National Library of Energy BETA

Sample records for oxygenates alcohols ethers

  1. High octane ethers from synthesis gas-derived alcohol

    SciTech Connect (OSTI)

    Klier, K.; Herman, R.G.; Bastian, R.D.; DeTavernier, S. . Dept. of Chemistry Lehigh Univ., Bethlehem, PA . Zettlemoyer Center for Surface Studies)

    1991-01-01

    The objective of the proposed research is to synthesize high octane ethers directly from coal-derived synthesis gas via alcohol mixtures that are rich in methanol and isobutanol. The overall scheme involves gasification of coal, purification and shifting of the synthesis gas, higher alcohol synthesis, and direct synthesis of ethers. Commercial acid and superacid resin catalysts were obtained and tested under one set of conditions to compare the activities and selectivities for forming the unsymmetric methylisobutylether (MIBE) by coupling methanol with isobutanol. It was found that both Nafion-H microsaddles and Amberlyst-15 resins are active for this synthesis reaction. While and the Nafion-H catalyst does form the MIBE product fairly selectively under the reaction conditions utilized, the Amberlyst-15 catalyst formed dimethylether (DME) as the major product. In addition, significantly larger quantities of the C{sub 4} hydrocarbon products were observed over the Amberlyst-15 catalyst at 123{degree}C and 13.6 atm. It has been demonstrated that methyltertiarybutylether (MTBE) MIBE, DME and diisobutylether (DIBE) are separated and quantitatively determined by using the proper analytical conditions. In order to gain insight into the role of superacidity in promoting the selective coupling of the alcohols to form the unsymmetric ether, the strengths of the acid sites on the catalysts are being probed by thermometric titrations in non-aqueous solutions. 18 refs., 20 figs., 4 tabs.

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

    SciTech Connect (OSTI)

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

    1999-11-15

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

  3. 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.

  4. 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.

  5. 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.

  6. 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.

  7. 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.

  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. 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.

  10. 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.

  11. 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.

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

    SciTech Connect (OSTI)

    Wolfe, R.

    1995-12-31

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

  13. 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

  14. MOF-based catalysts for selective hydrogenolysis of carbon–oxygen 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 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 of activity, making this a promising route for mild aryl-ether bond scission.

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

    SciTech Connect (OSTI)

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

    1985-04-23

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

  16. 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.

  17. 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.

  18. 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.

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

    DOE Patents [OSTI]

    Barger, Paul T. (Arlington Heights, IL)

    1996-01-01

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

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

    DOE Patents [OSTI]

    Barger, P.T.

    1996-09-24

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

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

    SciTech Connect (OSTI)

    Boyarski, Adam; /SLAC

    2008-07-02

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

  2. 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.

  3. 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

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

    SciTech Connect (OSTI)

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

    2014-08-25

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

  5. 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.

  6. 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.

  7. 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.

  8. 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.

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

    SciTech Connect (OSTI)

    Nexant Inc.

    2006-05-01

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

  10. 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.

  11. Process for producing dimethyl ether form synthesis gas

    DOE Patents [OSTI]

    Pierantozzi, Ronald

    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.

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

    SciTech Connect (OSTI)

    Klier, Kamil; Herman, Richard G

    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 Brnsted 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.

  13. 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.

  14. Alcohol conversion

    DOE Patents [OSTI]

    Wachs, Israel E.; Cai, Yeping

    2002-01-01

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

  15. CONVERSION OF DIMETHYL ETHER-BORON TRIFLUORIDE COMPLEX TO POTASSIUM FLUOBORATE

    DOE Patents [OSTI]

    Eberle, A.R.

    1957-06-18

    A method of preparing KBF/sub 4/ from the dimethyl ether complex of BF/sub 3/ is given. This may be accomplished by introducing the dimethyl ether complex of BF/sub 3/ into an aqueous solution of KF and alcohol, expelling the ether liberated from the complex by heating or stirring and recovering the KBF/sub 4/ so formed. The KBF/sub 4/ is then filtered from the alcohol-water solution, which may be recycled, to reduce the loss of KBF/sub 4/ which is not recovered by filtration.

  16. Conversion of dimethyl ether--boron trifluoride complex to potassium fluoborate

    DOE Patents [OSTI]

    Eberle, A.R.

    1957-06-18

    A method of preparing KBF/sub 4/ from the dimethyl ether complex of BF/sub 3/ is given. This may be accomplished by introducing the dimethyl ether complex of BF/sub 3/ into an aqueous solution of KF and alcohol, expelling the ether liberated from the complex by heating or stirring and recovering the KBF/sub 4/ so formed. The KBF/sub 4/ is then filtered from the alcohol-water solution, which may be recycled, to reduce the loss of KBF/sub 4/ which is not recovered by filtration.

  17. 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.

  18. 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

  19. 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.

  20. Carbon-carbon bond cleavage of 1,2-hydroxy ethers b7 vanadium(V) dipicolinate complexes

    SciTech Connect (OSTI)

    Hanson, Susan K; Gordon, John C; Thorn, David L; Scott, Brian L; Baker, R Tom

    2009-01-01

    The development of alternatives to current petroleum-based fuels and chemicals is becoming increasingly important due to concerns over climate change, growing world energy demand, and energy security issues. Using non-food derived biomass to produce renewable feedstocks for chemicals and fuels is a particularly attractive possibility. However, the majority of biomass is in the form of lignocellulose, which is often not fully utilized due to difficulties associated with breaking down both lignin and cellulose. Recently, a number of methods have been reported to transform cellulose directly into more valuable materials such as glucose, sorbitol, 5-(chloromethyl)furfural, and ethylene glycol. Less progress has been made with selective transformations of lignin, which is typically treated in paper and forest industries by kraft pulping (sodium hydroxide/sodium sulfide) or incineration. Our group has begun investigating aerobic oxidative C-C bond cleavage catalyzed by dipicolinate vanadium complexes, with the idea that a selective C-C cleavage reaction of this type could be used to produce valuable chemicals or intermediates from cellulose or lignin. Lignin is a randomized polymer containing methoxylated phenoxy propanol units. A number of different linkages occur naturally; one of the most prevalent is the {beta}-O-4 linkage shown in Figure 1, containing a C-C bond with 1,2-hydroxy ether substituents. While the oxidative C-C bond cleavage of 1,2-diols has been reported for a number of metals, including vanadium, iron, manganese, ruthenium, and polyoxometalate complexes, C-C bond cleavage of 1,2-hydroxy ethers is much less common. We report herein vanadium-mediated cleavage of C-C bonds between alcohol and ether functionalities in several lignin model complexes. In order to explore the scope and potential of vanadium complexes to effect oxidative C-C bond cleavage in 1,2-hydroxy ethers, we examined the reactivity of the lignin model complexes pinacol monomethyl ether (A), 2-phenoxyethanol (B), and 1,2-diphenyl-2-methoxyethanol (C) (Figure 1). Reaction of (dipic)V{sup V}(O)O{sup i}Pr (1a) or (dipic)V{sup v}(O)OEt (lb) with A, B, or C in acetonitrile yielded new vanadium(V) complexes where the alcohol-ether ligand was bound in a chelating fashion. From the reaction of 1b with pinacol monomethyl ether (A) in acetonitrile solution, (dipic)V{sup v}(O)(pinOMe) (2) (PinOMe = 2,3-dimethyl-3-methoxy-2-butanoxide) was isolated in 61 % yield. Reaction of 1b with 2-phenoxyethanol (B) in acetonitrile gave the new complex (dipic)V{sup v}(O)(OPE) (3) (OPE = 2-phenoxyethoxide), which was isolated in 76% yield. In a similar fashion, 1a reacted with 1,2-diphenyl-2-methoxyethanol (C) to give (dipic)V(O)(DPME) (4) (DPME = 1,2-diphenyl-2-methoxyethoxide), which was isolated in 39% yield. Complexes 2, 3, and 4 were characterized by {sup 1}H NMR and IR spectroscopy, elemental analysis, and X-ray crystallography. Compared to the previously reported vanadium(V) pinacolate complex (dipic)V(O)(pinOH) the X-ray structure of complex 2 reveals a slightly shorter V = O bond, 1.573(2) {angstrom} vs 1.588(2) {angstrom} for the pinOH structure. Complexes 3 and 4 display similar vanadium oxo bond distances of 1.568(2) {angstrom} and 1.576(2) {angstrom}, respectively. All three complexes show longer bonds to the ether-oxygen trans to the oxo (2.388(2) {angstrom} for 2, 2.547(2) {angstrom} for 3, and 2.438(2) {angstrom} for 4) than to the hydroxy-oxygen in the pinOH structure (2.252(2) {angstrom}).

  1. 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.

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

    DOE Patents [OSTI]

    Smith, Jr., Lawrence A.; Jones, Jr., Edward M.; Hearn, Dennis

    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.

  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. Structure and Reactivity of Alkyl Ethers Adsorbed on CeO2(111) Model Catalysts

    SciTech Connect (OSTI)

    F Calaza; T Chen; D Mullins; S Overbury

    2011-12-31

    The effect of surface hydroxyls on the adsorption of ether on ceria was explored. Adsorption of dimethyl ether (DME) and diethyl ether (DEE) on oxidized and reduced CeO{sub 2}(111) films was studied and compared with Ru(0001) using RAIRS and sXPS within a UHV environment. On Ru(0001) the ethers adsorb weakly with the molecular plane close to parallel to the surface plane. On the ceria films, the adsorption of the ethers was stronger than on the metal surface, presumably due to stronger interaction of the ether oxygen lone pair electrons with a cerium cation. This interaction causes the ethers to tilt away from the surface plane compared to the Ru(0001) surface. No pronounced differences were found between oxidized (CeO{sub 2}) and reduced (CeOx) films. The adsorption of the ethers was found to be perturbed by the presence of OH groups on hydroxylated CeOx. In the case of DEE, the geometry of adsorption resembles that found on Ru, and in the case of dimethyl ether DME is in between that one found on clean CeOx and the metal surface. Decomposition of the DEE was observed on the OH/CeOx surface following high DEE exposure at 300 K and higher temperatures. Ethoxides and acetates were identified as adsorbed species on the surface by means of RAIRS and ethoxides and formates by s-XPS. No decomposition of dimethyl ether was observed on the OH/CeOx at these higher temperatures, implying that the dissociation of the C-O bond from ethers requires the presence of {beta}-hydrogen.

  6. Structure and Reactivity of Alkyl Ethers Adsorbed on CeO(2)(111) Model Catalysts

    SciTech Connect (OSTI)

    Calaza, Florencia C; Chen, Tsung-Liang; Mullins, David R; Overbury, Steven {Steve} H

    2011-01-01

    The effect of surface hydroxyls on the adsorption of ether on ceria was explored. Adsorption of dimethyl ether (DME) and diethyl ether (DEE) on oxidized and reduced CeO{sub 2}(111) films was studied and compared with Ru(0001) using RAIRS and sXPS within a UHV environment. On Ru(0001) the ethers adsorb weakly with the molecular plane close to parallel to the surface plane. On the ceria films, the adsorption of the ethers was stronger than on the metal surface, presumably due to stronger interaction of the ether oxygen lone pair electrons with a cerium cation. This interaction causes the ethers to tilt away from the surface plane compared to the Ru(0001) surface. No pronounced differences were found between oxidized (CeO{sub 2}) and reduced (CeOx) films. The adsorption of the ethers was found to be perturbed by the presence of OH groups on hydroxylated CeOx. In the case of DEE, the geometry of adsorption resembles that found on Ru, and in the case of dimethyl ether DME is in between that one found on clean CeOx and the metal surface. Decomposition of the DEE was observed on the OH/CeOx surface following high DEE exposure at 300 K and higher temperatures. Ethoxides and acetates were identified as adsorbed species on the surface by means of RAIRS and ethoxides and formates by s-XPS. No decomposition of dimethyl ether was observed on the OH/CeOx at these higher temperatures, implying that the dissociation of the C-O bond from ethers requires the presence of {beta}-hydrogen.

  7. Reaction Pathways and Energetics of Etheric C−O Bond Cleavage Catalyzed by Lanthanide Triflates

    SciTech Connect (OSTI)

    Assary, Rajeev S.; Atesin, Abdurrahman C.; Li, Zhi; Curtiss, Larry A.; Marks, Tobin J.

    2013-07-15

    Efficient and selective cleavage of etheric C−O bonds is crucial for converting biomass into platform chemicals and liquid transportation fuels. In this contribution, computational methods at the DFT B3LYP level of theory are employed to understand the efficacy of lanthanide triflate catalysts (Ln(OTf)3, Ln = La, Ce, Sm, Gd, Yb, and Lu) in cleaving etheric C−O bonds. In agreement with experiment, the calculations indicate that the reaction pathway for C−O cleavage occurs via a C−H → O−H proton transfer in concert with weakening of the C−O bond of the coordinated ether substrate to ultimately yield a coordinated alkenol. The activation energy for this process falls as the lanthanide ionic radius decreases, reflecting enhanced metal ion electrophilicity. Details of the reaction mechanism for Yb(OTf)3-catalyzed ring opening are explored in depth, and for 1-methyl-d3-butyl phenyl ether, the computed primary kinetic isotope effect of 2.4 is in excellent agreement with experiment (2.7), confirming that etheric ring-opening pathway involves proton transfer from the methyl group alpha to the etheric oxygen atom, which is activated by the electrophilic lanthanide ion. Calculations of the catalytic pathway using eight different ether substrates indicate that the more rapid cleavage of acyclic versus cyclic ethers is largely due to entropic effects, with the former C−O bond scission processes increasing the degrees of freedom/particles as the transition state is approached.

  8. 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.

  9. 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.

  10. 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.

  11. 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.

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

    SciTech Connect (OSTI)

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

    1994-10-01

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

  13. 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.

  14. Aza crown ether compounds as anion receptors

    DOE Patents [OSTI]

    Lee, Hung Sui; Yang, Xiao-Oing; McBreen, James

    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.

  15. 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.

  16. 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.

  17. 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 ...

  18. 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.

  19. 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.

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

    DOE Patents [OSTI]

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

    2010-12-28

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

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

    SciTech Connect (OSTI)

    Waller, F.J.

    1997-11-01

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

  2. Alcohol fuels program technical review

    SciTech Connect (OSTI)

    1981-07-01

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

  3. Analysis of Oxygenated Compounds in Hydrotreated Biomass Fast Pyrolysis Oil Distillate Fractions

    SciTech Connect (OSTI)

    Christensen, Earl D.; Chupka, Gina; Luecke, Jon; Smurthwaite, Tricia D.; Alleman, Teresa L.; Iisa, Kristiina; Franz, James A.; Elliott, Douglas C.; McCormick, Robert L.

    2011-10-06

    Three hydrotreated bio-oils with different oxygen contents (8.2, 4.9, and 0.4 w/w) were distilled to produce Light, Naphtha, Jet, Diesel, and Gasoil boiling range fractions that were characterized for oxygen containing species by a variety of analytical methods. The bio-oils were originally generated from lignocellulosic biomass in an entrained-flow fast pyrolysis reactor. Analyses included elemental composition, carbon type distribution by {sup 13}C NMR, acid number, GC-MS, volatile organic acids by LC, and carbonyl compounds by DNPH derivatization and LC. Acid number titrations employed an improved titrant-electrode combination with faster response that allowed detection of multiple endpoints in many samples and for acid values attributable to carboxylic acids and to phenols to be distinguished. Results of these analyses showed that the highest oxygen content bio-oil fractions contained oxygen as carboxylic acids, carbonyls, aryl ethers, phenols, and alcohols. Carboxylic acids and carbonyl compounds detected in this sample were concentrated in the Light, Naphtha, and Jet fractions (<260 C boiling point). Carboxylic acid content of all of the high oxygen content fractions was likely too high for these materials to be considered as fuel blendstocks although potential for blending with crude oil or refinery intermediate streams may exist for the Diesel and Gasoil fractions. The 4.9 % oxygen sample contained almost exclusively phenolic compounds found to be present throughout the boiling range of this sample, but imparting measurable acidity primarily in the Light, Naphtha and Jet fractions. Additional study is required to understand what levels of the weakly acidic phenols could be tolerated in a refinery feedstock. The Diesel and Gasoil fractions from this upgraded oil had low acidity but still contained 3 to 4 wt% oxygen present as phenols that could not be specifically identified. These materials appear to have excellent potential as refinery feedstocks and some potential for blending into finished fuels. Fractions from the lowest oxygen content oil exhibited some phenolic acidity, but generally contained very low levels of oxygen functional groups. These materials would likely be suitable as refinery feedstocks and potentially as fuel blend components. PIONA analysis of the Light and Naphtha fractions shows benzene content of 0.5 and 0.4 vol%, and predicted (RON + MON)/2 of 63 and 70, respectively.

  4. Oxygen analyzer

    DOE Patents [OSTI]

    Benner, William H.

    1986-01-01

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

  5. Oxygen analyzer

    DOE Patents [OSTI]

    Benner, W.H.

    1984-05-08

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

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. Fuel Ethanol Oxygenate Production

    Annual Energy Outlook [U.S. Energy Information Administration (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 ...

  11. Oxygenates from synthesis gas

    SciTech Connect (OSTI)

    Falter, W.; Keim, W.

    1994-12-31

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

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. Magnetism in LithiumOxygen Discharge Product

    SciTech Connect (OSTI)

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

    2013-05-13

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

  17. 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.

  18. Raman spectra of methane, ethylene, ethane, dimethyl ether, formaldehyde

    Office of Scientific and Technical Information (OSTI)

    and propane for combustion applications (Journal Article) | SciTech Connect Raman spectra of methane, ethylene, ethane, dimethyl ether, formaldehyde and propane for combustion applications Citation Details In-Document Search This content will become publicly available on May 27, 2017 Title: Raman spectra of methane, ethylene, ethane, dimethyl ether, formaldehyde and propane for combustion applications Authors: Magnotti, G. ; KC, U. ; Varghese, P. L. ; Barlow, R. S. Publication Date:

  19. Laser-induced breakdown spectroscopy of alcohols and protein solutions

    SciTech Connect (OSTI)

    Melikechi, N.; Ding, H.; Marcano, O. A.; Rock, S.

    2008-04-15

    We report on the use of laser-induced breakdown spectroscopy for the study of organic samples that exhibit similar elemental composition. We evaluate the method for its potential application for the measurement of small spectroscopic differences between samples such as alcohols and water solution of proteins. We measure differences in the relative amplitudes of the oxygen peaks for alcohols and find that these correlate with the relative amount of oxygen atoms within the molecule. We also show that the spectra of proteins reveal differences that can be used for their detection and identification.

  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. Alcohol-fuel symposium

    SciTech Connect (OSTI)

    Not Available

    1980-01-01

    A symposium was conducted on the state-of-the-art of ethanol production and use. The following topics were discussed: ethanol as a fuel for internal combustion engines; ethanol production system design; the economics of producing fuel alcohol in form size plants; alternate feedstocks for ethanol stillage as a cattle feed; high energy sorghum, ethanol versus other alternative fuels; alcohol-fuel; legal and policy issues in ethanol production; and small scale fuel alcohol production. (DMC)

  2. Furfuryl alcohol cellular product

    DOE Patents [OSTI]

    Sugama, T.; Kukacka, L.E.

    1982-05-26

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

  3. Tropospheric oxidation mechanism of dimethyl ether and methyl formate

    SciTech Connect (OSTI)

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

    2000-02-17

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

  4. Extracting alcohols from aqueous solutions

    DOE Patents [OSTI]

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

    1984-01-01

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

  5. Utilization of Renewable Oxygenates as Gasoline Blending Components

    SciTech Connect (OSTI)

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

    2011-08-01

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

  6. 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.

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

    SciTech Connect (OSTI)

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

    2014-08-21

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

  8. 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.

  9. 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.

  10. 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.

  11. Artificial oxygen transport protein

    DOE Patents [OSTI]

    Dutton, P. Leslie

    2014-09-30

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

  12. 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.

  13. 2' and 3' Carboranyl uridines and their diethyl ether adducts

    DOE Patents [OSTI]

    Soloway, Albert H.; Barth, Rolf F.; Anisuzzaman, Abul K.; Alam, Fazlul; Tjarks, Werner

    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.

  14. Fermentative alcohol production

    DOE Patents [OSTI]

    Wilke, Charles R.; Maiorella, Brian L.; Blanch, Harvey W.; Cysewski, Gerald R.

    1982-01-01

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

  15. Solid state oxygen sensor

    DOE Patents [OSTI]

    Garzon, Fernando H. (Sante Fe, NM); Chung, Brandon W. (Los Alamos, NM); Raistrick, Ian D. (Los Alamos, NM); Brosha, Eric L. (Los Alamos, NM)

    1996-01-01

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

  16. Solid state oxygen sensor

    DOE Patents [OSTI]

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

    1996-08-06

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

  17. ESE Alcohol | Open Energy Information

    Open Energy Info (EERE)

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

  18. Production of hydrogen from alcohols

    DOE Patents [OSTI]

    Deluga, Gregg A.; Schmidt, Lanny D.

    2007-08-14

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

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

    Open Energy Info (EERE)

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

  20. 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.

  1. 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.

  2. Solid state oxygen sensor

    DOE Patents [OSTI]

    Garzon, Fernando H.; Brosha, Eric L.

    1997-01-01

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

  3. Exploratory study of coal-conversion chemistry. Quarterly report, June 20, 1980-September 19, 1980. [Diphenylmethane, diphenyl ether

    SciTech Connect (OSTI)

    Not Available

    1981-03-04

    This report describes work accomplished under two task: Task A, Mechanism of Cleavage of Key Bond types Present in Coals, and Task B, Catalysis of Conversion in CO-H/sub 2/O Systems. Under Task A, we have made additional measurements of catalytic carbon-carbon and carbon-oxygen bond cleavage in coal-related diphenylmethane and diphenyl ether structures. The results provide further support for, but do not definitely confirm, the tentative conclusion that the highly effective iron oxide catalysts involves oxidation to radical cation species. The homogeneous scission of carbon-oxygen bonds in diphenyl ether structure has also been studied. In the Task B studies of CO-H/sub 2/O systems, we typically obtain 50% benzene-soluble product material from 20 min. reaction of beneficiated Illinois No. 6 coal. This conversion level is obtained with aqueous solutions either at a starting pH above 12.6 or in neutral solutions with water-soluble catalysts present. We have studied a number of catalysts, including the potassium or sodium salts of molybdate, chromate, manganate, and tungstate; all are effective in the 3000 to 6000 ppM range. A striking result is that sodium nitrate at 6000 ppM is as effective as the metal salts. We found that the nitrate was converted to ammonium ion; also, formate was detected in the product aqueous phase. Finally, we find that catalytic quantities of sodium formate in CO/H/sub 2/O at pH 7 are effective in the conversion. However, in a control run in N/sub 2//H/sub 2/O, with a quantity of sodium formate equivalent to twice the molar quantity of hydrogen transferred to the coal in a successful run, the coal was converted to a product totally insoluble in benzene and with a lower hydrogen content than the starting coal.

  4. 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.

  5. An aging study of wire chambers with dimethyl ether

    SciTech Connect (OSTI)

    Jibaly, M.; Chrusch, P. Jr.; Hilgenberg, G.; Majewski, S.; Wojcik, R.; Sauli, F.; Gaudaen, J.

    1989-02-01

    The authors report results on the aging of different types of resistive and non-resistive wires in wire chambers filled with dimethyl ether (DME) of varying degrees of purity. Among the Freon impurities detected in our DME batches, only Freon-11 was found to contribute to the aging process. Of the resistive wires, Nicotin and Stablohm produced fast aging, whereas stainless steel withstood extended irradiation in purified DME (up to 1 C/cm) without any apparent damage. Gold-plated tungsten and molybdenum wires produced results comparable to those of the stainless steel.

  6. 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.

  7. Oxygen partial pressure sensor

    DOE Patents [OSTI]

    Dees, D.W.

    1994-09-06

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

  8. Oxygen partial pressure sensor

    DOE Patents [OSTI]

    Dees, Dennis W.

    1994-01-01

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

  9. Improving Ethanol-Gasoline Blends by Addition of Higher Alcohols |

    Broader source: Energy.gov (indexed) [DOE]

    Department of Energy Mixtures of ethanol, gasoline, and higher alcohols were evaluated to determine if they offer superior performance to ethanol/gasoline blends in meeting the Renewal Fuels Standard II. PDF icon deer12_ickes.pdf More Documents & Publications Vehicle Certification Test Fuel and Ethanol Flex Fuel Quality Impact of ethanol and butanol as oxygenates on SIDI engine efficiency and emissions using steady-state and transient test procedures Drop In Fuels: Where the Road Leads

  10. 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.

  11. 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.

  12. 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.

  13. Oxygen ion conducting materials

    DOE Patents [OSTI]

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

    2005-07-12

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

  14. Oxygen ion conducting materials

    DOE Patents [OSTI]

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

    2004-11-23

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

  15. Oxygen ion conducting materials

    DOE Patents [OSTI]

    Vaughey, John (Elmhurst, IL); Krumpelt, Michael (Naperville, IL); Wang, Xiaoping (Downers Grove, IL); Carter, J. David (Bolingbrook, IL)

    2003-01-01

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

  16. Integrated turbomachine oxygen plant

    SciTech Connect (OSTI)

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

    2014-06-17

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

  17. Fuel alcohol opportunities for Indiana

    SciTech Connect (OSTI)

    Greenglass, Bert

    1980-08-01

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

  18. Oxygen-Enriched Combustion

    Broader source: Energy.gov [DOE]

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

  19. Solid state oxygen sensor

    DOE Patents [OSTI]

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

    1997-12-09

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

  20. Syngas Mixed Alcohol Cost Validation

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

    1, 2013 DOE Bioenergy Technologies Office: Project Peer Review Syngas Mixed Alcohol Cost Validation Abhijit Dutta, NREL This presentation does not contain any proprietary, ...

  1. 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)].

  2. 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.

  3. Shape-selective catalysis in dimethyl ether conversion

    SciTech Connect (OSTI)

    Sardesai, A.; Lee, S.

    1999-07-01

    Coal-derived syngas can be effectively converted to dimethyl ether (DME) in a single-stage, liquid-phase process. This Liquid Phase Dimethyl Ether (LPDME) process utilizes a dual catalytic system, which comprises of a physical blend between the methanol synthesis and the methanol dehydration catalyst slurried in an inert mineral oil. Such produced DME has vast potential as a building block chemical in the petrochemical industry to produce value-added specialty chemicals. The current research efforts are made to exploit the utilization of shape-selective catalysis using zeolites to produce targeted petrochemicals, including lower olefinic hydrocarbons. The catalysts probed in this investigation include zeolites of different physical, morphological, and chemical configurations. The effect of acidity of ZSM-5 type zeolites as well as the effect of the different channel size and orientation of the zeolites on product selectivity and catalyst deactivation are examined. Results obtained from experimentation of this study show that ZSM-5 type zeolite with low acidity (high SiO{sub 2}/Al{sub 2}O{sub 3} ratio, in this case 150) exhibits the highest selectivity towards lower (C{sub 2}-C{sub 4}) olefins in general. Controlled selectivity toward targeted olefinic species can be accomplished via devising catalytic reaction systems in such a way that the structural property of the catalyst and reactive interaction between molecules in the pores are geared toward formation of targeted molecular species which also at the same time prevent the formation of less desirable products. The internal morphology of the catalyst also has a pronounced effect on the deactivation phenomenon, where it is observed that zeolites possessing high acidity and a unidimensional channel structure are prone towards catalyst deactivation by coking and pore blockage.

  4. 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.

  5. Farmstead production of fuel alcohol

    SciTech Connect (OSTI)

    Badger, P.C.; Pile, R.S.; Waddell, E.L. Jr.

    1981-01-01

    The Tennessee Valley Authority Agricultural Energy Applications Section (Muscle Shoals, AL) has designed and constructed a small-scale fuel alcohol production facility which can produce 10 gph of 190-proof alcohol. Information presented includes some factors relative to facility design, layout, and construction, plus operation and performance experiences.

  6. Syngas Conversion to Hydrocarbon Fuels through Mixed Alcohol Intermediates

    SciTech Connect (OSTI)

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

    2013-05-13

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

  7. Computational and experimental study of the effects of adding dimethyl ether and ethanol to nonpremixed ethylene/air flames

    SciTech Connect (OSTI)

    Bennett, Beth Anne V.; McEnally, Charles S.; Pfefferle, Lisa D.; Smooke, Mitchell D.; Colket, Meredith B.

    2009-06-15

    Two sets of axisymmetric laminar coflow flames, each consisting of ethylene/air nonpremixed flames with various amounts (up to 10%) of either dimethyl ether (CH{sub 3}-O-CH{sub 3}) or ethanol (CH{sub 3}-CH{sub 2}-OH) added to the fuel stream, have been examined both computationally and experimentally. Computationally, the local rectangular refinement method, which incorporates Newton's method, is used to solve the fully coupled nonlinear conservation equations on solution-adaptive grids for each flame in two spatial dimensions. The numerical model includes C6 chemical kinetic mechanisms with up to 59 species, detailed transport, and an optically thin radiation submodel. Experimentally, thermocouples are used to measure gas temperatures, and mass spectrometry is used to determine concentrations of over 35 species along the flame centerline. Computational results are examined throughout each flame, and validation of the model occurs through comparison with centerline measurements. Very good agreement is observed for temperature, major species, and several minor species. As the level of additive is increased, temperatures, some major species (CO{sub 2}, C{sub 2}H{sub 2}), flame lengths, and residence times are essentially unchanged. However, peak centerline concentrations of benzene (C{sub 6}H{sub 6}) increase, and this increase is largest when dimethyl ether is the additive. Computational and experimental results support the hypothesis that the dominant pathway to C{sub 6}H{sub 6} formation begins with the oxygenates decomposing into methyl radical (CH{sub 3}), which combines with C2 species to form propargyl (C{sub 3}H{sub 3}), which reacts with itself to form C{sub 6}H{sub 6}. (author)

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

    Office of Scientific and Technical Information (OSTI)

    Alcohol Dehydrogenase (CAD) Leads to Improved Saccharification Efficiency in Switchgrass Citation Details In-Document Search Title: Downregulation of Cinnamyl Alcohol Dehydrogenase ...

  9. 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.

  10. High Selectivity Oxygen Delignification

    SciTech Connect (OSTI)

    Lucian A. Lucia

    2005-11-15

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

  11. 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.

  12. SCALAR STRUCTURE OF TURBULENT PARTIALLY-PREMIXED DIMETHYL ETHER/AIR JET

    Office of Scientific and Technical Information (OSTI)

    FLAMES (Journal Article) | SciTech Connect SCALAR STRUCTURE OF TURBULENT PARTIALLY-PREMIXED DIMETHYL ETHER/AIR JET FLAMES Citation Details In-Document Search Title: SCALAR STRUCTURE OF TURBULENT PARTIALLY-PREMIXED DIMETHYL ETHER/AIR JET FLAMES Authors: Fuest, F. ; Magnotti, G. ; Barlow, R. S. ; Sutton, J. A. Publication Date: 2014-01-01 OSTI Identifier: 1167931 DOE Contract Number: SC0001198 Resource Type: Journal Article Resource Relation: Journal Name: Proceedings of the Combustion

  13. Scalar structure of turbulent partially-premixed dimethyl ether/air jet

    Office of Scientific and Technical Information (OSTI)

    flames (Journal Article) | SciTech Connect Scalar structure of turbulent partially-premixed dimethyl ether/air jet flames Citation Details In-Document Search This content will become publicly available on November 10, 2016 Title: Scalar structure of turbulent partially-premixed dimethyl ether/air jet flames Authors: Fuest, F. ; Magnotti, G. ; Barlow, R. S. ; Sutton, J. A. Publication Date: 2015-01-01 OSTI Identifier: 1251746 Grant/Contract Number: SC0001198 Type: Publisher's Accepted

  14. U.S. Oxygenate Production

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

    By: Product Area May-15 Jun-15 Jul-15 Aug-15 Sep-15 Oct-15 View History Fuel Ethanol 29,666 29,684 30,256 29,621 28,543 30,139 1981-2015 Methyl Tertiary Butyl Ether (MTBE) 1,634...

  15. Petroleum Supply Annual

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

    ... amyl methyl ether (TAME), tertiary butyl alcohol (TBA), and other aliphatic alcohols and ... amyl methyl ether (TAME), tertiary butyl alcohol (TBA), and other aliphatic alcohols and ...

  16. Alcohol fuel from Ohio farms

    SciTech Connect (OSTI)

    Jones, J.D.

    1984-01-01

    This booklet provides an introduction to technical, marketing, and regulatory issues involved in on-farm alcohol fuel production. Discussed are ethanol production provcesses, investment, potential returns, regulations and permits, and sources of financial and technical assistance. 2 figures. (DMC)

  17. 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.

  18. 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.

  19. Optical oxygen concentration monitor

    DOE Patents [OSTI]

    Kebabian, P.

    1997-07-22

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

  20. Mixed Alcohol Synthesis Catalyst Screening

    SciTech Connect (OSTI)

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

    2007-09-03

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

  1. Monolithic solid electrolyte oxygen pump

    DOE Patents [OSTI]

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

    1989-01-01

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

  2. 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.

  3. Optical oxygen concentration monitor

    DOE Patents [OSTI]

    Kebabian, Paul

    1997-01-01

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

  4. 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...

  5. 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...

  6. Direct Observation of the Oxygenated Species during Oxygen Reduction...

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

    Direct Observation of the Oxygenated Species during Oxygen Reduction on a Platinum Fuel Cell Cathode Friday, December 20, 2013 Fuel Cell Figure 1 Figure 1. In situ x-ray ...

  7. High pressure oxygen furnace

    DOE Patents [OSTI]

    Morris, Donald E.

    1992-01-01

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

  8. High pressure oxygen furnace

    DOE Patents [OSTI]

    Morris, D.E.

    1992-07-14

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

  9. Oxygen Transport Ceramic Membranes

    SciTech Connect (OSTI)

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

    2005-08-01

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

  10. Oxygen Transport Ceramic Membranes

    SciTech Connect (OSTI)

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

    2005-02-01

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

  11. Fuel cell oxygen electrode

    DOE Patents [OSTI]

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

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

  12. Fuel cell oxygen electrode

    DOE Patents [OSTI]

    Shanks, Howard R. (Ames, IA); Bevolo, Albert J. (Ames, IA); Danielson, Gordon C. (Ames, IA); Weber, Michael F. (Wichita, KS)

    1980-11-04

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

  13. 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.

  14. Alcohol Fuels - Combustion Energy Frontier Research Center

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

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

  15. 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.

  16. Oxygen Transport Membranes

    SciTech Connect (OSTI)

    S. Bandopadhyay

    2008-08-30

    The focus of this research was to develop new membrane materials by synthesizing different compounds and determining their defect structures, crystallographic structures and electrical properties. In addition to measuring electrical conductivity, oxygen vacancy concentration was also evaluated using thermogravimetry, Neutron diffraction and Moessbauer Spectroscopy. The reducing conditions (CO{sub 2}/CO/H{sub 2} gas mixtures with steam) as encountered in a reactor environment can be expected to have significant influence on the mechanical properties of the oxides membranes. Various La based materials with and without Ti were selected as candidate membrane materials for OTM. The maximum electrical conductivity of LSF in air as a function of temperature was achieved at < 600 C and depends on the concentration of Sr (acceptor dopant). Oxygen occupancy in LSF was estimated using Neutron diffractometry and Moessbauer Spectroscopy by measuring magnetic moment changes depending on the Fe{sup 3+} and Fe{sup 4+} ratio. After extensive studies of candidate materials, lanthanum ferrites (LSF and LSFT) were selected as the favored materials for the oxygen transport membrane (OTM). LSF is a very good material for an OTM because of its high electronic and oxygen ionic conductivity if long term stability and mechanical strength are improved. LSFT not only exhibits p-type behavior in the high oxygen activity regime, but also has n-type conduction in reducing atmospheres. Higher concentrations of oxygen vacancies in the low oxygen activity regime may improve the performance of LSFT as an OTM. The hole concentration is related to the difference in the acceptor and donor concentration by the relation p = [Sr'{sub La}]-[Ti{sm_bullet}{sub Fe}]. The chemical formulation predicts that the hole concentration is, p = 0.8-0.45 or 0.35. Experimental measurements indicated that p is about {approx} 0.35. The activation energy of conduction is 0.2 eV which implies that LSCF conducts via the small polaron conduction mechanism. Scanning transmission electron microscopy (STEM) and electron energy loss spectroscopy (EELS) were used to develop strategies to detect and characterize vacancy creation, dopant segregations and defect association in the oxygen conducting membrane material. The pO{sub 2} and temperature dependence of the conductivity, non-stoichiometry and thermal-expansion behavior of compositions with increasing complexity of substitution on the perovskite A and B sites were studied. Studies with the perovskite structure show anomalous behavior at low oxygen partial pressures (<10{sup -5} atm). The anomalies are due to non-equilibrium effects and can be avoided by using very strict criteria for the attainment of equilibrium. The slowness of the oxygen equilibration kinetics arises from two different mechanisms. In the first, a two phase region occurs between an oxygen vacancy ordered phase such as brownmillerite SrFeO{sub 2.5} and perovskite SrFeO{sub 3-x}. The slow kinetics is associated with crossing the two phase region. The width of the miscibility gap decreases with increasing temperature and consequently the effect is less pronounced at higher temperature. The preferred kinetic pathway to reduction of perovskite ferrites when the vacancy concentration corresponds to the formation of significant concentrations of Fe{sup 2+} is via the formation of a Ruddlesden-Popper (RP) phases as clearly observed in the case of La{sub 0.5}Sr{sub 0.5}FeO{sub 3-x} where LaSrFeO{sub 4} is found together with Fe. In more complex compositions, such as LSFTO, iron or iron rich phases are observed locally with no evidence for the presence of discrete RP phase. Fracture strength of tubular perovskite membranes was determined in air and in reducing atmospheric conditions. The strength of the membrane decreased with temperature and severity of reducing conditions although the strength distribution (Weibull parameter, m) was relatively unaltered. Surface and volume dominated the fracture origins and the overall fracture was purely transgranular. The dual phase membranes have been evaluated for structural properties. An increasing crack growth resistance was observed for the membranes heat-treated at 1000 C in air and N{sub 2} with increasing crack length. The combined effect of thermal and elastic mismatch stresses on the crack path was studied and the fracture behavior of the dual phase composite at the test conditions was analyzed. Ceramic/metal (C/M) seals are needed to form a leak-tight interface between the OTM and a nickel-base super alloy. It was concluded that Ni-based brazing alloys provided the best option in terms of brazing temperature and final operating conditions after analyzing several possible brazing systems. A mechanical testing procedure has been developed. This model was tested with model ceramic/metal systems but it is expected to be useful for testing concentric perovskite/metal seals.

  17. Oxygen Transport Ceramic Membranes

    SciTech Connect (OSTI)

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

    2005-02-01

    The present quarterly report describes some of the investigations on the structural properties of dense OTM bars provided by Praxair and studies on newer composition of Ti doped LSF. Thermogravimetric analysis (TGA) was carried out on La{sub 0.2}Sr{sub 0.8}Fe{sub 0.55}Ti{sub 0.45}O{sub 3-{delta}} to investigate oxygen deficiency ({delta}) of the sample. The TGA was performed in a controlled atmosphere using oxygen, argon, carbon monoxide and carbon dioxide with adjustable gas flow rates. In this experiment, the weight loss and gain of La{sub 0.2}Sr{sub 0.8}Fe{sub 0.55}Ti{sub 0.45}O{sub 3-{delta}} was directly measured by TGA. The weight change of the sample was evaluated at between 600 and 1250 C in air or 1000 C as a function of oxygen partial pressure. The oxygen deficiencies calculated from TGA data as a function of oxygen activity and temperature will be estimated and compared with that from neutron diffraction measurement in air. The LSFT and LSFT/CGO membranes were fabricated from the powder obtained from Praxair Specialty Ceramics. The sintered membranes were subjected to microstructure analysis and hardness analysis. The LSFT membrane is composed of fine grains with two kinds of grain morphology. The grain size distribution was characterized using image analysis. In LSFT/CGO membrane a lot of grain pullout was observed from the less dense, porous phase. The hardness of the LSFT and dual phase membranes were studied at various loads. The hardness values obtained from the cross section of the membranes were also compared to that of the values obtained from the surface. An electrochemical cell has been designed and built for measurements of the Seebeck coefficient as a function of temperature and pressure. Measurements on La{sub 0.2}Sr{sub 0.8}Fe{sub 0.55}Ti{sub 0.45}O{sub 3-{delta}} as a function of temperature an oxygen partial pressure are reported. Further analysis of the dilatometry data obtained previously is presented. A series of isotope transients under air separation mode (small gradient) were completed on the membrane of LSCrF-2828 at 900 C. Low pO{sub 2} atmospheres based on with CO-CO{sub 2} mixtures have also been admitted to the delivery side of the LSCrF-2828 membrane to produce the gradients which exist under syngas generation conditions. The CO-CO{sub 2} mixtures have normal isotopic {sup 18}O abundances. The evolution of {sup 18}O on the delivery side in these experiments after an {sup 18}O pulse on the air side reveals a wealth of information about the oxygen transport processes.

  18. Mechanisms of Selective Cleavage of C-O Bonds in Di-aryl Ethers in Aqueous Phase

    SciTech Connect (OSTI)

    He, Jiayue; Zhao, Chen; Mei, Donghai; Lercher, Johannes A.

    2014-01-02

    A novel route for cleaving the C-O aryl ether bonds of p-substituted H-, CH3-, and OH- diphenyl ethers has been explored over Ni/SiO2 catalysts at very mild conditions. The C-O bond of diphenyl ether is cleaved by parallel hydrogenolysis and hydrolysis (hydrogenolysis combined with HO* addition) on Ni. The rates as a function of H2 pressure from 0 to 10 MPa indicate that the rate-determining step is the C-O bond cleavage on Ni. H* atoms compete with the organic reactant for adsorption leading to a maximum in the rate with increasing H2 pressure. In contrast to diphenyl ether, hydrogenolysis is the exclusive route for cleaving an ether C-O bond of di-p-tolyl ether to form p-cresol and toluene. 4,4'-dihydroxydiphenyl ether undergoes sequential surface hydrogenolysis, first to phenol and HOC6H4O* (adsorbed), which is then cleaved to phenol (C6H5O* with added H*) and H2O (O* with two added H*) in a second step. Density function theory supports the operation of this pathway. Notably, addition of H* to HOC6H4O* is less favorable than a further hydrogenolytic C-O bond cleavage. The TOFs of three aryl ethers with Ni/SiO2 in water followed the order 4,4'-dihydroxydiphenyl ether (69 h-1) > diphenyl ether (26 h-1) > di-p-tolyl ether (1.3 h-1), in line with the increasing apparent activation energies, ranging from 93 kJ∙mol-1 (4,4'-dihydroxydiphenyl ether) < diphenyl ether (98 kJ∙mol-1) to di-p-tolyl ether (105 kJ∙mol-1). D.M. thanks the support from the US Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences & Biosciences. Pacific Northwest National Laboratory (PNNL) is a multiprogram national laboratory operated for DOE by Battelle. Computing time was granted by the grand challenge of computational catalysis of the William R. Wiley Environmental Molecular Sciences Laboratory (EMSL) and by the National Energy Research Scientific Computing Center (NERSC). EMSL is a national scientific user facility located at Pacific Northwest National Laboratory (PNNL) and sponsored by DOE’s Office of Biological and Environmental Research.

  19. 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.

  20. 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.

  1. Composite oxygen transport membrane

    SciTech Connect (OSTI)

    Christie, Gervase Maxwell; Lane, Jonathan A.

    2014-08-05

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

  2. OXYGEN TRANSPORT CERAMIC MEMBRANES

    SciTech Connect (OSTI)

    Dr. Sukumar Bandopadhyay; Dr. Nagendra Nagabhushana

    2000-10-01

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

  3. Conversion of Mixed Oxygenates Generated from Synthesis Gas to Fuel Range Hydrocarbon

    SciTech Connect (OSTI)

    Ramasamy, Karthikeyan K.; Gerber, Mark A.; Lilga, Michael A.; Flake, Matthew D.

    2012-08-19

    The growing dependence in the U.S. on foreign crude oil supplies and increased concerns regarding greenhouse gas emission has generated considerable interest in research to develop renewable and environmentally friendly liquid hydrocarbon transportation fuels. One of the strategies for achieving this is to produce intermediate compounds such as alcohols and other simple oxygenates from biomass generated synthesis gas (mixture of carbon monoxide and hydrogen) and further convert them into liquid hydrocarbons. The focus of this research is to investigate the effects of mixed oxygenates intermediate product compositions on the conversion step to produce hydrocarbon liquids. A typical mixed oxygenate stream is expected to contain water (around 50%), alcohols, such as methanol and ethanol (around 35%), and smaller quantities of oxygenates such as acetaldehyde, acetic acid and ethyl acetate. However the ratio and the composition of the mixed oxygenate stream generated from synthesis gas vary significantly depending on the catalyst used and the process conditions. Zeolite catalyzed deoxygenation of methanol accompanied by chain growth is well understood under Methanol-to-Gasoline (MTG) like reaction conditions using an H-ZSM-5 zeolite as the catalyst6-8. Research has also been conducted to a limited extent in the past with higher alcohols, but not with other oxygenates present9-11. Also there has been little experimental investigation into mixtures containing substantial amounts of water. The latter is of particular interest because water separation from the hydrocarbon product would be less energy intensive than first removing it from the oxygenate intermediate stream prior to hydrocarbon synthesis, potentially reducing overall processing costs.

  4. High Selectivity Oxygen Delignification

    SciTech Connect (OSTI)

    Arthur J. Ragauskas Lucian A. Lucia Hasan Jameel

    2005-09-30

    The overall objective of this program was to develop improved extended oxygen delignification (EOD) technologies for current U.S. pulp mill operations. This was accomplished by: (1) Identifying pulping conditions that optimize O and OO performance; (2) Identifying structural features of lignin that enhance reactivity towards EOD of high kappa pulps; (3) Identifying factors minimizing carbohydrate degradation and improve pulp strength of EOD high kappa pulps; (4) Developing a simple, reproducible method of quantifying yield gains from EOD; and (5) Developing process conditions that significantly reduce the capital requirements of EOD while optimizing the yield benefits. Key research outcomes included, demonstrating the use of a mini-O sequence such as (E+O)Dkf:0.05(E+O) or Dkf:0.05(E+O)(E+O) without interstage washing could capture approximately 60% of the delignification efficiency of a conventional O-stage without the major capital requirements associated with an O-stage for conventional SW kraft pulps. The rate of formation and loss of fiber charge during an O-stage stage can be employed to maximize net fiber charge. Optimal fiber charge development and delignification are two independent parameters and do not parallel each other. It is possible to utilize an O-stage to enhance overall cellulosic fiber charge of low and high kappa SW kraft pulps which is beneficial for physical strength properties. The application of NIR and multi-variant analysis was developed into a rapid and simple method of determining the yield of pulp from an oxygen delignification stage that has real-world mill applications. A focus point of this program was the demonstration that Kraft pulping conditions and oxygen delignification of high and low-kappa SW and HW pulps are intimately related. Improved physical pulp properties and yield can be delivered by controlling the H-factor and active alkali charge. Low AA softwood kraft pulp with a kappa number 30 has an average improvement of 2% in yield and 4 cP in viscosity in comparison to high AA pulp for the oxygen delignification. This difference is also seen for high-kappa SW kraft pulps with an average improvement of {approx}3% in yield and 3 cP in viscosity for low AA high kappa number 50 pulp. Low AA hardwood kappa number 20 pulp had an average improvement of {approx}4% in yield and 6-12 cP in viscosity as compared to high AA pulp. Lower kraft cooking temperature (160 vs. 170 C) in combination with the medium AA provides a practical approach for integrating high kappa pulping of hardwoods (i.e., low rejects) with an advanced extended oxygen delignification stage. ECF pulp bleaching of low and high kappa kraft SW and HW pulps exhibit comparable optical and physical strength properties when bleached D(EPO)D.

  5. Catalyst for producing lower alcohols

    DOE Patents [OSTI]

    Rathke, Jerome W.; Klingler, Robert J.; Heiberger, John J.

    1987-01-01

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

  6. Contiguous Platinum Monolayer Oxygen Reduction Electrocatalysts...

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

    Contiguous Platinum Monolayer Oxygen Reduction Electrocatalysts on High-Stability-Low-Cost Supports Contiguous Platinum Monolayer Oxygen Reduction Electrocatalysts on...

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

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

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

  8. Oxygen Transport Ceramic Membranes

    SciTech Connect (OSTI)

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

    2004-05-01

    The present quarterly report describes some of the investigations on the structural properties of dense OTM bars provided by Praxair and studies on newer composition of Ti doped LSF. In this report, in situ neutron diffraction was used to characterize the chemical and structural properties of La{sub 0.2}Sr{sub 0.8}Fe{sub 0.55}Ti{sub 0.45}O{sub 3-{delta}} (here after as L2SF55T) specimen, which was subject to measurements of neutron diffraction from room temperature to 900 C. It was found that space group of R3c yielded a better refinement than a cubic structure of Pm3m. Oxygen occupancy was nearly 3 in the region from room temperature to 700 C, above which the occupancy decreased due to oxygen loss. Dense OTM bars provided by Praxair were loaded to fracture at varying stress rates. Studies were done at room temperature in air and at 1000 C in a specified environment to evaluate slow crack growth behavior. The X-Ray data and fracture mechanisms points to non-equilibrium decomposition of the LSFCO OTM membrane. The non-equilibrium conditions could probably be due to the nature of the applied stress field (stressing rates) and leads to transition in crystal structures and increased kinetics of decomposition. The formations of a Brownmillerite or Sr2Fe2O5 type structures, which are orthorhombic are attributed to the ordering of oxygen vacancies. The cubic to orthorhombic transitions leads to 2.6% increase in strains and thus residual stresses generated could influence the fracture behavior of the OTM membrane. Continued investigations on the thermodynamic properties (stability and phase-separation behavior) and total conductivity of prototype membrane materials were carried out. The data are needed together with the kinetic information to develop a complete model for the membrane transport. Previously characterization, stoichiometry and conductivity measurements for samples of La{sub 0.2}Sr{sub 0.8}Fe{sub 0.55}Ti{sub 0.45}O{sub 3-{delta}} were reported. In this report, measurements of the chemical and thermal expansion as a function of temperature and p{sub O2} are described.

  9. SUPPORTED DENSE CERAMIC MEMBRANES FOR OXYGEN SEPARATION

    SciTech Connect (OSTI)

    Timothy L. Ward

    2002-07-01

    Mixed-conducting ceramics have the ability to conduct oxygen with perfect selectivity at elevated temperatures, making them extremely attractive as membrane materials for oxygen separation and membrane reactor applications. While the conductivity of these materials can be quite high at elevated temperatures (typically 800-1000 C), much higher oxygen fluxes, or, alternatively, equivalent fluxes at lower temperatures, could be provided by supported thin or thick film membrane layers. Based on that motivation, the objective of this project was to explore the use of ultrafine aerosol-derived powder of a mixed-conducting ceramic material for fabrication of supported thick-film dense membranes. The project focused on the mixed-conducting ceramic composition SrCo{sub 0.5}FeO{sub x} (SCFO) because of the desirable permeability and stability of that material, as reported in the literature. Appropriate conditions to produce the submicron SrCo{sub 0.5}FeO{sub x} powder using aerosol pyrolysis were determined. Porous supports of the same composition were produced by partial sintering of a commercially obtained powder that possessed significantly larger particle size than the aerosol-derived powder. The effects of sintering conditions (temperature, atmosphere) on the porosity and microstructure of the porous discs were studied, and a standard support fabrication procedure was adopted. Subsequently, a variety of paste and slurry formulations were explored utilizing the aerosol-derived SCFO powder. These formulations were applied to the porous SCFO support by a doctor blade or spin coating procedure. Sintering of the supported membrane layer was then conducted, and additional layers were deposited and sintered in some cases. The primary characterization methods were X-ray diffraction and scanning electron microscopy, and room-temperature nitrogen permeation was used to assess defect status of the membranes.We found that non-aqueous paste/slurry formulations incorporating dispersant, plasticizer and binder provided superior cracking resistance compared to simple water, alcohol, or polyethylene glycol (PEG) based formulations. With a formulation employing castor oil as dispersant, isopropyl alcohol/mineral spirits as solvent, polyvinyl butyral as binder, and dibutyl phthalate/PEG as plasticizer, sintered SCFO membrane layers approximately 5 {micro}m thick with no apparent cracks were prepared using spin coating with several coats and sintering cycles. A similar but more viscous formulation applied by doctor blade gave a {approx} 10 {micro}m thick membrane layer in one coat, but with some apparent cracking. We demonstrated that the membrane layer could be densified while retaining porosity in the chemically identical support. This was accomplished by pre-sintering the support in air (1050 C), which coarsened the grain size and provided a relatively stable plate-shaped granular microstructure, followed by membrane layer fabrication with the highly-sinterable aerosol powder. Final densification was conducted by sintering in nitrogen ({approx}1100 C), which provided accelerated sintering rates and led to the desired layered perovskite phase content. In spite of these successes, low-temperature pressure-driven permeation testing with N2 showed that even the best membranes were not sufficiently defect free for high-temperature oxygen permeation testing. The source of these defects were not readily apparent from scanning electron microscopy, though incomplete or nonuniform membrane layer coverage from edge to edge of the support was probably one important factor.

  10. Oxygen-reducing catalyst layer

    DOE Patents [OSTI]

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

    2011-03-22

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

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

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

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

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

    SciTech Connect (OSTI)

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

    2008-12-08

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

  13. Oxygen Transport Ceramic Membranes

    SciTech Connect (OSTI)

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

    2004-10-01

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

  14. Oxygen Transport Ceramic Membranes

    SciTech Connect (OSTI)

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

    2004-02-01

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

  15. Oxygen detection using evanescent fields

    DOE Patents [OSTI]

    Duan, Yixiang; Cao, Weenqing

    2007-08-28

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

  16. Formation of alcohol conversion catalysts

    DOE Patents [OSTI]

    Wachs, Israel E.; Cai, Yeping

    2001-01-01

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

  17. Pressure dispensable gelled alcohol fuel

    SciTech Connect (OSTI)

    Monick, J.A.

    1982-12-28

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

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

    DOE Patents [OSTI]

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

    2001-09-18

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

  19. The effect of catalyst ratio on catalytic performance in liquid phase dimethyl ether process

    SciTech Connect (OSTI)

    Guo Junwang; Niu Yuqin; Zhang Bijiang

    1997-12-31

    In the liquid phase dimethyl ether (LPDME) process, two functionally different catalysts are slurried together in an inert liquid medium. Syngas reacts on the surface of the methanol catalyst and methanol is dehydrated on the surface of the dehydration catalyst dispersed in the liquid. The process is adaptable to carbon monoxide-rich syngas derived from second generation coal gasifiers. The effect of catalyst ratio on catalytic performances of the dual catalyst was studied in liquid phase dimethyl ether synthesis from syngas at 280 C, 4.0 MPa. CO conversion, H{sub 2} conversion and DME productivity increased with an increase of catalyst ratio initially, reached their maximum at a catalyst ratio of 4.0--5.0, and then decreased. Methanol productivity and methanol equivalent productivity had a similar trend to that of DME productivity. DME selectivity and hydrocarbon selectivity increased with an increase in catalyst ratio whereas methanol selectivity decreased with catalyst ratio.

  20. 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.

  1. 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

  2. Oxygen Transport Ceramic Membranes

    SciTech Connect (OSTI)

    S. Bandopadhyay; N. Nagabhushana

    2003-08-07

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

  3. Oxygen Transport Ceramic Membranes

    SciTech Connect (OSTI)

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

    2005-11-01

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

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

    SciTech Connect (OSTI)

    Wallner, T.

    2011-08-01

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

  5. 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; Sztáray, Bálint

    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 9–14 eV photon energy range. Multiple isomers of neutral dimethyl ether dimer were considered, all of which may be present, and exhibited varying C–H⋯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.

  6. Production of alcohol from apple pomace

    SciTech Connect (OSTI)

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

    1981-12-01

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

  7. Process for the synthesis of unsaturated alcohols

    DOE Patents [OSTI]

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

    2007-02-13

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

  8. STEP 1: TO BE COMPLETED BY ALCOHOL TECHNICIAN

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

    Human Reliability Program (HRP) Alcohol Testing Form (Instructions for completing this form are attached.) STEP 1: TO BE COMPLETED BY ALCOHOL TECHNICIAN A. Employee Name ...

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

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

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

  10. Jilin Fuel Alcohol Company Ltd | Open Energy Information

    Open Energy Info (EERE)

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

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

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

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

  12. Oxygen Transport Ceramic Membranes

    SciTech Connect (OSTI)

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

    2003-11-01

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

  13. A lithium oxygen secondary battery

    SciTech Connect (OSTI)

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

    1987-08-01

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

  14. Oxygen Transport Ceramic Membranes

    SciTech Connect (OSTI)

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

    2004-05-01

    The present quarterly report describes some of the investigations on the structural properties of dense OTM bars provided by Praxair and studies on newer composition of Ti doped LSF. In this report, in situ neutron diffraction was used to characterize the chemical and structural properties of La{sub 0.2}Sr{sub 0.8}Fe{sub 0.55}Ti{sub 0.45}O{sub 3-{delta}} (here after as L2SF55T) specimen, which was subject to measurements of neutron diffraction from room temperature to 900 C in N{sub 2}. Space group of R3c was found to result in a better refinement and is used in this study. The difference for crystal structure, lattice parameters and local crystal chemistry for LSFT nearly unchanged when gas environment switched from air to N{sub 2}. Stable crack growth studies on Dense OTM bars provided by Praxair were done at room temperature in air. A bridge-compression fixture was fabricated to achieve stable pre-cracks from Vickers indents. Post fracture evaluation indicated stable crack growth from the indent and a regime of fast fracture. Post-fracture X-ray data of the OTM fractured at 1000 C in environment were refined by FullProf code and results indicate a distortion of the parent cubic perovskite to orthorhombic structure with reduced symmetry. TGA-DTA studies on the post-fracture samples also indicated residual effect arising from the thermal and stress history of the samples. The thermal and chemical expansion of La{sub 0.2}Sr{sub 0.8}Fe{sub 0.55}Ti{sub 0.45}O{sub 3-{delta}} were studied at 800 {le} T {le} 1000 C and at {approx} 1 x 10{sup -15} {le} pO{sub 2} {le} 0.21 atm. The thermal expansion coefficient of the sample was calculated from the dilatometric analysis in the temperature range between room temperature and 1200 C in air. A series of isotope transients under air separation mode (small gradient) were completed on the membrane of LSCrF-2828 at 900 C. Low pO{sub 2} atmospheres based on with CO-CO{sub 2} mixtures have also been admitted to the delivery side of the LSCrF-2828 membrane to produce the gradients which exist under syngas generation conditions. The CO-CO{sub 2} mixtures have normal isotopic {sup 18}O abundances. The evolution of {sup 18}O on the delivery side in these experiments after an {sup 18}O pulse on the air side reveals a wealth of information about the oxygen transport processes.

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

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

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

  16. Preparation and characterization of polymer blend based on sulfonated poly (ether ether ketone) and polyetherimide (SPEEK/PEI) as proton exchange membranes for fuel cells

    SciTech Connect (OSTI)

    Hashim, Nordiana; Ali, Ab Malik Marwan; Lepit, Ajis; Rasmidi, Rosfayanti; Subban, Ri Hanum Yahaya; Yahya, Muhd Zu Azhan

    2015-08-28

    Blends of sulfonated poly (ether ether ketone) (SPEEK) and polyetherimide (PEI) were prepared in five different weight ratios using N-methyl-2-pyrrolidone (NMP) as solvent by the solution cast technique. The degree of sulfonation (DS) of the sulfonated PEEK was determined from deuterated dimethyl sulfoxide (DMSO-d{sub 6}) solution of the purified polymer using {sup 1}H NMR method. The properties studied in the present investigation includes conductivity, water uptake, thermal stability and structure analysis of pure SPEEK as well as SPEEK-PEI polymer blend membranes. The experimental results show that the conductivity of the membranes increased with increase in temperature from 30 to 80°C, except for that of pure SPEEK membrane which increased with temperature from 30 to 60°C while its conductivity decreased with increasing temperature from 60 to 80°C. The conductivity of 70wt.%SPEEK-30wt.%PEI blend membrane at 80% relative humidity (RH) is found to be 1.361 × 10{sup −3} Scm{sup −1} at 30°C and 3.383 × 10{sup −3} Scm{sup −1} at 80°C respectively. It was also found that water uptake and thermal stability of the membranes slightly improved upon blending with PEI. Structure analysis was carried out using Fourier Transform Infrared (FTIR) spectroscopy which revealed considerable interactions between sulfonic acid group of SPEEK and imide groups of PEI. Modification of SPEEK by blending with PEI shows good potential for improving the electrical and physical properties of proton exchange membranes.

  17. Oxygen Transport Ceramic Membranes

    SciTech Connect (OSTI)

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

    2005-05-01

    The present quarterly report describes some of the investigations on the structural properties of dense OTM bars provided by Praxair and studies on newer composition of Ti doped Ti-substituted perovskites, La{sub 0.7}Sr{sub 0.3}Mn{sub 1-x}Ti{sub x}O{sub 3}, with 0 {le} x {le} 0.20, were investigated by neutron diffraction, magnetization, electric resistivity, and magnetoresistance (MR) measurements. All samples show a rhombohedral structure (space group R3C) from 10 K to room temperature. At room temperature, the cell parameters a, c and the unit cell volume increase with increasing Ti content. However, at 10 K, the cell parameter a has a maximum value for x = 0.10, and decreases for x > 0.10, while the unit cell volume remains nearly constant for x > 0.10. The average (Mn,Ti)-O bond length increases up to x = 0.15, and the (Mn,Ti)-O-(Mn,Ti) bond angle decreases with increasing Ti content to its minimum value at x = 0.15 at room temperature. Below the Curie temperature TC, the resistance exhibits metallic behavior for the x {le} 0.05 samples. A metal (semiconductor) to insulator transition is observed for the x {ge} 0.10 samples. A peak in resistivity appears below TC for all samples, and shifts to a lower temperature as x increases. The substitution of Mn by Ti decreases the 2p-3d hybridization between O and Mn ions, reduces the bandwidth W, and increases the electron-phonon coupling. Therefore, the TC shifts to a lower temperature and the resistivity increases with increasing Ti content. A field-induced shift of the resistivity maximum occurs at x {le} 0.10 compounds. The maximum MR effect is about 70% for La{sub 0.7}Sr{sub 0.3}Mn{sub 0.8}Ti{sub 0.2}O{sub 3}. The separation of TC and the resistivity maximum temperature T{sub {rho},max} enhances the MR effect in these compounds due to the weak coupling between the magnetic ordering and the resistivity as compared with La{sub 0.7}Sr{sub 0.3}MnO{sub 3}. The bulk densities of the membranes were determined using the Archimedes method. The bulk density was 5.029 and 5.57 g/cc for LSFT and dual phase membranes, respectively. The microstructure of the dual phase membrane was analyzed using SEM. It is evident from the micrograph that the microstructure is composed of dual phases. The dense circular regions are enclosed by the less dense, continuous phase which accommodates most of the pores. The pores are normally aggregated and found clustered along the dense regions where as the dense regions do not have pores. Upon closer observation of the micrograph it is revealed that the dense region has a clear circular cleavage or crack as their boundary. The circular cleavage clearly encompasses a dense region and which consists of no pore or any flaw that is visible. The size distribution of the dense, discontinuous regions is varying from 5 to 20 {micro}m with a D{sub 50} of 15 {micro}m. The grain size distribution was estimated from the micrographs using image analysis and a unimodal distribution of grains was observed with an average grain size of 1.99 {micro}m. The chemical compositions of the membranes were analyzed using EDS analysis and no other impurities were observed. The XRD analysis was carried out for the membranes and the phase purity was confirmed. The fracture toughness of LSFT membranes at room temperature has to be calculated using the Vickers indentation method. An electrochemical cell has been designed and built for measurements of the ionic conductivity by the use of blocking electrodes. Preliminary measurements on La{sub 0.2}Sr{sub 0.8}Fe{sub 0.55}Ti{sub 0.45}O{sub 3-{delta}} are reported. Modifications to the apparatus to improve the data quality have been completed. Electron microscopy studies of the origin of the slow kinetics on reduction of ferrites have been initiated. A series of isotope transients under air separation mode (small gradient) were completed on the membrane of LSCrF-2828 at 900 C. Low pO{sub 2} atmospheres based on with CO-CO{sub 2} mixtures have also been admitted to the delivery side of the LSCrF-2828 membrane to produce the gradients which exist under syngas generation conditions. The CO-CO{sub 2} mixtures have normal isotopic {sup 18}O abundances. The evolution of {sup 18}O on the delivery side in these experiments after an {sup 18}O pulse on the air side reveals a wealth of information about the oxygen transport processes.

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

    SciTech Connect (OSTI)

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

    2006-10-12

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

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

    DOE Patents [OSTI]

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

    2013-08-27

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

  20. 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.

  1. Alcohol injection cuts diesel consumption on turbocharged tractors

    SciTech Connect (OSTI)

    Edson, D.V.

    1980-07-21

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

  2. Third international symposium on alcohol fuels technology

    SciTech Connect (OSTI)

    1980-04-01

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

  3. 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.

  4. 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.

  5. dimethyl ether

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

    Predictive Simulation of Engines Transportation Energy Consortiums Engine Combustion ... Schematic representation of the experimental set-up. Shown in the figure is the jet-stirre...

  6. Methods for separating oxygen from oxygen-containing gases

    DOE Patents [OSTI]

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

    2000-01-01

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

  7. Hydrogen bond dynamics in bulk alcohols

    SciTech Connect (OSTI)

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

    2015-06-07

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

  8. Composite oxygen ion transport element

    DOE Patents [OSTI]

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

    2007-06-12

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

  9. Catalyst containing oxygen transport membrane

    DOE Patents [OSTI]

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

    2012-12-04

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

  10. Degradation of Imidazolium- and Quaternary Ammonium-Functionalized Poly(fluorenyl ether ketone sulfone) Anion Exchange Membranes

    SciTech Connect (OSTI)

    Chen, DY; Hickner, MA

    2012-11-01

    Imidazolium and quaternary ammonium-functionalized poly(fluorenyl ether ketone sulfone)s were synthesized successfully with the same degree of cationic functionalization and identical polymer backbones for a comparative study of anion exchange membranes (AEMs) for solid-state alkaline membrane fuel cells (AMFCs). Both anion exchange membranes were synthesized using a new methyl-containing monomer that avoided the use of toxic chloromethylation reagents. The polymer chemical structures were confirmed by H-1 NMR and FTIR. The derived AEMs were fully characterized by water uptake, anion conductivity, stability under aqueous basic conditions, and thermal stability. Interestingly, both the cationic groups and the polymer backbone were found to be degraded in 1 M NaOH solution at 60 degrees C over 48 h as measured by changes of ion exchange capacity and intrinsic viscosity. Imidazolium-functionalized poly(fluorenyl ether ketone sulfone)s had similar aqueous alkaline stability to quaternary ammonium-functionalized materials at 60 degrees C but much lower stability at 80 degrees C. This work demonstrates that quaternary ammonium and imidazolium cationic groups are not stable on poly(arylene ether sulfone) backbones under relatively mild conditions. Additionally, the poly(arylene ether sulfone) backbone, which is one of the most common polymers used in ion exchange membrane applications, is not stable in the types of molecular configurations analyzed.

  11. Alcohol Fuels Program technical review, Spring 1984

    SciTech Connect (OSTI)

    Not Available

    1984-10-01

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

  12. Fuel alcohol: the road to independence

    SciTech Connect (OSTI)

    Stull, C.B.

    1982-01-01

    This report describes the production of ethanol using an on-farm fuel alcohol still. Directions are given in lay-language, easily understandable to novices in the field of fermentation. Preparation of the mash, fermentation, and distillation are discussed along with some basic background information on these processes. The design and construction of the still is presented. Off-the-shelf equipment was used in the construction. Vats, pumps, and testing equipment used in the processing are described. Diagrams and a glossary are included. The alcohol produced is used for space heating of a house and greenhouse. (DMC)

  13. Improved fermentative alcohol production. [Patent application

    DOE Patents [OSTI]

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

    1980-11-26

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

  14. Mixed ether electrolytes for secondary lithium batteries with improved low temperature performance

    SciTech Connect (OSTI)

    Abraham, K.M.; Pasquariello, D.M.; Martin, F.J.

    1986-04-01

    Tetrahydrofuran (THF): 2-methyl-tetrahydrofuran (2Me-THF)/LiAsF/sub 6/ mixed solutions, despite their lower conductivity, have allowed significantly better low temperature performance in Li/TiS/sub 2/ cells than have THF/LiAsF/sub 6/, /sup 13/C NMR data suggest that this may be related to the structurally disordered Li/sup +/-solvates that exist in the mixed ether solutions. High cycling efficiencies for the Li electrode in THF:2Me-THF/LiAsF/sub 6/ solutions have been achieved by the use of 2Me-F as an additive. A 5 Ah capacity Li/TiS/sub 2/ cell has been cycled more than 100 times at 100, depth-of-discharge, with the cell capacity remaining at over 3 Ah at the 100th cycle.

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

    DOE Patents [OSTI]

    Peng, Xiang-Dong; Parris, Gene E.; Toseland, Bernard A.; Battavio, Paula J.

    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.

  16. 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.

  17. 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.

  18. 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.

  19. 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.

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

    DOE Patents [OSTI]

    Ross, David S.; Blessing, James E.

    1981-01-01

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

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

    SciTech Connect (OSTI)

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

    2014-09-10

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

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

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

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

  3. Farm alcohol fuel project. Final report

    SciTech Connect (OSTI)

    Demmel, D.

    1981-11-15

    The Small Energy Project is a research and demonstration effort designed to assist small farmers in the utilization of energy conservation techniques on their farms. The Farm Alcohol Project was designed to demonstrate the production of alcohol fuels on small farms in order to reduce purchased liquid fuel requirements. The Project considered the use of on-farm raw materials for process heat and the production of fuel grade, low prood ethanol in volumes up to 10,000 gallons per year. The fuel would be used entirely on the farm. The approach considered low-cost systems the farmer could build himself from local resources. Various crops were considered for ethanol production. The interest in farm alcohol production reached a peak in 1980 and then decreased substantially as farmers learned that the process of alcohol production on the farm was much more complicated than earlier anticipated. Details of Alcohol Project experiences in ethanol production, primarily from corn, are included in this report. A one-bushel distillation plant was constructed as a learning tool to demonstrate the production of ethanol. The report discusses the various options in starch conversion, fermentation and distillation that can be utilized. The advantages and disavantages of atmospheric and the more complicated process of vacuum distillation are evaluated. Larger farm plants are considered in the report, although no experience in operating such plants was gained through the Project. Various precautions and other considerations are included for farm plant designs. A larger community portable distillery is also evaluated. Such a plant was considered for servicing farms with limited plant equipment. The farms serviced would perform only fermentation tasks, with the portable device performing distillation and starch conversion.

  4. Comparing liquid fuel costs: grain alcohol versus sunflower oil

    SciTech Connect (OSTI)

    Reining, R.C.; Tyner, W.E.

    1983-08-01

    This paper compares the technical and economic feasibility of small-scale production of fuel grade grain alcohol with sunflower oil. Three scales of ethanol and sunflower oil production are modeled, and sensitivity analysis is conducted for various operating conditions and costs. The general conclusion is that sunflower oil costs less to produce than alcohol. Government subsidies for alcohol, but not sunflower oil, could cause adoption of more expensive alcohol in place of cheaper sunflower oil. However, neither sunflower oil nor alcohol are competitive with diesel fuel. 7 references.

  5. 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.

  6. Oxygen ion-beam microlithography

    DOE Patents [OSTI]

    Tsuo, Y.S.

    1991-08-20

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

  7. Device and method for separating oxygen isotopes

    DOE Patents [OSTI]

    Rockwood, Stephen D.; Sander, Robert K.

    1984-01-01

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

  8. 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.

  9. Limonene and tetrahydrofurfuryl alcohol cleaning agent

    DOE Patents [OSTI]

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

    1996-05-07

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

  10. Limonene and tetrahydrofurfurly alcohol cleaning agent

    DOE Patents [OSTI]

    Bohnert, George W.; Carter, Richard D.; Hand, Thomas E.; Powers, Michael T.

    1997-10-21

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

  11. Oil recovery by surfactant-alcohol waterflooding

    SciTech Connect (OSTI)

    Chen, C.S.; Luh, Y.

    1983-01-25

    Waterflooding process for the recovery of oil from a subterranean formation in which at least a portion of the injected water preferably comprises a preferentially oil-soluble alcohol, a sulfobetaine, a quaternary ammonium compound containing at least one long chain hydrocarbyl group and a quaternary ammonium compound with short chain hydrocarbyl groups. This formulation serves both as a surfactant and a mobility control agent.

  12. Limonene and tetrahydrofurfuryl alcohol cleaning agent

    DOE Patents [OSTI]

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

    1997-10-21

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

  13. Identification of an Archean marine oxygen oasis

    SciTech Connect (OSTI)

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

    2014-01-01

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

  14. Platinum Monolayer Electrocatalysts for Oxygen Reduction Reaction

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

    Platinum Monolayer Electrocatalysts for Oxygen Reduction Reaction Radoslav Adzic Co-workers: Jia Wang, Miomir Vukmirovic, Kotaro Sasaki, Stoyan Bliznakov, Yun Cai, Yu Zhang, ...

  15. Jupiter Oxygen Corporation | Open Energy Information

    Open Energy Info (EERE)

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

  16. DEVICE FOR CONTROL OF OXYGEN PARTIAL PRESSURE

    DOE Patents [OSTI]

    Bradner, H.; Gordon, H.S.

    1957-12-24

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

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

    SciTech Connect (OSTI)

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

    1994-09-01

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

  18. Catalyst Activity Comparison of Alcohols over Zeolites

    SciTech Connect (OSTI)

    Ramasamy, Karthikeyan K.; Wang, Yong

    2013-01-01

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

  19. 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

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. Electron momentum spectroscopy of dimethyl ether taking account of nuclear dynamics in the electronic ground state

    SciTech Connect (OSTI)

    Morini, Filippo; Deleuze, Michael Simon; Watanabe, Noboru; Kojima, Masataka; Takahashi, Masahiko

    2015-10-07

    The influence of nuclear dynamics in the electronic ground state on the (e,2e) momentum profiles of dimethyl ether has been analyzed using the harmonic analytical quantum mechanical and Born-Oppenheimer molecular dynamics approaches. In spite of fundamental methodological differences, results obtained with both approaches consistently demonstrate that molecular vibrations in the electronic ground state have a most appreciable influence on the momentum profiles associated to the 2b{sub 1}, 6a{sub 1}, 4b{sub 2}, and 1a{sub 2} orbitals. Taking this influence into account considerably improves the agreement between theoretical and newly obtained experimental momentum profiles, with improved statistical accuracy. Both approaches point out in particular the most appreciable role which is played by a few specific molecular vibrations of A{sub 1}, B{sub 1}, and B{sub 2} symmetries, which correspond to C–H stretching and H–C–H bending modes. In line with the Herzberg-Teller principle, the influence of these molecular vibrations on the computed momentum profiles can be unraveled from considerations on the symmetry characteristics of orbitals and their energy spacing.

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. Novel approaches to the production of higher alcohols from synthesis gas. Quarterly technical progress report No. 18, January 1, 1995-- March 31, 1995

    SciTech Connect (OSTI)

    1996-07-05

    A set of stirrer speed experiments using the Cu/ZnO methanol synthesis catalyst showed that introducing the gas feed into the reactor through an extended dip tube eliminated the dependency of catalyst performance on stirrer speed. The methanol productivity data from the reactor gas feed configuration tests conducted in December, 1994 and January, 1995, were correlated with stirrer speed. The influence on mass transfer on catalyst performance was clearly illustrated for each gas feed location. The ``high pressure, high temperature` zinc chromite methanol synthesis catalyst showed surprising activity at temperatures as low as 300{degree}C during the first successful stirred autoclave run with this catalyst. No C{sub 2{sup {plus}}} alcohols were detected, but significant levels of C{sub 2}-C{sub 4} olefins and dimethyl ether (DME) were produced. The presence of olefins suggests that higher alcohols might have formed and subsequently dehydrated. The slurry liquid, decahydronaphthalene, showed no evidence of decomposition during 15 days of continuous operation. 2 figs., 1 tab.

  10. New Oxygen-Production Technology Proving Successful

    Broader source: Energy.gov [DOE]

    The Office of Fossil Energy's National Energy Technology Laboratory has partnered with Air Products and Chemicals Inc. of Allentown, Penn. to develop the Ion Transport Membrane (ITM) Oxygen, a revolutionary new oxygen-production technology that requires less energy and offers lower capital costs than conventional technologies.

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

    DOE Patents [OSTI]

    Moore, Raymond H.; Eakin, David E.; Baker, Eddie G.; Hallen, Richard T.

    1991-01-01

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

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

    DOE Patents [OSTI]

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

    2016-03-08

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

  13. OXYGEN ENHANCED COMBUSTION FOR NOx CONTROL

    SciTech Connect (OSTI)

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

    2001-04-01

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

  14. Oxygen ion-conducting dense ceramic

    DOE Patents [OSTI]

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

    1997-01-01

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

  15. Oxygen ion-conducting dense ceramic

    DOE Patents [OSTI]

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

    1996-01-01

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

  16. Modelling Hydrogen Reduction and Hydrodeoxygenation of Oxygenates

    SciTech Connect (OSTI)

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

    2013-01-01

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

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

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

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

  18. An absolute calibration method of an ethyl alcohol biosensor...

    Office of Scientific and Technical Information (OSTI)

    biosensor based on wavelength-modulated differential photothermal radiometry Citation Details In-Document Search Title: An absolute calibration method of an ethyl alcohol biosensor ...

  19. Catalysts for Syngas-Derived Alcohol Synthesis - Energy Innovation...

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

    Return to Search Catalysts for Syngas-Derived Alcohol Synthesis Improves the conversion of syngas from natural gas, coal, or biomass National Energy Technology Laboratory Contact ...

  20. OXYGEN ENHANCED COMBUSTION FOR NOx CONTROL

    SciTech Connect (OSTI)

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

    2004-04-01

    Conventional wisdom says adding oxygen to a combustion system enhances product throughput, system efficiency, and, unless special care is taken, increases NOx emissions. This increase in NOx emissions is typically due to elevated flame temperatures associated with oxygen use leading to added thermal NOx formation. Innovative low flame temperature oxy-fuel burner designs have been developed and commercialized to minimize both thermal and fuel NOx formation for gas and oil fired industrial furnaces. To be effective these systems require close to 100% oxy-fuel combustion and the cost of oxygen is paid for by fuel savings and other benefits. For applications to coal-fired utility boilers at the current cost of oxygen, however, it is not economically feasible to use 100% oxygen for NOx control. In spite of this conventional wisdom, Praxair and its team members, in partnership with the US Department of Energy National Energy Technology Laboratory, have developed a novel way to use oxygen to reduce NOx emissions without resorting to complete oxy-fuel conversion. In this concept oxygen is added to the combustion process to enhance operation of a low NOx combustion system. Only a small fraction of combustion air is replaced with oxygen in the process. By selectively adding oxygen to a low NOx combustion system it is possible to reduce NOx emissions from nitrogen-containing fuels, including pulverized coal, while improving combustion characteristics such as unburned carbon. A combination of experimental work and modeling was used to define how well oxygen enhanced combustion could reduce NOx emissions. The results of this work suggest that small amounts of oxygen replacement can reduce the NOx emissions as compared to the air-alone system. NOx emissions significantly below 0.15 lbs/MMBtu were measured. Oxygen addition was also shown to reduce carbon in ash. Comparison of the costs of using oxygen for NOx control against competing technologies, such as SCR, show that this concept offers substantial savings over SCR and is an economically attractive alternative to purchasing NOx credits or installing other conventional technologies. In conjunction with the development of oxygen based low NOx technology, Praxair also worked on developing the economically enhancing oxygen transport membrane (OTM) technology which is ideally suited for integration with combustion systems to achieve further significant cost reductions and efficiency improvements. This OTM oxygen production technology is based on ceramic mixed conductor membranes that operate at high temperatures and can be operated in a pressure driven mode to separate oxygen with infinite selectivity and high flux. An OTM material was selected and characterized. OTM elements were successfully fabricated. A single tube OTM reactor was designed and assembled. Testing of dense OTM elements was conducted with promising oxygen flux results of 100% of target flux. However, based on current natural gas prices and stand-alone air separation processes, ceramic membranes do not offer an economic advantage for this application. Under a different DOE-NETL Cooperative Agreement, Praxair is continuing to develop oxygen transport membranes for the Advanced Boiler where the economics appear more attractive.

  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. Liver proteomics in progressive alcoholic steatosis

    SciTech Connect (OSTI)

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

    2013-02-01

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

  3. Electrocatalyst for alcohol oxidation in fuel cells

    DOE Patents [OSTI]

    Adzic, Radoslav R.; Marinkovic, Nebojsa S.

    2001-01-01

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

  4. Selective photooxidation of hydrocarbons in zeolites by oxygen

    DOE Patents [OSTI]

    Frei, Heinz; Blatter, Fritz; Sun, Hai

    1998-01-01

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

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

    SciTech Connect (OSTI)

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

    2012-11-01

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

  6. Petrochemical feedstock from basic oxygen steel furnace

    SciTech Connect (OSTI)

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

    1983-10-01

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

  7. Separation of Dimethyl Ether from Syn-Gas Components by Poly(dimethylsiloxane) and Poly(4-methyl-1-pentene) Membranes

    SciTech Connect (OSTI)

    Christopher J. Orme; Frederick F. Stewart

    2011-05-01

    Permeability and selectivity in gas transport through poly(4-methyl-1-pentene) (TPX) and poly(dimethylsiloxane) (PDMS) using variable temperature mixed gas experiments is reported. Selected gases include H2, CO, CH4, CO2, and dimethyl ether (DME). The DME data is the first to be reported through these membranes. In this paper, the chosen polymers reflect both rubbery and crystalline materials. Rubbery polymers tend to be weakly size sieving, which, in this work, has resulted in larger permeabilities, lower separation factors, and lower activation energies of permeation (Ep). Conversely, the crystalline TPX membranes showed much greater sensitivity to penetrant size; although the gas condensability also played a role in transport.

  8. 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.

  9. Office of Alcohol Fuels Program plan, FY 1981

    SciTech Connect (OSTI)

    1980-10-01

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

  10. 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.

  11. Oxygen-Enriched Combustion; Industrial Technologies Program ...

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

    in the combustion air or vacuum pressure swing adsorption units to remove some of the ... the cost of oxygen or of the vacuum pressure swing adsorption unit in the calculations. ...

  12. OXYGEN ENHANCED COMBUSTION FOR NOx CONTROL

    SciTech Connect (OSTI)

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

    2003-08-01

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

  13. Fundamentals, development and scaleup of the air=oxygen stratified downdraft gasifier

    SciTech Connect (OSTI)

    Reed, T.B.; Levie, B.; Graboski, M.S.

    1988-06-01

    In 1979 the US Department of Energy, Office of Alcohol Fuels, asked the Solar Energy Research Institute to develop a process for manufacturing methanol from biomass. This can be achieved by gasification of the biomass to a ''synthesis gas'' (syn-gas) (composed of primarily hydrogen and carbon monoxide) followed by catalytic conversion of the gas to methanol. The catalytic conversion of syn-gas is a well developed commercial process. There are a number of gasifiers for wood, but most of them make either a producer gas, high on nitrogen or a pyrolysis gas high in hydrocarbons. None were developed to make syn-gas. Thus the principal technical problem was to develop a gasifier to make synthesis gas from biomass. Work was performed at SERI from 1980--1985 which resulted in the development of a prototype 1 ton/day oxygen-biomass gasifier. In 1985 a program was undertaken for Congress by the US Department of Energy (DOE) to build a commercial scale (50--200 tons/day) medium energy gasifier, based on DOE or other research. A new company, Syn-Gas Inc. (SGI), research. A contract was awarded to SGI to modify the air gasifier for oxygen operation for this project. This modification allowed extended tests of the gasifier with oxygen to determine the possibility of scaling up the SERI-SGI gasifier to 50--200 tons/day.

  14. Engineering MulticomponentNanocatalystsfor Oxygen Reduction (Conference) |

    Office of Scientific and Technical Information (OSTI)

    SciTech Connect Engineering MulticomponentNanocatalystsfor Oxygen Reduction Citation Details In-Document Search Title: Engineering MulticomponentNanocatalystsfor Oxygen Reduction Authors: Guo, Shaojun [1] + Show Author Affiliations Los Alamos National Laboratory [Los Alamos National Laboratory Publication Date: 2014-03-27 OSTI Identifier: 1126640 Report Number(s): LA-UR-13-28233 DOE Contract Number: AC52-06NA25396 Resource Type: Conference Resource Relation: Conference: 247th ACS National

  15. Engineering MulticomponentNanocatalystsfor Oxygen Reduction (Conference) |

    Office of Scientific and Technical Information (OSTI)

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

  16. Oxygen ion-conducting dense ceramic

    DOE Patents [OSTI]

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

    1998-01-01

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

  17. Platinum Monolayer Electrocatalysts for Oxygen Reduction Reaction |

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

    Department of Energy Platinum Monolayer Electrocatalysts for Oxygen Reduction Reaction Platinum Monolayer Electrocatalysts for Oxygen Reduction Reaction Download presentation slides from the June 19, 2012, Fuel Cell Technologies Program webinar, "BNL's Low-Platinum Electrocatalysts for Fuel Cell Electric Vehicles (FCEVs)." PDF icon BNL's Low-Platinum Electrocatalysts for Fuel Cell Electric Vehicles (FCEVs) Webinar Slides More Documents & Publications Contiguous Platinum

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

    DOE Patents [OSTI]

    Tedder, Daniel W.

    1985-05-14

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

  19. OXYGEN ENHANCED COMBUSTION FOR NOx CONTROL

    SciTech Connect (OSTI)

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

    2002-01-01

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

  20. OXYGEN ENHANCED COMBUSTION FOR NOx CONTROL

    SciTech Connect (OSTI)

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

    2002-04-01

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

  1. 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.

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

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

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

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

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

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

  4. Testing Oxygen Reduction Reaction Activity with the Rotating...

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

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

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

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

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

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

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

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

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

    Open Energy Info (EERE)

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

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

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

    Oxygen-Enriched Combustion for Military Diesel Engine Generators Substantial increases in brake power and considerably lower peak pressure can result from oxygen-enriched diesel ...

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

    Office of Scientific and Technical Information (OSTI)

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

  10. OXYGEN ENHANCED COMBUSTION FOR NOx CONTROL

    SciTech Connect (OSTI)

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

    2000-07-01

    Increased environmental regulations will require utility boilers to reduce NO{sub x} emissions to less than 0.15lb/MMBtu in the near term. Conventional technologies such as Selective Catalytic Reduction (SCR) and Selective Non-Catalytic Reduction (SNCR) are unable to achieve these lowered emission levels without substantially higher costs and major operating problems. Oxygen enhanced combustion is a novel technology that allows utilities to meet the NO{sub x} emission requirements without the operational problems that occur with SCR and SNCR. Furthermore, oxygen enhanced combustion can achieve these NO{sub x} limits at costs lower than conventional technologies. The objective of this program is to demonstrate the use of oxygen enhanced combustion as a technical and economical method of meeting the EPA State Implementation Plan for NO{sub x} reduction to less than 0.15lb/MMBtu for a wide range of boilers and coal. The oxygen enhanced coal combustion program (Task 1) focused this quarter on the specific objective of exploration of the impact of oxygen enrichment on NO{sub x} formation utilizing small-scale combustors for parametric testing. Research efforts toward understanding any limitations to the applicability of the technology to different burners and fuels such as different types of coal are underway. The objective of the oxygen transport membrane (OTM) materials development program (Task 2.1) is to ascertain a suitable material composition that can be fabricated into dense tubes capable of producing the target oxygen flux under the operating conditions. This requires that the material have sufficient oxygen permeation resulting from high oxygen ion conductivity, high electronic conductivity and high oxygen surface exchange rate. The OTM element development program (Task 2.2) objective is to develop, fabricate and characterize OTM elements for laboratory and pilot reactors utilizing quality control parameters to ensure reproducibility and superior performance. A specific goal is to achieve a material that will sinter to desired density without compromising other variables such as reaction to binder systems or phase purity. Oxygen-enhanced combustion requires a facility which is capable of supplying high purity oxygen (>99.5%) at low costs. This goal can be achieved through the thermal integration of high temperature air separation with ceramic OTM. The objective of the OTM process development program (Task 2.3) is to demonstrate successfully the program objectives on a lab-scale single OTM tube reactor under process conditions comparable to those of an optimum large-scale oxygen facility. This quarterly technical progress report will summarize work accomplished for the Program through the first quarter April--June 2000 in the following task areas: Task 1 Oxygen Enhanced Coal Combustion; Task 2 Oxygen Transport Membranes; and Task 4 Program Management.

  11. SYNTHESIS OF NOVEL CROWN ETHERS BEARING THE exo-cis-2,3-NORBORNYL GROUP AS POTENTIAL Na+ AND K+ EXTRACTANTS

    SciTech Connect (OSTI)

    Robeson, R.M.; Bonnesen, P.

    2007-01-01

    The synthesis of a series of novel dinorbornyl-16-crown-5 and dinorbornyl-18-crown-6 ethers that incorporate the exo-cis-2,3-norbornyl moiety within the macrocycle framework is described. The key starting material for the crown ethers, exo-cis-2,3-norbornanediol, was successfully prepared on a large (>30g) scale in 88% yield from norbornylene by osmium tetroxide-catalyzed hydroxylation. The syn and anti isomers of the dinorbornyl-16-crown-5 ether family were prepared using diethylene glycol with ring closure achieved using a methallyl linkage. The isomers cis-syn-cis and cis-anti-cis di-norbornano-15-methyleno-16-crown-5 (6A and 6B) could be separated using column chromatography, and a single crystal of the syn isomer 6A suitable for X-ray crystal structure analysis was obtained, thereby confi rming the syn orientation. The syn and anti isomers of the dinorbornyl-18-crown-6 ether family were successfully prepared employing a different synthetic strategy, involving the potassium–templated cyclization of two bis-hydroxyethoxy-substituted exo-cis-2,3-norbornyl groups under high dilution conditions. Attempts to fully separate cis-syn-cis di-norbornano-18-crown-6 (10A) and cis-anti-cis di-norbornano-18-crown-6 (10B) from one another using column chromatography were unsuccessful. All intermediates and products were checked for purity using either thin layer chromatography or gas chromatography, and characterized by proton and carbon NMR. Crown ethers 6AB and 10AB are to our knowledge the fi rst crown ethers to incorporate the exo-cis-2,3-norbornyl moiety into the crown ring to be successfully synthesized and characterized.

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

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

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

  13. Oxygen generator for medical applications (USIC)

    SciTech Connect (OSTI)

    Staiger, C. L.

    2012-03-01

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

  14. Electro-autotrophic synthesis of higher alcohols

    DOE Patents [OSTI]

    Liao, James C.; Cho, Kwang Myung

    2015-10-06

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

  15. 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.

  16. OXYGEN ENHANCED COMBUSTION FOR NOx CONTROL

    SciTech Connect (OSTI)

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

    2003-02-01

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

  17. OXYGEN ENHANCED COMBUSTION FOR NOx CONTROL

    SciTech Connect (OSTI)

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

    2003-04-01

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

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

    DOE Patents [OSTI]

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

    1981-12-02

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

  19. Influence of Oxygen and pH on the Selective Oxidation of Ethanol on Pd Catalysts

    SciTech Connect (OSTI)

    Hibbitts, David D.; Neurock, Matthew

    2013-03-01

    The selective oxidation of ethanol on supported Pd is catalytically promoted by the presence of hydroxide species on the Pd surface as well as in solution. These hydroxide intermediates act as Brønsted bases which readily abstract protons from the hydroxyl groups of adsorbed or solution-phase alcohols. The C1AH bond of the resulting alkoxide is subsequently activated on the metal surface via hydride elimination to form acetaldehyde. Surface and solution-phase hydroxide intermediates can also readily react with the acetaldehyde via nucleophilic addition to form a germinal diol intermediate, which subsequently undergoes a second C1AH bond activation on Pd to form acetic acid. The role of O2 is to remove the electrons produced in the oxidation reaction via the oxygen reduction reaction over Pd. The reduction reaction also regenerates the hydroxide intermediates and removes adsorbed hydrogen that is produced during the oxidation.

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

    DOE Patents [OSTI]

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

    1990-09-25

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

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

    DOE Patents [OSTI]

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

    1990-09-25

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

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

    DOE Patents [OSTI]

    Roman, Ian C.

    1984-01-01

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

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

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

    Engine Using Transient Hardware-In-Loop Test Meth Cold-Start Performance and Emissions Behavior of Alcohol Fuels in an SIDI Engine Using Transient Hardware-In-Loop Test Meth ...

  4. Proceedings of the alcohol fuel production and utilization conference

    SciTech Connect (OSTI)

    Not Available

    1980-01-01

    A conference was held to provide farmers, businesses, industries, and specialty groups with the best available information on current and projected activities related to the production and utilization of biomass for alcohol fuels. All aspects of the alcohol fuel production and utilization process were discussed. From biomass sources, through conversion processes to end-use products and applications were topics discussed by numerous experts. Other experts took this basic information and put it together into total systems. Speakers presented overviews on alcohol fuel related activities on state, regional, and national levels. Finally, commercialization incentives, funding sources, environmental considerations, research developments, safety considerations, and regulatory requirements were discussed as factors which must be addressed when considering the production and utilization of alcohol fuels. Separate abstracts have been prepared for items within the scope of the Energy Data Base.

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

    DOE Patents [OSTI]

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

    1980-12-01

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

  6. Electrogenerative oxidation of lower alcohols to useful products

    DOE Patents [OSTI]

    Meshbesher, Thomas M.

    1987-01-01

    In the disclosed electrogenerative process for converting alcohols such as ethanol to aldehydes such as acetaldehyde, the alcohol starting material is an aqueous solution containing more than the azeotropic amount of water. Good first-pass conversions (<40% and more typically <50%) are obtained at operating cell voltages in the range of about 80 to about 350 millivolts at ordinary temperatures and pressures by using very high flow rates of alcohol to the exposed anode surface (i.e. the "gas" side of an anode whose other surface is in contact with the electrolyte). High molar flow rates of vaporized aqueous alcohol also help to keep formation of undesired byproducts at a low level.

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

    DOE Patents [OSTI]

    Elliott, Douglas C.; Werpy, Todd A.; Wang, Yong; Frye, Jr., John G.

    2003-05-27

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

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

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

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

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

    Office of Scientific and Technical Information (OSTI)

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

  10. Thermochemical Ethanol via Indirect Gasification and Mixed Alcohol

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

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

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

    SciTech Connect (OSTI)

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

    2015-10-31

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

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

    SciTech Connect (OSTI)

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

    1980-11-01

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

  13. Alcohol production from agricultural and forestry residues

    SciTech Connect (OSTI)

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

    1980-05-01

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

  14. Alcohol production from agricultural and forestry residues

    SciTech Connect (OSTI)

    Dale, L; Opilla, R; Surles, T

    1980-09-01

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

  15. Method of forming a dianhydrosugar alcohol

    DOE Patents [OSTI]

    Holladay, Johnathan E.; Hu, Jianli; Wang, Yong; Werpy, Todd A.; Zhang, Xinjie

    2010-01-19

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

  16. Ammonia producing engine utilizing oxygen separation

    DOE Patents [OSTI]

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

    2008-12-16

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

  17. Novel Membranes and Processes for Oxygen Enrichment

    SciTech Connect (OSTI)

    Lin, Haiqing

    2011-11-15

    The overall goal of this project is to develop a membrane process that produces air containing 25-35% oxygen, at a cost of $25-40/ton of equivalent pure oxygen (EPO2). Oxygen-enriched air at such a low cost will allow existing air-fueled furnaces to be converted economically to oxygen-enriched furnaces, which in turn will improve the economic and energy efficiency of combustion processes significantly, and reduce the cost of CO{sub 2} capture and sequestration from flue gases throughout the U.S. manufacturing industries. During the 12-month Concept Definition project: We identified a series of perfluoropolymers (PFPs) with promising oxygen/nitrogen separation properties, which were successfully made into thin film composite membranes. The membranes showed oxygen permeance as high as 1,200 gpu and oxygen/nitrogen selectivity of 3.0, and the permeance and selectivity were stable over the time period tested (60 days). We successfully scaled up the production of high-flux PFP-based membranes, using MTR's commercial coaters. Two bench-scale spiral-wound modules with countercurrent designs were made and parametric tests were performed to understand the effect of feed flow rate and pressure, permeate pressure and sweep flow rate on the membrane module separation properties. At various operating conditions that modeled potential industrial operating conditions, the module separation properties were similar to the pure-gas separation properties in the membrane stamps. We also identified and synthesized new polymers [including polymers of intrinsic microporosity (PIMs) and polyimides] with higher oxygen/nitrogen selectivity (3.5-5.0) than the PFPs, and made these polymers into thin film composite membranes. However, these membranes were susceptible to severe aging; pure-gas permeance decreased nearly six-fold within two weeks, making them impractical for industrial applications of oxygen enrichment. We tested the effect of oxygen-enriched air on NO{sub x} emissions using a Bloom baffle burner at GTI. The results are positive and confirm that oxygen-enriched combustion can be carried out without producing higher levels of NOx than normal air firing, if lancing of combustion air is used and the excess air levels are controlled. A simple economic study shows that the membrane processes can produce O{sub 2} at less than $40/ton EPO{sub 2} and an energy cost of 1.1-1.5 MMBtu/ton EPO{sub 2}, which are very favorable compared with conventional technologies such as cryogenics and vacuum pressure swing adsorption processes. The benefits of integrated membrane processes/combustion process trains have been evaluated, and show good savings in process costs and energy consumption, as well as reduced CO{sub 2} emissions. For example, if air containing 30% oxygen is used in natural gas furnaces, the net natural gas savings are an estimated 18% at a burner temperature of 2,500 F, and 32% at a burner temperature of 3,000 F. With a 20% market penetration of membrane-based oxygen-enriched combustion in all combustion processes by 2020, the energy savings would be 414-736 TBtu/y in the U.S. The comparable net cost savings are estimated at $1.2-2.1 billion per year by 2020, calculated as the value of fuel savings subtracted from the cost of oxygen production. The fuel savings of 18%-32% by the membrane/oxygen-enriched combustion corresponds to an 18%-32% reduction in CO{sub 2} emissions, or 23-40 MM ton/y less CO{sub 2} from natural gas-fired furnaces by 2020. In summary, results from this project (Concept Definition phase) are highly promising and clearly demonstrate that membrane processes can produce oxygen-enriched air in a low cost manner that will lower operating costs and energy consumption in industrial combustion processes. Future work will focus on proof-of-concept bench-scale demonstration in the laboratory.

  18. Solvent Modification in Ion-Pair Extraction: Effect on Sodium Nitrate Transport in Nitrobenzene Using a Crown Ether

    SciTech Connect (OSTI)

    Levitskaia, Tatiana G.; Lumetta, Gregg J.

    2005-10-31

    A comparative quantitative analysis of the effect of solvent modifiers on an ion-pair extraction of an inorganic salt by a crown ether was conducted. Two classes of the solvent modifiers that possess electron-pair donor (EPD) or hydrogen-bond donor (HBD) groups were investigated. The equilibrium constants corresponding to the extraction of sodium nitrate into nitrobenzene (NB) employing model neutral host cis-syn-cis-dicyclohexano-18-crown-6 (1) with and without solvent modifier were determined using the SXLSQI computer model. For a series of EPD modifiers—including tri-n-butyl- and tri-phenylphosphate, tri-n-butyl- and tri-phenylphosphine oxide, N,N-di-n-butyl- and N,N-di-phenyl acetamide—the enhancement of the NaNO3 extraction by 1 was found to be dependent on the hydrogen-bond acceptance ability of the modifier quantified by the b solvatochromic parameter. Application of the solvent EPD modifier improved solvation of the sodium ion, lowering the large energy barrier of Na+ partitioning into the extraction phase. A HBD modifier 3,5-di-t-butylphenol 8 that forms strong hydrogen bonds with nitrate anion in NB, exhibited even greater enhancement of the NaNO3 extraction by 1. The determined extraction constants were correlated with the b or a solvatochromic parameters of the solvent modifiers and linear trends were observed. Hydrogen bond interaction between 3,5-di-t-butylphenol 8 and nitrate anion in the presence of the sodium-loaded crown ether in the extraction phases was studied by vibrational spectroscopy. Formation of the simple 1:1 adduct was demonstrated.

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

    SciTech Connect (OSTI)

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

    2014-12-31

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

  20. Oxygen-producing inert anodes for SOM process

    SciTech Connect (OSTI)

    Pal, Uday B

    2014-02-25

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

  1. Electrical insulator assembly with oxygen permeation barrier

    DOE Patents [OSTI]

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

    1994-03-29

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

  2. Electrical insulator assembly with oxygen permeation barrier

    DOE Patents [OSTI]

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

    1994-01-01

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

  3. OXYGEN ENHANCED COMBUSTION FOR NOx CONTROL

    SciTech Connect (OSTI)

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

    2000-10-01

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

  4. Synthesis of oxygenate products for high volume fuels applications. Quarterly status report No. 5 for the period October through December 1995

    SciTech Connect (OSTI)

    Not Available

    1996-02-15

    A process variables study was carried out with crude DME as feed for the condensation with acetylene to C{sub 2} and higher alcohols. The addition of water to crude DME had a marked effect of promoting selectivity to ethanol, especially at the lower reaction temperatures tested. Experiments designed to reveal the effect of reactor flow rate and temperature demonstrated that lower rates and higher temperatures favored selectivity to propanol and butanol up to a maximum temperature of 460{degrees}C, beyond which selectivity diminished via decomposition reactions. Faster rates and lower temperatures favored selectivity to ethanol. Reactor conditions and feed compositions for optimum target alcohol selectivities have been identified. 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. Oxygen stabilized zirconium vanadium intermetallic compound

    DOE Patents [OSTI]

    Mendelsohn, Marshall H.; Gruen, Dieter M.

    1982-01-01

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

  6. OXYGEN ENHANCED COMBUSTION FOR NOx CONTROL

    SciTech Connect (OSTI)

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

    2002-08-01

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

  7. Geothermal source potential and utilization for alcohol production

    SciTech Connect (OSTI)

    Austin, J.C.

    1981-11-01

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

  8. Design report: small-scale fuel alcohol plant

    SciTech Connect (OSTI)

    Not Available

    1980-01-01

    The objectives of the report are to (a) provide potential alcohol producers with a reference design and (b) provide a complete, demonstrated design of a small-scale fuel alcohol plant. This report describes a small-scale fuel alcohol plant designed and constructed for the DOE by EG and G Idaho, Inc., an operating contractor at the Idaho National Engineering Laboratory. The plant is reasonably complete, having the capability for feedstock preparation, cooking, saccharification, fermentation, distillation, by-product dewatering, and process steam generation. An interesting feature is an instrumentation and control system designed to allow the plant to run 24 hours per day with only four hours of operator attention. Where possible, this document follows the design requirements established in the DOE publication Fuel From Farms, which was published in February 1980. For instance, critical requirements such as using corn as the primary feedstock, production of 25 gallons of 190 proof ethanol per hour, and using batch fermentation were taken from Fuel From Farms. One significant deviation is alcohol dehydration. Fuel From Farms recommends the use of a molecular sieve for dehydration, but a preliminary design raised significant questions about the cost effectiveness of this approach. A cost trade-off study is currently under way to establish the best alcohol dehydration method and will be the subject of a later report. Volume one contains background information and a general description of the plant and process.

  9. Economic analysis of small-scale fuel alcohol plants

    SciTech Connect (OSTI)

    Schafer, J.J. Jr.

    1980-01-01

    To plan Department of Energy support programs, it is essential to understand the fundamental economics of both the large industrial size plants and the small on-farm size alcohol plants. EG and G Idaho, Inc., has designed a 25 gallon per hour anhydrous ethanol plant for the Department of Energy's Alcohol Fuels Office. This is a state-of-the-art reference plant, which will demonstrate the cost and performance of currently available equipment. The objective of this report is to examine the economics of the EG and G small-scale alcohol plant design and to determine the conditions under which a farm plant is a financially sound investment. The reference EG and G Small-Scale Plant is estimated to cost $400,000. Given the baseline conditions defined in this report, it is calculated that this plant will provide an annual after-tax of return on equity of 15%, with alcohol selling at $1.62 per gallon. It is concluded that this plant is an excellent investment in today's market, where 200 proof ethanol sells for between $1.80 and $2.00 per gallon. The baseline conditions which have a significant effect on the economics include plant design parameters, cost estimates, financial assumptions and economic forecasts. Uncertainty associated with operational variables will be eliminated when EG and G's reference plant begins operation in the fall of 1980. Plant operation will verify alcohol yield per bushel of corn, labor costs, maintenance costs, plant availability and by-product value.

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

    Office of Scientific and Technical Information (OSTI)

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

  11. Recovery Act: Novel Oxygen Carriers for Coal-fueled Chemical...

    Office of Scientific and Technical Information (OSTI)

    Recovery Act: Novel Oxygen Carriers for Coal-fueled Chemical Looping Citation Details In-Document Search Title: Recovery Act: Novel Oxygen Carriers for Coal-fueled Chemical Looping ...

  12. Oxygen Catalysis: The Other Half of the Equation

    SciTech Connect (OSTI)

    Turner, J.

    2008-10-01

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

  13. Oxygen Carriers for Solid Fuel Chemical Looping Combustion Process - Energy

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

    Innovation Portal Oxygen Carriers for Solid Fuel Chemical Looping Combustion Process Regenerable Mixed Copper-Iron-Inert Support Oxygen Carriers National Energy Technology Laboratory Contact NETL About This Technology Publications: PDF Document Publication 13159553.pdf (405 KB) Technology Marketing Summary This patent-pending technology, "Regenerable Mixed Copper-Iron-Inert Support Oxygen Carriers for Solid Fuel Chemical Looping Combustion Process," provides a metal-oxide oxygen

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

    Office of Scientific and Technical Information (OSTI)

    on local lattice parameter measurements by scanning transmission electron microscopy. ... Subject: Oxygen Stoichimetry; Vacancy Ordering; Scanning Transmission Electron Microscopy ...

  15. Oxygen-Enriched Combustion for Military Diesel Engine Generators

    Broader source: Energy.gov [DOE]

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

  16. Dilute Oxygen Combustion Phase IV Final Report

    SciTech Connect (OSTI)

    Riley, M.F.

    2003-04-30

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

  17. Modeling and cold start in alcohol-fueled engines

    SciTech Connect (OSTI)

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

    1998-05-01

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

  18. Changes in mitogen-activated protein kinase in cerebellar granule neurons by polybrominated diphenyl ethers and polychlorinated biphenyls

    SciTech Connect (OSTI)

    Fan Chunyang; Besas, Jonathan

    2010-05-15

    Polybrominated diphenyl ethers (PBDEs) are used as additive flame retardants and have been detected in human blood, adipose tissue, and breast milk. Both in vitro and in vivo studies have shown that the effects of PBDEs are similar to the known human developmental neurotoxicants such as polychlorinated biphenyls (PCBs) on a molar basis. Previously, we reported that PBDE mixtures and congeners, perturbed calcium homeostasis which is critical for the development and function of the nervous system. In the present study, we tested whether environmentally relevant PBDE/PCB mixtures and congeners affected mitogen-activated protein kinase (MAPK) pathways, which are down-stream events of calcium signaling in cerebellar granule neuronal cultures. In this study, phosphorylated extracellular signal-regulated kinase (pERK)1/2, a widely studied MAPK cascade and known to be involved in learning and memory, levels were quantitated using western blot technique with phospho-specific antibodies. Glutamate (a positive control) increased pERK1/2 in a time- and concentration-dependent manner reaching maximum activation at 5-30 min of exposure and at doses >= 10 muM. Both Aroclor 1254 (a commercial penta PCB mixture) and DE-71 (a commercial penta PBDE mixture) elevated phospho-ERK1/2, producing maximum stimulation at 30 min and at concentrations >= 3 mug/ml; Aroclor 1254 was more efficacious than DE-71. DE-79 (an octabrominated diphenyl ether mixture) also elevated phospho-ERK1/2, but to a lesser extent than that of DE-71. PBDE congeners 47, 77, 99, and 153 also increased phospo-ERK1/2 in a concentration-dependent manner. The data indicated that PBDE congeners are more potent than the commercial mixtures. PCB 47 also increased phospho-ERK1/2 like its structural analog PBDE 47, but to a lesser extent, suggesting that these chemicals affect similar pathways. Cytotoxicity, measured as %LDH release, data showed that higher concentrations (> 30 muM) and longer exposures (> 30 min) are required to see cell death. These results show that PBDE mixtures and congeners activate MAPK pathway at concentrations where no significant cytotoxicity was observed, suggesting that perturbed intracellular signaling including MAPK pathway might be involved in the initiation of adverse effects, including learning and memory, related to these persistent chemicals.

  19. Thermodynamic properties and ideal-gas enthalpies of formation for butyl vinyl ether, 1,2-dimethoxyethane, methyl glycolate, bicyclo[2.2.1]hept-2-ene, 5-vinylbicyclo[2.2.1]hept-2-ene, trans-azobenzene, butyl acrylate, di-tert-butyl ether, and hexane-1,6-diol

    SciTech Connect (OSTI)

    Steele, W.V.; Chirico, R.D.; Knipmeyer, S.E.; Nguyen, A.; Smith, N.K.

    1996-11-01

    Ideal-gas enthalpies of formation of butyl vinyl ether, 1,2-dimethoxyethane, methyl glycolate, bicyclo-[2.2.1]hept-2-ene, 5-vinylbicyclo[2.2.1]hept-2-ene, trans-azobenzene, butyl acrylate, di-tert-butyl ether, and hexane-1,6-diol are reported. Enthalpies of fusion were determined for bicyclo[2.2.1]hept-2-ene and trans-azobenzene. Two-phase (solid + vapor) or (liquid + vapor) heat capacities were determined from 300 K to the critical region or earlier decomposition temperature for each compound studied. Liquid-phase densities along the saturation line were measured for bicyclo[2.2.1]hept-2-ene. For butyl vinyl ether and 1,2-dimethoxyethane, critical temperatures and critical densities were determined from the dsc results and corresponding critical pressures derived from the fitting procedures. Fitting procedures were used to derive critical temperatures, critical pressures, and critical densities for bicyclo[2.2.1]hept-2-ene, 5-vinylbicyclo[2.2.1]hept-2-ene, trans-azobenzene, butyl acrylate, and di-tert-butyl ether. Group-additivity parameters or ring-correction terms useful in the application of the Benson group-contribution correlations were derived.

  20. HIGH-RESOLUTION EXPANDED VERY LARGE ARRAY IMAGE OF DIMETHYL ETHER (CH{sub 3}){sub 2}O IN ORION-KL

    SciTech Connect (OSTI)

    Favre, C.; Wootten, H. A.; Remijan, A. J.; Brouillet, N.; Despois, D.; Baudry, A.; Wilson, T. L. E-mail: brouillet@obs.u-bordeaux1.fr E-mail: baudry@obs.u-bordeaux1.fr E-mail: aremijan@nrao.edu

    2011-09-20

    We report the first subarcsecond (0.''65 x 0.''51) image of the dimethyl ether molecule, (CH{sub 3}){sub 2}O, toward the Orion Kleinmann-Low nebula. The observations were carried at 43.4 GHz with the Expanded Very Large Array (EVLA). The distribution of the lower energy transition 6{sub 1,5}-6{sub 0,6}, EE (E {sub u} = 21 K) mapped in this study is in excellent agreement with the published dimethyl ether emission maps imaged with a lower resolution. The main emission peaks are observed toward the Compact Ridge and Hot Core southwest components, at the northern parts of the Compact Ridge and in an intermediate position between the Compact Ridge and the Hot Core. A notable result is that the distribution of dimethyl ether is very similar to that of another important larger O-bearing species, the methyl formate (HCOOCH{sub 3}), imaged at a lower resolution. Our study shows that higher spectral resolution (WIDAR correlator) and increased spectral coverage provided by the EVLA offer new possibilities for imaging complex molecular species. The sensitivity improvement and the other EVLA improvements make this instrument well suited for high sensitivity, high angular resolution, and molecular line imaging.

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

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

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

    2015-04-21

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

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

    SciTech Connect (OSTI)

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

    2015-04-21

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

  3. Magnetic interaction in oxygenated alpha Fe-phthalocyanines

    SciTech Connect (OSTI)

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

    2014-10-27

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

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

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

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

  5. Cathode architectures for alkali metal / oxygen batteries

    DOE Patents [OSTI]

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

    2015-01-13

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

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

    SciTech Connect (OSTI)

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

    2014-09-01

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

  7. 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.

  8. 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.

  9. Electrochemical Investigation of Li–Al Anodes in Oligo(ethylene glycol) Dimethyl Ether/LiPF6

    SciTech Connect (OSTI)

    Zhou, Y.N.; Yang, X.; Wang, X.J.; Lee, H.S.; Nam, K.W.; Haas, O.

    2010-11-01

    1 M LiPF{sub 6} dissolved in oligo(ethylene glycol) dimethyl ether with a molecular weight 500 g mol{sup -1} was investigated as a new electrolyte (OEGDME500, 1 M LiPF{sub 6}) for metal deposition and battery applications. At 25 C a conductivity of 0.48 x 10{sup -3} S cm{sup -1} was obtained and at 85 C, 3.78 x 10{sup -3} S cm{sup -1}. The apparent activation barrier for ionic transport was evaluated to be 30.7 kJ mol{sup -1}. OEGDME500, 1 M LiPF{sub 6} allows operating temperature above 100 C with very attractive conductivity. The electrolyte shows excellent performance at negative and positive potentials. With this investigation, we report experimental results obtained with aluminum electrodes using this electrolyte. At low current densities lithium ion reduction and re-oxidation can be achieved on aluminum electrodes at potentials about 280 mV more positive than on lithium electrodes. In situ X-ray diffraction measurements collected during electrochemical lithium deposition on aluminum electrodes show that the shift to positive potentials is due to the negative Gibbs free energy change of the Li-Al alloy formation reaction.

  10. Electrochemical Investigation of Li-Al Anodes in Oligo (ethylene glycol) Dimethyl ether/LiPF6

    SciTech Connect (OSTI)

    Y Zhou; X Wang; H Lee; K Nam; X Yang; O Haas

    2011-12-31

    LiPF{sub 6} dissolved in oligo(ethylene glycol) dimethyl ether with a molecular weight 5 g mol{sup -1} was investigated as a new electrolyte (OEGDME5, 1 M LiPF{sub 6}) for metal deposition and battery applications. At 25 C a conductivity of .48 x 1{sup -3} S cm{sup -1} was obtained and at 85 C, 3.78 x 1{sup -3} S cm{sup -1}. The apparent activation barrier for ionic transport was evaluated to be 3.7 kJ mol{sup -1}. OEGDME5, 1 M LiPF{sub 6} allows operating temperature above 1 C with very attractive conductivity. The electrolyte shows excellent performance at negative and positive potentials. With this investigation, we report experimental results obtained with aluminum electrodes using this electrolyte. At low current densities lithium ion reduction and re-oxidation can be achieved on aluminum electrodes at potentials about 28 mV more positive than on lithium electrodes. In situ X-ray diffraction measurements collected during electrochemical lithium deposition on aluminum electrodes show that the shift to positive potentials is due to the negative Gibbs free energy change of the Li-Al alloy formation reaction.

  11. 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)

  12. 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.

  13. Characterization of Particulate Emissions from GDI Engine Combustion with Alcohol-blended Fuels

    Broader source: Energy.gov [DOE]

    Analysis showed that gasoline direct injection engine particulates from alcohol-blended fuels are significantly different in morphology and nanostructures

  14. Synthesis of oxygenate products for high volume fuels applications. Quarterly technical progress report No. 1, November 1, 1994--January 31, 1995

    SciTech Connect (OSTI)

    1995-03-08

    Construction and setup of twin laboratory gas phase reactors with in-line Gas chromatographic analysers was completed. Calibration and C.G. analysis methods development were carried out, and spreadsheet programs were written for reduction of data to interpretable results. Initial tests were carried out with pentasil zeolite ASM-5 containing very low (0.1%) levels of mercury as potential catalysts for conversion of acetylene/methanol streams to 1,1-dimethoxyethane or to C{sub 2}{sup +} alcohols, both useful as high-oxygenate gasoline blending agents. Trace levels of both types of products were observed, although the predominant products were light olefins at lower reaction temperatures and aromatics at higher temperatures. It is anticipated that less acidic zeolites and/or Zn- containing catalysts will be more active for oxygenate production. Testing of these materials is underway.

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

    DOE Patents [OSTI]

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

    2013-11-26

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

  16. Dilute Oxygen Combustion Phase I Final Report

    SciTech Connect (OSTI)

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

    1997-10-31

    A novel burner, in which fuel (natural gas) and oxidant (oxygen or air) are separately injected into a furnace, shows promise for achieving very low nitrogen oxide(s) (NOx) emissions for commercial furnace applications. The dilute oxygen combustion (DOC) burner achieves very low NOx through in-furnace dilution of the oxidant stream prior to combustion, resulting in low flame temperatures, thus inhibiting thermal NOx production. The results of a fundamental and applied research effort on the development of the DOC burner are presented. In addition, the results of a market survey detailing the potential commercial impact of the DOC system are disclosed. The fundamental aspects of the burner development project involved examining the flame characteristics of a natural gas turbulent jet in a high-temperature (~1366 K) oxidant (7-27% O2 vol. wet). Specifically, the mass entrainment rate, the flame lift-off height, the velocity field and major species field of the jet were evaluated as a function of surrounding-gas temperature and composition. The measured entrainment rate of the fuel jet decreased with increasing oxygen content in the surrounding high-temperature oxidant, and was well represented by the d+ scaling correlation found in the literature. The measured flame lift-off height decreased with increasing oxygen content and increasing temperature of the surrounding gas. An increase in surrounding-gas oxygen content and/or temperature inhibited the velocity decay within the jet periphery as a function of axial distance as compared to isothermal turbulent jets. However, the velocity measurements were only broadly represented by the d+ scaling correlation. Several DOC burner configurations were tested in a laboratory-scale furnace at a nominal firing rate of 185 kW (~0.63 MMBtu/h). The flue gas composition was recorded as a function of furnace nitrogen content, furnace temperature, burner geometric arrangement, firing rate, and fuel injection velocity. NOx emissions increased with increasing furnace nitrogen content and furnace temperature, but remained relatively insensitive to variations in fuel injection velocity and firing rate. NOx emissions below 5-10-3 g/MJ (10 ppm-air equivalent at 3% O2 dry) were obtained for furnace temperatures below 1533 K (2300°F) and furnace nitrogen levels between 1 and 40%. CO emissions were typically low (<35 ppm). Detailed in-furnace species measurements revealed the importance of the interior furnace circulation patterns, as influenced by fuel and oxidant injection schemes, on pollutant emissions. The combustion stability traits of several DOC burner arrangements were ascertained through furnace pressure measurements, wit6h increased stability occurring as furnace temperature increased and as the separation distance between fuel and oxidant inputs decreased. Based on current market conditions, oxy-fuel conversion of batch steel reheat furnaces with a DOC burner is justified on the basis of lower utility costs alone. However, conversion of continuous steel reheat furnaces, which are responsible for most steel production, required additional economic incentives, such as further fuel savings, increased furnace productivity, or emission credits.

  17. Electrochemical oxygen pumps. Final CRADA report.

    SciTech Connect (OSTI)

    Carter, J. D. Noble, J.

    2009-10-01

    All tasks of the Work Plan of ISTC Project 2277p have been completed, thus: (1) techniques of chemical synthesis were developed for more than ten recipes of electrolyte based on cerium oxide doped with 20 mole% of gadolinium (CeGd)O{sub 2}, doped by more than 10 oxide systems including 6 recipes in addition to the Work Plan; (2) electric conductivity and mechanical strength of CeGd specimens with additions of oxide systems were performed, two candidate materials for the electrolyte of electrochemical oxygen pump (pure CeGd and CeGd doped by 0.2 wt% of a transition metal) were chosen; (3) extended studies of mechanical strength of candidate material specimens were performed at room temperature and at 400, 600, 800 C; (4) fixtures for determination of mechanical strength of tubes by external pressure above 40 atmospheres at temperature up to 700 C were developed and fabricated; and (5) technology of slip casting of tubes from pure (Ce,Gd)O{sub 2} and of (Ce,Gd)O{sub 2} doped by 0.2 wt% of a transition metal, withstanding external pressure of minimum 40 atmospheres at temperature up to 700 C was developed, a batch of tubes was sent for testing to Argonne National Laboratory; (6) technology of making nanopowder from pure (Ce,Gd)O{sub 2} was developed based on chemical synthesis and laser ablation techniques, a batch of nanopowder with the weight 1 kg was sent for testing to Argonne National Laboratory; (7) a business plan for establishing a company for making powders of materials for electrochemical oxygen pump was developed; and (8) major results obtained within the Project were reported at international conferences and published in the Russian journal Electrochemistry. In accordance with the Work Plan a business trip of the following project participants was scheduled for April 22-29, 2006, to Tonawanda, NY, USA: Manager Victor Borisov; Leader of technology development Gennady Studenikin; Leader of business planning Elena Zadorozhnaya; Leader of production Vasily Lepalovsky; and Translator Vladimir Litvinov. During this trip project participants were to discuss with the project Technical Monitor J.D. Carter and representative of Praxair Inc. J. Chen the results of project activities (prospects of transition metal-doped material application in oxygen pumps), as well as the prospects of cooperation with Praxair at the meeting with the company management in the following fields: (1) Deposition of thin films of oxide materials of complex composition on support by magnetron and ion sputtering, research of coatings properties; (2) Development of block-type structure technology (made of porous and dense ceramics) for oxygen pump. The block-type structure is promising because when the size of electrolyte block is 2 x 2 inches and assembly height is 10 inches (5 blocks connected together) the area of active surface is ca. 290 square inches (in case of 8 slots), that roughly corresponds to one tube with diameter 1 inch and height 100 inches. So performance of the system made of such blocks may be by a factor of two or three higher than that of tube-based system. However one month before the visit, J. Chen notified us of internal changes at Praxair and the cancellation of the visit to Tonawanda, NY. During consultations with the project Technical Monitor J.D. Carter and Senior Project Manager A. Taylor a decision was made to extend the project term by 2 quarters to prepare proposals for follow-on activities during this extension (development of block-type structures made of dense and porous oxide ceramics for electrochemical oxygen pumps) using the funds that were not used for the trip to the US.

  18. Dilute Oxygen Combustion Phase 2 Final Report

    SciTech Connect (OSTI)

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

    2005-09-30

    A novel burner, in which fuel (natural gas) and oxidant (oxygen or air) are separately injected into a furnace, shows promise for achieving very low nitrogen oxide(s) (NOx) emissions for commercial furnace applications. The dilute oxygen combustion (DOC) burner achieves very low NOx through in-furnace dilution of the oxidant stream prior to combustion, resulting in low flame temperatures, thus inhibiting thermal NOx production. The results of a fundamental and applied research effort on the development of the DOC burner are presented. In addition, the results of a market survey detailing the potential commercial impact of the DOC system are disclosed. The fundamental aspects of the burner development project involved examining the flame characteristics of a natural gas turbulent jet in a high-temperature (~1366 K) oxidant (7-27% O2 vol. wet). Specifically, the mass entrainment rate, the flame lift-off height, the velocity field and major species field of the jet were evaluated as a function of surrounding-gas temperature and composition. The measured entrainment rate of the fuel jet decreased with increasing oxygen content in the surrounding high-temperature oxidant, and was well represented by the d+ scaling correlation found in the literature. The measured flame lift-off height decreased with increasing oxygen content and increasing temperature of the surrounding gas. An increase in surrounding-gas oxygen content and/or temperature inhibited the velocity decay within the jet periphery as a function of axial distance as compared to isothermal turbulent jets. However, the velocity measurements were only broadly represented by the d+ scaling correlation. Several DOC burner configurations were tested in a laboratory-scale furnace at a nominal firing rate of 185 kW (~0.63 MMBtu/h). The flue gas composition was recorded as a function of furnace nitrogen content, furnace temperature, burner geometric arrangement, firing rate, and fuel injection velocity. NOx emissions increased with increasing furnace nitrogen content and furnace temperature, but remained relatively insensitive to variations in fuel injection velocity and firing rate. NOx emissions below 5-10-3 g/MJ (10 ppm-air equivalent at 3% O2 dry) were obtained for furnace temperatures below 1533 K (2300?F) and furnace nitrogen levels between 1 and 40%. CO emissions were typically low (<35 ppm). Detailed in-furnace species measurements revealed the importance of the interior furnace circulation patterns, as influenced by fuel and oxidant injection schemes, on pollutant emissions. The combustion stability traits of several DOC burner arrangements were ascertained through furnace pressure measurements, wit6h increased stability occurring as furnace temperature increased and as the separation distance between fuel and oxidant inputs decreased. Based on current market conditions, oxy-fuel conversion of batch steel reheat furnaces with a DOC burner is justified on the basis of lower utility costs alone. However, conversion of continuous steel reheat furnaces, which are responsible for most steel production, required additional economic incentives, such as further fuel savings, increased furnace productivity, or emission credits.

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

    SciTech Connect (OSTI)

    Manohar S. Sohal; J. Stephen Herring

    2008-07-01

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

  20. 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.

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

    SciTech Connect (OSTI)

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

    2013-08-01

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

  2. METHOD OF COMBINING HYDROGEN AND OXYGEN

    DOE Patents [OSTI]

    McBride, J.P.

    1962-02-27

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

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

    SciTech Connect (OSTI)

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

    2009-11-15

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

  4. Dilute Oxygen Combustion - Phase 3 Report

    SciTech Connect (OSTI)

    Riley, Michael F.

    2000-05-31

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

  5. Dilute Oxygen Combustion Phase 3 Final Report

    SciTech Connect (OSTI)

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

    2000-05-31

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

  6. 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.

  7. 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)

  8. Homogeneously dispersed, multimetal oxygen-evolving catalysts (Journal

    Office of Scientific and Technical Information (OSTI)

    Article) | SciTech Connect Homogeneously dispersed, multimetal oxygen-evolving catalysts Citation Details In-Document Search This content will become publicly available on March 24, 2017 Title: Homogeneously dispersed, multimetal oxygen-evolving catalysts Earth-abundant first-row (3d) transition-metal-based catalysts have been developed for the oxygen-evolution reaction (OER); however, they operate at overpotentials significantly above thermodynamic requirements. Density functional theory

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

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

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

  10. Webinar: Testing Oxygen Reduction Reaction Activity with the Rotating Disc

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

    Electrode Technique | Department of Energy Testing Oxygen Reduction Reaction Activity with the Rotating Disc Electrode Technique Webinar: Testing Oxygen Reduction Reaction Activity with the Rotating Disc Electrode Technique Above is the video recording for the webinar, "Testing Oxygen Reduction Reaction Activity with the Rotating Disc Electrode Technique," originally held on March 12, 2013. In addition to this recording, you can access the presentation slides. A text version of

  11. Direct Observation of Localized Radial Oxygen Migration in Functioning

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

    Tantalum Oxide Memristors Direct Observation of Localized Radial Oxygen Migration in Functioning Tantalum Oxide Memristors Direct Observation of Localized Radial Oxygen Migration in Functioning Tantalum Oxide Memristors Print Monday, 11 April 2016 14:29 As information bits of 0s and 1s are stored in crosspoint tantalum oxide memristors, or resistive random access memory (RRAM) cells, nanoscale-resolution in operando x-ray transmission spectromicroscopy is used to directly observe oxygen

  12. East Coast (PADD 1) Net Receipts of Crude Oil and Petroleum Products...

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

    RBOB for Blending with Alcohol* 2005-2009 RBOB for Blending with Ether* 2005-2009 GTAB* ... Notes: RBOB with Ether and RBOB with Alcohol are discontinued as of the January 2010 ...

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

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

    is the most efficient electrocatalyst for accelerating the oxygen reduction reaction in fuel cells. Under operating conditions, though, platinum catalysts can dissolve. When used...

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

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

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

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

    Office of Scientific and Technical Information (OSTI)

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

  16. Testing Oxygen Reduction Reaction Activity with the Rotating...

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

    Testing Oxygen Reduction Reaction Activity with the Rotating Disc Electrode Technique Date: Tuesday, March 12, 2013 Innovation for Our Energy Future Shyam S. Kocha: NREL Yannick ...

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

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

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

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

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

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

    2016-01-25

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

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

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

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

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

    Office of Scientific and Technical Information (OSTI)

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

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

    Office of Scientific and Technical Information (OSTI)

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

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

    Office of Scientific and Technical Information (OSTI)

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

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

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

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

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

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

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

  5. Interplay between gadolinium dopants and oxygen vacancies in...

    Office of Scientific and Technical Information (OSTI)

    theory plus Hubbard U investigation Citation Details In-Document Search Title: Interplay between gadolinium dopants and oxygen vacancies in HfOsub 2: A density functional theory ...

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

    Energy Savers [EERE]

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

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

    Energy Savers [EERE]

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

  8. Catalytic reduction system for oxygen-rich exhaust

    DOE Patents [OSTI]

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

    1999-01-01

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

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

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

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

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

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

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

  11. Kinetics of oxygen surface exchange on epitaxial Ruddlesden-Popper...

    Office of Scientific and Technical Information (OSTI)

    Kinetics of oxygen surface exchange on epitaxial Ruddlesden-Popper phases and correlations to first-principles descriptors Citation Details In-Document Search This content will ...

  12. Catalytic reduction system for oxygen-rich exhaust

    DOE Patents [OSTI]

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

    1999-04-13

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

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

    Office of Scientific and Technical Information (OSTI)

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

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

    SciTech Connect (OSTI)

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

    1982-01-01

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

  15. Alcohol-free alkoxide process for containing nuclear waste

    DOE Patents [OSTI]

    Pope, James M.; Lahoda, Edward J.

    1984-01-01

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

  16. Design for a small-scale fuel alcohol plant

    SciTech Connect (OSTI)

    Berglund, G.R.; Richardson, J.G.

    1982-08-01

    The paper describes the small-scale fuel alcohol plant (SSFAT) which was designed as a small-scale chemical processing plant. The DOE publication, Fuel from Farms, set forth the basic design requirements. To lower operating costs, it was important that all the processes required to produce alcohol were integrated. Automated control was also an important consideration in the design to reduce the number of operators and operator time, thus reducing operating costs. Automated control also provides better quality control of the final product. The plant is presently operating in a test mode to evaluate operating characteristics. The discussion covers the following topics - design requirements; plan operations; fermentation; distillation; microprocessor control; automatic control; operating experience. 1 ref.

  17. Electrocatalyst for alcohol oxidation at fuel cell anodes

    DOE Patents [OSTI]

    Adzic, Radoslav; Kowal, Andrzej

    2011-11-02

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

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

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

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

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

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

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

  20. Design for a small-scale fuel alcohol plant

    SciTech Connect (OSTI)

    Berglund, G.R.; Richardson, J.G.

    1982-08-01

    The fuel alcohol plant described in this article was designed, constructed and is being operated for the US DOE by EG and G Idaho. The plant can be operated by a single owner and produces 100 L of ethanol per hour and wet stillage for animal feed using corn as the primary feedstock. Existing technology and off-the-shelf equipment have been used whenever possible. The operation of the plant and microprocessor control of the process are described. (Refs. 1).

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

    DOE Patents [OSTI]

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

    1985-08-06

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

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

    DOE Patents [OSTI]

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

    1985-01-01

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

  3. Using physiologically based pharmacokinetic modeling to address nonlinear kinetics and changes in rodent physiology and metabolism due to aging and adaptation in deriving reference values for propylene glycol methyl ether and propylene glycol methyl ether acetate.

    SciTech Connect (OSTI)

    Kirman, C R.; Sweeney, Lisa M.; Corley, Rick A.; Gargas, M L.

    2005-04-01

    Reference values, including an oral reference dose (RfD) and an inhalation reference concentration (RfC), were derived for propylene glycol methyl ether (PGME), and an oral RfD was derived for its acetate (PGMEA). These values were based upon transient sedation observed in F344 rats and B6C3F1 mice during a two-year inhalation study. The dose-response relationship for sedation was characterized using internal dose measures as predicted by a physiologically based pharmacokinetic (PBPK) model for PGME and its acetate. PBPK modeling was used to account for changes in rodent physiology and metabolism due to aging and adaptation, based on data collected during weeks 1, 2, 26, 52, and 78 of a chronic inhalation study. The peak concentration of PGME in richly perfused tissues was selected as the most appropriate internal dose measure based upon a consideration of the mode of action for sedation and similarities in tissue partitioning between brain and other richly perfused tissues. Internal doses (peak tissue concentrations of PGME) were designated as either no-observed-adverse-effect levels (NOAELs) or lowest-observed-adverse-effect levels (LOAELs) based upon the presence or absence of sedation at each time-point, species, and sex in the two year study. Distributions of the NOAEL and LOAEL values expressed in terms of internal dose were characterized using an arithmetic mean and standard deviation, with the mean internal NOAEL serving as the basis for the reference values, which was then divided by appropriate uncertainty factors. Where data were permitting, chemical-specific adjustment factors were derived to replace default uncertainty factor values of ten. Nonlinear kinetics are were predicted by the model in all species at PGME concentrations exceeding 100 ppm, which complicates interspecies and low-dose extrapolations. To address this complication, reference values were derived using two approaches which differ with respect to the order in which these extrapolations were performed: (1) uncertainty factor application followed by interspecies extrapolation (PBPK modeling); and (2) interspecies extrapolation followed by uncertainty factor application. The resulting reference values for these two approaches are substantially different, with values from the former approach being 7-fold higher than those from the latter approach. Such a striking difference between the two approaches reveals an underlying issue that has received little attention in the literature regarding the application of uncertainty factors and interspecies extrapolations to compounds where saturable kinetics occur in the range of the NOAEL. Until such discussions have taken place, reference values based on the latter approach are recommended for risk assessments involving human exposures to PGME and PGMEA.

  4. Energy-efficient alcohol-fuel production. Technical final report

    SciTech Connect (OSTI)

    Not Available

    1982-01-01

    The proposed utilization schedule for the alcohol fuel plant and methane generator is to produce 180 proof ethanol during the spring, summer, and fall (April to October). The ethanol will be used in the farm tractors and trucks during the planting, growing, and harvesting seasons. Some alcohol can be stored for use during the winter. The still will not be operated during the winter (November to March) when the methane from the digester will be used to replace fuel oil for heating a swine farrowing building. There are tentative plans to develop a larger methane generator, which will utilize all of the manure (dairy, beef, horses, and swine) produced on the ISU farm. If this project is completed, there will be enough methane to produce all of the alcohol fuel needed to operate all of the farm equipment, heat the buildings, and possibly generate electricity for the farm. The methane generating system developed is working so well that there is a great deal of interest in expanding the project to where it could utilize all of the livestock waste on the farm for methane production.

  5. On-farm anaerobic digester and fuel alcohol plant

    SciTech Connect (OSTI)

    Not Available

    1985-01-01

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

  6. Total Blender Net Input of Petroleum Products

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

    - Reformulated, RBOB for Blending w Alcohol MGBC - Reformulated, RBOB for Blending w ... Notes: RBOB with Ether, RBOB with Alcohol, and Reformulated GTAB Motor Gasoline Blending ...

  7. Refinery & Blenders Net Input of Crude Oil

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

    - Reformulated, RBOB for Blending w Alcohol MGBC - Reformulated, RBOB for Blending w ... Notes: RBOB with Ether, RBOB with Alcohol, and Reformulated GTAB Motor Gasoline Blending ...

  8. Palladium-cobalt particles as oxygen-reduction electrocatalysts

    DOE Patents [OSTI]

    Adzic, Radoslav; Huang, Tao

    2009-12-15

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

  9. Effects of oxygen and catalyst on tetraphenylborate decomposition rate

    SciTech Connect (OSTI)

    Walker, D.D.

    1999-12-15

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

  10. Low NOx combustion using cogenerated oxygen and nitrogen streams

    DOE Patents [OSTI]

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

    2009-02-03

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

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

    DOE Patents [OSTI]

    Isaacs, Hugh S.; Romano, Anthony J.

    1977-01-01

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

  12. Willamette Oxygen Supplementation Studies : Annual Report 1994.

    SciTech Connect (OSTI)

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

    1994-09-01

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

  13. Homogeneously dispersed, multimetal oxygen-evolving catalysts

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

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

    2016-03-24

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

  14. Nanoparticulate-catalyzed oxygen transfer processes

    DOE Patents [OSTI]

    Hunt, Andrew T.; Breitkopf, Richard C.

    2009-12-01

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

  15. 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...

  16. Direct tuyere injection of oxygen for enhanced coal combustion

    SciTech Connect (OSTI)

    Riley, M.F.

    1996-12-31

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

  17. Altered cardiovascular reactivity and osmoregulation during hyperosmotic stress in adult rats developmentally exposed to polybrominated diphenyl ethers (PBDEs)

    SciTech Connect (OSTI)

    Shah, Ashini; Coburn, Cary G.; Watson-Siriboe, Abena; Whitley, Rebecca; Shahidzadeh, Anoush; Gillard, Elizabeth R.; Nichol, Robert; Leon-Olea, Martha; Gaertner, Mark; Kodavanti, Prasada Rao S.

    2011-10-15

    Polybrominated diphenyl ethers (PBDEs) and the structurally similar chemicals polychlorinated biphenyls (PCBs) disrupt the function of multiple endocrine systems. PCBs and PBDEs disrupt the secretion of vasopressin (VP) from the hypothalamus during osmotic activation. Since the peripheral and central vasopressinergic axes are critical for osmotic and cardiovascular regulation, we examined whether perinatal PBDE exposure could impact these functions during physiological activation. Rats were perinatally dosed with a commercial PBDE mixture, DE-71. Dams were given 0 (corn oil control), 1.7 (low dose) or 30.6 mg/kg/day (high dose) in corn oil from gestational day (GD) 6 through postnatal day (PND) 21 by oral gavage. In the male offspring exposed to high dose PBDE plasma thyroxine and triiodothyronine levels were reduced at PND 21 and recovered to control levels by PND 60 when thyroid stimulating hormone levels were elevated. At 14-18 months of age, cardiovascular responses were measured in four groups of rats: Normal (Oil, normosmotic condition), Hyper (Oil, hyperosmotic stress), Hyper PBDE low (1.7 mg/kg/day DE-71 perinatally, hyperosmotic stress), and Hyper PBDE high (30.6 mg/kg/day DE-71 perinatally, hyperosmotic stress). Systolic blood pressure (BP), diastolic BP, and heart rate (HR) were determined using tail cuff sphygmomanometry and normalized to pretreatment values (baseline) measured under basal conditions. Hyperosmotic treatment yielded significant changes in systolic BP in PBDE exposed rats only. Hyper PBDE low and high dose rats showed 36.1 and 64.7% greater systolic BP responses at 3 h post hyperosmotic injection relative to pretreatment baseline, respectively. No treatment effects were measured for diastolic BP and HR. Hyper and Hyper PBDE rats showed increased mean plasma osmolality values by 45 min after injection relative to normosmotic controls. In contrast to Hyper rats, Hyper PBDE (high) rats showed a further increase in mean plasma osmolality at 3 h (358.3 {+-} 12.4 mOsm/L) relative to 45 min post hyperosmotic injection (325.1 {+-} 11.4 mOsm/L). Impaired osmoregulation in PBDE-treated animals could not be attributed to decreased levels of plasma vasopressin. Our findings suggest that developmental exposure to PBDEs may disrupt cardiovascular reactivity and osmoregulatory responses to physiological activation in late adulthood. - Highlights: > We examined whether PBDE exposure could impact osmotic and cardiovascular regulation. > Hyperosmotic treatment yielded significant changes in systolic BP in PBDE exposed rats only. > PBDEs may disrupt cardiovascular and osmoregulatory responses to physiological activation.

  18. 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.

  19. Manipulation of the HIF–Vegf 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 0.00625–5 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 HIF–Vegf 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 Hippel–Lindau 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 HIF–Vegf 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.

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

    SciTech Connect (OSTI)

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

    2014-01-01

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

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

    DOE Patents [OSTI]

    Joshi, Ashok V.; Balagopal, Shekar; Pendelton, Justin

    2011-12-13

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

  2. Low cost hydrogen/novel membrane technology for hydrogen separation from synthesis gas, Phase 1. [Poly(etherimide) and poly(ether-ester-amide) membranes

    SciTech Connect (OSTI)

    Not Available

    1986-01-01

    During the last quarter several high performance membranes for the separation of hydrogen from nitrogen, carbon monoxide, hydrogen sulfide and carbon dioxide. The heat-resistant resin poly(etherimide) has been selected as the polymer with the most outstanding properties for the separation of hydrogen from nitrogen and carbon monoxide. Flat sheet and hollow fiber poly(etherimide) membranes have been prepared and evaluated with pure gases and gas mixtures at elevated pressures and temperatures. Multilayer composite poly(ether-ester-amide) membranes were also developed. These membranes are useful for the separation of carbon dioxide and hydrogen sulfide hydrogen. They have very high selectivities and extremely high normalized carbon dioxide and hydrogen sulfide fluxes. Separation of carbon dioxide/hydrogen streams is a key problem in hydrogen production from coal. The development of the two membranes now gives us two approaches to separate these gas streams, depending on the stream's composition. If the stream contains small quantities of hydrogen, the hydrogen- permeable poly(etherimide) membrane would be used to produce a hydrogen-enriched permeate. If the stream contains small quantities of carbon dioxide or hydrogen sulfide, the poly(ether-ester-amide) membrane would be used to produce a carbon dioxide/hydrogen sulfide-free, hydrogen-enriched residue stream. 6 fig., 4 tabs.

  3. Novel Vertimass Catalyst for Conversion of Ethanol and Other Alcohols into

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

    Fungible Gasoline, Jet, and Diesel Fuel Blend Stocks | Department of Energy Novel Vertimass Catalyst for Conversion of Ethanol and Other Alcohols into Fungible Gasoline, Jet, and Diesel Fuel Blend Stocks Novel Vertimass Catalyst for Conversion of Ethanol and Other Alcohols into Fungible Gasoline, Jet, and Diesel Fuel Blend Stocks Breakout Session 2-B: New/Emerging Pathways Novel Vertimass Catalyst for Conversion of Ethanol and Other Alcohols into Fungible Gasoline, Jet, and Diesel Fuel Blend

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

    SciTech Connect (OSTI)

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

    1995-12-31

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

  5. 01-12-1998 - Bench Top FIre Involving Use of Alcohol and Burner...

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

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

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

    SciTech Connect (OSTI)

    Blaser, Richard

    1980-11-01

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

  7. Hydrogen Production Using Hydrogenase-Containing Oxygenic Photosynthetic Organisms

    DOE Patents [OSTI]

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

    2006-01-24

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

  8. THERMOCHEMICAL CONVERSION OF FERMENTATION-DERIVED OXYGENATES TO FUELS

    SciTech Connect (OSTI)

    Ramasamy, Karthikeyan K.; Wang, Yong

    2013-06-01

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

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

    SciTech Connect (OSTI)

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

    2014-01-14

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

  10. Hydrogen production using hydrogenase-containing oxygenic photosynthetic organisms

    DOE Patents [OSTI]

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

    2006-01-24

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

  11. Probing oxygen vacancy concentration and homogeneity in solid-oxide

    Office of Scientific and Technical Information (OSTI)

    fuel-cell cathode materials on the subunit-cell level (Journal Article) | SciTech Connect Probing oxygen vacancy concentration and homogeneity in solid-oxide fuel-cell cathode materials on the subunit-cell level Citation Details In-Document Search Title: Probing oxygen vacancy concentration and homogeneity in solid-oxide fuel-cell cathode materials on the subunit-cell level Oxygen vacancy distributions and dynamics directly control the operation of solid-oxide fuel cells and are

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

    SciTech Connect (OSTI)

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

    2014-04-07

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

  13. Quick setting water-compatible furfuryl alcohol polymer concretes

    DOE Patents [OSTI]

    Sugama, Toshifumi; Kukacka, Lawrence E.; Horn, William H.

    1982-11-30

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

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

    SciTech Connect (OSTI)

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

    1994-08-01

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

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

    Broader source: Energy.gov [DOE]

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

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

    Broader source: Energy.gov [DOE]

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

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

    DOE Patents [OSTI]

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

    2011-01-25

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

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

    Open Energy Info (EERE)

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

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

    Office of Scientific and Technical Information (OSTI)

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

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

    Office of Scientific and Technical Information (OSTI)

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

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

    DOE Patents [OSTI]

    Looney, Brian B.; Denham, Miles E.

    2007-01-09

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

  2. Enhancing SNCR-aided combustion with oxygen addition

    DOE Patents [OSTI]

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

    2004-03-09

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

  3. Chronic alcohol consumption enhances iNKT cell maturation and activation

    SciTech Connect (OSTI)

    Zhang, Hui Zhang, Faya; Zhu, Zhaohui; Luong, Dung; Meadows, Gary G.

    2015-01-15

    Alcohol consumption exhibits diverse effects on different types of immune cells. NKT cells are a unique T cell population and play important immunoregulatory roles in different types of immune responses. The effects of chronic alcohol consumption on NKT cells remain to be elucidated. Using a mouse model of chronic alcohol consumption, we found that alcohol increases the percentage of NKT cells, especially iNKT cells in the thymus and liver, but not in the spleen or blood. Alcohol consumption decreases the percentage of NK1.1{sup −} iNKT cells in the total iNKT cell population in all of the tissues and organs examined. In the thymus, alcohol consumption increases the number of NK1.1{sup +}CD44{sup hi} mature iNKT cells but does not alter the number of NK1.1{sup −} immature iNKT cells. A BrdU incorporation assay shows that alcohol consumption increases the proliferation of thymic NK1.1{sup −} iNKT cells, especially the NK1.1{sup −}CD44{sup lo} Stage I iNKT cells. The percentage of NKG2A{sup +} iNKT cells increases in all of the tissues and organs examined; whereas CXCR3{sup +} iNKT cells only increases in the thymus of alcohol-consuming mice. Chronic alcohol consumption increases the percentage of IFN-γ-producing iNKT cells and increases the blood concentration of IFN-γ and IL-12 after in vivo α-galactosylceramide (αGalCer) stimulation. Consistent with the increased cytokine production, the in vivo activation of iNKT cells also enhances the activation of dendritic cells (DC) and NK, B, and T cells in the alcohol-consuming mice. Taken together the data indicate that chronic alcohol consumption enhances iNKT cell maturation and activation, which favors the Th1 immune response. - Highlights: • Chronic alcohol consumption increases iNKT cells in the thymus and liver • Chronic alcohol consumption enhances thymic Stage I iNKT cell proliferation • Chronic alcohol consumption enhances iNKT cell maturation in thymus and periphery • Chronic alcohol consumption induces Th1 immune response upon iNKT cell in vivo activation.

  4. Missing Oxygen Atoms Are Key to Robust Spintronic Material

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

    Missing Oxygen Atoms Are Key to Robust Spintronic Material Missing Oxygen Atoms Are Key to Robust Spintronic Material Print Friday, 01 April 2016 11:44 The endless pursuit of faster, more energy-efficient computers has led to the emergence of the field of spintronics, where the manipulation and detection of electron spins are utilized in electronic circuits. A particular class of materials called dilute magnetic oxides are promising candidates for spintronics applications because they exhibit

  5. Ab Initio Calculations of Even Oxygen Isotopes with Chiral

    Office of Scientific and Technical Information (OSTI)

    Two-Plus-Three-Nucleon Interactions (Journal Article) | SciTech Connect Initio Calculations of Even Oxygen Isotopes with Chiral Two-Plus-Three-Nucleon Interactions Citation Details In-Document Search Title: Ab Initio Calculations of Even Oxygen Isotopes with Chiral Two-Plus-Three-Nucleon Interactions Authors: Hergert, H. ; Binder, S. ; Calci, A. ; Langhammer, J. ; Roth, R. Publication Date: 2013-06-10 OSTI Identifier: 1102833 Type: Publisher's Accepted Manuscript Journal Name: Physical

  6. Sulfur Resistant Electrodes for Zirconia Oxygen Sensors - Energy Innovation

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

    Portal Sulfur Resistant Electrodes for Zirconia Oxygen Sensors Los Alamos National Laboratory Contact LANL About This Technology Technology Marketing SummaryTerbium-Yttrium-zirconium oxide (Tb-YSZ) is high-temperature, sulfur-resistant material for manufacture of electrodes for oxygen (O2) sensors. The Tb-YSZ sensor is resistant to sulfur and other acidic compounds present in exhaust gases and offers increased lifetime, stability, and accuracy over O2 sensors on the market

  7. Oxygen enhanced switching to combustion of lower rank fuels

    DOE Patents [OSTI]

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

    2004-03-02

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

  8. Method for making oxygen-reducing catalyst layers

    DOE Patents [OSTI]

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

    2010-06-22

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

  9. Oxygen-permeable ceramic membranes for gas separation

    SciTech Connect (OSTI)

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

    1998-02-01

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

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

    Office of Scientific and Technical Information (OSTI)

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

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

    SciTech Connect (OSTI)

    Munaò, Gianmarco; Urbic, Tomaz

    2015-06-07

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

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

    SciTech Connect (OSTI)

    Not Available

    1994-05-01

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

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

    SciTech Connect (OSTI)

    Gurwitz, Ron; Cohen, Rotem; Shalish, Ilan

    2014-01-21

    ZnO surfaces adsorb oxygen in the dark and emit CO{sub 2} when exposed to white light, reminiscent of the lungs of living creatures. We find that this exchange of oxygen with the ambient affects the integrity of the ZnO surface. Thus, it forms a basis for several interesting surface phenomena in ZnO, such as photoconductivity, photovoltage, and gas sensing, and has a role in ZnO electrical conduction. Using x-ray photoelectron spectroscopy on ZnO nanowires, we observed a decomposition of ZnO under white light and formation of oxygen-depleted surface, which explains photoconductivity by the electron donation of oxygen vacancies. Our findings suggest that the observed decomposition of the ZnO lattice may only take place due to photon-induced reduction of ZnO by carbon containing molecules (or carbo-photonic reduction), possibly from the ambient gas, accounting in a consistent way for both the reduced demands on the energy required for decomposition and for the observed emission of lattice oxygen in the form of CO{sub 2}. The formation of oxygen-vacancy rich surface is suggested to induce surface delta doping, causing accumulation of electrons at the surface, which accounts for both the increase in conductivity and the flattening of the energy bands. Using surface photovoltage spectroscopy in ultra high vacuum, we monitored changes in the deep level spectrum. We observe a wide optical transition from a deep acceptor to the conduction band, which energy position coincides with the position of the so called green luminescence in ZnO. This green transition disappears with the formation of surface oxygen vacancies. Since the oxygen vacancies are donors, while the green transition involves surface acceptors, the results suggest that the initial emission of oxygen originates at the defect sites of the latter, thereby eliminating each other. This suggests that the green transition originates at surface Zn vacancy acceptors. Removing an oxygen atom from a Zn vacancy completes the vacancy to become a full ZnO molecule vacancy, which does not produce deep levels. Our results explain why ZnO finds use as an electrical detector for oxygen and for carbon containing gas molecules. They may also shed new light on photocatalytic uses of ZnO. It is suggested that similar surface phenomena may affect other semiconducting oxides.

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

    SciTech Connect (OSTI)

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

    2013-09-01

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

  15. Natural Ores as Oxygen Carriers in Chemical Looping Combustion

    SciTech Connect (OSTI)

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

    2013-08-01

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

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

    SciTech Connect (OSTI)

    Andrienko, Daniil A. Boyd, Iain D.

    2015-11-15

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

  17. Surface control of epitaxial manganite films via oxygen pressure

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

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

    2015-03-11

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

  18. Influence of Intrinsic Hole Concentration on Oxygen Sensing Properties of

    Office of Scientific and Technical Information (OSTI)

    Hot-Spot Based Eu{sub 1-x}Ca{sub x}Ba{sub 2}Cu{sub 3}O{sub 7-{delta}}Ceramics (Journal Article) | SciTech Connect Influence of Intrinsic Hole Concentration on Oxygen Sensing Properties of Hot-Spot Based Eu{sub 1-x}Ca{sub x}Ba{sub 2}Cu{sub 3}O{sub 7-{delta}}Ceramics Citation Details In-Document Search Title: Influence of Intrinsic Hole Concentration on Oxygen Sensing Properties of Hot-Spot Based Eu{sub 1-x}Ca{sub x}Ba{sub 2}Cu{sub 3}O{sub 7-{delta}}Ceramics We report oxygen sensing behavior

  19. CRADA Final Report: Ionically Conductive Membranes Oxygen Separation

    SciTech Connect (OSTI)

    Visco, Steven J.

    2001-10-29

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

  20. Method and apparatus for producing oxygenates from hydrocarbons

    DOE Patents [OSTI]

    Kong, Peter C. (Idaho Falls, ID); Lessing, Paul A. (Idaho Falls, ID)

    1995-01-01

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

  1. Method and apparatus for producing oxygenates from hydrocarbons

    DOE Patents [OSTI]

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

    1995-06-27

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

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

    DOE Patents [OSTI]

    Schlichting, Mark R. (Chesterton, IN)

    1994-01-01

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

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

    DOE Patents [OSTI]

    Schlichting, M.R.

    1994-11-22

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

  4. Properties of reactive oxygen species by quantum Monte Carlo

    SciTech Connect (OSTI)

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

    2014-07-07

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

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

    SciTech Connect (OSTI)

    Chang, Tsun-Mei; Dang, Liem X.

    2014-09-04

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

  6. Migration mechanisms of oxygen interstitial cluste (Journal Article) |

    Office of Scientific and Technical Information (OSTI)

    SciTech Connect Migration mechanisms of oxygen interstitial cluste Citation Details In-Document Search Title: Migration mechanisms of oxygen interstitial cluste Understanding the migration kinetics of radiation- Authors: Xian-Ming Bai ; Anter El-Azab ; Jianguo Yu ; Todd R. Publication Date: 2013-01-01 OSTI Identifier: 1083247 Report Number(s): INL/JOU-13-29349 DOE Contract Number: DE-AC07-05ID14517 Resource Type: Journal Article Resource Relation: Journal Name: Journal of Physics: Condensed

  7. Recovery Act: Novel Oxygen Carriers for Coal-fueled Chemical Looping

    Office of Scientific and Technical Information (OSTI)

    (Technical Report) | SciTech Connect Recovery Act: Novel Oxygen Carriers for Coal-fueled Chemical Looping Citation Details In-Document Search Title: Recovery Act: Novel Oxygen Carriers for Coal-fueled Chemical Looping Chemical Looping Combustion (CLC) could totally negate the necessity of pure oxygen by using oxygen carriers for purification of CO{sub 2} stream during combustion. It splits the single fuel combustion reaction into two linked reactions using oxygen carriers. The two linked

  8. On-farm production of fuel-alcohol in Mid-America technical and economic potential

    SciTech Connect (OSTI)

    Hohmann, M.A.

    1980-03-01

    Alcohol fuel production is suggested as an alternative to high energy costs for the Mid-American farmer. The steps involved in producing alcohol from biomass are reviewed. Fermentation equipment and procedures are readily available. The utilization of by-products for animal feeds is discussed. Combustion characteristics and chemical properties of ethanol are reviewed. Estimates are made of costs involved in alcohol production in the mid-west region. Regional agricultural consumption of gasoline is estimated and 3 scenarios are developed. Benefits of on-farm fuel production are outlined. (DMC)

  9. Overview of fuel alcohol from agricultural crops with emphasis on the Tennessee Valley. Bulletin Y-171

    SciTech Connect (OSTI)

    Roetheli, J.C.; Pile, R.S.; Young, H.C.

    1982-02-01

    An overview is presented of the factors and concerns associated with producing fuel alcohol from agricultural crops. Areas covered include: an assessment of energy used in agriculture; a categorization of grain crop production, land suitable for energy crop production, and livestock production in the 201-county TVA region; a summary of technical and economic information on fuel alcohol production; a discussion of acreages required to produce fuel for benchmark farms in the Tennessee Valley and possible erosion impacts; and a discussion of other pertinent advantages and disadvantages of fuel alcohol production from crops.

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

    DOE Patents [OSTI]

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

    2003-07-15

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

  11. High-temperature potentiometric oxygen sensor with internal reference

    DOE Patents [OSTI]

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

    2011-11-15

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

  12. Blood storage device and method for oxygen removal

    DOE Patents [OSTI]

    Bitensky, Mark W.; Yoshida, Tatsuro

    2000-01-01

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

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

    SciTech Connect (OSTI)

    Kelly, Sen; Turner, Miles M.

    2013-09-28

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

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

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

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

    2016-03-08

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

  15. 01-12-1998 - Bench Top FIre Involving Use of Alcohol and Burner | The Ames

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

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

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

    DOE Patents [OSTI]

    Ingram, Lonnie O.; Conway, Tyrrell

    1992-01-01

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

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

    DOE Patents [OSTI]

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

    2003-05-20

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

  18. 5-Carbon Alcohols for Drop-in Gasoline Replacement - Energy Innovation

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

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

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

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

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

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

    DOE Patents [OSTI]

    Greene, Marvin I.; Gelbein, Abraham P.

    1984-01-01

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

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

    DOE Patents [OSTI]

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

    1984-10-16

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

  2. Controlled temperature expansion in oxygen production by molten alkali metal salts

    DOE Patents [OSTI]

    Erickson, Donald C.

    1985-06-04

    A continuous process is set forth for the production of oxygen from an oxygen containing gas stream, such as air, by contacting a feed gas stream with a molten solution of an oxygen acceptor to oxidize the acceptor and cyclically regenerating the oxidized acceptor by releasing oxygen from the acceptor wherein the oxygen-depleted gas stream from the contact zone is treated sequentially to temperature reduction by heat exchange against the feed stream so as to condense out entrained oxygen acceptor for recycle to the process, combustion of the gas stream with fuel to elevate its temperature and expansion of the combusted high temperature gas stream in a turbine to recover power.

  3. Electrochemical Investigation of Al–Li/LixFePO4 Cells in Oligo(ethylene glycol) Dimethyl Ether/LiPF6

    SciTech Connect (OSTI)

    Wang, X.J.; Zhou, Y.N.; Lee, H.S.; Nam, K.W.; Yang, X.Q.; Haas, O.

    2011-02-01

    1 M LiPF{sub 6} dissolved in oligo(ethylene glycol) dimethyl ether with a molecular weight, 500 g mol{sup -1} (OEGDME500, 1 M LiPF{sub 6}), was investigated as an electrolyte in experimental Al-Li/LiFePO{sub 4} cells. More than 60 cycles were achieved using this electrolyte in a Li-ion cell with an Al-Li alloy as an anode sandwiched between two Li x FePO{sub 4} electrodes (cathodes). Charging efficiencies of 96-100% and energy efficiencies of 86-89% were maintained during 60 cycles at low current densities. A theoretical investigation revealed that the specific energy can be increased up to 15% if conventional LiC{sub 6} anodes are replaced by Al-Li alloy electrodes. The specific energy and the energy density were calculated as a function of the active mass per electrode surface (charge density). The results reveal that for a charge density of 4 mAh cm{sup -2} about 160 mWh g{sup -1} can be reached with Al-Li/LiFePO{sub 4} batteries. Power limiting diffusion processes are discussed, and the power capability of Al-Li/LiFePO{sub 4} cells was experimentally evaluated using conventional electrolytes.

  4. 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.

  5. Engineering Ralstonia eutropha for Production of Isobutanol (IBT) Motor Fuel from Carbon Dioxide, Hydrogen, and Oxygen Project Final Report

    SciTech Connect (OSTI)

    Sinskey, Anthony J.; Worden, Robert Mark; Brigham, Christopher; Lu, Jingnan; Quimby, John Westlake; Gai, Claudia; Speth, Daan; Elliott, Sean; Fei, John Qiang; Bernardi, Amanda; Li, Sophia; Grunwald, Stephan; Grousseau, Estelle; Maiti, Soumen; Liu, Chole

    2013-12-16

    This research project is a collaboration between the Sinskey laboratory at MIT and the Worden laboratory at Michigan State University. The goal of the project is to produce Isobutanol (IBT), a branched-chain alcohol that can serve as a drop-in transportation fuel, through the engineered microbial biosynthesis of Carbon Dioxide, Hydrogen, and Oxygen using a novel bioreactor. This final technical report presents the findings of both the biological engineering work at MIT that extended the native branched-chain amino acid pathway of the wild type Ralstonia eutropha H16 to perform this biosynthesis, as well as the unique design, modeling, and construction of a bioreactor for incompatible gasses at Michigan State that enabled the operational testing of the complete system. This 105 page technical report summarizing the three years of research includes 72 figures and 11 tables of findings. Ralstonia eutropha (also known as Cupriavidus necator) is a Gram-negative, facultatively chemolithoautotrophic bacteria. It has been the principle organism used for the study of polyhydroxybutyrate (PHB) polymer biosynthesis. The wild-type Ralstonia eutropha H16 produces PHB as an intracellular carbon storage material while under nutrient stress in the presence of excess carbon. Under this stress, it can accumulate approximately 80 % of its cell dry weight (CDW) as this intracellular polymer. With the restoration of the required nutrients, the cells are then able to catabolize this polymer. If extracted from the cell, this PHB polymer can be processed into biodegradable and biocompatible plastics, however for this research, it is the efficient metabolic pathway channeling the captured carbon that is of interest. R. eutropha is further unique in that it contains two carbon-fixation Calvin–Benson–Bassham cycle operons, two oxygen-tolerant hydrogenases, and several formate dehydrogenases. It has also been much studied for its ability in the presence of oxygen, to fix carbon dioxide into complex cellular molecules using the energy from hydrogen. In this research project, engineered strains of R. eutropha redirected the excess carbon from PHB storage into the production of isobutanol and 3-methyl-1-butanol (branched-chain higher alcohols). These branched-chain higher alcohols can be used directly as substitutes for fossil-based fuels and are seen as alternative biofuels to ethanol and biodiesel. Importantly, these alcohols have approximately 98 % of the energy content of gasoline, 17 % higher than the current gasoline additive ethanol, without impacting corn market production for feed or food. Unlike ethanol, these branched-chain alcohols have low vapor pressure, hygroscopicity, and water solubility, which make them readily compatible with the existing pipelines, gasoline pumps, and engines in our transportation infrastructure. While the use of alternative energies from solar, wind, geothermal, and hydroelectric has spread for stationary power applications, these energy sources cannot be effectively or efficiently employed in current or future transportation systems. With the ongoing concerns of fossil fuel availability and price stability over the long term, alternative biofuels like branched-chain higher alcohols hold promise as a suitable transportation fuel in the future. We showed in our research that various mutant strains of R. eutropha with isobutyraldehyde dehydrogenase activity, in combination with the overexpression of plasmid-borne, native branched-chain amino acid biosynthesis pathway genes and the overexpression of heterologous ketoisovalerate decarboxylase gene, would produce isobutanol and 3-methyl-1-butanol when initiated during nitrogen or phosphorus limitation. Early on, we isolated one mutant R. eutropha strain which produced over 180 mg/L branched-chain alcohols in flask culture while being more tolerant of isobutanol toxicity. After the targeted elimination of genes encoding several potential carbon sinks (ilvE, bkdAB, and aceE), the production titer of the improved to 270 mg/L isobutanol and 40 mg/L 3-methyl-1-butanol. Semicontinuous flask cultivation supplied the cells with sufficient nutrients while minimizing the toxicity caused by isobutanol. Under this cultivation, the R. eutropha mutant grew and produced more than 14 g/L branched-chain alcohols over the duration of 50 days. These results demonstrate that R. eutropha carbon flux can be redirected from PHB to branched-chain alcohols and that engineered R. eutropha can be cultivated over prolonged periods of time for product biosynthesis. While this bioengineering work was being done at the Sinskey laboratory at MIT, the researchers at the Worden laboratory at Michigan State were working on the design and construction of the required specialty bioreactor for incompatible gasses (BIG) that would allow the safe feeding of microbes on Carbon Dioxide, Hydrogen, and Oxygen without explosive results. The early design and assembly work in year 1 incorporated a novel microbubble generator to maximize the bioavailability of gasses within the system comprised of small scale hollow fiber reactors. The early success of the microbubble generator eliminated the need to investigate potentially toxic surfactants within the system. For operational control, the system design incorporated a Opto22-based control network. The researchers also selected the specific hollow fiber material suitable for the bioreactor application. A variety of commercially available hollow fiber membranes were compared with regard to their pore sizes, cell affinity, and potential interference to cell viability assays. The selected membrane with its spongy layer was then tested for diffusivity of O2 and CO2. The instrumented system was then fully assembled for experimentally measuring the heterotrophic growth rate of immobilized R. eutropha cells. The requisite procedures for inoculation, measurement, and cleaning were established enabling the system performance to be validated under controlled laboratory conditions. In year 2, the researchers completed the Opto22 based cross-platform control network, and the system’s communications across the Sartorius fermentation system and Bruker gas chromatograph was established via open platform communications (OPC) protocol. Using the revised system, measurements were taken of the R.eutropha cell growth rate and substrate mass transfer rate in the hollow fiber membrane. Several IBT recovery strategies were explored and resin adsorption was determined to be optimal solution for lab scale operations. The adsorption capacity of the resin column was then measured and IBT desorption using methanol has been demonstrated. With the growing body of experimental data in hand, mathematical models were constructed to demonstrate and map the cellular kinetics, mass transfer of heterotrophic and autotrophic substrates in the hollow fiber, and the adsorption process in the resin column. A structured kinetic model was constructed to describe the competition between cell mass generation and IBT production. The reactor was then scaled up from single fiber to a membrane area of 180 cm2 and then further to 1 ft2. In Year 3 of the research, the IBT mass transfer across the membrane was characterized within the system with experiments to empirically measure the IBT diffusion coefficient in the BIG spongy layer. Using the refined mathematical models, the researchers are now able to explain the experimental observations and predict bioreactor performance under a wide range of experimental conditions. The Big system is able to demonstrate continuous controlled operations with the integrated IBT recovery system. Both heterotrophic and autotrophic production have been shown during continuous operation with heterotrophic and autotrophic stages. Performance of BIG system has been measured during continuous run with alternating heterotrophic growth on fructose and autotrophic product formation on H2, CO2, and O2. Volumetric productivities of IBT at 325 mg/(L day) and of 3M1B at 50 mg/(L day) were achieved, which were comparable to that achieved under heterotrophic conditions. Using the mathematical model, researchers are able to predict system performance for scaled-up BIG system. The apparent diffusion coefficient of IBT in the spongy layer of XM-50 hollow fiber membranes has been measured at various lumen liquid flow rates. The experiment is simulated in COMSOL to validate the results. The constructed COMSOL model is able to simulate BIG system performance in both batch and continuous mode. Mathematical simulations of the system performance have been run to identify the most crucial operational conditions, identifying the rate-limiting factors in autotrophic production of IBT, and quantitating the rate of IBT catabolism. Investigations of the productivity of the production system have suggested and the modeling of the system has revealed a particular sensitivity to the catabolism of the produced IBT by the engineered R. eutropha. Experiments have been designed and executed to quantify the IBT catabolism of R. eutropha, which open up possibilities for further system improvements through future, targeted bioengineering of the strain. Finally, the researchers at Michigan State performed an economic analysis of the system, based on the collective results, and their findings are presented in full within the report.

  6. Bimetallic Fe-Ni Oxygen Carriers for Chemical Looping Combustion

    SciTech Connect (OSTI)

    Bhavsar, Saurabh; Veser, Goetz

    2013-11-06

    The relative abundance, low cost, and low toxicity of iron make Fe-based oxygen carriers of great interest for chemical looping combustion (CLC), an emerging technology for clean and efficient combustion of fossil and renewable fuels. However, Fe also shows much lower reactivity than other metals (such as Ni and Cu). Here, we demonstrate strong improvement of Fe-based carriers by alloying the metal phase with Ni. Through a combination of carrier synthesis and characterization with thermogravimetric and fixed-bed reactor studies, we demonstrate that the addition of Ni results in a significant enhancement in activity as well as an increase in selectivity for total oxidation. Furthermore, comparing alumina and ceria as support materials highlights the fact that reducible supports can result in a strong increase in oxygen carrier utilization.

  7. Engineering Multimetallic FePt-based nanowires for enhancing oxygen

    Office of Scientific and Technical Information (OSTI)

    reduction and methanol oxidation reactions (Conference) | SciTech Connect and methanol oxidation reactions Citation Details In-Document Search Title: Engineering Multimetallic FePt-based nanowires for enhancing oxygen reduction and methanol oxidation reactions Authors: Guo, Shaojun [1] + Show Author Affiliations Los Alamos National Laboratory [Los Alamos National Laboratory Publication Date: 2014-04-28 OSTI Identifier: 1129839 Report Number(s): LA-UR-13-28235 DOE Contract Number:

  8. Engineering Multimetallic FePt-based nanowires for enhancing oxygen

    Office of Scientific and Technical Information (OSTI)

    reduction and methanol oxidation reactions (Conference) | SciTech Connect and methanol oxidation reactions Citation Details In-Document Search Title: Engineering Multimetallic FePt-based nanowires for enhancing oxygen reduction and methanol oxidation reactions × You are accessing a document from the Department of Energy's (DOE) SciTech Connect. This site is a product of DOE's Office of Scientific and Technical Information (OSTI) and is provided as a public service. Visit OSTI to utilize

  9. Engineering Multimetallic FePt-based nanowires for enhancing oxygen

    Office of Scientific and Technical Information (OSTI)

    reduction reaction and methanol oxidation reaction (Conference) | SciTech Connect reaction and methanol oxidation reaction Citation Details In-Document Search Title: Engineering Multimetallic FePt-based nanowires for enhancing oxygen reduction reaction and methanol oxidation reaction Authors: Guo, Shaojun [1] + Show Author Affiliations Los Alamos National Laboratory [Los Alamos National Laboratory Publication Date: 2014-04-28 OSTI Identifier: 1129838 Report Number(s): LA-UR-13-28232 DOE

  10. Engineering Multimetallic FePt-based nanowires for enhancing oxygen

    Office of Scientific and Technical Information (OSTI)

    reduction reaction and methanol oxidation reaction (Conference) | SciTech Connect reaction and methanol oxidation reaction Citation Details In-Document Search Title: Engineering Multimetallic FePt-based nanowires for enhancing oxygen reduction reaction and methanol oxidation reaction × You are accessing a document from the Department of Energy's (DOE) SciTech Connect. This site is a product of DOE's Office of Scientific and Technical Information (OSTI) and is provided as a public service.

  11. Observing Oxygen Atoms Move during Information Storage in Tantalum Oxide

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

    Memristors | Stanford Synchrotron Radiation Lightsource Observing Oxygen Atoms Move during Information Storage in Tantalum Oxide Memristors Saturday, April 30, 2016 Memristor technology, or resistive random access memory (RRAM), is a frontrunner for next generation computer memory, owing to the promise of long endurance, low power, nanoscale device size and fast operation.1 Memristor devices are typically made of a transition metal oxide sandwiched between two metallic electrodes, and

  12. Excited states in the active media of oxygen - iodine lasers

    SciTech Connect (OSTI)

    Azyazov, V N

    2009-11-30

    A review of investigations of kinetic processes in active media oxygen - iodine lasers (OILs) performed in the last decade is presented. The mechanisms of pumping and quenching of electronically and vibrationally excited O{sub 2} and I{sub 2} molecules are considered, and dissociation mechanisms of I{sub 2} in the active medium of the OIL are analysed. The values of kinetic constants of processes proceeding in the active media of OILs are recommended. (review)

  13. Residual Oxygen on Nb Heated to 500 C

    SciTech Connect (OSTI)

    Kirby, R.; King, F.K.; Padamsee, H.; /Cornell U., LEPP

    2005-06-10

    The superconducting accelerating cavities for the International Linear Collider will be constructed of high-residual resistivity ratio (RRR) niobium sheet. Excessive oxygen within the skin depth (several microns) will reduce the RRR and increase resistive losses. We measure the thickness of this oxide layer, following bakeout simulation, to be about 0.5 nm thick. The results suggest that this layer will very slowly disappear from the top five nm at 500 C.

  14. Ceramic Membranes for Hydrogen/Oxygen Production - Energy Innovation Portal

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

    Vehicles and Fuels Vehicles and Fuels Startup America Startup America Industrial Technologies Industrial Technologies Hydrogen and Fuel Cell Hydrogen and Fuel Cell Find More Like This Return to Search Ceramic Membranes for Hydrogen/Oxygen Production Ceramic Membranes Developed at Argonne May Bring Fuel-Cell Cars Closer to Reality Argonne National Laboratory Contact ANL About This Technology Technology Marketing Summary In the long term, hydrogen is expected to be the fuel of choice for both the

  15. Real Space Mapping of Oxygen Vacancy Diffusion and Electrochemical

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

    Transformations by Hysteretic Current Reversal Curve Measurements - Energy Innovation Portal Hydrogen and Fuel Cell Hydrogen and Fuel Cell Energy Storage Energy Storage Find More Like This Return to Search Real Space Mapping of Oxygen Vacancy Diffusion and Electrochemical Transformations by Hysteretic Current Reversal Curve Measurements Oak Ridge National Laboratory Contact ORNL About This Technology Technology Marketing SummaryElectrochemical energy storage and conversion systems based on

  16. Atomically Precise Electrocatalyst for Oxygen Evolution Reaction | Stanford

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

    Synchrotron Radiation Lightsource Atomically Precise Electrocatalyst for Oxygen Evolution Reaction Thursday, March 31, 2016 Traditional heterogeneous catalysts contain a range of particles sizes, crystallographic faces, and surface structures. This heterogeneity makes catalysts design a challenge because the active sites responsible for catalytic activity are simply not known. An emerging class of "atomically-precise" nanocatalysts can help alleviate this problem because they form

  17. Controllable positive exchange bias via redox-driven oxygen migration

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

    Gilbert, Dustin A.; Olamit, Justin; Dumas, Randy K.; Kirby, B. J.; Grutter, Alexander J.; Maranville, Brian B.; Arenholz, Elke; Borchers, Julie A.; Liu, Kai

    2016-03-21

    We report that ionic transport in metal/oxide heterostructures offers a highly effective means to tailor material properties via modification of the interfacial characteristics. However, direct observation of ionic motion under buried interfaces and demonstration of its correlation with physical properties has been challenging. Using the strong oxygen affinity of gadolinium, we design a model system of GdxFe1-x/NiCoO bilayer films, where the oxygen migration is observed and manifested in a controlled positive exchange bias over a relatively small cooling field range. The exchange bias characteristics are shown to be the result of an interfacial layer of elemental nickel and cobalt, amore » few nanometres in thickness, whose moments are larger than expected from uncompensated NiCoO moments. This interface layer is attributed to a redox-driven oxygen migration from NiCoO to the gadolinium, during growth or soon after. Ultimately, these results demonstrate an effective path to tailoring the interfacial characteristics and interlayer exchange coupling in metal/oxide heterostructures.« less

  18. Taguchi methods applied to oxygen-enriched diesel engine experiments

    SciTech Connect (OSTI)

    Marr, W.W.; Sekar, R.R.; Cole, R.L.; Marciniak, T.J.; Longman, D.E.

    1992-12-01

    This paper describes a test series conducted on a six-cylinder diesel engine to study the impacts of controlled factors (i.e., oxygen content of the combustion air, water content of the fuel, fuel rate, and fuel-injection timing) on engine emissions using Taguchi methods. Three levels of each factor were used in the tests. Only the main effects of the factors were examined; no attempt was made to analyze the interactions among the factors. It was found that, as in the case of the single-cylinder engine tests, oxygen in the combustion air was very effective in reducing particulate and smoke emissions. Increases in NO{sub x} due to the oxygen enrichment observed in the single-cylinder tests also occurred in the present six-cylinder tests. Water in the emulsified fuel was found to be much less effective in decreasing NO{sub x} emissions for the six-cylinder engine than it was for the single-cylinder engine.

  19. Taguchi methods applied to oxygen-enriched diesel engine experiments

    SciTech Connect (OSTI)

    Marr, W.W.; Sekar, R.R.; Cole, R.L.; Marciniak, T.J. ); Longman, D.E. )

    1992-01-01

    This paper describes a test series conducted on a six-cylinder diesel engine to study the impacts of controlled factors (i.e., oxygen content of the combustion air, water content of the fuel, fuel rate, and fuel-injection timing) on engine emissions using Taguchi methods. Three levels of each factor were used in the tests. Only the main effects of the factors were examined; no attempt was made to analyze the interactions among the factors. It was found that, as in the case of the single-cylinder engine tests, oxygen in the combustion air was very effective in reducing particulate and smoke emissions. Increases in NO[sub x] due to the oxygen enrichment observed in the single-cylinder tests also occurred in the present six-cylinder tests. Water in the emulsified fuel was found to be much less effective in decreasing NO[sub x] emissions for the six-cylinder engine than it was for the single-cylinder engine.

  20. SYSTEM DESIGN AND ANALYSIS FOR CONCEPTUAL DESIGN OF OXYGEN-BASED...

    Office of Scientific and Technical Information (OSTI)

    DESIGN OF OXYGEN-BASED PC BOILER Citation Details In-Document Search Title: SYSTEM DESIGN AND ANALYSIS FOR CONCEPTUAL DESIGN OF OXYGEN-BASED PC BOILER You are accessing a ...