crown ether) in an organic phase results in the synergistic enhancement of ion exchange and improved separation selectivity due to the receptor's strong and selective sodium binding. Moreover, combination of the hydroxy compound and the crown ether provides for mutually increased solubility, even in a non-polar organic solvent. Accordingly, application of Isopar{reg_sign} L, a kerosene-like alkane solvent, becomes feasible. This investigation involves examination of such dual-mechanism extraction phases for sodium extraction from simulated and actual salt cake waste solutions. Sodium salts can be regenerated upon the contact of the loaded extraction phases with water. Finally, conditions of potential extraction/strip cycling will be discussed.

  4. Greenhouse gases, Regulated Emissions, and Energy use in Transportation fuel-cyl

    Energy Science and Technology Software Center (OSTI)

    2000-06-20

    The GREET model estimates the full fuel-cycle energy use and emissions associated with various transportation fuels and advanced vehile technologies applied to motor vehicles. GREET 1.5 includes the following cycles: petroleum to conventional gasoline, reformulated gasoline, conventional diesel, reformulated diesel, liquefied petroleum gas, and electricity via residual oil; natural gas to compressed natural gas, liquefied natural gas, liquefied petroleum gas, methanol, Fischer-Tropsch diesel, dimethyl ether, hydrogen, and electricity; coal to electricity; corn, woody biomass, andmore » herbaceous biomass to ethanol; soybeans to biodiesel; flared gas to methanol, Fischer-Tropsch diesel, and dimethyl ether; and landfill gases to methanol. For a given fuel/transportation technology combination, GREET 1.5 calculates (1) the fuel-cycle consumption of total energy (all energy sources), fossil fuels (petroleum, natural gas, and coal), and petroleum; (2) the fuel-cycle emissions of GHGs -- primarily carbon dioxide (CO2), methane (CH4), and nitrous oxide (N20); and (3) the fuel-cycle emissions of five criteria pollutants: volatile organic compounds (VOCs), carbon monoxide (C0), nitrogen oxides (N0x), sulfur oxides (S0x), and particulate matter with a diameter measuring 10 micrometers or less (PM10). The model is designed to readily allow researchers to input their own assumptions and generate fuel-cycle energy and emission results for specified fuel/technology combinations.« less

  5. Molecular-Level Insights into the Reactivity of Siloxane-Based Electrolytes at a Lithium-Metal Anode

    SciTech Connect (OSTI)

    Assary, Rajeev S.; Lu, Jun; Luo, Xiangyi; Zhang, Xiaoyi; Ren, Yang; Wu, Huiming; Albishri, Hassan M.; El-Hady, D. A.; Al-Bogami, A. S.; Curtiss, Larry A.; Amine, Khalil

    2014-07-21

    A molecular-level understanding of the reactions that occur at the lithium-metal anode/electrolyte interphase is essential to improve the performance of LiO2 batteries. Experimental and computational techniques are applied to explore the reactivity of tri(ethylene glycol)-substituted trimethylsilane (1NM3), a siloxane-based ether electrolyte, at the lithium-metal anode. In situ/ex situ X-ray diffraction and Fourier-transform infrared spectroscopy studies provide evidence of the formation of lithium hydroxide and lithium carbonates at the anode upon gradual degradation of the metallic lithium anode and the solvent molecules in the presence of oxygen. Density functional calculations performed to obtain a mechanistic understanding of the reductive decomposition of 1NM3 indicate that the decomposition does not require any apparent barrier to produce lithium hydroxide and lithium carbonates when the reduced 1NM3 solvent molecules interact with the oxygen crossing over from the cathode. This study indicates that degradation may be more significant in the case of the 1NM3 solvent, compared to linear ethers such as tetraglyme or dioxalone, because of its relatively high electron affinity. Also, both protection of the lithium metal and prevention of oxygen crossover to the anode are essential for minimizing electrolyte and anode decomposition.

  6. Methods for degrading lignocellulosic materials

    DOE Patents [OSTI]

    Vlasenko, Elena (Davis, CA); Cherry, Joel (Davis, CA); Xu, Feng (Davis, CA)

    2008-04-08

    The present invention relates to methods for degrading a lignocellulosic material, comprising: treating the lignocellulosic material with an effective amount of one or more cellulolytic enzymes in the presence of at least one surfactant selected from the group consisting of a secondary alcohol ethoxylate, fatty alcohol ethoxylate, nonylphenol ethoxylate, tridecyl ethoxylate, and polyoxyethylene ether, wherein the presence of the surfactant increases the degradation of lignocellulosic material compared to the absence of the surfactant. The present invention also relates to methods for producing an organic substance, comprising: (a) saccharifying a lignocellulosic material with an effective amount of one or more cellulolytic enzymes in the presence of at least one surfactant selected from the group consisting of a secondary alcohol ethoxylate, fatty alcohol ethoxylate, nonylphenol ethoxylate, tridecyl ethoxylate, and polyoxyethylene ether, wherein the presence of the surfactant increases the degradation of lignocellulosic material compared to the absence of the surfactant; (b) fermenting the saccharified lignocellulosic material of step (a) with one or more fermentating microoganisms; and (c) recovering the organic substance from the fermentation.

  7. Methods for degrading lignocellulosic materials

    DOE Patents [OSTI]

    Vlasenko, Elena (Davis, CA); Cherry, Joel (Davis, CA); Xu, Feng (Davis, CA)

    2011-05-17

    The present invention relates to methods for degrading a lignocellulosic material, comprising: treating the lignocellulosic material with an effective amount of one or more cellulolytic enzymes in the presence of at least one surfactant selected from the group consisting of a secondary alcohol ethoxylate, fatty alcohol ethoxylate, nonylphenol ethoxylate, tridecyl ethoxylate, and polyoxyethylene ether, wherein the presence of the surfactant increases the degradation of lignocellulosic material compared to the absence of the surfactant. The present invention also relates to methods for producing an organic substance, comprising: (a) saccharifying a lignocellulosic material with an effective amount of one or more cellulolytic enzymes in the presence of at least one surfactant selected from the group consisting of a secondary alcohol ethoxylate, fatty alcohol ethoxylate, nonylphenol ethoxylate, tridecyl ethoxylate, and polyoxyethylene ether, wherein the presence of the surfactant increases the degradation of lignocellulosic material compared to the absence of the surfactant; (b) fermenting the saccharified lignocellulosic material of step (a) with one or more fermenting microorganisms; and (c) recovering the organic substance from the fermentation.

  8. Selection for increased desiccation resistance in Drosophila melanogaster: Additive genetic control and correlated responses for other stresses

    SciTech Connect (OSTI)

    Hoffmann, A.A.; Parsons, P.A. )

    1989-08-01

    Previously we found that Drosophila melanogaster lines selected for increased desiccation resistance have lowered metabolic rate and behavioral activity levels, and show correlated responses for resistance to starvation and a toxic ethanol level. These results were consistent with a prediction that increased resistance to many environmental stresses may be genetically correlated because of a reduction in metabolic energy expenditure. Here we present experiments on the genetic basis of the selection response and extend the study of correlated responses to other stresses. The response to selection was not sex-specific and involved X-linked and autosomal genes acting additively. Activity differences contributed little to differences in desiccation resistance between selected and control lines. Selected lines had lower metabolic rates than controls in darkness when activity was inhibited. Adults from selected lines showed increased resistance to a heat shock, {sup 60}Co-gamma-radiation, and acute ethanol and acetic acid stress. The desiccation, ethanol and starvation resistance of isofemale lines set up from the F2s of a cross between one of the selected and one of the control lines were correlated. Selected and control lines did not differ in ether-extractable lipid content or in resistance to acetone, ether or a cold shock.

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

    SciTech Connect (OSTI)

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

    1981-01-01

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

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

    DOE Patents [OSTI]

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

    2001-01-09

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

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

    SciTech Connect (OSTI)

    Bataineh, Hajem; Pestovsky, Oleg; Bakac, Andreja

    2015-02-11

    Oxidation of alcohols, ethers, and sulfoxides by ozone in acetonitrile is catalyzed by submillimolar concentrations of Fe(CH3CN)62+. The catalyst provides both rate acceleration and greater selectivity toward the less oxidized products. For example, Fe(CH3CN)62+-catalyzed oxidation of benzyl alcohol yields benzaldehyde almost exclusively (>95%), whereas the uncatalyzed reaction generates a 1:1 mixture of benzaldehyde and benzoic acid. Similarly, aliphatic alcohols are oxidized to aldehydes/ketones, cyclobutanol to cyclobutanone, and diethyl ether to a 1:1 mixture of ethanol and acetaldehyde. The kinetics of oxidation of alcohols and diethyl ether are first-order in [Fe(CH3CN)62+] and [O3] and independent of [substrate] at concentrations greater than ~5 mM. In this regime, the rate constant for all of the alcohols is approximately the same, kcat = (8 1) 104 M1 s1, and that for (C2H5)2O is (5 0.5) 104 M1 s1. In the absence of substrate, Fe(CH3CN)62+ reacts with O3 with kFe = (9.3 0.3) 104 M1 s1. The similarity between the rate constants kFe and kcat strongly argues for Fe(CH3CN)62+/O3 reaction as rate-determining in catalytic oxidation. The active oxidant produced in Fe(CH3CN)62+/O3 reaction is suggested to be an Fe(IV) species in analogy with a related intermediate in aqueous solutions. As a result, this assignment is supported by the similarity in kinetic isotope effects and relative reactivities of the two species toward substrates.

  12. Petroleum Market Model of the National Energy Modeling System. Part 1

    SciTech Connect (OSTI)

    1997-12-18

    The purpose of this report is to define the objectives of the Petroleum Market Model (PMM), describe its basic approach, and provide detail on how it works. This report is intended as a reference document for model analysts, users, and the public. The PMM models petroleum refining activities, the marketing of petroleum products to consumption regions, the production of natural gas liquids in gas processing plants, and domestic methanol production. The PMM projects petroleum product prices and sources of supply for meeting petroleum product demand. The sources of supply include crude oil, both domestic and imported; other inputs including alcohols and ethers; natural gas plant liquids production; petroleum product imports; and refinery processing gain. In addition, the PMM estimates domestic refinery capacity expansion and fuel consumption. Product prices are estimated at the Census division level and much of the refining activity information is at the Petroleum Administration for Defense (PAD) District level.

  13. ARTI Refrigerant Database

    SciTech Connect (OSTI)

    Calm, J.M.

    1992-11-09

    The database provides bibliographic citations and abstracts for publications that may be useful in research and design of air- conditioning and refrigeration equipment. The database identifies sources of specific information on R-32, R-123, R-124, R-125, R-134, R-134a, R-141b, R-142b, R-143a, R-152a, R-245ca, R-290 (propane), R- 717 (ammonia), ethers, and others as well as azeotropic and zeotropic and zeotropic blends of these fluids. It addresses lubricants including alkylbenzene, polyalkylene glycol, ester, and other synthetics as well as mineral oils. It also references documents on compatibility of refrigerants and lubricants with metals, plastics, elastomers, motor insulation, and other materials used in refrigerant circuits. A computerized version is available that includes retrieval software.

  14. Gamma Ray Radiolysis of the FPEX Solvent

    SciTech Connect (OSTI)

    B. J. Mincher; S. P. Mezyk; D. R. Peterman

    2006-09-01

    Slide presentation. FPEX contains a calixarene for Cs extraction, a crown ether for Sr extraction, Cs7SB modifier, and TOA to aid in stripping, in Isopar L diluent. The radiation stability FPEX must be evaluated prior to process use. Radiolytic degradation of species in solution are due to reaction with the direct radiolysis products of the diluent. In Isopar L, the reactive species produced include e-, H and alkane radicals, resulting in a reducing environment. However, in nitric acid, oxidizing hydroxyl (OH) and nitro (NO2) radicals dominate system chemistry. Thus, the nature of diluent and the presence of radical scavengers affect the results of irradiation. We report the preliminary results of a new program to investigate the radiolysis of FPEX using the 60Co irradiation of FPEX neat solvent, acid pre-equilibrated solvent and mixed aerated phases. The Cs and Sr distribution ratios were used as metrics.

  15. 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)

  16. Interaction of water with epoxy.

    SciTech Connect (OSTI)

    Powers, Dana Auburn

    2009-07-01

    The chemistries of reactants, plasticizers, solvents and additives in an epoxy paint are discussed. Polyamide additives may play an important role in the absorption of molecular iodine by epoxy paints. It is recommended that the unsaturation of the polyamide additive in the epoxy cure be determined. Experimental studies of water absorption by epoxy resins are discussed. These studies show that absorption can disrupt hydrogen bonds among segments of the polymers and cause swelling of the polymer. The water absorption increases the diffusion coefficient of water within the polymer. Permanent damage to the polymer can result if water causes hydrolysis of ether linkages. Water desorption studies are recommended to ascertain how water absorption affects epoxy paint.

  17. Mesoporous silica film from a solution containing a surfactant and methods of making same

    DOE Patents [OSTI]

    Liu, Jun (West Richland, WA) [West Richland, WA; Domansky, Karel (Cambridge, MA) [Cambridge, MA; Li, Xiaohong (Richland, WA) [Richland, WA; Fryxell, Glen E. (Kennewick, WA) [Kennewick, WA; Baskaran, Suresh (Kennewick, WA) [Kennewick, WA; Kohler, Nathan J. (Richland, WA) [Richland, WA; Thevuthasan, Suntharampillai (Kennewick, WA) [Kennewick, WA; Coyle, Christopher A. (Richland, WA) [Richland, WA; Birnbaum, Jerome C. (Richland, WA) [Richland, WA

    2001-12-11

    The present invention is a mesoporous silica film having a low dielectric constant and method of making having the steps of combining a surfactant in a silica precursor solution, spin-coating a film from this solution mixture, forming a partially hydroxylated mesoporous film, and dehydroxylating the hydroxylated film to obtain the mesoporous film. It is advantageous that the small polyoxyethylene ether surfactants used in spin-coated films as described in the present invention will result in fine pores smaller on average than about 20 nm. The resulting mesoporous film has a dielectric constant less than 3, which is stable in moist air with a specific humidity. The present invention provides a method for superior control of film thickness and thickness uniformity over a coated wafer, and films with low dielectric constant.

  18. A characterization and evaluation of coal liquefaction process streams. Quarterly report, January 1--March 31, 1997

    SciTech Connect (OSTI)

    Robbins, G.A.; Brandes, S.D.; Heunisch, G.W.; Winschel, R.A.

    1998-08-01

    Described in this report are the following activities: CONSOL characterized process stream samples from HTI Run ALC-2, in which Black Thunder Mine coal was liquefied using four combinations of dispersed catalyst precursors. Oil assays were completed on the HTI Run PB-05 product blend. Fractional distillation of the net product oil of HTI Run POC-1 was completed. CONSOL completed an evaluation of the potential for producing alkylphenyl ethers from coal liquefaction phenols. At the request of DOE, various coal liquid samples and relevant characterization data were supplied to the University of West Virginia and the Federal Energy Technology Center. The University of Delaware is conducting resid reactivity tests and is completing the resid reaction computer model. The University of Delaware was instructed on the form in which the computer model is to be delivered to CONSOL.

  19. A survey of Opportunities for Microbial Conversion of Biomass to Hydrocarbon Compatible Fuels

    SciTech Connect (OSTI)

    Jovanovic, Iva; Jones, Susanne B.; Santosa, Daniel M.; Dai, Ziyu; Ramasamy, Karthikeyan K.; Zhu, Yunhua

    2010-09-01

    Biomass is uniquely able to supply renewable and sustainable liquid transportation fuels. In the near term, the Biomass program has a 2012 goal of cost competitive cellulosic ethanol. However, beyond 2012, there will be an increasing need to provide liquid transportation fuels that are more compatible with the existing infrastructure and can supply fuel into all transportation sectors, including aviation and heavy road transport. Microbial organisms are capable of producing a wide variety of fuel and fuel precursors such as higher alcohols, ethers, esters, fatty acids, alkenes and alkanes. This report surveys liquid fuels and fuel precurors that can be produced from microbial processes, but are not yet ready for commercialization using cellulosic feedstocks. Organisms, current research and commercial activities, and economics are addressed. Significant improvements to yields and process intensification are needed to make these routes economic. Specifically, high productivity, titer and efficient conversion are the key factors for success.

  20. Ion Recognition Approach to Volume Reduction of Alkaline Tank Waste by Separation of Sodium Salts

    SciTech Connect (OSTI)

    Levitskaia, Tatiana G.; Lumetta, Gregg J.; Moyer, Bruce A.; Bonnesen, Peter V.

    2006-06-01

    The purpose of this research involving collaboration between Oak Ridge National Laboratory (ORNL) and Pacific Northwest National Laboratory (PNNL) is to explore new approaches to the separation of sodium hydroxide, sodium nitrate, and other sodium salts from high-level alkaline tank waste. The principal potential benefit is a major reduction in disposed waste volume, obviating the building of expensive new waste tanks and reducing the costs of low-activity waste immobilization. Principles of ion recognition are being researched toward discovery of liquid extraction systems that selectively separate sodium hydroxide and sodium nitrate from other waste components. The successful concept of pseudohydroxide extraction using fluorinated alcohols and phenols is being developed at ORNL and PNNL toward a greater understanding of the controlling equilibria, role of solvation, and of synergistic effects involving crown ethers. Studies at PNNL are directed toward new solvent formulation for the practical sodium pseudohydroxide extraction systems.

  1. Next Generation Extractants for Cesium Separation from High-Level Waste: From Fundamental Concepts to Site Implementation

    SciTech Connect (OSTI)

    Moyer, Bruce A.; Bartsch, Richard A.

    2003-06-01

    Calix[4]arenebiscrown-6 molecules are currently the selected technology for removal of radioactive cesium-137 from DOE nuclear wastes. By attachment of an acidic function to such molecules, the efficiency with which cesium ion can be extracted from an aqueous solution into an organic diluent is markedly increased since the requirement for concomitant extraction of an aqueous phase anion is avoided. Thus, cesium ion extraction by proton-ionizable calix[4]arenebiscrown-6 molecules may be the ''second-generation'' technology for removal of cesium-137 from DOE nuclear wastes. During Year 1 of this EMSP project, we have established synthetic routes to new, lipophilic, proton-ionizable calix[4]arenebiscrown-6 molecules to be evaluated for solvent extraction of cesium ion at Oak Ridge National Laboratory. Analogous calix[4]arenecrown-6 compounds are also being prepared to determine if even higher cesium ion selectivities can be obtained with extractants having a single crown ether unit.

  2. Next generation extractants for separation of cesium from high-level waste

    SciTech Connect (OSTI)

    Bartsch, R.A.; Zhou, H.; Delmau, L.H.; Moyer, B.A.

    2008-07-01

    Using calix[4]arene as a scaffold, lipophilic, proton-ionizable ligands for cesium ion extraction have been synthesized. In the 1,3-alternate conformation, lipophilic octyl groups are attached to distal oxygens on one side of the calix[4]arene molecule, and an alkylated benzo-crown-6 unit is connected to distal oxygens on the other side. One phenyl octyl ether unit bears an acidic group in the para-position which orients it directly over the polyether ring. Solvent extractions of trace cesium ion from aqueous solutions into toluene have been performed. The efficiency of cesium ion extraction as a function of the aqueous phase pH and the identity of the acidic group have been assessed. Promising results are obtained for this new series of cesium ion extractants. (authors)

  3. A pilot test of partitioning for the simulated highly saline high level waste

    SciTech Connect (OSTI)

    Chen, Jing; Wang, Jianchen; Jing, Shan

    2007-07-01

    It is a problem how to treat the highly saline high level waste (HLW). A partitioning process for HLW was developed at INET. The partitioning process includes the removal of actinides by TRPO extraction, the removal of Sr by crown ether extraction, and the removal of Cs by ion exchange. A 72-hour test was carried out in a pilot facility using the simulated HLW. Nd and Zr were used to simulate Am and Pu, respectively. The decontamination factors are >3000, >500, >1000, {approx}150 and {approx}94 for U, Nd, Zr, Sr and Cs, respectively. The results meet the requirement to change the highly saline HLW into a non-{alpha} and intermediate level waste. (authors)

  4. Studies on lanthanoid complexes of open chain multidentate ligands. VIII. Preparation and structural characterization of the undecacoordinate complex of neodymium nitrate with N,N{prime}-bis(4-methoxyphenyl)tetraglycollic diamide

    SciTech Connect (OSTI)

    Zhijian Liang; Xinmin Gan; Ning Tang; Minyu Tan; Kaibei Yu; Ganzu Tan

    1993-12-31

    The title compound [Nd(L)(NO{sub 3}){sub 3}]2CH{sub 3}CN was formed by reaction of neodymium nitrate with N,N{prime}-bis(4-methoxyphenyl)tetraglycollic diamide (L). The complex crystallizes in the monoclinic system, space group Cc with Z = 4, a = 21.305(6), b = 11.470(4), c = 14.436(3) {angstrom}, {beta} = 97.41(2), V = 3498(2) {angstrom}{sup 3}. The pentadentate organic ligand wraps around the neodymium ion which is also bonded to three bidentate nitrate groups, achieving uncommon undecacoordination with the following mean bond lengths: Nd-O(etheric), 2.703; Nd-O(carbonyl), 2.518; Nd-O(nitrate), 2.546 {angstrom}. 18 refs., 2 figs., 3 tabs.

  5. Phosphazene additives

    DOE Patents [OSTI]

    Harrup, Mason K; Rollins, Harry W

    2013-11-26

    An additive comprising a phosphazene compound that has at least two reactive functional groups and at least one capping functional group bonded to phosphorus atoms of the phosphazene compound. One of the at least two reactive functional groups is configured to react with cellulose and the other of the at least two reactive functional groups is configured to react with a resin, such as an amine resin of a polycarboxylic acid resin. The at least one capping functional group is selected from the group consisting of a short chain ether group, an alkoxy group, or an aryloxy group. Also disclosed are an additive-resin admixture, a method of treating a wood product, and a wood product.

  6. Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite

    DOE Patents [OSTI]

    Tierney, John W. (Pittsburgh, PA); Wender, Irving (Pittsburgh, PA); Palekar, Vishwesh M. (Pittsburgh, PA)

    1995-01-01

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  7. Kinetic, Spectroscopic, and Theoretical Assessment of Associative and Dissociative Methanol Dehydration Routes in Zeolites

    SciTech Connect (OSTI)

    Jones, Andrew J.; Iglesia, Enrique

    2014-11-03

    Mechanistic interpretations of rates and in situ IR spectra combined with density functionals that account for van der Waals interactions of intermediates and transition states within confining voids show that associative routes mediate the formation of dimethyl ether from methanol on zeolitic acids at the temperatures and pressures of practical dehydration catalysis. Methoxy-mediated dissociative routes become prevalent at higher temperatures and lower pressures, because they involve smaller transition states with higher enthalpy, but also higher entropy, than those in associative routes. These enthalpyentropy trade-offs merely reflect the intervening role of temperature in activation free energies and the prevalence of more complex transition states at low temperatures and high pressures. This work provides a foundation for further inquiry into the contributions of H-bonded methanol and methoxy species in homologation and hydrocarbon synthesis reactions from methanol.

  8. Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite for methanol synthesis

    DOE Patents [OSTI]

    Tierney, John W. (Pittsburgh, PA); Wender, Irving (Pittsburgh, PA); Palekar, Vishwesh M. (Pittsburgh, PA)

    1993-01-01

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100.degree.-160.degree. C. and the pressure range of 40-65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H.sub.2 /CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  9. Characterization of structures and surface states of the nanodiamond synthesized by detonation

    SciTech Connect (OSTI)

    Zou, Q.; Li, Y.G.; Zou, L.H.; Wang, M.Z.

    2009-11-15

    Nanodiamond is a relatively new nanomaterial with broad prospects for application. In this paper, a variety of methods were used to analyze comprehensively the structures and the surface states of the nanodiamond synthesized by detonation, for example, X-ray diffraction (XRD) spectroscopy, energy diffraction spectroscopy (EDS), high resolution transmission electron microscopy (HRTEM), Fourier transform infrared spectroscopy (FTIR), Raman spectroscopy (Raman) and differential scanning calorimeter (DSC). The results show that, the nanodiamond particles are spherical or elliptical in shape. The average grain size is approximately 5 nm. The surfaces of the nanodiamond contain hydroxy, carbonyl, carboxyl, ether-based resin, and other functional groups. The initial oxidation temperature of the nanodiamond in the air is about 550 deg. C, which is lower than that of the bulk diamond.

  10. Glycoconjugates and methods

    DOE Patents [OSTI]

    Bertozzi, Carolyn C.; Yarema, Kevin J.; Mahal; Lara K.

    2008-04-01

    Methods for making the functionalized glycoconjugates include (a) contacting a cell with a first monosaccharide, and (b) incubating the cell under conditions whereby the cell (i) internalizes the first monosaccharide, (ii) biochemically processes the first monosaccharide into a second saccharide, (iii) conjugates the saccharide to a carrier to form a glycoconjugate, and (iv) extracellularly expresses the glycoconjugate to form an extracellular glycoconjugate comprising a selectively reactive functional group. Methods for forming products at a cell further comprise contacting the functional group of the extracellularly expressed glycoconjugate with an agent which selectively reacts with the functional group to form a product. Subject compositions include cyto-compatible monosaccharides comprising a nitrogen or ether linked functional group selectively reactive at a cell surface and compositions and cells comprising such saccharides.

  11. Glycoconjugates and methods

    DOE Patents [OSTI]

    Bertozzi, Carolyn; Yarema, Kevin J.; Mahal, Lara K.

    2000-01-01

    Methods for making the functionalized glycoconjugates include (a) contacting a cell with a first monosaccharide, and (b) incubating the cell under conditions whereby the cell (i) internalizes the first monosaccharide, (ii) biochemically processes the first monosaccharide into a second saccharide, (iii) conjugates the saccharide to a carrier to form a glycoconjugate, and (iv) extracellularly expresses the glycoconjugate to form an extracellular glycoconjugate comprising a selectively reactive functional group. Methods for forming products at a cell further comprise contacting the functional group of the extracellularly expressed glycoconjugate with an agent which selectively reacts with the functional group to form a product. Subject compositions include cyto-compatible monosaccharides comprising a nitrogen or ether linked functional group selectively reactive at a cell surface and compositions and cells comprising such saccharides.

  12. Glycoconjugates And Methods

    DOE Patents [OSTI]

    Bertozzi, Carolyn; Yarema, Kevin J.; Mahal, Lara K.

    2005-08-30

    Methods for making the functionalized glycoconjugates include (a) contacting a cell with a first monosaccharide, and (b) incubating the cell under conditions whereby the cell (i) internalizes the first monosaccharide, (ii) biochemically processes the first monosaccharide into a second saccharide, (iii) conjugates the saccharide to a carrier to form a glycoconjugate, and (iv) extracellularly expresses the glycoconjugate to form an extracellular glycoconjugate comprising a selectively reactive functional group. Methods for forming products at a cell further comprise contacting the functional group of the extracellularly expressed glycoconjugate with an agent which selectively reacts with the functional group to form a product. Subject compositions include cyto-compatible monosaccharides comprising a nitrogen or ether linked functional group selectively reactive at a cell surface and compositions and cells comprising such saccharides.

  13. Glycoconjugates and methods

    DOE Patents [OSTI]

    Bertozzi, Carolyn; Yarema, Kevin J.; Mahal, Lara K.

    2002-10-01

    Methods for making the functionalized glycoconjugates include (a) contacting a cell with a first monosaccharide, and (b) incubating the cell under conditions whereby the cell (i) internalizes the first monosaccharide, (ii) biochemically processes the first monosaccharide into a second saccharide, (iii) conjugates the saccharide to a carrier to form a glycoconjugate, and (iv) extracellularly expresses the glycoconjugate to form an extracellular glycoconjugate comprising a selectively reactive functional group. Methods for forming products at a cell further comprise contacting the functional group of the extracellularly expressed glycoconjugate with an agent which selectively reacts with the functional group to form a product. Subject compositions include cyto-compatible monosaccharides comprising a nitrogen or ether linked functional group selectively reactive at a cell surface and compositions and cells comprising such saccharides.

  14. Heterogeneous catalyst for the production of acetic anhydride from methyl acetate

    DOE Patents [OSTI]

    Ramprasad, D.; Waller, F.J.

    1999-04-06

    This invention relates to a process for producing acetic anhydride by the reaction of methyl acetate, carbon monoxide, and hydrogen at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that contains an insoluble polymer having pendant quaternized phosphine groups, some of which phosphine groups are ionically bonded to anionic Group VIII metal complexes, the remainder of the phosphine groups being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for consecutive runs without loss in activity. Bifunctional catalysts for use in carbonylating dimethyl ether are also provided.

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

    DOE Patents [OSTI]

    Guon, Jerold (Canoga Park, CA)

    1981-01-01

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

  16. Trifluorostyrene containing compounds, and their use in polymer electrolyte membranes

    DOE Patents [OSTI]

    Choudhury, Biswajit (Kingston, CA); Roelofs, Mark Gerrit (Hockessin, DE); Yang; Zhen-Yu (Hockessin, DE)

    2009-07-21

    A fluorinated ion exchange polymer is prepared by grafting a monomer onto a base polymer, wherein the grafting monomer is selected from the group consisting of structure 1a, 1b and mixture thereof; ##STR00001## wherein Y is selected from the group consisting of --R.sub.FSO.sub.2F, --R.sub.FSO.sub.3M, --R.sub.SO.sub.2NH.sub.2 and --R.sub.FSO.sub.2N(M)SO.sub.2R.sup.2.sub.F, where in M is hydrogen, an alkali cation or ammonium; and R.sub.F and R.sup.2.sub.F are perfluorinated or partially fluorinated, and may optionally include ether oxygens; and n is between 1 and 2 for 1a, or n is between 1 and 3 for 1b. These ion exchange polymers are useful is preparing catalyst coated membranes and membrane electrode assemblies for fuel cells.

  17. Methanol synthesis using a catalyst combination of alkali or alkaline earth salts and reduced copper chromite

    DOE Patents [OSTI]

    Tierney, J.W.; Wender, I.; Palekar, V.M.

    1995-01-24

    The present invention relates to a novel route for the synthesis of methanol, and more specifically to the production of methanol by contacting synthesis gas under relatively mild conditions in a slurry phase with a catalyst combination comprising reduced copper chromite and basic alkali salts or alkaline earth salts. The present invention allows the synthesis of methanol to occur in the temperature range of approximately 100--160 C and the pressure range of 40--65 atm. The process produces methanol with up to 90% syngas conversion per pass and up to 95% methanol selectivity. The only major by-product is a small amount of easily separated methyl formate. Very small amounts of water, carbon dioxide and dimethyl ether are also produced. The present catalyst combination also is capable of tolerating fluctuations in the H[sub 2]/CO ratio without major deleterious effect on the reaction rate. Furthermore, carbon dioxide and water are also tolerated without substantial catalyst deactivation.

  18. Method for absorbing hydrogen using an oxidation resisant organic hydrogen getter

    DOE Patents [OSTI]

    Shepodd, Timothy J. (Livermore, CA); Buffleben, George M. (Tracy, CA)

    2009-02-03

    A composition for removing hydrogen from an atmosphere, comprising a mixture of a polyphenyl ether and a hydrogenation catalyst, preferably a precious metal catalyst, and most preferably platinum, is disclosed. This composition is stable in the presence of oxygen, will not polymerize or degrade upon exposure to temperatures in excess of 200.degree. C., or prolonged exposure to temperatures in the range of 100-300.degree. C. Moreover, these novel hydrogen getter materials can be used to efficiently remove hydrogen from mixtures of hydrogen/inert gas (e.g., He, Ar, N.sub.2), hydrogen/ammonia atmospheres, such as may be encountered in heat exchangers, and hydrogen/carbon dioxide atmospheres. Water vapor and common atmospheric gases have no adverse effect on the ability of these getter materials to absorb hydrogen.

  19. Oxidation resistant organic hydrogen getters

    DOE Patents [OSTI]

    Shepodd, Timothy J. (Livermore, CA); Buffleben, George M. (Tracy, CA)

    2008-09-09

    A composition for removing hydrogen from an atmosphere, comprising a mixture of a polyphenyl ether and a hydrogenation catalyst, preferably a precious metal catalyst, and most preferably Pt. This composition is stable in the presence of oxygen, will not polymerize or degrade upon exposure to temperatures in excess of 200.degree. C., or prolonged exposure to temperatures in the range of 100-300.degree. C. Moreover, these novel hydrogen getter materials can be used to efficiently removing hydrogen from mixtures of hydrogen/inert gas (e.g., He, Ar, N.sub.2), hydrogen/ammonia atmospheres, such as may be encountered in heat exchangers, and hydrogen/carbon dioxide atmospheres. Water vapor and common atmospheric gases have no adverse effect on the ability of these getter materials to absorb hydrogen.

  20. ARTI Refrigerant Database

    SciTech Connect (OSTI)

    Calm, J.M.

    1992-04-30

    The Refrigerant Database consolidates and facilitates access to information to assist industry in developing equipment using alternative refrigerants. The underlying purpose is to accelerate phase out of chemical compounds of environmental concern. The database provides bibliographic citations and abstracts for publications that may be useful in research and design of air- conditioning and refrigeration equipment. The complete documents are not included, though some may be added at a later date. The database identifies sources of specific information on R-32, R-123, R-124, R- 125, R-134a, R-141b, R142b, R-143a, R-152a, R-290 (propane), R-717 (ammonia), ethers, and others as well as azeotropic and zeotropic blends of these fluids. It addresses polyalkylene glycol (PAG), ester, and other lubricants. It also references documents addressing compatibility of refrigerants and lubricants with metals, plastics, elastomers, motor insulation, and other materials used in refrigerant circuits.

  1. Methods for chemical recovery of non-carrier-added radioactive tin from irradiated intermetallic Ti-Sb targets

    DOE Patents [OSTI]

    Lapshina, Elena V.; Zhuikov, Boris L.; Srivastava, Suresh C.; Ermolaev, Stanislav V.; Togaeva, Natalia R.

    2012-01-17

    The invention provides a method of chemical recovery of no-carrier-added radioactive tin (NCA radiotin) from intermetallide TiSb irradiated with accelerated charged particles. An irradiated sample of TiSb can be dissolved in acidic solutions. Antimony can be removed from the solution by extraction with dibutyl ether. Titanium in the form of peroxide can be separated from tin using chromatography on strong anion-exchange resin. In another embodiment NCA radiotin can be separated from iodide solution containing titanium by extraction with benzene, toluene or chloroform. NCA radiotin can be finally purified from the remaining antimony and other impurities using chromatography on silica gel. NCA tin-117m can be obtained from this process. NCA tin-117m can be used for labeling organic compounds and biological objects to be applied in medicine for imaging and therapy of various diseases.

  2. Pentan isomers compound flame front structure

    SciTech Connect (OSTI)

    Mansurov, Z.A.; Mironenko, A.W.; Bodikov, D.U.; Rachmetkaliev, K.N.

    1995-08-13

    The fuels (hexane, pentane, diethyl ether) and conditions investigated in this study are relevant to engine knock in spark- ignition engines. A review is provided of the field of low temperature hydrocarbon oxidation. Studies were made of radical and stable intermediate distribution in the front of cool flames: Maximum concentrations of H atoms and peroxy radicals were observed in the luminous zone of the cool flame front. Peroxy radicals appear before the luminous zone at 430 K due to diffusion. H atoms were found in cool flames of butane and hexane. H atoms diffuses from the luminous zone to the side of the fresh mixture, and they penetrate into the fresh mixture to a small depth. Extension of action sphear of peroxy radicals in the fresh mixture is much greater than that of H atoms due to their small activity and high concentrations.

  3. Method for separating metal chelates from other materials based on solubilities in supercritical fluids

    DOE Patents [OSTI]

    Wai, Chien M. (Moscow, ID); Smart, Neil G. (Workington, GB); Phelps, Cindy (Moscow, ID)

    2001-01-01

    A method for separating a desired metal or metalloi from impurities using a supercritical extraction process based on solubility differences between the components, as well as the ability to vary the solvent power of the supercritical fluid, is described. The use of adduct-forming agents, such as phosphorous-containing ligands, to separate metal or metalloid chelates in such processes is further disclosed. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is selected from the group consisting of .beta.-diketones; phosphine oxides, such as trialkylphosphine oxides, triarylphosphine oxides and alkylarylphosphine oxides; phosphinic acids; carboxylic acids; phosphates, such as trialkylphosphates, triarylphosphates and alkylarylphosphates; crown ethers; dithiocarbamates; phosphine sulfides; phosphorothioic acids; thiophosphinic acids; halogenated analogs of these chelating agents; and mixtures of these chelating agents. In especially preferred embodiments, at least one of the chelating agents is fluorinated.

  4. Performance and emissions characteristics of alternative fuels in spark ignition engines

    SciTech Connect (OSTI)

    Swain, M.R.; Maxwell, R.L.; Swain, M.N.; Bedsworth, K.; Adt, R.R. Jr.; Pappas, J.M.

    1984-01-01

    A formal ongoing program to characterize the performance and exhaust characteristics of automotive-type powerplants fueled by conventional and alternative fuels is reported. This report contains the information obtained during the past three years when four alternative fuels and two baseline fuels were evaluated in three engines. The four alternative fuels were a simulated gasoline made to represent coal derived gasoline, methyl aryl ethers blended at the 10% level in an unleaded gasoline, gasoline made from methanol, and a blend of Indolene plus methanol and higher alcohols. The two baseline fuels were, Indolene and Gulf unleaded regular gasoline. The engines tested were a pre-mixed carbureted SI (spark ignition) engine, a carbureted three-valve stratified-charge SI engine and a pre-mixed carbureted SI engine with a closed-loop three-way catalyst emission control system.

  5. Carbon-13 nuclear magnetic resonance characterization of network systems

    SciTech Connect (OSTI)

    Mertzel, E.A.; Perchak, D.R.; Ritchey, W.M.; Koenig, J.L.

    1988-04-01

    Solid-state C-13 NMR measurements are utilized to characterize the tetrafunctional epoxy, tetraglycidyl (diaminodiphenyl) methane, and the tetrafunctional amine, diaminodiphenyl sulfone. Intermolecular effective ether cross-links, amine junction points, and extent of reaction of the amine and epoxy are measured for the polymerization. Chemical reactions in the epoxy-amine system are discussed, and the reactivity ratio of the epoxy-amine system is calculated. Junction point measurements are made by the use of the dipolar dephasing relaxation experiment. The experimental data collected with C-13 NMR are then compared with the calculated data from a model developed in this laboratory. The information obtained in this study is sufficient to calculate the molecular weight between cross-links.

  6. Heterogeneous catalyst for the production of acetic anhydride from methyl acetate

    DOE Patents [OSTI]

    Ramprasad, Dorai (Allentown, PA); Waller, Francis Joseph (Allentown, PA)

    1999-01-01

    This invention relates to a process for producing acetic anhydride by the reaction of methyl acetate, carbon monoxide, and hydrogen at elevated temperatures and pressures in the presence of an alkyl halide and a heterogeneous, bifunctional catalyst that contains an insoluble polymer having pendant quaternized phosphine groups, some of which phosphine groups are ionically bonded to anionic Group VIII metal complexes, the remainder of the phosphine groups being bonded to iodide. In contrast to prior art processes, no accelerator (promoter) is necessary to achieve the catalytic reaction and the products are easily separated from the catalyst by filtration. The catalyst can be recycled for consecutive runs without loss in activity. Bifunctional catalysts for use in carbonylating dimethyl ether are also provided.

  7. Oxidation of aqueous pollutants using ultrasound: Salt-induced enhancement

    SciTech Connect (OSTI)

    Seymour, J.D.; Gupta, R.B.

    1997-09-01

    Ultrasound can be used to oxidize aqueous pollutants; however, due to economic reasons, higher oxidation/destruction rates are needed. This study reports enhancements of reaction rates by the addition of sodium chloride salt. Using 20 kHz ultrasound, large salt-induced enhancements are observed--6-fold for chlorobenzene, 7-fold for p-ethylphenol, and 3-fold for phenol oxidation. The reaction rate enhancements are proportional to the diethyl ether--water partitioning coefficient of the pollutants. It appears that the majority of oxidation reactions occur in the bubble-bulk interface region. The addition of salt increases the ionic strength of the aqueous phase which drives the organic pollutants toward the bubble-bulk interface. A first order reaction rate equation is proposed which can represent the observed enhancement with a good accuracy. A new sonochemical-waste-oxidation process is proposed utilizing the salt-induced enhancement.

  8. First Biomass Conference of the Americas: Energy, environment, agriculture, and industry. Proceedings, Volume 2

    SciTech Connect (OSTI)

    Not Available

    1993-10-01

    This conference was designed to provide a national and international forum to support the development of a viable biomass industry. Although papers on research activities and technologies under development that address industry problems comprised part of this conference, an effort was made to focus on scale-up and demonstration projects, technology transfer to end users, and commercial applications of biomass and wastes. The conference was divided into these major subject areas: Resource Base, Power Production, Transportation Fuels, Chemicals and Products, Environmental Issues, Commercializing Biomass Projects, Biomass Energy System Studies, and Biomass in Latin America. The papers in this second volume cover Transportation Fuels, and Chemicals and Products. Transportation Fuels topics include: Biodiesel, Pyrolytic Liquids, Ethanol, Methanol and Ethers, and Commercialization. The Chemicals and Products section includes specific topics in: Research, Technology Transfer, and Commercial Systems. Selected papers have been indexed separately for inclusion in the Energy Science and Technology Database.

  9. Photoimageable composition

    DOE Patents [OSTI]

    Simison, Kelby Liv; Dentinger, Paul

    2003-11-11

    The use of selected buffering amines in a photoimageable composition prevents process bias which with conventional photoresists causes designed features to be distorted, especially in corners and high resolution features. It is believed that the amines react with the catalysts, e.g., photoacids, generated to create an inert salt. The presence of the amines also increases resolution. Suitable photoimageable compositions includes: (a) a multifunctional polymeric epoxy resin that is dissolved in an organic solvent wherein the epoxy resin comprises oligomers of bisphenol A that is quantitatively protected by glycidyl ether and wherein the oligomers have an average functionality that ranges from about 3 to 12; (b) a photoactive compound; and (c) an amine that is selected from the group consisting of triisobutylamine, 1,8-bis(dimethylamino)naphthalene (also known as PROTON SPONGET.TM.), 2,2'-diazabicyclo[2.2.2] octane and mixtures thereof. The photoimageable composition is particularly suited for producing high aspect ratio metal microstructures.

  10. Photoimageable composition

    DOE Patents [OSTI]

    Dentinger, Paul; Krafick, Karen L.; Simison, Kelby Liv

    2005-02-22

    The use of photoacid generators including an alkoxyphenylphenyliodonium salt and/or bis(t-butylphenyl)iodonium salt in a photoimageable composition helps improve resolution. Suitable photoimageable compositions includes: (a) a multifuctional polymeric epoxy resin that is dissolved in an organic solvent wherein the epoxy resin comprises oligomers of bisphenol A that is quantitatively protected by glycidyl ether and wherein the oligomers have an average functionality that ranges from about 3 to 12; and a photoacid generator comprising an alkoxyphenylphenyliodonium salt and/or bis(t-butylphenyl)iodonium salt. Preferred alkoxyphenylphenyliodonium salts include 4-octyloxyphenyl phenyliodonium hexafluoroantimonate and 4-methoxyphenyl phenyliodonium hexafluoroantimonate. The photoimageable composition is particularly suited for producing high aspect ratio microstructures.

  11. Synthesis of acylphosphonites

    SciTech Connect (OSTI)

    Prishchenko, A.A.; Livantsov, M.V.; Lutsenko I.F.

    1987-12-10

    The authors showed earlier that (alkoxycarbonyl)phosphonites are obtained in high yields by the reactions of (dialkoxymethyl)phosphonites with alkyl chloroformates. In the present work the analogous reactions of the phosphonites with acyl chlorides were applied in the synthesis of the previously difficultly accessible acylphosphonites. The phosphonites are formed rapidly when mixtures of the reactants are boiled in ether. The IR spectra were determined on a IKS-22 spectrometer, the PMR spectra of a Tesla BS-467 spectrometer, and /sup 13/C and /sup 31/P NMR spectra on Varian FT-80A and Jeol FX-100 spectrometers; standards: TMS (/sup 1/H, /sup 13/C) and an 85% solution of H/sub 3/PO/sub 4/ in D/sub 2/O.

  12. Fuel-cycle energy and emissions impacts of tripled fuel economy vehicles

    SciTech Connect (OSTI)

    Mintz, M.M.; Wang, M.Q.; Vyas, A.D.

    1998-12-31

    This paper presents estimates of the full cycle energy and emissions impacts of light-duty vehicles with tripled fuel economy (3X vehicles) as currently being developed by the Partnership for a New Generation of Vehicles (PNGV). Seven engine and fuel combinations were analyzed: reformulated gasoline, methanol, and ethanol in spark-ignition, direct-injection engines; low sulfur diesel and dimethyl ether in compression-ignition, direct-injection engines; and hydrogen and methanol in fuel-cell vehicles. The fuel efficiency gain by 3X vehicles translated directly into reductions in total energy demand, petroleum demand, and carbon dioxide emissions. The combination of fuel substitution and fuel efficiency resulted in substantial reductions in emissions of nitrogen oxide, carbon monoxide, volatile organic compounds, sulfur oxide, and particulate matter smaller than 10 microns, particularly under the High Market Share Scenario.

  13. Consider the DME alternative for diesel engines

    SciTech Connect (OSTI)

    Fleisch, T.H.; Meurer, P.C.

    1996-07-01

    Engine tests demonstrate that dimethyl ether (DME, CH{sub 3}OCH{sub 3}) can provide an alternative approach toward efficient, ultra-clean and quiet compression ignition (CI) engines. From a combustion point of view, DME is an attractive alternative fuel for CI engines, primarily for commercial applications in urban areas, where ultra-low emissions will be required in the future. DME can resolve the classical diesel emission problem of smoke emissions, which are completely eliminated. With a properly developed DME injection and combustion system, NO{sub x} emissions can be reduced to 40% of Euro II or U.S. 1998 limits, and can meet the future ULEV standards of California. Simultaneously, the combustion noise is reduced by as much as 15 dB(A) below diesel levels. In addition, the classical diesel advantages such as high thermal efficiency, compression ignition, engine robustness, etc., are retained.

  14. Sensitivity of natural gas HCCI combustion to fuel and operating parameters using detailed kinetic modeling

    SciTech Connect (OSTI)

    Aceves, S; Dibble, R; Flowers, D; Smith, J R; Westbrook, C K

    1999-07-19

    This paper uses the HCT (Hydrodynamics, Chemistry and Transport) chemical kinetics code to analyze natural gas HCCI combustion in an engine. The HCT code has been modified to better represent the conditions existing inside an engine, including a wall heat transfer correlation. Combustion control and low power output per displacement remain as two of the biggest challenges to obtaining satisfactory performance out of an HCCI engine, and these are addressed in this paper. The paper considers the effect of natural gas composition on HCCI combustion, and then explores three control strategies for HCCI engines: DME (dimethyl ether) addition, intake heating and hot EGR addition. The results show that HCCI combustion is sensitive to natural gas composition, and an active control may be required to compensate for possible changes in composition. The three control strategies being considered have a significant effect in changing the combustion parameters for the engine, and should be able to control HCCI combustion.

  15. Atmospheric lifetimes and global warming potentials of hydrofluoroethers: Reactivity toward OH, UV spectra, and IR absorption cross sections

    SciTech Connect (OSTI)

    Orkin, V.L.; Villenave, E.; Huie, R.E.; Kurylo, M.J.

    1999-12-02

    The rate constants for the reactions of OH radicals with the fluorinated ethers, CHF{sub 2}-O-CHF{sub 2} (HFOC-134) and CF{sub 3}CH{sub 2}-O-CH{sub 2}CF{sub 3} (HFOC-356mff), were measured using the flash photolysis resonance fluorescence technique over the temperature range 277--370 K to give the following Arrhenius expressions: k{sub HFOC-356mff}(T) = (2.32{sub {minus}0.41}{sup +0.46}) x 10{sup {minus}12} exp{l{underscore}brace}{minus}(790 {+-} 47)/T{r{underscore}brace} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. On the basis of the analysis of the available experimental results, the following Arrhenius expression can be recommended for the rate constant of the reaction between OH and HFOC-134: k{sub HFOC-134}(T) = (0.82{sub {minus}0.24}{sup +0.34}) x 10{sup {minus}12} exp{l{underscore}brace}{minus}(1,730 {+-} 110)/T{r{underscore}brace} cm{sup 3} molecule{sup {minus}1} s{sup {minus}1}. Atmospheric lifetimes were estimated to be 24.8 years for HFOC-134 (23.8 years based on the results of this study alone) and 0.3 years for HFOC-356mff. Infrared absorption cross sections of HFOC-134, HFOC-356mff, and HFOC-125 (CHF{sub 2}-O-CF{sub 3}) were measured at T = 295 K from 500 to 1,600 cm{sup {minus}1} and the global warming potentials of the three compounds were estimated. Ultraviolet absorption spectra of the ethers were measured between 160 and 220 nm. The general pattern of reactivity of hydrofluoroethers toward OH is discussed.

  16. 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.

  17. 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.

  18. 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.

  19. Lead Research and Development Activity for DOE's High Temperature, Low Relative Humidity Membrane Program (Topic 2)

    SciTech Connect (OSTI)

    James Fenton, PhD; Darlene Slattery, PhD; Nahid Mohajeri, PhD

    2012-09-05

    The Department of Energys High Temperature, Low Relative Humidity Membrane Program was begun in 2006 with the Florida Solar Energy Center (FSEC) as the lead organization. During the first three years of the program, FSEC was tasked with developing non-Nafion proton exchange membranes with improved conductivity for fuel cells. Additionally, FSEC was responsible for developing protocols for the measurement of in-plane conductivity, providing conductivity measurements for the other funded teams, developing a method for through-plane conductivity and organizing and holding semiannual meetings of the High Temperature Membrane Working Group (HTMWG). The FSEC membrane research focused on the development of supported poly[perfluorosulfonic acid] (PFSA) Teflon membranes and a hydrocarbon membrane, sulfonated poly(ether ether ketone). The fourth generation of the PFSA membrane (designated FSEC-4) came close to, but did not meet, the Go/No-Go milestone of 0.1 S/cm at 50% relative humidity at 120 C. In-plane conductivity of membranes provided by the funded teams was measured and reported to the teams and DOE. Late in the third year of the program, DOE used this data and other factors to decide upon the teams to continue in the program. The teams that continued provided promising membranes to FSEC for development of membrane electrode assemblies (MEAs) that could be tested in an operating fuel cell. FSEC worked closely with each team to provide customized support. A logic flow chart was developed and discussed before MEA fabrication or any testing began. Of the five teams supported, by the end of the project, membranes from two of the teams were easily manufactured into MEAs and successfully characterized for performance. One of these teams exceeded performance targets, while the other requires further optimization. An additional team developed a membrane that shows great promise for significantly reducing membrane costs and increasing membrane lifetime.

  20. A membrane-free lithium/polysulfide semi-liquid battery for large-scale energy storage

    SciTech Connect (OSTI)

    Yang, Yuan; Zheng, Guangyuan; Cui, Yi

    2013-01-01

    Large-scale energy storage represents a key challenge for renewable energy and new systems with low cost, high energy density and long cycle life are desired. In this article, we develop a new lithium/polysulfide (Li/PS) semi-liquid battery for large-scale energy storage, with lithium polysulfide (Li{sub 2}S{sub 8}) in ether solvent as a catholyte and metallic lithium as an anode. Unlike previous work on Li/S batteries with discharge products such as solid state Li{sub 2}S{sub 2} and Li{sub 2}S, the catholyte is designed to cycle only in the range between sulfur and Li{sub 2}S{sub 4}. Consequently all detrimental effects due to the formation and volume expansion of solid Li{sub 2}S{sub 2}/Li{sub 2}S are avoided. This novel strategy results in excellent cycle life and compatibility with flow battery design. The proof-of-concept Li/PS battery could reach a high energy density of 170 W h kg{sup -1} and 190 W h L{sup -1} for large scale storage at the solubility limit, while keeping the advantages of hybrid flow batteries. We demonstrated that, with a 5 M Li{sub 2}S{sub 8} catholyte, energy densities of 97 W h kg{sup -1} and 108 W h L{sup -1} can be achieved. As the lithium surface is well passivated by LiNO{sub 3} additive in ether solvent, internal shuttle effect is largely eliminated and thus excellent performance over 2000 cycles is achieved with a constant capacity of 200 mA h g{sup -1}. This new system can operate without the expensive ion-selective membrane, and it is attractive for large-scale energy storage.